2nd International Conference on Integrated

Proceedings Volume 1: Environmentally Sustainable Innovative

www.iciem-conference.com

Approaches and MethodsAssessment

2nd International Conference on Integrated Environmental Management for Sustainable Development October 27-30, 2016 Sousse - Tunisia

ISSN 1737-3638 www.iciem-conference.com

Edited by: Boubakker Elleuch, University of Sfax, Tunisia

ISSN 1737-3638 Disclaimer Any papers included in these program reflect the personal opinion of the authors.

The publisher does not accept any liability for the correctness, accuracy or completeness of the information or for the observance of the private rights of any third parties. Any papers submitted by the authors do not necessarily reflect the editors’ opinion; their publication does not constitute any evaluation by the editors.

LABORA TO IRE . GÉNIE . ENVI

R ONNE ME NT . É CO T ECHNO LO GI E

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[ ESIAM ] Environmentally Sustainable Innovative Approaches and Methods

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PREFACE The 2nd ICIEM 2016, International Conference on Integrated Environmental Management for Sustainable Development seeks to create a tradition of a bi-annual gatherings of academia, industry and policy makers to build a series of environmental pollution monitoring systems and integrated management strategies. The conference will provide a forum for discussion amongst scientists, professionals and academia in different areas of the broader theme of environmental engineering and sciences. The wealth of information exchanged in this international meeting continues to be of great benefit to all involved in challenging environmental issues caused by the increase of pollutants loads discharged into natural environment ecosystems. Those challenges require the building of a regulatory framework and control strategies. This framework needs to be based on scientific evidence associated with exposure and health risk for pollution prevention and remediation strategies. The application of innovative remedial techniques and new scientific methods is key in order to reach sustainable development. It is therefore crucial to address the existing pollution problems, and protect public health as well as preserve the welfare of the environment. The application of cost-effective technologies for waste treatment and controls is much needed in order to make possible the implement of appropriate regulatory measures that insure success of broader policy in pollution prevention. Engineers and scientists working in this field need to be familiar with a wide range of issues including the physical processes of mixing and dispersion, and photochemical and biological developments. Hence, a continuous exchange of information between scientists in different parts of the world is essential. In recent years, environmental protection has emerged as a requirement that goes beyond the state borders to reach a global dimension. This awareness has resulted in numerous treaties, directives and conventions and even changed the way we do business. Protection of the environment, one of the pillars of sustainable development, is an absolute priority for the international community. In this context, the 2nd ICIEM conference aims to focus on relevant experiences, up-to-date scientific research and findings carried out all over the world to protect and preserve the environment. In addition, this meeting will allow the exchange of experiences to develop environmental protection strategies and pollution management tools.

Pr. Boubaker Elleuch

ICIEM chairman

5

COMMITTEES Publication committee • • • • • • • • • • •

Abbas Marok, Univ Tlemcen, Algeria Bouabker Elleuch, ENI SFAX, Tunisia

• Mohamed Sahbi Moalla, ISET SFAX, Tunisia • Nesrine Boujelben, ENI SFAX, Tunisia • Zied Marzouki, ENI Sfax, Tunisia

Baghdad Ouddane, Univ Lille, France Dominik Faust, TUD, Germany

Scientific committee

Hassan EL HADI, Univ Hassan II, Marocco

• Abdeltif Amrane, UMR CNRS, France

Mitsuteru Irie, Univ Tsukuba, Japan

• Abdelwaheb Aydi, FSB, Tunisia

Mohamed Ksibi, Univ Sfax, Tunisia

• Adel Kharoubi, ISSTE Gabes, Tunisia

Mongi Seffen, Univ Sousse, Tunisia

• Ahmed Ali Rashed , National Water Research Center, Egypt

Moomen Baroudi, Univ Liban, Liban

• Ahmed H. A. Dabwan, Tati University College, Malaysia

Ragab Ragab, ICID, UK

• Ahmed Kettab, ENP Alger, Algeria

Souad Benromdhane, EPA, USA

• Alain Grasmick, University de Montpellier II, France • Ali Sdiri, ENI Sfax, Tunisia

Honorary chairman • Hamed BEN DHIA, ENI, Sfax, Tunisia

• Amel Chabbouni, ENI Sfax, Tunisia • Amjad Kallel, ENI Sfax, Tunisia • Amor Djenina ,University de Tébessa, Algeria

General chairman • Boubakker Elleuch, ENI, Sfax, Tunisia

• Amr Abdelmeguid, CEDARE, Egypt • Bachir Achour, University Mohamed Khider- Biskra , Algeria • Baghdad Ouddane, University Lille 1, France

Springer representative • Dr. Nabil Khélifi

• Besma Mardassi, ISB Sfax, Tunisia • Cardoso Duarte José, U. London, UK

Publishing Editor Middle East & North Africa

• Chafai Azri, FS Sfax, Tunisia

Springer Research Group, Springer Nature,

• Dalel Belhaj, ENI Sfax, Tunisia

Germany

• Dalila Nedjraoui, USTHB Alger, Algeria • Dimitri Xanthoulis ,University de Liège , Belgique

Organizing committee • • • • • • • • •

• Fatma Aloulou, L3E, Tunisia

Ali Sdiri, ENI Sfax, Tunisia

• Farah Bouhamed, L3E, Tunisia

Dhoua Mabrouk; FLSH Sfax, Tunisia

• Fekher Jamoussi, Technopôle de Borj Cédria, Tunisia

Dorsaf Ben Othmen, FS Tunis, Tunisia

• Fekri Kammoun, FS Sfax, Tunisia

Farah Bouhamed, L3E, Tunisia

• Fouad Dabboussi, Lebanese University, Lebanon

Hichem Chourabia, Univ Sfax, Tunisia

• Gahdab Chakali, ENSA, Algeria

Mabrouk Eloussaief, FS Sfax, Tunisia

• Habib Abida, FS Sfax, Tunisia

Mehdi Nafa, Univ Badji Mokhtar-Annabaa, Algeria

• Habib Smida, FS Gabes, Tunisia

Mohamed Damak, L3E, Tunisia

• Hacib Ammami, INRGREF, Tunisia

Mohamed Moncef Serbaji, ENI SFAX, Tunisia

• Halima Chemani, University M‘Hamed Bougara, Algeria

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COMMITTEES • Hameed Bassim, University Sains Malaysia, Malaysia • Ikram Jaabiri, L3E, Tunisia • Imed Gargouri, University of Sfax, Tunisia • Iovu-Adrian Biris, FRM, Romania • Jalel Bouzid, ENI Sfax, Tunisia • Jamel Bouaziz, ENI Sfax, Tunisia • Lassaad Dassi, ISB Sfax, Tunisia • EL KHALIDI Khalid, University Chouaib Doukkali, Maroc • Kostas Chartzoulakis , NAGREF, Crete, Greece • Larbi Djabri, University Badjimokhar, Annaba, Algeria • Madhi Jaghbir, University of Jordan, Jordani • Maghnia Asmahane Bourabah, University of Tlemcen, Algeria • Mabrouk Eloussaief, FS Sfax, Tunisia • Mervat Elhoz, University de Balamand, Liban • Mohamed Ksibi, ISB Sfax, Tunisia • Mokhtar Bzioui , Water Resources Management, Morocco • Moncef Bouaziz, Univesity of Dresden, Germany • Moncef Khadhraoui, ENI Sfax, Tunisia • Moncef Zairi, ENI Sfax, Tunisia • Moneem Kallel, ENI Sfax, Tunisia • Moumen Baroudi, Lebanese University, Lebanon • Mounir Medhioub, FS Sfax, Tunisia • Mourad Ben Zina, ENI Sfax, Tunisia • Muhammad Shatanawi , University of Jordan, Jordan • Myriam Balaban, Editor In Chief of Desalination and Water Treatment Journal, Italy • Nadia El Bahnasway, WRRI, Egypt • Nadim Farajalla , American University of Beirut, Lebanon • Nesrine Boujelben, ENI Sfax, Tunisia • Nesrine Turki, L3E, Tunisia • Noureddine Gaaloul, INRGREF, Tunisia • Noureddine Soltani,Badji Mokhtar University, Algeria • Raoul Caruba, University of Nice, France • Ratiba Mitiche, ENP Alger, Algeria • Redouane Choukr-Allah, University Hassan II, Morocco

• • • • • • • • • • • • • •

Ridha Hachicha, ENI Sfax, Tunisia Rim Baccar, L3E, Tunisia Saadia Benmamar, ENP, Alger, Algeria Salem El Bouri, FS Sfax, Tunisia Sami Sayedi, CBS Sfax, Tunisia Samir Bouaziz, ENI Sfax, Tunisia Sanja Frka Milosavljević , Boskovic Institute, Croatia Tahar Mechechi, ENI Sfax, Tunisia Ulku Yetis, Mid. East Tech.University, Ankara, Turke Wali Ahmed, ISBS, Tunisia Wiem hamza, L3E, Tunisia Zied Marzouki, ENI Sfax, Tunisia Zohra Kraiem, ENI Gafsa, Tunisia Zouheir Elouaer , ENI Sfax, Tunisia

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KEYNOTES

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KEYNOTES

KEYNOTE 1 Thursday, October 27, 2016

(12:00 - 13:00) / Room 1

Title: Variabilité saisonnière et paramètres forçant les processus diagénitiques en milieux aquatique Presented by: Pr. Baghdad OUDDANE Full Professor in Lille 1 University, France

KEYNOTE 2 Friday, October 28, 2016 (08:30 - 09:30) / Room 1 Title: Springer Workshop: How to get published in a scientific journal Presented by: Dr. Nabil Khélifi Publishing Editor Middle East & North Africa Springer Research Group, Springer Nature, Germany

KEYNOTE 3 Saturday, October 29, 2016

(08:30 - 09:30) / Room 1

Title: Environmental Education and Health The Road to a New Job Market for the 21 st Century Presented by: Dr Souad BEN ROMDHANE Environmental Protection Agency, USA

9

KEYNOTES

KEYNOTE 4 Sunday, October 30, 2016

(18:15 - 19:00) / Room 1

Title: Eau et Changements Climatiques : Spécificités des Zones Arides, la Tunisie en exemple Presented by: Pr Hamed BEN DHIA Full Professor in University of Sfax, Tunisia

Table of Contents Phytochimic and pharmacological studies of some Central African medicinal plants with antidiabetic properties Koane Jean-Noël, Gouollaly Tsiba, Syssa-Magale Jean-Laurent, Ouamba Jean-Maurille

001

FROM BIOMORPHIC FORM TO ACTIVE ARCHITECTURAL ENVELOPE: RESPONSE TO ENVIRONMENTAL CONCERNS Hamimed Meriem, Derradji Mohamed

016

Assessment of marine pollution from Bay of Monastir, Tunisia Mohamed Damak , Monom Kalel

026

REGENERATION AND REUSE WASTE FROM AN EDIBLE OIL REFINERY Boukerroui Abdelhamid, Belhocine Lydia, Ferroudj Sonia

032

ADSORPTION OF TERPENES COMPOUNDS ONTO PALYGORSKITE Sana Ghrab , Mabrouk Lousaief, Marc Cretin, Stéphanie Lambert, Samir Bouaziz , Mourad Benzina

046

ENCAPSULATION OF Pb/Zn REJECTS IN METAKAOLIN BASED GEOPOLYMER K.Bouguermouh, N.Bouzidi,L.Mahtout, T.Hassam, S.Mouhoub

060

Adsorption of Basic Dye from Aqueous Solution by Nanocomposite Materials A. Nait-Merzoug, O. Guellati , A. Benjaballah , Z. Belouettar , I. Janowska , D. Bégin , N. Manyala and M. Guerioune

074

Study of binary mixture of biocomposites (PLA/cellulose fibers): structure-properties Khadija Mbarki , Adel Sayari, Fahmi Bedoui, Boubaker Elleuch

088

Polylactic acid thermoplastic starch mixture: properties Khadija Mbarki, Adel Sayari, Boubaker Elleuch

096

Gypsum plaster production from phosphogypsum Raida Moalla, Foued Khmiri, Lotfi Kamoun, Moncef Zairi

102

Photocatalytic Properties of Fe-TiO /HY zeolite: Effect of iron composition on degradation of 2

Methylene Blue under UV and Visible light irradiation Foura Ghania, Soualah Ahcène

110

ADSORPTIVE REMOVAL OF CATIONIC AND ANIONIC DYES FROM AQUEOUS SOLUTION BY UTILIZING ALMOND SHELL AS BIOADSORBENT Achraf Ghorbal, Rim Ben Arfi, Sarra Karoui, Karine Mougin

120

Aerosol optical properties of Western Mediterranean basin from multi-year AERONET data Jamel Benkhalifa , Jean François Léon , Mabrouk Chaabane

136

GEOCHEMISTRY OF METAL TRACES IN SEDIMENT CORES OF THE BAY OF ALGIERS Boulahdid Mostefa, Houria Athmani, Olivier Radakovitch, Jean-Paul Ambrosi et Nadia Hocini

150

HEAVY METAL REMOVAL FROM İNDUSTRİAL WASTEWATER USİNG MAGNETİC LATEX PARTİCLES FUNCTİONALİZED WİTH ITACONİC ACİD AS NANOADSORBENT. ZIED MARZOUGUI, AMEL CHAABOUNI, ABDELAHAMID ELAISSARI, BOUBAKER ELLEUCH

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Phytochimic and pharmacological studies of some Central African medicinal plants with antidiabetic properties

KOANE Jean-Noël1, GOUOLLALY Tsiba2, SYSSA-MAGALE Jean-Laurent3, OUAMBA JeanMaurille4 1Department of Chemistry, Faculty of Science, University of Bangui, Central African Republic E-mail: [email protected]/ [email protected]/ [email protected] 2Unit of Chemistry of the Plant and the Life, Faculty of Science, Marien-Ngouabi University, Brazzaville Congo E-mail: [email protected] 3 Department of Chemistry, Faculty of Science, University of Bangui, Central African Republic E-mail: [email protected]/ [email protected] 4 Unit of Chemistry of the Plant and the Life, Faculty of Science, Marien-Ngouabi University, Brazzaville Congo E-mail: [email protected]

Abstract For thirty years, diabetes is a real public health problem worldwide. It results in abnormally high blood sugar measured in the blood several months apart, at a concentration greater than 1.4 gr. per liter at fasting and it affects all age groups. It is a chronic metabolic disease that occurs when the pancreas does not secrete insulin, insulindependent (type I) usually affects young individuals age 30 or when the pancreas does not produce enough insulin secretion and that it is in deficit; form of diabetes found in adults and obese: diabetes non-insulindependent (type II). Besides these two forms of diabetes are primitive, there are diabetes secondary to other diseases, diabetes and gestational diabetes Mady. Indeed, given the dissatisfaction found in modern medicine, traditional herbal tracks seem to reinforce potential interest, including the process of development, from plant to phytomedicine through appropriate scientific methods, could offer a credible alternative, for communities.

Keywords: phytochemical, pharmacological, medicinal plants, antidiabetic.

1.

Introduction

Nowadays, the endemic diseases like the onchocercose, hepatitis, the malaria, the diabetes or the AIDS are parmis the plagues against which, the Third World countries in general and the countries African in particular must face means, especially financier, limités.Les consequences which result from it are inter alia: rise of certain drugs which are not accessible in the majority from the populations often far away from the centers from health;

the demonstration, for

socioculturelles reasons, of a certain mistrust of the people alive in particular in rural zones with regard to modern medicine, preferring to turn itself near the traditional guérisseurs who very often do not control concepts like proportioning of the remedies to be managed with their patients. 2nd ICIEM 2016, International Conference on Integrated Environmental Management for Sustainable Development

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The corollary of all this is a morbidity and a mortality increasing which slow down the development of the countries concerned and by there accentuates the poverty of their populations To solve these specific problems of public health in Central Africa, in particular, one of the ways seems to us to be the use and the valorization of the medicinal plants in which our forests abound with profusion and who already were the proof of their effectiveness. Within the framework of our research project in order to obtain the Ph.D doctorate and to contribute our modest share to solve the problems of public health, we focused our attention on one of these plagues, the diabetes, which was recognized by the World Health Organization (WHO) as being an urgent priority on the national and international level [1, 2]. Indeed, the rate of prévalence of the diabetes in the world, according to forecasts' made by experts [3] was 4% either 135 million people in 1995, this rate would reach 5,4% or 300 million people into 2025. The strongest progressions of this disease insidious and crawling will be observed in the countries in the process of development: one will have an increase of 17% indeed is a progression from 84 to 228 million patients between 1995 and 2025. During the same period in Central Africa the progression of the rate of prévalence of the diabetes will be among most significant, thus passing from 72000 to 210000 diabétiques [4]. In Central Africa, a good fringe the diabétiques ones is currently old between 40 to 65 years [ 5 ] which has as a by-effect to blame our policy of development, insofar as this category of patients are workers who play a significant role in the construction of the nation. They will have rather, during the many years when they are supposed to produce, to face chronic complications of their disease, which will imply the use of the resources for their constant medical follow-up, very often expensive for the State and their family [ 6,7 ]

It is finally advisable to stress that the

objective of African Traditional the Pharmacopée program and Medicine of the CAMES is to place at the disposal of the African populations Traditional Drugs Improved (MTA) in order to solve the crucial problem of drugs, and to gradually create the conditions of the establishment of the future African pharmaceutical industry. Unfulfilled objectives since the development of this program, brought the 13th Conference on the African Traditional Pharmacopeia and Medicine (PMTA), held in Yaoundé (Cameroun) from the 06 to December 10 2004, to react to the critics of the Steering committee (Audit of the AUF), and to suggest creation inside the program, with an aim of rationalization, three geographical areas with each one of it of target pathologies in addition to the VIH/SIDA: 1. West Africa: Paludism; 2. Central Africa: Hypertensives and metabolic diseases; 3. East Africa and Madagascar: diarrheal diseases. For the continuation of the program, it was necessary of identification of the Research projects – Development worked out in each under area and fascinating of account the targeted concerns, the Secretariat-general of the CAMES giving the responsability itself to seek the financings necessary to the realization of the activities. Network PMTA Central Africa, creates in December 2005 and coordinated of Professor Jean-Maurille OUAMBA, takes part in work on the diarrheal

2nd ICIEM 2016, International Conference on Integrated Environmental Management for Sustainable Development

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diseases by gathering the data of under area on the question through thesis or research projects of which this one.

2. Objectives of the study 2.1. General Objective This research protocol is designed to contribute to better knowledge of plants used in the pharmacopoeia and traditional medecine in Central Africa, specifically those used by traditional healers for treatment of diabetes.

2.2. Objectifs spécifiques The study intends to achieve the following objectives: •

Inventory and identify medicinal plants used in traditional treatments of

diabetes. •

Verify and prove by ethno-medical procedures, the effectiveness of key

plants to retain. •

Extract the active ingredients and medicinal properties for the development

of herbal medicines. •

Highlight the main chemical groups in plant extracts.

•

Evaluate the pharmacological activities.

•

Isolate the active fractions after selective extraction.

•

Purify the active fractions to isolate the active principles.

•

contribute to finding solutions to health problems of the population of

Central Africa in general and particularly in the context of diabetes improved quality of life there of. These are the reasons that lead us to conduct this study in view to make our modest contribution to the research undertaken in this particular sector in Central and / or Congo Brazzaville under development, rational management and sustainable use of GR renewable, conservation of biodiversity and cultural heritage of scientific and indigenous knowledge.

3. Materials and methods 3.1. Plant material Usually five (5) medicinal species have been identified and inventoried in Bangui and its surroundings during the treatment of diabetes by traditional healers (see table1)


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Vernacular Scientific name

Bodies

(Family)

used

names

Medical

+ Vulgar names (Issongo)

Morinda Lucida

The decoction of bark

Leaves,

Bth. (Rubiaceae)

Mokekele

Bark

and foliage is used for toilet diabetic Two small wrists cut

Persea americana Mill.

Leaves

Avocado

(Lauraceae)

leaves into small pieces, infuse a liter of water to drink during the day

Ocimum

The disease diabetes

gratissimum L.

Leaves

Ngbanda

consume the macerated leaves

(Lamiaceae)

as a beverage

Citrus

Moguembeg

aurantifolia L.

Leaves

uembe

(Rutaceae)

Against diabetes, the decoction of fresh leaves mixed

Citronnier

with honey The leaves mixed with

Paullinia pinnata L.

Leaves

Gagambolo

(Sapindaceae)

lightly toasted sesame is consumed by the patient three times

Table1: Five selected medicinal plants used against diabetes The plant material consists of leaves, roots, barks harvested in the area of Bangui and its surroundings. These plants are also used traditionally to treat many diseases. Their botanical identification was carried out at the Faculty of Science Department of Materials Science at the University of Bangui. The samples are dried at room temperature in the laboratory of direct sunlight and then ground and extracted.

3.2. Methods The following methodology is adopted : •

Ethnobotanical Survey : -

Identification of traditional healers;

-

The collection of botanical specimens of plants designated by the study

team by traditional healers; -

Documentary research on the pharmacological properties of these plants

harvested and their various uses in traditional medicine in African pharmacopoeia (Congolese, Cameroonian, Senegalese and Central we have). 2nd ICIEM 2016, International Conference on Integrated Environmental Management for Sustainable Development

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•

Study phytochemical :

Many solvents will be used for the extraction of plant material. The different parts of the herbal substance are selected from the therapeutic uses of traditional healers as the solvent used. The extraction can be cold (maceration) or hot (Soxhlet). Subsequently, these different extractions will be performed in the laboratory of chemistry, a chemical screening will be performed on crude extracts of different samples to highlight the family of alkaloids, triterpenes, flavonoids, sterols, tannins, saponins, etc.., D According to the method described by Abayomi (1996). Finally, we will end the isolation, purification and structure determination of active principles: to achieve, it is necessary to use analytical techniques for separation and / or characterization.

The

technique most

commonly

used

is the High Performance Liquid

Chromatography (HPLC) in order to isolate the active extracts to fractionate and purify them. The use of infrared (IR), Mass Spectrometry (MS), etc.. Allows us to identify the molecular structure of compounds. •

Evaluation of pharmacological activities:

This task boils down to evaluating the toxicity and anti-hyperglycemic with the assistance of biologists network Apay Central Africa. •

Literature:

It will be put to therapeutic uses to compare species identified through our work in the plants studied in other pharmacopoeias including the Congo, Senegal and the ethnobotany of the expedition conducted by the Central Empire.

4. Expected 1.

Establishment of a database on plants antiglycémiantes potential (chemical

screening of extracts, evaluation of the biological activity of fractions, isolation of active principles, correlation "structure - activity); 2.

Confirmation or denial of the application areas of these plants and their

pharmaceutical interest; 3.

Publication of results (annual reports, scientific papers, patents, and

possibly work); 4.

Defending a doctoral thesis at the University Ngouabi;

5.

In the medium term, the formulation of improved traditional medicines.


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5. Results Plants (Bodies)

solvents

EtOH

Extraction Method

Type of extract

Macération

PPM EtOH

Reflux

PPR EtOH

Ultraso

30

PPU 30EtOH

70

PPU 70EtOH

°C

n °C

EtOH 80%

Macération

PPM EtOH80

Reflux

PPR EtOH80 30

Ultraso

°C

n

80

70 °C

EtOH 70%

Macération

PPM EtOH70

Reflux

PPR EtOH70

Ultraso

°C

n °C

70

PPM EtOH60

Reflux

PPR EtOH60 30

Ultraso

°C 70

PPU 70EtOH 60

Macération

PPM EtOH50

Reflux

PPR EtOH50 30°

Ultraso

C

n

PPU 30EtOH 50

70° C

PPU 70EtOH 50

Macération

PPM EtOH40

Reflux

PPR EtOH40 30°

Ultraso

C

n

PPU 30EtOH 40

70° C


PPU 30EtOH 60

°C

EtOH 40%

PPU 70EtOH

Macération

n

EtOH 50%

PPU 30EtOH 70

70

Paullinia pinnata

EtOH 60%

PPU 70EtOH 80

30

L. (leaves)

PPU 30EtOH

PPU 70EtOH 40

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Persea americana Benth. (leaves)

EtOH

PAM EtOH

EtOH 50%

PAM EtOH50

EtOH 70%

PAM

EtOH

70%

Ocimum gratissimum L. (leaves)

EtOH

OGM EtOH

EtOH 50%

OGM EtOH5 0

EtOH 70%

OGM EtOH7

Macération

0

Morinda lucida L. (leaves, Barks) Citrus aurantifolia L. (leaves)

EtOH

MLM EtOH

EtOH 50%

MLM EtOH50

EtOH 70%

MLM EtOH70

EtOH

CAM EtOH

EtOH 50%

CAM EtOH50

EtOH 70

CAM EtOH70

Table 2: Preparation of solvent extracts according to the used extraction technologies

5.1. Based solvents extraction yield Each crude extract for each organ (leaves and peels), we calculated solvent extraction yield, the results obtained are presented in Table 3 below.

botanical species

organ

Extr

(Initial weight =

action

10g)

solvent EtOH

Paullinia pinnata L.

Leaves

EtOH 50 ETO H70 EtOH

Ocimum gratissimum L.

Leaves

EtOH 50 ETO H70

Citrus Limonum Risso

Leaves


EtOH

extrac t Masse

A mount (%)

(g) 0,46 0,70 0,65 0,41 0,70 0,66 0,40

4, 6 7, 0 6, 5 4, 1 7, 0 6, 6 4, 0

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EtOH 50 ETO

EtOH

americana Benth.

ETO

EtOH

6, 7 6, 6 2, 0 3,

0,33

50 ETO

3 3,

0,37

H70 EtOH

7 3,

0,34

EtOH

Leaves

9

0,20

EtOH

L.

3,

0,66

H70

Morinda lucida

6

0,67

50

Barks

5,

0,39

EtOH

Leaves

5

0,56

H70

Persea

5,

0,55

4 4,

0,45

50 ETO

5 4,

0,40

H70

0

Table 3: Extraction yield based solvents

The strongest returns whatever the organ of selected plant extracts hydroethanolic correspond to 50% and 70% (V / V) or (3.3 to 7.0%), against the ethanol extract 95 ° (2.2 -4.6%). It notes that the leaves of Paullinia pinnata, Ocimum gratissimum, Persea americana and exhibit the highest levels.

Botanical name

Organ (200g)

Extraction

Mass

solvent Petroleum ether

0 ,78

Chlorofor Paullinia pinnata

m

Leaves

1

Ethyl Methanol 2nd ICIEM 2016, International Conference on Integrated Environmental Management for Sustainable Development

1,1 6

,75

Acetate

yield (%)

(g)

8,4 7

0 ,24

3,7 7

1

65,

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3,63 Water

97 4

,26

61

Petroleum ether

1 ,04

Ocimum

Leaves

gratissimum

1 ,06

Methanol Water

5,0 8

Ethyl Acetate

4,9 6

Chlorofor m

20,

1 ,01

5,0 3

1 2,89

44, 15

7 ,68

26, 35

Table 4: liquid-liquid fractionation Yield We also note that the leaves of paullinia pinnata and Ocimum gratissimum always exhibit the

highestlevels. Plant

plant

(organ)

material mass (g)

Mass of oil (g)

yield (%)

Color

Citrus Limonum Risso.

100

0,06

0,06

(Leaves)

light yellow

Ocimum gratissimum L.

100

0,2

0,2

(Leaves)

dark yellow

. Table 5: essential oil yield of leaves of Citrus limonum Risso. Inspection of Table XIV shows that high yields are observed in the leaves of Ocimum gratissimum, low in leaves of citrus limonum Risso. and the two oils are completely different colors.

5.2

. Identification of major chemical groups

5.2.1.

Reaction tubes by identification

The results of the chemical screening performed on the bark of Morinda lucida Benth. and on the leaves of Paullinia pinnata L.; Citrus limonum Risso. ; Morinda Lucida Benth. ; Ocimum L. gratissimum; Persea americana Mill. are summarized in Table 6. 2nd ICIEM 2016, International Conference on Integrated Environmental Management for Sustainable Development

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This table shows that the different plant extracts revealed generally at different levels, the presence of thirteen (13) chemical families of sixteen (16) sought. So we note the presence of: saponins, flavonoids, alkaloids, steroids and terpenoids, tannins, leucoanthocyanins, free quinones, phlobatannins, amino acids, mucilage, sugars and holosides, reducing compounds, cardiac glycosides and coumarin. a total lack of it shows: anthraquinone, tétrahydrocannabiols and carotenoids.


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Caroténoïdes

Coumarines

Tétrahydrocannabiols

cardiotoniques

Hétérosides

Anthraquinones

Composés réducteurs

Oses et Holosides

Mucilages

Acides Aminés

Phlobatanins

Quinones libres

Leucoanthocyanes

Tanins

Alcaloïdes

Flavonoïdes

Saponosides

chemical families

Stéroïdes et terpénoïdes

ISSN 1737-3638

Plant (Organ) Citrus Limonum Risso. (F)

(31 8)

Morinda lucida Benth. (F) Morinda lucida Benth. (E) Ocimum gratissimum Linn. (F) Paullinia pinnata Linn. (F) Persea americana Mill. (F)

(F) : Leaves ;

(E) : Bark ;

+ +

(50)

+

+

+

+ +

+

+

+

+

+

+

+

+

+

+

+

++

+

+

++

(15 0)

-

+

(20 0)

+

+

+

++

+

+ +

-

+

(32 5)

+

-

+

(15 0)

+

+

+ +

( ) : index foam ;

+

+

+++ : abundant ;

+ ++ : Way ;

+ + : Low ;

t : trace ;

+ - : absent

Table 6: phytochemical profile of various extracts of plants selected by tube reactions 2nd ICIEM 2016, International Conference on Integrated Environmental Management for Sustainable Development

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Tannins, coumarins and saponins are present in the different samples respectively except in the bark extracts of Morinda lucida Benth and leaves Morinda lucida Benth. We note the absence of mucilage, reducing compounds, anthraquinones, tétrahydrocannabiols and carotenoids in extracts of leaves of Paullinia pinnata Linn.et of Ocimum gratissimum Linn, but the cardiac glycosides, amino acids, sugars and exist holosides in these two plants in trace. leaf extracts Citrus limonum Risso. are rich in saponins, flavonoids, tannins, amino acids, mucilages and coumarins followed traces of cardiac glycosides. We note, a total absence of (steroids

and

terpenoids,

saponins,

phlobatannins,

anthraquinone,

leucoanthocyanins,

tétrahydrocannabiols and carotenoids) in extracts of leaves of Morinda lucida Benth while the bark extracts of this plant contain. Leaf extracts of Persea americana Mill, are rich in saponins, flavonoids, alkaloids, tannins, leucoanthocyanins, free quinones, mucilage, glycosides and cardiac coumarines while amino acids and coumarins exist as trace.

5.3.

Thin Layer Chromatography extracts

Research and confirmation of chemical families on TLC is totally oriented on two types of metabolites. 5.3.1. Primary metabolites - Amino acids In this work, only free amino acids were studied. We chose to look for in the 5 species amino acids mentioned above. The chromatograms of the two migration systems (Figure 1).

Figure 1: Chromatogram amino acids Extrait hydroéthanolique. Solvents of migration : n-butanol/ acide acétique/ eau, (7/2,5/2,5 V/V/V). PP-F: Leaves of paullinia pinnata ; CA-F: Leaves of Citrus Limonum Risso. ; OG-F: Leaves of ocimum gratissimum ; ML-E: Bark of morinda lucida ; ML-F : Leaves of morinda lucida ; PA-F : Leaves of persea americana 1 : (S)-(+) - Aspartic acid ; 2 : Wistaria ; 3 : L(+) Arginine; 4: L-Tyrosine. Revealing : ninhydrine It is found in all that:


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• The chromatograms of the extracts of leaves paullinia pinnata, Persea americana have much less clear spots, but are observed purple streaks indicating the presence of certain amino acids in the plant. But an assay would quantify the levels of these amino acids in each plant; • The chromatograms of the extracts of Citrus Limonum Risso leaves., Ocimum gratissimum L. and Morinda lucida Benth. and bark of Morinda lucida Benth. exhibit sharper chromatographic profiles with some spots that could match the Glycine and L-Tyrosine. -Secondary metabolites Two types of secondary metabolites (polyphenols and terpenes and sterols) were sought.

-polyphenols The chromatographic profiles of alcoholic extracts (50% v / v) of the five plants after revelation of the plate Neu and exposing the plate to UV (λ = 365 nm) remain dominated by flavonoids and phenolic acids.

Figure 2: CCM hydoéthnoliques extracts (50% v / v) of the five plants PP-F, CA-F, OG-F, ML-F, PA-F et ML-E on silica gel plate. Eluent: ethyl acetate / formic acid / water (8/1/1 v / v / v) Revelation: Reagent Neu + UV 365 nm There is a succession of different fluorescence bands in the six bodies of the five selected plants: •

bark extract of Morinda lucida Bth: The yellow-orange bands Rf (0.01) characterizing

a flavonic glycoside substituted for two more dare and blue Rf (0.98) which we attribute to a phenol acid; •

Leaf Extract Citrus Limonum Risso. : The clear yellow bands Rf (021; 0.32; 0.48;

0.64) which we attribute to the flavonoids and blue Rf (0.13 and 0.97) to phenolic acids; •

Extract from the leaves of L. pinnata paullinia: The orange yellow and blue bands of

Rf (0.32 and 0.75), respectively, which we attribute to the flavonoids and phenols acids;


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•

Leaf Extract Persea americana Mill. : Yellow fluorescence bands clear of Rf (0.5)

attributable to phenolic acids; •

Leaf extract of Ocimum L. gratissimum: the fluorescence bands, yellow-orange Rf

(0.32 and 0.53) and yellow-green Rf (0.27 and 0.86) attributable flavonoids and light green Rf (0.51 and 0.97) to phenolic acids; •

Extract from the leaves of Morinda lucida Bth. : Fluorescence bands are light yellow

Rf (0.97 and 0.32), which are due to flavonoids. It should be noted the yellow fluorescent orange band Rf (0.01) is due to a glycoside substituted flavonic over two monosaccharides; •

Terpenes and sterols;

•

Highlighting terpenes thin layer (TLC) (Figure 3) reveals after spraying Anisaldehyde

a series of spots of color (yellow, orange yellow, purplish pink, dark purple), due to terpenes, sterols and saponins.

Figure

3:

CCM

chloroform

extracts

of

leaves

of

five

plants

silica gel plate, eluent: petroleum ether / ethyl acetate (80/20), Developer: UV Visible and anisaldehyde sulfuric heating Thus Figure 3 below gives the values of the front reference (Rf) of the chloroform extracts.

Rf

extra

R

cts f1

f2

P P-F P O C

f7

f8

,80

,95

,37

,41

,79

,95

,37

,55

,52

,57

,78

,84

,94

0 ,30

M

f6

0 ,60

A-F

f5

0 ,30

G-F

f4

0 ,62

A-F

f3

,82

0


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L-F

,38 M

L-E

,42

,54

,64

,75

,43

,55

,67

,87

,80

,88

,95

0 ,28

Table 7: References Frontales (R) compounds of chloroform extracts of five Plants

6. Resources At the plateau technique, we will benefit from the technical platform of the University of Bangui University Ngouabi which have been operating for 6-7 years, doctoral studies, and particularly, we will build the skills and materials scientist Doctoral Enhancement of aromatic plants, medicinal and food-medicament, the Regional Centre of Excellence AUF "Training and Research on Pharmacopoeia and African Traditional Medicine" and the Network of Central Africa Apay CAMS headquartered Ngouabi University of Brazzaville and placed under the coordination of Professor Jean-Maurille Ouamba.

7. References bibliographiques 1.

World Health Organization (1997). Non Communicable Disease Prevention

and Control: Report bye the Director General EB 101/14. Geneva, W.H.O. 2.

World Health Organization (1997): World Health Report: Conquering

Suffering, Enriching Humanity. Geneva, W.H.O, 152-156p. 3.

King H., Aubert R.E. et Herman W.H. (1998). Global Burden of Diabetes,

1995-2025. Diabetes Care, 21, 1414 – 31p. 4.

Cooper R., Rotimi C., Kaufman J., Owoaje E., Fraser H., Forrester T., Wilks

R., Riste L. et Cruikshank J.K. (1997). Prevalence of NIDDM among population of the African diaspora. Diabetes Care, 20, 343 -348. 5.

King H. et Rewers M. WHO (1993) Ad Hoc Diabetes reporting Group, Global

estimates and impaired glucose tolerance in adults. Diabetes Care, 16, 157 -177. 6.

Kerarho J. Adam J.G.(1974), pharmacopée Sénégalaise traditionnelle,

plantes médicinales et toxiques, Edition Vigot et frère, Paris. 7.

Adjanohoum

E.

1988,

Contribution

aux

études

ethnobotaniques

et

floristiques en République Populaire du Congo. ACCT. Paris 605 P.


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FROM BIOMORPHIC FORM TO ACTIVE ARCHITECTURAL ENVELOPE: RESPONSE TO ENVIRONMENTAL CONCERNS

Hamimed Meriem1, Derradji Mohamed2 1

Phd candidate, Department of architecture, University of Constantine 3 [email protected]

2

Senior lecturer, Department of architecture, University of Constantine 3 [email protected]

Abstract. The research consists of studying the importance of new technological systems based on natural or organic elements in the composition of a dynamic architectural envelope in order to achieve the creation of qualitative and sustainable environmental atmosphere inside buildings located in hot arid areas in Algeria. The main idea is to use concepts based on the potential of nature as an instrument that helps us to make smart, active and appropriate architectural envelopes.

This research aims to clarify biomorphic opportunities that can offer organic inspiration to develop architectural systems for regulating environmental atmospheres. The process of natural examples in fauna and flora can be imitated to improve the efficiency of cooling systems, natural ventilation, shade and protection systems from solar radiation to achieve comfort conditions in hot arid areas. How to design an active - intelligent - biomimetic architectural envelope inspired by natural or biological elements in order to achieve qualitative and sustainable environmental ambiences? This work will thoroughly analyze and imitate biological systems, using new technologies in the design and construction of active environmentally compatible envelopes.

The objective of this research is to attract the attention of designers to a new global style product, and how that thinking affects contemporary architecture. Moreover, this study allows, the development of knowledge based on bio-inspiration to educate young designers, engineers and investors in the building on the enormous changes that promises in the design of architectural envelopes and technologies for the control and regulation of environmental ambiences.

Keywords: Biomimicry, active architectural envelope, new technologies, environment, imitation


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1. Introduction “Nature is a universal and safe teacher for the beholder” [Carlo Goldoni] [1]. Nature has developed its system for billions of years and they work in harmony with each other. Animals, plants are "qualified engineers." They have found what works, what is appropriate and what resists. This is why nature is regarded as the eternal and universal master in history and in all areas. Therefore the inspiration from nature is not new, but it has recently started to be scientifically formulated in the form of several concepts such as the biomorphic, biomimicry, bionics or bio-inspiration. The science of biomimicry, biomorphism imitates nature through the study of the form, function, behavior and ecosystems of biological organisms to create non-biological systems. The various intelligent systems of biomorphic architecture is inspired from the ecosystems of biological organisms such as the thermoregulatory capacity of the human skin, the opening and closing of flowers in response to the sun light, the adaptability of the skin of many animals to the seasonal changes of temperature.

“The human spirit can produce many inventions through the implementation of various instruments contributing to the same goal. However, it never will be more beautiful, simpler or more suitable than those of nature because in her inventions to it, nothing is lacking and nothing is superfluous” [Leonardo DE Vinci] [2] Therefore to control and regulate the sustainable environmental atmospheres, several researchers have addressed the issue of the design of a technological process deduced from a biological or natural mechanism like Elghawaby, M. [3], BADARNAH K. L. [4] and Ménézo Ch. [5]... The results of their research show that bio-inspiration is a promising field for the development of sustainable technology for the conditioning of the building environment.

2.

From bıomorphıc to biomimetic approach

From the era of the caves to that of nanotechnology, and like everything that comes from the human race, architecture has always evolved as she underwent influences of all kinds: technological, political, economic, philosophical, and well others. Towards the end of the 20th century, changes occurred in the dominant architectural style, when architects were trends to mark the break with their elders of the modern movement under the influence of contemporary manners of the new generation on the one hand, and the leading development of new technologies for the construction of the other. At the beginning of the century, new pressures are threatening the architecture as they threaten the whole society. The environment is constantly changing and creating new challenging situations to cope with. Air movement, relative humidity, air temperature, solar radiation, air quality, and noises are considered basic environmental factors affecting the building and its occupants. To this end, researchers have developed many architectural designs according to the 2nd ICIEM 2016, International Conference on Integrated Environmental Management for Sustainable Development

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requirements and conditions of the era, among which we find the notion of "back to nature", which enabled the realization of a flexible architecture, fluid and dynamic. "The biomorphic architecture" therefore, has become the essential course of this reference to Mother Nature, and thanks to this trend as the façade took another dimension and become a place of experimentation in intension to master the formal aspect of the architectural work. We are witnessing the emergence of a new concept that is "the architectural envelope" which expresses the plastic and aesthetic appearance of the architectural project. On the other hand, and in a society or lifestyle has completely changed and users have become more demanding in terms of comfort, well-being; new technologies have been gradually paramount position in the architectural field and be more relevant in terms of profitability and sustainability. This deliberate progression stimulated the architects to focus on the functional side of this architectural envelope. The objective therefore is to reduce energy consumption rates and mitigate the adverse effects on the environment. These are also major factors that encourage researchers to delve into natural and organic systems to find biotechnological solutions, respectful of the environment.

2.1. Architectural and biological approaches Living organisms have unique integration geometries and techniques that allow them to adapt to different environments [6]. Through more than 3.8 billion years, “living organisms have been perfecting and optimizing their wares without consuming fossil fuel, polluting the planet or risking their future” [7]. The discipline, in which solutions are obtained by emulating nature’s functional analogies, strategies, mechanisms, and processes, is addressed in the current work. Biomimetic is equivalent to the German word bionik (or bionic), which was coined by Otto Schmidt in the 1950s. Biomimetic is about the transfer of nature’s strategies into technology for innovation [3]. Biomimetic is not a new idea; humans have been seeking solutions in nature since the existence of humanity. One of the early documented examples of biomimetic is the study of bird flight by Abbas Ibn Firnas (810-887) (figure 1) and later by Leonardo da Vinci (1452-1519) (figure 2), which led to the first controlled airplane in 1903 by the Wright brothers. The field of biomimicry is an emerging field in architecture, where its potential application is being explored and evaluated [3].

Figure 1 Bird Man [8]


Figure 2 Da-Vinci-glider [9]

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Bionics, biomorphic, bio-inspired, are scientific terms to express a knowledge from nature. This is the science that studies the natural phenomena and then imitates or draws its processes and mechanisms for adapting technological systems to operate in the building. This approach has recently started to be scientifically affirmed, and emerge as a new trend in contemporary architecture.

Today, science has invented many products inspired by nature. The study of bird flight has led to many inventions of flying machines, the study of the process of vision helped invent cameras, anatomy and mechanisms of mobility of human beings allowed creating robots machines, biomimetic Mercedes car is inspired by the boxfish for aerodynamic efficiency (figure 3) , the Olympic swimsuit inspired by shark skin (figure 4).

Figure 3 The biomimetic car "Mercedes" and the boxfish [10]

Figure 4 The company Speedo designs since 2004 jerseys inspired by the characteristics of the skin of sharks [11]


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Bio- inspiration, flora, fauna or entire ecosystems are emulated as a basis for design, has also influenced architecture as the other areas. It allowed the development of new expressions such biomorphic tendency whish was developed by the English architect Arthur in its two projects: the “kidney” house (figure 5) and the “Corn on the Cob” (figure 6).

Figure 5 Arthur Quarmby, the kidney house, 1964 [12]

Figure 6 Arthur Quarmby, Corn on the Cob, 1962

During the same period, many architects and engineers, as Frei Otto, Frank Lloyd Wright and others, have designed their buildings by copying natural forms whose structures and proportions are impressive by creating new architectural designs such as the Olympic Stadium Munich (Figure 7), the Guggenheim museum in New York, the headquarters of SC Johnson & Son Inc. with mushroom columns (Figure 8) and the price tower that mimics the structure of the tree, etc [14]

Figure 7 The Munich Olympic stadium designed by Frei Otto who inspires the spider web structure [15]


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Figure 8 The headquarters of S.C. Johnson & Son Inc and its columns inspired from the shape of mushroom [16] However, this influence began theses last years to address the functioning, processes and mechanisms and especially the area of sustainability. Some researchers believe that the “biomorphic” approach cannot be limited to the concern of the architectural expression and looking for flexibility, fluidity of natural and biological forms. They started to question the ability to mimic the functional mechanisms of natural and organic components to provide cooling, energy production and even to desalinate water for example. The evolution of this concern led to a new “Biomimetic” approach which aims to build a sustainable world by drawing and imitating nature and impressive applications. This development implies that the biomorphic approach (formal aspect) and biomimetic (functional aspect) can provide new research methods of technological processes in the field of design and construction of the building. These will be designed to function as living organisms with maximum efficiency and minimal environmental impact.

2.2. Active architectural envelope -response to environmental 5B

concerns: The issue of environmental damage related to human activity mobilizes for several decades various categories from politics, scientific community, or more generally civil society. Politicians, environmental activists have managed to sufficiently alert the public about the potential dangers of climate change and biodiversity loss, for the "sustainable development" which is seen as one of the greatest challenges of the 21st century. In order to achieve the creation of qualitative and sustainable environmental atmospheres it is important to develop new technological systems inspired by natural or biological elements. The design of a dynamic, active architectural envelope using biomimetic techniques can present a good alternative to environmental concerns. The objective of this research is to determine how this type of envelope can be designed and implemented by imitating its adaptive


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form and mechanisms from the bio-natural environment. The design of dynamic, active architectural envelope using biomimetic techniques can present a good alternative to environmental concerns. Inspired by the nature can offer many possibilities of processes and mechanisms that will help to develop and improve non-organic systems such as ventilation and cooling mechanisms, protection and shading devices from solar radiation… To achieve results it is important to understand the thermal behavior of natural or biological species appropriate to the local environment and find out how can be applied sustainably in areas with hot climate.

2.3.

The Algerian context:

In Algeria, and after independence, the country has launched major construction programs, regardless of the energy consumption of buildings. Another point to make; is that of increasing the level of life of Algerians; these involve a request for greater comfort. Thus increasing the demand for energy is set to become a crucial problem. It is therefore urgent for Algeria to be part of a new vision based on the efficient use of energy as a factor for competitiveness and sustainable development especially in the tertiary sector, which proves to be the most consuming sector energy in Algeria. According to a study by APRUE (the National Agency for the promotion and rationalization of energy), energy consumption grew very rapidly (7% / year since 2000) and is over 41% overall domestic consumption. This important sector, also called service sector includes various industries, business, tourism (hotels, restaurants), education, health, government, financial sector and other private services [17]. To solve these problems of energy consumption and take account of environmental problems resulting in the service sector, a group of experts APRUE, the Development Centre of Renewable Energies (CDER), the National Centre for studies and Construction industry research (CNERIB) and the German development cooperation agency (GIZ) launched a design and construction guide called the "active architectural envelope"[17]. During the last decade, several projects were carried out in Algeria, which focused on sustainability, simplicity and intelligent architecture such as the Airport Mohamed Boudiaf Constantine (Figure 9) and The Sheraton hotel of Annaba (which is under construction) (Figure 10).


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Figure 9 the Airport Mohamed Boudiaf Constantine [18]

Figure 10 The Sheraton hotel of Annaba[19]

Both projects show that in Algeria, the application of active architectural envelopes focuses on technological systems and building automation to ensure proper monitoring of environmental and energy environments. In addition, these envelopes reveal the non-appropriation of technology systems imported from Europe to climatic and environmental conditions of the country. This fact, challenges us to learn how local natural or biological systems are functioning in such Impressive way and to apply these biomimetic concepts in buildings in warm climates to create an agreeable comfort for occupants.

Conclusion The issue thus raised leads us to conclude that in addition to biomorphic appearance, an applied technology to the building for the control of environmental ambiences inspired by natural or biological elements is a basic parameter for the design of an active, sustainable and profitable architectural envelope. The development of biomimetic/biomorphic architectural envelopes allows the diversity of expression, innovation of environmental ambience and control systems, good integration with the local landscape and adaptation to climatic and environmental conditions. With the diversity and the richness in fauna and flora well adapted to the environmental and climatic conditions of the country, I personally consider that the bio-inspiration has not only a future in my country, but it is our future. It's a departure runway for an extensive program of research of technological systems inspired by natural and biological processes for the design of architectural envelopes to control and regulate sustainably the environmental ambiences.


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References

[1] Carlo Goldoni, Nature & Environnement : https://fr.pinterest.com/nkgalatea/natureenvironment/ [2]

Universal

Leonardo,

Remaking

nature,

study

of

Lily:

http://www.universalleonardo.org/trail.php?trail=544&work=217 [3] Mahmoud Mohamed ELGHAWABY.2013. « Vers un confort thermique grâce à des concepts d'enveloppes de bâtiments, inspirés de la nature : Le mur respirant comme un exemple biomimétique approprié aux bâtiments en zones chaudes ».PhD theses. National School of Architecture of Marseille. [4] Lidia BADARNAH KADRI.2012. “Towards the LIVING envelope: Biomimetics for building envelope adaptation”. PhD theses. Israel Institute of Technology geboren te Haifa. [5] Christophe Ménézo, envelope building specialist, holder of the energy innovations brought by the INSA Lyon Foundation. [6] Lidia BADARNAH KADRI. Paper. “Living Envelopes: Biomimicry for adaptive building envelopes”. Green Building Innovation: Façade Research Group. [7] The Architecture Annual 2007-2008. “Biomimicry for innovation in architecture”, P 54, Delft University of Technology. [8] Bird Man, Muslim Heritage, “Abbas Ibn Firnas, Bird Man”, page 03, Cordoba Daily New AD 875. [9]

Leonardo

da

Vinci’s

inventions,

inventions

for

flight,

the

glider:

http://www.leonardodavincisinventions.com/inventions-for-flight/leonardo-da-vincis-glider/ [10] The biomimetic car "Mercedes" and the boxfish: 05 inventions inspired by nature, the boxfish

and

the

Mercedes

-

Benz

Bionic

Car:

http://www.unionguanajuato.mx/articulo/2015/03/23/ciencia/5-inventos-inspirados-en-lanaturaleza [11] The company Speedo designs since 2004 jerseys inspired by the characteristics of the skin

of

sharks,

Arodynamics

science

and

biomimetics,

the

skin

of

the

shark:

http://tpebiomimetique.e-monsite.com/pages/biomimetique/quelques-exemples/la-peau-durequin.html [12] Arthur Quarmby, the kidney house, 1964, Processus Naturels architectures, page 04, FRAC Centre [13] Arthur Quarmby, Corn on the Cob, 1962, Processus Naturels architectures, page 02, FRAC Centre. [14] Elghawaby Mahmoud. Paper. “Biomimicry: A new approach to enhance the efficiency of natural ventilation systems in hot climate”, International seminar Arquitectonics Network, Architecture and Research, Barcelona 1st June 2010


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[15] The Munich Olympic stadium designed by Frei Otto who inspires the spider web structure:

https://www.theguardian.com/artanddesign/architecture-design-

blog/2015/mar/11/frei-otto-the-titan-of-tent-architecture [16] The headquarters of S.C. Johnson & Son Inc and its columns inspired from the shape of mushroom:http://www.curbed.com/2015/10/5/9914538/frank-lloyd-wright-sc-johnsonadministration-building [17] [Le Soir d’Algérie Press Service, 18 November 2015, A Guide to rationalize energy consumption

in

the

building

sector:

http://www.lesoirdalgerie.com/articles/2015/11/18/article.php?sid=187322&cid=2 [18] The Airport Mohamed Boudiaf Constantine: http://www.vitaminedz.org/kaddouchemaamar-ancien-controleur-aerien-l-aeroport-de-co/Photos_159_185745_25_1.html [19] The Sheraton hotel of Annaba: http://www.dzfoot.com/2015/04/08/can-2017-hotels66295.php


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Assessment of marine pollution from Bay of Monastir, Tunisia

Mohamed DAMAK1, Monom KALEL2 1 laboratoire de Génie de l'Environnment et de l'Ecotechnologie (GEET) LR16ES19 [email protected] 2 laboratoire de Génie de l'Environnment et de l'Ecotechnologie (GEET) LR16ES19 Abstract

Abstract. This study aims to identify the state of the marine environment of the bay of Monastir by studying the repair of benthic foraminifera and the physico-chimical analysis of the sediment.. The partical size characterization showed for all sites studied a sandy texture to ending. The organic matter contents are relatively high along the bay of monastir and remarkably high at the bay of oued El-malah of Khniss, oued Essouk of Lamta and near the port of teboulba. The heavy metal analysis showed relatively low levels compared to the reference’s threshold. The study of population of benthic foraminifera showed that assemblages identified in the bay are dominated by carbonate species characteristics of shallow Mediterranean environments, confined and protected. It is essentially the case by Ammonia becarii, Elphidium crispum and Peneroplis planatus. Keywords: Monastir bay, benthic foraminifera, Marine sediments, heavy metals

1.

General Guıdelınes

The continental shelves occupy the seabed between the coast and the top of the slope. They reflect better than most other sedimentary environments complexity own exchange and transit processes to external geodynamic areas. This results from the diversity of hydrodynamic control factors, morphological, climatic, chemical and biological as well as that it exercised the existence of numerous sedimentary traps. According to the United Nations Environment Programme (UNEP, 2009), 80% of marine pollution comes from land and anthropogenic (produced by human activities). Much of the toxic substances released or present in a watershed will eventually join the marine environment via rivers, canals and lagoons. Toxic are of industrial origin (hydrocarbons, heavy metals, chemicals, radionuclides ..), agricultural (nutrients, fertilizers, pesticides ...), or just from the inhabitants or users of the watershed (solid or liquid waste , residues of wastewater treatment plants, pollutants in the runoff ...). Chemical analyzes to determine and know the level of contamination of sediment, but give little information about its "biological quality". Traditionally, macrofauna (bivalves, polychaete worms ...) is used for such purposes; a laborious and therefore expensive method. In this context, the benthic foraminifera are rarely used. However, they are excellent biological indicators of eutrophication, whether original, natural or human. Indeed, benthic foraminifera respond quickly 2nd ICIEM 2016, International Conference on Integrated Environmental Management for Sustainable Development

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to changes in their environment, where pollution and environmental changes can lead to a radical transformation of the population, composition and morphology of foraminifera. Indeed, Monastir Bay is home not only to a significant number of major coastal developments such as ports dispute, the drain Khniss, hotel projects, textile industries but also a widely pollution organic, due to sewage discharges and stations of fish farms. The fundamental objective of this study is to come through a pragmatic approach to the overall environmental identification Bay Monastir and identifying existing palé oceanographic praxis (quantifiable markers unobservable parameters) by studying the distribution of benthic foraminifera and the analysis of physical-chemical parameters of the sediment. Rather, this study aims to better understand the interactions between benthic foraminifera and their environment, and the impact of those interactions on their density - diversity and morphology of their test. It therefore identifies two complementary approaches and interrelated: an ecological approach, and a physicochemical approach.

2.

Monastir bay

The study area belongs entirely administratively to the governorate of Monastir (Fig. 1). It extends along the coastline of the Bay of Monastir Khniss to Ras Dimas (Bkalta). On an area of about 17,000 hectares, the Bay of Monastir is closed to the east by the shallows joining Dzira peninsula of Ras Dimas at Kuriat islands, small, and, further north, the wide over a length of the order of 20 km. On the west side, the bay is closed on the peninsula of Monastir. His earthly side made a total length of about 35 Km from the marina of Monastir to the tip of Ras Dimas (APAL, 2009). The coast of Monastir Bay is an important industrial center, the textile and clothing industries sector is the first industrial sector of the region. Agriculture in the region of Monastir is diverse and is mainly based on the olive, vegetables, dairy and fisheries

Figure 1:Location of Bay of Monastir (From Google Earth).


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3.

Material and methods

The sites were chosen based sources of organic pollution, fluvial and different arrangements made (port, cornice ...). In total, ten sites were chosen in the Bay of Monastir To assess the impact of pollution in the bay of Monastir, a series of analyzes were conducted for each site, sediment and water from the sea, namely: Physico-chemical analyzes of water from the sea. Physico-chemical analysis and grain size of the sediment. Biological sediment analyzes.

4.

Results of physicochemical analyzes

The objective of this work is to characterize the physicochemical parameters of seawater in the Bay of Monastir. Indeed, the following table shows the different results of analyzes that were performed. Analysis of micro metal was made in sediments than in the water because of the role of "memory" plays vis-à-vis pollution support. The heavy metal content is low. Indeed, concentrations of trace metals to the measured stations is between 14 and 20 ppm zinc, 12 and 44 ppm chromium, 3 and 9 ppm for copper, and only 4 ppm for lead at the BM5 station. Especially, the nickel and cadmium levels were not detectable when the contents are less than 0.05 ppm and 0.01 ppm respectively.

5.

CONTRIBUTIONS of benthic foraminifera

This study indicates for the first time the distribution of benthic foraminifera along the Bay of Monastir. In the next step, while relying on several previous studies (Debenay et al., 1996; Licari et al., 2003, in Murray, 2006), species that represent more than 5% were considered the most species important, while those representing less were considered to trace and were not considered in the analyzes. In total 40 species were observed where only 13 dominant species (> 5%). The distribution of species observed in the intertidal zone along Monastir Bay are shown in Figure 2


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Figure 2:Abundances of species identified along the coast of the Bay of Monastir. A total of 13 dominant species of foraminifera (Ammonia becarii, Ammonia parkinsoniana, Elphidium crispum, Lobatula lobatula, Penerolpis pertusus, Peneroplis planatus, Quinqueloculina berthelotiara var. Wiesneri, Quinqueloculina seminula, Rosalina sp., Siphonaperta aspera, sorites orbiculus, Triloculina trigonula, Vertebralina striata ) were observed throughout the study area. Species richness varies between 2 and 8 species depending on the station. Indeed, BM0 station shows the greatest wealth with 8 species, followed by BM1 and BM9 stations with 6 species. Any time the BM2 stations, and BM4 BM5 show only 2-3 species..

6.

Conclusion

The objective of this study was to determine the quality of coastal sediments of the coastline of the Bay of Monastir. For this, several approaches have been discussed in this work from the physicochemical characterization of the sediment in the study of benthic communities. The studied chemical compounds are organic matter and heavy metals. This is justified on the one hand, by the known toxicity for both compounds and secondly, by the presence in the study area from point sources (industries, fishing ports, ONAS, fluvial input, confined space following a development) emitting these pollutants. The bio-indicator used is the benthic foraminifera. The choice of this body returns to its demonstrated sensitivity to these contaminants as across the individual and the population level. The evaluation of the metallic contamination of the study area showed a generalized surface enrichment, Cr and Zn, and a punctual enrichment, Pb and Cu. This enrichment following port activity along the coast and fluvial inputs, where pollutants are transported through longshore drift.


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The study of benthic foraminifera stands showed that assemblages identified in the study area are dominated by carbonate species characteristic of Mediterranean shallow environments, confined and protected. This is essentially the species Ammonia becarii, Elphidium crispum, Peneroplis planatus, Quinqueloculina seminula, Vertebralina striata. These assemblies vary greatly in terms of species richness, density and abundance based stations.


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REGENERATION AND REUSE WASTE FROM AN EDIBLE OIL REFINERY Boukerroui Abdelhamid1*, Belhocine Lydia1, Ferroudj Sonia1 1

LTMGP Laboratory, University of Bejaia, 06000, Algeria *E-mail: [email protected]

Abstract A spent bleaching earth (SBE) from an edible oil refinery has been regenerated by thermal processing followed by washing with a solution of hydrochloric acid (1M). Optimal regeneration conditions have been controlled by decolorization tests of degummed and neutralized crude soybean oil. Optimal values (temperature: 350°C, carbonization time: 01 hour and HCl concentration: 1M ) gave a material very efficient for an oil processed by the regenerated spent bleaching earth (RSBE). After treatment by RSBE, the chlorophyll-a and β-carotenes observed respectively at 430, 454 and 483 nm, value of λ max , are very much decreased. The RSBE material obtained was characterized by several techniques (FTIR, SEM). The results show that the heat treatment did not affect the mineral structure of RSBE. The results obtained after decolorization of edible oil with a regenerated spent bleaching earth indicate that during the process, the resultant oil did not undergo any changes in the free fatty acid content. In addition, the peroxide value and color of decolorized oil are reduced. Keywords: spent bleaching earth, decolorization, Soybean oil, regeneration, pigments.

INTRODUCTION The refining process of crude edible oil includes four operations; degumming, neutralization, bleaching and deodorization. After its degumming and neutralization operations during the refining process, the crude edible oil still contains undesirable substances [Dijkstra, 2013]. Those substances limit the conservation of oil and degrade its quality by altering the taste and color properties of this product, which affects its market value by giving it an aspect that is not appreciated by the consumer. This color is due to the presence of pigments in the crude edible oil, such as chlorophyll-a and β-carotene [Dijkstra, 2013; Foletto et al., 2013; Pohndorf et al., 2016]. Among undesirable substances, the crude edible oil contains also soap residues, free fatty acids, phosphatides and metals at trace concentrations [Dijkstra, 2013; Gil et al., 2014; Pal et al., 2015]. The bleaching operation is carried out by means of porous materials with a strong adsorption power, which are clays called bleaching earths, activated by heating with strong acids (Foletto et al., 2013; Komadel 2016 ; Didi et al., 2009; Hussin et al., 2011]. These materials eliminate the undesirable elements such as the dyes (chlorophyll-a and β-carotene) and other residues (soap residues, traces of heavy metals…) contained in the crude edible oil [Hussin et al., 2011; Pohndorf et al., 2016; Foletto et al., 2013; Skevin et al, 2012]. After use in bleaching oil, the material loses its adsorption properties which were acquired during the acid activation and becomes solid waste pollutant called spent bleaching earth (SBE). The SBE contains about up to 30% w/w of residual oil that rapidly oxidises to the point of spontaneous autoignition [Pollard, 1993].


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The Bejaia city has two edible oil refineries (COGB-Labelle and Cevital) that generate many tons per year of pollutant waste bleaching earth. These wastes are dumped in the landfill without any treatment to prevent possible contamination of the environment, which over time, particularly acute problem for the management and storage of these solid wastes. To minimize the risk of pollution, the mastery of oil refining technology must be accompanied by the control of reducing the solid waste. To solve the problem of waste products, some edible oil refining factories have opted for the reduction of bleaching earths used. Moreover, the reduction of amount of bleaching earth added to the bad controls of temperature and contact time causes an incomplete decolorization. Indeed, during the deodorization step that occurs by high temperature processing (240-270 °C), all the thermally degradable pigments, undesirable elements or volatile compounds, such as, aldehydes, ketones and alcohols are removed by vacuum distillation [Kreps et al, 2016, Silva et al., 2014]. Therefore, these substantial color reductions increase air pollution. In other hand, the solution must pass through the regeneration and reuse of spent bleaching earth. This has incited many authors who devoted her research works [Boukerroui et al, 2000, ; Mana et al, 2011 ; Wambu et al, 2009 ; Tsai et al. 2002; Pollard et al., 1993; Ng et al., 1997]. This present study is a continuity of previous work [Boukerroui and Ouali, 2000; Meziti and Boukerroui, 2011] which reports the study of the efficiency of a heat treatment by regeneration method followed by washing acid and the optimization of the most influential physicochemical parameters on bleaching crude edible oil. The best adsorbent material was characterized by using FTIR and SEM methods. The effectiveness of the spent earth regeneration method is controlled by decolorization tests on degummed and neutralized edible oil. Finally, measuring some value, such as free fatty acid, peroxide and color of the bleached oil permit to verify the validity of our regeneration method and to conclude on the quality of the oil obtained.

2. MATERIALS AND METHODS 2.1. Materials The spent bleaching earth (SBE), the virgin bleaching earth (VBE) and neutral oil (NO) (degummed and neutralized oil) were obtained from an edible oil refining factory COGB-Labelle (Bejaia). Thermal processing of SBE was conducted in a temperature programmed muffle oven (Carbolite 1800 apparatus). The FTIR spectra of SBE, VBE and the regenerated spent bleaching earth (RSBE) (lozenge of KBr 1%) were carried out with SHIMADZU FTRI 8400 spectrometer, in the range 4000-400 cm-1. SEM observations of the SBE, VBE and RSBE have been carried out with Quanta 200 scanning electron microscope. All chemicals used are analytical grade.

2.2. Methods 2.2.1. Regeneration of spent bleaching earth The spent bleaching earth is heated at temperatures varying from 300°C to 600 °C during one hour. The sample regenerated materials were noted R followed by temperature of oven. The regenerated materials were


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followed by bleaching tests using edible oil. All notations of regenerated materials and treated oils are given in Table 1. The more efficiency regenerated material in bleaching oil was followed in some cases by leaching with hydrochloric acid (0.1 and 1M) or NaOH (0.1 M) with 5% w/w ratio. The HCl or NaOH- leached samples were washed with distilled water, until neutral pH. The resulting materials are dried at 80°C during 24 hours, sieved (50 µm) and then stored in air-tight plastic bottles in desiccators for further use. The best values of these physicochemical parameters allowed us to evaluate the efficiency of the regeneration method. 2.2.2. Bleaching test To avoid undesired side-reactions, the crude oil treatment was achieved under a vacuum of 25-30 mm Hg, which was maintained throughout the experiment [Kheok and Lem, 1982]. The degummed and neutralized crude edible oil (neutral Oil) was preheated at 80 °C in an oil bath. When the oil reached this temperature, RSBE was added. The bleaching experiment was carried out over a temperatures range of 80–120 °C with degummed soybean oil containing 2 % (w/w) of regenerated spent bleaching earth (RSBE). The mixture was continuously agitated under those conditions for about 15 to 30 minutes. The suspension was centrifuged at 6000 rpm for 5 min and then filtered through Whatman No.5 paper to separate the clear oil and RSBE [Boukerroui and Ouali, 2000, Aung et al., 2015]. The color change in the bleached oil was determined by using a UV-visible spectrophotometer (Model: UV1800 Shimadzu UV Spectrophotometer). The oil sample was diluted with petroleum ether (1:4 v/v) and the bleaching capacity of RSBE was determined by measuring absorbance at 430 nm, at 454 nm and at 483 nm, which were the maximum absorptions observed in the wavelength range between 400 and 800 nm. The bleaching capacity, or % uptake, was calculated according to the following equation [Aung et al., 2015, Boukerroui and Ouali, 2000]:

Equation 1

Where

Aλ0 and Aλ are the optical densities at wavelength λ max (430, 454 and 483 nm) of the unbleached

(neutral oil) and bleached oil (treated oil) respectively. All bleaching parameters used in this study are given in the Table 1. Examined oils are noted with the following abbreviations: •

NO: Neutral Oil or unbleached oil.

•

Processed oils are noted by the letter O followed by abbreviations of materials used for

their bleaching (see Table 1).


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Table 1. Experimental conditions of regeneration of SBE and notation of obtained materials and corresponding bleaching oil Parameters

Values

Notation of obtained

Corresponding oil

earth

Heating temperature (°C)

Leaching

NaOH

concentration Leaching

HCl

300

R300

OR300

350

R350

OR350

400

R400

OR400

450

R450

OR450

500

R500

OR500

550

R550

OR550

600

R600

OR600

0.1M

R350/0.1M-NaOH

OR350/0.1M-NaOH

0.1 M

R350/0.1M-HCl

OR350/0.1M-HCl

1M

R350/1M-HCl

OR350/1M-HCl

concentration

2.2.3. Determination of quality criteria for bleached and crude oil Standard quality parameters, including free fatty acids (FFA) content, color, and peroxide values (PV) were analyzed for crude (neutral oil), bleached and refined soybean oil samples. The sample color was determined according to the AOCS Official Method Cc 13e-92, using a Lovibond Tintometer Color Scale at 70 °C [AOCS, 1998 ]. Free Fatty Acids content (FFA) and Peroxide (PV) were determined according to the AOCS Official Method Ca 5-40, by titration and Cd 8-53, respectively [AOCS, 1998].

3. RESULTS AND DISCUSSIONS 3.1. Optimizing of the physicochemical parameters 3.1.1. Effect of heating temperature treatment The absorbance spectra between 400 and 800 nm of the unbleached or Neutral Oil and bleached soybean oils obtained after his treatment by different regenerated spent bleaching earths, heated into 35–600 °C, interval of temperature of oven, were show in Fig. 1.


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Absorbance

2.5

OR300 OR350 OR400 OR450 OR500 OR550 OR600 Neutral Oil

2.0

1.5

1.0

0.5

0.0 400

500

600 Wavelength (nm)

700

800

Figure 1. Visible absorption spectra of unbleached and bleached oil by regenerated bleaching earth heated into interval 350-600 °C (Temperature of oil: 90 °C, w/w 2%, time= 15 min) The absorption spectra show three distinct maxima occurred at 430, 454 and 483 nm (Fig. 1). Similar results have been reported in many other studies [Gonzales-Pradas et al., 1994; Kondal et al., 2001; Sarier and Guler, 1988]. The maximum absorption at 430 nm corresponds to the band of chlorophyll-a, while those observed at 454 and 483 nm are the bands of β-carotene [Gonzales-Pradas, et al., 1994; Sarier and Guller, 1988]. According to literature, carotenoids are the predominant pigment in soybean oil [Kondal et al., 2001]. However, the decolorization was mainly due to the reduction of carotenoids and chlorophyll compounds present in the crude oil. The maximal absorbance peaks of decolorized oils at λ max were reduced –they are lower than crude soybean oils (Neutral Oil)- due to the removal of coloring pigments during the bleaching operation. The color decrease was maximal in 400 - 600°C interval of heating temperature of oven. The intensity of band at three picks cited before decrease with increasing of the heating temperature, and then stabilizes at 400°C. For practical and economical reasons, the regenerated SBE must be as efficient as a commercial virgin earth. It is known that an acidic treatment of clays improves their adsorptive properties and bleaching power [Boukerroui and Ouali, 2000, Tsai et al. 2002]. For the further steps we fixed the heating temperature of oven at 350 °C during 1 hour.


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3.1.2. Effect of the leaching Fig. 2 shows visible absorption spectra of oil bleached with R350 at two acid concentrations (0.1 and 1M) and NaOH (0.1M). It can be seen in this Figure that the intensity at 430, at 454 and at 483 nm absorption bands decreases when the leaching acid concentration increases. This implies that the acid concentration affects the bleaching power of R350.

0.50 OR350 Neutral Oil OR350/1M HCl OR350/0.1M HCl OR350/0.1M NaOH

0.45

absorbance

0.40 0.35 0.30 0.25 0.20 0.15 0.10 0.05 0.00 400

500

600

700

800

Wavelength (nm)

Figure 2. Visible absorption spectra of neutral and bleached oil by regenerated and leached materials (Temperature of oil 90 °C, w/w 2%, time= 15 min) The % uptake values calculated at 430, at 454 and at 483 nm by using Eq. 1, were reported on Table 2. The results show clearly the effect of leaching on bleaching power of regenerated clays. The observations on spectra seeing in Fig 2 are confirmed by % uptake values calculated and reported in Table 2. The % uptake values show the improvement brought by the increase of the HCl concentration. The SBE heated for one hour at 350°C and leached by molar HCl (R350/1M) presents a superior bleaching efficiency: •

The % uptake at 430 nm is 53.97% after leaching when it was 23.73 % without

leaching. •

At 454 nm, % uptake values was 31.77 and becomes 66.13 % after leaching.

•

It increases to 36.09 for 69.01 % at 483 nm.

These results indicate that SBE has been regenerated and recovered some of its initial sorptive properties. OR350/0.1M NaOH spectrum of Figure 2 show that washing regenerated clay with NaOH 0.1 M aqueous solution didn’t give any more sensitive effect on bleaching efficiency of material. In Table 2, this observation is


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confirmed by % uptake values (25.85 %, 33.99 % and 38.85 %) calculated for three wavelengths (430, 454 and 480 nm respectively). Therefore, the HCl 1M leaching clean the pore from residuals substances of carbonized oil and permit more exhibitions of alumina compound present in clay structure. It’s know , the aluminum sites on the clay structure play a vital role in the sorption of pigments molecules from the soybean oil [Silva et al. 2014]. Table 2 : Effect of leaching on bleaching efficiency of RSBE Wavelenght λ

Type of Oil

% uptake at λ max

(nm) 430

454

480

Neutral Oil (NO)

23.73

OP350/0.1M NaOH

25.85

OP350/0.1M HCl

51.36

OP350/1M HCl

53.97

Neutral Oil (NO)

31.77

OP350/0.1M NaOH

33.99

OP350/0.1M HCl

61.25

OP350/1M HCl

66.13

Neutral Oil (NO)

36.09

OP350/0.1M NaOH

38.85

OP350/0.1M HCl

65.85

OP350/1M HCl

69.01

In the other hand, the mesopores or surface area of material (not reported here) did not only relate to decolorization capacity but associated alumina and active silica contents which might be an important factor [Aung et al 2015]. Acid leaching clears the porosity and number of acid centers from mineral impurities present on the surface of material and that largely affect their bleaching properties [Zaki et al., 1986 , Silva et al., 2014; 2013]. 3.2. Optimization of physicochemical parameters affecting bleaching edible oil 3.2.1. Effect of heating temperature of oil The SBE heated at 350°C for 1 hour and leached with 1M HCl solution was used for edible oil bleaching heated for 15 minutes at 80-120 °C interval. The spectra obtained were shown in Fig 3. It can be seen in this Figure that the maximal intensity at the 430, 454 and 483 nm absorption bands decreases when the temperature values increase. This implies that the heating of oil affects the bleaching power of R350/1M. The maximum temperature of heating can be retained is 100 °C because after this value the increasing in bleaching properties is null. The % uptake values calculated at λ max were reported on the Table 3.


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4

absorbance

3 OR350/1M at 100°C OR350/1M at 110°C OR350/1M at 120°C OR350/1M at 80°C OR350/1m at 90°C Neutral Oil

2

1

0 400

500

600 Wavelength (nm)-)

700

800

Figure 3. Effect of heating on bleaching efficiency of regenerated spent bleaching earth ( w/w 2%, time= 15 min).

Table 3. Influence of heating on bleaching efficiency of regenerated spent bleaching earth Wavelength

Temperature (°C)

(%) uptake at λ max

80

52.71

90

62.94

100

74.54

110

74.54

120

74.54

80

64.42

90

73.30

100

86.87

110

86.87

120

86.87

80

67.33

90

77.45

100

88.97

110

88.97

120

88.97

(nm) 430

454

483

The Table 3 results show that the % uptake value is approximately constant after heating temperature of 100 °C for the three values of λmax. 2nd ICIEM 2016, International Conference on Integrated Environmental Management for Sustainable Development

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The SBE treated in oven at 350°C during one hour and leached with 1M HCl has efficiency for bleaching soybean oil (2 % w/w) heated at 100 °C. 3.2.2. Effect of contact time Figure 4 shows the kinetic study of the bleaching crude edible oil by the regenerated material R350/1MHCl for 15, 20, 25 and30 min (interval of contact time oil/material).

2.6 2.4

absorbance

2.2

OR350/1M-HCl for 15min OR350/1M-HCl for20min OR350/1M -HClfor 25min OR350/1M-HCl for 30min Neutral Oil

2.0 1.8 1.6 1.4 1.2 1.0 0.8 0.6 0.4 0.2 0.0 400

500

600

700

800

Wavelength (nm)

Figure 4. : Influence of contact time on bleaching efficiency of regenerated bleaching earth (100 °C, 2 % w/w) . The maximal absorbance peaks of decolorized oils at λ max were reduced and the decreasing was maximal for 15 min of contact time. However the peaks of decolorized oils at λ max (430, 454 and 483 nm), observed previously were full disappeared due to the complete removal of coloring pigments (chlorophyll-a and β-carotene) during the bleaching operation. So the spectra at 15, 20, 25 and 30 minutes show the same allures (they have given the same results). Therefore, a decolorization process for 15 minutes is largely sufficient to remove the major colour pigments of chlorophyll and carotene present in crude oil. The optimum decolorization conditions were 2 %, 100 °C, 15 min. These parameters of the bleaching oil add to regenerated conditions (heating Temperature of oven 350 °C and leaching by HCl 1M) have given results which are consistent with many other studies [Kondal et al., 2001; Pal et al, 2015; Silva et al., 2013]. 3.3. Determination of quality criteria parameters of bleached and neutral oil Free fatty acids (FFA), peroxide value and color are three quality parameters used to evaluate bleaching earths. Values of these parameters are reported in Table 4 for unbleached and bleached oils.


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Table 4. : Quality of unbleached and bleached oils Oil

Free fatty acid (%)

Peroxide

Color

value (PV) (meq

as oleic

O 2 /Kg)

Red (R)

Yello w (Y)-

acid neutral oil (unbleached

0,05

4.2

0.5

50

0,05

1,8

0,3

2,7

Bleached oil by (VBE)

0,08

1,1

0,3

8

Standard values

0,2

5

oil) Bleached oil by (OR350/1M-HCl) Y+R < 10

The FFA values are very close, and confirm that OR350/1M-HCl gives bleached oil with better quality than this one obtained by commercial VBE. In addition, this implies that the regeneration method used here does not affect the quality parameters of the treated oil. Furthermore, Table 4 shows that regenerated SBE eliminates major part of peroxide present in the crude oil. The peroxide value decreases from 4.2 to 1.8 after the bleaching process. Concerning the color removal, the RSBE is more efficient than VBE material (mainly yellow color). For to conclude, the FFA peroxide value and color of the treated oil have remained under the standard values. 3.4. Characterization of regenerated spent bleaching earth The regenerated materials were characterized by FTIR and SEM methods of SBE, VBE and RSBE. 3.4.1. FTIR analysis Fig 5 shows the presence of unsaturated oil in the SBE, exhibiting peaks at 2926, 2851, 1760 cm-1 (C=O), 1460 (C=C or O-H bond) and 1383 cm-1 [Tsai et al. 2002].


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R350 R550 R600 VBE SBE

100 95 90 85 80 75 70 65 60 55 50 45 40 35 30 25 20 15 10 5 0 4000

1646 2851 2926

17601460 1383

1640

1640

659

3444 1016 3500

3000

2500

2000

Wave number (cm)

1500

1000

500

-1

Figure 5. FTIR spectra of R350 (a), VBE (b) , SBE (c) and R600 (d). The FTIR spectra (see Fig. 5) confirms the presence of the structure of montmorillonite in the materials in particular the band near 3460–3650 cm-1 attributable to the stretching vibrations of the interlayer water molecule. The band at 1650 cm-1 corresponds to the hydroxyls vibration, 1050 cm-1 (Si–O stretching), 792 cm-1 (Si–O vibration of quartz impurities), and below 520 cm-1 (Si–O–Al bending) [Meziti and Boukerroui, 2011; Tsai et al., 2002]. The VBE, R350, R600 and SBE spectra are similar, but the last exhibits the characteristic residual oil bands (spectrum c): •

A large shoulder at 3250 cm-1, attributable to the stretching vibrations of OH of

carboxylic acids (free fatty acids). •

2850 and 2920 cm-1, stretching vibration of C–H of saturated carbonaceous chains of oil

and the free fatty acids. •

1760 cm-1, strong stretching vibration of ester carbonyl of residual oil.

•

1460 cm-1, stretching vibration of C=C of oil and/or deformation vibration of OH of the

free fatty acids. •

1383 cm-1 deformation vibration of C-H oh methyl

These bands disappear after the heat treatment. It implies that the organic residues adsorbed in the pores are completely eliminated by the physicochemical treatment from regeneration [Meziti and Boukerroui, 2011; Tsai et al., 2002]. As for the spectra (a) and (c) they are practically identical. This indicates that the heat treatment followed by washing does not seem to modify the structure of montmorillonite of bleaching earth.


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3.4.2. SEM analysis The Fig. 6 shows the SEM image of the regenerated spent bleaching earth R350 leached by HCl (1M) used in this study for the soybean oil bleaching and to compare SEM images of SBE and VBE materials.

a

b

c

Figure 6. Scanning electron micrograph (SEM) of regenerated spent bleaching earth R350 (a), SBE (b) and VBE (c) with an enlargement of 5 µm Fig 6 shows that surface morphology of three materials were different. In Fig. 6 a, it can be observed that the regenerated earth particles show different shapes and irregular surface. In fact, thermal treatment at 350 °C had made more porous structure comparing to SBE sample. The surface morphology of R350 has undertaken significant changes under the thermal treatment combined acid leaching and making same porous if we compare with VBE surface morphology (Fig. 6c). The surface of the SBE (Fig. 6b) appears to be smooth due to oil residues and others substances adsorbent during the decolorization process. The SEM images revealed that the spent bleaching earth recognized her porous structure after thermal treatment and the regenerated material surface has become more porous. The heat regeneration helps in the restoration of the pores [Boey, 2011] Therefore, it is evident the material has found his adsorptive properties then the adsorbent material tends to improve bleaching capacity [Ng et al, 1997; Boukerroui and Ouali, 2000]. Therefore, the specific surface area does play a certain role in decolorization of crude soybean oil due to that it increased the solid–liquid contact area [Aung et al., 2015; Foletto et al, 2013; Gil et al., 2014].


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CONCLUSION The spent bleaching earth (SBE) can be regenerated by heating at 350°C for one hour, followed by leaching with M HCl solution. This process gives a good adsorbent with better bleaching properties under these conditions: temperature and contact time 100 °C, 15 min respectively. However the SEM image exhibits the reappearance of a good porous structure in the regenerated material.

REFERENCES

Aung, L. L., Tertre, E., Suksabye, P.,·Worasith, N., Thiravetyan, P., 2015. Effect of Alumina Content and Surface Area of Acid‑Activated Kaolin on Bleaching of Rice Bran Oil. J. Am. Oil Chem. Soc. 92, 295–304. http://dx.doi.org/10.1007/s11746-014-2583-2. AOCS. (1998). Methods and recommended practices of the American Oil Chemists' Society. Champaign. Boey P.L., Ganesan S., Maniam G. P., Regeneration and Reutilization of Oil-Laden Spent Bleaching Clay via in Situ Transesterification and Calcination, J Am Oil Chem Soc, 2011, 88 (8), pp 1247–1253. DOI 10.1007/s11746-011-1781-4 Boukerroui, A., Ouali, M. S., 2000. Regeneration of a spent bleaching earth and its reuse in the refining of an edible oil. J. Chem. Technol. Biotechnol. 75, 773- 776. Didi M. A., Makhoukhi B., Azzouz A., Villemin D., «Colza oil bleaching through optimized acid activation of bentonite. A comparative study», Applied Clay Science 42 (2009) 336-344 Dijkstra, A. J., 2013. Edible Oil Processing from a Patent Perspective, Chapter 7: Bleaching. ed. Springer New York, pp173-198. http://dx.doi.org/10.1007/978-1-4614-3351-4_7. Eliche-Quesada D., Corpas-Iglesias F.A., Utilisation of spent filtration earth or spent bleaching earth from the oil refinery industry in clay products, Ceramics International 40 (2014) 16677 – 16687. http://dx.doi.org/10.1016/j.ceramint.2014.08.030 Enos W. Wambu , Gerald K. Muthakia , Joseph K. wa-Thiong'o , Paul M. Shiundu , Regeneration of spent bleaching earth and its adsorption of copper (II) ions from aqueous solutions, Applied Clay Science 46 (2009) 176–180 Gil, B., Kim, M., Kim, J. H., Yoon, S. H., 2014. Comparative study of soybean oil refining using rice hull silicate and commercial adsorbents. Food Sci. Biotechnol. 23(4), 1025-1028. http://dx.doi.org/10.1007/s10068-014-0139-8. Foletto E. L., Paz D. S., Gündel A., Acid-activation assisted by microwave of a Brazilian bentonite and its

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Kreps F., Kyselka J., Burcova Z., Schmit S., Rajchl A., Filip V., Haz A., Jablonsky M., Sladkova A., Surina I., Influence of deodorization temperature on formation of tocophenol esters and fatty acids polymers in vegetable oil , Eur. J. Lipid. Sci. technol; 2016, 118, 0000-0000. DOI: 10.1002/ejlt.201600027 Meziti, C., Boukerroui, A., 2011. Regeneration of a solid waste from an edible oil refinery Ceramics Int. 37, 1953-1957. http://dx. doi:10.1016/j.ceramint.2011.02.016 Ng K.F., Nair N.K., Liew K.Y. , and Ahmad M. Noor, Surface and Pore Structure of Deoiled Acid and Heat-Treated Spent Bleaching Clays, JAOCS, Vol. 74, no. 8 (1997) Pal, U. S., Patra, R. K.,.Sahoo, N. R., Bakhara, C. K, Panda, M. K., 2015. Effect of refining on quality and composition of sunflower oil. J. Food Sci. Technol. 52 (7), 4613–4618. http://dx.doi.org/10.1007/s13197014-1461-0. Komadel Peter, Acid activated clays: Materials in continuous demand, Applied Clay Science Applied Clay Science 131 (2016) 84–99. http://dx.doi.org/10.1016/j.clay.2016.05.001 Pohndorf, R.S., Cadaval, Jr. T.R.S., Pinto, L. A. A., 2016 . Kinetics and thermodynamics adsorption of carotenoids

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chlorophylls

in

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bran

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bleaching.

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http://dx.doi.org/10.1016/j.jfoodeng.2016.03.028 Pollard S. J. T., Sollard C. J., Perry R., The reuse of spent bleaching earth: A feasibility study in waste minimization for the edible oil industry, Bioresource technology 45 (1993) 53-58 Pradas, E.G., Sanchez, M.V., Viciana, M.S., Campo, A.G., 1994. Adsorption of chlorophyll-a from acetone solution on natural and activated bentonite J. Chem. Technol. Biotechnol. 61,175-178 . Sarier, N., Guler, C., 1988. β-Carotene adsorption on acid activated montmorillonite. J. Am. Oil Chem. Soc. 65(5), 776-790. Silva S. M., Klicia Sampaio, A., Ceriani, R., Verhé, R., Stevens, C., De Greyt, W., Meirelles, A.J.A., Adsorption of carotenes and phosphorus from palm oil onto acid activated bleaching earth: Equilibrium, kinetics and thermodynamics, Journal of Food Engineering 118 (2013) 341–349. Silva S. M., Klicia Sampaio, A., Ceriani, R., Verhé, R., Stevens, C., De Greyt, W., Meirelles, A.J.A., Effect of type of bleaching earth on the final color of refined palm oil, LWT - Food Science and Technology 59 (2014) 1258-1264 Skevin, D., Domijan, T., Kraljic, K., Kljusuric, J. G., Nederal, S., Obranovic, M., 2012. Optimization of bleaching parameters for soybean oil. Food Technol. Biotechnol. 50 (2), 199–207. Tsai W.T., Chen H.P., Hsieh M.F., Sun H.F., Chien S.F., Regeneration of spent bleaching earth by pyrolysis in a rotary furnace, Journal of Analytical and Applied Pyrolysis 63 (2002) 157–170 Zaki I., Abdel-Khalik M., Habashi G. M., (1986) Acid leaching and consequent pore structure and bleaching capacity modifications of Egyptian clays. Colloid Surf 17:241–249


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ADSORPTION OF TERPENES COMPOUNDS ONTO PALYGORSKITE

Sana GHRAB 1*, Mabrouk LOUSAIEF1, Marc CRETIN2, Stéphanie LAMBERT3, Samir BOUAZIZ 1, Mourad BENZINA 1 1 Laboratoire « Eau, Energie et Environnement » (LR3E), code : LR99ES35

Ecole Nationale d’Ingénieurs de Sfax, Université de Sfax, B.P.W3038, Sfax-Tunisie 2 Institut Européen des Membranes, ENSCM-UM2-CNRS (UMR 5635), Université de Montpellier 2, cc047, place E. Bataillon, 34293 Montpellier Cedex 5, France 3 Laboratoire de Génie Chimique, B6a, Université de Liège, B-4000 Liège, Belgium [email protected]

Keywords: Terpenic volatile organic Compounds , Palygorskite, Essential oil, enviromental application.

Abstract The present work aimed to study the processes of the synthesis insecticidal formulation. The active compounds of essential oil of eucalyptus globulus were fixed in the palygorskite by adsorption process. Two samples types of palygorskites were used; raw and modified palygorskite. The palygorskite clays were characterized by several physicochemical techniques including X-Ray Diffraction (XRD) and Fourier Transformed Infra Red (FTIR) analyses. Results show that the raw clay has a fibrous structure with calcite impurities. These structures and physicochemical properties of palygorskite raw and organo-clays give it the potential of material adsorbent. Results show that the adsorption capacity strongly depends on affinity between terpenic compounds and organic cations rather than on interlayer distance of organo-palygorskite clays. The highest adsorption capacity of terpenic compounds is obtained with palygorskite modified by DDDMA. These results revealed the potential utility of the S1-DDDMA as adsorbents for the uptake of terpenic compounds in environmental applications.

1.

Introductıon

Many plants such as Aromatic plants produce terpenic volatile organic compounds (TVOC) diffusing into the atmosphere and the soil. This volatiles organic compounds are necessary for two reasons, the first is a cooperation with other species, to attract pollinating insects or the auxiliaries of the phytophagous insect [1] antagonistic fungi [2]; the second consists of a elaboration of dissuasive substances to resist to pest organisms such insects, pathogenic microorganisms [3] and competitive plants [2]. Otherwise the function of the protection plant performed by Essential oils. The essential oil are volatile, aromatic oily liquids; natural products with


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terpenic structure described by an intense smell. Hence it is necessary to use the essential oil with her important insecticidal activity in environmental application. The palygorskite was selected as a good adsorbent for fixed terpenic volatiles organic compounds (TVOC). The palygorskite have a high surface area and a large number of silanol groups on its surface. Palygorskite is a hydrated magnesium silicate mineral with fibrous morphology, and possesses rectangular channels contained exchangeable Ca cations, zeolitic water, and water molecules bound to coordinative unsaturated metal ion centers, which situated at the edges of the Ribbons [4]. However, raw palygorskite, which has permanent negative charges [5], so surface modification by cationic surfactants, is needed to reverse its surface charge if palygorskite is applied to organic compounds adsorption. In this study, palygorskite from Gafsa, Tunisia was selected to adsorb TVOC from essential oil of Eucalyptus globulus. The TVOC was fixed on various palygorskite adsorbent (raw clay and modified clay) thanks to the co-adsorption process. To understand the adsorption mechanism, kinetic study and adsorption was determined.

2. methods 2. 1. Chemical materials Two quaternary ammonium halides bearing long alkyl chains have been used for modifying palygorskite clay. The hexadecyltrimethylammonium bromide (HDTMA) (96% pure, provided by Fluka Analytica) and didodecyldimethylammonium bromide (DDDMA) (98% pure, provided by Fluka Chemika).

2.2. Adsorbate The essential oil of Eucalyptus globulus (Eg) was purchased from Aromessence Society located in Tunisia. The essential oil was obtained by hydrodistillation using a modified Clevenger-type apparatus. The essential oil of Eg was kept at 4 °C in a sealed brown vial until its use.

2. 3. Synthesis of the organopalygorskite clay Palygorskite was obtained from Gafsa, Tunisia. The Organo-palygorskites were subsequently synthesized according to a combined procedure previously described by [6]. Raw palygorskite (S1) was purified by sedimentation and the < 2µm fraction was collected and dried at 60°C/48h. The sample was ground thourgh a 200 mesh sieve and sealed in a glass tube for use. 10 g of S1 was dispersed in 1000 mL of NaCl solution (1M), stirred at about 1050 rpm for 24h. Several washing of Na-S1 were performed until a negative test of AgNO 3 . Then 10 g of Na-S1 powder was firstly dispersed in 1000 mL of distilled water. The whole was maintained under agitation for 1 h before organic modification. HDTMA and DDDMA are used for the easy exchange with the inorganic compensator exchangeable cation S1 [7]. 2 CEC of HDTMA or DDDMA solutions were then added to Na-S1 dispersions (under stirring) at a flow rate of 3.5 mL/min using a peristaltic pump. The resulting dispersions were aged at room temperature for 24 h. After pillaring reaction, the solutions were washed several times with distilled water so as to remove the excess of organic species. The resulting clays were finally dried at 60° for 24 h, and ground in an agate mortar in order to obtain a fine powder.


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2. 4. Characterization The mineralogical analysis of the raw sample was carried out by XRD (Philips X’Pert Diffractometer) on the powder of total rock and the oriented aggregates; normal (N), was treated with ethylene glycol (T) and heated at500°C for 2 h (H). The XRD spectrum of oriented aggregates is presented in figure 1. FTIR transmittance measurements were carried out between 600 and 4000 cm-1 on a Nexus 870 FTIR spectrophotometer according to ATR technical.

2.5. Adsorption Essential oil of Eg which is rich in TVOC [8]. The aim of this part of the work is interpreting the fixation of TVOC of Eg essential oil onto raw palygorskite (S1) and modified palygorskite (S1-HDTMA, S1-DDDMA) through adsorption processes. The kinetic of adsorption were determined by batch reactor in stoppered Pyrex tubes. Firstly, kinetic study was carried out in described tubes containing 10 mL of a Eg solution diluted to 1/20 in acetone, a constant mass of 50 mg of S1, S1-HDTMA and S1-DDDMA. The adsorbed amount of TVOC was quantified after 0, 1, 2, 5, 8, 16 and 24 h. Subsequently, after the attainment of the equilibrium of adsorption, the dispersions were filtered and the equilibrium concentration of TVOC (the equilibrated supernatant phase) was determined by gas chromatography (GC-FID).The gas chromatography (Shimadzu type) used was equipped with a Flame Ionisation detector (30 mL of hydrogen, 300 mL of air,30 mL of nitrogen) and with a column HP-SM (5% phenyl methyl siloxane) (Agilent), length: 30 m, diameter: 250 µm; film 0.25 µm). The gas carrier was nitrogen with a flow rate of 1 mL min-1. The range of temperature was between 40 and 230 °C at 5 °C min-1280 °C at 30 °C min-1and between 230 °C and then it was maintained at 280 °C for 5 min. The injector and detector were maintained at 250 °C and 280 °C, respectively. The injection was done in split mode with a split ratio of 1/10. Adsorptions kinetic were determined using external calibration for each compound of the essential oils. The adsorbed amount was calculated as:

𝑞𝑞𝑡𝑡 =

𝑛𝑛0 −𝑛𝑛𝑡𝑡 𝑚𝑚

Where n 0 is the moles of TVOC in the initial solution of essential oil; n t is the moles of terpenic component in the supernatant. m is the amount of adsorbent (g)

3.Fındıngs and Argument 3.1. Characterization of palygorskite clay Diffractograms recorded on the powder total rock (S1) and oriented aggregates (normal (N), was treated with ethylene glycol (T) and heated at 500˚C for 2 h (H)) are presented figure 1 and allow to determine the mineralogical composition of S1 given in table 1. The raw clay S1 is mainly composed of palygorskite (43%) associated to kaolinite (5%), smectite (1%), calcite (40%), quartz (6%), dolomite (3%) and feldspath (2%) (Table 1).


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Table 1. Mineralogical composition of S1 sample clay Total rock mineralogy (weight %) Clays minerals Palyg orskite Sa mple S1

43

Ka olinite

Non clay minerals S mectite

5

1


C alcite

Q uartz

40

Do lomite

6

Fel despath

3

2

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10

20

30


40 20

50

25

Ka

3,57276 [Å]

20

3,34105 [Å] Pa

3,57053 [Å] Ka/Sm

3,84690 [Å] Sm

20

1,60171 [Å]

15

4,45899 [Å] Ph

15

4,25083 [Å] Sm

4,45561 [Å] Ph

15

1,81644 [Å] Qu/Ka

2,09152 [Å] Ca/Ka

10

5,38633 [Å] Pa

10

2,28135 [Å] Qu/Ca

6,39200 [Å] Pa

7,13761 [Å] Ka

10,54165 [Å] Pa 10

2,45450 [Å] Qu

S1

2,88597 [Å] Do

5

7,12261 [Å] Ka

5

3,34141 [Å] Qu 3,02958 [Å] Ca

10,32629 [Å] Pa

14,09012 [Å] Sm

18,91486 [Å] Sm

5

3,23992 [Å] Pa

4,46075 [Å] Ph 4,25050 [Å] Qu 3,84740 [Å] Ca

7,14123 [Å] Ka

14,46146 [Å] Sm 10,35219 [Å] Pa

4,50572 [Å] Sm

10,43585 [Å] Sm 19.94733 [Å] Pa

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S1-H

Position [°2Theta]

25

S1-T

Position [°2Theta]

S1-N

Position [°2Theta] 25

Position [°2Theta]

60

Ph: phyllosilicates, Sm: smectite, Pa: Palygorskite, Ka: kaolinite, Qu: quartz, Ca: calcite, Do: dolomite

Figure 1. Diffractograms of total rock and oriented aggregates of S1 sample

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The XRD patterns of raw palygorskite S1 and modified palygorskite S1-HDTMA and S1-DDDMA are shown in figure 2. In general, no obvious differences on the XRD patterns were observed between raw and modified palygorskite, the changes of the (110) reflection position were also minor. For instance, S1, S1-HDTMA and S1DDDMA showed corresponding reflections at 10.35 Å, 10.44 Å and 10.1 Å, respectively. Thus, modification with organic surfactants did not noticeably change the structure of palygorskite during the intercalation process, the surfactants had to move not only through the pores of the palygorskite clay, but also through channels and they replaced exchangeable cations. The surfactants attached also on the surface of the rod-like crystals can reduce the aggregation of the particle [9].

10,425 Å

S1-DDDMA

S1-RAW

10,352 Å

10,350 Å

S1-HDTMA

10

20

Position [2 Theta]

Figure 2. Diffractograms of raw palygorskite (S1) and modified palygorskite (S1-HDTMA and S1-DDDMA). The FT-IR spectra of S1, S1-HDTMA, S1-DDDMA are reported in figure 3. The band between 3000-4000 cm-1 of S1 is associated with the stretching vibration of hydroxyl groups which are coordinated to the octahedral magnesium and the tetrahedral silicon [10]. The band at 3646 cm-1for S1 has been attributed to the symmetric stretching modes of molecular water coordinated to the magnesium (or alternative cations of palygorskite) at the edges of the channels. Bands in the 1200-400 cm-1 area are characteristic of silicate; the band at 1000 cm-1for raw palygorskite has been attributed to the asymmetric stretching modes of Si–O–Si [11]. The O–H bending band appears at 929 cm-1[12]. Compared to modified peaks of palygorskite, there is a new adsorption peak at 2938 cm-1, which can be attributed to antisymmetric C–H stretching of the terminal CH 3 - groups [13]. These results indicate that HDTMA and DDDMA were been successfully introduce onto S1.


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detail S1-Raw S1-HDTMA S1-DDDMA

2938

2916

2916 2938

4500

4000

3500

3000

2500

2000

1500

1000

500

-1

Wavenumbers (cm )

Figure 3. FT-IR spectra of raw palygorskite (S1) and modified palygorskite (S1-HDTMA and S1-DDDMA).

3. 2. Adsorption studies 3.2.1. Adsorption kinetics The adsorption kinetics describing the rate of the TVOC retention is one of the key features defining the adsorption efficiency. The time profil of TVOC adsorption for the investigated palygorskites is shown in figure 4. The adsorption process is fast at the beginning of the reaction due to the adsorption of TVOC on the surface sites of palygorskite, then it becomes slow due to the diffusion of TVOC from the surface sites to the fibrous layer of the adsorbent [14]. Therefore, Experimental results indicate that the maximum amount of adsorption is reached after 8 h.


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Figure 4. Effect of contact time on TCOV adsorption onto raw palygorskite (S1) and modified palygorskite (S1-HDTMA and S1-DDDMA).

In order to investigate the adsorption mechanism, the adsorption curves were fitted with three models: the pseudo-first-order adsorption, the pseudo-second-order adsorption and the intraparticle diffusion models. The coefficients values of all TCOV adsorbed by S1,S1-HDTMA and S1-DDDMA were calculated. These constants checked the correlation of kinetic studies with the pseudo-second order kinetic model (table 2). The correlation coefficient for the pseudo-second order kinetic model was near 0.99, indicating that the adsorption absolutely in agreement with pseudo-second-order kinetic model and the adsorption process demonstrated to be controlled by chemisorption process [15]. Furthermore, the theoretical qe values acquired from the second-order kinetic model are in accordance with the experimental qe values. The adsorption process is not uniform for all compounds compared the type of adsorbent. Moreover, the qe of β-humulene is constant without development. Against the amount of adsorption of


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4-methyl-2-pentyl acetate, α-pinene, 1.8-cineole, caryophyllene and isopinocarveol improved slightly with the sample S1-HDTMA. K 2 had used to characterize chemisorptions involving valency forces through the sharing or exange of compensateur ions of palygorskite clay and TCOV [16]. Further the adsorption constant rate expressed by K 2 is improved by the sample S1-DDDMA for all compounds TCOV. Tableau 2. Adsorption rate constants obtained from pseudo second order kinetic model of 4-methylpentyl acetate, alpha-pinene and 1.8 cineole. 4-methyl-2-pentyl

Alpha-pinene

acetate S 1-Raw

S 1-

1-

HDTMA

DDDMA

0 2

.803

0 .994

2

e (mol/g)

.37E-05

.03E+04

1-Raw

.999

.04E-05

2

3

1-

HDTMA

DDDMA 0

7

4

0

7

2

6

1

1-

HDTMA

DDDMA 0

4

2

0 .994

5 .14E-05

6 .72E+03

S

1-

.989

.01E-05

.11E+05

S

0 .813

.56E-06

.87E+05

S 1-Raw

.999

.98E-06

.56E+04

S

1-

.993

.98E-06

.02E+04

S

0 .768

.47E-05

.70E+04

S

0

3

1

2

(g/mol

S

1,8 Cineole

4 .55E-05

1 .69E+04

1 .72E+04

h)

Tableau 3. Adsorption rate constants obtained from pseudo second order kinetic model of isopinocarveol, caryophyllene and beta-humulene. Isopinocarveol S 1-Raw

S

e (mol/g)

.664

1-

HDTMA

DDDMA

2

.17E+06

.793

.59E-07

1-

HDTMA

DDDMA 0

.982

.80E-06

.38E+05

.727

.79E-06

1-

HDTMA

DDDMA 0

.979

.27E-05

0 .997

2 .24E-06

4 .28E+02

S

1-

2

8 .50E+05

S

0

1

3 .73E+05

1-Raw

.997

.28E-06

S

0

2

1

Beta-humulene S

1-

1

3 .17E+06

S

0

2

2 .60E+06

1-Raw

.998

.27E-07

S

0

3

1

2

(g/mol

0 .990

.17E-07

S

1-

0 2

Caryophyllene

1 .69E-06

6 .12E+05

1 .07E+06

h)


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Moreover the curve of intraparticle diffusion does not pass through the origin, which indicates that the kinetics adsorption process is not limited by the intraparticle diffusion of TCOV molecule with in raw and modified palygorskite. These results obtained from kinetic study indicate the adsorption mechanism of TCOV onto palygorskites is performed by two step process. Other study concerning the adsorption of terpenic compounds by clay confirms the main results [17].


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Figure 5. . intraparticule diffusion kinetic model of TCOV adsorption onto raw palygorskite clay (S1) and modified palygorskite clay (S1-HDTMA and S1-DDDMA).

Conclusion 2nd ICIEM 2016, International Conference on Integrated Environmental Management for Sustainable Development

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The current study investigated the use of organoclays for environmental applications in terms of attachements of TCOV from essential oil of Eucalyptus globulus. Their structural properties of organoclays were examined using various techniques. In most studies of the intercalation of the surfactants on clay materials such as smectite, leading to expanded basal spacings [18]. But in our study the intercalation of HDTMA and DDDMA were confirmed by FT-IR analyses despite the interlayer space of the clays were not increased. The modified palygorskites were found to be more efficient for TCOV adsorption than the raw palygorskite due to the hydrophobicities proprieties acquired. The palygorskite intercalated with higher surfactant loading as well as those intercalated with DDDMA tend to afford better uptakes of the TCOV. Further he adsorption system fitted well with pseudo-second order model and the intra-particle diffusion is not controlling step.

Reference [1] Paré, P.W. and Tumlinson, J.H. (1996). Plant volatile signals in response to herbivore feeding. The Florida Entomologiste. Volume 79, n°2, p 93-10. [2] Duke, S.O. (1990). Natural pesticides from plants. Advances in new crops. J. Janick, and J.E. Simon, éd. Timber press, Portland, Oregon, USA, 540 [3] Berenbaum, M.R. (1995). The Chemistry of defence: theory and practice. Chemical ecology: the chemistry of biotic interaction Thomas, E., and Meinwald, J., éd. National Academy of Science Washington DC, 224 pp. [4] Bradley, W. F. (1940). Structure scheme of attapulgite. Am. Mineral. p 25, 405. [5] Ozcan, A.; Sahin, M.; Ozcan, A. S. (2005). Adsorption of nitrate ions onto sepiolite and surfactantmodified sepiolite. Adsorption Science Technology. volume 23, p 323–334. [6] Dammak. N., Ouledltaeuif. O., Fakhfakh. N., Benzina. M. (2014) Adsorption equilibrium studies for Oxylene vapour and modified clays system.surface and interface analysis. Volume 46, P 457-464. [7] Hongping He , Lingya Ma,JianxiZhu, Ray L. Frost, Benny K.G. Theng, Faïza Bergaya. (2014).Synthesis of organoclays: A critical review and some unresolved issues. Applied Clay Science. volume 100, p 22–28. [8] DR Batish, HP Singh, RK Kohli, S Kaur .(2008). Eucalyptus essential oil as a natural pesticide. Forest Ecology and Management. Volume 256, 2166–2174. [9] Yuan, X., et al., (2007). Synthesis and characterization of poly (ethylene terephthalate)/ attapulgite nanocomposites. Journal of Applied Polymer Science. volume 103 (2), pp 1279–1286. [10] Jun Han, Xuefeng Liang, YingmingXu, YuanjianXu. (2015). Removal of Cu2+ from aqueous solution by adsorption onto mercapto functionalized palygorskite. Journal of industrial and Engineering Chemisty. Volume 23, p 307-315. 2nd ICIEM 2016, International Conference on Integrated Environmental Management for Sustainable Development

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[11] E. Balan, A. Marco Saitta, F. Mauri, G. Galas. (2001). First principles modeling of the infrared spectrum of kaolinite. American Mineralogist Journal of Earth and Planetary Materials. Volume 86. p 1321–1330 [12] M. Eloussaief, N. Kallel, A. Yaacoubi, M. Benzina. (2011). Mineralogical identification, spectroscopic characterization, and potential environmental use of natural clay materials on chromate removal from aqueous solutions. Chemical Engineering Journal. Volume 168, Issue 3, p 1024–1031. [13] P. Tuccimei, S. Mollo, M. Soligo, P. Scarlato, and M. (2015). Castelluccio.Real-time setup to measure radon emission during rock deformation: implications for geochemical surveillance. Geosci.Instrum.Method. Data Syst., 4, 111–119. [14] S. GHRAB, N. BOUJELBEN, M. MEDHIOUB, F. JAMOUSSI. (2014). Chromium and nickel removal from industrial Wastewater using Tunisian clay. Desalination and Water Treatment. Volume 52, p 2253–2260. [15] Pérez. J. T., M. Solache-Rıós and A. Colıń-Cruz. (2008). Sorption and desorption of dye Remazol Yellow onto Mexican surfactant-modified clinoptilolite-rich tuff and a carbonaceous material from pyrolysis of sewage sludge. Water Air Soil Pollution, 187 (303–313). [16] Hassan. S. S. N., S. N. Awwad and A. H. A. Aboterika. (2008). Removal of mercury (II) from wastewater using camel bone charcoal. Journal of Hazardous Materials, 154 (992–997). [17]

Marie Goletti Mbouga Nguemtchouin, Martin Benoît Ngassoum, Richard Kamga, Serge Lagerge,

Emmanuelle Gastaldi, Pascale Chalier, Marc Cretin. (2015). Characterization of inorganic and organic clay modified materials: An approach for adsorption of an insecticidal terpenic compound. Applied clay sciences 104. P 110-118. [18] He Hongping, Frost L. Ray, Zhu Jianxi. (2004). Infrared study of HDTMA+ intercalated montmorillonite. Spectrochimica Acta. Part A, volume 60, p 2853–2859. [19] Yunfei Xi, Megharaj Mallavarapu, Ravendra Naidu. (2010). Adsorption of the herbicide 2,4-D on organo-palygorskite. Applied clay sciences. volume 49. p 255-261.


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ENCAPSULATION OF Pb/Zn REJECTS IN METAKAOLIN BASED GEOPOLYMER K.Bouguermouh1, N.Bouzidi1,L.Mahtout1, T.Hassam1, S.Mouhoub1 1

Laboratory of Materials Technology and Process Engineering (LTMGP). University of Bejaia Targua Ouzemmour Road, Bejaia 06000, Algeria [email protected] [email protected] [email protected] [email protected] [email protected]

Abstract: The objective of this study is the encapsulation of two heavy metals Pb and Zn wastes resulting from the treatment of Pb/Zn ore. The Pb/Zn rejects are encapsulated in Na- geopolymer based on metakaolin of Algerian kaolin. However, various amount (0, 5, 10 and 15 wt %) of rejects are introduced within the paste of Na-geopolymers. The physico-chemical characterization and durability of the samples in the alkaline, acid and neutral solutions were studied. The leaching test of the obtained samples shows that the heavy metals are effectively immobilized in the Na- geopolymer, which is attributed to the incorporation of heavy metals (Pb/Zn) in the geopolymer network.

The results of the IR spectroscopy shows that not change in the basic structure of NaG10%

geopolymers, this involve the resistance of these materials to the various attack solutions. The results indicated a successful inertization of the Pb/Zn rejects into the Na-Geopolymers. Keywords: Geopolymer, Pb/Zn reject, Encapsulation, AAS, Infrared spectroscopy, Environment.

1. Introductıon The synthesis of geopolymers consists an alkaline activation of aluminosilicates materials at room or slightly high temperature. They are today materials of choice because of their use for construction and encapsulation of certain toxic waste because of their high mechanical resistance, their weak withdrawal, the weak emission of CO 2 during their synthesis, and their resistance to acid medium,… etc (Krausova Rambure, 2013). The interest of geopolymers in various applications increased, in particular for the encapsulation of waste. The geopolymeric structure was thus tested for incorporation of the nuclear waste. Geopolymerization is thought to occur through dissolution, migration and polymerization of Al and Si precursor species (from metakaolin or fly ash) as well as surface reaction on surface of undissolved particles (Luna et al., 2007). In the geopolymer framework, aluminum is four coordinated to oxygen atoms, therefore, a negative charge is created and thepresence of cations


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such as Na+, K+, Li+, Ca2+, and NH 4+ is essential to balance the negative charge of Al (Rahier et al., 2007). Heavy metals are significant components of many industrial and residual wastes, and preventing their release into the ecosystem is of great interest.There are also many areas world wide where soils have become contaminated with heavy metals, and the treatment of these soils to prevent mobility of contaminants is becoming very essential (Zhang et al., 2008). The immobilization of heavy metals must be durable and resistant against leaching. The studies showed that the geopolymers can undergo aggressive conditions during several months without deterioration on the surface contrary to Porthland cement. The alkaline reaction during the geopolymers formation influence the density, limits the infiltration of the acid elements and sulfates in the gopolymr system and thus prevents potential degradation ( Krausova Rambure, 2013). The objective of this study is the encapsulation and the stabilization of two heavy metals Pb and Zn resulting from treatment of Pb/Zn ore in a sodium geopolymers based on metakaolin of TAMAZERT situated at El-Milia, Jijel in the north-western of Algeria. In fact, various amount of waste are introduced in the geopolymers pastes.

2. Materials and methods 2.1.

Materials

Algerian kaolin (commercial product) named KT from Tamazert situated at El-Milia, Jijel whose chemical composition determined by x-ray fluorescence is given in Table 1 is selected for its high content in kaolinite (66 wt%) (Bouzidi et al., 2013, Bouzidi et al., 2014) and used after calcination at 750°C named MKT. It is primarily made up of silica 48.50 wt % and alumina 33.9 wt % and the contents of alkaline cations as potassium is relatively high. It should be noted the presence of hematite (Fe 2 O 3 ) relatively important (2.25-2.50 wt %). Commercial solution of sodium silicate provided by Woellner whose molar ratio Si/Na equal to 1.7 is used as well as sodium hydroxide (NaOH) provided by Biochem in pastilles form whose purity is 99% are used for the formulation of geopolymers. A laboratory waste of Pb/Zn whose chemical composition is selected in table 2 was used as heavy metal source. It is consisted of 0.334 wt % and 0.498 wt% of Lead Dioxide Pb 2 O 5 and Lead Oxide PbO respectively and 5.965 wt% of Zinc Oxide ZnO. Concentrated HNO 3 was used to stabilize the solution after filtration.

Table 1. Chemical and mineralogical composition of kaolin KT.


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Oxides

Wt %

SiO 2

48.50

Al 2 O 3

33.90

Fe 2 O 3

2.25-2.50

TiO 2

0.21

CaO

0.08

MgO

0.39

K2O

2.75-3.10

Na 2 O

0.08

LOI

10.50

SiO 2 / Al 2 O 3

1.43 66% Kaolinite, 9% Quartz, 13%

minéralogy

Muscovite, 2% Albite, 8% Orthose, 0.4% Anatase/Rutile, 2% Geothite, 0.6% Organic matter

LOI : loss on ignition

As shown on table 2, the Pb/Zn reject powder contains substantial amount of MnO,Fe, Zn, Ca, Na, K and Pb but only trace amount of Cu, As, Sr and Mg. The Pb/Zn reject powder exhibits high leachability for Mn,Fe, Zn, Ca, Na, K and Pb and trace elements Cu, As, Sr and Mg in acidic condition. Table 2. Chemical composition of Pb/Zn reject. Oxid

wt%

es

Oxid

Wt%

es Na 2

1.552

PbO

0.498

MgO

0.270

TiO 2

0.557

Al 2 O

12.74

MnO

12.34

49.99

Fe 2 O

6.849

O

1

3

SiO 2 4

3

P2O5

0.334

CuO

0.069

SO 3

0.578

ZnO

5.965

K2O

1.896

As 2 O

0.178

3


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2.

CaO

8.038

SrO

0.021

Rb 2 O

0.022

2. Methods of characterization

The chemical compositions of kaolin and reject were determined by using the X fluoressence (PanAnalytical PerlX 3). The various powders’ diffractograms presented were obtained on Brucker D 8 of DebyeSherrer instrument type using Cu Kα (λKα = 1,5406 Å) radiation and a back graphite monochromator. The analysis range is between 5 and 80° with a step of 0.02° and an acquisition time of 8 s. The crystalline phases present in material are identified by comparison with standards pdf (Powder Diffraction Files) of the ICDD (International Center for Diffraction Data). The mineralogical analysis was carried out on the raw materials before and after calcinations and geopolymers formulations before leaching test. Fourier-Transform Infrared (FTIR) Spectroscopy analysis were obtained by SCHIMADZU 8400 spectrophotometer. The IR spectra were gathered over a range of 400 to 4000 cm−1. The preparation of sample consists in mixing 1wt% of powder with 99wt% of KBr to form a pellet with 10 mm diameter.

2.

3. Synthesis of geopolymer pastes

The reactive mixture is obtained by initially dissolving sodium hydroxide in sodium silicate solution and then the metakaolin and various amount (5 wt%, 10 wt% and 15 wt%) of Pb/Zn reject powders are introduced with the geopolymers paste. The mixtures thus obtained are placed in cylindrical molds (15 mm diameter and 30 mm height) treated at 70°C during 24 hours. The different stages of geopolymers elaboration are shown in figure 1. The nomenclature and molar composition of the different mixtures are reported in table 3.


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Dissolution of hydroxide pellets in an alkali silicate Manual stirring Addition of Metakaolin +Pb/Zn reject powders. Closed molds 70°C-24h Geopolymers

Pilot samples: XRD and FTIR.

Samples for Leaching test: AAS and FTIR.

Figure 1. Processing stages of geopolymers elaboration.

Table 3. The composition of the mixtures prepared according to the molar ratio of the species present. Samples

% Pb/Zn reject

Si/Al

Na/Al

NaG0%

0

2.08

1.02

NaG5%

5

2.25

1.54

NaG10%

10

2.18

0.95

NaG15%

15

2.24

0.93

2.4. Leaching of heavy metals Samples aged 1 day and 28 days were immersed at a liquid to solid (L/S) ratio of 10 L/kg in the following leaching solutions: deionized water, 0.1 M HCl and 0.1 M NaOH. Leaching tests were carried out on samples at 25 °C and 250 rpm for 24 h in sealed plastic containers in order to prevent continued absorption of carbon dioxide from the atmosphere. The leachates were then filtered and acidified

with

concentrated

HNO 3

solution

and

analyzed

using

an

atomic

Absorption

spectrophotometer (SHIMADZU AA6501F).

3.

Results and discussions


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3.1.

XRD analysis

The X-ray diffractogram of KT presented in Figure 2 (a) shows that the product is a complexe mixture of several mineralogical phases; we note that the kaolinite is the majority mineralogical phase. Further we note the existence of impurities: quartz, muscovite and much less of albite. During the heat treatment (Figure 2 (a)) we note the disappearance of peaks corresponding to kaolinite, this is due to the formation of metakaolin (the dehydrated kaolinite) or amorphization of metakaolinite represented by the dome at 22-32 °2θ, the heat treatment therefore causes the transition from a crystalline (kaolinite) in a disordered phase (metakaolinite) by a collapse of the crystal lattice phase. In addition, peaks related to quartz and muscovite remains unchanged after heat treatment. The results also show that the Pb/Zn reject (figure 2(b)) is consisted of quartz, muscovite, little kaolinite, dolomite and other secondary phases such as feldspar, pyrite, little gypsum and zincite.

(a)

Q Mu

(b)

Q

4000 3500

Q K

3000

Intensity (Counts)

Q

Mu

Q

Q Q

Q K

MKT T

Q

Q

Q

K

K KQ KK Ab

10

20

K

30

1500

D Mu

G Q

60

2 Theta (°)

Mu

MuK

10

20

K D

Q

1000 500

T

50

2000

P

KT 40

2500

Ab

Intensity (u. a)

Q Mu

Ab

C

Q Ab K D AbC

KQ Q

P Z D

0 30

40

50

60

70

80

2 Théta (°)

Figure 2. X-Ray Diffractograms of (a) : kaolin KT and (b) : Pb/Zn reject. (K: Kaolinite (00001-0527), Q: Quartz (00-001-0649), Mu : Muscovite (00-002-0467), Ab : Albite (00-009-0466), G : Gypse (00-021-0816), D : Dolomite (00-036-0426), P : Pyrite (00-002-1366), Z : Zincite (00-0030752)). Figure 3 show the XRD patterns of geopolymers. The result shows a semicrystalline structure and some peaks of raw materials are present but with a reduced intensity which is attributed to the crystalline phases not reacted, such as quartz around 20°2θ and 26°2θ, and muscovite around 35°2θ as well as feldspar, zincite and pyrite in the X-ray diffractograms of NaG5%, NaG10% and NaG15%. the peak which corresponds to sodium bicarbonate (NaHCO 3 ) and sodium carbonate (Na 2 CO 3 ) are


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resulting from the chemical reaction which occurs between the residual sodium hydroxide (aqueous) and carbon dioxide from the air (Gao et al., 2013). It has been shown that quartz is unreactive widely. According to Zhang and al. (2008) the persistence of peaks corresponding to the quartz and muscovite in X -ray diffraction patterns of geopolymers indicates that it does not participate in the geopolymerization process, but their intensities were slightly lower due to a dilution effect (Criado et al, 2007, Elimbi et al, 2011). One also notes the presence of domes between 22-35°2θ, which is the typical model of XRD for a geopolymer (Zhang et al, 2014).

Q 2000

1500

Intensity (u.a)

Mu Q Mu

D Mu P Z Ab Mu Ab

Q Q

P Q

Q

(d) 1000

(c) 500

(b)

Sc Mu

Mu Q

Q

(a)

0 10

20

30

40

50

60

2 Théta (°)

Figure 3. X-Ray Diffractograms of (a) : NaG0%, (b) : NaG5%, (c) : NaG10% et (d) : NaG15%. Q: Quartz (00-001-0649), Mu : Muscovite (00-002-0467), Ab : Albite (00-009-0466), D : Dolomite (00036-0426), P : Pyrite (00-002-1366), Z : Zincite (00-003-0752), SC: NaHCO 3 (00-002-0712), Na 2 CO 3 (00-037-0451)).

3.

2. FTIR analysis of synthesis geopolymers before the leaching test

FTIR analysis of NaG0% (Figure 4 A) and NaG5%, NaG10% and NaG15% geopolymers after incorporation of Pb/Zn reject (Figure 4 B) shows that the main band at approximately 1003 cm− 1 and 1010 cm− 1 is attributed to Si-O-Si. There is also the presence of other bands which are visible in the infrared spectrum; The bands between 3400-3200 cm-1 and 1652 cm-1 are attributed to stretching vibrations of (H-O) and deformation of (H-O-H) in the water molecules absorbed or present in cavities in the geopolymers structure (Chee, 2006,Van Jaarsveld and Van Deventer, 1996, Essaidi et al., 2014, Soro, 2003 ). The band located at 1409 cm−1 is designed as characteristic of HCO 3 −, and the bands at 1378 cm−1, 1448 cm−1 and 1456 cm−1 are identified as characteristic peaks of CO 3 2 – (Innocent et al., 2010). According to figure 4 we note that the bands located at 862 cm− 1 and at 882 cm− 1 in NaG0% and NaG5% geopolymers respectively attributed to Al–OH stretching band is disappeared in NaG10% and NaG15% specta due to the increasing of percentage incorporation of the Pb/Zn reject. 2nd ICIEM 2016, International Conference on Integrated Environmental Management for Sustainable Development

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B

706 cm-1

3600-3200 cm-1

0,0

1378 cm-1

1652 cm-1

A

60

50 0,2

2371

30 1409 1652

862 698

1448

20

565 471 10

(c)

400 471

0,8

1448

1,0

1010

549

(b)

1,2 1,4

1456

882

1,6

3600-3200 1010

0 4000

549

0,6

Transmittace (%)

Transmittance (%)

1441

0,4

40

471 565 408 479

(a)

1003

1,8

1010

3500

3000

2500

2000

1500

1000

2,0 4000

500

wavenumbers (cm-1)

3500

3000

2500

2000

1500

1000

500

Wavenumbers (cm-1)

Figure 4. FTIR spectra of A: NaG0% geopolymer before incorporation of Pb/Zn reject, B: geopolymers spectra after incorpotation of Pb/Zn reject with (a): NaG5%, (b): NaG10% and (c): NaG15%.

3.3. Leaching test of Pb and Zn from different samples The leaching was investigated using deionized water, 0.1 M HCl and 0.1 M NaOH solutions. These leaching solutions were selected to approximate certain conditions to which geopolymers may be exposed. Hydrochloric acid solution replicates either acid mine drainage hydrometallurgical waste or galvanizing effluent conditions. Sodium hydroxide solution was used in order to compare its leaching effect with hydrochloric acid (effect of pH). The results of the atomic absorption spectroscopy show that lead Pb is untraceable in all the solutions what proves its encapsulation in the geopolymers matrix. In the case of Zn (Figure 5), traces were detected in the various mediums knowing that geopolymers 28 days old give the smallest % compared to those 1 day old. The NaG10% sample 28 days old has a stable behavior in the different pH mediums which explain its high capacity to retain Zn. The dissolution of Zn depends on the pH of mediums and the % of incorporation on waste; In an acid medium the highest % of leaching Zn is in NaG15% for the two batches of geopolymers.

0,025

% leaching Zn

0,025

% leaching Zn

0,03

(a)

0,02

0,015 0,01

0,005

0,03

(b)

0,02 0,015 0,01

NaG5% NaG10% NaG15%

0,01

0,005

0

NaG5% NaG10% 2 ICIEM 2016, International Conference on Integrated Environmental Management for Sustainable Development nd

0,02

0,015

0,005

0

(c)

0,025

% leaching Zn

0,03

0

NaG15%

NaG5% NaG10% NaG15% Page 67

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Figure 5. % leaching Zn in various medium (a): Dionised water, (b): HCl, (c): NaOH. With Geopolymers aged 24 h

and Geopolymers aged 28 days.

The results of IR spectroscopy of NaG10% 1 day and 28 days aged geopolymers presented in figure 6 A and 6 B respectively show that there is not change between the pilot samples before the leaching test with those after the test which prove that the basic structure of NaG10% geopolymer was not affected by the various mediums. In all the samples spectra, there was an increase in the wave number of the bands in the region of 1600 and 3450 cm-1, which were attributed to bending vibrations (H–O–H) and stretching vibration (–OH) due to weakly bound H 2 O molecules adsorbed on the surface or trapped in the large

690 cm-1 557 cm-1 479 cm-1

1010 cm-1

B

80

70

70

60 50

(c)

40

(b)

30

(a)

20

Transmittance (%)

Transmittance (%)

1652 cm-1

90

80

1402 cm-1

A

698 cm-1 557 cm-1 479 cm-1

1010 cm-1

90

1394 cm-1

1644 cm-1

cavities (Bakharev, 2005).

60

(f)

50

(e)

40 30

(d)

20

3600-3200 cm-1

10 0 4000

3500

3000

10

2500

2000

1500

1000

500

wavenumbers (cm-1)

0 4000

3600-3200 cm-1

3500

3000

2500

2000

1500

1000

500

Wavenumbers (cm-1)

Figure 6. FTIR spectra of A: NaG10% geopolymer 1 day aged and (B): NaG10% geopolymer 28 days aged after leaching test in (a): Dionised water, (b): HCl and (c): NaOH.

Geopolymerization is thought to occur through dissolution, migration and polymerization of Al and Si precursors species (from metakaolin or fly ash) as well as surface reaction on surface of undissolved particles (Luna et al., 2007). There exist two possibilities of immobilization of heavy metals. One of the possibilities is the physical immobilization by the capture of the toxic elements in the pores of the solid matrix.


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Another possibility is the immobilization of heavy metals by their replacement of a component with the same valence which is the case of this study proved by the Infrared spectroscopy.Indeed, The Pb function will be after compensating the negative charge of aluminum. Heavy metal like Pb has two cations (divalent), which is identical to Ca. We can suppose that this heavy metal could replace Ca during the structuring of the matrix. Ca2+ would behave like Na+ i.e., it would compensate the negative charge of aluminum ion (Fang and Kayali, 2013), which forms a tetravalent hydroxide (Al(OH) 4 ). A study on the fixing of heavy metals in geopolymer materials based on lignite fly-ashes was carried out by Minaríková et Skvara, 2005. They looked at the effectiveness of immobilization of Cd, Cu, Cr, Pb and Zn by studying leaching in deionized water then carried out by atomic absorption spectrometry analysis. The values of leaching were different for each metal. The most promising results of the immobilization were for zinc, which is not possible to solidify in Porthland cement. For other metals (Pb, Cd…) the Porthland cement matrix showed better results in leaching compared to geopolymers. It was observed that addition of heavy metals had not caused formation of new crystalline phases. Palomo and al. 2003, proposed the three following possibilities of incorporation of Pb in the system of HSC: Addition: HSC + Pb → Pb-C-S-H Substitution: HSC + Pb → Pb-S-H + Ca Precipitation of new components: Pb + OH + Ca + SO 4 → mixture of salts Many authors (Van Jaarsveld and Van Deventer, 2005, Galiano et al., 2011) emphasize the importance of pH value on the degree of leaching of immobilized toxic ions. In this study, the solutions obtained after leaching were highly alkaline due to the release of free alkali in the aquatic environment, but in all cases the pH values were similar (10.32–13.14) except for NaG15% in HCl medium where the pH do not exceed 4.50. Thus, the pH value had a decisive influence on the differences in the leaching behavior of the geopolymers contrary to Nikolić et al. (2014) results. The Si/Al and Al/Na molar ratio play an important role when geopolymers are exposed to aggressive environment. Fernandez-Jimenez and Palomo (2005) showed that best resistance is obtained when M/Al (M: Alkali cation) molar ratio close to 1 which is the case of NaG10% sample with Na/Al molar ratios of 0.95 (Table 2). The presented results clearly confirmed the higher effectiveness of Na-geopolymers based on Tamazert metakaolin in the immobilization of lead and Zinc when Si/Al and Na/Al molar ratio are equal to 2 and 1 respectively.

5. Conclusions The characterization of synthesized geopolymers before and after the leaching test showed that: •

XRD of pilot samples have a semi crystalline structure presented by the

dome around (22°2θ-34°2θ). However, secondary phases such as quartz, muscovite, pyrite 2nd ICIEM 2016, International Conference on Integrated Environmental Management for Sustainable Development

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and zincite are still present. Moreover, new peaks corresponding to NaHCO 3 were formed this is due to the reaction between the excess NaOH which had not reacted during the geopolymerisation reaction with air CO 2 . •

The results of the atomic absorption spectroscopy showed that lead Pb is

untraceable in all the solutions what proves its encapsulation in the matrix of geopolymers. In the other hand, traces (small %) of Zinc were detected in the various mediums knowing that geopolymers 28 days ages gives the smallest % compared to those 1 day age. •

The NaG10% sample with 28 days ages has a stable behavior independently

of pH of mediums. FTIR analysis shows that not change between the samples before and after the leaching test proof that the basic structure of the geopolymers was not affected during the leaching test.

References Bakharev, T. (2005) Resistance of geopolymer materials to acid attack.Cement and concrete Research, 35:658 – 670.

Bouzidi, N., S. Aissou, N. Concha-Lozano, P. Gaudon, G. Janin, L. Mahtout, D. Merabet (2014) Effect of Chemico-Mineralogical Composition on Color of Natural and Calcined Kaolins. COLOR research and application, 39: 499-505.

Bouzidi, N., A. Bouzidi, P. Gaudon, D. Merabet, P. Blanchart (2013) Porcelain containing anatase and rutile nanocrystals. Ceramics International.39:489–495

Chee, H.O. (2006) Performance of concrete containing metakaolin as cement eplacement material. Master thesis, University Technology, Malaysia. Criado, M., A. Fernández-Jiménez, A. Palomo (2007) Study of the effect of the SiO 2 /Na 2 O ratio on the alkali activation of fly ash. Cement and Concrete research. 37: 9–671. Elimbi, A., HK. Tchakoute, D. Njopwouo (2011) Effects of calcination temperature of kaolinite clays on the properties of geopolymer cement. Construction and Building Materials, 25:2805–2812. Essaidi, N., B.Sameta, S.Bakloutia, S. Rossignol (2014) Feasibility of producing geopolymers from two different Tunisian clays before and after calcination at various temperatures. Applied Clay Science, 88–89:221– 227.

Fang, Y. and O. Kayali (2013) The fate of water in fly ash-based geopolymers. Construction and Building Materials, 39:89-94.


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Fernandez-Jimenez, A., A. Palomo (2005) Characterisation of fly ash. Potential reactivity as alkaline cements. Fuel, 8: 2259-2265. Galiano, Y.L., C.F. Pereira, J. Vale (2011) Stabilization/solidification of a municipal solid waste incineration residue using fly ash-based geopolymers. Journal of Hazardous Material, 185:373–381. Gao, X.X., E. Joussein, S. Rossignol., P. Michaud (2013) Behavior of metakaolin-based potassium geopolymers in acidic solutions. Journal of Non-Crystalline Solids. 380:95–102.

Innocent B., D. Pasquier, F. Ropital, F. Hahn, J. M. Léger, K. B. Kokoh (2010) FTIR spectroscopy study of the reduction of carbon dioxide on lead electrode in aqueous medium. Applied Catal. B Environment, 94: 219–224.

Krausova Rambure, K. (2013) Vers de nouvelles matrices minérales pour l’immobilisation et la valorisation des déchets ultimes de l’incinération des déchets ménagers. Thèse de Doctorat, Université de Paris Est.

Luna, Y., X.Querol, D. Antenucci, , E. Jdid, C.F.Pereira, , J. Vale (2007). Immobilization of ametallurgical waste usingfly ash-based geopolymers. World of Coal Ash (WOCA), 7–10, Kentucky, USA. Minaríková M. and F. Škvára (2005) Fixation of heavy metals in geopolymeric materials based on brown coal fly ash. proceeding, 4th International Conference on Geopolymers, Juin 26.- Aout 1, Saint Quentin, France, 8. Nikolić, V., M. Komljenović, N. Marjanović, Z. Baščarević, R. Petrović (2014) Lead immobilization by geopolymers based on mechanically activatedfly ash. Ceramics International, 40: 8479–8488. Rahier, H., J. Wastiels, M. Biesemans, R.Willem, G. Van Assche, B. Van Mele (2007). Reaction mechanism, kinetics and high temperature transformations of geopolymers. Journal of Material Science, 42:2982–2996.

Palomo, A. and M. Palacios (2003) Alkali-activated cementitious materials: Alternative matrices for the immobilisation of hazardous wastes. Part II. Stabilisation of chromium and lead. Cement and concrete research, 33:289-295.

Soro, N.S. (2003) Influence des ions fer sur les transformations thermiques de la kaolinite. PhD thesis, University of Limoges, France.

Van Jaarsveld, J. G. S. and J. S. J. Van Deventer (1996) The potential use of geopolymeric materials to immobilise toxic metals: Part I Theory and applications. Minerals Engineering, 10:659-669.


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Van Jaarsveld, J.G.S., J.S.J. van Deventer, L. Lorenzen (1998) Factors affecting the immobilization of metals in geopolymerizedfly ash. Metallurgical Material Transaction. 29:283–291. Zhang, J., J. L. Provis, D. Feng, J.S.J. Van Deventer (2008). Geopolymers for stabilization of Cr6+, Cd2+ and Pb2+. Journal of Hazardous Material, 157: 587–598.

Zhang, M., T. El-Korchi, G. Zhang, J. Liang, M. Tao (2014) Synthesis factors affecting mechanical properties. Microstructure and chemical composition of red mud–fly ash based geopolymers. Fuel,134:315–325.


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Adsorption of Basic Dye from Aqueous Solution by Nanocomposite Materials

A. Nait-Merzoug 1,5*, O. Guellati 1,2,3,*, A. Benjaballah 1, Z. Belouettar 1, I. Janowska 3, D. Bégin 3, N. Manyala 4 and M. Guerioune 2 1

Université Mohamed Cherif Messadia de Souk Ahras, Fac. Sci, BP. 1553, 41000-Souk-Ahras, ALGERIA. [email protected] and [email protected] and [email protected]

2

Laboratoire d’Etude et de Recherche des Etats Condensés (LEREC), Département de Physique, Université Badji-Mokhtar de Annaba, BP. 12, 23000 Annaba, ALGERIA. [email protected] and [email protected]

3

Institut de Chimie et Procédés pour l'Energie, l'Environnement et la Santé (ICPEES) ECPM - CNRS - UdS, 25 rue Becquerel, 67087 Strasbourg Cedex 2, FRANCE. [email protected] and [email protected]

4

Department of Physics, Institute of Applied Materials, SARCHI Chair in Carbon Technology and Materials, University of Pretoria, Pretoria 0028, SOUTH AFRICA. [email protected]

5

Laboratoire des Science et Techniques de l’Eau et d’Environnement (LSTEE), Université Mohamed Cherif Messadia de Souk Ahras, Fac. Sci, BP. 1553, 41000-Souk-Ahras, ALGERIA.

Abstract. The environment has become a major concern in our society, thus encouraging the development of new processes and materials for the improvement of decontamination methods. Different techniques were used for the elimination of certain soluble pollutants in industrial and domestic effluents. Adsorption is one of the processes adopted for the pollutants removal, because of its great capacity to purify contaminated water. Activated carbon is the adsorbent most commonly used but it is very expensive and requires regeneration. This has encouraged in directing research to treatment methods using less expensive materials and easy to synthesize and regenerate. In this perspective, our work is to test a new hydroxide based nanocomposite as new kind of adsorbent. The obtained results confirm that this type of nanocomposite has a very good affinity for our organic pollutant which is methylene blue (MB). The study of the influence of various parameters allowed us to conclude that the best removal rates require very stringent operating conditions which must be taken into a consideration. Nevertheless, pH affects very significantly on the retention on the kind of pollutant, without forgetting the equilibrium time required to reach the saturation of each adsorbent material. Also, surface functions and textural properties play an important role in the adsorption phenomena.

Keywords: Adsorption, methylene blue, nanocomposite, NiCo carbonate hydroxides, basic dyes.

1. Introduction Frequently large amounts of colored waste water are generated in industries which use dyes to impart a desired color to their products (textile, food, paper, plastics …), and are discharged into natural streams with undesirable consequences to the environment and to the human health [1].


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Apart from the unpleasant aesthetic appearance, the presence of dyes in natural streams can cause serious harm to the aquatic life by increasing toxicity and chemical oxygen demand as well as by hindering photosynthetic phenomena through reduction of light penetration [2]. Also, some dyes such as methylene blue can cause injuries to humans and animals by direct contact (eye burns), inhalation (rapid or difficult breathing) or ingestion (nausea, vomiting, mental confusion, …) [3]. Over the years, various methods of waste water treatment have been reported and adsorption is one of the most widely accepted techniques in terms of its cost effectiveness, versatility, simplicity and ease operation [4–6]. The use of nanoscale composite materials has been reported over the years by quite a number of researchers for the treatment of waste water. Some include the remediation of tributyltin using Fe 3 O 4 , activated carbon and Fe 3 O 4 /activated carbon composite material reported by Ayanda et al. [7], the synthesis of supported nanoscale zero-valent iron (nZVI) was reported by Zhang et al. [8] where nZVI supported on exfoliated graphite was used for the removal of nitrate. Sheela et al. [9] and Rahmani et al. [10] investigated the adsorption of heavy metals onto nanoscale zinc oxide and alumina, respectively. In addition, Frost et al. [11] used palygorskite supported zero-valent iron for the removal of methylene blue (MB) and Shahryari et al. [12] reported the adsorption of MB onto carbon nanotubes. However, no work has been reported on the use of Ni-Co based hydroxide nanocomposites for the removal of MB from aqueous solution until no. Generally, mixed transition metal oxides, typically ternary metal oxides with two different metal cations, have received an upsurge of interest in recent years due to their promising roles in many energy- and environment- related applications. In particular, layered double hydroxides (LDHs) are a class of inorganic multi-metal materials composed of metal cations (divalent and trivalent metal) in the host layer and balanced by ionic anion species in the interlayer space as shown figure 1 [13]. Consequently, developing the transition metal oxide, hydroxide and carbonate hydroxide nanomaterials, especially based of Co- and/or Ni-, as inexpensive replacements for noble metal catalysts, have recently attracted considerable attention because of their earth abundant nature, low cost, environmentally friendly, multiple valence state and high theoretical activity [14].


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Figure 1. An example of two different structures: Brucite (hydroxide) and Hydrotalcite (hydrated carbonate hydroxide) (top) and Layered Double Hydroxide “LDH” (down) [14].

To our knowledge, there is no report regarding the removal of methylene blue (MB) over the Ni-Co hydroxide nanocomposite until now. Therefore, our aim in this investigation is to (i) synthesize the Ni-Co hydroxide based nanocomposite as an adsorbent using simple and low cost hydrothermal method [15, 16]; (ii) investigate the adsorption behavior of MB onto our nanocomposite adsorbent and (iii) analyze the adsorption kinetics and isotherms of MB adsorption onto the nanocomposite adsorbent using the theoretical models.

2. Experimental Procedure 2.1.

Reagents and solutions preparation

All of the reagents were of analytical grade with the mass fraction purity of 0.99 and used as received without further purification. 2.1.1.

Adsorbent Preparation

Heterometallic Ni and Co based hydroxide nanocomposites were prepared using a simple and low cost hydrothermal synthesis system at 180 °C as growth temperature during 6h. The used Nickel and Cobalt precursors were Nickel (II) chloride hexahydrate (NiCl 2 .6H 2 O) and Cobalt (II) chloride hexahydrate (CoCl 2 .6H 2 O), in 1:2 molar ratio respectively, dissolved in dionised water. 2.1.2.

Adsorbate

Methylene blue (MB) obtained from Merck was used for all experiments. The MB was chosen in this study because of its complicated chemical structure as shown in figure 2. It is resilient to


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fading on exposure to light and its strong adsorption onto solids. The maximum absorption wavelength of this dye is 668 nm.

Figure 2. Methylene blue (MB) molecular. 2.2.

Adsorption Experiments

Batch adsorption experiments were carried out in a water bath with a shaking speed of 500 rpm. In general, 0.1g of the Ni-Co based hydroxide nanocomposite were added into 100 cm3 of MB solutions of desired initial concentrations at a natural 6.5 pH in flask and stirred in a controlled temperature shaker at 298 °K. At predetermined time intervals, the samples were removed from the solution by filtration. The effect of pH on the MB adsorption onto the nanocomposite adsorbent was studied over a pH range of 2.0 to 12.0. The pH was adjusted by adding aqueous solutions of 0.1M HCl or 0.1M NaOH. The adsorption kinetics was determined by the analysis of the adsorption capacity from the aqueous solution at different time intervals. For adsorption isotherms, MB solution of different concentrations was incubated with the adsorbent under stirring until the achieved equilibrium. The concentration of MB dye was determined at 664 nm using an UV-vis spectrophotometer JENWAY 6705. The equilibrium adsorption capacity of our adsorbate onto the Ni-Co based hydroxide nanocomposite was evaluated by using the mass balance equation:

(1) Where C 0 and Ce are the initial and the equilibrium concentrations of dye, m is the adsorbent mass and V is the solution volume. 2.3.

Characterization Techniques

The structural characterization of the synthesized Ni-Co carbonate hydroxide based adsorbent was investigated by powder X-ray diffraction (XRD) using a XRD D8 ADVANCE-BRUKER AXS diffractometer equipped with a copper anticathode tube “Cu Kα radiation” (λ = 1.5406 Å) and a graphite monochromator rear operating at 40 kV-40 mA and employing a scanning rate of 0.2°.s-1. The XRD patterns of all specimens were recorded in the 10° to 90° 2θ range. Their morphological analysis was characterized using FESEM (JEOL 6700-FEG microscope) in order to control the quality, structure and overall morphology of the adsorbent support.


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Fourier-Transform Infrared (FTIR) spectra of these Ni-Co carbonate hydroxide based nanocomposites were recorded using a Bruker Vertex 77v spectrometer in the 400 to 4000 cm-1 range with 4 cm-1 resolution and with Opus software analysis system. Moreover, specific area surface and pore distribution measurements were carried out on a Tristar (Micromeritics, ASap 2420, P/P0 = 10-6 to 1) sorptometer, using N 2 as adsorbent at liquid nitrogen temperature, through N 2 adsorption/desorption isotherms and the Barrett–Joyner–Halenda (BJH) method, respectively. Before measurements, the samples were already out-gassed under vacuum at room temperature to avoid products transformation during all the night in order to desorb impurities and moisture from its surface. Absorbance measurements were performed using a double-beam JENWAY 6705 (UV-Vis) spectrophotometer (Japan) in a wavelength range with a spectral bandwidth of 4 nm. The solution pH has been measured with a pH-meter model HI 8014, HANNA Instruments (Italy).

3.

Results and Discussion 3.1.

Adsorbent Charactrization

Figure 3 shows the crystallographic identification of the obtained nanocomposite used as adsorbent based of Ni and Co which were attributable to hydrotalcite configuration, as illustrated in figure 1. Consequently, the main XRD peaks of the nanocomposite adsorbent used in this investigation can be assigned to cobalt carbonate hydroxide hydrate (Co(CO 3 ) 0,5 (OH). 0,11 H 2 O JCPDF no. 48-0083) with orthorhombic structure (a = 8,792 Å, b = 10,15 Å and c = 4,433 Å) and nickel carbonate hydroxide more hydrate, zaratite, (Ni 3 (CO 3 )(OH) 4 . 4 H 2 O JPCDS No. 16-1164). These results show that the adsorbent is based on bi-structure or bi-carbonate hydroxide of Ni and Co nanocomposite.

10

20

30

-- --

--

--

--

--

-----

--

--

---

--

--

-- --

-- --

--

Intensity (a.u.)

--

-- Co(CO3)0.5(OH). 0.11H2O [048-0083] -- Ni3(CO3)(OH)4. 4H2O [16-1164]

40

50

60

70

80

90

2θ (°)

Figure 3. XRD spectrum of the synthesized Ni-Co based carbonate hydroxide nanocomposite synthesis using hydrothermal method.


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The representative high magnification FESEM micrograph (Fig. 4) of the obtained Ni-Co based carbonate hydroxide nanocomposite shows the nanorod fiber morphology in package form of this kind of nanohydroxide which will be used as adsorbent material for MB elimination.

Figure 4. High magnification FESEM micrograph of Ni-Co based carbonate hydroxide nanocomposite used as adsorbent.

Moreover, the successful preparation of this kind of bi-structure nanocomposite based of NiCo carbonate hydroxide is proved by FTIR analysis as shown in figure 5a. In general, there are three absorption bands zone: up 3200 cm-1 and around 1500 cm-1 as regards the intercalated molecules mentioned above as well as other absorption bands below 1000 cm−1 which are associated with M–O stretching and M–OH bending vibrations (in our case M = Co, Ni) [17].

Co-O/Ni-O

3000

CO2

Co-OH/Ni-OH

3500

-2 CO 3

CH /CH 3 2

O-H

O-H from H2O

Absorbtion

hydroxyde

4000

2500

2000

1500

1000

500

Wave number (cm-1)

Figure 5. FTIR analysis spectrum of Ni-Co based hydroxide nanocomposite used as adsorbent.


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The results of the specific surface area and pore volume-size distribustion of the Ni-Co based carbonate hydroxide nanocomposite adsorbent were listed in Table 1. The N 2 adsorptiondesorption experiments show that the surface area of our adsorbent is around 12.2602 ± 0.3469 m²/g. The average pore width is 4.5102 nm indicating that Ni-Co based carbonate hydroxide nanocomposite is a mesoporous material. Figure 6 shows the adsorption-desorption isotherms and pore size distribution of the nanocomposite adsorbent used in this investigation.

10

0,03 Isotherm Linear Plot

Pore Volume (cm³/g)

Quantity (mmol/g)

BJH Adsorption dV/dlog(w) Pore Volume

Quantity Adsorbed Quantity desorbed

8

6

4

2

0

0,02

0,01

0,00

0,0

0,2

0,4

0,6

0,8

1,0

1,2

0

20

40

60

Relatif Pressure P/P0

80

100

120

140

Pore Width (nm)

Figure 6. (left) The N 2 adsorption-desorption isotherm linear plot and (right) pore size distribution of Ni-Co based carbonate hydroxide nanocomposite adsorbent.

Table 1. Specific surface area S BET , pore surface area, volume and size of the adsorbent supports used in this investigation.

Specific Adsorbent support

surface area (S BET )

hydroxide

a

surface area 2

2

(m /g)

12.2602

16.065

(m /g) Ni-Co

Pore

Pore volume

b

(cm3/g) 0.0181 13

Pore sizec (nm)

4.5102

a

BJH Adsorption cumulative surface area of pores.

b

BJH Adsorption cumulative volume of pores between 1.7000 nm and 300.0000 nm diameter

c

BJH Adsorption average pore diameter (4V/A).


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3.2. 3.2.1.

Adsorption Process Investigation Effect of Contact Time and Initial MO Concentration

MB was chosen as a model dye to assess the adsorption capacity of the Ni-Co based carbonate hydroxide nanocomposite as adsorbent. A series of systematic experiments have been performed to examine the MB adsorption with this kind of nanocomposite adsorbent in aqueous solution. Figure 7 shows the effect of the contact time on the adsorption capacity of MB onto the nanocomposite at different initial concentrations. It can be seen that the adsorption rates of the cationic dye onto the considered adsorbent were considerably rapid within the first 20 min for all of the concentrations. Thereafter, the adsorption proceeded slowly with contact time before reaching a plateau value after 50 min. The high adsorption rate within the initial 20 min was attributed to the adequate free adsorptive sites and a high dye concentration gradient. The kinetic results showed also that the curves of contact time are single and continuous leading to equilibrium. These curves indicate the possible monolayer coverage of the dye on the surface of nanoscale adsorbent. Moreover, we can see that the adsorption process was found to be closely dependent on the initial concentrations. The amount of MB adsorbed increased evidently with increasing the initial concentration. This could be a result of an increase in the driving force of concentration gradient to overcome the mass transfer resistance of the dye between the aqueous phases and the solid phases with the increase in the initial concentration [18, 19]. 30

0,05 g

0,1 g

0,2 g

25

Qt (mg/g)

20 15 10 5 0 0

10

20

30

40

50

60

70

80

90 100 110 120

Time (min) Figure 7. Kinetics of MB uptake by Ni-Co based hydroxide nanocomposite for various initial dye concentrations (conditions: sorbent dosage = 0.1g (100 ml)-1; stirring speed = 500rpm; T = 25°C; pH initial). 3.2.2.

Effect of the Adsorbent amount

The amount of available surface area under an effectively constant metal surface is one of the most significant experimental variables affecting contaminant reduction rate. The effect of adsorbent dosage on MB sorption is shown in figure 8. As shown, we can say that the amount 2nd ICIEM 2016, International Conference on Integrated Environmental Management for Sustainable Development

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decreases with an increase in sorbent dose. The increase in sorbent dose at constant dye concentration and volume will lead to unsaturation of sorption sites through the sorption process. 20

20 ppm

10 ppm

5 ppm

Qt (mg/g)

15

10

5

0 0

10

20

30

40

50

60

70

80

90 100 110 120

Time (min) Figure 8. Effect of sorbent dosage on the MB sorption by Ni-Co based carbonate hydroxide nanocomposite (conditions: initial dye concentration = 20 mg l-1; stirring speed = 500rpm; T =25°C; pH initial). 3.2.3.

Effect of pH on the Adsorption Process

As shown in figure 9, we note that the removal efficiency of MB increases with increasing the initial pH from 2 to 12. We can also note that at pH = 2, the removal efficiency is minimal (18.23 %). However, for the pH values ranging from 4 to 6 the efficiency of the decoloration is better with rates of 29.7 and 60.9 %. In addition, it is noted that the rates are significantly important for pH 8, 10 and 12, where the removal rates are, respectively, 71.5, 85.5 and 97.9 %. This can be explained by the fact that at low values on the initial pH, the surface of nanocomposite adsorbent would be surrounded by H+ ions which reduce the interaction of MB with the sites of the adsorbent, under the effect of repulsive forces. Therefore, the decrease of the adsorption rate at low pH values may be due to the high concentration and high mobility of H+ ions which are preferentially adsorbed more than the ions dye. With increasing pH, the overall surface area of the adsorbent becomes negative where an increase in the adsorption efficiency of the cationic dye (MB) is noted [20].


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100 90

Removal efficiency (%)

80 70 60 50 40 30 20 10 0 0

2

4

6

8

10

12

14

pH

Figure 9. pH dependence of MB adsorption on the nanocomposite adsorbent (with initial dye concentration = 20 mg/l; Ni-Co Hydroxide nanocomposite dosage = 0.1g (100 ml-1); stirring speed = 500rpm; T= 25°C).

3.2.4.

Adsorption Isotherms

The Langmuir isotherm assumes monolayer coverage of adsorbate over a homogeneous adsorbent surface. While the Freundlich isotherm supposes a heterogeneous surface with a non uniform distribution of adsorption heat over the surface and a multilayer adsorption can be expressed [21, 22]. 

The Langmuir isotherms can be expressed as:

…….(2)

where: C e : The equilibrium concentration, expressed in (mg L-1), Q e : The product quantity adsorbed per unit of adsorbent mass, expressed in (mg / g), Q m : The theorical maximum adsorption capacity, expressed in (mg /g), K L : The thermodynamic equilibrium constant. 

The Freundlich equation can be expressed as [23]:

… (3) Where K F and 1/n are Freundlich isotherm constants related to adsorption capacity and adsorption intensity, respectively. If Eq. (3) applies, a plot of log Q e versus log C e will give a straight line of slope 1/n and intercept K F .


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The calculated Langmuir parameter (R L and Q m ), Freundlich parameters (K F and 1/n) for the adsorption isotherms are presented in the table 2. By comparing the values of the correlation coefficients (R2) for the two models, we find that the Langmuir model yields the best fit (R2 = 0.999). The correlation coefficient of Freundlich isotherm equation (R2 = 0.985) is lower, so it is not suitable to describe the adsorption equilibrium process.

Table 2: Isotherm parameter correlation coefficients calculated by Langmuir and Freundlich adsorption models. Langmuir isotherm Q m (mg/g) 45.6621

Freundlich isotherm

R 2

0 .999

RL

KF

1/n

R2

0.9

8.54

1.510

0.98

556

54

1

56

Also, the value of R L determines that the adsorption process is irreversible (R L =0), linear (R L =1), favorable (0< R L 1) [23]. In our case, the R L value was found in the range of 0-1 which indicates the favorability of adsorption.

4. Conclusion Removal of methylene blue (MB) was investigated in this work using Ni-Co based carbonate hydroxide nanocomposite as adsorbent from aqueous solution. The results show that this new kind of nanocomposite can be a favorite nanoscale adsorbent to remove hazardous dyes. The influence of initial adsorbate concentration, solution pH, adsorbate amount and contact time on the adsorptive behavior was examined carefully. Consequently, the basic pH (pH= 12) favored the process of adsorption. The adsorption capacity is strongly dependent on the dyes concentration and the adsorbent dosage. Also, the Ni-Co hydroxide nanocomposite has a shorter equilibrium time. The Langmuir model can be used to explain the adsorption equilibrium behavior of MB from aqueous solution onto the Ni-Co carbonate hydroxide based nanocomposite at room temperature.

Acknowledgement The present work is in the part of a national project CNEPRU (E03420130009) financially supported by the Algerian-MHESR. The authors would like to acknowledge Th. Romero and O. Guellati for performing FESEM and adsorbent production and characterization.


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References [1] Malik, P.K (2003). Use of activated carbon prepared from sawdust and rice-husk for adsorption of acid dyes: A case study of Yellow 36. Dyes Pigm, 56: 39–49. [2] Bulut, Y. et H. Aydin (2006). A kinetics and thermodynamics study of methylene blue adsorption on wheat shells. Desalination, 194: 259– 267. [3] Hameed, B.H., A.T.M. Din, A.L. Ahmad (2007). Adsorption of methylene blue onto bamboo-based activated carbon: Kinetics and equilibrium studies. J. Hazard. Mater, 141: 819– 825. [4] Nigam, P., M I.Banat, D. Singh, R. Marchant (1996). Microbial process for decolorization of textile effluent containing azo, diazo and reactive dyes. Process Biochem, 31:435–442. [5] Garg, V.K.,R. Gupta, B. Yadav, R. Kumar (2003). Dye removal from aqueous solution by adsorption on treated sawdust. Bioresour. Technol, 89: 121–124. [6] Fatoki, O.S.,O.S. Ayanda, F.A. Adekola, B.J. Ximba (2013). Sorption of triphenyltin chloride to nFe 3 O 4 , fly ash and nFe 3 O 4 /fly ash composite material in seawater. Clean Soil Air Water, 42: 472–479. [7] Fatoki, O.S.,O.S. Ayanda, F.A. Adekola, B.J. Ximba (2014). Remediation of tributyltin contaminated seawater by adsorption using nFe3O4, activated carbon and nFe 3 O 4 /activated carbon composite material. Water Air Soil Pollut, 224: doi:10.1007/s11270-013-1684-0. [8] Zhang, H.,Z. Jin, L. Han, C. Qin (2006). Synthesis of nanoscale zero-valent iron supported on exfoliated graphite for removal of nitrate. Trans. Nonferr. Met. Soc. China, 16: 345–349. [9] Sheela, T., Y. Arthoba Nayaka, R. Viswanatha, S. Basavanna, T.G. Venkatesha, T.G (2012). Kinetics and thermodynamics studies on the adsorption of Zn(II), Cd(II) and Hg(II) from aqueous solution using zinc oxide nanoparticles. Powder Technol, 217: 163–170. [10] Rahmani, A., H. Zavvar Mousavi, M. Fazli (2010). Effect of nanostructure alumina on adsorption of heavy metals. Desalination, 253: 94–100. [11] Frost, R.L., Y. Xi, H. He (2010). Synthesis, characterization of palygorskite supported zero-valent iron and its application for methylene blue adsorption. J. Colloid Interface Sci, 341: 153–161. [12] Shahryari, Z., A.S. Goharrizi, M. Azadi (2010). Experimental study of methylene blue adsorption fromaqueous solutions onto carbon nanotubes. Int. J. Water Res. Environ. Eng, 2: 016–028.


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[13] Yang. Q., Lu, Z., Lei, X., Chang, Z., Luo, L. et Sun, X (2013). Metal oxide and hydroxide nanoarrays : hydrothermal synthesis and applications as supercapacitors and nanocatalysts. Progress in Natural Science: Materials International, 23(4): 351-366. [14] Dussault L (2005). Etude physico-chimique d'oxydes mixtes issus d'hydroxydes doubles lamellaires. Application à la synthèse de nanofilaments de carbone. Thèse doctorat. Ecole doctorale des sciences exactes et de leurs applications. L'université de Pau et des Pays de L'Adour. [15] Byrappa, K. et Adschiri T (2007). Hydrothermal technology for nanotechnology. Progress in Crystal Growth and Characterization of Materials, 53: 117-166. [16] Hayashi, H. et Hakuta, Y (2010). Hydrothermal synthesis of metal oxide nanoparticles in supercritical water. Materials, 3: 3794-3817. [17] Chang, Y., Juan, Y., Changtai, Z., Xiaoming, F., Gang, W. et Jieshan Q (2014). Nanohybrids from NiCoAl-LDH coupled with carbon for pseudocapacitors: understanding the role of nano-structured carbon. Nanoscale, 6: 3097-3104. [18] Ai, L. H., H.Y.

Huang, Z.L. Chen, X. Wei, J. Jiang (2010). Activated

carbon/CoFe2O4 composites: Facile synthesis, magnetic performance and their potential application for the removal of malachite green from water. Chem. Eng. J, 156: 243–249. [19] Ai, L. H., J. Jiang (2010). Fast removal of organic dyes from aqueous solutions by AC/ferrospinel composite. Desalination, 262: 134–140. [20] Hamdaoui. O (2006). Batch study of liquid-phase adsorption of methylene blue using cedar sawdust and crushed brick. J Hazard Mater, 135(1-3):264-273. [21] Hameed, B.H, A.T.M. Din, A.L. Ahmad (2007). Adsorption of methylene blue onto bamboo-based activated carbon: Kinetics and equilibrium studies. J. Hazard. Mater, 141 : 819–825. [22] El Qada E.N., S.J. Allen, G.M. Walker (2006). Adsorption of methylene blue onto activated carbon produced from steam activated bituminous coal: a study of equilibrium adsorption isotherm, Chem. Eng. J, 124: 103–110. [23] Jain, M., V K. Garg, K. Krishna (2010). Adsorption of hexavalent chromium from aqueous medium onto carbonaceous adsorbents prepared from waste biomass. J. Hazard. Mater, 91: 949–954.


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Study of binary mixture of biocomposites (PLA/cellulose fibers): structure-properties Khadija Mbarki1 , Adel Sayari1, Fahmi Bedoui2, Boubaker Elleuch1 1

National School of Ingeneering Sfax, 3E, Tunisia Email: [email protected] 1

National School of Ingeneering Sfax Email: [email protected]

2

Compiegne universiy of technology France Email: [email protected]

Abstract Biodegradable composites were prepared using microfiber cellulose (MFC) as the reinforcement and polylactic acid (PLA) as a matrix. PLA is polyester of lactic acid, linear, aliphatic thermoplastic with rigidity and clarity similar to polystyrene (PS) and poly (ethylene terephthalate) (PET).The composites were prepared with different MFC content, up to 20% wt, 5 average particle size was used (300μm-8 μm). The dynamic mechanical thermal analysis (DMTA) showed the storage modulus was increased with the addition of MFC. The X-ray diffraction (XRD) studies on the materials showed that the composites were more crystalline than the pure components. The mechanical properties and crystallization of the composites were studied through mechanical thermal analysis (DMTA), tensile strength, differential scanning calorimetry, thermogravimetric analysis, X ray diffraction and scanning electron microscopy. The incorporation of all kinds of cellulose increased the stiffness of the composites compared to pure PDLA. Keywords: biodegradable polymers, PLA, DMA, DSC, DRX

1. Introduction Natural polymers, biopolymers and synthetic polymers based on annually renewable resources are the basis for the twenty-first-century portfolio of sustainable, eco-efficient plastics. The interest on these polymers is considerable in the prospect to decrease of the world resources in oil and in a concern to limit the contribution of plastics to the waste disposal. The subject is vast and hence it is a daunting task to summarize their remarkably rich and multi-faced area related to these biopolymers fields. The interest to use environmentally friendly materials has increased during the past years because of growing environmental concerns and increasing scarcity of fossil resources. Biodegradable polymers like poly (lactic acid) (PLA), Polycaprolactone (PCL), and polybutylene succinate (PBS) are promising polymers with high biodegradability and good mechanical properties for industrial applications. PLA is made from renewable resources, exhibiting good processability with melting temperatures around 170°C, similar to polypropylene which is one of the most commonly used plastics. On the other hand, the disadvantages of PLA, such as lower impact toughness and low capability of resisting thermal deformation, need to be overcome. The incorporation of reinforcements could improve the impact toughness and thermal stability of PLA. Compared to synthetic counterparts, cellulosic fibers exhibit many advantages such as low density, low cost, high strength-to-weight ratios, easy processing, and especially their renewability and


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recyclability. Significant research has reported the advances in cellulosic fiber reinforced PLA composites, demonstrating better mechanical properties than those of cellulose reinforced PE or PP composites. Polylactide or poly (lactic acid) (PLA) is the front runner in the emerging bio-plastics market with the best availability and the most attractive cost structure. It is biodegradable for different applications ranging from medical to packaging, resorbable and biodegradable under industrial composting conditions. It can be produced by condensation directly from its basic building block lactic acid, which is derived by fermentation of sugars from carbohydrate sources (corn, sugarcane…). But, higher molecular weights of PLA are achieved by ring-opening-polymerization (ROP) of cyclic lactide dimer. Generally, PLA is made into useful items using thermal process like injection molding and extrusion. Therefore, its rheological properties, especially its shear viscosity, have important effects on thermal processes. Despite all its advantages, some properties of PLA such as inherent brittleness, poor melt strength, narrow processing window and low thermal stability pose considerable scientific challenges and limit their large scale-applications.

Recently, some developments in modification of PLA including copolymerization, blending, compounding and additives were highlighted to improve its relevant properties. Currently, natural fiber reinforced polymer composites technology is focused on creating low cost, high performance and lightweight materials to replace pure polymers or glass fiber composite. The advantages of using lignocellulosic fibers as reinforcements in different polymer are reduced weight, relatively good stiffness and strength, as well as low cost and ease of disposal. The potential property improvement of any composite material depends on the degree of dispersion and the degree of interaction/adhesion between the matrix and reinforcing phase. The use of reinforcements that provide large surface area is considered as a method for obtaining better interaction between the matrix and reinforcement, leading to better mechanical properties, heat resistance, dimensional stability, etc. The potential property improvement of any composite material depends on the degree of dispersion and the degree of interaction/adhesion between the matrix and reinforcing phase. The five kinds of cellulose fibers with different scales are promising in reinforcing PDLA based bio-composites. It is an interesting to know which kind of cellulosic fibers has the best performance and how the scale of the cellulosic fibers affects the mechanical and crystalline properties of the composites. In this study the cellulose fibers were used as reinforcement of poly (D-lactic acid) (PDLA) bio-composites. The effects of cellulose loading on the mechanical properties of the PDLA composites were comparatively studied by mechanical testing. Scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) were applied to study the morphologies and structures of the cellulose. The crystallinity and crystalline morphology, which had significant influence on the mechanical and thermal properties of the PDLA


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composites, were also studied by differential scanning calorimetry (DSC), wide angle X-ray diffraction.

2. Materials and Methods 2.1. Materials PDLA used as a matrix was purchased from Natureplast, France. The microcellulose fiber used as the reinforcement is a powder with a particle size of 8 to 300 μm. It was supplied by Arbocel, Germany, and contained >99% of cellulose. The physical and chemicals characteristics of all reinforcements are summarized in table I.

2.2. Methods 2.2.1. Thermal analysis Behavior of PLA/MFC blends on elevating temperature was monitored by means of thermogravimetric

(TG),

differential

thermogravimetric

(DTG),

and

differential

scanning

calorimetric (DSC) methods. Samples (~20mg) were placed in pan hermetically closed with lids, and heated under helium from room temperature to 500 °C at the 5 °C/min rate of the temperature increase. 2.2.2. Mechanical testing The mechanical properties of composites were measured using an Instron universal testing machine with a crosshead speed of 2mm/min and a load cell of 100 KN. The tensile testing was performed according to the ISO 527 standard for tensile testing on composites and plastics. At least three specimens were tested for each composition, and the results are presented as an average for tested samples. 2.2.3. Crystallinity studies (DRX) X-ray diffraction was used to study the crystallinity of the pure components and MCC composites. The angle of incidence is varied from 10 to 60. 2.2.4. Scanning electron microscopy (SEM) The morphology of used MCF was studied using a scanning electron microscope (SEM), with an acceleration voltage of 20 kV.

3. Results and discussion 3.1. Thermal analysis Thermal analysis TGA carried out to investigate the effect of processing on the thermal decomposition of PLA Polylactide (PLA) and thermoplastic starch (TPS) are two of the most promising bio-based materials currently available on the market. 3.2. Mechanical results Tensile tests were conducted in order to determine the effects of the cellulose fibers on the Young’s modulus.


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Dynamic Mechanical Thermal Analysis (DMTA) was using to study the tan delta temperature and dynamic modulus of different composite systems. (Figure 1) 3.3. Scanning Electron Microscopy The morphology of used fibers MFC, as well as composite microstructure was studied using a scanning electron microstructure (SEM). Table I: Characteristics of the Cellulosic fibers

UFC

BE6

B60

B00

BC2

Cellu

~99

~99

~99,

~99

~99

Oxid

Max

~0,

~

~

~

e ash whit eness

0 15%

3%

03%

05%

03%

Min

80%

85 %

79

81

(10% Aver

5

57

57

57

57

age particle

6

18

60

120

300

pHvalue

size

μm 12 μm Bulk

density Toxi

μm

140 g/l 240

μm 230

g/l 300

No

μm 180

g/l 220g/l

No

No

μm 150

g/l 185 No

70 g/l 90 g/l No

Dynamic Mechanical Thermal Analysis (DMTA) was conducted using a Rheometrics Scientific, to study the tan delta temperature and dynamic modulus of different composite systems. Heating rate was 3°C/min, strain rate was 1mm/s, and frequency was 1Hz. The mechanical performance of composites is expected to depend on the following factors:1) adhesion between the PLA matrix and cellulosic reinforcements, 2) volume fraction of the fibers,3) aspect ratio of the reinforcements, 4) fiber orientation and 5) the degree of crystallinity of the matrix. The DMTA (dynamic mechanical thermal analysis) of PLA/MFC composites was performed to investigate if the addition of the MFC would improve the thermal properties. Six materials PLA, PLA/B00, PLA/B600, PLA/BC200, PLA/UFCM8, and PLA/BE600-10TG were tested to see the possible interaction between the PLA matrix and MFC.


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Figure1: DMTA curves for PLA 20% MFC composites: a) tan delta

Figure1: DMTA curves for PLA 20% MFC composites: b) dynamic modulus

Figure 1 shows how the addition of different contents of MCF influenced the tan delta and dynamic modulus of PLA. Figure1) a) shows the effect of MFC content on the tan delta peak. It is possible to see that the tan delta peak (α-transition) is slightly shifted to higher temperature with increased average particle size of MFC. The tan delta peak of PLA was measured to be approximately at 57, 47°C and that was increased to 61, 80°C for MFC composites.

3.2. Crystallinity studies DRX was used to study the crystallinity of the pure components and composites. The relative crystallinity of the MFC, PLA and PLA/MFC were investigated with wide-angleX-ray diffraction. Fig2. (A) Shows X-ray diffractograms of MFC, (B) PLA and (C) PLA/MFC. The addition of MFC affects the degree of crystallinity of PLA film.


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Fig.2. X-ray diffraction patterns of MFC (A), PLA (B) and PLA/TPS (C) 3.3. Thermal analysis Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) have been the conventional and most popular techniques used to study the thermal stability and decomposition of starch. Fig. 4 shows a typical process of weight loss during heating of PLA/MFC, as measured by TGA and DSC. It can be seen that there are two major weight loss phases.

Fig.3. DSC curves of PLA/MFC and PLA

3.4. Morphology


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The overview and detailed appearance of the used MFC is shown in figure. It can be seen from the figure that the MFC is in particulate form and the particle dimensions are in the range of 300-8 µm. it can also be seen that the MFC exists as aggregates of crystalline cellulose entities. It is also possible to see some nano fibrils on the MFC particle surfaces.

References

1) Bedoui, F., and Cauvin, L., (2012). Elastic properties prediction of nano-clay reinforced polymers using hybrid micromechanical models, Computational materials science (2012). 2) Gelineau, P., Stepień, M., Weigand, S., Cauvin, L., Bédoui, F., (2015). Elastic properties prediction of nano-clay reinforced polymer using multi-scale modeling based on a multi-scale characterization, Mechanics of Materials (2015). 3)Mathew, A. P., Oksman, K., & Sain, M. (2006). The effect of morphology and chemical characteristics of cellulose reinforcements on the crystallinity of polylactic acid. Journal of Applied Polymer Science, (2006).


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Polylactic acid thermoplastic starch mixture: properties Khadija Mbarki1, Adel Sayari2, Boubaker Elleuch1 1

National School of Ingeneering Sfax, 3E Email: [email protected] 2

National School of Ingeneering Sfax Email: [email protected]

Abstract The significance and numerous applications of products resulting from reactions of starch with fatty acids induced our interest in checking thermal reaction of maize starch with olive oil. All films were free of any plasticizer additives. The major factors affecting the esterification reaction were optimized. The changes in the structure of starch were verified by FTIR, DSC, ATG, scanning electron microscopy and RX. Behavior of the thermoplastic starch-PLA blends was monitored by means of RX, SEM, differential scanning calorimetric DSC and ATG revealed thermal transitions. Keywords: PLA, starch, IR, DSC, RX

1. Introduction In the last 20 years, the production and use of plastic materials in the world has increased enormously, worsening the problem of waste disposal. Growing interest in the environmental impact of discarded plastics has directed research on the development of plastics that degrade more rapidly in the environment. As a result of the increasing awareness concerning the human impact on the environment, the last decade has seen the development of efficient solutions to produce new environmentally friendly materials. Particular attention has been paid to the replacement of conventional petroleum-based plastics by materials based on biopolymers. The biopolymers produced from renewable resources are an elegant and innovating answer to replace conventional petroleum-based products and fit with a real sustainable development approach. However, to obtain suitable and competitive materials, some of their properties have to be enhanced (lower brittleness, moisture sensitivity, ect). Consequently, even if the potential of these bio-based materials have been pointed out, until now, they are not widely used to replace non-degradable plastics. The common approach to tune their behaviors consists in the elaboration of multiphase materials, e.g., blends or composites. Biopolymers like soy-oil based epoxy, starch based polymers, Polycaprolactone (PCL), polyhydroxy butyrate (PHB), polylactic acid (PLA, and polyester amide have been investigated by scientists as a potential matrix for biodegradable and environmental friendly composites. Polylactide (PLA) and starch are two of the most promising bio-based materials currently available on the market. Starch is a naturally occurring polysaccharide that has been widely studied for many years in the field of materials. Starch molecules are composed of hundreds or thousands of D-glucose units which are joined together by the α-D (1-4) glucosidic linkages to form linear polymer chains (amylose) and α-D (1-4) linkages with α-D (1-6) glucosidic side chains to form branched chains (amylopectine). However, the hydrophilic nature of starch is a major constraint that seriously limits the development 2nd ICIEM 2016, International Conference on Integrated Environmental Management for Sustainable Development

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of starch-based materials. Chemical modification has long been studied as a way to solve this problem, and to produce waterproof materials. Esterification with organic acids (from acetic to fatty acids) is known to result in a thermoplastic, and hydrophobic materials. The introduction of an ester group into polysaccharides constitutes an important synthetic task, because it permits to modify their original hydrophilic nature and to obtain enhanced or new thermal. In fact, reactions on starches to prepare highly substituted derivatives are not easily. (… )The multitude of biopolymer blends in the prior art are to great extent constructed on the basis of starch or use starch as a minority component. Polylactic acid is a versatile polymer made from renewable agricultural raw materials and is fully biodegradable. Therefore, it is interesting to study if the incorporation of reinforcements can improve the toughness and thermal stability. In the present study, PLA based biodegradable composites are prepared with thermoplastic starch.

2. Materials and Methods 2.1. Materials Maize starch was a commercial product (Tunisia) and Olive oil (Tunisia). PDLA used as a matrix was purchased from Natureplast, France. 2.2. Methods 2.2.1. Synthesis of fatty starch esters Dried maize starch: olive oil 1:0.5 (mole of D-glucose unit/mole of oleic acid) blends were placed in Erlenmeyer and heated at 120 °C for 48 hours equipped with mechanical stirrer. When the reaction was completed, hot methanol (50 ml) was added and precipitated starch ester was filtered by suction with washing twice with 50 ml of hot methanol followed by 24 h vacuum drying at 50 °C. 2.2.2. Thermal analysis Behavior of the starch: olive oil 1:0.5 (mole of D-glucose unit/mole of oleic acid) blends on elevating temperature was monitored by means of thermogravimetric (TG), differential thermogravimetric (DTG), and differential scanning calorimetric (DSC) methods. Samples (~20mg) were placed in pan hermetically closed with lids, and heated under helium from room temperature to 500 °C at the 5 °C/min rate of the temperature increase. 2.2.3. Scanning electron microscopy (SEM) The morphology of used MCF was studied using a scanning electron microscope (SEM), with an acceleration voltage of 20 kV. 2.2.4. Fourier transformation infra red (FTIR) spectra The spectra were recorded in KBr discs using a FTIR. The spectra were recorded in the region of 4000–400 cm-1 with 32 scans and 4 cm-1 resolution.

3. Results and discussion 3.1. Fourier transformation infra red (FTIR) spectra The FTIR spectra of native and modified starch confirmed esterification. In the spectrum of pure starch (Fig. 1(A)), a strong broad band between 980–1200 cm-1 with three peaks was the most 2nd ICIEM 2016, International Conference on Integrated Environmental Management for Sustainable Development

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characteristic band for a polysaccharide. It was attributed to the C–O stretching vibrations. This band was also observed in the spectra of starch esters. Relevant three peaks were better resolved manifesting cancellation of certain hydrogen bonds in starch. Another characteristic band was observed between 3000 and 3500 cm-1. It was assigned to the hydroxyl group stretching vibrations. The maximum of that peak moved from original 3299 cm-1 for native starch, and 3383 cm-1 for heated plain starch to over 3400 cm-1 for ester. The broad signal at 3300–3700 cm−1is attributed to the vibration of the O-H groups. The bands at 2924 and 2852 cm−1 are ascribed to C-H vibrations, mainly of the fatty acid chain and the glucose unit. At 1740 cm−1 appears the C=O vibration of the ester group. Another ester signal is visible at 1157 cm−1. The intensive signal at 1020 cm−1 is ascribed to the C-O-C ring vibration of the glucose units of the starch. It is visible,that the intensity of the C-H signals as well as the ester signals. These changes could be interpreted in terms of decrease in the concentration of hydrogen-bonded hydroxyl groups, as they were converted into ester groups. In the FTIR spectrum (Fig. 1(B)) of the product of the thermally induced reaction of maize starch with linoleic acid (mole/0.5 mole) a new weak band above 1740 cm-1 appeared. That band was absent in the spectra of linoleic acid and, of course, potato starch. The appearance of the band above 1740 cm-1 could be considered as an argument for the esterification of linoleic acid with starch, because the vibrations of the carbonyl group in ester used to reside in this region. The band at 2837 cm-1 was assigned to the aliphatic C–H stretching vibrations. A band at 1740 cm-1 in the FTIR spectrum of the product from the reaction of starch with olive oil taken equimolarily was the most convincing evidence for the esterification of starch. Also in the spectrum of the product from the reaction of starch, the most intensive band was located at 1740 cm-1. It corresponded to the carbonyl stretching vibrations in the ester.

Fig.1.ATR-FTIR spectrum of Starch (A) and thermoplastic starch (B)

3.2. X-ray diffraction


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The relative crystallinity of the TPS, PLA and PLA/TPS were investigated with wide-angle-Xray diffraction. Fig2. (A) Shows X-ray diffractograms of TPS, (B) PLA and (C) PLA/TPS. The addition of TPS affects the degree of crystallinity of PLA film.

C Fig.2. X-ray diffraction patterns of starch ester (A), PLA (B) and PLA/TPS (C) 3.3. Thermal analysis Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) have been the conventional and most popular techniques used to study the thermal stability and decomposition of starch. Fig. 5 shows a typical process of weight loss during heating of thermoplastic starch, as measured by TGA and DSC. It can be seen that there are two major weight loss phases. The first phase represents the evaporation/dehydration that begins immediately after the temperature is increased and finishes at around 100 ◦C. The second weight loss phase corresponds to the thermal decomposition, which commences at around 300 ◦C. In the DSC curve of dried maize starch heated under helium. The first endothermic effect appeared around 256°C; it corresponded to the melting of starch. Up to 258°C, there was no weight loss associated with this step as shown by the TG curve. This stage resulted from a slow dextrinisation. At 258°C a fast, 42% weight loss was noted as an effect of exothermic at 298 °C process. That effect corresponded to the beginning of the thermal decomposition of starch. Subsequent, fast, 2% weight loss at 396°C could be assigned to the evolution of low molecular products formed without participation of the atmospheric.


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Fig.3.TG/DTG curves of thermoplastic starch

Fig. 4. DSC curves of thermoplastic starch

3.4. Scanning electron microscopic (SEM) The film PLA/20%TPS were prepared by casting chloroform solution without addition of plasticizer. The mixture formed a gel on cooling. The microstructure of mixture PLA/TPS and TPS was studied by SEM. Fig.4 (A) shows a SEM micrograph of a thermoplastic starch. Fig.4 (B) shows a thin section of pla.20% TPS blend.

A

B Fig.5. Scanning electron microscopic micrographs of thermoplastic starch (A) and PLA/TPS

(B)

4. Conclusion The starch esters with olive oil could be synthesized without organic solvents ,obviously, the Mw, and reaction yield were significantly lower than such parameters determined for the reactions carrying with dispersed (gelatinized or pregelatinized starch), and more reactive acid derivatives (for instance acid chloride). However, in such case there were no environmental, and safety problems. The starch esters were more hydrophobic as proven by their solubility in certain organic solvents. In our further studies new products with improved hydrophobicity will be checked as components of traditional biodegradable plastics developed from maize starch, and synthetic polymers blends

References


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1) Kapusniak, J., & Siemion, P. (2007). Thermal reactions of starch with long-chain unsaturated fatty acids. Part 2. Linoleic acid. Journal of Food Engineering, 78(1), 323–332. 2)Winkler, H., Vorwerg, W., & Wetzel, H. (2013). Synthesis and properties of fatty acid starch esters. Carbohydrate Polymers, 98(1), 208–216.


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Gypsum plaster production from phosphogypsum Raida Moalla1, Foued Khmiri2, Lotfi Kamoun2, Moncef Zairi1 1

Laboratoire 3E, Ecole Nationale d’Ingénieurs de Sfax, PB 1173, 3038, Université de Sfax, Tunisie. [email protected] [email protected] 2

Groupe Chimique Tunisien (GCT), DRU Sfax - 3000 Sfax [email protected] [email protected]

Abstract: Phosphogypsum (PG) is mainly produced as a byproduct of the manufacture of phosphate fertilizers where phosphate rock is treated with sulfuric acid. For a ton of wet process phosphoric acid, there are approximately 5 tons of PG generated. This production of PG poses environmental and storage problems. This situation requires the adoption of strict policies to limit pollution and encourage valorization of this byproduct. The PG is constituted mainly of hydrated calcium sulfate and some impurities such as P2O5, fluorine, organic matter, heavy metals and radioactive elements. The impurities in PG greatly restrict its industrial use in building materials. The objective of this work is to develop a process for the purification of PG using aqueous sulfuric acid solution. The findings of the purification process and proposed pilot plant are presented in this paper. The βhemihydrate gypsum plaster produced with purified PG was found to have strength properties similar to those produced from mineral gypsum.

Keywords: Phosphogypsum, impurities, Purification process, pilot plant, Plaster

1. Introductıon Phosphogypsum (PG) is a byproduct of the phosphoric acid fertilizer industry (Ajam et al., 2009). The world production of PG is estimated to 200 Million tons per year (Yang et al., 2009). This high quantity poses environmental and storage problems (Tayibi et al., 2009). This situation requires the adoption of strict policies to limit pollution and encourage valorization of this byproduct (Garg et al., 20011). The PG contains some impurities such as phosphate, fluoride, heavy metals, alkalis and organic matter. Thus, it is essential to remove these impurities prior to use the PG (Singh, M., 2002). There are various ways to treat PG for utilization in building materials. The treatment methods can be divided into three different types, namely, chemical, physical, and thermal methods of treatment. Sometimes a specific process employs a combination of these different approaches to treat the PG (Potgieter et al., 2003). In the present study, a process for the purification of PG using aqueous sulfuric acid is developed. The physicochemical characterization of the PG before and after the purification is


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reported in the paper. A pilot plant for the purification of PG is proposed. The Results obtained of βhemihydrate gypsum plaster produced with purified PG in terms of setting time and compressive strength were excellent.

2. Materials and Methods 2.1.

Lab-scale experiments 2.1.1.

Raw Material

PG samples were procured from the PG stack at Sfax city, Tunisia. Samples were produced by the hemihydrate- dihydrate process. The average chemical composition of the PG samples is given in Table 1. The pH of PG samples has been found to be around 3.7. Table1. Major element contents of the PG samples

Con stituent wt .(%)

CaO

SO4

31.2

45.7

8

0

P2O 5

Na 2 O+ K 2 O

1.5 7

0.3

1

TOC

F

0.6

1.2 9

TOC: Total Organic Carbon

2.1.2.

Purification of phosphogypsum in lab-scale

The purification experiments were carried out in a stirred tank reactor of 10 l volume. The reactor was immersed in a thermostatic bath. Stable reactor temperature was maintained at 60°C .To perform an experiment, the reactor was loaded with a quantity of PG and a volume of aqueous sulfuric acid solution (3% to 5% H 2 SO 4 ) (in the proportion 1:3 by volume). The stirring was set at 200 rpm for 30 min. Afterward, the solution was floated for 30 min using a flotation cell, filtered through a buchner funnel, washed with water (1.5 l per 1 kg of PG) and dried 24 hours at 65°C ( Figure 1).


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Aqueous sulfuric acid solution

Unpurified PG

Homogenization

Filtrate

Floatation

Floatation foam

Filtration

Filter cake

Water

Washing

Filtrate

Humic Substances

Drying

Purified PG

Figure. 1 Flow diagram for phosphogypsum purification process in lab-scale 2.2.

Pilot-scale experiments

Pilot scale experiments were conducted under more realistic conditions in order to support the results from lab-scale experiments. In addition the purification of PG in pilot scale plant is more representative for full-scale operation. 2.2.1.

Purification of PG in pilot-scale

The experiment was carried out in a pilot-scale plant built at the Groupe Chimique Tunisien at Sfax city. Two reactors, referred to as R0 3 (400 l) and R0 2 (60 l) were used in the study and shown in Figure 2. Process temperature in the reactors were maintained at 60°C by pumping hot water through a stainless steel coil fitted inside the reactor using an electric flow heater and circulation pump. In the first reactor, To the 26 kg/h of PG there are added 40 l/h of water, thus giving a pulp containing 30.2% of solid material. The pulp was transferred to R0 2 .After, 30l/h of water and 1.8l/h of a concentrated sulfuric acid solution (98%) were added to the pulp and the mixture is introduced into a conventional floatation installation. The purifed pulp is filtered and is washed with 35 l/h of water. After washing, there are obtained 26.7 kg of purified PG containing 20% of free water, 53l/h of expressed liquor which is recycled the homogenization step in R0 3 , and 34 l/h of water of water which has served for washing the filter cake.


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Figure. 2 Flow diagram for phosphogypsum purification process in pilot-scale

The pilot plant consisted of major equipments, such as Reactors, Flotation Cells, pumps, Filter and motors (Figure 3).


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(a)

(b)

(c)

(d)

Figure. 3 Major equipments (a) Reactor R0 3 (b) Reactor R0 2 (c) Flotation Cells (d) Filter

2.3.

Preparation and testing of β-hemihydrate

The β-hemihydrate plaster (β -CaSO 4 . 1/2H2 O) was produced by calcining purified PG at 130–160°C for 4 hours. The plaster was tested for various physical properties according to the French Standard EN 13279-2 (Part 2)


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3. FINDINGS AND ARGUMENT 3.1.

Lab-scale experiments

After purification, the impurities (P 2 O 5 , F, Na 2 O+ K 2 O and TOC) were decreased and the pH was increased (3.7 to 6.3) (Figure 4a). The analysis by ICP shows that the major toxic impurities are reduced after purification (Figure 4b). (a)

(a)

(b)

Figure. 4 Variation of impurities in the PG before and after purification in lab-scale 3.2.

Pilot-scale experiments

After purification in pilot-scale the impurities (P 2 O 5 , F, Na 2 O+ K 2 O and TOC) were decreased and the pH was increased (3.7 to 6.1) (Figure 5a). The analysis by ICP shows that the major toxic impurities are reduced after purification (Figure 5b).

Figure. 5 Variation of impurities in the PG before and after purification in Pilot-scale 2nd ICIEM 2016, International Conference on Integrated Environmental Management for Sustainable Development

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3.3.

Physical properties of gypsum plaster

The purified PG can produce gypsum plaster (CaSO 4 .1/2H 2 O) of improved setting and strength characteristics (Tableau 2).

Tableau 2. Physical properties of gypsum plaster Sample

Gypsum

number

used

Consist

Setting

ency (%)

time (min) I

Purified PG Mineral

2

gypsum

53 74

F

6 .20

1 8.50

7 .00

sive strength (MPa)

inal

nitial 1

Compres

2 0.00

4.54 4.1

4. Conclusion and recommendations -

Laboratory studies carried out for the purification of phosphogypsum using sulfuric acid

solution showed that the water removable impurities, P 2 0 5 , F, organic matter and alkalies can be reduced considerably by this treatment and the pH can be increased. -

The analysis by ICP shows that the major toxic impurit ies are eliminated after

purification. -

Based on laboratory studies conducted, a pilot plant has been proposed for the

purification of phosphogypsum to be adopted by the industry in the commercial scale -

The purified PG can produce gypsum plaster (CaSO 4 .1/2H 2 O) of improved setting and

strength characteristics. -

The plaster can be used as building materials

References Ajam, L.,Ben Ouezdou, M., Felfoul, H.S., Mensi, R. E.(2009). Characterization of the Tunisian phosphogypsum and its valorization in clay bricks. Construction and Building Materials, 23(10): 3240-3247


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Yang, J., Liu, W., Zhang, L., Xiao, B. (2009). Preparation of load-bearing building materials from autoclaved

phosphogypsum.

Construction

and

Building

Materials

23:687–693.

doi:10.1016/j.conbuildmat.2008.02.011 Tayibi, H., Choura, M., Lopez, F. A., Alguacil, F. J., Lopez –Delgado, A. (2009). Environmental impact

and

management

of

phosphogypsum

Review.

J

Environ

Manage,

90:

2377–2386.

doi:10.1016/j.jenvman.2009.03.007 Garg, M., Minocha, A. K., Jain, N. (2011). Environment hazard mitigation of waste gypsum and chalk: Use in construction materials. Construction and Building Materials, 25(2): 944-949 Potgieter, J. H., Potgieter, S. S., McCrindle, R. I., Strydom, C. A. (2003). An investigation into the effect of various chemical and physical treatments of a South African phosphogypsum to render it suitable as a set retarder for cement. Cement and Concrete Research,33(8) : 1223-1227 NF EN 13279-2(2004) : Liants-plâtres et enduits à base de plâtre pour le bâtiment - Partie 2 : Méthodes d'essai [in French]


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Photocatalytic Properties of Fe-TiO 2 /HY zeolite: Effect of iron composition on degradation of Methylene Blue under UV and Visible light irradiation Foura Ghania, Soualah Ahcène Laboratoire de Physico-chimie des Matériaux et Catalyse, Faculté des Sciences Exactes, Université de Bejaia, (06000), Bejaia, Algérie

[email protected]

Abstract. Zeolite supported Fe-doped TiO 2 photocatalysts were synthesized for the sake of

improving the recovery and photocatalytic efficiency of TiO 2 . The materials were characterized by X-ray diffraction (XRD) and Fourier transforms infrared spectroscopy (FT-IR). XRD results demonstrated that the anatase is the stable phase of TiO 2 supported on zeolite and no rutile phase was observed in the supported catalysts calcined at 450°C. Improved dispersion and restrained crystalline size of TiO 2 could be found after supporting the TiO 2 on HY and that Ti–O–Si bonds did not form between the HY bulk and the supported TiO 2 .The photocatalytic activity was evaluated by the degradation of methylene blue in aqueous solution. TiO 2 supported HY zeolite showed enhanced photodegradation due to its high adsorption capacity on which the pollutant molecules are pooled closely and hence degraded effectively. The results show also that the Fe concentration play important role on the photocatalytic activity of the samples. The 10 % Fe-doped TiO 2 /zeolite calcined at 400 °C exhibits higher photocatalytic activity than that of the other samples.

Keywords: Fe-TiO 2 , TiO 2 /zeolites, Methylene Blue, Photocatalytic degradation

1.

Introduction

Among all of the semiconductors photocatalysts, titanium dioxide TiO 2 is close to be an ideal bench mark photocatalyst in the environmental photocatalysis applications because of its many desirable properties such as inexpensive and readily available, biologically and chemically inert, and good photoactivity [1-3]. In fact, there is the relatively wide band gap of TiO 2 (3.2 eV) which absorbs only 3–5% energy of the solar spectrum and restricts its applications to UV excitation source. Therefore, several approaches have been explored to extend the optical absorption of TiO 2 into the visible light region, and thus aim to enhance its photocatalytic activity. Doping with transition metals such as Cr, Fe, Co, Mo, Mn and V, or their ions [4, 5] has been demonstrated to enable the enhancement of the visible light absorption by narrowing the band gap or 2nd ICIEM 2016, International Conference on Integrated Environmental Management for Sustainable Development

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introducing intra-band gap energy states. Moreover, immobilization of TiO 2 powder on solid supports, such as ceramic [6], silica [7,8], activated carbon [9], clay [10,11] and zeolite [12,13] where photons are adsorbed is a desirable feature for effective photodegradation is an alternative convenient method to solve the problem of the post-treatment catalyst powder recovery and facilitate the photocatalyst usage for long-term applications. In this paper, we tried to use these two strategies, i.e. doping of TiO 2 with Fe3+ metal ions and supporting on a zeolite to have a photocatalyst with high catalytic activity in oxidation and degradation of methylene blue (MB) under UV and visible light.

2.Methods 2.1. Photocatalyst preparation

HY zeolite powders (surface area= 840 m2/g) were mixed up with decuple distilled water and heated up to

70°C. Subsequently, TIPT solution (the theoretical proportion of

TiO 2 in the photocatalyst was 25 wt. %) and Fe (NO 3 ) 3 ·9H 2 O solution (the nominal ratios of Fe3+ to TiO 2 were 3.0, 6.0, 8.0, 10, 12%, respectively) were added dropwise into the mortar and the pH of the suspension solution was adjusted to about 3. The system was vigorously stirred at 70°C for 4 h. After aging for 12 h, the products were repeatedly washed with deionized water and then dried at 80 °C for finally calcined at 450°C for

2 h. The above samples were

3 h in a muffle furnace and then the photocatalysts were

acquired. As comparison, pure TiO 2 were also prepared using the same procedure except for the addition of zeolite. 2.2. Characterization of photocatalyst

The crystalline structure of the photocatalyst was measured using X-ray diffraction (XRD, X Pert Pro Panalytical) with a Cu K˛ source. The samples were analyzed in a 2θ range of 10–80° to identify the crystalline phase. IR spectra of the samples were recorded using a Shimadzu FT-IR spectrometer with KBr pellets. The samples were analyzed in the wave number range of 400–4000 cm−1. The BET specific surface area was measured by N 2 adsorption at low temperature on surface area analyzer (ASAP 2000). 3. Photocatalysis experiments The experimental setup based on a rectangular photocatalytic reactor with workable area of 9cm×45 cm, made out of plexi glass. The wastewater to be treated is falling as a thin film from the top of the chamber on to the photocatalyst nanoparticles 2nd ICIEM 2016, International Conference on Integrated Environmental Management for Sustainable Development

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immobilized on glass plat (8cm x 44cm). The sample to be treated (1000mL of dye solution) was stored in a reservoir and was continuously circulated in the system by a peristaltic pump at adjustable flow rate. The reservoir was open to the air to insure sufficient oxygenation. The solution in the reservoir was continuously stirred to keep the solution homogeneous. Artificial irradiation was provided by 15WUV Germany lamp with peak intensity at 254 nm, positioned above the reactor. The lamp was turned on at the beginning of each experiment. The immobilized photocatalyst nanoparticles were washed after every run by circulating deionized water with a few drops of 30% hydrogen peroxide under UV irradiation, so that the immobilized photocatalyst was regenerated. The distance between the solution and the UV source was adjusted according to the experimental conditions. At different reaction times obtained with experimental design, 2,5mL sample were taken and the remaining BM was determined using a spectrophotometer at λmax = 665nm and calibration curve. The removal efficiency of the dye was calculated by the following equation: % =

𝐶0 − 𝐶𝑡 × 100 𝐶0

Where C 0 is the initial concentration of the dye and C t is its concentration at time t.

Figure 1.The experimental setup of photocatalytic reactor


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3. Results and discussion 3.1. XRD analysis

Figure 2 shows the XRD patterns of TiO 2 , HY and TiO 2 /HY doped with different dosage of iron ions. It can be seen that the XRD patterns of the TiO 2 /HY photocatalysts obviously change contrasted with that of zeolite. The peaks at 2θ=25, 37, 48, 54, 55, 63 ascribed to that of anatase TiO 2 are observed. No correspondent peaks to Fe phases are identified, even at the highest Fe concentration. It can be possibly inferred that: (i) the concentration of Fe-doping is so low that it cannot be detected by XRD; (ii) Fe ions may insert into the structure of titania and locate at interstices or occupy some of the lattice sites of TiO 2 due to the similar radii of Ti(IV) (0.76A˚) and Fe(III) (0.79A˚), forming an iron– titanium solid solution [14-17]. As shown in the XRD pattern of pure TiO 2 , the characteristic peaks of anatase besides rutile can be seen. The average crystallite sizes of TiO 2 in the TiO 2 /zeolite and pure TiO 2 are calculated by applying the Scherrer’s formula on the anatase (1 0 1) diffraction peak at 25° and are about 13–14nm and 19 nm, respectively. It indicates that the zeolite inhibits the growth of TiO 2 crystallite sizes.

Figure2. XRD patterns of: (a) pure TiO 2 , (b) TiO 2 /HY and (c) Fe-TiO 2 /HY 3.2. FT-IR analysis


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Figure 3 shows the FT-IR spectra of pure TiO 2 , HY, TiO 2 /HY and 10%Fe/TiO 2 /HY in the range of 400–4000cm−1.

Figure3. FT-IR spectra of : (a) pure TiO 2 , (b) zeolite HY, (c) TiO 2 /HY and (d) 10%FeTiO 2 /HY The board peak around 3437cm−1 and 1637cm−1 can be assigned to the O–H stretching and bending vibration of adsorbed water, respectively. As shown in the spectrum of zeolite, the weak peaks between 800–400cm−1 correspond to Si–O–Si flexural vibration [18]. In contrast to the FT-IR spectra of pure TiO 2 and zeolite, the spectra of TiO 2 /zeolite and Fe/ TiO 2 /zeolite obviously change. The board peak appears between 800 and 400cm−1 owing to the superposition of Ti–O and Si–O bond. The strongest absorption peak at 1047 cm-1 is assigned to the framework stretching vibration band of Si (Al)-O in tetrahedral Si(Al)O (4) in HY zeolite, its position is unchanged at 450°C treatment temperature, indicating that zeolite structure is not destroyed at 450°C. But no obvious band was observed at the region of 950-960 cm-1 assigned to the antisymmetric stretching vibration of Ti-O-Si bond [19]. It is suggested that no strong chemical interaction took place between TiO 2 and zeolite, hence TiO 2 may be only disperse on the surface of zeolite, or encapsulate partly the zeolite cavity. 3.3. Photocatalytic activity 3.3.1. Effect of TiO 2 loaded on HY zeolite

The performance of prepared TiO 2 /HY catalyst was examined for the decolorization of MB, and the results are shown in Fig.4. A controlled experiment was conducted under 2nd ICIEM 2016, International Conference on Integrated Environmental Management for Sustainable Development

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four different conditions including photolysis and reaction in the presence of the bare HY, TiO 2 , and TiO 2 /HY catalysts. Each experiment was performed in the dark for 1h to achieve adsorption–desorption equilibrium before irradiation under a UV lamp at room temperature for 4h with constant stirring. The experiments under dark conditions removed less than 1% of the MB after 4 h of contact time, which indicated the importance of visible light in this study. Under photolysis, 6% of the MB was decolorized; this may be because of the degradation of the substance after long exposure to UV light. Only 35% and 39% of the MB was removed when using bare HY under dark and UV light conditions, respectively. The porosity of the catalyst surface may play an important role in adsorption, as previously reported for liquid–gas adsorption systems used to treat wastewater [20]. The use of TiO 2 under UV light resulted in 85 % decolorization of MB, which was very higher than the same reaction under dark conditions. However, the removal percentage increased up to 94% when using TiO 2 /HY. The reason is that supporting TiO 2 on the zeolite increases its adsorption capacity and results in the higher concentration of dye molecules around the TiO 2 particles. So the interaction of photo-generated active species with dye molecules is enhanced. However, good dispersion of TiO 2 increases the active sites around the adsorbed molecules and the degradation rate of pollutant becomes faster. Furthermore the strong electrostatic field present in the zeolite framework can effectively separate the electrons and holes produced during photo-excitation of TiO 2 and so resulted in lower recombination of them and higher photodegradation efficiency. This result reveals that TiO 2 /HY is a potential photocatalyst semiconductor.

Photolysis ZeoliteHY TiO2 TiO2/HY

1,1 1,0 0,9 0,8 0,7

C/C0

0,6 0,5 0,4 0,3 0,2 0,1 0,0 0

50

100

150

200

250

Irradiation timie (min)

Figure4. Photodegradation of MB in the presence of HY zeolite and TiO 2 /HY zeolite under UV- irradiation [C BM =10mgl-1, pH=11, W=1gl-1, T=25°C] 2nd ICIEM 2016, International Conference on Integrated Environmental Management for Sustainable Development

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3.3.2. Effect of Fe doped TiO 2 /HY zeolite

Fig.5 shows the degradation curves of MB solution catalyzed by the photocatalysts doped with different dosage of Fe3+. It can be observed that the decolorization rates of MB solution are higher than that of the undoped TiO 2 /zeolite. The decolorization rates begin to increase as the iron concentrations between 2% and 10% and then decrease again as the iron concentration up to 10%. This result is similar to the previous study reported

by

Navio et al. [21] which indicates that the photocatalytic activities of Fe/TiO 2 /zeolite photocatalysts strongly depend on the concentration of iron ions. An appropriate concentration of iron ions can act as intermediates for photo-generated holes and electrons transfer, and inhibit the recombination of holes and electrons [22]. The recombination rate increases with the dopant concentration because the distance between trapping sites in a particle decreases with the number of dopants. On the contrary, if the iron concentration is very low, there are fewer trapping sites available, thus reducing the photocatalytic activity [23].

1,1

TiO2/HY 3% Fe/TiO2/HY 6% Fe/TiO2/HY 8% Fe/TiO2/HY 10% Fe/TiO2/HY 12% Fe/TiO2/HY

Adsorption

1,0 0,9 0,8

C/C0

0,7 0,6 0,5 0,4 0,3 0,2 0,1 0,0 0

50

100

150

200

250

300

Irradiation time (min)

Figure5. Decolorization rate of MB solution catalyzed by photocatalysts doped with different dosage of iron ions under visible light irradiation [C BM =10mgl-1, pH=11, W=1gl-1, T=25°C]


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4. Conclusion Zeolite HY supported Fe (3+) - TiO 2 photocatalysts were successfully prepared in this study. The zeolite could inhibit the growth of TiO 2 crystallite sizes. The TiO 2 particles were either as nanoparticles or clusters attaching to the zeolite surface. The doped Fe ions might diffuse into TiO 2 lattices to form the Fe–O–Ti bond and the band gap energy (Eg) of 10%Fe/TiO 2 /zeolite reduce in comparison with that of undoped TiO 2 /zeolite. The reduction in the band gap of Fe/TiO 2 /zeolite could give TiO 2 the capacity to absorb light at lower energy levels. The decolorization rates of MB strongly depended on the concentration of iron ions. An appropriate concentration of iron ions (10%) could act as intermediates for photogenerated holes and electrons transfer, and inhibited the recombination of photogenerated electron and hole pair, thus reducing the photocatalytic activity.

References [1] M.R. Hoffmann, S.T. Martin, W. Choi, D.W. Bahnemann, Environmental applications of semiconductor photocatalysis, Chem. Rev. 95 (1995) 69–96. [2] I. Catanzaro, G. Avellone, G. Marc, M. Saverini, L. Scalici, G. Sciandrello, L. Palmisano, Biological effects and photodegradation by TiO 2 of terpenes present in industrial wastewater, J. Hazard. Mater. 185 (2011) 591–597. [3] M.N. Chong, B. Jin, C.W.K. Chow, C. Saint, Recent developments in photocatalytic water treatment technology: a review, Water Res. 44 (2010) 2997–3027. [4] J.F. Zhu, Z.G. Deng, F. Chen, J.L. Zhang, H.J. Chen, M. Anpo, J.Z. Huang, L.Z. Zhang, Appl. Catal. B 62 (2006) 329–335. [5] O. Carp, C.L. Huisman, A. Reller, Prog. Solid State Chem. 32 (2004) 133–177. [6] Sunada F, Heller A. Effects of water, salt water, and silicone overcoating of the TiO 2 photocatalyst on the rates and products of photocatalytic oxidation of liquid 3octanol and 3-octanone. Environmental Science & Technology 1998; 32:282-6. [7] Chen Y, Wang K, Lou L. Photodegradation of dye pollutants on silica gel supported TiO 2 particles under visible light irradiation. Journal of Photochemistry and Photobiology A: Chemistry 2004; 163:281-7.


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[8] Xu Y, Zheng W, Liu W. Enhanced photocatalytic activity of supported TiO 2 : dispersing effect of SiO 2 . Journal of Photochemistry and Photobiology A: Chemistry 1999; 122:57-60. [9] Hermann J, Matos J, Disdier J, Guillard C, Laine J, Malato S, Blanco J. Solar photocatalytic degradation of 4-chlorophenol using the synergistic effect between titania and activated carbon in aqueous suspension. Catalysis Today 1999; 54:255-65. [10] Ooka C, Yoshida H, Suzuki K, Hattori T. Highly hydrophobic TiO 2 pillared clay for photocatalytic degradation of organic compounds in water. Microporous and Mesoporous Materials 2004; 67:143-50. [11] Sun Z, Chen Y, Ke Q, Yang Y, Yuan J. Photocatalytic degradation of cationic azo dye by TiO 2 /bentonite nanocomposite. Journal of Photochemistry and Photobiology A: Chemistry 2002; 149:169-74. [12] T.Z. Tong, J.L. Zhang, B.Z. Tian, F. Chen, D.N. He, Preparation of Fe3+-doped TiO 2 catalysts by controlled hydrolysis of titanium alkoxide and study on their photocatalytic activity for methyl orange degradation, J. Hazard. Mater. 155 (2008 572– 579. [13] M.I. Litter, J.A. Navio, Photocatalytic properties of iron-doped titania semiconductors, J. Photochem. Photobiol., A 98 (1996) 171–181.

[14] C.A. Castro-Lopez, A. Centeno, S.A. Giraldo. (2010) Fe-modified TiO 2 photocatalysts for the oxidative degradation of recalcitrant water contaminants. Catal. Today; 157, 119–124. [15] J.G. Yu, Q.J. Xiang, M.H. Zhou. (2009) Preparation, characterization and visible-light driven photocatalytic activity of Fe-doped titania nanorods and first-principles study for electronic structures. Appl. Catal. B; 90, 595–602. [16] C.Y. Wang, C. Bottcher, D.W. Bahnemann, J.K. Dohrmann, (2003) A comparative study of nanometer sized Fe (III)-doped TiO 2 photocatalysts: synthesis, characterization and activity. J. Mater. Chem; 13, 2322–2329.


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[17] J. Zhu, W. Zheng, B. He, J. Zhang, M. Anpo, (2004) Characterization of Fe–TiO 2 photocatalysts synthesized by hydrothermal method and their photocatalytic reactivity for photodegradation of XRG dye diluted in water. J. Mol. Catal. A: Chem; 216, 35–43. [18] D.I. Petkowicz, R. Brambilla, C. Radtke, C.D.S. Da Silva, Z.N. da Rocha, S.B.C. Pergher, J.H.Z. dos Santos. (2009) Photodegradation of methylene blue by in situ generated titania supported on a NaA zeolite. Appl. Catal. A; 357, 125–134. [19] C.M. Zhu, L.Y. Wang, L.R. Kong, X.Yang, L.S.Wang, S.J.Zheng, and al. (2000) photocatalytic degradation of azo dyes by supported TiO 2 +UV in aqueous solution. Chemosphere; 41, 303-309. [20] H. Chen, A. Matsumoto, N. Nishimiya, K. Tsutsumi.(1999) Preparation, characterization and photoactivity of TiO 2 microparticles in Y-Zeolite. Colloids Surf; 157, 3295–3305. [21] J.A. Navio, J.J. Testa, P. Djedjeian, J.R. Padron, D. Rodriguez, M.I. Litter, (1999) Iron doped titania powders prepared by a sol–gel method. Part II: photocatalytic properties. Appl. Catal., A; 178, 191–203. [22] T.Z. Tong, J.L. Zhang, B.Z. Tian, F. Chen, D.N. He, (2008) Preparation of Fe3+doped TiO 2 catalysts by controlled hydrolysis of titanium alkoxide and study on their photocatalytic activity for methyl orange degradation. J. Hazard. Mater; 155, 572–579. [23] M.I. Litter, J.A. Navio, (1996) Photocatalytic properties of iron-doped titania semiconductors. J. Photochem. Photobiol. A; 98, 171–181.


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ADSORPTIVE REMOVAL OF CATIONIC AND ANIONIC DYES FROM AQUEOUS SOLUTION BY UTILIZING ALMOND SHELL AS BIOADSORBENT Achraf Ghorbal1,2, Rim Ben Arfi1, Sarra Karoui1, Karine Mougin3 1

Research Unit UR11ES80, National Engineering School of Gabes, University of Gabes, Tunisia, [email protected]

2

Higher Institute of Applied Sciences and Technology of Gabes, University of Gabes, Tunisia, [email protected] 3

Institute of Materials Science of Mulhouse, CNRS - UMR 7361, France, [email protected]

Abstract. The almond shell (Prunus dulcis) is a food residue, that was used as bioadsorbent for the removal of Eriochrome Black T (EBT) and Malachite Green (MG) dyes from aqueous solutions. The biomaterial was characterized by specific surface area (BET), scanning electron microscopy (SEM), infrared spectroscopy (FTIR), thermal analysis (TGA) and X-ray diffraction (XRD). The effects of initial pH of solution, adsorbent dosage, contact time and initial dye concentration on MG and EBT adsorption were studied using batch contact mode at 22 °C. The kinetic studies showed rapid sorption dynamics following a second-order kinetic model. Dye adsorption equilibrium data were fitted well to the Freundlich isotherm for cationic and anionic dyes. The adsorption of the dyes was exothermic (ΔH° = -1.7 kJ/mol for EBT and -32 kJ/mol for MG). The reaction was accompanied by a decrease in entropy (ΔS°< 0 for MG and EBT). The negative values of ΔG° indicated the spontaneity of the MG adsorption process. However, the positive values of ΔG° showed that the EBT biosorption by the Tunisian almond shell is a non-spontaneous reaction. Keywords: Almond shell, Bioadsorbent, Eriochrome Black T, Malachite Green, Adsorption.

1. Introduction Discharging of effluents from textile, leather, and paper industries into receiving water may cause adverse impacts on the ecosystems. Indeed, the presence of dyes in these water bodies reduces light penetration which can decrease photosynthetic activity and cause esthetic problems. In addition, many dyes or their metabolites in water bodies even at low concentration can cause a variety of diseases and disorders in living organisms such as allergy, skin irritation, and cancer. Several water treatment techniques such as ozonation, coagulation/flocculation, chemical oxidation, and photocatalytic degradation have been employed for the removal of dyes. Among treatment technologies, the adsorption process has received a lot of attention due to its simplicity, high efficiency, eco-friendly nature as well as the availability of a wide range of low cost adsorbents.


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Adsorption by activated carbon is an effective technique for wastewater treatments. However, it is an expensive adsorbent due to its high manufacturing cost. Biomaterials could be considered as a promising alternative to expensive materials due to their low commercial value and relative abundance. Consequently, many investigators have studied the feasibility of using low-cost and easily available natural materials such as peanut husk (Sadaf et Bhatti, 2013), sugarcane bagasse (Zhang et al., 2011), and egg shell (Arami et al., 2006) to clean up dye-contaminated water. Almond shell is a relatively abundant lignocellulosic agricultural by-product, in Tunisia, with a production of about 70000 tons in 2012 (Maaloul et al., 2016) but it is not much valorized. This agricultural waste can be put to good use as a biosorbent for dyes removal from industrial effluents. To the best of our knowledge the use of Tunisian almond shell as a low-cost biosorbent for the removal of dyes from water has not been investigated. In this study, we chose Malachite Green (MG), a cationic dye, and Eriochrome Black T (EBT), an anionic dye. These candidates have been identified as problematic dyes in effluents because of their resistance to fading under exposure to sunlight, and complex chemical structure. In addition, the selected model dyes have wider applications in a variety of different fields, such as biology, chemistry and industries. So, removing such dyes from aqueous solutions is of utmost necessity. In the present work, the Tunisian almond shell (referred to as TAS) was studied as a bioadsorbent for cationic and anionic dyes. The biomaterial was characterized (in terms of physical, thermal and chemical properties). Biosorption studies were carried out under various parameters such as biosorbent particle size, contact time, temperature, adsorbent dosage, pH and initial dye concentration. Kinetic data and sorption equilibrium isotherms were carried out in batch process and were analyzed using different models.

2. Materials and Methods 2.1. Materials and apparatus Malachite Green (MG) and Eriochrome Black T (EBT) respectively acquired from Loba Chemicals and Panreac AppliChem, were used without further purification. The detailed information of MG and EBT used in this study is given in Table 1. They were both dissolved in the distilled water to form solutions of 100 mg/L. Their pH was regulated by HCl of 0.1 mol/L and/or NaOH of 0.1 mol/L solutions. Almond shells were supplied by a local farmer and originated from almond trees (Prunus dulcis) cultivated in the region of Sfax (Tunisia). TAS were milled in a Retsch SM100 mill (Retsch GmBH, Germany) and sieved to obtain various size fractions of 1 mol% Pt> 1 mol% Au > 1 mol% Ag > Pure. Our results are similar compared with that founded by Sangpour et al.: Au-TiO 2 > Ag-TiO 2 > TiO 2 thin filmssynthesised by radio frequency reactive magnetron cosputtering method (Sangpour et al. 2010).

80

Degradation % of MB

70 60

Sol0 after UV irradiation Pure 1 mol% Ag 1 mol% Au 1 mol% Pd 1 mol% Pt

71

69

67

50 40

51 30

30

20 10

15

0 5

Time (h)

Figure 2. Histograms displaying the degradation % of MB of Sol 0 and solutions with pure TiO 2 and 1 mol% M-TiO 2 films under UV irradiation during 5 hours

4. Conclusion The characterization of doped TiO 2 films, prepared by spin-coating method, by XRD and Raman revealed that all samples were anatase phase films with a crystalline size around 16 nm. UVVis study exhibit the transparency and the surface uniformity of films, also the decrease of band gap after doping. The photocatalytic activity shows that 1 mol% Pd-TiO 2 films had the highest photocatalytic activity (71 %) in MB degradation reaction under UV irradiation. References Chandrasekharan N and Kamat P V (2000) Improving the photoelectrochemical performance of nanostructured TiO 2 films by adsorption of gold nanoparticles. J. Phys. Chem. B, 104, 10851-10857. Danish M, Ambreen S, Chauhan A and Pandey A (2015) Optimization and comparative 2nd ICIEM 2016, International Conference on Integrated Environmental Management for Sustainable Development Page 229

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evaluation of optical and photocatalytic properties of TiO 2 thin films prepared via sol–gel method.Journal of Saudi Chemical Society, 19, 557–562. Demirci S, Dikici T, Yurddaskal M, Gultekin S, Toparli M and Celik E (2016) Synthesis and characterization of Ag doped TiO2heterojunction filmsand their photocatalytic performances.Applied Surface Science, 390,591–601. Fretwell R and Douglas P (2001) An active, robust and transparent nanocrystalline anatase TiO 2 thin film —preparation, characterisation and the kineticsof photodegradation of model pollutantsJournal of Photochemistry and Photobiology A: Chemistry, 143,229–240. Gotic M, Ivanda M, Popovic S, Music S, Sekulic A, Turkivic A and

Furic K (1997) Raman

investigation of nanosized TiO 2 . J. Raman Spectrosc., 28, 555–558. Fretwell R and Douglas P (2001) An active, robust and transparent nanocrystalline anatase TiO 2 thin film —preparation, characterisation and the kineticsof photodegradation of model pollutants. Journal of Photochemistry and Photobiology A: Chemistry, 143,229–240. MellottN P, DurucanC, PantanoC G andGuglielmiM (2006) Commercial and laboratory prepared titanium dioxide thin films forself-cleaning glasses: Photocatalytic performance and chemical durability. Thin Solid Films, 502, 112–120. Sangpour P, Hashemi F and Moshfegh A Z (2010) Photoenhanced Degradation of Methylene Blue on Cosputtered M:TiO 2 (M = Au, Ag, Cu) Nanocomposite Systems: A Comparative Study. J. Phys. Chem. C, 114, 13955–13961 Sen S, Mahanty S, Roy S, Heintz O, Bourgeois S and Chaumont D (2005) Investigation on sol–gel synthesized Ag-doped TiO 2 cermet thin films. Thin Solid Films, 474, 245–249. Sheng Z, Wu Z, Liu Y and Wang H (2008). Gas-phase photocatalytic oxidation of NO over palladium modified TiO2 catalysts. Catalysis Communications 9,1941–1944 Singh MK, Agarwal A, Gopal R, Swarnkar RK and Kotnala RK (2011) Dumbbell shaped nickel nanocrystals synthesized by a laser induced fragmentation method. J Mater Chem, 21, 11074–11079. Silva C G, Juarez R, Marino T, Molinari R and Garcia H(2010) Influence of excitation wavelength (UV or Visible Light) on the photocatalytic activity of titania containing gold nanoparticles for the generation of hydrogen or oxygen from water. J. Am. Chem. Soc., 133, 595–602 Soler-Illia G J A A, Angelomé P C, Fuertes M C, Grosso D and Boissiere C (2012) Critical Aspects in the Production of Periodically Ordered Mesoporous Titania Thin Films. Nanoscale, 4, 2549– 2nd ICIEM 2016, International Conference on Integrated Environmental Management for Sustainable Development Page 230

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2566. Sta I, Jlassi M, Hajji M, Boujmil M F, Jerbi R, Kandyla M, Kompitsas M and Ezzaouia H (2014) Structural and optical properties of TiO 2 thin films prepared by spin coating. J Sol-Gel SciTechnol, 72, 421–427. Swanepoel R (1983) Determination of the thickness and optical constants of amorphous silicon. J Phys E SciInstrum, 16, 1214–1222. Primo A, Corma A and Garcia H (2012) Titania supported gold nanoparticles as photocatalyst. Phys. Chem. Chem. Phys., 13, 886–910 Tauc J, Grigorovici R and Vancu A (1966) Optical Properties and Electronic Structure of Amorphous Germanium. Phys Status Solid, 15, 627-637. Warren BE (1990) X-ray diffraction. Dover, New York 251–259. Yogi Ch, Kojima K, Wada N, Tokumoto H, Takai T, Mizoguchi T and Tamiaki H (2008) Photocatalytic degradation of methylene blue by TiO 2 film and Au particles-TiO 2 composite film. Thin Solid Films, 516, 5881–5884. Zhang W F, He Y L, Zhang M S, Yin Z and Chen Q (2000) Raman scattering study on anatase TiO 2 nanocrystals. J. Phys., D, Appl. Phys., 33, 912–916. Zhao L, Yu Y, Song L, Hu X and Larbot A (2005) Synthesis and characterization of nanostructured titania film for photocatalysis. Applied Surface Science, 239, 285–291.

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Seasonal variation in biomarker responses in Donax trunculus from the gulf of Annaba (Algeria): implication of marine pollution Akila AMIRA1,2, Isma MERAD2 and Noureddine SOLTANI2 1

Department of Biology, Faculty of Sciences, Chadli Benjdid University, 36000-El Tarf, Algeria [email protected] 2

Laboratory of Applied Animal Biology, Department of Biology,

Faculty of Sciences, Badji Mokhtar University, 23000-Annaba, Algeria [email protected] [email protected]

Abstract. Many chemical contaminants induce in aquatic organisms such as bivalve mollusks the oxidative stress that can be used as a biomarker in biomonitoring programs of ecosystem quality. The aim of the present study was to test various biomarkers responses in an edible mollusk, Donax trunculus (Mollusca, Bivalvia) associated with environmental pollution in the gulf of Annaba (Northeast Algeria). The biomarkers selected were the neurotoxicity marker acetylcholinesterase (AChE), the phase II detoxifying enzyme glutathione S-transferase (GST) and metallothioneins (MTs), involved in the homeostasis and the detoxification mechanisms of heavy metals. Samples were collected seasonally ( September 2014 and January, April and July 2015) from two sites located over the gulf of Annaba: the first site El Battah is far away from the sources of pollution, while the second Sidi Salem is contaminated by various sources from anthropogenic activities. The results demonstrated a decrease in the activities of AChE in D. trunculus collected from Sidi Salem compared to that from El Battah site, while an increase in GST activity and a low MT levels were registered in Sidi Salem samples comparatively with those of El Battah. The overall results suggest that the biomarker responses at Sidi Salem site reflects the presence of certain pro-oxidative compounds such as heavy metals that can lead to oxidative stress in Donax trunculus.

Keywords: Gulf of Annaba, Donax trunculus, Pollution, Biomarkers.

1. Introductıon Industrial and municipal wastewater, agricultural activities, and atmospheric inputs are the main routes by which chemical contaminants enter the marine environment (Gherras Touahri et al., 2016). Organisms in aquatic environments are generally exposed to a complex mixture of chemicals, including the parent compounds and their transformation products, causing multiple damages to organisms, population and ecosystem (Bolognesi and Cirillo, 2014). Therefore, monitoring


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approaches should have an integrative character combining chemical and ecological aspects with abiotic and biotic parameters (Schettino et al., 2012). Bivalves belong to the first choice species as bioindicators for environmental and chemical stress. They are sentinel benthic organisms living as filter-feeders and exposed to different environmental compartments (Helmholz et al., 2016). Due to their wide distribution, resistance to variable environmental conditions, which predispose them to the direct absorption and accumulation of a wide spectrum of waterborne chemicals they are prolific tools for biomonitoring of chemical pollution (Boillot et al., 2015; Orbea et al., 2006). Donax trunculus L. is an edible mollusk widely used as bioindicatior species (Soltani et al., 2012; Tlili et al., 2013). Moreover, the possibility to measure several biochemicals, cellular and physiological biomarkers, make bivalves suitable organisms for investigating the effects of chemical pollutants (Regoli et al., 2014). Biomarkers include a variety of molecular, cellular or physiological alterations measurable in model organisms in response to pollutants or other environmental stress factors (Moore et al., 2006). Numerous types of biomarkers are now commonly employed in aquatic studies, acetylcholinesterase (AChE) is involved in the hydrolysis of the neurotransmitter acetylcholine. AChE is strongly inhibited by organophosphate and carbamate pesticides, and also by metals (Martinez-Tabche et al., 2001; Monserrat et al., 2002; Bainy et al., 2006), giving rise to functional disorders of the central nervous system. The measurement of AChE inhibition in marine organisms has been widely used as an indicator of environmental contamination by these compounds (Blaise et al., 2006).The glutathione S-transferases (GSTs) are a multiple-enzyme family involved in phase II detoxification processes and are used as biomarkers of several groups of pollutants including organochlorine pesticides, PCBs and petrochemical products in invertebrates (Fitzpatrick et al., 1997; Hoarau et al., 2001; Lima et al., 2007), and has been recently identified as a suitable biomarker for monitoring chemical pollution in highly productive marine coastal ecosystems (Vidal-Liñán et al., 2010). Metallothioneins are low molecular weight, cysteine-rich cytosolic proteins and able to bind to a number of metals, such as Ag, Cd, Co, Cu, Hg, Ni, Pb, Pd, and Zn (Ng et al., 2007; Frank et al., 2008). In general, MTs are involved in different biological processes, i.e., homeostasis of essential metals, detoxification of toxic metals, and cell protection against oxidative stress (Dabrio et al., 2002; Geffard et al., 2005; Ng et al., 2007). The main objective of the present study was to study the in situ seasonally responses of some biochemical biomarkers (AChE, GST, MTs) in D. trunculus originating from a polluted site (Sidi Salem) and a relatively clean site (El Battah) in the Gulf of Annaba.

2. Materials and methods 2.1. Presentation of sampling sites The gulf of Annaba is located in the east of Algeria. It is limited by the Rosa Cap (8° 15 ' E and 36° 38 ' N) in the East and by the Garde Cap (7° 16 ' E and 36° 68 ' N) in the West. El Battah site (36°50 ' N - 8° 50 ' E), is located about 30 km to the East of Annaba far from any human activities, and is considered as a relatively clean site. Sidi Salem site (36° 50 ' N - 7° 47 ' E),


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located about 1 km to the East of Annaba city, receiving industrial and domestic wastewater, and considered as the polluted area (Fig 1).

2.2. Samples Collection Mollusc bivalve (D. trunculus) with the same range shell length (25 ± 1 mm) were collected seasonally (Autumn 2014, Winter, spring and summer 2015) from two sampling sites (El Battah and Sidi Salem) and transferred to the laboratory.

2.3. Biochemical procedure The mantle of each mussel species was dissected and samples were prepared for biomarker analyses. Determinations of AChE activity were performed using a method described by Ellman et al. (1961) with the use of acetylthiocoline (ASCh) as substrate. The activity rate was measured as change in absorbance/min at 412 nm (ext. coef. 13,6 mM/cm). Activity was expressed as µ mol/min/mg protein. GST activity was measured using 1-chloro-2,4-dinitrobenzene (CDNB) as substrate in a final reaction mixture containing 1 mM CDNB and 5 mM reduced glutathione. The activity rate was measured as change in optical density (OD/min) at 340 nm (ext. coeff. 9.6 mM/ cm) and the final activity was expressed as µmol/min/mg protein. The protein content was evaluated according to Bradford (1976) using serum albumin as standard (BSA, Sigma). MTs were determined according to the method of Viarengo et al. (1997). The mantles samples were homogenized in three volumes of 20 mM Tris-sucrose buffer with 0.1 % ß-mercapto ethanol and 0.5 mM PMSF, followed by ethanol/ chloroform extraction. After incubation with DTNB, the samples absorbance was read at 412 nm. The levels of MT (MT-SH) were calculated assuming the relationship: 1 mol MT-SH = 20 mol GSH and expressed as µg of MTs per mg of fresh weight (FW).

3.3. Statistical analysis The normality of data was verified using the Kolmogorov-Smirnov test, and the homogeneity of variances was checked by Levene’s test. Results are presented as mean ± standard deviation (SD). Comparison of mean values between sites was estimated by Student’s t-test. The effect of seasons and sites was made using two-way analysis of variance (ANOVA). All statistical analyses were performed using MINITAB Software (Version 16, PA State College, USA). A significant difference was assumed when p< 0.05.


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Figure 1. Location of the two sampling sites in the Gulf of Annaba: Sidi Salem (1) and El Battah (2).

3. Results 3.1. Acetylcholinesterase activity AChE activity in the mantle of D. trunculus was significantly inhibited in Sidi Salem compared to El Battah in autumn (p 0.05), (p carbohydrate > protein. Keywords: Inclined Tube/BioFilm-Membrane Bioreactor (IT/BF-MBR), High-rise building, Prototype system, Microbial EPS (Extracellular Polymeric Substances), Non-potable water reuse purpose

1. Introductıon Recently, high-rise buildings have been recognized as one of main sources of water pollution in cities if their wastewaters are not appropriately handled. Environmental impact of nutrients especially nitrogen and phosphorus from high-rise building on deterioration in water quality of water resources is one of the main concerns since nitrogen and phosphorus are biostimulants for the growth of aquatic plants. Various studies on wastewater treatment and recycling by submerged membrane bioreactor (MBR) have been performed using raw wastewater from domestic wastewater


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(Tao et al., 2005; Marti et al., 2012; Ratanatamskul et al., 2012). The incorporation of domestic wastewater and liquid fraction of kitchen to an aerobic membrane bioreactor was also tested to develop an integrated decentralized sanitation system (Montalbo et al., 2005).

Consideration on

improvement of the membrane bioreactor to achieve zero excess sludge discharge was investigated using the inclined-plate membrane bioreactor (Xing et al., 2006; Fontanos et al, 2011).

The

advantages of the submerged membrane bioreactor system are that it can reduce space for a wastewater treatment plant due to no requirement of a sedimentation tank and help upgrade treatment-plant capacity of a conventional activated sludge. Moreover, it is possible to operate membrane bioreactor

at lower range of

DO concentrations for simultaneous nitrification-

denitrification in a long sludge retention time design (Metcalf and Eddy, 2003). Therefore, the membrane bioreactor can be considered as one of promising treatment technologies for large cities with land limitation. Nevertheless, the problem of membrane fouling is one of main concern in running the membrane bioreactor (MBR) system, that needs an appropriate method to prevent or control membrane fouling phenomena. Here, the inclined tube was introduced as a pre-treatment system for the MBR system. The inclined tube was selected as a filter media in order to sieve or filter large particles and also to remove organic pollutants in the feed wastewater by the biofilm growth on filter media, prior to entering the aerobic degradation zone, using the MBR system. Furthermore, nutrients can also diffuse into the attached biofilm and are further utilized

and

metabolized by microorganisms in the biofilm.

In this research, a novel IT/BF-MBR or Inclined Tube/BioFilm-Membrane Bioreactor system has been developed as a compact on-site wastewater recycling system with less excess sludge wastage and also with the ability of biological nutrient removal purpose. This Inclined Tube/BioFilm-Membrane Bioreactor (IT/BF-MBR) system consists of

the first step biofilm

compartment(BF1), the second-step biofilm compartment (BF2), then followed by aerobic compartment with the submerged membrane module for the purpose of establishing a compact biological nutrient removal and water reuse system. The two stage biofilm process can function as a pre-treatment step for aerobic MBR, and can also function as an inclined tube settler to concentrate sludge at the tank bottom. As a result, sludge digestion under anaerobic condition at the tank bottom can proceed. The necessity of a pre-treatment step for the MBR plant was also previously suggested by previous researchers (Frechen et al., 2008; Schier et al., 2009). Then, the IT/BF-MBR system can provide a high potential for treatment and reuse of wastewater from highrise building in a longer period for system operation. membrane bioreactor (MBR) within the same

The incorporation of the biofilm process to

tank has become more attractive

in this study

because the membrane can retain all biomass and consequently maintain high SRT condition.

Here, the aim of the present research was to investigate effect of hydraulic retention time, HRT on performance

of

the IT/BF MBR system with return sludge recirculation from aerobic

compartment to BF1 and BF2 compartment in treating COD, nutrients (nitrogen and phosphorus) for long term operation. Special attention was given to better understand the mechanisms, behaviours 2nd ICIEM 2016, International Conference on Integrated Environmental Management for Sustainable Development

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and reliability of the system in treating low strength sewage.

Moreover,

the microbial EPS

characteristics in terms of main components such as protein, carbohydrate and lipid were also investigated in order to obtain information for prevention of membrane fouling in the long-term operation.

2. Materials and Methods 1B

2.1 Description of the prototype IT/BF-MBR system The prototype IT/BF-MBR system had a total tank size of 0.6 x 2.35 x 2.4 m. with a total working volume of 3.38 cubic meters. The reactor was divided into four main compartments as equalization, anoxic, anaerobic and aerobic compartments.

For the

working volume of

equalization, first-stage biofilm (BF1), second-stage biofilm (BF2) and aerobic compartments were 0.66, 0.68, 0.68 and 1.16 cubic meters, respectively.

The height of inclined tubes installed inside

BF1 and BF2 were set to be 0.5 m, which could promote settling zone together with anaerobic condition.

A PVDF (Polyvinylidene difluoride) hollow fiber microfiltration membrane module

having surface area of 6 m2 and pore size of 0.4 µm. was installed inside the aerobic compartment. P

P

The MBR unit has a maximum water production capacity of 4 m3/day. The crossflow filtration was P

P

achieved by air pump with capacity of 10 litres/min. The biomass from the aerobic compartment was initially recirculated to the BF1 and BF2 compartments at the same low recirculation rate 50% of the feed flowrate. At present, the system has been operated without sludge wastage for more than 8 months. The schematic diagram of the IT/BF-MBR is shown in Figure 1.

2.2 Wastewater The IT/BF-MBR system received raw wastewater from a 20-floor Mahittaladhibesr Building in Chulalongkorn University, Bangkok at

average feed flowrate

3.5 m3/day. P

P

Here, the

raw

wastewater was mainly from toilet and canteen.


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2.10m

(1)

(2)

(3)

0.50m

(5) (5)

ตัวกลาง

(5)

(4) (7)

Permeate

2.40m (6) 0.46 m

0.47m

0.47m

0.80m

2.35 m

Feed

Figure 1. Schematic diagram of the prototype IT/BF-MBR system (1) Equalization compartment (2) First-stage Inclined-tube BioFilm (BF1) (3) Second-stage Inclined-tube BioFilm(BF2)

(4)Aerobic compartment (5) Inclined

tube (6) Diffuse aeration equipment (7) Submerged membrane module

2.3 Microbial EPS extraction method The microbial EPS were extracted using formamide and sodium hydroxide. carbohydrate content in the EPS was then measured using

The

the Anthrone method (Gaudy, 1962)

with glucose as the standard. The protein content in the microbial EPS was determined using the Lowry method with bovine serum albumin as the standard (Lowry et al, 1951). The total lipid content was extracted from the sludge, pre-treatment and then adding methanol/chloroform (1:2, v/v). After 5 min centrifugation, the supernatant was treated with sodium chloride (0.9% w/v). The mixture was centrifuged and a lipid extract was obtained. Total lipid content after extraction was measured by evaporating the organic solvents and drying in the oven at 45 degree celcius for 15 minutes and accurately weighing.

2.4 Analytical methods DO concentration in the reactor was measured using a DO meter (InPro 6820, Mettler – Toledo) and the pH was monitored using a pH-electrode (InPro 3030, Mettler-Toledo). Chemical oxygen demand (COD) was determined according to Standard Method 5220 (APHA,1998). Samples 2nd ICIEM 2016, International Conference on Integrated Environmental Management for Sustainable Development

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were filtered using cellulose acetate syringe filters with pore size of 0.45

µm before the

measurements of NO 3 -N, NO 2 -N and effluent phosphate in the supernatant. NO 3 -N, NO 2 -N and phosphate were measured using ion chromatography, Shimadzu, Prominence HIC-NS. Particle size distribution analysis was performed using the Laser particle size analyzer (Malvern Instrument Ltd.).

3. Results and Discussion 3.1 Environmental parameters

Operating environmental parameters inside the IT/BF-MBR for all experiments are shown in Table 1. Once, The feed wastewater entered anaerobic inclined-tube compartments (BF1 and BF2) and aerobic compartments in the IT/BF-MBR system, the pH were found to be in the range of 6.9-7.4, 7.0-7.4 and 7.0-7.6 for BF1,BF2 and aerobic compartment, respectively. Therefore, there is no need for pH adjustment in operating the IT/BF-MBR system in treating domestic wastewater. For dissolved oxygen (DO) inside the aerobic compartment of the IT/BF-MBR was maintained nearly 2.0 mg/L as energy-saving MBR system and for providing sufficient oxygen for nitrification. DO level inside the aerobic membrane compartment was found to be in the range of 2.0-2.4 mg/L. Therefore, pH and dissolved oxygen concentration were not limiting factors to cause any problem on nitrification and organic removal efficiencies by the IT/BF-MBR system.

Table 1. Operating environmental factors: pH and DO in the IT/BF-MBR system System Compartment

Operating environmental factors

pH

DO (mg/L)

BF1

6.9-7.4

0.2-0.5

BF2

7.0-7.4

0.2-0.5

Aerobic

7.0-7.6

2.0-2.4

3.2 Organic removal performance Variation of system hydraulic retention time, HRT to 4.4, 6 and 9 hrs did not affect the performance of the IT/BF-MBR system in treating organic carbon from wastewater as illustrated in Figure 2. Since the COD concentrations in the effluent were always lower than 10 mg/l, together with the COD removal efficiencies were above than 90% for all experiments suggesting that stable treatment performance of the system could be achieved. These data indicated that the system could provide a consistent high efficiency of COD removal, although the system was operated at short HRT of 4.4 hrs. The advantages of the IT/BF MBR system are the overall combination of a 2nd ICIEM 2016, International Conference on Integrated Environmental Management for Sustainable Development

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membrane separation unit and

biochemical activity of the biofilm and also

biomass in the IT/BF-MBR process.

suspended growth

Also, the influent characteristics show that the wastewater

sometimes contained high amounts of colloidal organic matters which can deteriorate treatment performance of a conventional activated sludge process. Nevertheless, this can be considered to cause less problem for stable treatment-performance by using the IT/BF-MBR system.

The

important aspect concerns the operation concept regarding the inclined-tube biofilter as a pretreatment step is that the biofilter helps sieve and filter large colloidal particle in BF1 and further degrade organic matters in the second-stage biofilter (BF2) before entering the aerobic membrane compartment, as more than 70% of total COD in the feed wastewater could be apparently reduced in the BF2 tank.

As a result, colloidal and soluble organic matters were removed before entering

the aerobic membrane compartment. Then, the soluble COD was further removed in the following aerobic compartment by high biomass of aerobic microorganisms that were retained by the membrane unit. Final effluent was proved to have excellent COD concentration lower than 10 mg/L, that can be further reused for building application.

3.3 Phosphorus removal performance During the whole operation period for the IT/BF-MBR, changes in concentration of total phosphorus in the influent, BF1 and BF2 compartments, aerobic compartment and effluent with variation of HRTs at 4.4, 6 and 9 hrs are shown in Figure 3. Total phosphorus concentration in the feed wastewater could be found in the range of 0.2-0.8 mgP/L. Significant amount of phosphorus removal could be achieved with the IT/BF-MBR system.

The average phosphorus concentration in

the effluent from BF2 was approximately 1.0 mg/L and then lower in the aerobic compartment to 0.3 mg/L. Phosphorus removal efficiency was found to be 90.2%. The main phosphorus- removing process was mainly by EBPR (Enhanced Biological Phosphorus Removal) as appeared in the profile of phosphorus removal,illustrated in Figure 4. With sludge recirculation from aerobic compartment to BF1 at 50%, the phosphorus release phenomena were observed in BF1 and BF2 compartments, and finally were uptaken by the biomass in aerobic compartment.


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Figure 2. COD removal in each compartment of the IT/BF-MBR reactor

Figure 3. Changes in phosphorus concentration in each compartment of the IT/BF-MBR reactor

3.4 Nitrogen removal performance Figure 5 presents the performance of the IT/BF-MBR system for TKN-N reduction with variation of system HRTs to 4.4, 6 and 9 hrs.

It is shown that a significant reduction in TKN-N

concentration was obtained by the IT/BF-MBR system. Nitrogen was removed from the wastewater through incorporation in biomass (BF1 and BF2 compartments) and nitrification (aerobic 2nd ICIEM 2016, International Conference on Integrated Environmental Management for Sustainable Development

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compartment). This significant reduction in TKN-N concentration from 35 mgN/L to less than 5 mg/L could be attributed to simultaneous nitrification-denitrification process due to the IT/BF-MBR system had sludge recirculation ratio at 50%.

The very stable nitrification in the aerobic

compartment was resulted from sufficient DO (dissolved oxygen), which was in a range of 2.0 – 2.4 mg/l. Moreover, small amount of DO remaining (0.2-0.5 mgN/L) from sludge recirculation did not affect denitrification activities in the BF1 and BF2 compartments. The concentrations of nitrite and nitrate ions were significantly low as can be seen in Figure 6. Therefore, the IT/BF-MBR system can be operated eventually at shorter HRT of 4.4 hrs ( aerobic compartment HRT was only 2 hrs).

Figure 4. Profile of phosphorus reduction in the IT/BF-MBR reactor

Figure 5.

Change

in

nitrogen concentrations in each compartment of

the IT/BF-MBR

reactor


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3.5 Particle size distribution inside the IT/BF-MBR reactor Particle size distribution of the particulate matters obtained

from each compartment

(BF1,BF2 and aerobic compartment) of the IT/BF-MBR reactor is shown in Figure 7. It was found that total particulate matters in BF1, BF2 and aerobic compartments had the average sizes of D50% at 65.85, 63.45 and 65.96 µm, respectively.

With the size range distribution from D10% to D90%,

overall particulate matters found in the IT/BF-MBR reactor had variation in size range from 19.15 to 164.01 µm. It means that the particle size of particulate matters are larger than the pore size of membrane (0.4 um), so these particulate matters can be significantly retained inside the system and further biodegraded by microorganisms in the IT/BF-MBR reactor.

3.6 Characterization of the microbial EPS in the IT/BF-MBR system Microbial EPS(Extracellular Polymeric Substances) are biopolymers mainly consisting of polysaccharides, proteins, nucleic acid and lipids (Adav et al., 2008) in either form sludge flocs or biofilms. These components in microbial EPS can promote membrane fouling in long-term system operation as confirmed by atomic force microscopy observation (Tian et al., 2011).

Table 2

summarized the quantities of EPS extracted from the biomass in BF1,BF2 and aerobic compartment. The results for biomass indicated that the collected EPS was primary composed of carbohydrates, proteins and lipids.


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Figure 6. Profiles of nitrogen concentrations in the IT/BF-MBR reactor (a) ammonia, (b) nitrate, (c) nitrite nitrogen

Each gram of MLSS in the sludge from BF1 compartment contained proteins,

7.475 ± 0.186 mg carbohydrates and

120.056 ± 3.562 mg of

compartment, each gram of MLSS in the sludge contained

7.475 ± 0.186 mg lipids.

For BF2

0.318 ± 0.019 mg proteins, 5.685 ±

0.546 mg carbohydrates and 119.90 ± 7.517 mg of lipids. Also, the aerobic compartment with the submerged membrane installation, the sludge content per each gram of MLSS contained 0.356 ± 0.012 mg proteins, 7.129 ± 0.058 mg carbohydrates and

119.897 ± 17.07 mg of lipids. Therefore,

the main microbial EPS inside the system were carbohydrate and lipid, rather than protein. These EPS content could result in membrane fouling in long run operation.

Figure 7. particle size distribution inside the IT/BF-MBR reactor

Table 2 EPS component of sludge from each compartment inside the IT/BF-MBR reactor


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Compartment

BF 1

Carbohydrate

Protein

Lipid

(g/gMLSS)

(g/gMLSS)

(g/gMLSS)

7.475 ± 0.186

0.396 ± 0.021

120.056 ± 3.562

BF 2

5.685 ± 0.546

0.318 ± 0.019

119.90 ± 7.517

Aerobic

7.129 ± 0.058

0.356 ± 0.012

119.897 ± 17.07

3.7 Microscopic examination of sludge in the IT/BF-MBR reactor by the Phase contrast method for analysis of cell morphologies Figure 8(a) demonstrated microbial complexity of an MBR sludge by Gram staining. Also, Figure 8(b) showed a complex microbial cluster of Gram negative filamentous and coccobacilli bacteria or diplococci-arranged cluster dominate in the sludge.

Gram negative tetrad-arranged

cocci bacteria or G-bacteria were observed according to their characteristic arrangement of four cells in the sludge as shown in Figure 8(c).

G-bacteria have been though to effectively assimilate

soluble organic matters in wastewater, therefore, these types of bacteria are one of dominant population in microbial community inside the IT/BF-MBR system under mesophilic temperaturerange condition.

Figure 8(d) illustrates Gram positive bacilli and filamentous Gram negative

bacteria within the sludge among the complex microbial structure.

The predominant of Gram

negative bacteria found in the MBR system were also reported (Munz et al.2008; Silva et al.,2012).

4. Discussion on potential wastewater reuse application The potential wastewater reuse application after treatment with the IT/BF-MBR system was evaluated here by comparing the treated effluent quality with the Japanese Ministry of Land, Infrastructure and Transport’s Reuse water quality criteria, 2005 for building application.

The

wastewater reuse application for toilet-flushing and garden watering has been highly concerned here due to large amount of water demand for many high-rise buildings. From Table 3, these data show that

the

effluent quality from the IT/BF-MBR system in terms of pH, turbidity, odor,

appearance and E.Coli could comply with the reuse water quality criteria that are required for toilet flushing and garden watering.

Therefore,

the IT/BF-MBR can be considered as


an

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alternative compact decentralized wastewater treatment system for high-rise building wastewater reuse purpose.

a)

Microbial floc characteristics inside IT/BF-MBR b) microbial cluster of Gram negative filamentous and coccobacilli bacteria

C) Gram negative tetrad-arranged cocci bacteria d) Gram positive bacilli and filamentous or “G” bacteria

Gram negative bacteria within the

sludge

Figure 8.

Microbial complexity and cell morphology of

biomass inside the IT/BF-MBR

reactor

5. Conclusion The IT/BF-MBR system could perform as a single compact reactor for high-rise building wastewater treatment without sludge wastage in long-term operation. From the overall results, the IT/BF-MBR system could successfully operate with HRT at least 4.4 hrs. The system could achieve high efficiencies above 99% in terms of turbidity and SS removal.

Stable treatment effiencies of

above 90% for COD, ammonia nitrogen and total phosphorus removal could be achieved in long-term operation of the IT/BF-MBR system. Moreover, very stable nitrification activity was observed in the aerobic MBR compartment.

Furthermore, water quality of the treated effluent could comply with

the standard of reuse water quality for toilet flushing and garden watering purposes.


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6. Acknowledgement This research work is financially supported by Japan International Cooperation Agency (JICA) under Research and Development of Water Reuse Technology in Tropical Region (Water InTro) Project.

Table 3. Comparison of effluent quality from the IT/BF-MBR reactor with Japanese Ministry of Land, Infrastructure and Transport’s Reuse water quality criteria, 2005

Wastewater reuse criteria Paramet ers

Effluent quality

Toilet flushing

Garden watering

pH

7.5-8.3

5.8-8.6

5.8-8.6

Turbidit

0 - 0.1

Less than 2

Less than 2

Not

Not unpleasant

Not unpleasant

unpleasant

Not unpleasant

Not unpleasant

Not detected

Not detected

y (NTU) Odor Appeara nce

Not unpleasant

E.Coli

7.

Not detected

References Adav S., Lee D.J. (2008).

Extraction of

extracellular polymeric substances from

aerobic granules with compact interior structure. J.Hazardous meterials: 154, 1120-1126. APHA (1998). Standard Methods for the Examination of Water and Wastewater,20th ed., American Public Health Association, Washington, DC. Frechen,F.B., Schier W., and Linden C. (2008). Pretreatment of municipal MBR applications. Desalination: 231 (1-3), 108-114. Fontanos PM, Yamamoto K, Nakajima F. (2011). Effect of upflow velocity on the performance of an inclined plate membrane bioreactor treating municipal wastewater. Water Sci Tech.: 64(5):1102-7. Marti E., Monclús H., Jofre J., Roda I.R., Comas J. and Balcázar J.L. (2012). Removal of

microbial

indicators

from

municipal

wastewater

by

a

membrane

bioreactor

(MBR). Bioresource Technology: 102 (8), 5004–5009. Metcalf and Eddy (2003). Wastewater Engineering-Treatment and Reuse ( 3rd edn.), McGraw-Hill, New York.


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Montalbo,M.,Samarakoon,S.M.S.,Visvanathan,C.,Fukushi,K.and Yamamoto,K. (2005). Development of an integrated decentralized sanitation system using aerobic membrane bioreactor. Proceeding of the Third international Symposium on Southeast Asian Water Environment, 6-8 December 2005-Asian Institute of technology, Bangkok, Thailand. Munz G.,Gualtiero M.,Salvadori L.,Claudia B. And Claudio L.(2008). Process efficiencyand microbial monitoring in MBR and CASP treatment of tannery wastewater. Bioresource Technology: 99, 8559–8564. Ratanatamskul C., Glingeysorn N. And Yamamoto K. (2012). The BNR-MBR(Biological Nutrient Removal-Membrane Bioreactor) for nutrient removal from high-rise building in hot climate region. Membrane and Water Treatment Journal: 3(2), 133-140. Schier W., Frechen,F.B. and Fischer St. (2009).

Efficiency of mechanical

pretreatment on European MBR plants. Desalination: 236 (1-3), 85-93. Silva A.F., Carvalho,G., Oehman, A., Ferreira,M.L., Nieuwenhuijzen,A.V., Reis,M.A. and Crespo,T.B. (2012). Microbial population analysis for nutrient removal related organisms in membrane bioreactors. Appl Microbiol Biotechnol.: 93, 2171-2180. Tao,G.,Kekre,K.,Wei,Z.,Lee,T.,Viswanath,B.

and

Seah,H.

(2005).

Membrane

bioreactors for water reclamation. Wat.Sci.Tech.: 51 (6-7), 431-440. Tian Y., Chen L., Zhang S., Cao C. and

Zhang S. (2011).

Correlating membrane

fouling with sludge characteristics in membrane bioreactors: An especial interest in EPS and sludge morphology analysis. Bioresource Technology: 102 (19), 8820–8827. Xing C.H., Yamamoto K., Fukushi K.(2006). Performance of an inclined plate membrane bioreactor at zero excess sludge discharge. J.Memb Sci: 275: 175-186.


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Orius laevigatus (Insecta; Heteroptera) local strain, a promising agent in biological control of Frankliniella occidentalis (Insecta; Thysanoptra) in protected pepper crops in Tunisia

Mohamed ELIMEM1 ; Ahlem HARBI 2 ; Essia LIMEM-SELLEMI 2 ; Soukaina BEN OTHMEN 2 ; Brahim CHERMITI 2 1

Ecole Supérieur D’Agriculture de Mograne, 1121, Mograne, Tunisie 1

[email protected]

2

Institut Supérieur Agronomique de Chott-Mariem, 4042, Chott-Mariem, Tunisie

2

2

[email protected]

2

[email protected]

[email protected] 2

[email protected]

Abstract Frankliniella occidentalis Pergande (1895) (Thysanoptera; Thripidae) is the most common worldwide western flower thrips. F. occidentalis has a cosmopolitan distribution and a wide host-plant range. The management of F. occidentalis has been always relied on chemical and biological methods. However, within the Integrated Pest Management (IPM) concept, knowledge of the beneficial local insects as important feature of biological control approach is still an active area for research. This work aim to evaluate and enhance the efficiency of local thrips predator strains Orius laevigatus (Heteroptera; Anthocoridae) to control F. occidentalis. The study is mainly relied on the investigation of the most convenient dose and release rate of O. laevigatus against F. occidentalis. The minute pirate bug O. laevigatus were collected on flowers of Chrysanthemum coronarium Linneaus (Asterales; Asteraceae) growing in an uncultivated field in the region of Chott-Mariem (Sousse, Tunisia). Two doses and three predator’s releases frequencies were tested in nine pepper crop greenhouses already infected by F. occidentalis. Results showed at first that O. laevigatus local strain had been successfully installed in all pepper crop greenhouses regardless doses and releases’ frequencies. Moreover, this predator when released two or three times with a time laps of one week at a dose of 1 individual per m² was able to control thrips populations. In fact, a decrease of F. occidentalis populations has been reported one week after the first release and its maintain at very low levels under harmfulness threshold. In addition, it turned out that the predatory bug when employed three times at a dose of 0.5 individual per m² or just once with a dose of 1 individual per m², produced a late impact on thrips populations that was shown after a delay of 3 to 5 weeks after the first release despite its successful installation and the decrease of the pest population. These results demonstrated the effectiveness of this predatory bug to control F. occidentalis populations and that it may be used as an alternative way to substitute use of chemical pesticides. 2nd ICIEM 2016, International Conference on Integrated Environmental Management for Sustainable Development

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Key words: Biological control, local strain, predator, thrips, pepper

Introduction The Western Flower Thrips (WFT), also known as Frankliniella occidentalis Perande 1895 (Thysanoptera; Thripidae) is a cosmopolitan and phytophagous thrips species that may attack many host plant species that belong to several botanical families (Lewis 1973; Loomans and van Lenteren 1995). Although F. occidentalis has been reported since the nineteen’s in Tunisia, the species still considered as a quarantine pest due to its ability to transmit viruses such as the Tomato Spot Wilt Virus (TSWV) and the Impatiens necrotic spot wilt virus (INSWV) (Belharrath et al. 1994; Kirk 2001; Kirk and Terry 2003; Cloyd 2009). Even though chemical insecticides are the most employed means to control WFT populations, several means are also considered (Grasselly 1996; Shelton et al. 2006). Among the alternatives, the use of beneficial insects has shown to be efficient as biological control agent against

WFT. Predators are a promising means of controlling WFT,

especially species belonging to the Anthocoridae family such are those of the genus Orius among which O. laevigatus, O. majuscules and O. tristicolor in greenhouses crop particularly cucumber, pepper, sweet pepper, and roses (Loomans & van Lenteren, 1995; Parker et al., 1995; Elimem and Chermiti 2012). The predatory bug O. laevigatus is the most used species to control F. occidentalis in pepper crop greenhouses in many Mediterranean countries and also the Atlantic coast (Sanchez and Lacasa 2002). The aim of this study is to evaluate the efficiency of O. laevigatus local strain collected from Chrysanthemum coronarium flowers and released at different doses and frequencies in pepper crop greenhouses.

Material and methods This work was carried out during 2011 at nine experimental greenhouses belonging to the Agricultural Support Station of Nebhana in the region of Monastir. Each greenhouse had an area of 500m² and contained four rows of plants, each of which was formed by two lines of pepper. The experimental set up in all the greenhouses was a randomized complete block design, with each line divided into eight blocks. One pepper plant was randomly chosen from each block and three flowers were taken from the different strata (upper, median and lower), making a total of 96 flowers per greenhouse. The first greenhouse G1 was considered as a control greenhouse where no releases were done in order to study F. occidentalis dynamic population. Predators of thrips were collected from flowers of C. coronarium that were growing in an uncultivated field at the High Institute of Agronomy of Chott-Mériem, Sousse, Tunisia. C. coronarium flowers were collected on April 27th, May 04th and May 10th 2011 (one day before each release). The flowers were then put into plastic bags to prevent the insects from escaping. In the laboratory, predators were collected using an aspirator and then placed in special vials designed for predator releases. C. coronarium pollen was added to the vials to ensure that the predators had enough food until their release. Polystyrene was also added to the vials to prevent pollen crowding and predator stifling. Predator identification was done according to Pericart (1972)’s identification keys. The releases frequencies, applied doses and dates are presented in Table 1.


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Table 1. Dates, doses and frequencies of O. Laevigatus releases in the pepper crop greenhouses.

Greenhous es

Ar ea

G1 G2 G3 G4 G5 G6 G7 G8 G9

frequencies 50

0 m² 50 0 m² 50 0 m² 50 0 m² 50 0 m² 50 0 m² 50 0 m² 50 0 m² 50 0 m²

Releases

Individuals

Doses

number

-

-

3

500

3

500

2

500

2

500

1

500

1

500

3

250

3

250

1 individual /m² 1 individual /m² 1 individual /m² 1 individual /m² 1 individual /m² 1 individual /m² 0.5 individual /m² 0.5 individual /m²

Results The obtained results in control greenhouse G1 showed a typical WFT dynamic population. Thrips number tended to increase progressively approaching hot season to reach a mean number of 4.43 and 5.82 thrips per flower respectively on June 02nd and 09th 2011 (Fig. 1).

Figure 1. Thrips populations in the control greenhouse G1. 2nd ICIEM 2016, International Conference on Integrated Environmental Management for Sustainable Development

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In greenhouses G2 and G3, where O. laevigatus was released three times at a dose of 1 individual per m², the WFT populations increased progressively from the beginning of the study till the end of April. However one week after the first release, thrips number in both greenhouses decreased. This decline was maintained after the second and third release to reach 0.08 and 0.04 on 09th June 2011 respectively in G2 and G3. Regarding predator, a continuous increase in both greenhouses from the first week after the first release till

Thrips per flower

2 1,5

Thrips Thripspar perfleurs flower Oriuspar perfleurs flower Orius

0,5 0,45 0,4 0,35 0,3 0,25 0,2 0,15 0,1 0,05 0

R1 R2 R3

1 0,5 0

Orius per flower

the end of study has been reported (Fig. 2 and Fig. 3).

Dates

Figure 2. Thrips and O. laevigatus populations in greenhouse G2 (R1: 1st release, R2: 2nd release, R3 :

Thrips per flower

6 5

Thrips Thripspar perfleurs flower Orius Oriuspar perfleurs flower

R1

4

0,5 0,45 0,4 0,35 0,3 0,25 0,2 0,15 0,1 0,05 0

R2 R3

3 2 1 0

Dates Figure 3. Thrips and O. laevigatus populations in greenhouse G3 (R1: 1st release, R2: 2nd release, R3 : 3rd release). Regarding greenhouses G4 and G5, where 1 individual per m² was released twice, thrips population decreased one week after the first release till arriving to 0.04 and 0.06 thrips per flower June 09th 2011 respectively in G4 and G5. O. laevigfatus populations showed a continuous increase since their first release till the end of the study (Fig. 4 and Fig.5).


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Orius per flower

3rd release).

Thrips per flower

2,5 2


0,4 0,35 0,3 0,25 0,2 0,15 0,1 0,05 0

R1 R2

1,5 1 0,5 0

Orius per flower

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Dates

Thrips per flower

1,2

R1

1

R2

Thrips Thripspar perfleurs flower Orius par Orius perfleurs flower

0,8 0,6 0,4 0,2 0

0,4 0,35 0,3 0,25 0,2 0,15 0,1 0,05 0

Orius per flower

Figure 4. Thrips and O. laevigatus populations in greenhouse G4 (R1: 1st release, R2: 2nd release).

Dates Figure 5. Thrips and O. laevigatus populations in greenhouse G5 (R1: 1st release, R2: 2nd release). Concerning greenhouses G6 and G7, where 1 individual per m² was released once, thrips population decreased three weeks after the first release in G6. In G7, WFT showed a decline one week after the first release and it increased later. However, it dropped again four weeks after the first release. Unless the other greenhouses, O. laevigatus populations increased slowly at first and then it reached mean numbers around 0.3

2,5 2 1,5

0,5 0,45 0,4 0,35 0,3 0,25 0,2 0,15 0,1 0,05 0

Thrips Thripspar perfleurs flower Orius per flower Orius par fleurs

R1

1 0,5 0

Orius per flower

Thrips per flower

predator per flower on June 09th 2001 (Fig. 6 and Fig. 7).

Dates

Figure 6. Thrips and O. laevigatus populations in greenhouse G6 (R1: 1st release).


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Thrips per flower

4 3

Thrips Thripspar perfleurs flower Orius per flower Orius par fleurs

0,5 0,45 0,4 0,35 0,3 0,25 0,2 0,15 0,1 0,05 0

R1

2 1 0

Dates st

Figure 7. Thrips and O. laevigatus populations in greenhouse G7 (R1: 1 release). In greenhouses G8 and G9, where half dose of the predator was applied, results showed that F. occidcentalis population did not decrease one week after the first release. However, it started to decline one week after the third release. Regarding predator populations development, O. laevigatus appeared one week after the first release with low mean numbers and it continued to increase slowly till reaching values

2,5 2


1,5

R3 R2 R1

1 0,5 0

0,5 0,45 0,4 0,35 0,3 0,25 0,2 0,15 0,1 0,05 0

Orius per flower

Thrips per flower

surrounding 0.3 individuals per m² in both greenhouses (Fig. 8 and Fig. 9).

Dates Figure 8. Thrips and O. laevigatus populations in greenhouse G8 (R1: 1st release, R2: 2nd release, R3 :

3 2,5

Thrips Thripspar perfleurs flower Oriuspar perfleurs flower Orius

0,5 0,45 0,4 0,35 0,3 0,25 0,2 0,15 0,1 0,05 0

R3 R2

2 1,5

R1

1 0,5 0

Orius per flower

Thrips per flower

3rd release).

Dates Figure 9. Thrips and O. laevigatus populations in greenhouse G9 (R1: 1st release, R2: 2nd release, R3 : 3rd release).


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Discussion Monitoring of O. lavigatus local strain in all greenhouses has shown a progressive increase of the population after each release. In fact, this proves that this local strain had been successfully installed in all greenhouses regardless doses or frequencies. Tommasini and Maini (2002) indicated that appearance of the predator after each release confirms the establishment of the species. In addition, predator population did not stop increasing continually. Moreover, this local strain showed an effectiveness to control WFT populations in all greenhouses. In G2 and G3 where three released were applied with a dose of 1 individual per m² and G4 and G5 where two released were done with the same dose, same results were observed with the same impact on F. occidentalis populations. This shows that two releases with 1 individual per m² are enough to control thrips populations in pepper greenhouses. These results are consistent with those previously mentioned by Sanchez et al. (1997) showing that O. laevigatus must be released twice with a dose of 1 individual per m² to guarantee its installation in the greenhouses and the control of the WFT. Same authors mentioned that the first release has an impact on thrips population causing thus its decrease, while the second release is recommended to improve predator installation in the greenhouse. Regarding half dose, Sanchez et al. (1997) indicated that release of O. laevigatus twice causes its installation which will be improved by the second release. In fact, this concords with results found in greenhouses G8 and G9. Within the same context, Tommasini et Maini (2002) reported that in the case of use of Orius species local strains such as O. laevigatus at a dose of 1 individual per m², predator number was higher in pepper flowers than those of the WFT. In fact, this was observed in greenhouses G2, G3, G4 and G5. These results prove the effectiveness of the local strain and its ability to control the WFT populations. Chamber et al (1993) found that release of 1 individual of O. laevigatus per pepper plant may guarantee thrips population’s control. Weintraub et al. (2011) indicated that O. laevigatus was able to reduce thrips populations with no differences between the doses of 2 individuals per m² and 6 individuals per m² and that it’s able to control the WFT with very low doses. On the other hand, it must be noted that different releases and doses employed during this study did not only make WFT populations decrease but they maintained it under low mean values. Comparison between this biological mean of control and other ones such as use of chemical pesticides or natural pesticides showed that thrips populations increase later after products’ application. Elimem and Chermiti (2011) mentioned that F. occidentalis populations increase again just one week after natural and chemical pesticides application. Wang et al. (2001) mentioned same results that WFT populations decrease immediately after chemical pesticides applications and increase later, while greenhouses treated by O. strigicollis showed a progressive decrease of thrips number without increasing again.

References Belharrath B., Ben Othmann M.N., Garbous B., Hammas Z., Joseph E., Mahjoub M., Sghari R., Siala M., Touayi M. et Zaidi H. 1994. La défense des cultures en Afrique du Nord, En considérant le cas de la Tunisie. Allemagne, Rossdorf : 372p. Chambers R.J., Long S. et Helyer N.L. 1993. Effectiveness of Orius laevigatus for the control of Frankliniella occidentalis on cucumber and pepper in the UK. Biocontrol and Technology 3: 295-307. Cloyd R.A. 2009. Western Flower Thrips (Frankliniella occidentalis) Management on Ornamental Crops Grown in Greenhouses: Have We Reached an Impass? Pest technology 3 (1): 1-9. Elimem M. et Chermiti B. 2012. Use of the predators Orius laevigatus and Aeolothrips spp. to


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control Frankliniella occidentalis populations in greenhouse peppers in the region of Monastir, Tunisia. Integrated Control in Protected Crops, Mediterranean Climate IOBC-WPRS Bulletin 80 : 141146. Elimem M. et Chermiti B. 2011. Frankliniella occidentalis (Pergande) (Thysanoptera; Thripidae) Sensitivity to Two Concentrations of a Herbal Insecticide “Baicao 2” in a Tunisian Rose Crop Greenhouse. Floriculture and Ornamental Biotechnology. (5)1: 68-70. Grasselly, D. 1996. Le thrips Frankliniella occidentalis, Les possibilité de lutte. Phytoma-la défense des cultures 483: 61-63. Kirk W.D.J. 2001. The pest and vector from the west: Frankliniella occidentalis. Thrips and Tospoviruses. Australian National Insect Collection, Canberra, Australia. Proceeding of the 7th International Symposium on Thysanoptera and Tospovirus :33-42. Kirk W.D.J. et Terry L.I. 2003. The spread of the western flower thrips Frankliniella occidentalis (Pergande). Agricultural and Forest Entomology (5): 301-310. Lewis T. 1973. Thrips. Their biology, ecology and economic importance. Acad. Press, London and New York: 349p. Loomans A.J.M. et van Lenteren J.C. 1995. Biological control oh thrips pests : a review on thrips parasitoids. Wageningen Agricultural University Papers, 95-1, Wageningen, The Netherlands: 237p. Parker B.L., Skinner M. et Lewis T. 1995.Thrips Biology and Management. The University of Vermont Burlingtone, Vermont and the Instute of Arable Crops Research Harpenden, Hertfordshire, NATO ASI Series, A: 276, Plenum Press, New York and London: 652p. Pericart J. 1972. Hémiptères. Anthocorides, Cimicidae et Microphysidae de l’Ouest Paléarctique. Faune de l’Europe et du Bassin Méditerranéen. 6ème ed. Paris, Masson et Cie éditeurs: 169-172. Sánchez J.A. et Lacasa A. 2002. Modeling population dynamics of Orius laevigatus and O. albidipennis (Hemiptera: Anthocoridae) to optimize their use as biological control agents of Frankliniella occidentalis (Thysanoptera: Thripidae). Bulletin of Entomological Research 92: 77-88. Sanchez J.A., F. Garcia A. Lacasa, L. Gutierrez M. Oncina J. Contreras et Gomez Y.J. 1997. Response of the Anthocorids Orius laevigatus and Orius albidipennis and the Phytoseiid Amblyseius cucumeris for the control of Frankliniella occidentalis in commercial crops of sweet peppers in plastic houses in Murcia (Spain). Bull. OILB-SROP., 20: 177–85. Shelton A.M., Zhao J.Z., Nault B.A., Plate J., Musser F.R. et Larentzakie E. 2006. Patterns of insecticide resistance in onion thrips (Thysanoptera: Thripidae) in onion fields in New York. Journal of Economic Entomology 99(5): 1798-1804. Tommasini M.G. et Maini S. 2002. Thrips control on protected sweet pepper crops: enhancement by means of Orius laevigatus releases. Thrips and tospoviruses: proceedings of the 7th international symposium on thysanoptera. 249-255 Wang C.L., Lee P.C. et Wu Y.J. 2001. Field augmentation of Orius strigicollis (Heteroptera: Anthocoridae) for the control of thrips inTaiwan. Food and Fertilizer Technology Center, Taipei. ROC. Exten. Bull. 500: 1-9. Weintraub P.G., Pivonia S. et Steinberg S. 2011. How many Orius laevigatus are needed for effective western flower thrips, Frankliniella occidentalis, management in sweet pepper? Crop Protection 30: 1443-1448.


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Study of the acid-base properties of lignocellulosic fibers and correlation with the adsorbing capacity Zeineb Raddaoui1, Aida Kesraoui1,2, Mongi Seffen1,2 1Laboratory of Energy and Materials (LABEM) High School of Sciences and Technology of Hammam Sousse BP 4011Hammam Sousse (Sousse University-Tunisia). e-mail :[email protected] 2Laboratory of Energy and Materials (LABEM) High School of Sciences and Technology of Hammam Sousse BP 4011Hammam Sousse (Sousse University-Tunisia) .FP4BATIW project

Abstract: The objectives to find the relationship between acid-base property of two types of lignocellulosic fibers: Posidonia Oceanica (PO) and Wheat bran (WB); at the purified state and modified state; and the adsorptive power of two types of anionic textile dyes: the methyl orange (MO) and the other cationic methylene blue (MB). The surface functions were determined by “Boehm titrations” and point of zero charge, of the adsorbent. Spectrophotometer (FTIR) and morphological structure by (SEM) were used to in order study the chemical interactions between the surface of the adsorbent/adsorbate. The adsorption kinetics of the textile dye was studied using the equations of pseudo-first-order; pseudo-second-order and the fractal model of Brouers-Stolongo. The experimental results have showed that the maximum quantity adsorbed of cationic dye is higher than for the case of the anionic dye for various adsorbents. Modeling adsorption kinetics showed that the adsorption of methylene blue and methyl orange for both biomasses follows BS model. Except for the purified and activated PO where adsorption kinetics of the BM follow the and the pseudo-second order. Keywords : Biosorption- Kinetics- Modelling- Posidonia oceanica- Wheat bran

Introduction Water is a vital element whose importance at the planetary level is unceasingly pointed out. Actually, the industrial and agricultural activities generate significant rejections following the example dyes, heavy metals, etc. which very often are poured without any control in the environment (Hem Lata et al., 2007). The synthetic dyes currently occupy a significant place in the industrial sector (Leon.G et al., 2015). They are largely used in the industry of paper, cosmetic and in particular in textile industry (Ben Hamissa.A.M et al., 2013). The intensive use of the dyes in the life generated problems in the environment. The methylene blue and methyl orange are two dyes contained mainly in the industrial effluents, they are non-biodegradable and toxic for the plants, the aquatic animals and the human (Chahrazeo.D et al., 2015). The methylene blue affects the watery ecosystem negatively, because it reduces the diffusion of the sunlight, thus inhibiting the photosynthesis of the aquatic plants (Ndi J.N et al., 2013). The methyl orange is azo_dye used in several industries. The estimation of the risks of cancer forces to fix a limiting concentration at 3.1 μg/L of azo_dye in drinking water. To exceed this concentration, methyl orange has carcinogenic and genotoxic, effects and can cause nausea and vomiting (Tcheka et al., 2015). It is thus significant to treat the effluents of industries containing the MB or MO before their rejection in the environment. To mitigate this situation, several methods of decontamination were developed, namely: adsorption (Meral Topcu.S et al., 2012),coagulation-flocculation (Mohd Ariffin A.H et al., 2009), ultrafiltration (Anouar Ben Fradj et al., 2014), reverse osmosis (Thirdpong.S 2nd ICIEM 2016, International Conference on Integrated Environmental Management for Sustainable Development

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et al., 2009) and biological treatment (Balakrishnan R.B et al., 2011). These techniques have some limitations that include requirement of large amount of supporting material and generation of large amount of secondary waste. Bio-sorption based on a mix of interactions between adsorbate and adsorbent including electrostatic interaction, complexation ;adsorption ,acid-base interaction… is one of the most studied dye removal technique that leads to producing high-quality purified water with a low cost process. The adsorption based procedure was widely used due to its high efficiency, capacity and ability for large scale dye removal application (Mokhtari et al., 2016). The aim of this work is to study the acid-base properties of lignocellulosic fibers modified by activation in acidic media to improve their capacity to methylene blue retention. The lignocellulosic fibers studied for the removal of methylene blue (cationic dye) and orange methyl (anionic dye) were: the Posidonia oceanica (PO) and Wheat bran (WB).The surface of materials were characterized for by Boehm titration, point of zero charge measurements, Infrared spectroscopy, UV-Visible; and scanning Electron Microscopy.

Materials and Methods 2.1

Adsorbent preparation raw biomass

Posidonia oceanica’s balls (Fig.1.a) were collected on the beach Boujaafar (Sousse, Tunisia). Wheat bran (Fig.1.b) constitutes approximately 15-20% of the total weight of grain of Wheat (Lu et al., 2014). The two biomasses were washed with distilled water to remove sand and other impurities. After the cleaning phase, the fibers were crushed into small pieces (40 𝜇𝑚-500 𝜇𝑚) and dried in an oven at 70°C until obtaning constant weight. Thereafter, the fibers were retained in desiccators for subsequent uses. (a)

(b)

Fig.1: (a) Posidonia oceanica’s balls and (b) wheat bran 

Chemical composition of two lignocellulosic fibers

The chemical composition of wheat bran and P.oceanica were determined by using common procedures, which are described below. Extractives: The evaluation of extractives waxes and fat was carried out in according to common standards, namely, (Test Method T204 cm-07) using the properites of solubility ethanol (62%)-toluene (38%) (Test Method T204 cm-07) and solubility in hot water for 1h then ammonium oxalate 1% at 85°C for 2 h, solubility in Sodium chlorite (1.5 g) and glacial acetic acid (0.5 mL) were added to the flask and the mixture was refluxed at 80°C for 1 h the procedure was repeated four times until the turned white material (Test Method T212 om-07). Hemicellulose: Fiber residues were taken in a flask containing distilled water (100 mL) and Potassium hydroxide (24%). Cellulose: the rest is putting in a sodium hydroxide solution (4.3%) for 24 h. 

Cellulose extracted from the biomass (delignification and Bleaching)

The cellulose extraction was performed using the follow protocol (B.Douissa et al., 2016). The two biomasses (20 g) were first treated with 100 mL of a 3 mol/L sodium hydroxide solution placed in a heated ball inside a heating assembly with reflux at 100°C for 4 h. The residue was collected by filtration, washed with distilled water, and then dried in an oven for 16 h at 50°C. In order to eliminate the pectin, fats as well lignin. In fact, 10 g of cellulose were agitated with NaClO solution (100 mL; pH10) at 50°C for 2 hour. After filtration, the residue was washed thoroughly with distilled water, dried in sunlight for two days, and then stored in plastic bottles for further use.



Biomass activation with phosphoric acid


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10 g of each raw sample (P.oceanica and Wheat bran) was mixed with 200 mL of H 3 PO 4 solution (0.2 M) and kept stirring during 2, 4 and 6 hours. The products obtained were filtered and washed with distilled water several times. The products were then dried at 50°C for 24 h. 2.2•

Characterization of materials : Surface studies Determination of acid-base properties of lignocellulosic fiber: Boehm Method

The Acidic sites and basic sites existing at the surface of the adsorbent were determined by the acid– base titration method proposed by Boehm (1994). Aqueous solutions of NaHCO 3 (0.05 mol/L), Na 2 CO 3 (0.05 mol/L) and NaOH (0.05 mol/L) were prepared. A volume of 25 mL of these solutions was added to 0.5 g of the samples, shaking for 48 h and then filtered. The excess of base was then determined by back titration using NaOH (0.05 mol/L) and HCl (0.025 mol/L). All titrations were carried out at room temperature. The number of acidic sites was determined under the assumptions that NaOH neutralizes carboxylic, lactonic and phenolic groups; that Na 2 CO 3 neutralizes carboxylic and lactonic groups; and that NaHCO 3 neutralizes only carboxylic groups (Sarah L et al., 2010). •

Determination of the point of zero charge pH (pH PZC ) of biosorbent

The PZC is a pH at which the surface has zero net charge; where the balance of protons, H+, sorbed and desorbed is null without the surface charge is necessarily zero. It is a characteristic of amphoteric surfaces and is determined by the type of surface sites on solids; their structures and the adsorption ability of the surface (M.A.M Sallh et al., 2011). 0.1g of samples of biosorbent was mixed with 50 mL of 0.01 M NaCl at different pH values from 2 to 12 and taken under agitation during 48 h. •

Determination of possible binding sites by FTIR analysis

The interaction between the functional groups of adsorbate and adsorbent may play a crucial role in biosorption process. The functional groups in the adsorbent were analyzed by Fourier transform infrared spectrometry (PerkinElmer Spectrum two). In order to determine the functional groups of P.oceanica and Wheat barn at state purify and at state modify (attacked by phosphoric acid), 1 mg of sample was crushed and mixed with 150 mg of potassium bromide (KBr) in a mortar. The transmission spectrum was performed with 4 cm-1 resolution and the spectrum was corrected for a KBr background. •

SEM (Scanning Electron Microscopy) Analysis

Scanning electron microscopy (SEM) has been a primary tool for characterizing the surface morphology and fundamental physical properties of the adsorbent. SEM was performed by using a JEOL JSM 5400 Scanning Microscope after coating them with gold using a JEOL JFC-1199E ion sputtering device. 2.3-

Batch biosorption studies

The biosorption experiments were carried out in batch reactor by adding 0.6 g dried biomass in 50 mL of dye solution with pH 1.5 for MO and 10 for MB, and at ambient temperature. The initial pH was adjusted by dilute solutions of HCl or NaOH. All experiments were performed in triplicate. The negative controls (without biomass) were simultaneously studied in order to ensure that the biosorption process was due only by the adsorbent. The concentration of MB and MO (Table 1) were determined by a UV-visible spectrophotometer double faisceaux analysis (FT-IR) (Camspec M550) at λmax of 665 and 508 nm for MB and MO respectively. The amount of dyes retained by the adsorbent was determined by the equation 1: 𝑸𝒂 =

𝑪𝒊−𝑪𝒕 × 𝒎

𝑽 (mg/g)

(1)

where C i and C t (mg/L) are the liquid-phase concentrations of dye at initial and the residual dye

concentration at any time, respectively, V is the volume solution (L) and m is the mass of the adsorbent (g).


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Table 1. Chemical Structure and Some Properties of dyes used Dye

Chemical formula

Mol

s

Molecul

ar mass

ar formula

El max

property

(g/ mol) Met

nm) 319

hylene bleu

ectrical

C 16 H +

.86

18 N 3 S

-

Cl

C 65

ationic

(MB) Met

327

hyl

C 14 H 14 +

.33

N 3 O 3 S Na

A 08

nionic

orange(MO) 2.4-

Kinetic modeling

Three kinetic models : pseudo first-order, pseudo second-order and Brouers-Stolongo were used to fit the experimental data of MB and MO adsorption onto adsorbents. The non-linear forms of pseudo first-order (Lagergern.S, 1898) and pseudo second order (Ho Y.S et al., 1999) kinetic equations are given as follows, respectively: 𝐝𝐐 =K 1 𝐝𝐭

(Q e -Q)

𝒅𝑸 = 𝒅𝒕

(2)

k 2 (Q e -Q) 2

(3)

Where Qe and Q are the amounts of MB or MO adsorbed (mg/g) at equilibrium and at time t (min) respectively, and K 1 , K 2 are the rate constants adsorption. On the other hand, the kinetics data were fitted with the pseudo BSf (n,𝛼) (Brouers et al., 𝒕

Q = Qe [1 - (1 + (n - 1) (𝜻𝒄)𝜶 )-1/ (n-1)

2006) kinetics modeling.

(4)

Where : n is a fractional reaction order which results from the fact that, due to the complexity of the system, all the reactive sites might not be able to participate in the reaction processes. 𝛼, is a “fractal time”

exponent expressing memory effects due to the heterogeneity of the sorption free energies and the resulting distribution of reaction constants given by the Arrhenius law.

Results and discussion 1a)

Characterization of two lignocellulosic fibers Biochemical composition of wheat bran and P.oceanica

The chemical composition of bran wheat and P oceanica, which are widely available cellulosic biomass-based, were characterized to determine if they had the potential for use as a starting raw material. Table 2 presents the results of Biochemical analysis of Posidonia oceanica (PO) and Wheat bran (WB). We can notice that both substrates contain similar amounts of hemicellulose but WB is richer in lignin than PO. However the choice of these biomasses appears interesting because they contain the same hemicellulose content while lignin and cellulose are quite different. Table 2: Biochemical analyses of P.oceanica and Wheat bran B iomass

Cell ulose(%)

P O

ulose(%) 42.8

L ignin (%)

37.4

5 W

B

Hemicell

ectin(%) 9

.26 24.1

P

38.9

and fat (%) 5

4.71

This study

9

8.7

Aida Kesraoui et

.78 1

8.9

Ref

Waxes

.4


al.,2015

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b)

Method of Boehm and point of zero charge

The surface chemistry of lignocellulosic fibers shows that the Surface is heteroatom. These heteroatoms form functional organic groups such as phenol (which is found in the lignin in the phenolic substances, in tannins), carboxyl (which exists in the pectin), lactone (which is found in hemicellulose by exchanging the proton : protonation). All these group can be controlled from the surface acid (R-CO-OH 2 +), neutral (R-CO-OH, R-OCO, Ar-OH) and basic (CO-O-, Ar-O-). Boehm titration method was used to determine the surface chemistry and the amount of functional groups such as phenolic, lactonic, and carboxylic. In fact, the distribution of functional groups and chemical composition of the cellulose derived and activated biomass surface play an important role in its adsorption capacity. pHpzc is closely related at the change of acidic or basic properties. When pHPZC: the surface of the biomass is negatively charged so it’s able to adsorb the cationic dye (MB). Table3 : Surface chemical properties of sample : Boehm titration ; pH PZC Adsorbents

Acidic function

Basic

(mmol/g)

function

C arboxylic P.oceanica Extracted cellulose for PO Pretreated PO by H 3 PO 4 Pretreated PO by H 3 PO 4 Pretreated PO by H 3 PO 4

0

Wheat Barn

0 .9

Extracted cellulose for Wheat Barn

0 .5

Pretreated Wheat barn by H 3 PO 4 (2h)

0 .7


0 .68


0 .6

.96

.84

.02

0.5 .8

.77 0

.01

.23 0.6

0

0 .05

0.75

0

0

.25

.69

.04

.07

1.22

0

0

.39

.21

.09

.1

0.59

0

0

.5

.8

.013

.1

0.61

0

0

.4

.84

.001

.3

0.62

0

0

.19

.86

.009

.09

0.55

0

0

.33

.54

.032

.06

.7

0

0

0

1.45 .39

.02

.04

.77

0

0

0

otal

.17

.12

.79

(6h)

0

0

(mmol/g)

L actonic

.2

.4

(4h)

henolic

1 .02

(2h)

P

H PZC

0.3 .66

.71

Table 3 shows that the carboxylic acid is predominant in relation to other acid function. In addition, the amount of basic groups is higher than the total amount of acidic groups for PO and WB. These results suggest that PO and extracted cellulose of WB have a basic character. While, WB and extracted cellulose PO, basic and total amount of acidic groups are almost equal. These results suggest that cellulose has an amphoteric character. Concerning all pretreated samples by H 3 PO 4 , the total amount of acidic groups is higher


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than the basic groups. These results show that PO and WB have changed of character and have become acidic after pretreated by H 3 PO 4 . c)

SEM Morphology

The morphological features and surface characteristics of adsorbent P.oceanica, and activated, Wheat bran were examined using SEM and depicted in Fig.2.(a),(b) and (c), respectively. Fig 2.(a) put in evidence the fibrous structure of P.oceanica. Fig.2.(b) shows that the surface of WB is quite heterogeneous and presents a fairly compact internal structure without any pores. The spheres exist in the surface WB are the granule starch (Pasqualone et al.,2016). Fig.2.(c) shows that the surface of wheat bran treated with H 3 PO 4 acid for 6 hours of agitation contains pores of different sizes which is attributed to the effect of treatment with strong phosphoric acid. The presence of these pores provides a large surface area for dye-surface interaction. Therefore, the increase of the adsorption capacity of the biomass.

(a)

(b)

(c)

Fig.2. SEM micrographs of P.oceanica(a), wheat bran (b), wheat bran activated (6h)

d)

Fourier transforms infrared spectroscopy (FTIR) analysis

FT-IR spectra as shown in Fig.3 and 5 present the development of surface textures of the activated biomass (P.oceanica, wheat bran). According to the literatures, it was found that biomasses present the IR band around 3436.2 cm-1 assigned to –OH vibration al stretching of hydroxyl groups. Bond occurring at 1427 cm1

ascribed to oxygen functionalities such as highly conjugated C=O stretching in carboxylic groups. Moreover,

FT-IR spectra of P.oceanica and wheat bran activated for 2,4 and 6h showed the decreasing of intensity of aliphatic bands around 2923.29 and 2852.62 cm-1 and also C=O stretching vibration of carbonyl groups around 1642.54 cm-1 and 1706.7 cm-1, the IR band around 1118.29 cm-1 assigned to stretching C-O-C of lactonic and alcohols, phenols, ethers and the IR band located at 614 cm-1 attributing to in-plane ring deformation. The main surface functional groups present were presumed to be phenols, carboxylic acids, all of which are typical acidic functional groups. After MB adsorption : For P.Oceanica : The creating of a new peak at 3650cm-1 is observed corresponding to the hydroxyl groups (M.D.Dey et al., 2015). This peak is most remarkable in the PO after 6h of agitation win H 3 PO 4 acid solution (fig.4.c).The peak at 1706.7 cm-1 corresponding to the carbonyl vibration (C=O) is becoming increasingly intense 57.96% to 61.5%.

In the wavelength range of 15009, at the basic the OH- concentration increases with the electrolysis time the copper reacts to generate Cu(OH) 2 (s) species [24]. Similar pH condition was indicated by Martins et al, the pH = 10.0 is suggested as the best pH for the simultaneous removal of metals under

operating

conditions

studied [6]. The

copper speciation

diagram

(Figure 2)

was

constructed using the MEDUSA software This diagram indicates the predominance of Cu2+ specie in the pH 8. A plausible explanation to the degradation-related difference would be to the difference in the extents of the free forms of the ions and their corresponding EDTA complexes. The strong coordinating bonds between the carboxylic groups and the metallic ion would prevent the decarboxylation occurrence, which is a key step of the EDTA degradation [19] At the anode, the main electrochemical reactions include water electrolysis, and hydroxyl ion and EDTA oxidation. At the cathode, water electrolysis, and hydronium and copper ion reduction. The reactions at the anode and cathode occur simultaneously and are competitive to each other [24].These results are in tune with those of Frim et al. [31], Motekaitis et al. [32]. 3.1.3 Effect of applied current intensity Applied current intensity is one of the main operating parameters directly affecting process of EF performance and operating cost. To investigate the effect of current intensity on the removal 2nd ICIEM 2016, International Conference on Integrated Environmental Management for Sustainable Development Page 496

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yield, a series of experiments were carried out on solutions containing a constant pollutants with current intensity being varied from 200 to 800 mA. Figure 5, a semi-logarithmic plot, showing the normalised concentrations profiles of the studied metal ions for typical EF runs, where the initial pH was fixed at 9. The removal rate of all studied metal ions increased upon increasing current intensity. The highest current (0.8 A) produced the quickest removal rate, with a 82.69% concentration reduction occurring just after 20min. This expected behaviour is easily explained by the increase of bubbles generationrate,resulting in a more efficient and faster removal, when the current is increased [33,34]. Moreover, it was previously shown that the bubble size decreases within creasing current density[35] However, these parameters should be kept at low level to achieve a low-cost treatment

100

80

R (%)

60

200 mA 500 mA 800 mA

40

20

0 0

50

100

150

200

250

300

Time (min)

Figure 5-Removal efficiency of copper as a function of time at different current intensity: EDTA/Cu=0.6; [Cu2+]=100mg/l; pHinitial=9; [NaCl]=10 g/l 2

Comparing the results obtained in this study with similar ones described by other authors [36-38], it can be observed that the current density did not prove to give meaningful results in the studied range. The electrochemical reaction was found to be limited, probably due to diffusion, resulting in a linear relationship between the current intensity and the Cu removal. The increase of tension promoted an increase in bubbles swarm, nevertheless insufficient to increase the Cu removal.

3.2 REMOVAL OF COPPER BY EC The mechanisms being involved in the abatement of pollutants via EC process are of importance for heavy metal removal. One of these mechanisms is the removal of organic matter, which consists of the organic complex former for the present case, by indirect oxidation apparently through chlorine species formed from chloride ions (according to Eqs.(7)–(9))[39]. The increase in pH is a consequence of the following cathodic reaction taking place during the EC process [40] and the

heavy metal removal with EC is hydroxide precipitation of heavy metals by increasing the


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solution pH. 2H2O+2é→H2+2OH-

(6)

2Cl-(aq)→Cl2(g)+2é

(7)

Cl2(g)+H2O→HOCl(aq)+H+Cl-

(8)

HOCl↔H++ClO-

(9)

Organic polluant +ClO-→Produits

(10)

The EC process implied the degree of mineralization e.g. complete oxidation of the organic matter. However, complete oxidation of the organic matter is not required to free the heavy metal bound by organic complex former. Organic matter (organic complex former) undergoes the structural changes by which it loses its complexing ability. This may take place at a certain extent of oxidation and the complexed metals convert into free metal forms which are removed by the hydroxide precipitation. The increase in pH is a consequence of the following cathodic reaction taking place during the EC process [40,41] As mentioned in the literature, increasing the electrolyte (NaCl) concentration accelerates inorganic and organic pollutant removals, decreases the power consumption and shortens the reaction time. In addition, chloride may generate chlorine/hypochlorite serving as an oxidizing agent during EC process at a proper pH range (pH < 11) and for an appropriate electrode material e.g. stainless steel[39,42]. The chlorine/hypochlorite couple oxidizes the pollutants thereby getting reduced to chloride ions [6]. Therefore, in order to determine the effect of electrolyte concentration on the process performance, set of EC experiments was carried out at varying chloride concentrations at the optimum applied current intensity of 200 mA and original pH (=9) of the effluent. A sample complexe EDTA/Cu=0.6, and the chloride concentration was then increased up to 15 g/L. Generally, EDTA can form stable complexes with any free cation present in the water, the efficiency of complexation depending on both the thermodynamics and kinetics of the reaction[40]. Figure 6 illustrates time-dependent changes in removal efficiency as a function of chloride concentration during the EC process. From the figure it is clear that the present chloride concentration of 10 mg/L was sufficient for the removal of organic complex former and provided a yield removal of 53.33 % after 5 h. On the otherhand, increase in chloride concentration did not enhance removal efficiencies of copper even resulting in a decrease in the process performance. A slight decrease in copper removal rates with increasing chloride concentration was evident. These findings were all in accordance with the literature data [43] where no significant effect of chloride concentrations was observed over 10 g/L while increasing chloride 60

concentrations.

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R(%)

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Figure 6 -Removal efficiency of copper as a function of time at different NaCl concentrations : EDTA/Cu=0.6 ; [Cu2+]=100mg/l; pHinitial=9; I=200 mA

3.3 REMOVAL OF EDTA BY EC A study of the EDTA degradation by the active chlorine formed in an electroflotation cell

equipped

with

a

graphite

anode

and steel-made cathode was undertaken, NaCl

concentration, applied current intensity on the EDTA degradation efficiency were examined. 3.3.1 Effect of chloride ion concentration In order to determine the effect of electrolyte concentration on the process performance, an intensity current of 500 mA was applied, containing 400 mg.L–1of EDTA, NaCl concentration being varied from 200 to 800 mA. The results shown in Fig. 7 indicate a significant decomposition was observed when chloride ions were added. A quantitative degradation (>80%) was observed after 5 h of electrolysis. The set of reactions involved in such oxidative degradation of EDTA by the in situgenerated active chlorine is given below. Reactions (8), (9), and (10) took place in the solution and were pH-dependent. The ionic strength (I) is a measure of the electrical potential of the solution. Generally,

in

ECF

process,

the

increase

in

ionic strength

causes

an

expansion

in

conductivity, and this usually leads to a gain in removal efficiency [19] Other Authors [44] have observed a similar effect on an Ir-SnO2 electrode. It is worth noting that the complete absence of Cl- is detrimental to EDTA mineralization, causing a decrease of the abatement efficiency. These results point out that ClO- plays a key role in the degradation not only of EDTA but also of its oxidation products. At the beginning of the electrochemical treatment, a fraction of the charge is expended in Cl- oxidation, resulting in low efficiency of EDTA degradation. However, as soon as hypochlorite becomes available in the bulk, the synergic effect with the electrodic heterogeneous oxidation leads to a fast EDTA decay. The degradation trend, which becomes more evident upon increasing Cl- concentration [45]

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R(%)

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Figure 7 -Removal efficiency of copper as a function of time at different NaCl concentrations: [EDTA]=400mg/L ;pHinitial=9; I=200 mA

3.3.2 Effect of the current intensity The impact of the current intensity on the EDTA degradation extent was examined and the results are shown in Fig. 8.

90 80 70

R(%)

60 50 40 30

200 mA 500 mA 800 mA

20 10 0 0

50

100

150

200

250

300

Time(min)

Figure 8 -Removal efficiency of copper as a function of time at different NaCl concentrations :[EDTA]=400mg/L ;pHinitial=9; [NaCl]=10g/L

It can be noticed that an increase in the current intensity speeded up the degradation. After 5 h of electrolysis, the degradation extent was estimated to be 59.09 % for 200 mA and 85.71% for 800 mA.. According to, the produced amount of active chlorine went up by raising the current intensity, accelerating reaction (5) and, consequently, improving the degradation yield. Hence,itcan be easily deduced that an increase in the applied current density accelerated requirements.The hypochlorite ion is in equilibrium with hypochlorous acid and their distribution strongly depends on solution pH. Neutral or acid conditions favor the formation of the acid, whereas hypochlorite is the predominating species at high pH values [46].

4.CONCLUSION AND RECOMMENDATİONS The following concluding statements can be drawn from the present study: - A basic pH promotes appreciable removal efficiencies. Under a suitable pH, there is no need of using additives such as coagulants and collectors. - For EDTA–metal mixed solutions, in absence of chlorides, metal removal by EF is inhibited by EDTA presence. In addition, removal efficiency is governed by EDTA concentration. 2nd ICIEM 2016, International Conference on Integrated Environmental Management for Sustainable Development Page 500

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- Simultaneous removal of the metal and the complexing agent is feasible. Culminating elimination can be reached applying the following parameters at their optimal values: time, pH, current intensity, and chlorides concentration. - It would be interesting to continue this work by studying the effect of other parameters such as the anode material, the geometric factors, the hydrodynamic regime, other metals and other organic compounds.

References

[1] K. Rajeshwar, J.G. Ibanez, Environmental Electrochemistry, Academic Press, UK, 1997 [2] Kuokkanen V, Kuokkanen T, Ramo J, Lassi U. Recent applications of electrocoagulation in treatment of water and wastewater – a review. Green Sustain Chem 2013;3: 89–121. [3] Chopra AK, Sharma AK, Kumar V. Overview of electrolytic treatment: an alternative technology for purification of wastewater. Arch Appl Sci Res 2011;3:191–206. [4] Kurniawan TA, Chan GYS, Lo WH, Babel S. Physico-chemical treatment techniques of wastewater laden with heavy metals. Chem Eng J 2006;118:83–98. [5] Matis KA, Mavros P. Recovery of metals by ion flotation from dilute aqueous solutions. Sep Purif Methods 1991;20:1–48 [6] Izabel de Oliveira da Motaa , José Adilson de Castro , Rui de Góes Casqueira , Angelo Gomes de Oliveira Junior . Study of electroflotation method for treatment of wastewater from washing soil contaminated by heavy metals. j mater res technol; 4(2):109–113 [7] M. Sillanpaa and A. Oikari, Chemosphere, 32 (1996) 1485–1497.[2]

B. Nörtemann, Appl.

Microbiol. Biotechnol., 51 (1999) 751–759. [8] Hinck, M.L., Ferguson, J., Puhaakka, J., 1997.

Resistance of EDTA and DTPA to aerobic

biodegradation. Wat. Sci. Tech. 35 (2e3), 25-31. [9] M. Tucker, L. Barton, B. Thomson, B. Wagener and A. Aragon, Waste Manag., 19 (1999) 477–82 [10] P.A. Babay, C.A. Emilio, R.E. Ferreyra, E.A. Gautier, R.T. Gettar and M.I. Litter, Int. J. Photoenergy, 3 (2001) 193–200. [11] Y. Ku, L.S. Wang and Y.S. Shen, J. Hazard. Mater., 60 (1998) 41–55 [12] Fu, F.L., Tang, B., Wang, Q., Liu, J.Y.,. Degradation of Ni–EDTA complex by Fenton reaction and ultrasonic treatment for the removal of Ni 2+ ions. Environ. Chem. Lett. 2010. 8, 317–322 [13] J.A. Frim, J.F. Rathman and L.K. Weavers, Water Res., 37 (2003) 3155–3163 [14] S. Chitra, K. Paramasivan, P.K. Sinha and K.B. Lal, J. Cleaner Prod., 12 (2004) 429–435 [15] P.R. Gogate and A.B. Pandit, Adv. Environ. Res., 8 (2004) 501–551 [16] G. Chen, Sep. Purif. Technol., 38 (2004) 11–41 [17] Jiraroj et al., 2006) Jiraroj, D., Unob, F., Hagège, A., 2006. Degradation of Pb–EDTA complex by a H2O2/UV process. Water Res. 40, 107–112, [18]

J.W.,

Jiang,

H.W.,

Hanna,

S.B.,

James,

W.J.,

1972.

Anodic

oxidation

of

ethylenediaminetetraacetic acid on Pt in acid sulphate solution. Journal of the Electrochemical Society 119, 5742nd ICIEM 2016, International Conference on Integrated Environmental Management for Sustainable Development Page 501

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580. [19] A.

Khelifa a ,

S.

Aoudj a,b,∗ ,

S.

Moulayc ,

M.

De

Petris-Wery d. A

one-step

electrochlorination/electroflotation process for the treatment of heavy metals wastewater in presence of EDTA. Chemical Engineering and Processing 70 (2013) 110– 116 [20] complexing agent and heavymetal [21] Troster, I., Fryda, M., Herrmann, D., Schafer, L., Hanni, W., Perret, A., Blaschke, M., Kraft, A., Stadelmann, M., 2002. Electrochemical advanced oxidation process for water treatment using DiaChem ,electrodes. Diamond and Related Materials 11, 640-645. [22] [J.Rodier, Analysede l’eau.9 th ed., Dunod, Paris.2009] [23] Jih-Hsing Chang, Amanda V. Ellis, Cheing-Tong Yan , Cheng-Hung Tung .The electrochemical phenomena and kinetics of EDTA–copper wastewater reclamation by electrodeposition and ultrasound. Separation and Purification Technology 68 (2009) 216–221] [24] Carlos Barrera-Díaz, Bernado Frontana-ubie, Bryan Bilyeu. Removal of organic pollutants in industrial wastewater with an integrated system of copper electrocoagulation and electrogenerated H 2 O 2 . Chemosphere 105 (2014) 160–164. [25] Beverskog,B., Puigdomenech, I., 1997. Revised Pourbaix diagrams for copper at 25– 300 C. J. Electrochem. Soc. 144, 3476–3483 [26]Chopra AK, Sharma AK, Kumar V. Overview of electrolytic treatment: an alternative technology for purification of wastewater. Arch Appl Sci Res 2011;3:191–206. [27] Kurniawan TA, Chan GYS, Lo WH, Babel S. Physico-chemical treatment techniques of wastewater laden with heavy metals. Chem Eng J 2006;118:83–98. [28]Zouboulis AI, Goetz L. Ion flotation as a tool for speciation studies selective separation in the system Cr3+ /Cr 6+ . Toxicol Environ Chem 1991;31-32:539–47 [29] M. Sillanpää, M. Orama, J. Rämö and A. Oikari, Sci. Tot. Env. 267 (2001) 23–31. [30] E. Gilbert and S. Hoffmann-Glewe, Water Res., 24 (1990) 39–44. [31] J.A. Frim, J.F. Rathman and L.K. Weavers, Water Res., 37 (2003) 3155–3163 [32] R.J. Motekaitis, B. Cox, P. Taylor and A.E. Martell, Can. J. Chem., 6 (1982) 1207. [33] P.H. Holt, G.W. Barton, M. Wark, A.A. Mitchell, A quantitative comparison between chemical dosing and elecrtocoagulation, Colloids Surf. A Physicochem. Eng. Aspects 211 (2002) 233–248. [34] N. Adhoum, L. Monser, Decolourization and removal of phenolic compounds from olive mill wastewater by electrocoagulation, Chem. Eng. Proc. (2004) [35] N.K. Khosla, S. Venkatachalam, P. Somasundaran, Pulsed electrogeneration of bubbles for electroflotation, J. Appl. Electrochem. 21 (1991) 986–990. [36] Burns SE, Yiacoumi S, Tsouris C. Microbubble generation for environmental and industrial separations. Sep Purif Technol 1997;11:221–32. [37] Chen

G.

Electrochemical

technologies

in

wastewater treatment.

Sep

Purif

Technol

2003;28:1–31. [38] Monsour LB, Ksentini I, Elleuch B. Treatment of wastewaters of paper industry by coagulation-electroflotations. Desalination 2007;208:34–41. 2nd ICIEM 2016, International Conference on Integrated Environmental Management for Sustainable Development Page 502

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[39] D. Rajkumar, B.J. Song, J.G. Kim, Electrochemical degradation of Reactive Blue 19 in chloride medium for the treatment of textile dyeing wastewater with identification of intermediate compounds, Dyes Pigments 71 (2006) 244–250. [40]Is¸ ık Kabdas ¸lı, Tülin Arslan, Tu˘ gba Ölmez-Hancı, Idil Arslan-Alaton, Olcay Tünay .Complexing agent and heavy metal removals from metal plating effluent by electrocoagulation with stainless steel electrodes. Journal of Hazardous Materials 165 (2009) 838–845 [41]M.Y.A. Mollah, R. Schennah, J.R. Parga, D.R. Cocke, Electrocoagulation (EC)—science and applications, J. Hazard. Mater. B84 (2001) 29–41. A.K. Golder, A.N. Samanta, S. Ray, Removal of trivalent chromium by electrocoagulation, Sep. Purif. Technol. 53 (2007) 33–41 [42] D. Rajkumar, J.G. Kim, Oxidation of various reactive dyes with in situ electrogenerated active chlorine for textile dyeing industry wastewater treatment, J.Hazard. Mater. 136 (2006) 203–212 [43] I. Arslan-Alaton, I. Kabdas¸ lı, Y. S ¸ ahin, Effect of operating parameters on the electrocoagulation of simulated acid dyebath effluent, Open Environ. Biol. Monit.J. 1 (2008) 1–7 [44]Regina Costa, C., Olivi, P., 2009. Effect of chloride concentration on the electrochemical treatment of a synthetic tannery wastewater. Electrochim. Acta 54, 2046e2052. [45] Christian Durante, Marco Cuscov, Abdirisak Ahmed Isse, Giancarlo Sandona`,Armando Gennaro. Advanced oxidation processes coupled with electrocoagulation for the exhaustive abatement of Cr-EDTA, waterresearch45(2011)2122e2130 [46] A. Khelifaa , S. Aoudj , S. Moulay , M. Hecini , M. De Petris-Wery. Degradation of EDTA by insitu electrogenerated active chlorine in an electroflotation cell. Desalination and Water Treatment ,7 (2009) 119– 123.


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CONTRIBUTION À L’EVALUATION DE LA POLLUTION PAR LES METAUX LOURDS DE L'ESPECE DE POISSON PELAGIQUE Trachurus trachurus (LINNE, 1758) (LA SAUREL) SUR LE LITTORAL DE SKIKDA

Souheïla AZZOUZ 1*, Ahlem BOUKROUMA 1 et Kamel BOUZERDOUNA 1 1

Département SNV, Faculté des sciences, Université du 20 août 55, SKIKDA 21000 ALGÉRIE. * Courriel : [email protected]

Résumé Le caractère durable et la tendance accumulatrice ont fait de la pollution par les métaux lourds un problème environnemental et public majeur dont l'importance est devenue de plus en plus préoccupante. Dans ce travail, nous avons essayé de rechercher les teneurs de neuf éléments traces métalliques (Hg, Pb, Cd, Cu, Fe, Zn, Cr, Ni, Mn) dans quatre différents tissus (Branchies, chair, foie et gonades) d'un poisson pélagique la Saurel Trachurus trachurus (linné, 1758) pêchée dans le golfe de Skikda pour évaluer le taux de contamination métallique au niveau du site d’étude. L’analyse des métaux dans les poissons à été réalisé par spectrophotométrie d’Absorption Atomique a flamme. D’après les résultats obtenus et à l’aide d’une étude statistique, on constate que l’accumulation métallique par le foie est en général largement supérieur dans les quatre oranges avec des dépassements observés par rapport à la valeur de référence pour le nickel au nivaux des branchies, foie et chair. Aussi, des dépassements observés par rapport à la valeur guide pour le mercure dans quelques individus. Pour le Cuivre, Plomb et le Chrome les moyennes détectées sont négligeables (nulles) dans les différents organes. Donc on peut déduire que la présence ou l’absence des métaux lourds dans les tissus peut être un indicateur réel du degré de contamination du site.

Mots clés : Eléments traces métalliques, golfe de Skikda, la Saurel Trachurus trachurus, quatre différents tissus, étude statistiques.


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Elaboration of a TiO 2 -P25@n-TiO 2composite in Sol-Gel Micromixing Reactor. Application to Photocatalysis

Fanou Guy Didier 1, 2, Yao Benjamin 2, Kanaev Andrei 1, Traoré Mamadou 1 ,ChhorKhay1 1

Laboratoire des Sciences des Procédés et des Matériaux (LSPM-CNRS) - Université Paris 13 Nord/ Institut Galilée/ France. [email protected] 2

Laboratoire des Procédés de Synthèse, de l’Environnement et des Energies NouvellesLAPISEN/ INP-HB/ Cote d’Ivoire. [email protected]

Abstract

Titanium-oxo-alkoxy nanoparticles coated on P25-TiO 2 surfacepermit to fabricate

new photocatalytic composite TiO 2 -P25@n-TiO 2 particles which are immobilized on a glass support by dip coating. The oxo-TiO 2 nanoparticles are prepared in the micro-mixing sol-gel reactor with rapid reagent mixing and particle size control.The photocatalytic test of the films is conducted on ethylene degradation in a continuous-flow fixed bed reactor. A kinetics study indicates a significant presence of both zero and first order reaction. . Keywords: Sol gel, Photocatalysis, Nano-composite, Ethylene, Kinetics

The photocatalytic oxidation of volatile organic compounds and microorganisms is a very attractive alternative technology for air and water treatment. In many applications, TiO 2 is used to oxidize organic pollutants. In order to increase the photo catalytic efficiency, a composite TiO 2 P25@n-TiO 2 wedeveloped using a sol-gel micro- mixing reactor [1].

1. Experimental The precursors (TTIP), preliminary dissolved in 2-propanol, was injected under nitrogen pressure into the turbulent mixing zone (Re=4500) of sol gel reactor where the oxo-TiO 2 nanoparticles around 5.2 nm, nearly mono-disperse, were generated. These colloids were subsequently mixed with P25-TiO 2 and immobilized on glass beads of 1 mm diameter by dip coating [2]. The schema of the sol-reactor reactor with temperature and atmosphere control and in-situ particles generation is shown in figure 1. The reactor consists of three main parts: two thermostatics containers, T-mixing element and container, which receives the prepared solution. The photocatalytic activity of the material is evaluated via the photooxidation of ethylene.


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The experiment was performed using a tubular fixed bed reactor equipped with six fluorescent lamps (F8T5-BLB) producing a strong emission line centered at 365 nm [3] Fig 2.

Injection pressures Solenoid

H2O in 2-propanol liquid coolant

TTIP in 2propanol

T-Mixer

Thermostated reactor liquid coolant

Figure 1 schema of the sol-gel micro-mixing reactor

Figure 2 Experiment setup for the photocatalytic test of the ethylene photodegradation

2. Results The films are characterized by X-ray diffraction, Raman spectroscopy, specific surface area measurements (BET) and by transmission electron microscopy (TEM). The photocatalytic efficiency of the composite material prepared by micro-mixing is significantly higher than that obtained from manual mixing. This result can be explained by i) the enhancement of particles surface area ii) the intrinsic photocatalytic activity of homogeneous oxoTiO 2 particles and their ability to improve mechanical properties of the composite films by


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strengthening chemical bonds involved in the connection of TiO 2 -P25 particles and the glass substrate. Kinetics study was carried out with the ethylene concentration ranging from 40 to 300 ppm. TheFit with experimental data using the phenomenological expression proposed by Emeline et al. [4] and adapted to a fix-bed continuous-flow reactor [3] results in the reaction orders n=0.46±0.02 (Figure 3). This indicates a significant presence of both zero and first order reaction kinetics.

ln ( Cin / Cout )

4

3

n = 0.46 +/- 0.02

2

1

0 0

50

100

150

200

250

300

Cin, ppm

Figure 3 The conversion rate versus ethylene concentration. The fit is shown by the solid line.

The concentration dependence of the ethylene photooxidation rate can be explained by the Langmuir- Hinshelwood (L-H) model that takes into account chemical processes given below:

S + hν → S * −1

(1)

S * τ→ S

(2)

kd / ka → Cads C ←

(3)

kr C + S *  →p

(4)

where S, S*, C, C ads and p stand correspondingly for the ground-state and activated surface sites, gaseous and adsorbed pollutant concentrations and reaction products concentration and τ, k a , k d and k r are correspondingly excited state lifetime, adsorption, desorption and reaction constants. This model permits clearly distinguishing between the two contributions (of 0 and 1 orders reactions) to the total process kinetics. These contributions are shown in Fig. 4.


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reaction order, %

100

1-order

0-order

75

50

25

0 0

50

100

150

200

250

300

Cin

Figure 4. The contribution of first and zero reaction order to the total kinetics process The result can be summarized as the following: -at the concentration of ethylene C in < 100 ppm the 1 order regime dominates. -at the concentration of ethylene C in > 100 ppm the 0 order regime dominates. References [1] Y. Chen, D. D. Dionysiou, Appl. Catal. B: Environ. 62 (2006) 255. [2] R. Azouani, A. Soloviev, M. Benmami, K. Chhor, J.-F. Bocquet, A. Kanaev, J. Phys. Chem. C 2007, 111, 16243 [3] S. Tieng, A. Kanaev, K.Chhor, App.Catal. A 399 (2011) 191 [4] A.V.Emeline, V. Ryabchuk, N. Serpone, Journal of Photochemistry and Photobiology A: Chemistry, 133 (2000) 89


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INTERACTION OF POLYSTYRENE CO STYRENE SULFONATE WITH METHYLENE BLUE IN AQUEOUS SOLUTION Souha BEN MAHMOUD1,2 Wafa ESSAFI1, and Ahmed Hichem HAMZAOUI3 1

Laboratoire Matériaux, Traitement et Analyse - Institut National de Recherche et d’Analyse Physico-Chimique, Pôle Technologique de Sidi Thabet, 2020 Sidi Thabet-Tunisie E-mail: [email protected] 2

Institut Nationales des sciences appliquées et technologie, INSAT, Centre Urbain Nord BP 676 - 1080 Tunis Cedex, Tunisie.

3

Laboratoire de Valorisation des Matériaux Utiles - Centre National des Recherches en Sciences des Matériaux, BP 95, Hammam Lif 2050, Tunisie

Abstract: The interaction of a cationic phenothiazine dye, Methylene blue (MB) with poly-(sodium styrene sulfonate) f –co(styrene) 1-f , (PSSNa f), has been investigated by spectrophotometric method. The polyelectrolyte induced metachromasy resulting in a blue shift of the absorption maxima of the dye, in agreement with the formation of a dye H-aggregates. The stability of the polyelectrolyte/dye complexes in aqueous solutions was studied as a function of polyelectrolyte chain length, polyelectrolyte concentration, polyelectrolyte electrostatic charge density f, NaCl salt addition, THF addition and THF treatment. It was found that the stoichiometry of PSS-MB complex evaluated by the molar ratio method is 4:1. Reversal of

metachromasy was observed upon tetrahydrofurane (THF) addition, while THF treatment does not affect the complex and allows recovering its initial state. Finally, thermodynamic parameters of the interaction between the polyelectrolyte and the dye at different temperatures, have been evaluated to determine the binding constant and as a consequence, the stability of the complexes.

Keywords: water treatment, dye, flocculent, polyelectrolyte, dye/polyelectrolyte complex

INTRODUCTION The release of colored wastewaters from industry like textile, in effluents can affect among another the viability of aquatic species1, that’s why water-soluble dyes are very injurious and their presence in water even at low concentrations is undesirable. So, their highly required decontamination is based typically on coagulation/flocculation, oxidation and adsorption in combination with biological treatments. Numerous investigations have been done to elucidate the interaction between dye and polyelectrolyte of opposite sign, in aqueous solutions, by different techniques such as absorbance, fluorescence and circular dichroism yielding significant knowledge. Many scientists have pointed the importance of the coulombic electrostatic interactions between polyelectrolytes and dyes for that purpose, but a detailed analysis of the influence of the various parameters is still missing. The strength and the stability of such molecular aggregation depend on different physical chemical parameters related either to the dye and to the polyelectrolyte, it can involve the structure of the dye and that of the polyelectrolyte, their concentration, ionic strength, solvent composition, …. As flocculent, we focus on typical 2nd ICIEM 2016, International Conference on Integrated Environmental Management for Sustainable Development

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polyelectrolyte which is Polystyrene co-styrene sulfonate, having a structural aspect; it bears an aromatic group to which the negative charge is directly attached. Few studies reported the interaction of Polystyrene sulfonate with cationic dye and the characteristics of the polyelectrolyte were kept constant during the study. In the present work, we are interested to analyze in detail the effect of the variation of physical chemical parameters intrinsic to the polystyrene sulfonate such as the polyelectrolyte electrostatic charge density, the chain length, the polyelectrolyte concentration,… on the polyelectrolyte/dye interaction. The chosen cationic model dye is methylene blue. As far as other external parameters related to the solvent such as the ionic force, the effect of added organic solvent tetrahydrofuran “THF” in the aqueous solution and THF treatment were also investigated and they can be indeed cases encountered in practice for aqueous rejected effluents. Finally, several interaction parameters such as binding constant, stoichiometry of the dye–polyelectrolyte complex and thermodynamic parameters were evaluated.

METHODS The polyelectrolyte used in this study is poly-(sodium styrene sulfonate) f –co-(styrene) 1-f , abbreviated PSSNa, it is a copolymer of styrene and sodium styrene sulfonate. It was prepared by post-sulfonation of polystyrene based on the Makowski procedure 2, that enables partial sulfonation varying from 0.3 (the limit for solubility in water) and 1 (fully charged). The cationic phenothiazine dye, Methylene blue, abbreviated as MB was purchased from Fluka. A dye solution of 1 × 10−4 mol L-1 and a polyelectrolyte stock solution of 1×10−3 mol L-1 were prepared separately. The investigated solution is prepared by adding aliquots of polyelectrolyte solution (ranging from 0 to 6 ml in order to vary the ratio of the polyelectrolyte to dye) to a fixed volume of 2 ml of the dye solution. The final volume of the solution was adjusted to 10 ml by adding deionised H 2 O, making the final dye concentration in the solution at 2.10-5 mol L-1. Absorption was measured using a LABOMED UV-visible double beam spectrophotometer UVD 3000, with a matched pair of cells of 1 cm path length, between 200 and 800 nm. All measurements were performed at 25◦C ± 0.1◦C except when we studied the temperature effect.

FINDINGS AND ARGUMENT The polyelectrolyte poly-(sodium styrene sulfonate) f –co-(styrene) 1-f is effective to induce metachromasy in the MB dye, as H-aggregates. The optimal chain lengths enhancing metachromsy for PSS f = 1 range from 20700 g mol-1 and 554.550 g mol-1. On the other hand, as the electrostatic charge density f increases the interaction PSSNa-MB is more favored, meaning that the fully charged PSSNa (f = 1) is the optimal polyelectrolyte for PSSNaMB aggregation. Moreover, the binding constant K c is higher for the fully charged PSSNa f = 1 than for f = 0.37, in agreement with a more stable complex for the fully charged PSSNa f = 1. This result implies that in practice, it is more advantageous to use the fully charged PSSNa f = 1 inducing greater degree of metachromasy than PSSNa f = 0.37, at the same polyelectrolyte concentration. The addition of sodium chloride salt, induced changes in the spectra showing clearly the gradual destabilization of PSSNa-MB complex causing its reverse metachromasy only at sufficient amounts of salt, because of the presence of short range aromatic/aromatic interaction between dye and polyelectrolyte. This behavior is the signature that the interaction between MB and PSSNa are also of electrostatic nature. 2nd ICIEM 2016, International Conference on Integrated Environmental Management for Sustainable Development

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We detail in what follows the effect of THF addition. The dye absorption of PSSNa (N = 2692, f = 1 at P/D = 5) aqueous solutions as a function of THF addition is presented in Fig.1. It emerges that as THF increases, the metachromatic band shifts to higher wavelengths and its intensity decreases and that corresponding to the monomer increases however, slightly. From an addition of 17% of THF in the solvent mixture, the metachromic band is completely disturbed and shifted from 590 nm to 610 nm, while the dimeric band observed previously in pure water appears again and its intensity increases, as well as the intensity of the monomer band. Indeed, the latter increases considerably and reaches that of dye in pure water dealing with complete reversal of metachromasy. So, the absorption spectra of the dye evolve under THF addition and become similar to that of dye in pure water. Moreover, beyond sufficient amount of added THF, the intensity of the dimeric form becomes constant and lower to that of dye in pure water, while that of the monomer form becomes high and close to that of dye in pure water. THF addition causes reversal of metachromasy and predominance of the monomer form at the expense of the dimeric form in comparison to the case in pure water. This behaviour is similar to that observed when urea or alcohols were added to cationic dyes including MB, complexed with anionic polyelectrolytes.

Figure 1. Absorbance variation spectrum of PSSNa (N = 2692, f = 1) as a function of THF addition, at P/D = 5. Finally, the “THF treatment”, investigated for the first time 3 for Polyelectrolyte-dye systems shows a full reversibility of this system under this action.

CONCLUSION This study shows the influence of the the different physical chemical parameters; either related to the solvent or to the polyelectrolyte, on the PSSNa/MB complex. As an extension of this work, it will be interesting to investigate the interaction of MB with other highly charged quenched polyelectrolytes that not bear aromatic ring, in order to assess the electrostatic component versus hydrophobic one in that kind of systems. 1

G. Bayramoglu, M. Y. Arica, J .Hazard. Mater, 2007, 143, 135-143.


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2

H. S Makowski, R. D Lundberg and G. S. Singhal. U.S Patent 3870841, 1975 to Exxon Research and

Engineering Company. 3

S Ben Mahmoud, A H Hamzaoui and W Essafi, Mediterranean Journal of Chemistry 2016, 5, 493-507.


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Thermal Infrared Scanning for Evaluation Oil Plume Thickness Contaminating Groundwater.

Khalil Ibrahim Al-Samarrai1, Abdussalam M. Bahron1, Abdussalam M. Al-Fituri2 1 University of Tripoly, Faculty of Engineering 2 College of Engineering Technology

ABSTRACT The characteristic that all objects emit a certain amount of black body radiation as a function of their temperatures was used in tracing the distribution of temperature in that black body. Generally speaking, the higher an object's temperature, the more infrared radiation is emitted as black-body radiation. A special camera can detect this radiation in a way similar to the way an ordinary camera detects visible light. It works even in total darkness because ambient light level does not matter. This makes it useful for rescue operations in wells.

A thermographic camera which is called an infrared camera or thermal imaging camera is a device that forms an image using infrared radiation, similar to a common camera that forms an image using visible light. Instead of the 400–700 nanometre range of the visible light camera, infrared cameras operate in wavelengths as long as 14,000 nm (14 µm). Their use is called thermography.

These uses include environmental control, building/art analysis, medical functional diagnostics, and car guidance and collision avoidance systems.

For use in temperature measurement the brightest (warmest) parts of the image are colored white, intermediate temperatures reds and yellows, and the dimmest (coolest) parts black. A scale should be shown next to a false color image to relate colors to temperatures.

The area where the idea is applied located at Al Giran site west of Tripoli the capital of Libya. Al Giran subjected to an oil leakage took place along the W10 Al Zawya-Tripoli pipeline. Taking the advantage of difference between temperature of the water and oil with their ambient, thermal scanning executed in the polluted site in order to measure the thickness and areal extent of oil plume polluting the groundwater.

Temperature of the fluids (Oil and Water) measured along selected depth of the 25 drilled wells. The 2nd ICIEM 2016, International Conference on Integrated Environmental Management for Sustainable Development Page 516

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measured temperatures showed variation along the depth from ambient temperature, as well as aerially. Different shots of IR Thermography applied for different depths at (20m, 23m, 26m, & 29m). This variations in oil and water temperatures enabled detecting the water oil contact and its areal distribution in the polluted site subjected to remediation. The shots taken for the selected depths indicate the effective of this method as a helpful tool in tracing oil contamination thickness. Each shot record the distribution of temperature in each mentioned depth. Comparing the time and cost of the technique applied with sampling groundwater technique appeared to be fast and cheaper, besides giving more informative data.


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MODELING OF THE CATALYTIC PHOTO DEGRADATION OF THE METHYLENE BLUE IN THE PRESENCE OF TIO2 SUPPORTS ON PLATES OUT OF GLASS AITATMANE Abdenour1, BOUROUINA-BACHA Saliha2 1 Laboratory of genius of the environment university of Bejaia (06000) Algeria

[email protected] 2 Laboratory of genius of the environment university of Bejaia (06000) Algeria

[email protected]

Keywords: TiO2, Methylene blue, photodegradation, photoreactor, regression equation .

INTRODUCTION Water purification is one of the most important technologies for human life. Various methods for water purification have been studied, ultraviolet light irradiation( Connelly et al., 2007), reverse osmosis (Schafer et al., 2003), ultrafiltration (Arthanareeswaran and al, 2008), and activated carbon treatment (Lee and Walker, 2006). Recently, the strong oxidation ability of TiO2 photocatalysts has received growing attention (Fujishima and Honda, 1972; Fujishima and al., 2008; Hirakawa and Nosaka, 2002; Serpone, 2006).. TiO2 photocatalysts can decompose organics, contaminants, noxious or malodorous chemicals, and bacteria into the less harmful CO2 and H2O with only solar light irradiation. The research and development of photocatalyst that can beplaced or float on water surface is of great importance for extendingits application range, including plating TiO2 film on glass surface (F. Magalhaes et al,2009; J.M. Liu and al, 2011) coating TiO2on polymer (such as expanded polystyrene)surface (L. Machado and al, 2006; J.W. Shi et al, 2009), loading TiO2on the surface of light inorganic carrierand so on(J.W. Shi and al, 2010; P.W. Huo and al, 2010; B. Wang and al, 2012; D. Wu and al, 2012). In this work, one is interested in the study of the kinetics of photodegradation of a basic dye: methylene blue, under natural irradiation and with room temperature, in the presence of a TiO2 photo-catalyst supported on plates out of glass. The reaction of degradation is implemented in a continuous photoreactor containing the thin layer of catalyst. On the basis of plan isovariant by rotation, of the regression equations are elaborate connecting the rate of degradation according to the experimental conditions and the catalytic characteristics of the deposit. The modeling of the reaction of photocatalytic degradation of methylene blue was carried out by the means of correlations between the constants speed and the operating conditions. Statistical tests made it possible to check the significance of the various models.


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METHODS photocatlysor The photocatalysor used is TiO2. Its crystalline structure makes up of anatase (97%) and rutile (3%). It has a specific surface, average diameter of the grains and that density is parameters which vary according to the parameter of preparation of our plates. Method of preparation of the plates The method adopted in this work to fix TiO2 on the surface of the glass plates is method PMTP (Previously Made Titanium Powder) with various operating conditions (concentrations (C), temperatures (T) and residence time (ts)) who are determines by a Minitab16 software. Method of analysis Before approaching the photocatalytic reaction, a mass m mg of powder catalyst was supported on a plate out of ordinary glass and containing this plate one produced an photo-engine for draft a solution of methylene blue has a concentration of 3mg/l under natural irradiation during 80 minutes. Measurements of the absorptance were taken using a spectrophotometer UV visible standard NANOCOLOR UV/VIS (MACHERY-NAGEL-MN) with the wavelength of 665 nm. Modeling of the process of degradation of the methylene blue Modeling by Minitab 16 of the reaction of photocatalytic degradation of methylene blue was carried out by the means of correlations between the constants speed and the operating conditions. Statistical tests made it possible to check the significance of the various models.

FINDINGS AND ARGUMENT By taking account of all the coefficients, the regression equation in coded variables are written: q(g/g) = 0,314617 + 0,05811*x 1 - 0,0809*x 2 + 0,0354*x 3 + 0,08365*x 1 2 + 0,04492*x 2 2 + 0,02539*x 3 2 0,1581*x 1 *x 2 - 0,0197*x 1 *x 3 – 0,0024*x 2 *x 3 The positive sign of the concentration and temperature coefficients (x1) (x3) indicates that great values of these parameters improve the reaction of degradation. Whereas the increase in the residence time goes against this degradation (negative sign of the coefficient of x2). To check the good adjustment of model and to validate the regression, of the tests of Fischer-Snedecor are carried out. Rough these results notes of it that the model present step of skew; le-P values corresponding to the lack of adjustment (lack off made) is higher than 0,05 and the coefficient of correlation adjusted is all higher than 90%, indicates that less than 10% only variations of this answer are not well `not explained' by the model.


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Fig 1. layout of the Iso-answers for the degraded quantity of Blue of methelyne The fig 1 represented the lines of the Iso-answers for the degraded quantity of Blue of methelyne according to the three operating conditions (concentrations (C), temperatures (T) and residence time (ts)). According to these curves we notices that the zones of evolution of the degraded quantity of blue methylene highest correspond to the green zones and one can guarantee a good output of degradation if the catalyst plates are prepared with a concentrated solution of semiconductor and when cooking is led during a shortest residence time to the highest temperature.

Conclusion: The aim had by this modeling is to test the effectiveness of the thin layers elaborate under various operating conditions while following the evolution of the degraded quantity of methylene blue compared to 1g of semiconductor The evolution of three calculated answers is linear according to the measured answers. The high values of the coefficients of correlation confirm that the selected models make it possible to return account of more than 95% of the variations of the answer (quantity of methylene blue degraded).


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Photodegradation of 3-[3,4-(dichlorophenyl)-1-methoxy-1methylurea by iron oxide- oxalate system: Degradation mechanism Hind MECHAKRA1, Tahar SEHILI2 1

Laboratoire des Sciences et Technologies de l’Environnement (LSTE), Faculté des Sciences Exactes, Université Frères Mentouri Constantine, Algérie.

 [email protected] 2

Laboratoire des Sciences et Technologies de l’Environnement (LSTE), Faculté des Sciences Exactes, Université Frères Mentouri Constantine, Algérie.

 [email protected] Keywords: Linuron, iron oxide, Fe 2 O 3 , By-products.

INTRODUCTION During the twentieth century, agricultural pollution have contributed to the degradation of the quality of surface water and groundwater. This pollution is not without impact on the environment and human health. Herbicides are the most widely used type of pesticides in agriculture. These chemicals are generally toxic and nonbiodegradable [1]. In this work, a natural iron oxide (NIO) was used in presence of oxalic acid (OxA) for application to the decontamination of aqueous effluent resulting from activities related to the development and use of pesticides. This study examined the oxidation of a chlorophenylurea herbicide (linuron) in a synthetic solution. The intermediates were identified by UHPLC-HR / MS to elucidate degradation pathways. The results showed that the process NIO/ Oxalate/ UV can be used effectively in the treatment of wastewater.

METHODS Photodegradation was conducted in a Pyrex glass cell (diameter of 2 cm and capacity of 50 mL) with a cooling water jacket placed in an elliptical chamber. The sample solution was illuminated with a fluorescent lamp (Philips TLAD 15W/05) which dominantly emits radiation at 365 nm. The concentration of Linuron (LN) was analyzed by means of a HPLC Shimadzu system, equipped with a photodiode detector (Shimadzu SPD-20A) and a Supelco HC-C18 column (5μm, 250 mm× 4.6 mm). The details of experiments are described in our previous work [2].

FINDINGS AND ARGUMENT NIO was morphologically characterised by different analytical methods, and the results showed that the ore was composed principally by hematite αFe 2 O 3 [2]–[4] . Photodegradation of LN was followed in different systems (Fig. 1 (a)). In the absence of irradiation (NIO/ OxA system), 42.2% of the herbicide was degraded after 180 min.


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The value of the constant pseudo-first-order rate (k) was estimated at 1.1 × 10-2 min-1 (R2 = 0.98). The irradiation of the LN solution, containing 1.0 g.L-1 of NIO and 10-3 M of OxA, showed a percentage removal of 96.4% after 60 minutes. The first order constant was determined to 6.0 × 10-2 min-1 (R2 =0.99). Dissolved Fe (II) was measured during the reaction (Figure 1 (b)). The results indicate that there is a strong generation of Fe (II), which comes from the photodissolution of iron oxide. The Fe (III) – oxalate complex produce Fe2+ species by photo-reduction of Fe3+ species dissolved. Intermediates were identified by UPLC-HR / MS to better understand the degradation mechanism. Photoproducts formed in the early stages of the oxidation of LN by NIO / OxA / UV process in aqueous solution at 30 minutes were identified, after extraction with diethyl ether, by UPLC-HR / MS. The UPLC chromatogram showed six photoproducts which were identified by their molecular weight and by comparison with the base given. In addition to these six compounds, other degradation products can exist in the system. However, they are not detected due to the high polarity of the column and the low concentrations used. Compared to previous studies, the metabolic pathways involved in the phenylureas degradation show great similarities, mainly involving the estate of N-demethylation of N-methyl urea-substituted and N-demethylation and N-demethoxylation of N-methoxy N-methylurea, which occur via a hydroxymethyl group and optionally of the intermediate N-formyl [5]. These results are not consistent with the hypothesis of Katsumata and al. [6] and Tahmasseb and al. [7] which suggest that the first attack of •OH occurs in the oxomethyl group of LN. Based on the intermediates and the results of previous research, LN degradation pathways by the system: UV/ NIO/ Oxalate are proposed in Scheme I.

(a)

(b)

Fig. 1 : (a) Photodegradation of linuron (4×10-5 M) in different systems at 365 nm, (b) Concentration of dissolved Fe2+ for the NIO / OxA / UV system. [NIO]= 1 g.L−1, [OxA]= 10−3 M.


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CH3 NH

CH3

OH NH

N

N OCH3

OCH3 Hydroxylation

O

O Cl

Cl

Cl

Cl

R''

Demethoxylation CH3 NH

Hydroxylation/ Dechloration

CH3 NH

N OCH3

N H

O HO

O Cl

CH3

Cl NH

Cl

N OCH3

Demethylation

O Cl OH

NH2

NH

R, R', R''

NH

R' O

C

Cl

NH2

O

Cl

R Cl-, NO3-, CO2, H2O...

Produits d'ouverture du cycle

R, R', R''

N C O

Scheme I: Degradation pathways of 3- [3,4- (dichlorophenyl) -1-methoxy-1-methylurea] (Linuron) by the photocatalytic process: NIO/ Oxalate/ UV.

References [1]

M.J. Cerejeira, P. Viana, S. Batista, T. Pereira, E. Silva, M.J. Valerio, A. Silva, M. Ferreira, and

A.M. Silva-Fernandes, Pesticides in Portuguese surface and ground waters, Water Res. 37, vol. 37, pp. 1055–1063, 2003. [2]

H. Mechakra, T. Sehili, M. A. Kribeche, A. A. Ayachi, S. Rossignol, and C. George, Use of natural

iron oxide as heterogeneous catalyst in photo-Fenton-like oxidation of chlorophenylurea herbicide in aqueous solution: Reaction monitoring and degradation pathways, J. Photochem. Photobiol. A, vol. 317, pp. 140–150, Feb. 2016. [3]

S. Belaidi, T. Sehili, L. Mammeri, and K. Djebbar, Photodegradation kinetics of 2,6-dimetylphenol

by natural iron oxide and oxalate in aqueous solution, J. Photochem. Photobiol. A, vol. 237, pp. 31–37, Jun. 2012. [4]

M. E. A. Kribéche, H. Mechakra, T. Sehili, and S. Brosillon, Oxidative photodegradation of

herbicide fenuron in aqueous solution by natural iron oxide α-Fe [5]

2

O 3 , Environ. Technol., pp. 1–11, Aug. 2015.

J. Fenoll, M. Martínez-Menchón, G. Navarro, N. Vela, and S. Navarro, Photocatalytic degradation

of substituted phenylurea herbicides in aqueous semiconductor suspensions exposed to solar energy, Chemosphere, vol. 91, no. 5, pp. 571–578, Apr. 2013. [6]

H. Katsumata, S. Kaneco, T. Suzuki, K. Ohta, and Y. Yobiko, Degradation of linuron in aqueous

solution by the photo-Fenton reaction, Chem. Eng. J., vol. 108, no. 3, pp. 269–276, 2005. [7]

L. Amir Tahmasseb, S. Nélieu, L. Kerhoas, and J. Einhorn, “Ozonation of chlorophenylurea

pesticides in water: reaction monitoring and degradation pathways,” Sci. Total Environ., vol. 291, no. 1–3, pp. 33– 44, May 2002.


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Optimization of nutritional conditions for production of antimicrobial compounds by Sa198 of Saccharothrix isolated from a Saharan soil

Laassami Affaf1, Boudjella Hadjira2, Bakour Leila3 and Sabaou Nasserdine4 Laboratory of Biology of Microbial Systems (LBSM), Ecole Normale Supérieure de Kouba. BP. 92, 16308, VieuxKouba, Algiers, Algeria. 1

[email protected] 2

[email protected]

3

[email protected] 4

[email protected]

Abstract Sa198 of Saccharothrix is an actinobacterium strain isolated from an Algerian Saharan soil sample during a screening program of search for new antimicrobial molecules. The strain showed a very strong activity against bacteria and fungi. In this work, the influence of some carbon sources on antimicrobial activity production and growth was investigated on a synthetic medium supplemented with corn steep liquor as nitrogen source. The carbon sources tested were glucose, fructose, sucrose, dextrin and sodium acetate. The strain showed maximum antimicrobial activity production with sucrose as carbon source, on the 6th day and pH 8. Keywords: Saccharothrix, antibiotics, production, carbon sources, SM medium, kinetics.

Introduction Unfortunately, the development of resistant microbial strains significantly reduced the effectiveness of antibiotics, thus prompting the search for new antimicrobial agents. Several published studies have reported the emergence of new bacterial strains resistant to many antibiotics (Katsumi et al.2005; Sekhsokh et al. 2008). Studies on the emergence of multidrug-resistant bacteria responsible for nosocomial infections have also been reported in Algeria (Touati et al.2006; Aggoune-Khinache et al. 2008; Messai et al. 2008). Actinobacteria are particularly interesting for their high capacity to produce secondary metabolites with diverse chemical structures (Valan Arasu et al. 2008). It has been estimated that approximately two-thirds of natural antibiotics have been isolated from actinobacteria, and about 75% are produced by members of the genus Streptomyces (Solanki et al. 2008). However, in recent years, the rate of discovery of new antibiotics in the genus Streptomyces has been declining and isolation of other actinobacteria genera appears to be necessary to find novel strains producing commercially valuable antibiotics. Many interesting antibiotics are also produced by other genera of actinobacteria as Micromonospora, Nocardia, Nocardiopsis, Saccharothrix, Actinomadura, Actinoplanes, Amycolatopsis, Saccharopolyspora, and Streptosporangium (Genilloud et al. 2011).


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The Algerian Saharan soils showed that they are a rich source of actinobacteria producing new antimicrobial agents (Sabaou et al. 1998; Lamari et al. 2002; Zitouni et al. 2004b; Boudjella et al. 2010; Merrouche et al. 2010). In this context, the SA198 strain of Saccharothrix isolated from a Saharan soil sample which showed in the primary screening, an interesting antimicrobial activity against bacteria and fungi. The objective of this work was first to determine the spectrum of activity of the strain against a largest panel of microorganisms, and the carbon source suitable for optimal antimicrobial activity production in shake culture media.

Methods The antagonistic properties of the strain were first determined by the agar cross streak method on ISP2 medium using various target microorganisms. Then, fermentation of the strain was performed in shake Erlenmeyer flasks, by following the kinetics of production, growth and pH. A basal synthetic culture medium (SM) supplemented with corn steep liquor (CSL 50 g/L) was used to test the effect of different carbon sources on the production of antimicrobial agents. The carbon sources included glucose, fructose, sucrose, dextrin and Na acetate (10 g/L). Antimicrobial agents production was measured by the agar well diffusion method, and the growth, by dry cell weight.

Findings and argument The results of the antagonism test showed that the strain has good antifungal and antibacterial activity. These results allowed us to retain Bacillus subtilis (Bs), Staphylococcus aureus (Sa) and Umbelopsis ramanniana (Ur) as target strains to be used in production kinetics. The results of the production kinetics indicated that among the five carbon sources tested, sucrose allowed the maximum antimicrobial activity production (Figure 1). It was followed by the glucose, fructose and dextrin. No production was obtained with Na acetate. The result with sucrose as the best source of carbon correlates with that obtained by Islam et al. (2009) and Thakur et al. (2009). The production kinetics of the results indicated a strong antifungal activity against Ur (Figure 2) is observed in the fermentation medium, after 1 day with an inhibition zone of 24 mm in diameter, in an increasing manner until the 6th day to reach its maximum (48 mm). The antibacterial activity against Sa and Bs starts the second day with an inhibition zone of 15 mm diameter. The activity against Bs marked its maximum on day 3 with a value of 20 mm. The activity against Sa recorded on day 3 is 17 mm. This production is partially associated with growth. Its maximum is achieved at alkaline pH. In other optimization works on the production of antibiotics, where activity is measured at different pH, it appears that the maximum production occurs at basic pH (Hata et al, 1971. Larpent and Boar, 1989; Larpent-Gourgaud and Boar, 1992; Jain et al, 2011).


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Inhibition diameter (mm)

Umbelopsis ramanniana 50

Sucrose Glucose Fructose Dextrine Na acetate

30

10

1

2

3

4

5

6

7

8

9

10

Time (days)

Figure 1. Antifungal activity against Umbelopsis ramanniana of Sa198 strain in culture medium MS-CSL

9 8 7

Sucrose

50

12 8

30

4 10 1

2

3

4

5

6

7

8

9

10

Biomass (g/L)

Inhibition diameter (mm)

PH

supplemented with carbon sources.

0

Time (days)

Bs

Sa

Ur

Biomass (g/L)

Figure 2. Kinetics of production of antimicrobial activities, growth and pH of the Sa 198 strain cultured in the MS-CSL-sucrose.

Conclusion We conclude from these kinetics, that the best production of antimicrobial activities by Sa.198 strain occurs in MS medium with the sucrose as carbon source of and the maximum production occurs at basic pH.


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Utilisation des argiles pour stabiliser des émulsions pharmaceutiques TOUZOUIRT Saida1, AHMED ZAID Toudert2, NABIEV Mohamed3 1

Faculté des sciences, Université Mouloud Mammeri, BP 17 Tizi-Ouzou, Algérie [email protected]

2

Laboratoire de valorisation des énergies fossiles, Département de Génie Chimique, Ecole Nationale Polytechnique, Ave Pasteur, Hassen Badi, El-Harrach Alger, Algérie [email protected] 3

Faculté des hydrocarbure et de la chimie, Université M’hamed Bougara, Avenue de l’indépendance, Boumerdes, Algérie [email protected]

Keywords: Bentonite, émulsion de Pickering, stabilité, industrie pharmaceutique

RESUME L’émulsion est une forme très répandue dans les applications pharmaceutiques et cosmétiques, et les tensio-actifs synthétiques utilisés pour stabiliser ce système dispersé posent un problème écologique. L’émulsion stabilisée par des particules solides (émulsion de Pickering) vient pour régler ce problème. Le but de ce travail est d'étudier la stabilité des émulsions de Pickering en utilisant des particules d'argile. L’optimisation des paramètres opérationnels à savoir la concentration en bentonite, en bromure de cétyltriméthylammonium (CTAB) et en NaCl a été réalisée en utilisant la méthodologie des surfaces de réponse (RSM).

INTRODUCTION L’utilisation des médicaments est indispensable dans notre vie quotidienne, ils peuvent être d’origine naturelle ou synthétique. Le problème actuel est la gestion des déchets provenant de l’industrie pharmaceutique qui influe négativement sur l’environnement. Parmi les substances les plus dangereuses pour l’environnement on trouve les tensioactifs synthétiques.[1] Ce sont des éléments essentiels pour stabiliser les émulsions. L’un des défis majeurs est de trouver un moyen pour stabiliser ces émulsions en utilisant moins de tensioactifs. Une solution adéquate est d’utiliser des émulsions de Pickering dans le domaine pharmaceutique. Celles-ci sont en effet stabilisées par des particules solides qui peuvent avantageusement remplacer les

tensioactifs synthétiques, en contribuant ainsi à la préservation de

l’environnement. Les émulsions de Pickering ont été utilisées pour la première fois par Pickering en 1907. La bentonite,

matière première naturelle par excellence a déjà été utilisée pour stabiliser des émulsions de

Pickering dans différents domaines industriels.[2-5] Afin d’optimiser les quantités des constituants de l’émulsion qui ont un effet direct sur la stabilité et rechercher une formule la plus stable possible, nous avons fait appel à la méthodologie des plans d’expériences 2nd ICIEM 2016, International Conference on Integrated Environmental Management for Sustainable Development

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qui permet d’organiser les expériences de manière à obtenir le maximum d’informations tout en utilisant le minimum d’essais expérimentaux. La méthodologie dite des surfaces de réponse a permis de repérer les domaines de concentrations des additifs qui permettent d’obtenir des émulsions stables. En particulier, les résultats montrent que le taux élevé d'argile, de l’ordre de 7 %, conduisent à une bonne stabilité de l'émulsion.

METHODES La phase aqueuse est préparée en mélangeant la bentonite, le CTAB, et le NaCl sous agitation à une vitesse de 670 tr/min durant 90s. La phase huileuse est ensuite ajoutée goutte à goutte en maintenant l’agitation à la même vitesse à l’aide d’un agitateur à hélices de marque Heidolph modèle RZR1. On passe ensuite à l’homogénéisation du mélange durant 15 min à une vitesse de 14500 tr/min à l’aide d’un homogénéisateur du type Ultra-Turrax de marque IKA, modèle T10 pour petits volumes. Les émulsions préparées sont conservées à température ambiante pour l’étude de la stabilité physique. Avec un plan composite centré, il est possible de déterminer des surfaces de réponse, ce qui permet de rechercher les réponses optimales et de repérer les valeurs des facteurs étudiés qui conduisent à cet optimum. La méthodologie permet de modéliser les réponses en fonction des facteurs, en vue de prédire le comportement du système dans des conditions opératoires données. Un plan composite centré mis en œuvre à l’aide du logiciel Modde, version 6 [6], nous a permis d’étudier 17 formulations d’émulsion H/E avec le rapport 30/70. La composition des émulsions formulées est donnée dans le tableau1. Tableau 1. Les constituants de l’émulsion, leurs quantités et les rôles joués dans la formulation Matière

Quantit

Rôle joué

Origine

és Maghnia Bentonite

3–7%

Agent

fournie

monium bromide (CTAB)

0.015– 0.05%

NaCl

société

BENTAL

(Algérie)

stabilisant Cetyltrimethylam

par la

gracieusement

Agent

BIOCHEM Chemopharma

stabilisant 0.015-

0.05%

Améliore

la

MERCK Eurolab

floculation et la stabilité

CONCLUSİONS ET ARGUMENT Les réponses choisies pour l’étude de la stabilité des émulsions de Pickering formulées sont la viscosité, le taux de crémage et la taille des gouttelettes. Les résultats montrent que la concentration en bentonite est le facteur le plus important pour les trois réponses étudiées. Ce facteur agit positivement sur la viscosité et négativement sur le taux de crémage et la taille des gouttelettes.


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Modèles décrivant les réponses étudiées L’étude statistique indique la validité du modèle et nous permis d’écrire le modèle mathématique pour chacune des réponses comme suit: R

Viscosité (Pa.s)

Taux de crémage (%)

éponse

Taille

des

gouttelettes (µm) M

Y = 0.110 + 0.124 X 1 + 2

0.031 X 1 + 0.020 X 3

odèle R

Y = -8.327 X 1 + 5.955 X 12

2

0.938

Y = 60.576 – 22.755 X 1 + 17.762 X 1 2 + 10.772 X 1 X 3

0.918

0.812

2

où X 1 , X 2 , X 3 représentent respectivement les concentration en Bentonite, en CTAB et en NaCl. Le module d’optimisation fournit un ensemble de solutions possibles reliées à un paramètre (Log D) qui mesure la distance (ou l’écart) globale avec la réponse ciblée (Target).

Phase d’optimisation Nous avons utilisé le module « optimizer » du logiciel Modde 6 pour rechercher la formule optimale. L’optimiseur de ce module utilise une procédure simplexe de Nelder Mead avec les modèles calculés pour chaque réponse pour optimiser la fonction désirabilité globale en tenant compte des contraintes du système. Les propriétés désirées pour la formule sont les suivantes : Une viscosité élevée qui empêche ou ralentit le phénomène de déstabilisation avec une valeur cible (Target) de 0.4Pa*s et (min) de 0.1 Pa*s ; une faible taille des gouttelettes, et un taux de crémage nul. Le module d’optimisation fournit un ensemble de solutions possibles reliées à un paramètre (Log D) qui mesure la distance (ou l’écart) globale avec la réponse ciblée (Target). L’optimiseur renvoie la solution la plus proche de l’optimum global indiquée par une valeur de log(D) la plus faible. Les solutions indiquent toutes des taux élevés en argile et des taux faibles en sel, avec des taux variables de CTAB. Nous avons choisi la solution correspondant à la composition suivante : 7% d’argile, 0.015mol/L en NaCl et 0.02% de CTAB.

CONCLUSION Il est possible de formuler des émulsions stables avec des concentrations très faibles en tensioactif en utilisant des particules solides comme la bentonite. Les résultats montrent que 7% de bentonite algérienne peuvent stabiliser une émulsion durant 22mois en combinaison avec une faible concentration en CTAB et en NaCl.


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REFERENCES BIBLIOGRAPHIQUES 1.

Cui, Y., M. Threlfall, and J.S. van Duijneveldt, Optimizing organoclay stabilized

Pickering emulsions. J Colloid Interface Sci, 2011. 356(2): p. 665-71. 2.

Aguzzi, C., et al., Use of clays as drug delivery systems: Possibilities and limitations.

Applied Clay Science, 2007. 36(1–3): p. 22-36. 3.

Guillot, S., et al., Internally structured pickering emulsions stabilized by clay mineral

particles. J Colloid Interface Sci, 2009. 333(2): p. 563-9. 4.

Reger, M. and H. Hoffmann, Hydrophobin coated boehmite nanoparticles stabilizing oil

in water emulsions. J Colloid Interface Sci, 2012. 368(1): p. 378-86. 5.

Nciri, H., et al., Influence of clay addition on the properties of olive oil in water

emulsions. Applied Clay Science, 2009. 43(3–4): p. 383-391. 6.

Modde Software, Version 6, Umetrics AB, 1993-2001


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Improving Anaerobic Digestion of Waste Activated Sludge by Electro-Fenton Pre-treatment

Sonia Khoufi1; Emna Feki2 and Sami Sayadi3 Laboratory of Environmental Bioprocesses,Centre of Biotechnology of Sfax, BP 1177, 3018 Sfax, Tunisia. 1

2

[email protected]; [email protected]; [email protected]

Abstract This study presents the combination of electro-Fenton (EF) reaction and anaerobic digestion for waste activated sludge (WAS) treatment. The results have shown that the EF is a feasible process for disintegration of WAS flocs. The organic substrates were released into the liquor, which induced the increases of soluble COD. A high percentage of organic matter solubilization that exceeds 25% was obtained after EF treatment. Results of anaerobic treatment have shown that when the reactor was fed with EF processed sludge higher methane production rates were obtained in comparison to raw WAS. Keywords: waste activated sludge; electro-Fenton; solubilization; anaerobic digestion; biogas yield

Introductıon In the last few years, the number of municipal wastewater treatment plants in Tunisia was increased significantly which results in the production of large quantities of waste activated sludge (WAS) that should undergo stabilization. Aerobic stabilization of WAS has been shown to cause poorer dewatering properties and at the same time, increases the biopolymer content in solution [1]. For this reason, anaerobic digestion process of sludge is often employed to reduce the mass of solids, reduce their pathogen content and lead to an energy recovery bonus in the form of methane gas production. The rate-limiting step for anaerobic digestion of WAS is the hydrolysis step [2]. This step is both slow and incomplete because the individual cell membranes are not significantly degraded in conventional anaerobic digestion [3]. In order to improve hydrolysis and anaerobic digestion performance, using cell lyse pretreatments is one possible and effective route. Therefore, several methods to solubilize or hydrolyze sludge cells prior to anaerobic digestion have been developed, which include mechanical [4], chemical [5] and thermal treatments [6]. Recently, there has been considerable interest in identifying new technologies that are capable of meeting more stringent treatment standards. For this purpose, advanced oxidation processes (AOPs) have a more prominent role in the treatment of waste because it provides some significant advantages such as quite compact and easy operation and automation, no chemical additives, a shorter retention time, high sedimentation velocities, more easily dewatered and reduced amount of sludge due to the lower water content. Fenton technology is one of the commonly used AOPs. Here, ferrous iron is used to initiate and catalyse the decomposition


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of H 2 O 2 and produce hydroxyl radical (•OH) in Fenton system. Fenton’s reagent has been mainly used to improve the dewatering property and reduce sludge production [7]. Ming-he and Chao-ha [8] examined the minimization of excess sludge produced in the MBR with the help of the sludge Fenton oxidation. It was found that Fenton oxidation can disrupt the cell walls and cause the release of plasm from the cells, thus increasing the content of soluble organics and soluble nitrogen in the solution. Therefore, in this study we present the main results of our study about the effect of this EF method on physicochemical characteristics and anaerobic digestion enhancement of WAS.

Methods The electrolysis reactor is formed by one pair of anodic and cathodic electrodes (cast iron plates) which are positioned approximately 1.5 cm apart from each other. The current input was supplied by a convergy power supply. The EF reaction started by adding H 2 O 2 and by supplying current to electrolysis reactor. The digester was initially inoculated with a sludge obtained from a municipal wastewater treatment plant and was acclimated for 3 months. The influent was fed one time into the reactor using a pump. The gas flow rate of the reactor was measured by liquid displacement.

Fındıngs and Argument Results has demontrated that in comparison to raw WAS, biogas production of pretreated sample was observed to be important at mesophelic and thermophelic condition without indication of inhibition. Furthermore, the highest biogas production rates were obtained during the mesophilic digestion of WAS. The biogas yield at the end of fermentation in serum bottles containing pretreated WAS were 0.146 and 0.125 L biogas/g VS respectively at mesophilic and thermophilic condition where an enhancement of biogas production about 2.3 and 5 fold was noted, respectively. This finding proves that the anaerobic digestion was improved, and that WAS is more readily and rapidly digested after EF pretreatment. To prove these results, AD experiments were conducted in a CSTR and the fermentation was lasted for 80 days. The applied organic loading rate and biogas production vs. fermentation time are recorded in Fig. 1. From this figure, the biogas production increased with the increase of OLR. It reached 1.4 L/d at an OLR of 4 g COD/L reactor/d. An increase of biogas yield was also shown. It fluctuated between 0.1 and 0.25 L/g COD introduce at OLR of 0.75-2 g COD/L reactor/day. With the increase of time fermentation, an improvement of biogas yield was observed. It reached to an average value of 0.45 L/g COD introduced at an OLR of 4 g COD/L reactor/d. However, a biogas yield about 0.05 L/g COD was obtained by digesting raw WAS (data not shown). This demonstrate the positive effect of EF the anaerobic digestion of WAS.


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Fig.1: Evolution of organic loading rate and biogas production during anaerobic digestion of pretreated WAS.

Conclusion This study represents the first scientific attempt on the application of electro-Fenton oxidation pretreatment for improving WAS anaerobic digestion. From the date reported above, EF is an effective technology for improving the disintegration/hydrolysis and the anaerobic digestion performance of WAS. The stimulation of anaerobic digestion can be explained by: (i) the improvement of biodegradability, (ii) the acceleration of biochemical hydrolysis reactions prior to anaerobic digestion and (iii) the increase of methanogens activity in the presence of iron.

Acknowledgment Thanks to the financial support provided by‘‘Contrats Programmes Ministère de l’Enseignement Supérieur et de la Recherche Scientifique and by the International Foundation for Science (Research Grant Agreement No W/5412-1).

References [1]

Y. Liu and J.H. Tay, “Strategy for minimization of excess sludge production from the activated sludge process,”

Biotechnol. Adv., vol. 19, pp. 97–107, 2001. [2]

C. Bougrier, J. Delgenès and H. Carrère, “Impacts of thermal pre-treatments on the semi-continuous anaerobic digestion of

waste activated sludge,” Biochem. Eng. J., vol. 34, pp. 20–27, 2007. [3]

S. Borowiski and J. S. Szopa, “Experiences with the dual digestion of municipal sewage,” Biores. Technol., vol. 98 ( 6),

pp. 1199-1207, 2007. [4]

C. Schuster, “Mechanical sewage sludge treatment,” Chem. Ing. Tech., vol. 79, pp. 1871–1881, 2007.

[5]

I. Dogan and F.D. Sanin, “Alkaline solubilization and microwave irradiation as a combined sludge disintegration and

minimization method,” Water Res., vol. 43, pp. 2139–2148, 2009. [6]

D. Jolis, “High-solids anaerobic digestion of municipal sludge pretreated by thermal hydrolysis,” Water Environ. Res., vol.

80, pp. 654–662, 2008. [7]

R. Dewil, J. Baeyens and E. Neyens, “Fenton peroxidation improves the drying performance of waste activated sludge,” J.

Hazard. Mater., vol. 117, pp. 161–170, 2005. [8]

H. Ming-he and W. Chao-hai, “Performance of membrane bioreactor (MBR) system with sludge Fenton oxidation process

for minimization of excess sludge production,” J. Hazard. Mater., vol. 176 (1-3), pp. 597-601, 2010.


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THE ANAEROBIC CO-DIGESTION OF HOUSEHOLD WASTE AND DROMEDARY DUNG FOR BIOGAS AND BIOFERTILIZER PRODUCTION

Benaissa Kheira1,2, Dadamoussa Belkhir1, Bendraoua Abdelaziz2, Drici Habiba1, Labed Brahim1 1

Laboratory of scientific research Sciences & Environment (Bio-resources, Geochemistry-physic, Legislation and SocioEconomic Development),University Centre of Tamanghasset, 10034 Tamanrasset, Algeria

2

Department of Industrial and Organic Chemistry, Faculty of Chemistry, University of Sciences and Technology of Oran Mohamed Boudiaf, BP, 1504 El-Mnaouar, 31000 Oran, Algeria [email protected]

Keywords: Biogas, biotechnology, environment, municipal solid waste, dromedary dung, energy.

ABSTRACT In an effort to convert waste to energy in a green process, five digesters with 5 liters capacity were operated to study the effect of dry co-digestion of household waste (HW) and dromedary dung (DD) manure without continuous stirring on biogas product quality and efficiency. The inoculation was made by sewage sludge water (SSW). The pH, Conductivity, DO, BOD, COD, Clfree, Cltotal, Ptotal, NO3-, NO2-, Ntotal, TOC, C/N were investigated during experiment period (over 30 days). The result had shown that the methane yield from the mixture of the HW with the DD and SSW, the DD with the SSW, and the DD with HW, respectively, in mesophilic (T= 35°C) conditions was about 75%, 68% and 57%. This study had indicated that the co-digestion of the DD, the HW and the SSW is highly desirable substrate for anaerobic digestion with regards to their well balanced nutrient, high methane yield and biofertilizer quality.

INTRODUCTION Algeria is experiencing a pressing need for household waste management. Currently, according to the National Cadastre for Solid Waste Generation, approximately more than 30 tons of municipal solid waste are generated per day. Energetic valorization of municipal solid waste (MSW) seems to be an alternative solution for sustainable development of Algeria, while at the same time minimizing the global warming impact resulting from methane emissions in landfills and fossil fuel consumption reduction. The present study describes a laboratory scale experimental evaluation of the biogas production from five different mixing in batch reactors, under similar conditions for 30 days at 35°C, allowing for microbial biomass growth. It is then important to define the ultimate biogas potential and methane yield for several solid substrates, which this study is being the first on biogas production from the dromedary dung of Tamanrasset region (southern Algeria).

METHODS The Five-liter flasks were used as biodigester hermetically sealed. The exact volume of each bottle was defined by weighing the water contained in the bottle. Substrates were made up from the digestion of the organic


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fraction of municipal solid wastes (waste from fruits and vegetables) (MSW), sewage sludge water (SSW) and dromedary dung (DD) and co-digestion of mixing manures, under mesophilic conditions. A conditioned room was provided with a thermostat with 35°C. The substrates had been through size reduction and were sampled just before the injection to the digester and daily during experiment period. The substrates were allowed to digest for more than 30 days at 35°C. The batch digesters were mixed in line with minimally intermittently mixed by turning the flask 180° and back up again at each sampling. The batch digestion flasks were set up as a BMP experiment, with the aim to study the substrates potential for biogas and methane production rates. pH, DO, COD, P total , N total , TOC, C/N were measured using SX736 multiparameter for physico-chemical parameters and Hach DR1900 spectrophotometer for chemical analyses. The biogas produced was determined directly through positive liquid displacement and the methane yield quality was tested by flame test. Table 1. Caracterisation of sampled input materials.

Item

N °

p H

D O

T S (%)

OD

(mg/L) DD

D 1

DD + HW

.7 D

2 DD + SSW

D

SSW + DD +

.8

.16

0

5

.2

1

0 .24

2.1

5

3 927

2

4 089.54

1 933.3

17 5.373

412.91

4025.8

9.12

4

8

16

2 6900

(mg/L)

13

2

1

(mg/L)

86.9

3.212

7356

OC

22

1

T

otal

718.8

3.164

6972

1 6

4

3

Nt

14 5.946

5461

1

.8 D

(mg/L)

5

3

0

6

otal

2013

1.9

.1

4

8

0

7

D

SSW+ HW

0

6

Pt

(mg/L)

.1

.2

3 HW

6

C

3 645.45

2 265.2

3 761.52

DO, dissout oxygen; TS, total solids; COD, chemical oxygen demand; P total , total phosphorus; N total , total nitrogen; TOC, total organic carbon.

FINDINGS AND ARGUMENT As waste analysis is one of the most important steps in the anaerobic digestion process, knowing the general composition of the input material to the system is essential for calculating the amount and composition of the biogas produced as well as the amount of energy contained in the biogas. Dromedary dung used as feedstock in this study, taken from a camel farm in Tamanrasset (southern Algeria). The inoculation sludge was collected from the Office National d’Assainissement (ONA) of the city of Tamanrasset. Characteristics of the household waste (HW) collected from the university restaurant (CUTam), the dromedary dung (DD) and the sewage sludge water (SSW) are summarised in Table 1.


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Digestion of mixtures with dromedary dung, household waste and sewage sludge water (DD+HW+SSW, DD+SSW and DD+HW) yielded significantly higher biogas potentials (75%, 68% and 57%) when compared to dromedary dung, household waste alone (45%) is justified by the benefits of co-digestion. However, the lower volume of biogas was product from the mixing of sewage sludge water and household waste (SSW+HW). In general, anaerobic co-digestion produces higher amounts of biogas and methane than anaerobic digestion of the individual substrates separately (T. Cestonaro et al., 2015; Pagés-Díaz et al., 2015; Borowski and Kubacki, 2015; Yong et al. 2015). The lower levels of biogas produced by substrate containing the mixing of sewage sludge water and household waste (SSW+HW) resulted mainly from the high content of fatty acids which provides a barrier to chemical and biological degradation and inhibitates the process of anaerobic digestion. A pre-treatment with NaOH was performed here (at the 7th day of digestion). The pH of samples had reached adequate values, possibly due to the formation of organic acids. The duration of the experiment observed for all experimental conditions was 30 days. The test of the flame was made but there were good flame just for the D4, D3 and D1, respectively. Table 2 shows the characteristics of the final biofertilizer. Two important factors correlating with the chemical composition of the biofertilizer were initial characteristics of the manure (Table 1) and the conversion efficiency of the organic fraction into biogas, which altered the concentration of nutrients in the medium. In general, biofertilizers are used as sources of nutrients rather than to modify the physical properties of the soil. Neverless, it is important to evaluate biofertilizer stability to ensure that, when applied to the soil, the biofertilizer will not behave as a manure in natura (fresh manure). The result (see Figure 1) showed that the C/N ratio of all manures is ranging from 20 to 25, which presents good quality of well balanced nutrient biofertilizers. Table 2. Caracterisation of the final biofertilizers obtained by anaerobic digestion.

Item

T °

S (%)

OC (mg/L)

DD .8

46.14

DD + 2

1.9

2 2.3

76 3

1

137.5

2 3.8

83 4

1

637.5

SSW+ HW

2.5

750

SSW + DD + HW

2

88

DD + SSW

/N

34 1

HW

C

2 5

75 5

2.1


150

2 1.8

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Figure 1. C/N. Results from the digestion experiment of five flasks.


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Study Nutrition Facts of a Sub Product Agro Food and Beverage Used In Domestic Ruminant Boudersa Hind, Haddi Mohamed laid To evaluate the nutritional value, the determination of the chemical composition of animals feed and agree-food residues is done by studying some important physicochemical characteristics such as total sugars, nitrogenous matter, and this in order enhance these vegetable by-products that can have a very high nutritional quality which can replace the concentrates very expensive or complete the fodder deficit, incorporating in the diet of animals and also to protect the environment of the large pollution resulting from waste. In our work, we analyzed is wheat bran and the agree-food industry residue which is the orange residue. Our results show that the orange residue has an average of total sugars significantly higher (47.49). On the other hand, the chemical analysis of the residue shows that orange residues contain an average rate in nitrogenous material (5.80). Which can be considered to be more digestible? The agree-food by-products are under significant but varying nutritional quality. They are rich in digestible energy and provide opportunities for use in several categories of ruminants and especially orange pulps which are very important residues of the nutritional point of view, as they may be gradually incorporated into the diet of

feed rich in nitrogen (wheat bran), for

example, respecting the levels of a inputs to prevent the decrease in rumen pH which can cause acidosis problems to animals.

Keywords: valorization; chemical composition; agree -food by-products; ruminants


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OPTIMIZATION OF PROCESS OXIDATION FOR TREATMENT OF PARACETAMOL S. SLAMANI, F. ABDELMALEK, M. R. GHEZZAR, A. ADDOU Laboratoire des Sciences et Techniques de l’Environnement et de la Valorisation (STEVA), Faculté́ des sciences et de la technologie, Université de Mostaganem, 27000, Mostaganem, Algérie [email protected]

Keywords: Degradation, paracetamol, Fenton, Gliding arc, post-disccharge.

Introductıon Paracetamol (PCM) is a common analgesic drug widely used in the world; it poses a great problem for the aquatic environment. Advanced oxidation processes (AOPs) are the promising technologies employing hydroxyl radicals (•OH) to degrade refractory pollutants. In the present study, the treatment of PCM by gliding arc discharge (GAD) process was investigated, the gaseous species formed in the discharge, and especially the •OH radicals, induce strong oxidizing effects in the target solution. Nowadays, research has been focused on application of combined treatments in water/wastewater for removal of pharmaceuticals compounds. Consequently, in our study, the degradation of aqueous solutions of paracetamol was performed by coupling of GAD and Fenton oxidation.

Methods The PCM degradation was assessed by the reduction in total organic carbon (TOC) and the decrease in concentration of PCM solution followed by HPLC.

Discussion and Conclusions The results have shown the removal efficiency in term of PCM and its intermediates disappearance followed by HPLC and mineralization. The GAD generates active species; some of them are long life water-soluble moieties and are responsible for temporal post-discharge reactions (TPDR). Peroxynitrite (ONOO−) involved in postdischarge phenomena. Peroxynitrite may be formed according to Figure 1:[1]


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Discharge

Nitrous acid Peroxynitrous acid Nitric acid

•

OH

•

+ − + − + − N 2 + O2 → NO → H , NO2 → H , ONOO → H , NO3

H 2O2 Figure 1. Peroxynitrite plasma humid air formation. The Fenton reaction played a role of accelerating removal by the formation of additional •OH radicals leading to an efficient and complete pollutant degradation.

Reference :

[1] Merouani.D. R, Abdelmalek. F, Ghezzar. M. R, Semmoud. A, Addou. A, Brisset. J. L. (2013). Influence of Peroxynitrite in Gliding Arc Discharge Treatment of Alizarin Red S and Postdischarge Effects. Ind. Eng. Chem. Res. 52:1471−1480


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The physico chemical and biological treatment of PAH contained in polluted marine sediments. 1

Krachai Naima , 1Hadjel Mohamed

1

Laboratoire Sciences, Technologie et Génie des Procédés LSTGP Université des sciences et de la technologie d’Oran MB.

Emails: [email protected], [email protected], [email protected]

Keywords: Marine sediments, Pollution, PAH, contamination, treatment, degradation.

Abstract The introduction by man, directly or indirectly, of substances or energy into the environment that can cause deleterious effects such as harm to living resources, hazards to human health, hindrance to marine activities, including fisheries , deterioration of quality of seawater for its use and reducing opportunities in the field of leisure. The most contaminants of concern for the marine environment are those that show a persistence in the environment, an ability to be transported over long distances, a tendency to bioaccumulate and vis-à-vis toxicity of non-target organisms. The identification of environmental contamination by PAHs therefore often requires the implementation of effective analytical techniques. Among the listed PAHs benzo (a) pyrene (the most studied for toxicity) and fluoranthene (the most widespread in the environment. PAHs are relatively refractory compounds to biological degradation. The last thirty years, research on the degradation of PAHs led to the isolation of many species of bacteria capable of fungi and algae to degrade the low molecular weight PAHs (2-3 aromatic rings). The biggest PAHs are generally recalcitrant to microbial attack, some fungi and algae are able to transform. Our study is to make an assessment of pollution at the west coast Algerian who has become a highly polluted area saw the daily ocean dumping of urban and industrial wastewater. To promote Polluted sediment PAH, a method of treatment and degradation was developed, these PAHs have been treated namely Physico-chemical and biological for reuse in other business areas such as construction .


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GIBBERLIC ACID AND SALICYLIC ACID EFFECTS ON SEED GERMINATION AND SEEDLINGS GROWTH OF OKRA (ABELMOSCHUS ESCULENTUS L.) UNDER SALT STRESS. Yakoubi Fatima1, Belkhodja Moulay2 1,2

Laboratory of Plant Physiology, Department of Biology, Faculty of Science of nature and life, University of Oran 1 Ahmed Ben Bella, Algeria. Email

[email protected] [email protected]

Keywords: Abelmoschus esculentus L., gibberellic acid (AG3), salicylic acid (SA), phytohormons, salinity.

INTRODUCTION Seed germination is a critical stage for the survival of species. Salinity affects the germination, growth and yield of many crops. However, the exogenous application of natural plant growth regulators has been reported as one of the mitigation strategies. In this context, this work aims to test the effect of hormonal priming on germination and growth of okra (Abelmoschus esculentus L.) under induced salt stress. The germination and growth of seedlings okra are assessed by testing the effect of two levels of NaCl (0, 50 and 100 mM) in the presence or absence of gibberellic acid at 50 µM in the first part, and the 100 µM salicylic acid in the second part of experimentation.

METHODS Okra Seeds were surface sterilized in 2% sodium hypochloride for 7 min and thoroughly washed with distilled water. Seeds were pre-soaked in the hormonal solutions for 12 hours. After imbibition, the solution was decanted off and the seeds were re-dried near to their original weight for 12 h. The pre-soaked seeds were then placed in 9 cm Petri dishes containing double layer of filter paper. Experiment was designed in randomized complete block design (RCBD) in combination of NaCl stress treatments. All Petri dishes were then transferred to a controlled plant growthchamber under 16 hours’ photoperiod, 26±2°C temperature.


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Germination of seeds studied parameters concern precocity (BELKHODJA, 1996) and the mean germination time (TMG) (CORBINEAU and COME (2006)), while the growth parameters of young seedlings of one week old are estimated by measuring the length, the fresh and dry weight of hypocotyls and radicles of seedlings. Finally, the biochemical response of seedlings is evaluated by assaying soluble proteins by the method of (BRADFORD, 1976).

FINDINGS AND ARGUMENT The results show that NaCl significantly reduced precocity and the tmg, The earliness of germination and the TMG were strongly affected by salinity. Including 100 mM where germination is delayed by 48 hours compared to the control, against a 50 mM, the rate of raw sprouted seeds does not exceed 6%. The same observations are reported by KAYA and al. (2006) and ZEMANİ (2009). This seed germination delay caused by salt stress, can be justified by the fact that the seed submitted to salt stress does can not after a certain time put in place mechanisms to adjust its internal osmotic pressure (BLISS et al., 1986 JAOUADI and al., 2010). Seedling growth is severely affected by salinity. A gradual decrease in the length of hypocotyls and radicles of seedlings was recorded with increasing salt concentrations. MA et al. (1999) and SHAHEEN et al. (2014) indicating that the okra is a sensitive species to salt. The decrease observed in okra plant is explained by the fact that NaCl works by increasing the osmotic pressure of the medium, which prevents the absorption of water through the root system (MARSHNER, 1995; Navarro et al., 2002) and leads therefore, a reduction in growth. This increase and the more marked in the leaves than in roots The dry weight of roots and hypocotyls decreased significantly compared to non-saline conditions, while the stress induced increases in the soluble protein content in leaves and roots of okra seedlings. This increase could come from defense reactions of plants deal with stress (LEPENGUE and al., 2012), because under salt stress proteins, accumulate and act as osmotic regulators (AHMAD and al., 2003), such as proteins HSE (Heat Chock Protein) (TOMANEK and SOMERO 2002) and LEA (late embryogenesis abundent) (HAND and al., 2011) The application of hormones causes a significant change in behavior vis-à-vis seeds of salt stress; Indeed, the study of two plant hormones showed that the seeds undergoing combined treatments NaCl / AG3, NaCl / AS, have a high germination capacity than those treated with NaCl alone while accelerating seed germination. Similarly these plant hormones played an important role in improving the yield of above and below ground biomass.

Conclusion Okra is a sensitive species in salt, and tolerance is largely dependent on the applied NaCl concentration. The most depressing effect was obtained in the concentration of 100 mM NaCl.


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However, pretreatment of seeds with gibberellic acid (GA 3) and salicylic acid (SA) can contribute to mitigating the deleterious effects of salt stress and improve seed germination and seedling growth of okra. The gibberellic acid (AG3) 50 µM, seems more effective in mitigating the negative effects of salt stress compared to salicylic acid. This appears clearly superior in both salinity levels tested.


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Communication type: Poster Presentation Session: Biological and Physicochemical treatment

Valorization of agro industrial by-products and wastes for biosurfactants production DerguineLouizaa, Gana-KebboucheSalimab, Djenane Djamel c a,c

: Laboratoire de recherche sur la qualité et la sécurité des aliments, Université Mouloud Mammeri de Tizi Ouzou, Algérie.

b

: Laboratoire VALCOR, Département de Biologie, Université M’Hammed Bougara de Boumerdès, Algérie. [email protected]

Abstract: Biosurfactants are amphiphilic compounds produced by a variety of yeasts, bacteria and filamentous fungi. They have a wide range of applications in food, cosmetics and pharmaceutical industries and also have environmental applications. The unique properties of biosurfactants such us environmental compatibility, biodegradability, low toxicity, resistance to extreme conditions of temperature, pH and salinity, make them potential alternative for syntheticsurfactants.However,the high price of productivity and low yields, make the biosurfactants not competitiveyet withtheir chemical counterparts .One of the strategies overcoming this problem is to search a low effective media and cheap substrates for biosurfactants production .In this study one hundred yeast strains isolated from different samples in Algeria were screened for biosurfactants production. All of the yeast isolates were grown in mineral salt medium (MSM) with addition of 2% (v/v) crude oil as carbon source. The presence of biosurfactants was evaluated by the emulsification index (E24), dropcollapse test, oil spreading test, CTAB agar test and hemolytic activity. Thirty strains were positive for almost all the qualitative tests, they were identified by morphological, physiological and biochemical tests. More interestingly one isolate was the best strain for biosurfactants production with an emulsification index of 65.72%, it was identified using 5.8s-rDNA Analysis. This isolate produced biosurfactant optimally at pH 6, temperature of 30°C and agitation of 200 rpm. Furthermore, the isolate produced biosurfactants when grown in low-cost fermentative medium based on agro industrial by-products and wastes aiming to valorize industrial wastes and cost reduction like whey, molasses,Corn steep liquor and date juice with E24 of respectively 61.53%, 58.33%, 38.88% and 80%.TLC and FTIR characterization of produced biosurfactants showed that the strain produce glycolipid biosurfactants. Key-words:Yeasts, biosurfactants, E24test, optimization, valorization.


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Effect of different agricultural wastes types on the yield of oyster mushroom (Pleurotus ostreatus)

Zainab ,M.T.Jaafar ., Dahash .N.M. , Hassan .L.R. Directorate of agricultural Researches / Ministry of science and Technology . P.O.Box. 675 Email : [email protected]

Abstract Advances in mushroom technology and management strategies are needed to address urban development around farms; increased intensity of cropping systems; and grower's requirement for improved mushroom yield, quality and shelf life. When cultivation the oyster mushrooms, we must put ability use locally low-cost wastes in this agriculture , so the aim of this study is to : evaluate the better performance of oyster mushroom in different substrate compositions as well as to find out the better substrate for mushroom cultivation .It was used three types of agricultural wastes ( wheat straw , leaves of date , fibers of date tree ) .The results demonstrate that the wheat straw was the best in the yield performance , it gave average weight 0f fruit bodies 106.6 gram with number of 15.3 fruit bodies , mushroom size was 7.05,9.2 9 cm in diameter and stipe length was 5.2 cm .While in date fiber gave yield of 105 gm /fruit body , with number 10 .5 of fruit body , mushroom size 7 .3,5.3 cm in diameters , and stipe length was 7 cm , and lastly in date leaves gave average weight 73.3 gm of fruit body , with mushroom size 5.5 ,5.5 cm in diameter and stipe length was 8 cm . Key word : oyster mushroom , mushroom size , yield performance.

Introduction: Mushrooms of Pleurotus spp. are commonly known as oyster mushrooms which occupy the second position among cultivated edible mushrooms worldwide due to their nutritional and medicinal values

.

Mushroom cultivation presents an economically important biotechnological industry that has distinguish expanded all over the world in the last few years. Mushroom cultivation mainly depends on the agriculture crop residues.These crop resides are abundantly available in our country It is primarily used as cattle feed and remaining part is burnt or spread in the field. Agro-wastes contain about 80% cellulose, hemi-cellulose, and lignin which are not easily degradable, but most of the edible fungi posses enzyme system which degrade these components. Thus mushroom cultivation can avoid environmental pollution by recycling agricultural wastes and can also convert straw into easily digestible animal feed (RAM AND KUMAR 2010).


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METHODS: Spawn Preparation Mycelium of P. ostreatus was obtained from Cairo university / center of food biotechnology The mucelium was grown on wheat grains .Incubation was achieved darkly at 24°C ± 1°C for 3 weeks until the complete growth of mycelia . 3% of spawn was used on wet based of the substrate for inoculation these substrates (Singh and Singh, 2011) . Cultivation and Yield Performance Three types of Substrates were cultivated (wheat straw, date leaves, date fibers) using layers in depth 5 cm ,spawn added then another layer of substrate added until filling then closed. Incubation was achieved darkly at 24°C ± 1°C for 3 weeks until the complete growth of mycelia in the whole packet. 10°C for 48 h was carried out as cold shock to induce pin heads formation, packets opened with 24°C ± 1°C, 80-90% humidity, lighted using fluorescent light, and aerated twice per today so primordial form that developed to fruiting bodes, which harvested in best yield size (Epogee, 2011).

Finding and Arguments Three different types of substrates were investigated to determine the growth and yield of P. ostreatus. Mycelial growth is a preliminary step that creates suitable internal conditions for fruiting. Thus, outstanding growth of mycelium is a vital factor in mushroom cultivation (Pokhrel et al. 2009). Colonization of the substrate was completed in between 22.40-26.00 days of incubation. Similarly primordial initiation on various substrates was also observed in between 26.40-31.60 days of incubation. The total day for the first harvest of mushroom took between 32-37 days, depending on substrate used. The results demonstrate that the wheat straw was the best in the yield performance it gave average weight 0f fruit bodies 106.6 gram with number of 15.3 fruit bodies , mushroom size was 7.05,9.2 9 cm in diameter and stipe length was 5.2 cm .While in date fiber gave yield of 105 gm /fruit body , with number 10 .5 of fruit body , mushroom size 7 .3,5.3 cm in diameters , and stipe length was 7 cm , and lastly in date leaves gave average weight 73.3 gm of fruit body , with mushroom size 5.5 ,5.5 cm in diameter and stipe length was 8 cm .

CONCLUSION Mushroom cultivation is one of the efficient ways by which residues can be recycled. P. ostreatus grown on different substrates are nutritious with high protein ,fiber and low fat. It may also offer economic incentives for agribusiness to examine these residues as valuable resources and develop new enterprises to use them to produce nutritious mushroom products. Therefore, the mushroom cultivation may become one of the most profitable agribusiness that could produce food products from different substrates and help to dispose them in an environment friendly manner.

Recommendations: The need for education and research :Mushroom growers need both experience and education. Mushrooms are often thought of as an easy crop to produce with a high price potential. People often find 2nd ICIEM 2016, International Conference on Integrated Environmental Management for Sustainable Development Page 555

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mushroom cultivation is not as easy as they thought it would be. Much of the necessary knowledge must be acquired through practical experience, but understanding the principles of mushroom cultivation demystifies the process, allowing the grower to successfully adapt and develop cultivation methods


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Physiological effects of Pergularia tomentosa extract alone or in combination with the aggregation pheromone, phenylacetonitrile, on Schistocerca gregaria nymphs Meriem Miladi1, Khemais Abdellaoui1, Mouna Ben Cheikh1, Iteb Boughattas2, Fatma Acheuk3, Monia Ben Halima-Kamel1 1

Département des Sciences Biologiques et de la Protection des Végétaux, Institut Supérieur Agronomique de ChottMariem, 4042, Université de Sousse, Tunisia. 2

Laboratoire de Biochimie et de Toxicologie Environnementale, Institut Supérieur Agronomique de Chott-Mariem, 4042, Université de Sousse, Tunisia.

3

Département de Biologie, Faculté des Sciences, Université M’hamed Bougara, Avenue de l’indépendance, 35000 Boumerdes, Algeria.

Abstract and keywords For an environmentally and sustainable approach to locust control, the active fraction of P. tomentosa (AFP) (Asclepiadacae) and the aggregation pheromone, phenylacetonitrile (PAN), were evaluated against Schistocerca gregaria nymphs. Firstly, the plant extract was investigated alone by exposing the freshly emerged (0–1 day-old) nymphs to three concentrations 0.06, 0.24 and 0.96% denoted, respectively as AFPC1, AFPC2 and AFPC3.

Other experiments were conducted to assess the effect of AFP and PAN in binary

combination. The PAN has been associated at three concentrations (0.5, 1 and 2%) to the lethal concentrations of AFP LC 25 and LC 50 . Nymphs were treated either topically with a homogeneous mixture (PAN + AFP: 1v/1v) or exposed to PAN for 2, 4 and 6 hours and then treated by the AFP. Results showed that the AFP exhibited toxicity against S. gregaria nymphs with an LC 50 value of 0.8 and 0.41%, respectively for topical application and ingestion after 11 days of treatment. AFP toxicity was also demonstrated by perturbation of the moult processes. In fact, we noted that treated insects present exuviations difficulties due to the impossibility to reject the old integuments causing mortality in the 5th instar larvae. Histological study of foregut revealed alterations in the epithelial cells and a total disorganization of the structure of this organ. Toxicity bioassays also showed that the combination of PAN with the AFP significantly increased the larvae mortality. The pheromone has affected the health of treated insects which becomes more sensitive to the AFP. Indeed, treated larvae become hyperactive and disoriented and have a higher level of cannibalism. Immunological studies (prohemocytes and plasmatocytes) in the haemolymph of treated nymphs show physiological stress explaining their increased sensitivity to AFP. Biochemical analysis demonstrated that the PAN induced GSTs and reduced the activity of AChE on S. gregaria nymphs. The PAN seems also to have a solitarising effect on gregarious nymphs of S. gregaria. Keywords: S. gregaria, P. tomentosa, phenylacetonitrile, toxicity, Stress biomarkers.

Introductıon Migratory locusts represent the most important crop pests in Africa and Asia. Because the dangers associated with the use of synthetic insecticides like environmental pollution, development of insecticide resistance and adverse effects on non-target organisms, new environmentally friendly methods of locust


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control are becoming increasingly important. Research in recent years has been turning more towards selective biorational pesticides. Among these botanical insecticides have attracted the greatest attention and have been reviewed extensively (Abdellaoui et al. 2013). In the same context, Hassanali et al. (2005) discovered that Phenylacetonitrile (PAN), a pheromone produced by the adult male of the desert locust has effects on the behavior of the larvae and it sensitivity to insecticides. The present investigation is an attempt to explore the effects of the active fraction of P. tomentosa (AFP) and the aggregation pheromone, phenylacetonitrile (PAN), against S. gregaria nymphs.

Methods Treatments The effects of the AFP on S. gregaria nymphs were investigated by exposing the freshly emerged (0–1 day-old) larvae to three concentrations 0.06, 0.24 and 0.96%. The freshly emerged larvae (n = 30 for each concentration), procured from the stock culture, were treated topically, by applying 2 µL of AFP solution on their dorsum with a micro-applicator, or by ingestion. For ingestion, the AFP was sprayed on the food of larvae. Mortality data were corrected using Abbott’s formula (Abbott, 1925). The lethal concentrations (LC 25 and LC 50 values) with their 95% confidence limits were calculated using the Probit analysis (Finney, 1971). The PAN was associated to the lethal concentrations of AFP, LC 25 and LC 50 , at three concentrations 0.5, 1 and 2%. Larvae were treated by two methods: topically with combined treatment (AFP+PAN: 1v/ 1v) or by exposure to PAN (2, 4 and 6h) followed by AFP application.

Histology and immune system study Histological procedures were conducted according to Martoja and Martoja (1968). The foregut was dissected in physiological liquid (Ringer’s solution) and fixed in Bouin’s solution for 3 days. Transverse sections (7 µm) were stained with Mallory liquid. For haemocyte counting, 3 µL of haemolymph was placed on a glass slide and smeared to a thin film. The smears were first stained with diluted MayGrunwald stain for 3 min, then washed with distilled water and stained for a second time with diluted Giemsa for 10 min then washed again in distilled water (Guzo and Stolz, 1987). The haemocytes were observed under light microscope with 100 × oil immersion objective and identified according to Gupta (1979). Enzymatic assays The acetylcholinesterase activity (AChE) was determined according to the method of Ellman et al. (1961) and the glutathione S-transferase (GST) activity was measured by the method of Habig et al. (1974).

Fındıngs and Argument -

The results reported in table 1 show that the AFP exhibited insecticidal activity against S.

gregaria nymphs with an LC 50 value of 0.8 and 0.41%, respectively for topical application and ingestion. AFP toxicity was demonstrated by exuviations difficulties causing larval mortality and increased percentage of abnormal imagos emerging.


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Table 1. Toxicity of the active fraction of P. tomentosa against S. gregaria nymphs. LC 25 a,b

LC 50 a,b

2

square (χ ) To pical application

0.22

0.80

(0.32-

(0.51 -

0,51)

In gestion

P-

Chi f

value

0

date pedicels (19.47 mg/g). As results, the present study shows these wastes tested can be acceptably used as sorbent materials for the removal of acid dyes from synthetic aqueous solutions but in acidic medium. Keywords: removal, bemacid yellow, low-cost sorbent materials, kinetics, equilibrium.

1.Introduction Synthetic dyes are extensively used for dyeing and printing in industries. Their presence in watercourses is aesthetically unacceptable and may be visible at concentration as low as 1 ppm [1]. Moreover, they may also affect photosynthetic activity in aquatic systems by reducing light penetration [2]. Among the various types of dyes, various acidic dyes are used to color nylon, wool, sole in textile industries, paper and leather. This class of dyes is the most problematic, because they tend to pass through conventional treatment systems unaffected [3]. As a result, there is a search for low-cost, naturally occurring, abundant sorbent materials that can serve as viable alternatives to activated carbon.


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ISSN 1737-3638 This work compares the sorption performances of three biological wastes namely: orange (Tomson variety) peel, pomegranate peel and date pedicels, as sorbent materials for the removal of bemacyd yellow (acid dye), as a model of acid dyes, from synthetic aqueous solutions. These materials are abundantly available in Algeria, hence cost effective sorbents. Dye sorption equilibrium and kinetics tests at solution initial pH value of 2.20 were performed in batch conditions. The influence of some parameters such as: contact time and initial dye concentration on dye sorption kinetics, has been studied. Two simplified kinetic models including a pseudo firstorder and pseudo second-order models were selected to analyse the dye sorption kinetics. In order to describe the dye sorption isotherms mathematically and to obtain information about the maximum dye sorption capacity of each sorbent tested, the experimental sorption equilibrium data were analysed using only the Langmuir model.

2. Methods

2.1. Sorbents: In this work, three agricultural solid wastes: orange (Tomson variety) peel, pomegranate peel and date pedicels, were used as sorbent materials, because there are cheap and highly available lignocellulosic wastes in Algeria. These wastes were purchased from a local market in autumn-winter 2011 in the form of large flakes. Firstly, there were cut in small pieces, sun/air dried at ambient temperature during many days and oven-dried at 80 °C for 24 h. To be used as sorbent materials, these wastes were washed thoroughly with tap water to remove all the adhering dirt particles until no colour was observed, rinsed using a distilled water until the pH of solution was stabilized, filtered and then oven-dried at 80°C for 24 h. Then, there were crushed and sieved to keep only the size range 1.25-2 mm.

2.2. Dye: Bemacid yellow E-TL (Bezema Suisse) as a commercial salt with unknown structure, was kindly donated by SOITEX Company located in the City of Tlemcen-Algeria and used as received without further purification, in single component aqueous solutions. 2 000 mg/L stock solutions of dye were prepared in distilled water. All working solutions of the desired concentration were prepared by successive dilutions.

2.3. Sorption experiments

2.3.1 Uptake kinetics: In each sorption kinetics experiment, 2L volume of dye solution of known initial concentration in the range of 50-300 mg/L and solution initial pH adjusted to 2.20, was added to 2 g of each sorbent in a beaker agitated vigorously by a magnetic stirrer using a water bath maintained at a constant temperature of 25±1 °C. Samples from the clear supernatant, at appropriate time intervals, were pipeted from the reactor by the aid of the very thin point pipette, which prevented the transition to solution of sorbent samples. Their dye concentrations were determined using a UV-visible spectrophotometer (Lange Hach, model DR 5000, USA) by monitoring the absorbance changes at a wavelength of maximum absorbance: λ max = 390 nm. The dye uptake q t (mg dye/g sorbent) was determined by Eq. (1) as follows: q t = ( C o - C t ) x V/m


(1)

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ISSN 1737-3638 where C o and C t are the initial and time dye concentration (mg/L), respectively, V is the volume of solution (mL); and m is the sorbent weight (g) in dried form.

2.3.2. Uptake equilibrium: The dye equilibrium isotherms were determined by contacting a constant mass 0.200 g of each sorbent material with equal volumes of dye solution 200 ml of different initial dye concentrations in the range: 25-700 mg/L with an initial solution pH adjusted to 2.20 by adding small amounts of HCl 1N. The mixture obtained was agitated in a series of 250 ml conical flasks for a period of 24 h at room temperature (25 ± 1°C). The mixture pH was not controlled after the initiation of experiments. At equilibrium, the final pH was measured. The equilibrium concentration of unbound dye was determined with a UV-visible spectrophotometer as previously described. The equilibrium dye uptake q e (mg dye/g adsorbent) was determined by Eq. (2) as follows: q e = ( C o – C e ) x V/m

(2)

where: C o and C e are the initial and equilibrium dye concentration (mg/L), respectively, V is the volume of solution (mL), and m is the sorbent weight (g) in dry form.

3. Findings The present study has shown that the three wastes tested in this work, can be acceptably used as sorbent materials for the removal of bemacid yellow from synthetic aqueous solutions but in acidic medium. For each sorbent, the quantity of dye sorbed at equilibrium was initial dye concentration dependent: it increased with increasing of initial dye concentration. In general, the necessary time to reach equilibrium was in the range 9-10 h. The sorption kinetics of bemacid yellow by each sorbent was well described by a pseudo-second order rate model. A good fitting of dye sorption equilibrium data was obtained with Langmuir model in all the range of concentrations studied. Under the investigated experimental conditions, the maximum dye sorption capacities obtained by these sorbents followed the order: pomegranate peel (30.81 mg/g) > orange peel (29.59 mg/g)) > date pedicels (19.47 mg/g). These results are encouraging in spite there are still several very important aspects to clarify.

REFERENCES

[1] Zollinger H., (1991), Color chemistry: synthesis, properties and applications of organic dyes and pigments, 2nd Edition, VCH Publisher, New York. [2] O’Mahony T., Guibal E, Tobin J.M., (2002), Reactive dye biosorption by Rhizopus arrhizus biomass, Enzyme Microbiology and Technology, 31, 456-463. [3] Robinson, T., McMullan, G., Marchant, R. and Nigam, P. (2001). Remediation of dyes in textile effluent: a critical review on current treatment technologies with a proposed alternative. Bioresource Technology. 77: 247–255.


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Adsorption of Reactive Dyes from aqueous solution by dirty bentonite

Kahina Bentaleb1,2, Kheira Chinoune1, Zohra Bouberka1,2, Bagdad Ouddane3, Ulrich Maschke1 1

Laboratoire Physico-Chimie des Matériaux - Catalyse et Environnement – LPCM-CE, Université des Sciences et de la Technologie d’Oran Mohamed Boudiaf (USTO-MB), BP 1505, El M’naouer, 31000 Oran, Algeria E-mail: [email protected] 2

Unité Matériaux et Transformations – UMET (UMR CNRS N° 8207), Bâtiment C6, Université Lille 1 - Sciences et Technologies, 59655 Villeneuve d’Ascq Cedex, France E-mail: [email protected]

3

Laboratoire de Spectrochimie Infrarouge et Raman (LASIR), UMR CNRS N°8516, Université Lille 1 – Sciences et Technologies, 59655 Villeneuve d’Ascq Cedex, France E-mail: [email protected]

Keywords: Dirty bentonite, Reactive dyes, Rate kinetics, Adsorption studies, Thermodynamic parameters.

Abstract The preparation of magnesium hydroxide coated bentonite, B-Mg(OH) 2 composite, and its capacity to remove anionic reactive dyes; Procion blue HP (PB) and Remazol brilliant blue R (RB) from aqueous solution were reported in this study. The adsorbent was characterized by X-ray fluorescence analysis, X-ray powder diffraction, thermal gravimetric analysis, Brunauer Emmett Teller surface area analysis; scanning electron microscopy, and Fourier transform infrared spectroscopy. The effectiveness of B-Mg(OH) 2 composite to remove dyes was examined at different initial concentrations, pH, temperature and ionic strengths. At pH = 2, the maximum dye adsorption was found as 98.2% for RB and 87.8% for PB. Kinetic studies revealed that adsorption follows a pseudo-second-order model, and rate constants were evaluated. The Langmuir monolayer adsorption capacities of PB and RB in aqueous solution were estimated at 298 K as 40.22 and 66.90 mg/g, respectively. A temperature uptake from 278 K to 313 K induced an increase of adsorption for both dyes and the process was found to be physiosorptive, endothermic and spontaneous. Higher concentration or more valence of anions of electrolytes in dye solution caused decreasing dye adsorption efficiency of B-Mg(OH) 2 composite.


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Adsorption of 2,4-dichlorophenol from aqueous solution using modified Algerian geomaterial

Kahina Bentaleb1,2, Kheira Chinoune1, Zohra Bouberka1,2, Chems Eddine GHERDAOUI1,2, Bagdad Ouddane3, Ulrich Maschke1 1



3


Keywords: Adsorption, natural geomaterial, 2,4-dichlorophenol, isotherms, kinetics.

Abstract

The present study provides information about adsorption behaviour of 2,4-dichlorophenol (2,4-DCP) using modified Algerian Geomaterial (GM) as low cost and durable adsorbent material. Dodecyl and cetyl-trimethyl ammonium salts (DTAB and CTAB, respectively) were successfully applied to modifiy GM, and the resulting composites were denoted as GM-DTAB and GM-CTAB, respectively. Characterization of GM, GM-DTAB and GM-CTAB was carried out using X-ray diffraction, infrared spectroscopy, and surface area analysis. The results show increased sorption 2,4-DCP on the GM composites compared to natural GM. Effects of adsorption process parameters (adsorbent dose, pH, contact time, and initial 2,4-DCP concentration) have been investigated. Experiments results revealed that the optimum pH was obtained between 4 and 6 for 2,4-DCP removal. Adsorption mechanisms were evaluated using different adsorption isotherm models (Langmuir, Freundlich, and Temkin isotherms). Adsorption kinetics were investigated for intra-particle diffusion, Elovich and pseudosecond order reaction. It has been shown that 2,4-DCP could be adsorbed to high extent, more than 70 weight %, from aqueous solution using affordable modified GM.


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UV-visible light induced degradation of brominated flame retardants, dispersed in polymers Abdelouahab Nadim1, Zohra Bouberka1,2, Said Eddarir3, Bagdad Ouddane4, Ulrich Maschke1 1


2

Laboratoire Physico-Chimie des Matériaux - Catalyse et Environnement – LPCM-CE, Université des Sciences et de la Technologie d’Oran Mohamed Boudiaf (USTO-MB), BP 1505, El M’naouer, 31000 Oran, Algeria E-mail: [email protected]

3

Laboratoire de Chimie Bioorganique et Macromoléculaire (LCBM), Faculté des Sciences et Techniques, Marrakech, Morocco 4


Keywords: Persistant organic pollutants, polybrominated flame retardants, UV-visible irradiation.

Abstract Brominated flame retardants (BFR) represent chemical substances used within the framework of fire protection, to reduce the risks of ignition and propagation of fire. One finds them in a large product range like electrical and electronic equipments, textile and fabrics, wirings etc. The BFR comprise several families, whose principal one gathers Polybromodiphenylethers (PBDE), which are known under three major molecules: penta-BDE, octa-BDE and deca-BDE. These BFR have found widespread applications particularly as additives to polymeric resins and plastics. It is because of their “PBT” properties (persistence, aptitude for bio-accumulation and toxicity), that PBDE gradually became object of restrictions of use within European Union (U.E.) (ROHS) and other countries. In the present work, we investigate the degradation of BFR under different conditions. UV-visible light induced degradation processes were successfully applied as function of a large number of experimental parameters such as the energy of radiation, exposure time, and concentration of the initial toxic species. In particular, a certain number of debrominated intermediates, resulting from radiation of various BFR in organic media, were studied by spectroscopical and chromatographical techniques, namely UV-visible and Fourier transform infrared spectroscopies, high performance liquid chromatography (HPLC), as well as by gas chromatography coupled with mass spectroscopy. The degradation kinetics was followed by several analytical methods, it has been shown that the rate of degradation of BFR can reach more than 90%.


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Removal of polychlorinated biphenyls from organic media

Chems Eddine Gherdaoui1,2, Kahina Bentaleb1,2, Zohra Bouberka1,2, Bagdad Ouddane3, Ulrich Maschke1 1



3


Keywords: Environment, persistant organic pollutants, polychlorinated biphenyls.

Abstract Polychlorinated biphenyls (PCBs) are persistent toxic compounds in the environment. A high fire resistance, low electrical conductivity and slow degradation, make them useful as dielectrics in transformers and large capacitors, as heat exchange fluids, as paint additives, in carbonless copy paper and in plastics. Given their potential health hazard for humans and wildlife, the Stockholm convention in 2001 classified PCP and PCBs as Persistent Organic Pollutants. The safe and economical degradation of these compounds is one of the urgent problems for mankind because of their toxicity and carcinogenicity. PCBs are strongly resistant to biodegradation due to their chemical stability. Two methods of decontamination prove to be particularly relevant, namely the exposure of the PCBs to UV-visible radiation and their adsorption by the implementation of solids (with preliminary activation if necessary) such as nanomaterials based on clays. The application of other solids such as activated carbon and activated aluminas was also considered. The primary objective of this contribution is to evaluate the feasibility of using these processes for the removal of PCBs from organic media. The initial objective will be to study the influence of the UV-visible irradiation parameters on the effectiveness of the method, by measuring the photodegradation rate of the chlorinated derivatives.


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Comparative study of the toxicity of phenolic compounds of coriander (Coriandrum sativum L) and false fennel (Aneth graveolens) on Galleria mellonella (Lepidoptera, Pyralidae). Effect on feed intake Trebuchet Ms, 14 Font Sıze, Bold, Centered)

OULEBSIR-MOHANDKACI Hakima1, BOUYAHIAOUI Husseyn2, BABA AISSA Ahmed2, BADAOUI Said2 et AIT KAKI Sabrina3 1

Laboratory of Valorization and Conservation of Biological Resources, Faculty of Sciences, University M'hamed Bougara of Boumerdes, BP35000, Algeria ([email protected]) 2

Department of Biology, Faculty of Sciences, University M'hamed Bougara of Boumerdes, BP35000, Algeria. ([email protected])

3

Laboratory of Soft Technologies, Valorization, Physico-chemical of Biological Material and Biodiversity. University M’hamed Bougara of Boumerdès. 35000, Algeria. ([email protected])

Keywords: coriander, fennel false, Galleria mellonella, insecticidal activity, feed intake.

Introductıon (Heading Trebuchet Ms, 11 Font Size, Bold) The use of plant extracts as an insecticide has long been known. Indeed, several plants have been used as control agents against insects. Moreover, the wax moth (Galleria mellonela) is widely distributed around the world, causing serious problems in beekeeping. These problems are related to the destruction of the wax and the transmission of pathogens to bees.

Methods This study aims assessment of toxic effects of total polyphenols coriander (Coriandrum sativum L) and false fennel (Aneth graveolens) on L5 larvae of the wax moth Galleria mellonella and their effects on food intake. After, the realization of a phytochemical screening for the purpose of isolation and identification of phenolic compounds false fennel and coriander, we processed the fifth stage larvae of Galleria mellonela by administration by gavage of polyphenols.


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Fındıngs and Argument Treatment of larva by administration of polyphenols by oral gavages, resulted high mortality rates especially for the high dose (30

ɥl / m l) w hich ga

day for coriander. On the treatment by the tannins, it was noted that their insecticidal activity against Gallerea mellonella is less than that of polyphenols for the two plants studie The results feed intake, show that the amount consumed by the larvae treated with polyphenols is low, and these individuals stop eating from the 3rd day after treatment. This indicates that the chemical composition of phenolic compounds Umbelliferae has antifeeding properties towards Galleria mellonella. The results feed intake, show that the amount consumed by the larvae treated with polyphenols is low, and these individuals stop eating from the 3rd day after treatment. This indicates that the chemical composition of phenolic compounds Umbelliferae has antifeeding properties towards Galleria mellonella.

Perspectives emerge from this research; we should consider carrying out prior testing under natural conditions on the infected beehives to assess the effectiveness of these extracts in the fight against Galleria mellonella, and accurate identification the compounds responsible for the larvicidal activity of polyphenols work.


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Estimation of land-sea flux of suspended matter in the Algerian Basin: Application of Ocean Color Algorithms

Romaissa HARID1, Malik AIT KACI2, Fouzia BACHARI-HOUMA3 1

Ecole Nationale Supérieure des Sciences de la Mer et de l’Aménagement du Littoral (ENSSMAL), Laboratoire des Écosystèmes Marins et Littoraux (ECOSYSMARL) E-mail: [email protected]

2

Ecole Nationale Supérieure des Sciences de la Mer et de l’Aménagement du Littoral (ENSSMAL), Laboratoire de conservation et de valorisation des ressources marines (LCVRM) E-mail: [email protected]

3

Ecole Nationale Supérieure des Sciences de la Mer et de l’Aménagement du Littoral (ENSSMAL), Laboratoire des Écosystèmes Marins et Littoraux (ECOSYSMARL) E-mail: [email protected]

Keywords: Ocean color, chlorophylle, suspended matter, Algerian basin, Marine pollution.

abstract Spatial measurements are increasingly used for monitoring marine environment. In remote sensing, the concentration of chlorophyll pigments is derivable from satellite data related to natural electromagnetic radiation (passive remote sensing). The presence of suspended matter from the terrigenous inputs causes a modification and/or disruption in the seasonal cycle of phytoplankton in the Algerian basin. It also leads an overestimation of the chlorophyll concentration in the coastal areas, turbidity and hydrodynamics. These suspended matter influence the penetration of light into the water, major parameter for phytoplankton production, and are also likely to carry pollutants and nutrients. This study, analyzing the temporal variation of phytoplankton surface under the influence of suspended matter in the coastal zone of the Algerian Basin, by using two complementary methods: satellite observation (Ocean Color) and in-situ measurements. The MODIS data (Moderate Resolution Imaging Spectroradiometer) are treated by the ocean color algorithms to perform time series of chlorophyll-a (Chla), The optical properties of water and suspended matter, are analyzed to estimate the land-sea flux of terrigenous inputs in coastal areas in the Algerian basin. In-situ measurements were also realized to identify the phytoplankton species present in a coastal area in the center of the Algerian Basin (Bay of Bou Ismaïl). In-situ measurements of chlorophyll-a and other parameters were conducted to validate the bio-optical algorithms measuring the concentration of Chl-a This work aims to create a zoning in Algerian basin depending on the landsea flux of suspended matter: discrimination of different Types of coastal water masses.


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Introductıon The marine pollution in the Algerian basin and as in many Mediterranean zones is due to many factors (domestic throw, different forcing, the circulation of water masses…) it causes a set of physical, ecological and social, as results of anthropogenic activity. So, the Algerian basin presents itself as a particularly interesting study site. It is characterized by an oligotrophic ecosystem submitted to anthropogenic pressure in spring and summer and by high concentrations of chlorophyll and nutrients salt in autumn-winter (with a coast-wide gradient on the surface) (D'Ortenzio, et al., 2009) and present a specific surface circulation. Indeed, the phytoplankton is the first link in the marine food chain. It plays a major role in the carbon cycle at the global level and consequently in climate changes. In remote sensing, the interaction of electromagnetic radiation with the ocean surface present information on phytoplankton. Bio-optical algorithms permit to obtain with reliable way chlorophyll-a concentration in surface water. Remote sensing ‘ocean color’ would be an invaluable help for the marine environment monitoring. This study analyzes the temporal variation of the chlorophyll-a concentration and the suspended matter in the Algerian basin to estimate the land-sea flux using satellite and in-situ measures. The objective of this work is to determine the influence of terrigenous and anthropogenic contribution on the seasonal cycle of phytoplankton in coastal waters of the Algerian basin.

Methods Determination of chlorophyll-a, suspended matter and optical properties of water: - Satellite methods: The signal measured by the satellite sensor represents the luminance of solar irradiance reflected by the superficial layer of the ocean. To process, analyze and interpret this signal in the surface layer of the Algerian Basin, the procedure was as follows: - Observation satellites: In this work we used the MODIS sensor (Moderate Resolution Imaging Spectroradiometer, NASA) onboard the AQUA satellite : Launched in May 2002 at 705 km of altitude, with 1 km of spatial resolution of. - SeaDAS (SeaWiFS Data Analysis System) : is the software used to the processing and analysis satellite images in this study. It is an open-source software, which has been developed by NASA to view, process and control the quality of all products from SeaWiFS. It also allows viewing of ocean products MODIS. Identification of phytoplankton: after sampling, the species were identified in the laboratory under an inverted microscope. physicochemical parameters: temperature, salinity, pH, dissolved oxygen, chlorophyll-a and suspended matter were sampled also and measured using the protocols described in Aminot et Kérouel 2004.

Fındıngs and Argument Monthly and annual averages were calculated to visualize the evolution and the temporal variation of the surface chlorophyll-a concentration.


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Figure 1. Annual and monthly average of Chl-a concentration in the Algerian basin [2003-2015] The Algerian Basin is an area where we see the less interannual variations of Chl-a concentration (between 0,02 and 0.5 mg/m3) (figure 1). A south-north gradient of phytoplankton biomass is also observed. These variations are maximal for the spring period in the month of February-March (figure 1). This increase in the Chl-a concentration during the winter in the Algerian basin was already been ascertained by D’ortenzio and Ribera d’Alcala (2009). They are minimal for the summer in the month of July-August (figure 1) because of the exhaustion of nutrient salts. In turbid and dynamic Algerian coastal areas, the presence of suspended metter tends to induce disturbances in the seasonal cycle of phytoplankton. The large flux of matter between land and sea in the Algerian coast essentially comes from the inputs of wadis. The influence of land-sea flux of the MES on the Chl-a concentration is clearly shows in figure 2 estimate by satellite in a coastal area in the center of the Algerian Basin (Bay of Bou Ismaïl). İndeed, these materials also absorb in the blue and reflect the green-yellow radiation (thus requiring an improvement of calculation algorithms of Chl-a concentration in Algerian coastal waters influenced by MES, which is an ongoing study).

Oued Mazafran

Oued Nador

Figure 2. representation of the Chl-a concentration (right) and surface MES (left) during the campaign of August 2015 in the Bay of Bou Ïsmail The satellite analysis of spatio-temporal dynamics of the MES concentration and Chl-a concentartion in the Algerian coastal zone between 2003 and 2015, allowed us to estimate the land-sea flux of MES. An important seasonal variability transport from the mouths is remarkable. In the case of the Bay of Bou Ïsmail, we have found very high MES concentrations at the mouth of Mazafran wadis with a maximum value of 36,06 mg/m-3.

References Aminot, Alain et Kérouel, Roger. 2004. Hydrologie des écosystèmes marins: Paramètres et analyses. Brest : Ifremer, 2004.


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D'Ortenzio, F et Ribera d'Alcalà, M. 2009. On the trophic regimes of the Mediterranean Sea: a satellite analysis. Italie : Biogeosciences, 2009


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MODELLING THE BUBBLE HYDRODYNAMİC AND MASS TRANSFER İN AN ELECTROFLOTATİON COLUMN

Issam KSENTINI1, Lassaad BEN MANSOUR1 Laboratory of Applied Fluid Mechanics – Process Engineering and Environment Sciences Faculty of Sfax, B.P.1171, 3000 – Tunisia Tel: +216 98 657 061 e-mail: [email protected]

Keywords:modelling, hydrodynamic, mass transfer, electroflotation.

INTRODUCTION In this work, the bubble hydrodynamic and the mass transfer in an electroflotation column was studied. In fact, the diameter and the rise velocity of bubbles generated by the electroflotation process was calculated using the method of video recording and image processing. The effect of both liquid phase physicochemical characteristics and current density applied at the electrodes of the electroflotation column on the bubble flow regimes has been studied. In the other hand, the oxygen mass transfer was also studied. The volumetric mass transfer coefficient (KLa) wasmeasured using the unsteady state method with anoxygen probe (Consort C932) in order to calculate the volumetric mass transfer coefficient Kla. Empirical models based in nonlinear regressions were elaborated summarizing hydrodynamic and mass transfer results. These models will be very usefulwhen using the electroflotation process inthe treatment of industrial wastewater.

METHODS The methodology of video recording and image processing was used to study the bubble hydrodynamic. The measurements were performed in a lab scale electroflotation column equipped with insoluble electrodes. The electroflotation column and the equipment used to determine bubble characteristics are shown in Fig. 1.

Fig. 1. Electroflotation column and equipment for the determination of bubble characteristic


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The material used to calculate the bubble diameter by image analysis are an analogue video camera (25 frames per second), an acquisition card, a PC equipped with appropriate image analysis software (Photoshop CS4 from Adobe and Virtual Dub 1.6), and a double 50 watt power halogen spots.A wire of a known diameter (149 µm) was inserted into the column and videotaped. This wire is used as the calibration factor. Then, images were extracted and treated with an appropriate suite of shape filters. In order to get a sufficiently representative bubble size, 50 bubbles were at least measured in each case. The technique of illuminating bubbles with diffuse back light was adopted. It leads to better image quality. In fact, after applying the shape filter, clear dark bubbles appear on white background which makes easy the measurement of bubble size. The volumetric mass transfer coefficient (KLa) wasmeasured using the unsteady state method with anoxygenprobe (Consort C932) placed midway in theEF cell. The oxygen concentration was reduced to zeroby adding sodium sulphite (Na 2 SO 3 ) and2 mg/L of cobalt ions. This work focused mainly on the effect of density, surface tension and viscosity of liquid phase on the hydrodynamic and the oxygen mass transfer. So, in addition to tap water, two model aqueous solutions were prepared.

(a solution of Anionic Surface Tension {polymethacrylate of Sodium} and a solution of Cationic

Surface Tension {Benzyl dimethyl n-Hexadecyl})

FINDINGS AND ARGUMENT Focusing in bubble hydrodynamic, the main experimental work consisted in determining the bubble diameter, the bubble rise velocity and gas retention. These parameters are the key to calculate the Reynolds number and then Kla. Modelling our long experimental results lead to these empirical models :

= d exp ( 2,98.10−3 × J − 3, 01.10−3 × ρ + 4,569 × σ + 85,987 × µ + 0, 475 ) = V exp ( 7,54.10−3 × J − 6, 74.10−3 × ρ + 6,904 × σ − 14, 496 × µ + 7, 014 ) = Re exp ( 8,377.10−3 × J + 9,508.10−2 × ρ + 3, 203 × σ + 28, 459 × µ − 96,39 ) = ε G exp ( 5, 282.10−3 × J − 1, 705.10−2 × ρ − 2, 45 × σ + 16,182 × µ + 12, 689 )

The effect of temperature was also studied :

d 0,133 + 3, 08.10−4 × J − 5,92.10−4 × T + 9,12.10−7 × J 2 + 7, 06.10−6 × T 2 − 6,13.10−7 × J × T = V= 4,538 − 2, 6.10−2 × J − 2, 21.10−2 × T + 2, 62.10−4 × J 2 + 2, 63.10−4 × T 2 + 9,94.10−5 × J × T Re = 3, 777 − 4,56.10−2 × J − 7,36.10−2 × T + 1,54.10−4 × J 2 + 4, 28.10−4 × T 2 + 6, 09.10−4 × J × T 0, 018 − 2,53.10−5 × J − 2.10−4 × T + 4,54.10−7 × J 2 + 3,1.10−6 × T 2 + 1, 05.10−6 × J × T ε= G


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Finally, modelling the oxygen mass transfer results lead to :

= K L a exp ( 5, 7010−3 J − 9,56 σ + 7, 22 10−3 ρ + 32, 40 µ − 13,80 ) a exp ( 2, 4410−3 J − 9, 02 σ + 3, 28 10−2 ρ + 23,1µ − 25,85 ) = = K L exp ( 2,810−3 J − 1,90 σ − 2,96 10−3 ρ + 50,93µ − 10, 43 ) K L a = 1.9510−5 J 0.67 T 0.41 a = 68.11 J 0.35 T 0.23 K L = 2.39 J 0.33 T 0.20 These models are used when optimizing the treatment of wastewaters by electroflotation. In fact, if we look for example to reduce the suspended solids rate contained in any industrial effluent, we have to work in a laminar regime. Resolving such model will give us the optimized operating parameter values. Whereas, if we plan to reduce the COD contained in any wastewater, we have to maximize the oxygen transfer rate. Here also, these models are very valuable.


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Highly stable and sensitive amperometric immunosensor for the determination of salmonella at cross linked pectin stabilized gold nanoparticles decorated graphene nanosheets Amani chrouda1,2, Khaoula Zinoubi1,Ibtissem Chakroun3, Hatem Majdoub1, Abdrazzek Maaref1 1 Laboratoire des Interface et matériaux avancés, Faculté des Sciences, Monastir 5000, Tunisia. 2 Université de Lyon, Université Claude Bernard Lyon 1, Institut des Sciences Analytiques, UMR CNRS 5280, 5 Rue de la Doua, 69100 Villeurbanne Cedex, France 3Laboratoire d’Analyse, Traitement et Valorisation des Polluants de l’Environnement et des Produits, Faculté de Pharmacie de Monastir, Rue Avicenne 5000, Monastir, Tunisia E-mail adress: [email protected]

Abstract In this report, we have successfully fabricated an immunosensor for detection of Salmonella in water. Herein, we have described a simple electrochemical method for the deposition of the calcium ions cross linked pectin film (CCLP) along with gold nanoparticles (GNPs) on the graphene (GR) modified glassy carbon electrode (GCE) and applied for the fabrication of immunosensor and detection of Salmonella in water. The building of the immunosensor was evaluated in each step by cyclic voltammetry (CV) and impedance spectroscopy (EIS).The electrochemical detection was done based on on Differentiel Pulse Voltametry in Ferri-/Ferrocyanide (FeCN 6 )3-/4electrolyte.From the results, the sensitivity range is from 0,5 to 109 CFU/ml and LOD is calculated as 101 CFU/ml. The developed immunosensor also have high selectivity, stability, reproducibility and reusability. Keywords: Immunosenor, Pectin, Ochratoxin A, Graphene, Gold nanoparticles.

Introductıon: The Gram-negative bacterium Salmonella is a major foodborne pathogen for humans and animals. This pathogen is known as a major factor in gastro intestinal infections and is associated with numerous hospitalisations and deaths allover the world. Salmonella can be found in meat, eggs, milk and beverage. Among the over 2500 serotypes of Salmonella, one of the most common serotype related to human disease is Salmonella enteric serovar typhimurium (S. Typhimurium) (Kim et al.,2015; Lee etal.,2015; Ma et al.,2014). Traditional methods of detection of this pathogen are based on the combination of preenrichment steps, culturingon Salmonella-Shigella (SS) agar plates, and serological validation of suspicious colonies. Although these approaches can provide reliable results, they are quite time consuming and can take up to 5 days to obtain a result. Due to these drawbacks, the development of new and faster approaches for bacteria detection is a core activity in contemporary microbiology.


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Pectin (polygalacturonicacid) is a good candidate for forming a supra molecular polymer composite because it has two hydroxyl groups and one carboxylic group which lead to multiple hydreogen bonds that form a flexible and robust film. Remarkably, pectin contains –OH and –COOH functional group which can be used to support the nanoparticles. In this work, we introduce a simple and fast electrochemical method for the deposition CCLC coating on the electrode surface. We employed CCLC as the stabilizing agent for the formation of gold nanoparticles on grapheme nanosheets. Notably, here we use simple electrochemical process to reduce gold salts to Au nanoparticles while GO simultaneously reduced to reduced graphene. In fact, CCLC has served as a robust, highly stable and reproducible scaffold for the assembly of gold and graphene nanosheets. Immobilization of antibody molecules without leaching from the electrode surface is crucial to development of efficient immunosensor system. –COOH functional group pectin is found to provide an excellent platform for stable immobilization via covalent linkage between the oxygen functional groups of pectin and amino groups of the antibody.

Methods Cyclic voltammetry is an electro-analytical method based on measuring the current flow resulting from the reduction or oxidation of the test compounds in solution under the effect of a controlled variation of the potential difference between two electrodes. Impedance spectroscopy is to analyze the system response function of the frequency of alternating excitation signal. The impedance measurement of an electrochemical system is achieved by applying a constraint to the system in the form of a sinusoidal variation of electric potential difference, of frequency f = ω / 2π. To study the behavior of an electrochemical system has a given indicator electrode, the potential difference is imposed between the working electrode and a reference electrode (potential fixed suppose), the stress returns to superimpose a sinusoidal variation. ∆E (t) of the potential of the working electrode has a fixed value E (E 0 is generally selected so as to have a zero current) in the electrochemical cell.

Fındıngs and Argument


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200 150

GCE CCLC/GCE AuNPs-CCLC/GCE GO/AuNPs-CCLC/GCE

Current (µA)

100 50 0 -50 -100 -150 -200 -0,2

0,0

0,2

0,4

0,6

Potential/V (vs. Ag/AgCl)

Figure1. Cyclic voltammograms of modified and unmodified GCEs in 0.1 M KCl solution containing 5 mM [Fe(CN) 6 ]3-/4 at a scan rate of 100 mV s-1. The charge transfer rate at the electrode/solution interface can be evaluated well by CV. Here we compared the charge-transfer behavior at the bare GCE, CCLC/GCE, NPsAu-CCLC/GCE and GO/NPsAu-CCLC/GCE in 0.1 M KCl solution using the [Fe(CN) 6 ]3-/4- couple as a redox probe. The recorded CVs are all shown in Fig.1.


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New complex compounds of functionalized Dehydroacetic acid units and N, N dimethyl amino benzaldehyde : the synthesis, catecholase study and electrochemical properties

Salima Tabtia, Amel Djedouani b,c , Samra Rahmounid, Samir Romdhanee and Rachid Touzanif,g. a

Laboratoire Matériaux et systèmes électroniques, Universite Mohamed el Bachir El Ibrahimi, El Anasser, 34000, Bordj Bou Arreridj, Algeria Email : [email protected] b

Laboratoire de Physicochimie Analytique et Cristallochimie des Materiaux Organometalliques et Biomoleculaires, Universite Constantine 1, 25000, Constantine, Algeria c

Ecole Normale Superieure de Constantine, Ville Universitaire Ali Mendjeli, 25000, Constantine, Algeria d

e f

Faculte des Sciences, Universite Sétif –el baz- 19000, Sétif, Algeria

Département de Physique, Faculté des Sciences de Tunis. Campus Universitaire 2092 El Manar Tunis, Tunisie

Laboratoire de Chimie Appliquée et Environnement, LCAE-URAC18, COSTE, Faculté des Sciences, Université Mohamed Premier, BP524, 60000 Oujda, Morocco ; g

Faculté Pluridisciplinaire Nador BP 300, Selouane 62702 Nador, Morocco ;

Keywords: α, β –unsaturated ketones, Electrochemistry, catechol, cyclic voltametry

In this study, the treatment of α,β-unsaturated carbonyl compounds, obtained by the reaction of dehydroacetic acid (DHA) and heteroaromatic aldehyde results in the formation of a heterocyclic compound, named 4-hydroxy-3-[(2E)-3-(4- (dimethylamino)phenyl)prop-2-enoyl]-6-methyl-2H-pyran-2-one (HL) in good yield that depending upon the reaction conditions. The ligand HL behaves as a monoanionic bidentate OO chelating agent. Its structure was characterized using the usual spectral characterization such as electronic absorption, by FT-IR, and 1H NMR in addition to mass and elemental analyses. M(II) coordination compounds of Cu, Co and Ni with a this ligand (HL) derived from the condensation of DHA with aromatic amine were synthesized and characterized by several techniques, including elemental analysis , UV-Vis, FT-IR, EPR and 1HNMR spectral studies. The analytical values indicated that the water and ammoniac fractions coordinate to the metal ions. Based on these studies, the general formulae [M(L) 2 (H 2 O)] (M(II) = Cu) is proposed for the complexe. Electrochemical behavior of the complexs has been investigated by cyclic voltametry on glassy carbon electrode in acetonitrile at 100 mV/s scan rate. This study indicates that the reduction process corresponding to CuII/CuI is electrochemically quasi-reversible in complex of copper. Cathecolase study of HL reveals an important result for the oxidation of catechol.


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AEFFICIENT REMOVAL OF THE TRIARYLMETHANE DYE MALACHITE GREEN FROM AQUEOUS SOLUTION USING MILLED ALMOND SHELL Rim Ben Arfi1, Sarra Karoui1, Karine Mougin2, Achraf Ghorbal1,3 1

Research Unit UR11ES80, National Engineering School of Gabes, University of Gabes, Tunisia, [email protected] 2

Institute of Materials Science of Mulhouse, CNRS - UMR 7361, France, [email protected]

3

Higher Institute of Applied Sciences and Technology of Gabes, University of Gabes, Tunisia, [email protected]

ABSTRACT In the present work, the Tunisian almond shell (referred to as TAS) was used as a new low-cost natural sorbent for the removal of cationic dye (Malachite Green MG) from aqueous solutions. Tunisian almond shells were characterized by several techniques XRD, FTIR, TGA/DTA, optical microscopy, and Atomic Force Microscopy. Batch mode experiments were conducted to assess the effects of process variables such as particle size of biosorbent, initial dye concentration, initial pH, biosorbent dosage, contact time, and temperature. The experimental data fitted very well the pseudo-second-order kinetic model. The TAS was found to be very effective adsorbent for MG adsorption. Keywords: Eco-material, Almond shell, Bioadsorbent, Malachite Green, biosorption.

INTRODUCTION Dyes, representing an important class of pollutants among others, are often discharged in the form of colored wastewater by textile industries, pulp mills, and dye manufacturing industries. Many of these colored compounds are toxic, posing great potential threat to aquatic lives and human beings. Adsorption is one of the most effective methods for dye removal from aqueous solutions. Activated carbon is currently the most commonly and widely used adsorbent for the adsorption of pollutants such as dye from liquid effluents, due to its large surface area, multi-porous structure, and thermo-stability. However, its use is limited due to its high cost and low selectivity. Therefore, the use of low-cost, easily obtained, high efficiency, and eco-friendly adsorbents has been investigated as an ideal alternative to the current expensive methods of removing dyes from wastewater. Agriculture is an important sector of the Tunisian economy and almond shell is a relatively abundant lignocellulosic agricultural by-product, in Tunisia, with a production of about 70000 tons in 2012 (FAO STAT data, 2012) but it is not much valorized. Currently, the main focus of the Tunisian almond industry is the seed and related foodstuffs and consequently the other fruit parts (shells and hulls) are considered agricultural residues.


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The use of the Tunisian almond shell (referred to as TAS) in organic wastewater treatment could help in agroindustry diversification by providing a new market for agro-wastes. Malachite green is a triarylmethane dye, which is most widely used for coloring purpose, amongst all other dyes of its category. Malachite green, discharged into receiving waters even at low concentrations, will affect the aquatic life and cause detrimental effects in liver, gill, kidney, intestine, and gonads. In humans, it may cause irritation to the gastrointestinal tract upon ingestion. Contact of malachite green with skin causes irritation and redness and pain. The aim of this study was to investigate the potential of using Tunisian almond shell as a low-cost adsorbent for the removal of the basic dye malachite green from aqueous solution. The effects of important factors such as initial solution pH, dye concentration, contact time, biomass dosage, particle size, and temperature on the malachite green adsorption were studied. The Langmuir, Freundlich, and Temkin adsorption isotherms were employed to quantify the adsorption equilibrium. Several kinetic equations (i.e., pseudo-first order equation, pseudo-second order equation, Elovich equation, and intraparticle diffusion model) were applied to investigate the adsorption mechanisms.

MATERIALS AND METHODS Adsorbate The basic dye used in this study was malachite green purchased from LobaChemie. MG has molecular formula C 23 H 25 N 3 CIN 2 (Mol. wt. 364.911 g/mol). The maximum wavelength of this dye is 616 nm. The dye stock solution was prepared by dissolving accurately weight dye in distilled water to the concentration of 1g/L. The experimental solutions were obtained by diluting the dye stock solution in accurate proportions to needed initial concentrations.

Figure 1. Chemical structure of Malachite Green (MG).

Preparation of the bioadsorbent Almond shells were collected from a nearby market (Gabes, Tunisia) as a solid waste. The collected materials were then washed with distilled water for several times to remove all the dirt particles. The washed materials were broken into small pieces (0.5–2 cm) and dried in a hot air oven at 50°C for 48h. Then ground and finally screened to obtain various particle sizes. Therefore, the TAS was dried at 50°C for 24h in an oven and then stored in a desiccator for further use.


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Adsorption experiments Batch experiments were carried out in duplicate at room temperature (22°C) by combining variable masses of the adsorbents with 250 mL of dye solutions under orbital agitation at 320 rpm for 300 min. Initial solution pH was adjusted depending on the type of experiment. Adsorption mixture was sealed with parafilm to avoid evaporation. Upon equilibrium, the suspensions were separated by gravity and the remaining dye concentration was determined by spectrophotometry (PG Instruments Ltd., UK) at 616 nm. The amount of adsorbed dye onto the adsorbent was expressed as Adsorption Capacity q (mg/g) and calculated as shown in Equation (1) q

=(C 0

-

C t )V/W

(1) where C 0 and C t (mg L-1) are the liquid-phase concentrations of malachite green at initial and any time t, respectively, V is the volume of malachite green solution (L) and W is the weight of the bioadsorbent (g).

FINDINGS AND ARGUMENT The results revealed the potential of Tunisian Almond Shell, an agricultural waste material, to be a lowcost adsorbent for removing cationic dye from aqueous solutions. The biosorption performance is affected by various parameters, i.e. pH, contact time, biosorbent concentration, particle size, temperature and initial dye concentration. The kinetic modeling study has shown that the experimental data were found to follow the pseudosecond order model.

Figure 2. AFM topographic image of TAS particles.


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Integrated Coastal Management (ICM) for sustainable development in coastal zones: Case study of the Sfax city-Tunisia Mohamed Moncef Serbajia, Chafai Azrib and Khaled MedhioubC (a)

University of Sfax, National Engineering School of Sfax, Sokra Road PB: 1173 Sfax 3038, Tunisia (b) (c)

University of Sfax, Faculté des Sciences de Sfax

University of Sfax, Institut Préparatoire aux Etudes d’Ingénieurs de Sfax

E-mail: [email protected] The coastal zone of Sfax region is a particular ecosystem that includes some sensitive areas such as wetlands of Thyna and the Kerkennah island, shoreline, urban and industrial zones, etc. This ecosystem constitutes a space of particular importance both on the economical plan, by the value of the natural resources, and on the environmental plan, by the sensitive and fragile coast knowing a multiform exploitation for a long time and sheltering an important urban agglomeration plus the essential industrial activities. The study revealed that several factors such as coastal geomorphology, water pollution, bathymetry, climatic conditions, non sustainable use of the natural resources and the damages of industrial pollution on some coastal areas could affect severely this ecosystem.

Problematic: The coastal areas around the world share a number of characteristics that define both their value and their vulnerability (Fedra and Feoli, 1998): • The coastal zone shows a high population density with a large number of urban conglomerations, and in consequence, in most countries, a fast population growth; • Again as a consequence, they are characterized by a high concentration of economic and in particular industrial activities with all the resulting problems of resource consumption an overexploitation, with their subsequent pollution and degradation which can be found everywhere. Sea pollution, for example, has been a severe problem over the years especially in the Channel SfaxKerkennah. In addition, the socio-economic problems of rapid urban development have an obvious and often dominating spatial aspect, which makes coastal zone management a spatial problem. The list of problems includes: destruction of natural coastal habitat, wastewater discharges, dumping of solid waste, beach erosion and conflicting land uses. As economy on coastal zones increases there are increased pressures on natural resources which render very difficult to foresee the environmental dynamics without proper scientific and high level technological tools.

Methods: Thus, only an integrated approach of all environmental and socio-economical aspects could help us to solve problems met in this coastal area. The Geographical Information System (GIS), carried out within this 2nd ICIEM 2016, International Conference on Integrated Environmental Management for Sustainable Development Page 604

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work, allowed the elaboration of a geo-referenced database easily updated, having for objective the treatment and the coherent exploitation of main data relative to the coastal ecosystem of the Sfax region, and the monitoring of their various components evolving continually. Existing maps and High resolution Satellite images were used for the land use monitoring.

Results: The data were analyzed with GIS and statistical tools which allow processing and displaying of coastal information. They offer significant advantages such as the ability to handle large databases and to integrate data from a wide range of sources.

Conclusion: The coastal zone of Sfax region has already reached a critical level of pollution, corresponding to those

extremely

vulnerable

areas.

Thus,

the

sustainable development of

this

region

need

to

encourage concerted actions of urbanization, which meet the housing needs, infrastructure and community facilities and recreation to improve the quality of life. Keywords: GIS; Remote sensing; Coastal ecosystem; Integrated approach; Urban management; Environment; Pollution; Vulnerability.


Desk-scale production of biogas from molasses wastewater Janet Mabuza, Boitumelo Matshediso, Seth Apollo, Tumisang Seodigeng, Aoyi Ochieng

166

Rapid analysis of antibiotic residues in urban wastewater of south Sfax WWTP by ultra-highperformance liquid chromatography coupled to quadrupole-linear ion trap tandem mass spectrometry Harrabi Malek, Fatma Aloulou ,Sara Rodriguez-Mozaz, Saulo Verela ,Elluech Boubaker

174

Antibacterial activity of henna (Lawsonia inermis) extracts against Pseudomonas aeruginosa. Aicha Lattab, Rachid Djibaoui, Abeda Rabi And Hichem Dahah.

186

Environmental characterization of the southern coastal area of Sfax: Heavy metal concentration in the surface marine sediments Ikram Naifar ,Raja Zmemla, Boubakker Elleuch

196

Isolation of potassium releasing bacteria from soil and assessment of its ability in potassium nutrition of Tomato Mohammad Reza Sarikhani , Mitra Ebrahimi, Shahin Oustan, Naser Aliasgharzad, Omid Madani

208

Synthesis, characterization and photocatalytic behaviour of noble metals doped Titania thin films Cherif Moslah, Muhammad Monirul Islam, Geogria Petropolou, Nagia S.Tagiara, Maria KandylaP, Mohamed KsibiP, George A.MousdisP

224

Seasonal variation in biomarker responses in Donax trunculus from the gulf of Annaba (Algeria): implication of marine pollution Akila AMIRA, Isma MERAD And Noureddine SOLTANI

232

Effects of cadmium concentrations on bioaccumulation and depuration in the marine bivalve Donax trunculus Soumeya BELABED And Noureddine SOLTAN

246

BIOLOGICAL CONTROL OF WILT DISEASE COMPLEX ON TOMATO CROP CAUSED BY MELOIDOGYNE JAVANICA AND FUSARIUM OXYSPOUM F.SP. LYCOPERSICI BY VERTICILLIUM LEPTOBACTRUM Hajji-Hedfi Lobna , Regaieg Hajer, Larayedh Asma, Chihani Noura and Horrigue-Raouani Najet

258

Anaerobic treatment of landfill leachate:organics degradation and biogaz production Yosr Smaoui, Jalel Bouzid, Sami Sayadi

268

SYNTHESIS AND CHARACTERISATION OF MAGNETIC β-CYCLODEXTRIN LATEX NANOPARTICLES AS NANOADSORBENT FOR REMOVAL OF TETRACYCLINE ANTIOBIOTICS Zied Marzougui, Amel Chaabouni, Abdelahamid Elaissari, Boubaker Elleuch

278

One-pot synthesıs of 3,4-dıhydropyrımıdın-2(1H)-ones via Biginelli reaction catalysed by Cu(NO ) under solvent-free condıtıons Kouachi Kahina, Yahi Nora, Khiar Chahinaz

3 2

288

BIOCONTROL OF PRATYLENCHUS VULNUS ASSOCIATED WITH APPLE ROOTSTOCK USING VERTICILLIUM LEPTOBACTRUM Chihani Noura, Regaieg Hajer, Larayedh Asma , Khlifi Raoudha , Hajji Lobna, Horrigue-Raouani Najet

297

SOURCES AND DISTRIBUTION OF HYDROCARBONS IN SURFACE COASTAL WATERS FROM THE GULF OF GABES (TUNISIA, SOUTHERN MEDITERRANEAN SEA) Fourati Rania, Tedetti Marc, Guigue Catherine, Goutx Madeleine, Zaghden Hatem, Sayadi Sami, Elleuch Boubaker

305

Effects of irrigation with treated olive mill wastewater on soil properties Mseddi Salma, Damak Fadwa, Smaoui Yosr,Kallel Monem

319

Simulation par le Logiciel « HEC-RAS » de l’Onde de l’Ecoulement Due à la Rupture d’un Ouvrage de Retenue Cas de la Retenue de Bensberka-Oued Taga (W. Batna). Messaoud Ghodbane, Abderrahmane Boudoukha and Aissam Gaagai

325

ENHANCED ADSORPTİON OF BİSPHENOL A FROM WATER BY MAGNETIC Β-CYCLODEXTRIN LATEX NANOPARTICLES Zied Marzougui, Amel Chaabouni, Abdelahamid Elaissari, Boubaker Elleuch

335

THE POTENTIAL USAGE OF KESAMBI (SCHLEICHERA OLEOSA L) OIL FOR BIODIESEL PRODUCTION USING ALUMINA SUPPORTED ZINC OXIDE SOLID CATALYST Nyoman Puspa Asri, Siswannti Soe’eib, Bambang Poedjojono, Suprapto

341

A Novel Prototype IT/BF-MBR (Inclined Tube/Biofilm-Membrane Bioreactor) for High-rise Building Wastewater Recycling : Effect of Hydraulic Retention Time on Long-term Performance for Biological Nutrient Removal Chavalit Ratanatamskul, Nutsinee Suksusiang and Kazuo Yamamoto

349

Orius laevigatus (Insecta; Heteroptera) local strain, a promising agent in biological control of Frankliniella occidentalis (Insecta; Thysanoptra) in protected pepper crops in Tunisia Mohamed Elimem ; Ahlem Harbi ; Essia Limem-Sellemi ; Soukaina Ben Othmen ; Brahim Chermiti

363

Study of the acid-base properties of lignocellulosic fibers and correlation with the adsorbing capacity Zeineb Raddaoui, Aida Kesraoui, Mongi Seffen

371

Elaboration of a hybrid fiber material lignocellulosic metal oxides and study of these performances in decontamination water S. Bouzaabia, A. Kesraoui, M. Seffen

385

Fatty acids, essential oils, polyphenols content and antioxidant activity from leaves of Quercus ilex L. (Fagaceae) collected in Djabel Zagouan (Tunisia) Sana Dallali, Ahmed Marichali, Kerkeni Amel, Hela Belhadj Ltaief, Sebei Houcine.

397

Food web structure of halophile species (Dunaliella salina, Fabrea salina and Artemia salina): an experimental study ChirazLadhar, Khaled Athmouniand Habib Ayadi

413

Thymus capitatus (L) Hoff et Link from Guelma « Algeria »; « Botanical study and Antimicrobial Activity of the Essential oil ». Dr Laredj.H , Abid.K Et Amoura.K

427

Study and characterization of sediment of Reghaia lake improving quality of water by coupling electrocoagulation and nanofiltration Souad Derkaoui, Amel Benhadji, Hayet Djelal, And Mourad Taleb Ahmed.

435

Management of soil organic matter and carbon storage in mediterranean fruit orchard Aissa Arous,Kamel gargouri, Vittoria Pastore, Assunta Maria Palese, Egidio Lardo, Giuseppe Celano

451

ANALYSIS OF ADHESIVELY BONDED REPAIRS IN WIND TURBINE BLADES DAMAGED BY AN ACCIDENTAL IMPACT Fayçal Mili, Toufik Achour

467

Involvement of Pseudomonas spp fluorescent in the mechanisms of soil suppressiveness to fusarium wilts Bensaid Fatiha and Benchabane Messaoud

477

Elimination of Amoxicillin from wastwater by Electrocoagulation and Nano-filtration Aimad OULEBSIR, Hannane TOUNSI, Toufik CHAABANE, Sivasankar VANKATRAMAN, André Darchenand Rachida MAACHI

485

Simultaneous elimination of Inorganic (Cu) and organic (EDTA) pollutants by Electroflotation/Electro-chlorination process from wastewater Lakel Farida, Chaabane Toufik, Sivasankar Venkatraman, André Darchen and Maachi Rachida

491

CONTRIBUTION À L’EVALUATION DE LA POLLUTION PAR LES METAUX LOURDS DE L'ESPECE DE POISSON PELAGIQUE Trachurus trachurus (LINNE, 1758) (LA SAUREL) SUR LE LITTORAL DE SKIKDA Souheïla Azzouz, Ahlem Boukrouma Et Kamel Bouzerdouna

505

Elaboration of a TiO -P25@n-TiO composite in Sol-Gel Micro- mixing Reactor. Application to 2

2

Photocatalysis Fanou Guy Didier , Yao Benjamin , Kanaev Andrei , Traoré Mamadou ,ChhorKhay

507

INTERACTION OF POLYSTYRENE CO STYRENE SULFONATE WITH METHYLENE BLUE IN AQUEOUS SOLUTION Souha Ben Mahmoud Wafa Essafi, And Ahmed Hichem Hamzaoui

512

Thermal Infrared Scanning for Evaluation Oil Plume Thickness Contaminating Groundwater. Khalil Ibrahim Al-Samarrai, Abdussalam M. Bahron, Abdussalam M. Al-Fituri

516

MODELING OF THE CATALYTIC PHOTO DEGRADATION OF THE METHYLENE BLUE IN THE PRESENCE OF TIO2 SUPPORTS ON PLATES OUT OF GLASS Aitatmane Abdenour, Bourouina-Bacha Saliha

518

Photodegradation of 3-[3,4-(dichlorophenyl)-1-methoxy-1-methylurea by iron oxide- oxalate system: Degradation mechanism Hind Mechakra, Tahar Sehili

522

Optimization of nutritional conditions for production of antimicrobial compounds by Sa198 of Saccharothrix isolated from a Saharan soil Laassami Affaf, Boudjella Hadjira, Bakour Leila and Sabaou Nasserdine

526

Utilisation des argiles pour stabiliser des émulsions pharmaceutiques Touzouirt Saida, Ahmed Zaid Toudert, Nabiev Mohamed

530

Improving Anaerobic Digestion of Waste Activated Sludge by Electro-Fenton Pre-treatment Sonia Khoufi; Emna Feki and Sami Sayadi

534

THE ANAEROBIC CO-DIGESTION OF HOUSEHOLD WASTE AND DROMEDARY DUNG FOR BIOGAS AND BIOFERTILIZER PRODUCTION Benaissa Kheira, Dadamoussa Belkhir, Bendraoua Abdelaziz, Drici Habiba, Labed Brahim

538

Study Nutrition Facts of a Sub Product Agro Food and Beverage Used In Domestic Ruminant Boudersa Hind, Haddi Mohamed laid

542

OPTIMIZATION OF PROCESS OXIDATION FOR TREATMENT OF PARACETAMOL S. Slamani, F. Abdelmalek, M. R. Ghezzar, A. Addou

544

The physico chemical and biological treatment of PAH contained in polluted marine sediments. Krachai Naima , Hadjel Mohamed

546

GIBBERLIC ACID AND SALICYLIC ACID EFFECTS ON SEED GERMINATION AND SEEDLINGS GROWTH OF OKRA (ABELMOSCHUS ESCULENTUS L.) UNDER SALT STRESS. Yakoubi Fatima, Belkhodja Moulay

548

Valorization of agro industrial by-products and wastes for biosurfactants production DerguineLouiza, Gana-KebboucheSalima, Djenane Djamel

552

Effect of different agricultural wastes types on the yield of oyster mushroom (Pleurotus ostreatus) Zainab ,M.T.Jaafar ., Dahash .N.M. , Hassan .L.R.

554

Physiological effects of Pergularia tomentosa extract alone or in combination with the aggregation pheromone, phenylacetonitrile, on Schistocerca gregaria nymphs Meriem Miladi, Khemais Abdellaoui, Mouna Ben Cheikh, Iteb Boughattas, Fatma Acheuk, Monia Ben Halima-Kamel

558

Magnetic susceptibility as indicator of environmental pollution of sediment in Sebkha Halk El Menjel, Tunisian Sahel Najoua Gharsalli, Elhoucine Essefi and Chokri Yaich

562

Dynamic adsorption of organic matter contained in industrial phosphoric acid on raw and pillared Bentonite Wiem Hamza, Mourad Benzina

564

INFLUENCE OF PARTICLE SIZE ON METHYLENE BLUE REMOVAL FROM SYNTHETIC AQUEOUS SOLUTION USING ORANGE PEEL AS A SORBENT MATERIAL H. Benaïssa, M. Boumediène, B. George, S. Molina, A. Merlin

568

COMPARATIVE STUDY OF SORPTIVE PROPERTIES OF VARIOUS LOW-COST SORBENT MATERIALS FOR BEMACID YELLOW (ACID DYE) REMOVAL FROM SYNTHETIC AQUEOUS SOLUTIONS. H. Benaïssa, A. Benaïssa

572

Adsorption of Reactive Dyes from aqueous solution by dirty bentonite Kahina Bentaleb, Kheira Chinoune, Zohra Bouberka, Bagdad Ouddane, Ulrich Maschke

576

Adsorption of 2,4-dichlorophenol from aqueous solution using modified Algerian geomaterial Kahina Bentaleb, Kheira Chinoune, Zohra Bouberka, Chems Eddine GHERDAOUI, Bagdad Ouddane, Ulrich Maschke

578

UV-visible light induced degradation of brominated flame retardants, dispersed in polymers Abdelouahab Nadim, Zohra Bouberka, Said Eddarir, Bagdad Ouddane, Ulrich Maschke

580

Removal of polychlorinated biphenyls from organic media Chems Eddine Gherdaoui, Kahina Bentaleb, Zohra Bouberka, Bagdad Ouddane, Ulrich Maschke

582

Comparative study of the toxicity of phenolic compounds of coriander (Coriandrum sativum L) and false fennel (Aneth graveolens) on Galleria mellonella (Lepidoptera, Pyralidae). Effect on feed intake Oulebsir-Mohandkaci Hakima, Bouyahiaoui Husseyn, Baba Aissa Ahmed, Badaoui Said Et Ait Kaki Sabrin

584

Estimation of land-sea flux of suspended matter in the Algerian Basin: Application of Ocean Color Algorithms Romaissa HARID, Malik AIT KACI, Fouzia BACHARI-HOUMA

586

MODELLING THE BUBBLE HYDRODYNAMİC AND MASS TRANSFER İN AN ELECTROFLOTATİON COLUMN Issam Ksentini, Lassaad Ben Mansour

590

Highly stable and sensitive amperometric immunosensor for the determination of salmonella at cross linked pectin stabilized gold nanoparticles decorated graphene nanosheets Amani chrouda, Khaoula Zinoubi,Ibtissem Chakroun, Hatem Majdoub, Abdrazzek Maaref

594

New complex compounds of functionalized Dehydroacetic acid units and N, N dimethyl amino benzaldehyde : the synthesis, catecholase study and electrochemical properties Salima Tabti, Amel Djedouani , Samra Rahmouni, Samir Romdhane and Rachid Touzani

598

AEFFICIENT REMOVAL OF THE TRIARYLMETHANE DYE MALACHITE GREEN FROM AQUEOUS SOLUTION USING MILLED ALMOND SHELL Rim Ben Arfi, Sarra Karoui, Karine Mougin, Achraf Ghorbal

600

Integrated Coastal Management (ICM) for sustainable development in coastal zones: Case study of the Sfax city-Tunisia Mohamed Moncef Serbaji Chafai Azri and Khaled Medhioub

604

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ICIEM 2016