al., 1996; and Betsey , 2006). So, the Sediments ...... 1000 mg/L (provided from Alfa Aesar a Johnson Matthey Company/ Germany) by successive dilutions with ...
University of Baghdad
Assessment and Sources of some Heavy Metals in Mesopotamian Marshes A Thesis Submitted to the University of Baghdad, College of Science for Women, Biology Department In Partial Fulfillment of the Requirements for the Degree Of Doctor of Philosophy In Ecology ‐ Environmental Pollution By Mohammed Jawad Salih Al‐Haidarey M.Sc. in Ecology, University of Babylon, College of Science, Biology Department, 2003
Supervised by A.Prof. Dr. AbdulRahman A. Al‐Kubaisi & Prof. Dr. Ali A.Z. DouAbul
March 2009
ﺑﹺ ﺴﻢﹺ ﺍﷲِ ﺍﻟﺮﺣﻤﻦﹺ ﺍﻟﺮﺣﻴﻢﹺ ﻭﻟﹶﺌﻦ ﺳﺄﹶ ﹾﻟﺘﻬﻢ ﻣﻦ ﻧﺰﻝﹶ ﻣﻦ ﺍﻟﺴﻤﺎﺀِ ﻣﺎﺀً ﻓﹶﺄﹶ ﺣﻴﺎ ﺑﹺﻪ ﺍ ﹾﻟﺄﹶ ﺭﺽ ﻛﺜﹶ ﺮ ﻫ ﻢ ﻟﹶﺎ ﺪ ﻟﻠﱠﻪ ﺑ ﹾﻞ ﺃﹶ ﹾ ﻣﻦ ﺑ ﻌﺪ ﻣ ﻮﺗﻬﺎ ﻟﹶﻴﻘﹸﻮﹸﻟﻦ ﺍﻟﻠﱠ ﻪ ﹸﻗﻞﹺ ﺍ ﹾﻟﺤ ﻤ ﻳ ﻌﻘﻠﹸﻮﻥﹶ. ﺻﺪﻕ ﺍﷲ ﺍﻟﻌﻠﻲ ﺍﻟﻌﻈﻴﻢ ﺍﻟﻌﻨﻜﺒﻮﺕ ،ﺍﻻﻳﺔ 63
Dedication: I would like to dedicate this work To My parents My family My wife Ekram, & her family My dear children Batool and Jaafer and to My best friends and supervisors Whose love, support, and constant encouragement made this all possible
Mohammed Jawad S. Al-Haidarey March, 2009
I
Acknowledgement I would like to express my gratitude to the following individuals for their support throughout this study: Sincerely I would like to thank my advisors Dr. AbdulRahman Al-Kubaisi, and Dr. Ali A. DouAbul for their continuous confidence, advice, patience, and for their encouragement. Special thanks to Collage of Science for Women and Department of Biology Stuff for their cooperation and helped me. Many thanks to Dr. Fikrat Majeed Hassan for his continuous confidence, advice, patience, and for his encouragement. Special thanks to: Marine Science Center / Basrah University especially Dr. Hamed Talib Al-Saad, Dr. Dawood and them stuff for their cooperation and assistance in data collection, Dr. Barry Warner (University of Waterloo-Wetland Research Center) for giving me the opportunity to visit The University of Waterloo and the course of Wetlands Ecology, Dr. Taro Asada (University of Waterloo-Wetland Research Center) who provided endless me with help, contacts and the statistical analyses procedures, Vicky Jackson (University of Waterloo-Biology Department) for support, kindness, and constant encouragement. Thanks are due to all of my friends and fellow graduate students for making time of research more enjoyable, especially Adel H. Talib, Mohammed A. R. H. Al-Kinzawi, Mushtaq F. Karromi, Hussain A. Sabti, Eyad M. Jabur, and Sama M. Samer, Many many thanks to Iraqi Foundation field team for their cooperation and helped me, especially haider Amed, Hussam Jabur, Mustafa Fadel, Ali and Hussain. II
Summary: Heavy Metals have a great ecological significance due to their toxicity and accumulative behavior. Drainage and restoration processes took place in the Iraqi wetlands; therefore, we don’t know much about heavy metals (HMs) in this unstable ecosystem. Due to the restoration progression, thus it is important to understand distribution, load, budget, and bio‐accumulation of HMs in Mesopotamian Marshes ecosystem after rehabilitation and the reintroduction of water. Therefore the present study aims: To take place the general background about the concentration of heavy metals (As, Cd, Cr, Co, Cu, Mo, Mn, Zn, Pb, Se, Fe, and Ni ) in Mesopotamian marshes by monthly monitoring of heavy metal concentrations and some physiochemical properties in the Central, Al‐Hawizeh and Al‐Hammar marshes in dissolved part (two stations in each: Beginning of Baghdadia, Middle of Baghdadia, Um Al‐Wared, UmNj1, Al‐Nagarah, and Al‐Bargah respectively). To determine the loading of HMs in Al‐ Hawizeh marsh, by calculating of HMs in input streams (five stations: Al‐Adel Old, Al‐Adel, Al‐Zubair, Abu‐ Khassaf, and Al‐Musharah) and outlet streams (two stations: Al‐Kassarah, and Al‐ Suwayib), to answer whether the marsh is a source or sink of HMs. To assess weather, are there relationship between heavy metal concentrations and water & sediment quality or not the researcher chose ten stations in Al‐Hawizeh Marsh (Al‐Adaim 1, Al‐ Adaim 2, Al‐Soda north, UmNj1, UmNj2, Al‐Baidah, Um Al‐Wared, Al‐Souda south, Majnoon, and Lissan Ejerda) To monitoring the fate and cycling of heavy metal concentrations in Al‐Hawizeh marshes. To answer the possibility of using the Viviparus bengalensis snails and Potamogeton perfoliatus submerged plants as bio‐indicators. The results showed that the highest concentrations of the studied HMs were recorded during the summer months, while the lowest values were recorded in the spring months, except the Selenium element was no detection concentrations. All the HMs was more than Iraqi limitations for freshwater quality, except Arsinic (As), Selenium (Se), and Cooper (Cu) were in the range of Iraqi limitations. Al‐Hawizeh Marsh was sinking for: 63%As, 38% Cu, 33% Zn , 30% Mo, 27% Pb, & 8 % Cd; transformer to 93% Cd 73% Pb, 70%Mo, 68% Zn, 62% Cu, & 37% As; and source for 42% Cr, 28% Fe , 23%Mn, 15%Co, & 6% Ni. The water temperature (WT), total suspended solid (TSS), total hardness (TH), calcium (Ca2+), magnesium (Mg2+), and chloride (Cl‐) values were in completely dried stations > semidried stations > wet stations; EC, salinity, turbidity, total dissolved solids (TDS), carbonates (HCO3‐),& sulfate (SO42‐) values were in completely dried stations > wet stations > semidried stations; pH & dissolved oxygen (DO) were in semidried stations > wet stations > completely dried stations. The clay was more percentage at the southern parts of Al‐Hawizeh Marsh (completely dried part). III
The high percentages of total organic matter (TOM%) & total organic carbon (TOC%) in sediments were in Aug. while the low percentages were in May. The mean concentrations of the HMs in the dried stations were more than that in the wet stations. There were spatial and temporal variance among the stations and the period of study. The highest values of exchangeable and residual heavy metals in Particulates were in the wet and semidried stations, while the lowest values were in the completely dried stations. There were spatial and temporal changes in the HM concentrations in particulate phase among the study stations & among the period of sampling. The HM concentrations in the particulates phase are much more than dissolved phase. There were positive correlations between increasing of HMs concentration and grain size. According to Igeo, the sediments of Al‐Hwaizeh Marshes was suffering from strongly polluted with: Arsinic (As) in South Al‐Soda station; Cobelt (Co) in Um‐El.Nia'j2 station; Molebedum (Mo) in all stations. The sediments of Al‐Hwaizeh Marshes were suffering from moderately to strongly polluted for: As in Al‐Adaim1, Al‐Adaim2, Um‐El.Nia'j1, Lesan Ejerda, & Majnon stations; Cadimum (Cd) was in Um‐El.Nia'j1 & South Al‐Soda; Co & Mo were just in Um Al‐Wared station; Lead (Pb) was just in Um‐El.Nia'j1 station; Zinc (Zn) was in Al‐Adaim1, Um‐El.Nia'j2, North Al‐Soda, Um Al‐Wared, Lesan Ejerda, & Majnon stations; Iron (Fe) was in all stations; and Manganise (Mn) was in all stations. The sediments of Al‐Hwaizeh Marshes were unpoluted to modrerat values of: As was in North Al‐Soda, Um Al‐Wared, & Al‐Baidah stations; Cd was in Al‐Adaim1, Al‐Adaim2, Um‐El.Nia'j2, Lesan Ejerda, North Al‐Soda, Um Al‐Wared, Al‐Baidah & Majnon stations; Co was in just North Al‐Soda station; Mo was in South Al‐Soda, & Lesan Ejerda; Niickal (Ni) was just in Um Al‐Wared; Pb was in Al‐Adaim1, Al‐Adaim2, Um‐El.Nia'j2, Lesan Ejerda, south Al‐Soda, North Al‐Soda, Um Al‐Wared, & Majnon stations; and Mn was just in Um‐El.Nia'j2 station. The Um‐El.Nia'j2 station was unpolluted with As metal; all stations were unpolluted with Co, Se, & Cu, while just Um Al‐Wared & Al‐Baidah stations were unpolluted with Pb metal. The concentrations of HMs in Potamogeton perfoliatus plant were in completely dried > semidried > permanently wet. Potamogeton perfoliatus was not considered to be a good bioindicator for Cr in all phases, and it was good indicator for others in water and sediments. The V. bengalensis was not considered to be a good bioindicator for Cd, Pb, Cu, and Zn, and it was a good bioindicator of As, Co, Cr, Ni, Mo, & Fe in sediments, and a good bioindicator of As, Co, Cr, Pb, Ni, Mo, and Cu in water column. The BCF values for all elements were more than BSF values. HMs in V. bengalensis and P. perfoliatus, come from same sources. IV
No Dedication Acknowledgements Summary Table of Contents List of Tables List of Figures List of Annexes List of Acronyms
Table of Contents Title
Page I II III V VIII VIII X XII
Chapter One Introduction and literature Review (1) 1. Introduction 1.1. Sources of heavy metals in the aquatic ecosystems 1.1.1. Nonpoint source pollution 1.1.2. Point source 1.2. Biological Effects of HMs 1.3. Environmental Fate of HMs 1.3.1. Sediment‐Water partitioning 1.3.2. Transport and deposition in catchments 1.3.3. Cycling of HMs in aquatic ecosystems 1.4. Mesopotamian Marshes background 1.5. Literature Review 1.5.1. HMs in Water 1.5.2 HMs in Sediments 1.5.3. Snail as bioindicators 1.5.4. Plants as bioindicator 1‐6 Aims of the Study Chapter Two Materials and Methods (2) 2.1. The study Site 2.1.1. General description of sampling sites 2.1.1.1. Al‐Hawizeh Marsh 2.1.1.1.1. Input stations 2.1.1.1.2. Outlet stations 2.1.1.1.3. Open water marsh stations 2.1.1.1.4. Shallow marshes stations 2.1.1.2 The Central Marshes 2.1.1.3. Al‐Hammar Marshes
1 2 3 3 4 4 5 5 6 6 6 7 8 10 11 11 13
14 15 15 15 16 16 17 18 19 20 V
2.2 2.2.1 2.2.2 2.2.2.1 2.2.2.2 2.2.2.3 2.2.2.4 2.2.3 2.2..4 2.2.5 2.2.6 2.2.7 2.2.7.1 2.2.7.2 2.2.7.3 2.2.8 2.2.8.1 2.2.8.2 2.2.8.3 2.2.8.3.1 2.2.8.3.2 2.2.8.4 2.2.8.4.1 2.2.8.4.2 2.2.8.5 2.2.8.6 2.2.9 2.2.10
Materials and methods Sampling collection strategy General sampling procedures Water Sediments Sub‐merged plant samples Snail samples Field measurements
Water discharge Total suspended solid (TSS) Total Hardness (TH), Ca2+, and Mg2+ ,HCO3‐, Cl‐, and SO42‐concentration Sediments analysis Sediments EC and pH TOC % and TOM% Grain size analysis (%) Heavy Metals Analysis methods Dissolved phase Particulate metals Exchangeable metals Residual metals Sediments Exchangeable metals Residual metals Plants Samples Snails Samples The laboratories of did this work Calculation of Bio‐concentration Factor (BCF), Biota Sediment Factor (BSF), and Geoaccumulation Index (Igeo) 2.2.11 Calculation of the load 2.2.12 Statistical analysis Chapter Three The Results (3) 3.1 The results of monthly monitoring of HMS concentration in the Central, Al‐Hawizeh and Al‐Hammar marshes 3.1.1 The environmental parameters 3.1.2 Dissolved heavy metals 3.2 The results of loading of HMs in Al‐ Hawizeh marsh 3.3 The relationship between heavy metals concentrations and water/sediment quality in Al‐Hawizeh Marsh 3.3.1 Water quality
26 26 26 26 26 26 27 28 28 30 30 30 30 30 30 30 30 31 31 31 31 32 32 32 32 32 32 33 33 33
36 37 37 37 43 49 49 VI
3.3.2 3.3.3 3.3.3.1 3.3.3.2 3.3.3.2.1 3.3.3.2.2 3.3.3.3 3.3.3.3.1 3.3.3.3.2 3.4
Sediment quality Heavy Metals Dissolved heavy metals Particulate HMs phase Exchangeable HMs Residual HMs Sediments HMs Exchangeable HMs. Residuals HMs The results of Bellamya (Viviparus) bengalensis snails and Potamogeton perfoliatu plant as bio‐indicators of HMs in Al‐Hawizeh Marsh 3.4.1. Plant’s heavy metals 3.4.2. Snail’s heavy metals
51 53 53 56 58 60 63 63 67 70 70 74
Chapter Four The Discussion (4) 4.1 Monthly monitoring of the concentration of heavy metals in the Central, Al‐Hawizeh and Al‐Hammar marshes in dissolved phase 4.1.1 Water Quality 4.1.1.1 Water temperature (WT) 4.1.1.2 Salinity (Sal) and Electrical Conductivity (EC) 4.1.1.4 Dissolved Oxygen (DO) 4.1.1.5 Hydrogen Ion Concentrations (pH) 4.1.1.6 Total dissolved solids (TDS) 4.1.1.7 Total suspended solids (TSS) 4.1.1.8 Total hardness (TH), Calcium concentrations (Ca+2),& Magnesium concentrations (Mg+2) 4.1.2 Dissolved Heavy Metals 4.2 The load of HMs in Al‐ Hawizeh Marsh 4.3 The relationship between heavy metals concentrations and water/sediment quality 4.3.1 Water quality 4.3.2 Sediments quality 4.3.2.1 Soil texture 4.3.2.2 pH value 4.3.2.3 Electrical conductivity 4.3.2.4 TOC and TOM % 4.3.3 Heavy metals 4.3.3.1 Dissolved phase 4.3.3.2 Particulate phase
78 79 79 79 79 80 80 81 82 82 84 85 88 88 89 89 89 90 90 91 91 93
VII
4.3.3.3 4.4 4.4.1 4.4.2
Heavy metals in Sediment Can Bellamya (Viviparus) bengalensis snails and potamogeton perfoliatus plant be used as bio‐indicators ? Potamogeton perfoliatus (P. perfoliatus ) submerged plants as bioindicator Bellamya (Viviparus) bengalensis Snail as Bioindicators
94 96 97 98
Conclusion and Recommendations The Conclusion The Recommendations
103 104 List of Tables
Table No. 2‐1 2‐2 2‐3 2‐4 2‐5 3‐1 3‐2 3‐3 4‐1
Fig. No. 2‐1 2‐2 2‐3 2‐4 2‐5 2‐6 3‐1 3‐2
Title The geographical positions of studied stations (GPS) The sampling Program of the study (2006) A list of instruments that were used in field and lab works. The degree of metal pollution in terms of seven enrichment classes.. The average natural contents in Shale rocks of heavy metals. The monthly variation of some water quality parameters in the Mesopotamian Marshes (2006) The seasonally variation of some water parameters The seasonally variation of some sediment parameters. Comparative of HMs load in present study with Mediterranean Basin.
Page 25 27 34 35 35 38 50 52 87
List of Figures Title Page Mesopotamian Marshes Map, Southern Iraq 22 The seventeen study site stations in Al‐Hawizeh Marsh (2006). 23 The study stations of three marshes (Central, Al‐Hammar, and Al‐ 24 Hawizeh Marshes) monitoring (2006). Potamogeton perfoliatus plant image. 27 Bellamya (Viviparus) bengalensis Snails image. 28 Cross section of a stream divided into vertical sections for measurement 29 of water flow and discharge. The monthly variables of As(A), Cd(B), Co(c), Cr(D), Mo(E), …….. in 40 Central, and Al‐Hammar stations during the study period (2006). Mean concentrations of HMs (ppm) in the study sites during the study 43 period (2006).
VIII
3‐3
3‐4 3‐5 3‐6 3‐7 3‐8 3‐9 3‐10 3‐11 3‐12 3‐13
3‐14
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3‐18
3‐19
The water input (A), outlet (B), and Comparative among average of input, outlet, and net of outlet water discharge (C) during May, Aug, and Dec (2006) in the Al‐Hawizeh Marshes. The load of heavy metals in the st.1 (Ton/Month) during 2006, in the Al‐ Hawizeh Marshes. The load of heavy metals in the st.2 (Ton/Month) during 2006, in the Al‐ Hawizeh Marshes. The load of heavy metals in the st.3 (Ton/Month) during 2006, in the Al‐ Hawizeh Marshes. The load of heavy metals in the st.4 (Ton/Month) during 2006, in the Al‐ Hawizeh Marshes. The load of heavy metals in the st.5 (Ton/Month) during 2006, in the Al‐ Hawizeh Marshes. The load of heavy metals in the st.6 (Ton/Month) during 2006, in the Al‐ Hawizeh Marshes. The load of heavy metals in the st.7 (Ton/Month) during 2006, in the Al‐ Hawizeh Marshes. The input and outlet load of heavy metals during the period of study (2006) in the Al‐Hawizeh Marshes. The triangle of soil texture in study stations in the Al‐Hawizeh Marshes during (2006). The mean dissolved concentration of: As(A), Cd(B), Co(C), Cr(D), Mo(E), Ni(F), Pb(G),Se(H), Zn(I), Cu(J), Fe(K), and Mn(L) ppm during the period of study(2006) in the Al‐Hawizeh Marshes. The mean exchangeable particulate concentration of: As(A), Cd(B), Co(C), Cr(D), Mo(E), Ni(F), Pb(G),Se(H), Zn(I), Cu(J), Fe(K), and Mn(L) ppm during the period of study(2006) in the Al‐Hawizeh Marshes. The mean of residual particulate concentration of: As(A), Cd(B), Co(C), Cr(D), Mo(E), Ni(F), Pb(G),Se(H), Zn(I), Cu(J), Fe(K), and Mn(L) ppm during the period of study (2006) in the Al‐Hawizeh Marshes. The mean of exchangeable: As(A), Cd(B), Co(C), Cr(D), Mo(E), Ni(F), Pb(G),Se(H), Zn(I), Cu(J), Mn(K), and Fe(L) ppm in sediments during the period of study(2006) in Al‐Hawizeh Marshes. The mean and standard error of: As(A), Cd(B), Co(C), Cr(D), Mo(E), Ni(F), Pb(G),Se(H), Zn(I), Cu(J), Fe(K), and Mn(L) ppm in residual phase in the sediment of Al‐Hawizeh Marshes, during the period of study(2006). The concentration and standard error of plant’s: As(A), Cd(B), Co(C), Cr(D), Mo(E), Ni(F), Pb(G),Se(H), Zn(I), Cu(J), Fe(K), and Mn(L) ppm during the period of study (2006). The mean and standard error concentration of snial’s: As(A), Cd(B), Co(C), Cr(D), Mo(E), Ni(F), Pb(G),Se(H), Zn(I), Cu(J), Fe(K), and Mn(L) ppm during the period of study(2006) in Al‐Hawizeh Marshes.
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45 45 46 46 47 47 48 48 51 53
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IX
List of Annexes Annex (1) Title
Table Page No. 1 The median, standard deviation (Std.Dev), standard error (Std. Err), size of 106 sample, minimum (Min), and maximum (Max) of studied physio‐chemical parameter of the three Mesopotamian Marshes during the study period (2006). 2 The correlations among heavy metals concentrations and studied physio‐ 106 chemicals parameters in the three Mesopotamian Marshes (r= 0.11, p >0.05).
1
2
3
4
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6
7 8 9
Annex (2) Title The mean, median, standard deviation (Std.Dev), standard error (Std. Err), minimum (Min), and maximum (Max) of water quality parameter during (2006) in Al‐Hawizeh Marsh. The mean, median, standard deviation (Std.Dev), standard error (Std. Err), minimum (Min), and maximum (Max) of some sediments quality during (2006) in Al‐Hawizeh Marsh. The mean, median, standard deviation (Std.Dev), standard error (Std. Err), minimum (Min), and maximum (Max) of dissolved HMs (ppm) during (2006) in Al‐Hawizeh Marsh. The mean, median, standard deviation (Std.Dev), standard error (Std. Err), minimum (Min), and maximum (Max) of exchangeable HMs in the particulate (ppm) during (2006) in Al‐Hawizeh Marsh. The mean, median, standard deviation (Std.Dev), standard error (Std. Err), minimum (Min), and maximum (Max) of residual HMs in the particulate (ppm) during (2006) in Al‐Hawizeh Marsh. The mean, median, standard deviation (Std.Dev), standard error (Std. Err), minimum (Min), and maximum (Max) of exchangeable HMs in the sediments (ppm) during (2006) in Al‐Hawizeh Marsh. Table (8): The mean, median, standard deviation (Std.Dev), standard error (Std. Err), minimum (Min), and maximum (Max) of residual. The correlations among HM concentrations in dissolved phase and physio‐ chemicals parameters in Al‐Hawizeh Marsh during (2006). The HM analysis of variance (ANOVA, F values at r=0.05) of Al‐Hawizeh Marsh stations and seasons (2006).
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X
10 11 12 13
1 2 3
4 5 6 7 8 9 10 11 12 13
The correlations among particulate HM concentrations in exchangeable phase and physio‐chemicals parameters in Al‐Hawizeh Marsh during (2006). The correlations among particulate HM concentrations in residual phase and physio‐chemicals parameters in Al‐Hawizeh Marsh during (2006) . The correlations among sediment HM concentrations and some sediment parameters in Al‐Hawizeh Marsh during (2006) . The geochemical index of studied HMs in Al‐Hawizeh Marsh during the study period (2006). Annex (3) Title The mean, median, standard deviation (Std.Dev), standard error (Std. Err), Min, and Max of HMs in the tissues of Potamogeton perfoliatu plant (ppm) during (2006) in Al‐Hawizeh Marsh. The mean, median, standard deviation (Std.Dev), standard error (Std. Err), Min, and Max of HMs in the tissues of Viviparus bengalensis snails (ppm) during (2006) in Al‐Hawizeh Marsh. The bio‐concentration Factor (BCF), and Bio Sedimentation Factor (BSF) of HMs in P. perfoliatus plant and V. bengalensis snails studied stations during (2006). The correlations among different phases of water sediments and biota of Arsenic (As) in Al‐Hawizeh Marsh during (2006) . The correlations among different phases of water sediments and biota of Cadmium (Cd) in Al‐Hawizeh Marsh during (2006) . The correlations among different phases of water sediments and biota of Cobalt (Co) in Al‐Hawizeh Marsh during (2006) . The correlations among different phases of water sediments and biota of Chrome (Cr) in Al‐Hawizeh Marsh during (2006). The correlations among different phases of water sediments and biota of Selenium (Se) in Al‐Hawizeh Marsh during (2006). The correlations among different phases of water sediments and biota of Lead (Pb) in Al‐Hawizeh Marsh during (2006). The correlations among different phases of water sediments and biota of Zinc (Zn) in Al‐Hawizeh Marsh during (2006). The correlations among different phases of water sediments and biota of Nickel (Ni) in Al‐Hawizeh Marsh during (2006) . The correlations among different phases of water sediments and biota of Manganese (Mn) in Al‐Hawizeh Marsh during (2006) . The correlations among different phases of water sediments and biota of
119 119 120 120
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126 126 127 127 127 128 128 129 129 130 XI
14 15
Molybdenum (Mo) in Al‐Hawizeh Marsh during (2006) . The correlations among different phases of water sediments and biota of Iron (Fe) in Al‐Hawizeh Marsh during (2006) . The correlations among different phases of water sediments and biota of Cooper (Cu) in Al‐Hawizeh Marsh during (2006).
130 131
List of Acronyms Ad1 Ad2 Al‐Bur Al‐Nag As B.albagh BCF Bed BSF DO EC HM Igeo LesEj M.albagh Maj Mg2+ pH Sali SO42‐ Sod.N Sod.S TDS TH TOC TOM TSS Tur UmNj UmWd WT
Al‐Adaim 1 station Al‐Adaim 2 station Al‐Burgah station Al‐Nagarah station Arsenic Beginning Al‐Baghdadia station Bio‐Concentration Factor Al‐Bedah station Bio‐Sedimentation Factor Dissolved Oxygen Electrical Conductivity Heavy metal Geo‐accumulation Index Lissan Ejerda station Middle Al‐Baghdadia station Majnoon station Magnesium ion Hydrogen Ion Concentration Salinity Sulfate ion Al‐Soda North station Al‐Sod South Station Total dissolved solids Total hardness Total organic carbons Total organic matters Total suspended solids Turbidity Um El‐Nia’aj station Um Al‐Wared station Water temperature XII
Chapter One
Introduction and Literature Review 1
Chapter One: Introduction and literature Review 1. Introduction: Generally, the human environment is defined as a biosphere that includes the land cover, atmosphere and many types of organisms. The biosphere is large and verey complex, but it is branched to small units pursuant to the relation between living beings and arranges environment such as earth, water, and air (FAO, 1994). Pollution is defined as any change (sudden or gradual) in the physical, chemical, and bioproperties in environment and its compostions (Irabii, 2001). Main subject of pollutants for water are suspended solids, heavy metals, oils and greases, oxygen demand and organic compound (UNEP 2003). Heavy metals (HMs) are elements having atomic weights between 63.546 and 200.590 (Kennish, 1992), and a specific gravity greater than 4.0 (Bradl, 2005). The normal metal content in aquatic environment has not been clearly defined, since it varies from one place to another according to geological nature of the catchment area. Such data are essential to impact of pollution sources, and for the study of transfer to man by various means (Hynes, 1970). Davies (1980) defined the HMs as those elements in the periodic table with a density of greater than 6 g.cm‐3, although lower densities and other properties are commonly taken as a basis for distinguishing heavy metals from other elements of the periodic table (Forstner and Wittmann, 1983; Jarvis, 1983; and Fergusson, 1990). The healthy water bodies have a balance of plant and animal life represented by great species diversity. Pollution disrupts this balance, resulting in a reduction in the variety of individuals and dominance of the surviving organisms (Viessman, et al., 1985). Over the past decade, although there has been an increasing attention to persistent organic contaminants, greenhouse gases and global warming, toxic heavy metals in the aquatic environment remains an enduring threat. Continued introduction of metals into the aquatic environment by industrial processes, domestic practices and mining have ensured that the levels of contamination continue to be a problem Anthropogenic emissions of heavy metals exceed the fluxes from natural sources (Nriagu, 1990). Living organisms require trace amounts of some heavy metals, including cobalt, copper, iron, manganese, molybdenum, vanadium, strontium, and zinc for metabolism but may become toxic at certain concentrations. Excessive levels of essential metals, however, can be detrimental to the organism. Non‐essential heavy metals of particular concern to surface water systems are cadmium, chromium, mercury, lead, arsenic, and antimony (Frenet, 1981; Kennish, 1992; Al‐Taee, et al., 2007; and Hussein, et al., 2007). All heavy metals exist in surface waters in colloidal, particulate, and dissolved phases, although dissolved concentrations are generally low (Kennish, 1992). The colloidal and particulate metal may be found in: 1‐ Hydroxides, oxides, silicates, or sulfides. 2‐ Adsorbed to clay, silica, or organic matter. The soluble forms are generally ions or unionized organometallic chelates or complexes. The solubility of heavy metals in surface waters is predominately controlled 2
Chapter One: Introduction and literature Review by the water pH, the type and concentration of ligands on which the metal could adsorb, and the oxidation state of the mineral components and the redox environment of the system (Wood, 1989; and Bradl, 2005). So, we can say the HMs in aquatic ecosystems subdivided into: Dissolved part, and Particulates (Exchangeable, and Residual). There are six forms of metals that associated with sediments. In the first one these metals are associated with the sediment in the most labile obtaind manner; these are called exchangeable metals. The second fraction extractes is united mainly with carbonates and is highly sensitive to pH changes. In the third the metals bonded to Mn oxide and partly amorphous Fe oxide and in the fourth one, amorphous and poorly crystalline Fe oxide. In the fifth, the metals associated with the organic material and sulfides are released. Finally, the residual fraction, a portion of metals that are strongly bonded to the lithogenic minerals of the sediments. Speciation is not only very useful for determining the degree of associations of the metals in the sediment and to what extent they may be remobilized in to the environment (Forstner et al., 1990), but also for distinguishing those metals with a lithogenic origin from those with origin . According to Izquierdo, et al.(1997), metals with an anthropogenic origin are mainly obtained in the first extractions, while in the last stage of the process, the residual fraction is obtained, corresponding to metals with lithogenic origin, and according to Chester and Voutsinou (1981) the HMs in the sediments are subdivided just in to two parts: Exchangeable, and Residual. 1‐1. Sources of the Heavy Metals in the Aquatic Ecosystems: Heavy metals may be introduced into the aquatic environment as a result of natural weathering, erosion and transport processes, as well as from a range of anthropogenic activities. The principal natural sources of heavy metals in the atmosphere are wind‐ blown soils, volcanic eruptions, sea spray, forest fires and biogenic aerosols. Natural geochemical processes within terrestrial and aquatic environments are dominated by weathering and erosional processes. The transport and subsequent deposition of heavy metals in natural environments are dominated by hydrological processes. As many heavy metals have low solubility under the range of redox potential (Eh) and pH conditions usually encountered in non‐ contaminated environments, their redistribution is often associated with the erosion, transport and selective deposition of fluvial and limnic sediments (Nriagu, 1989; and Nriagu & Pacyna, 1988). Aquatic ecosystems throughout the world have endured chronic inputs of heavy metals from industrial processing, mining, combustion of fossil fuels, effluents from sewage treatment plants and atmospheric deposition. Some aquatic organisms are stressed by this contamination, which, in turn, impacts the ecosystem as a whole (Knutson et al., 1987). The world‐wide anthropogenic input of heavy metals into aquatic ecosystems quantified as of 1988 were 9.1,112,237,114, and 138 (in thousands of tones per year) for Cd, Cu, Zn, Pb and Ni; respectively (Nriagu & Pacyna 1988). The broad distribution patterns of metals released into the environment means that they cannot be efficiently recovered or recycled. 3
Chapter One: Introduction and literature Review Nonpoint source pollution: Natural: Chemical and physical weathering of igneous and metamorphic rocks and soils often release heavy metals into the sediment and into the air. Other contributions include the decomposition of plant and animal detritus, precipitation or atmospheric deposition of airborne particles from volcanic activity, wind erosion, forest fire smoke, plant exudates, and oceanic spray (Kennish, 1992). Anthropogenic: Surface runoff from mining operations usually has a low pH and contains high levels of metals such as iron, manganese, zinc, copper, nickel and cobalt. The composition of fossil fuels pollutes the atmosphere with metal particulates that eventually settle to the land surface. Urban stormwater runoff often contains metals from roadways and atmospheric fallout. Currently, anthropogenic inputs of metals exceed natural inputs (Kennish, 1992). 1‐1‐2. Point sources: Domestic wastewater effluent contains metals from metabolic wastes, corrosion of water pipes, and consumer products. Industrial effluents and waste sludges may substantially contribute to metal loading (Bradl, 2005). Currently, anthropogenic inputs of metals exceed natural inputs. Excess metal levels in surface water may pose a health risk to humans and to the environment. 1‐2. Biological Effects of HMs: Metal ions in the environment are bio‐magnify in the food chain and accumulated in tissues. Therefore, their toxic effects are especially pronounced in animals of higher trophic levels such as humans. In most cases, however, there is no specific treatment for heavy metal removal. While the heavy metal ions may be accumulated in the sludge of biological treatment seeps, which leads to a purification of the liquid phase. Ingestion of metals may pose great risks to human health. Metals such as lead and cadmium will interfere with essential nutrients of similar appearance, such as calcium (Ca2+) and zinc (Zn2+)(Tien & Huang, 1991; and Jamil, 2001 ). Many organisms are able to regulate the metal concentrations in their tissues. Fish and Crustacea can excrete essential metals, such as copper, zinc, and iron that are present in excess. Some can also execrate non‐essential metals, such as mercury and cadmium, although this is usually met with less success. Research has shown that aquatic plants and bivalves are not able to successfully regulate metal uptake (Bradl, 2005). Thus bivalves tend to suffer from metal accumulation in polluted environments. In aquatic systems, bivalves often serve as biomonitor organisms in areas of suspected pollution (Kennish, 1992). Shellfishing waters are closed if metal levels make shellfish unfit for human consumption (Jamil, 2001). Metal uptake rates will vary according to the organism and the metal in question. Phytoplankton and zooplankton often assimilate available metals quickly because of their high surface area to volume ratio. The ability of fish and invertebrates to adsorb metals is largely dependent on the physical and chemical characteristics of the metal.
4
Chapter One: Introduction and literature Review For example; the exception of mercury, little metal bioaccumulation has been observed in aquatic organisms (Kennish, 1992). Natural metal recycling in the environment makes metal recovery the only effective way of preventing heavy metals from poisoning the environment. The toxicity is largely a function of the water chemistry and sediment composition in the surface water system (Jamil, 2001). According to Gunther & Yang (1968); Jamil (2001); and Bradl (2005), the slightly elevated metal levels in natural waters may cause the following sublethal effects in aquatic organisms: 1‐ Histological or morphological change in tissues. 2‐Changes in physiology, such as suppression of growth and development, poor swimming performance, changes in circulation. 3‐ Change in biochemistry, such as enzyme activity and blood chemistry. 4‐ Change in behavior. 5‐ Changes in reproduction. Metals may enter the systems of aquatic organisms via three main pathways (Jamil, 2001; and Bradl, 2005): 1‐Free metal ions that are absorbed through respiratory surface (e.g., gills) are readily diffused into the blood stream. 2‐Free metal ions that are adsorbed onto body surfaces are passively diffused into the blood stream. 3‐Metals that are sorbet onto food and particulates may be ingested, as well as free ions ingested with water. 1‐3. Environmental Fate of HMs: The behavior of metals in natural waters is a function of the substrate sediment composition, the suspended sediment composition, and the water chemistry. Sediment composed of clay, fine sand, and silt which generally have higher levels of adsorbed metal than quartz, feldspar, and detrital carbonate‐rich sediment. Metals also have a high affinity for humic acids, organo‐clays, and oxides coated with organic matter (Bradl, 2005). Of particular significance in quantifying the spatial and temporal trends in metal transport and in assessing the relative significance of the various heavy metal pathways is the partitioning of metals between suspended sediment and water; the mechanisms by which heavy metals are retained in the particulate fraction and the post‐depositional stability of sediment‐associated metals within the river corridor (Stumm & Morgan, 1981; Forstner & Wittmann, 1983; Forstner, 1983; Salomons & Forstner, 1984; Lunt et al., 1989; Fergusson, 1990; and Horowitz, 1991) 1‐3‐1. Sediment‐ water partitioning In river systems, trace metal concentrations in suspended solid are greater than in the water column, although trace metal partitioning is a function of the characteristics of the metal ion, particle size, organic content and sediment concentration (Rygwelski, 1984). 5
Chapter One: Introduction and literature Review An understanding of the contribution made by the sediment‐associated fraction to the total load requires knowledge of the effects of particle size, organic matter content, sediment surface area and the surface coatings on the suspended particles. Furthermore, the individual and combined effects of Eh and pH have a well documented impact on the partitioning of metals between sediments and the water column (Stumm & Morgan, 1981; Salomons &Forstner, 1984; and Fergusson, 1990). The fraction of heavy metals carried with suspended sediment, particle size is one of the most important physical controls as the key to understanding the environmental impact of trends in metal behaviour lies in quantifying the metal associations in sediments and the reactions which occur between sediments, water and biota (Forstner, 1983; Engstrom & Wright, 1984; Bengtsson & Enell, 1986; Horowitz, 1991; and Horowitz et al., 1993). 1‐3‐2. Transport and Deposition in Catchments The route that metals take through a catchment depends on whether they are discharged directly into water courses, into the atmosphere or onto the land, or whether they are discharged in liquid, solid or gaseous phases. Because metals are often associated with particulate transport, their dispersal through catchment systems is largely a function of hydraulic conditions which control 1) Sorting, according to differences in particle density and particle size; 2) mixing processes, where uncontaminated sediments are added to the aquatic system; and, 3) storage and deposition on the floodplain, fluvial substrate, lakes, reservoirs and estuaries (Graf, 1990). Deposition on the floodplain is controlled by the magnitude and frequency of overbank flows and the hydraulic conditions on the floodplain, whereas in basin substrates, the deposition and ingress of fine grained sediments into and through the amour layer is often associated with hydraulic controls, such as stream power (Hughes, 1992). 1‐3‐3.Cycling of HMs in aquatic ecosystems Upon entering aquatic systems, metals move downward through the water column towards the sediment during which time they can be accumulated by pelagic organisms (fish, zooplankton and phytoplankion). Ultimately, metals reach the sediment which serve both as a source and sink (Livett, 1988). These substances tend to sorb to sediments and organic materials by adsorption (scavenging), co‐precipitation, and cellular internalization by organisms and eventually become highly concentrated in the sediments. Most HMs become bioavailable to sediment‐dwelling organisms, which can disperse toxins via predation and/or bioavailability to organisms at higher tropic levels, eventually impacting human consumers. Phytoplankton and periphyton are primary producers in an aquatic ecosystem and comprise the first trophic level, they adsorb pollutants and transfer metals to the next trophic level, the micro zooplankton, which in turn regenerates metal contaminants either by fecal pellets or through predation by higher trophic level organisms (Twiss et al., 1996; and Betsey , 2006). So, the Sediments are the principal sink for heavy metals in an aquatic environmental, but when the environmental conditions change, sediments 6
Chapter One: Introduction and literature Review can act as a source. To assess the environmental impact of polluted sediments, information on total concentration alone is not sufficient because HMs are present in different chemical forms in sediments (metal carbonates, oxides, sulfides, organometallic compounds, etc.). Only part of the metals present can be easily remobilized. Thus, the chemical form of the metals in the sediment is of great significance in determining behavior in the environment and their remobilization potential (Rauret et al., 1988) 1‐4. Mesopotamian Marshes Background: The Mesopotamian marshland in southern Iraq, has enormous ecological and environmental importance. It represents habitats for biodiversity, wildlife, and cultural richness; a 5000‐year‐old culture, heir to the ancient Sumerians and Babylonians (UNEP, 2002; and Ochsenschlager, 2004). They are considered by many to be the “cradle of western civilization” and are often referred to as the Garden of Eden (Nicholson & Clark, 2002). Moreover, it is the main stopover on the Siberia‐African bird migration route (UNEP, 2002; Evans, 2002; Richardson et al., 2005; and Richardson & Hussain, 2006), and a crucial filter that cleanses the rivers as they flow into the Gulf( Saeed et al., 1999; Al‐Ghadban et al., 1999; and Richardson et al., 2005). The Iraqi marshlands are one of the finest and most extensive natural wetland ecosystems in Europe and western Asia (Evans, 2002). Around 85% of the Mesopotamian Marshlands have been lost mainly as a result of drainage and damming, (UNEP, 2002). Most of the damage was done between 1991 and 1995, and most dramatic change occurred between 1993 and 1994 (the vegetation cover was reduced by 79 % )(Munro & Touron, 1997). Currently, restoration by re‐flooding of drained marshes is proceeding, and the ecological effects of this massive water diversion need elaborated research. Hence, the reflooding of southern Iraq’s Mesopotamian marshes is now a giant ecosystem‐level experiment (Richardson & Hussain, 2006). The great bulk of information available on the fauna, flora and ecology of the wetlands of Iraq were obtained prior to the onset of the Iran/Iraq war in 1980, when large areas of wetland, especially in Mesopotamia, remained more or less intact. Dam‐ building activities on the Tigris and Euphrates Rivers in recent years, both within Iraq and upstream in Turkey and Syria, are known to have resulted in the loss of much of the former wetland habitat, while major hydrological engineering works in Lower Mesopotamia within the last few years have caused, and continue to destroy wetlands on a massive scale (Richardson & Hussain, 2006). The larger wetlands within this complex ecosystem are: The Al‐Hammar and its associated marshes south of the Euphrates, The Central Marshes (a vast complex of permanent lakes and marshes north of the Euphrates and west of the Tigris), & Al‐ Hawizeh Marsh and its associated marshes (extending east from the Tigris into neighboring Iran). These wetlands drain southeast wards into the Gulf via the Shatt Al‐ Arab waterway (Rushdi et al., 2006). 1‐5. LITERATURE REVIEW: Trace metals enter southern Iraqi marshes from both natural and anthropogenic sources (Mustafa, 1985; Abaychi & Al‐Saad, 1988; and Al‐Saad, 1995). Natural sources include storm dustfall, erosion or crustal weathering and decomposition of the biota in 7
Chapter One: Introduction and literature Review the water, whereas the anthropogenic sources include sewage wastes, industrial effluent, automobile effluent, petroleum and fertilizer industry effluent (FAO, 1994). Trace metals are also incorporated into the food chain from fish either from water via gills or from sediments and marine organisms via the gut track (Al‐Saad et al., 1997). The Shatt Al‐Arab and adjacent area receive trace metals from different sources (Al‐Khafaji, 1996). The previous studies on Mesopotamian Marshes environment were substantial work has been done during past decades looking at the physical‐chemical parameters in running freshwater ecology in southern parts of Iraq such as the Shatt A‐Arab River, Shatt Al‐Basrah, and Khwar Al‐Zubair (Saad, 1978; and Abaychi & Al‐Obaidy, 1987). Little is known about water habitat in the marshlands due to desiccation (1980’s and 1990’s) and restrictions. Before desiccation of Iraqi marshlands, many studies were conducted especially for water from Al‐Hammar marshes (Mohammad, 1965; Pankow et al., 1979; Maulood et al., 1981; Al‐Mousawi & Whitton, 1983; Al‐Zubaidy, 1985; Al‐ Lamy, 1986; Kasim, 1986; Hassan, 1988; Al‐Sayab, 1988; Abed, 1989; Al‐Rikaby, 1992; and Al‐Mousawi & Hussein, 1992 ). A comprehensive study for southern Iraqi water was conducted by Al‐Sahaf (1975), in which parameters measured were acceptable for acceptable water quality. Aqrawi & Evans (1994) studied the sedimentation in Iraqi marshes by collecting sediment samples during 1990. For Al‐Hawizeh marshes, the only study conducted was that by Wali (1967) which was concerned with social, agricultural, living and transportation affairs, and Al‐ Hilli (1977) did study about the plant ecology of Mesopotamian Marshes in 1977. However few studies have been undertaken, however, addressing the distribution of heavy metals in Iraq inland standing water, whereas some work has already appeared on running water (Abaychi & Douabul, 1985; Sheriff, et al., 1992; Al‐Saadi, et al., 1999; and Abaychi, 1995). Heavy metals in both standing and running Iraq inland waters received little attention; their normal content, geochemical cycles and their distributions in our aquatic environment have not been clearly identified (Al‐Haidarey, 2003). Just few months after the re‐flooding of the Mesopotamian marshes, lots of scientist, universities professors, Ministries, and organizations started to study and investigate the new re‐flooded system, such as: Iraqi Foundation (IF) teem (2003) studied the water quality in the Mesopotamian marshes; Richardson, et al. (2005) studied the ecological assessment of Al‐Hammar, Central Marsh, and Al‐Hawizeh marshes after being re‐ flooded. In this study, used the Ecosystem Functional Assessment (EFA) method to estimate the overall ecosystem health; in this study showed that the nearly 20% of the original 15,000‐square‐kilometer marsh area was re‐flooded by March 2004, but the extent of marsh restoration was unknown. High‐quality water, nonsaline soils, and the densest native vegetation were found in the only remaining natural marsh, the Al‐ Hawizeh, located on the Iranian border. Although substantially reduced in area and under current threat of an Iranian dike, it had the potential to be a native repopulation center for the region. Rapid reestablishment, high productivity, and reproduction of native flora and fauna in reflooded former marsh areas indicate a high probability for successful restoration, 8
Chapter One: Introduction and literature Review provided the restored wetlands are hydraulically designed to allow sufficient flow of non contaminated water and flushing of salts through the ecosystem; Al‐Kinzawi (2007) studied the biomass and biodiversity of aquatic plants in Central marsh; Neghamish & Ali (2005) have studied the physical and chemical properties of water for many locations of Thi‐Qar Marshes during July‐August 2004. 1‐5‐1. HMs in Water: The HMs in water resources has important repercussion for the environment and for human health, as a results there have been many studies in different region of the world designed to evaluate the degree of HMs pollution of a given system (Dilek & Ahmet , 2004; Ahmet, et al., 2005 ; and Dilek & Ahmet, 2006) Few studies were about the HMs pollution along the Tigris, Euphrates, and Shatt Al‐ Arab River. In Shatt Al‐Arab River Abaychi & Douabul (1985), and Abaychi & Al‐Saad (1988) studied HMs, they recorded higher concentration of Ni and V. Al‐Saad (1995) and Al‐ Khafaji (1996) studied dissolved and particulate phase of HMs in waters of NW region of the Arabian Gulf, they found seasonal variation in concentration of different elements. Al‐Hajaj(1997) described the distribution of HMs in waters and sediments in the Al‐ Ash’ar and Al‐Khandaq channels that which associated with Shatt Al‐Arab River, she found that there were negative significant correlation between increasing of HMs and the density of algae. Kassim, et al. (1997) studied six heavy metals (Cd, Pb , Ni , Zn , Mn and Cu) at the upper region of the Euphrates river, they recorded clear seasonal variation in their concentrations in filtered water. These concentrations were much higher in the suspended particles, and they found that HM concentrations in the Upper Euphrates lower than their concentrations in Tigris River. Sabri, et al. (1993) studied the concentrations of Cd, Cu, Co, Fe, Zn, Mn, Pb and Ni in water in Tigris River at Samarra, they recorded that concentrations in water were either significantly lower or within the Iraqi river water standards and the average clean river water of the world. Variations in the concentrations of heavy metals in suspended solids were interpreted to be due to local differences in current velocity and distance from the shore line (from sewage source of the residential sector). Results stress the importance of the suspended solids in transportation of heavy metals in Tigris River. Higher concentrations of Co, Mn and Fe are discussed in relation to sedimentation process and the nature of the river basin. Al‐Imarah et al. (2000), have a comprehensive study for determination of HMs in water from southern Iraq, which covers Tigris River, Al‐Izz River within the marshes, Shatt Al‐Arab, Shatt Al‐Basrah and Khor Al‐Zubair has been conducted that the concentration of HMs were higher than allowed levels by WHO (1971) and Iraqi limitations for freshwater quality. Al‐Saadi, et al. (2002) studied HMs in the Habbaniya lake (Cu, Cd, Pb, Ni, Mn, and Zn), Zn had the highest concentration among the studied metals in filtered water and suspended particles with an average of 4.08 μg/l and 26088 μg/g, respectively. Al‐Saa’don (2002) recorded the concentration of Pb , Cd, Cr, Co, and Cu were slight to high in Khor Al‐Zubair and Shatt Al‐Basrah comparable to those in other world. 9
Chapter One: Introduction and literature Review In Thiqar Government marshes, Al‐Khafaji (2005) found that the concentration of trace metals in water samples were high, that revealed the expected pollution in this area. This pollution could be arises from different sources, natural and anthropogenic, as listed above. Salman (2006) found that the heavy metals (Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) in the Euphrates River were in the permissible range of values reported for fresh water by the WHO, but they were more than that recorded by Abaychi & DouAbal (1985), in Shatt Al‐Arab River; and Al‐Taee (1999) in Al‐Hilla River. Al‐Shawi (2006) studied the physiochemical parameters in three stations in Al‐ Hammar Marsh. He listed the HMs concentrations during his study in order to compare them with the previous studied which was done before the desiccation. Hassan (2007) found the concentrations of Pb and Cd in the Shatt Al‐Arab River were much higher than normal background values and the ranges of Pb and Cd concentrations were higher than Iraqi standards of trace metals. In Shatt Al‐Hilla River Al‐ Taee, et al., (2007) studied the levels of non‐essential HMs(Al, Cd, Pb, and Hg). The concentrations of the elements, during the investigation period, were within the elevated values (comparing these results with the WHO guidelines for the domestic waters). Hussein, et al., (2007) investigated the essential trace metals concentrations (chromium, cobalt, copper, iron, manganese, molybdenum, nickel, selenium, vanadium and zinc) in Shatt Al‐Hilla River. Their study demonstrated that the concentrations of the elements fall within the high values, indicating that waste materials had been thrown into the river which became polluted. Concentrations of cobalt, iron and manganese were within the WHO limits. Adam et al. (2007) determined ten chemical elements (Al, As, Ca, Cu, Fe, Pb, Li, Mg, Hg , and Zn in water of 12 sites from southern Iraqi marshland, they recorded Calcium and Magnesium values were the highest in the range, and higher in Al‐Izz river of Central Marsh. Iron in the concentration of 0.02 mg/l was recorded in Al‐Izz river of central marsh and Al‐Tarabah village of Al‐Hawiezah marsh only. Zinc is distributed widely in Iraqi marshes, the highest recorded value for Zn was in Abu‐Ijel Marsh , Copper was in a lower concentrations and reported values in certain places only with the highest value in Um‐ Nakhlah. Mercury and Aluminum each were recorded in one site, 0.11 mg/l Mercury in Al‐Izz river and 13 mg/l Al in South of Al‐Hawiezh marsh. Lead, Lithium, and Arsenic were absent in this study. Al‐Haidarey (2009) studied the diurnal change of HMs in the Al‐ Kufa River, his results showed that the variations were caused by biological activity in the River (photosynthesis–respiration reactions), there were negative diurnal concentrations between pH, DO, chlorophyll‐a, and primary productivity with metals concentration. Generally during the sunny hours, the heavy metals concentrations were less than during the nocturnal hours. Some HMs values were more than the permissible range of values reported for fresh water by the WOH at night hours (V, Cd, Cr, and Pb). 1‐5‐2. HMS IN SEDIMENTS: On a weight per square meter basis, the uppermost‐surficial sediments constitute the largest HMs reservoir in aquatic systems. Once accumulated in sediments, the 10
Chapter One: Introduction and literature Review metals continue to pose a threat to aquatic life due to re‐suspension into the water column from geochemical re‐cycling (Santschi, et al., 1986; Wagemann, et al., 1994; Campbell & Tessier, l996; Ahmet, et al., 2005 ), accumulation in benthic fauna that feed on sediments and through food chain transfer, including organo‐elements (Luoma, et al., 1992; Lemly, 1993; Hare, et al.,1994; and MacFarlane, et al.,2006). Many studies in different region from the world have used the sediments of the wetlands as indicator for pollution (Forstner, 1983; Engstrom & Wright, 1984; Bengtsson & Enell, 1986; Horowitz, 1991; Horowitz, et al., 1993; Bradle, 2005; Dilek & Ahmet, 2006; and Syrovetnik, et al., 2007). In Arabian Gulf, Al‐Hashimi & Salman (1985) showed that the concentration of Ag, Cd, Co, Cu, Fe, Mn, Ni, Pb, V, and Zn were within the natural limits and for below the levels of pollution. Al‐Edanee, et al. (1991) studied HMs in the sediments of Khor Al‐ Zubair and they showed that the concentrations of most HMs were in the residual more than them in exchangeable phase. Al‐Abdali, et al. (1996) found that the positive correlations between increasing of trace metals concentration and decreasing of carbonate and grain size. In Shatt Al‐Arab River and Khor Al‐Zubair, Al‐Saa’don (2002) investigated the correlation among TOC, hydrocarbons and HMs, and the correlations were positive significant. Hassan (2007) showed that the concentrations of Pb and Cd in the Shatt Al‐Arab River sediments were higher than Iraqi standards and WHO, and that there were a significant variation in the Pb and Cd concentrations during winter and spring. He found that there was a significant correlation among the concentration HMs and TOC. Al‐Imarah, et al. (2007) studied the Levels of the trace metals Cd, Co, Cu, Fe, Mn, Ni, Pb and Zn in sediments from southern Iraqi wetlands represented by the three main marshes, (Al‐Haweizah, Central and Al‐Hammar), the Shatt Al‐Arab, Garmat Ali and the northern Arabian Gulf. The highest mean concentrations of trace metals in sediments (in μg/g) were 35.92 (Cd), 836.46 (Co), 48.69 (Cu), 18,435.50 (Fe), 3,648.28 (Mn), 486.95 (Ni), 5435.5 (Pb) and 539.8 (Zn) at Central Marsh, Central Marsh, Central Marsh, Al‐ Haweizah, Qurna, Garmat Ali, Qurna and Qurna respectively. Certain sites along Shatt Al‐Arab River receive huge amounts of wastes from municipal, industrial and commercial facilities, which might increase the levels of pollutants in water and sediments, as it is found in Ras Al‐Beesha at the top north of the Arabian Gulf as pollutants in the particulate phase of water are separate and precipitate. 1‐5‐3. Snail as Bioindicators : Freshwater mollusks – snails and bivalves‐ have been used frequently as bioindicator organisms. Two important advantages of snail and bivalves over most other freshwater organisms for biomonitoring are their large size and limited mobility, in addition, they are abundant in many types of freshwater environments and are relatively easy to collected and identify (Jamil, 2001). The interaction of benthic organisms with a pollutant adsorbed on the sediments is more difficult to characterize. In this case, there is contact interstitial water, free water, and solid particulates. A simplified hypothesis consists of allowing that the organisms are exposed to interstitial water, which enables that use of habitual toxicity assays to characterize the effects (Dickson, et al., 1987). 11
Chapter One: Introduction and literature Review Many researchers used mollusks as bioindicators to determine the levels of HMs in the aquatic environments (Boalch, et al.,1981; Salanki, et al., 1982; Axiak & Schembri, 1982; Weimin, et al.,1993; Al‐Adrise, 2002; MacFarlane, et al.,2006 ; DeWeese, et al., 2007). Few workers used Invertebrates as bioindicator to determine the levels of heavy metals in Iraqi aquatic systems , Mustafa (1985) mentioned to determine the level of HMs in Shatt Al‐Arab River , and investigate the possibility of using the fresh water Corbicula fluminae as bioindicator for HMs pollution, he studied the Cd, Cu, Ni, Mn, Pb, and Zn elements , he founed that there was significant correlation between the concentration of particulate HMs and those extracted from tissue, this could be attributed to the fact that this mussel is a filter feeder. Salman (2006) studied some trace elements in Corbicula fluminaeو and Unio tigridis which collected from Euphrates River, and he found that there were high concentrations of HMs in their tissues. 1‐5‐4. Plants as bioindicator: Freshwater aquatic plants are those that are physiologically adapted to surviving in permanent or semi‐permanent freshwater ecosystems. Aquatic plants are known in accumulating metals from their environment (Outridge & Noller, 1991; and Ali & Soltan, 1999) and affect metal fluxes through those ecosystems (Jackson, et al., 1994; and St‐ Cyr, et al., 1994). The concentrations of metals in aquatic plants can be more than 100 000 times greater than in the associated water (Albers & Camardese, 1993). Certain aquatic plant species can be used as bioindicators of low level environmental contamination that might be difficult to detect. Of importance too is the fact that contaminated aquatic vegetation can be a source of food for a variety of herbivores and detritivores, leading to the possibility of bioaccumulation of metals in higher trophic levels of the food chain (Crowder, 1991; and Devi, et al., 1996). Several studies have shown that wetlands are very effective in removing HMs from polluted waters (Qian, et al., 1999; and Yang, et al., 2008). Different wetland plant species differ, however, in their abilities to take up and accumulate various HMs in their tissues (Rai, et al., 1995). Recently, wetland plant species with abnormally high capacities of trace element (Cu, Ni, Zn and so on) removal from water were identified (Zayed, et al., 1998; and Zhu, et al., 2003) duckweed (Lemna minor L.) and water hyacinth [Eichorniacrassipes (Mart.) Solms‐Laubach] were excellent accumulators Cd, Se and Cu. Typically, submerged species have been found to accumulate relatively high HM concentrations when compared with emergent species (Kara, 2005; and Al‐Byati, 2008) In the Turkey wetlands (Sultan Marsh), Dilek & Ahmet (2006) studied HMs in aquatic plant tissues; they found that the Potamogeton (P.) pectinatus accumulated heavy metals more than those of G. densa. Therefore, all plants can be used as biological indicators while determining environmental pressures; however, Phragmites australis has proved more appropriate (Al‐Haidarey, 2003). Ahmet, et.al., (2005) showed that the tissues of Phragmites australis accumulated heavy metals more than those of Ranunculus sphaerosphermus. The heavy metal accumulation in different parts of plants followed the sequence: root > stem > leaf. Dilek & Ahmet (2004) found that the Leaves of T. angustifolia accumulated less heavy metal than the corresponding roots. There was 12
Chapter One: Introduction and literature Review a significant relationship between Cd concentration in samples of plants and water pH value. It has been found that the tissues of T. angustifolia accumulate more heavy metals than the tissues of P. pectinatus, while Al‐Haidarey (2003) found match results but with Phragmites australis plant. In Iraq, numerous researcher used the aquatic plant as bioindicator for HMs pollution (Abaychi & Al‐Obaidy, 1987; Ibrahim, 1993; Al‐Taee, 1999; Al‐Saadi, et al., 2002; Algam, 2002 ; Sabri, et al.,2001; Al‐Haidarey, 2003; and Salman, 2006). In Mesopotamian Marshes, Al‐Saad et al., (1994) studied the distribution and concentrations of HMs in aquatic plants of Al‐Hammar Marshes , they found that the concentrations of Fe, Mn, Pb, Ni, and Zn in plants studies were lower than the baseline concentrations, while those for Cd, Cr, and V were relatively higher; Awad and Mahdi (2005) studied a HMs in aquatic plants from different regions of southern Iraqi marshes (Amara & Basrah). The results showed that the heavy metals content of plants had wide different concentration ranges which revealed that these plants concentrate and accumulate these metals from their environment ( water and sediment). Awad et al.(2008) analyzed a trace metals (Cd, Pb, Cu, Zn, Mn and Fe) in six species of aquatic plant (P. Crispus , P. nodosus, Ceratophyllum demersum, Salvinia natans, Potamogeton pectinatans, Salicornia herbaceal, and Vallisneria spiralis) and sediments of Al‐Hawizeh and Al‐Hammar marshes, the results showed higher concentration of HMs in sediment than in plants. No significant differences were observed in trace metals concentrations in aquatic plants and sediment samples for both Al‐Hawizeh and Al‐ Hammar marshes. Generally, the levels of the studied metals in plants and sediments of region were lower than the other compared areas of the world. 1‐6 Aims of the study: Nowadays, Heavy Metals have a great ecological significance due to their toxicity and accumulative behavior. They contrary to most pollutants are not bio‐degradable and undergo a global eco‐biological cycle in which natural waters are the main pathway (Nurenburg, 1984). Drainage and restoration processes took place in the Iraqi wetlands; therefore, we don’t know much about HMs in this unstable ecosystem. Therefore the present study aimed to: 1. To take place the general background about the concentration of heavy metals in the Mesopotamian marshes by monthly monitoring of the concentration of heavy metals and some physiochemical properties in the Central, Al‐Hawizeh and Al‐ Hammar marshes in dissolved part. 2. To evaluate the behavior and mobility of HMs in Al‐Hawizeh Marsh 3. To determine the loading of HMs in Al‐ Hawizeh marsh to answer whether the marsh is a source or sink of heavy metals. 4. To assess weather are there relationship between heavy metal concentrations and water & sediment quality? 5. To monitor the fate and cycling of heavy metal concentrations in Al‐Hawizeh marshes. 6. To answer if we can use Bellamya (Viviparus) bengalensis snails and Potamogeton perfoliatus (P. perfoliatus submerged plants as bioindicator, to indicate the presence of heavy metals in the Mesopotamian marshes. 13
Chapter Two: Material and methods
Chapter Two Material and Methods
14
Chapter Two: Material and methods
2.1. The Study stations: 2.1.1. General Description of the sampling sites: Twenty one station were chosen in the three main Mesopotamian Marshes (Fig. 2‐1 & 2‐ 2) based on general morphology, vegetation, and the presence or absence of population in each site; the geographical coordinates of the stations (Table 2‐1) are determined by mean of GPS. 2.1.1.1 Al‐Hawizeh Marsh: The Hawizeh Marsh lies to the east of the Tigris River, straddling the Iran‐Iraq border ( between 31° 00’‐31º45’ N, 47° 25’‐47º 50’ E; (Scott, 1995)). The Iranian section of the marshes is known as Al‐Azim Marsh where it is fed primarily by the Karkeh River. In Iraq, this marsh is largely fed by two main distributaries departing from the Tigris River near Amarah city, known as Al‐Musharah and Al‐Kahla. During spring flooding the Tigris may directly overflow into the marshes. Extending for about 80 km from north to south, and 30 km from east to west, It occupy an area between 2500‐3500 Km2 during the flooding season (mid of March to the end of May), (UNEP 2001, Fig. 2‐1). The northern and central parts of the marshes are permanent, but towards the southern sections they become increasingly seasonal in nature. The permanent marshes have moderately dense vegetation, alternating with open stretches of water. Large permanent lakes up to 6 m deep are found in the northern parts of the marshes. Al‐Hawizeh and its associated marshes are considered to be the largest within the Mesopotamian (Wali, 1967). Although, Al‐Hawizeh is fortunately less affected in comparison to Al‐Hammar and the Central Marshes since it has water inputs from Al‐Karkheh River in the Iranian territories (Scott, 1995; UNEP, 2001). However, the loss of water changed the region significantly and divided it into three distinct areas: The northern east part of Al‐ Hawizeh, which is close to the Iraq‐Iran border remained wet; The center section also retained water, however it became drastically reduced compared to its original size. The geomorphology of this area help to save the water from the surrounding areas and it has a water discharge from the area which never been dried. The southern part was dried completely and became a desert. According to CRIM (2006), Al‐Hawizeh including Al‐Sanna’f marsh occupy an area between 650 to 1500 Km2, and the total length of the marsh was about 80 Km and the average width is 30 Km. In this study 17 stations are chosen at Al‐Hawizeh Marsh because : (1) it is the largest marsh, by volume and area in Iraq, (2) socio‐economically important; sustaining a large human population and wildlife habitat critical for endemic and non endemic biodiversity (Evans, 2001) , (3) limited scientific knowledge of Al‐Hawizeh due to the inaccessibility of Al‐ Hawizeh marsh, (4) an area of Al‐Hawizeh which was never dried in the 1990’s provides a background level of heavy metals concentrations to compare with, (5) it is a potential RAMSAR (is an international treaty for the conservation and sustainable utilization of wetlands, i.e., to stem the progressive encroachment on and loss of wetlands now and in the future, recognizing the fundamental ecological functions of wetlands and their economic, cultural, scientific, and recreational value, it is named after the town of Ramsar in Iran) site and by studying this marsh it will provide scientific information useful to national and international communities (Scott, 1995), (6) Al‐Hawizeh Marsh has diverse biological habitats in contrast to Al‐Hammar and the Central marshes (Stattersfield et. al., 1998) . It provides resources for local human communities, important habitat for migrating birds and 15
Chapter Two: Material and methods
it is also the major source of the natural hydrology in the Middle East. These unique marshlands are comprised of permanent and seasonal open water; vast reed beds, mudflats and seasonally inundated plains (UNEP, 2001). 2.1.1.1.1. Input stations: In this study chosen 5 inlet stations includs : a. Al‐Ka'hla River stations: (St. 1, 2, 3, 4): Al‐Ka'hla River feeds Al‐Hawizeh Marshes via three main tributaries: 1. Al‐Adel (Al‐Husa'chi) tributary: 25 Km length feeds Al‐Hawizeh via a set of pipes (CRIM, 2006). Al‐Husaichi is divided into two branches, Al‐Adel (St. 1) and Al‐Adel old (St. 2), 5 Km before entering the Marsh from these two branches pipes are installed to allow water into the marsh, and Al‐Husaichi passes through large agricultural fields. The drainage water from these fields enters directly into the river which can be a potential source of water contamination, as the fields are heavily fertilized. 2. Al‐Zubair tributary (St. 3): This tributary is of 22 Km length, it has two main branches that flow into Al‐Ma'eel channel (CRIM, 2006) which runs directly into Al‐Hawizeh. Small villages are located along the river, which are highly populated, and heavily utilize Al‐Zubair (Wali ,1967; and UNEP, 2001). 3. Abu Kassaf (Umm Al‐Toos) tributary (St. 4): Small villages are found along the river affecting the water quality of Umm Al‐Toos (UNEP, 2001), 25 Km length and feeds Al‐Hawizeh directly (CRIM, 2006). 4. Al‐Musharah River (St. 5): It extends from the Amarah governorate via Al‐Musharah city into Al‐Hawizeh. The total length of Al‐Musharah is about 64 Km; the designed capacity of its regulator is about 100 m3 .sec‐1 but the actual operating capacity is 50 m3 .sec‐1 (CRIM 2006). Fifteen irrigation channels drown water from Al‐Musharah River, some of these channels feed directly Al‐ Sanna'f marsh. The water level in this river undergoes large fluctuations; the highest level occurs during the flooding season (end of March early April). The lowest water levels occur in the summer; due to the retention of water in upstream reservoirs and in the Al‐Sannaf marsh. With such demand on Al‐Musharah river prior to reaching Al‐Hawizeh greatly decreases the amount of water entering Al‐Hawizeh (Walli , 1967). 2.1.1.1.2. Outlet stations: There are two main outlets of Al‐Hawizah : Al‐Kassara and Al‐Suwayb rivers (Fig. 2‐2). The water is controlled by regulators installed in these two rivers. This prevents flooding of cities down stream during the flooding season (CRIM, 2006). a. Al‐Kassara River (St. 6): Two small rivers, Al‐Kassara old and Al‐Kassara new, merge together, forming Al‐Kassara River. The length of Al‐Kassara old and Al‐Kassara new are 15 Km and 10 km respectively. Their combined water discharge capacity is 200m3/sec. This river flows from the north part 16
Chapter Two: Material and methods
of Al‐Hawizeh and flows directly into the Tigris River . Al‐Kassara River experiences heavy macrophytes growth, including reeds and papyrus, these plants impede the movement of water (CRIM 2006). b. Al‐Swab River (St. 7): Al‐Swab River is one of the water outlets of Al‐Hawizeh. It flows from the southern part of Al‐Hawizeh Marsh directly flowing into Shat Al‐Arab River. 50 Km length, with a 600m2.sec‐1 water discharge capacity (CRIM 2006, Fig. 2‐2). 2.1.1.1.3. Open water marsh stations : a. Al‐Adaim Marsh (Ad1 and Ad2)(St. 8, 9): Al‐Adaim is located in the north east section of the Al‐Hawizeh. It occupies an area between 40‐80 Km2 and receives water from both Iraq and Iranian rivers. Al‐Sanna'f is seasonal channel / marsh (87.5 Km2) is located in the north‐west of Al‐ Hawizeh Marsh. According to the topography of the area, Al‐Sanna'f marsh is quite higher than Al‐Hawizeh. During the flooding season the extra surface water runs from the Al‐ Sanna'f marsh, the higher elevation to Al‐Hawizeh via Al‐Faisal channel. When the snow melts in the Iranian and Turkish mountains the water level increasesin both the Tigris and the Al‐Karkhah rivers. This excess water raises the water level of Al‐Sanna’f marsh which in turn enters north Al‐Hawizah (Al‐Adaim Marsh). Al‐Karkeh River originates in the mountains of Iran, and discharges into Al‐Hawizeh Marshlands. In 2001, Iran completed a large dam on this river, which has halted water flow to the marshlands. Plans are underway to transfer water from the Karkheh reservoir to Kuwait via a 540‐km pipeline, supplying Kuwait with 200 million gallons of freshwater per day (Partow 2001). The Al‐Karkheh River (850 Km length) enters on the north east side of Al‐ Hawizeh marsh (Al‐Adaim Marsh), from Iran. It’s annual discharge into Al‐Hawizeh marsh is about 256x107 m3. The dominant plant species are Potomogeton crispus, Potamogeton perfoliatus, Najas marina and Najas minor. Since this area is closed to the Iraq‐Iran border, there are no human populations established there. b. Al‐Soda north (Sod.N) (St. 10): Al‐Soda north is located in the north of the Al‐Hawizeh. It occupies an area between 20‐ 30 km2. This area receives water from Al‐Musharah River. Potomogeton crispus, Potamogeton perfoliatus, Ceratophyllum derasum, and Phrugmites astralus are the dominant plant species. In the northern portion of this marsh there is a small village called Al‐Musharah village.
c. Um El‐Nia’aj (UmNj1 & UmNj2)(St. 11, 12): Um El‐Nia’aj is the largest water body and located in the north western section of Al‐ Hawizeh. It occupies an area between 140‐200 Km2. The main water sources of Um El‐Nia’aj are Al‐Zubair and Umm Al‐Toos rivers. This area has a various plant species like Phragmites australus, Ceratophyllum demrasum, Potomogeton leucenus, Potamogeton perfoliatus, 17
Chapter Two: Material and methods
Najas marin, and Najas minor. Large villages are established near this marsh such as Abu Khassaf village. d. Al‐Baidah (Bed) (St. 13): Al‐Baidah is located in the east of Al‐Hawizeh, close to the Iraq‐Iran boarder. It occupies an area between 6‐12 Km2. The water body is dominated by Myrophyllum spicatum and Potamogeton perfoliatus. During the Iraq‐Iran war the ecosystem of this marsh was destroyed, including Macrophyte beds and the fisheries. Small individual fisheries operating in this area can no longer support a large population as it once did. 2.1.1.1.4. Shallow Marshes stations: a. Um Al‐Wared (UmWd)(St. 14): Um Al‐Wared marsh is located in the north west of Al‐Hawizeh, just below Um El‐Nia’aj open water body, Al‐Husaychi River is an important water source for Um Al‐Wared ; and it has a connecting channel with Um El‐Nia’aj. When the water level increases in Um El‐Nia’aj, water flows through Al‐Doob channel directly into Um Al‐Wared. The flow is reversed when the water level in Um El‐Nia’aj decreases. Um Al‐Wared marsh is dense with the presence of Phragmites ustralus The growth pattern of Phragmites ustralus communities make it hard to delineate Um Al‐Wared from surrounding shallow marshes. This marsh is also dominated by Potomogeton leucenus, Potamogeton perfoliatus and Potomogeton crispus. Um Al‐ Wared is abundant with natural resources, supporting local communities. a. Al‐Souda south (Sod.S)(St. 15): Al‐Souda south marsh is located in the center of Al‐Hawizeh. It is difficult to define a boundary for this marsh because it is continuous with the surrounding marshes, such as Umm Al‐Nia’aj and Umm Al‐Warid marsh. The water flows from the north via Umm Al‐ Warid and Umm Al‐Nia’aj into Al‐Souda south marsh. The marsh is so close to the central embankment which divides the marsh in to northern and southern parts. Majority of the water of from Al‐Souda south flows out of Al‐Hawizeh through the Al‐Kassara outlet river. Al‐Souda south marsh supports a lot of local fisheries. The dominant plant species of this marsh are Phragmites ustralus, Potamogeton perfoliatus, and Najas marin. b. Majnoon (Maj)(St. 16) : Majnoon marsh is the closest to Al‐Swaib Outlet River. Majority of the water exits Al‐ Hawizeh by Al‐Swaib flowing through Majnoon marsh. c. Lissan Ejerda (LesEj)(St. 17): Lissan Ejerda lies to the North of Majnoon marsh, receiving water which flows through several pipes in the central embankment. Lissan Ejerda marsh is dominated by Phragmites ustralus, Potamogeton perfoliatus, and Najas marin, while Majnoon marsh is dominated by Phragmites ustralus, Potamogeton perfoliatus, and Myrophyllum spicatum. Lissan Ejerda and Majnoon marshes share the southern part of Al‐Hawizeh. The main feature of the southern part of Al‐Hawizeh marsh is the embankments. There were at least ten embankments built across Al‐Hawizeh (Fig. 2‐2), splitting the marshes into several marshlands. Lissan Ejerda and Majnoon are the largest marshlands in the southern part of Al‐Hawizeh marsh. 18
Chapter Two: Material and methods
2.1.1.2 The Central Marshes: Located immediately above the confluence of the two Mesopotamian rivers, the Central Marshes are at the heart of he Mesopotamian wetland ecosystem. Bounded by the Tigris River to the east and the Euphrates River in the south, the area is roughly delimited by a triangle between Al Nasiriyah, Qalat Saleh and Al Qurnah. Receiving water influx mainly from an array of Tigris distributaries, most of which branch off from the Shatt Al‐Muminah and Majar Al‐ Kabir, as well as the Euphrates along its southern limit, the Central Marshes cover an area of about 3,000 km2. During flood periods this may extend to well over 4,000 km2 (Andrew, 2005, Fig: 2‐1 ). Interspersed with several large open‐water bodies, this freshwater marsh complex is otherwise densely covered in tall reed beds. Al Zikri and Umm Al Binni Marsh are some of the notable permanent lakes which are located around the centre of these marshes, and are approximately 3m deep and (Thesiger, 1964). Along the marshes’ northern fringes, dense networks of distributary deltas are the site of extensive rice cultivation. The Central Marshes are considered to be a highly important breeding, staging and wintering area for large populations of a broad variety of waterfowl species. Difficulty of access, however, has limited comprehensive ornithological investigations of the site. Endemic sub‐species of the Smooth‐coated Otter have been reported in the region (Scott, 1995). Most of the known major archaeological resources are outside the marshes, with the exception of some within the Central Marshes. A greater amount would be initially required to completely re‐flood the marshes, accounting for seepage into the ground and for a greater rate of evapotranspiration over the dry marshlands compared to the fully flooded marshlands. The larger Central Marsh may require a larger water flow, up to 9 bm3/year, to sustain it. In the Central Marshes chosen two stations (Fig. 2‐3) : a. Beginning Al‐Baghdadia (B.albagh)(St. 18), and b. Middle Al‐Baghdadia (M.albagh)(St. 19): These are freshwater lakes, with chemical precipitation of calcareous sediment along with terrigenous material (terrigenous sediments are those derived from the erosion of rocks on land; that is, that are derived from terrestrial environments, consisting of sand, mud, and silt carried by rivers, their composition is usually related to their source rocks). The waters of the marshes are clear. Along the marsh’s northern fringes, dense networks of distributary (is a stream that branches off and flows away from a main stream channel) deltas are the sites of extensive rice cultivation. Water depth reach to 1.5m, several agricultural activities, buffalo farm, and fisheries activities near by, and there are some small village beside our stations . Macrophytic floras are: Phragmites ustralus, Typha domingensis, Potamogeton perfoliatus, Najas marin, Ceratophyllum demersum , Myrophyllum spicatum, and Tamarix sp. (native to drier areas). 2.1.1.3. Al‐Hammar Marshes: The Al‐Hammar Marsh represents about 21% of the total marshland in the southern Iraq. The marsh area comprises 2,800 km2 of permanent marsh and lake, expanding to over 4,500 km2 during periods of seasonal and temporary inundation. Al Hammar Lake, which dominates the marshes, is the largest water body in the lower Euphrates. It is approximately 19
Chapter Two: Material and methods
120km long and 25km at its widest point. Slightly brackish due to its proximity to the Gulf, the lake is eutrophic and shallow, the current velocity and the annual discharge are 454 m3.sec‐1, and 14.3km3 respectively. The daily mean temperature is between 12.4° at Jan to 33.9° at Aug. The annual mean of rain fall between 84–396mm, and the dry period lies between Jun ‐ Oct (Anon, 1986), the mean daily evaporation and sunshine duration are 9.4mm and 9.2hr respectively (Al‐Saadi and Al‐Mousawi, 1988, & Al‐Saadi, et al., 1989). The Al‐Hammar Marsh is situated south of the Euphrates, extending from near Nasiriyah in the west to the outskirts of Basra on Shatt Al‐Arab River in the east. To the south, saline lakes, sabkhas, and the sand dune belt of the Southern Desert borders the marshes. Maximum depth at low water levels is 1.8m and about 3m at high water mark (Maltby, 1994). During the summer, large parts of the littoral zone dry out, and banks and islands emerge in many places. Fed primarily by the Euphrates River (which constitutes the northern limit of these marshes), these waters drain at Qarmat Ali into the Shatt Al‐Arab. A considerable amount of water from the Tigris River, overflowing from the Central Marshes, also nourishes the Al‐ Hammar Marshes. Groundwater recharge is another likely source of replenishment. The Al Hammar marsh complex boasts one of the most important waterfowl areas in the Middle East, both in terms of bird numbers and species diversity. The vast and dense reed beds provide ideal habitat for breeding populations, while the eco‐tonal mudflats support shorebirds. Globally significant concentrations of migratory waterfowl have been recorded during winter, and although not properly surveyed, the area is likely to host similarly high numbers during the spring and autumn seasons (Scott, 1995). Rice is cultivated in the distributaries of the Interior Delta regions at the eastern and northern ends of the Al‐Hammar Marsh, and at the northern end of the Central Marshes. Southern Iraq the home of perhaps 5% of the world’s total oil reserves. The largest oilfields in southern Iraq include Rumayllah, North Rumayllah, West Qurnah (all located within or adjacent to the Hammar Marsh), and Majnoon (located within the Haweizeh Marsh). The lake is oxygen‐deprived and brackish. Sediments within the lake are gray calcareous silts. During the summer, large parts of the shoreline dry out, and banks and islands emerge. The lake is surrounded from the north and northeast by freshwater marshes characterized by more terrigenous and organic‐rich sediment and extensive reed beds. The sources of the rivers and their lakes and marshes have changed greatly through time, as evidenced by maps during the past few centuries, and other verbal accounts. Lake Hammar is though to be formed as recently as 600A.D. (Rzoska, 1980). At times, more than 80% of the Tigris discharge goes to this marsh, while the Euphratis River disappears in it., and its discharges directly to the Shatt al‐Arab. It has been estimated that the Al‐Hammar Marsh has historically required a water flow of 3.6 billion cubic meters per year (bm3/yr) to maintain a level sufficient for the needs of fishing and rural life (Kassim & Al‐Saadi, 1995). In this marsh chosen two stations: a. Al‐Nagarah (Al‐Nag) (St. 20): This station is so closed with the Shatt Al‐Arab River (Al‐Mashab, and Al‐Salal) with water depth reach to 5m at tide, high turbidity, several agricultural activities, buffalo farm, and fisheries activities near by. Macrophytic flora were: Ceratophyllum demersum, Phragmites ustralus, Typha domingensis, Potamogeton perfoliatus, Najas marin, and Myrophyllum spicatum. The plant leaves covered with salt (Fig: 2‐3). 20
Chapter Two: Material and methods
b. Al‐Burgah (Al‐Bur)(St. 21): This station is considered as an open shallow water marsh area with light transparency reach to the bottom. The dominant plants are similar to that in previous station but more abundance, as well as some filaments algae. The plant leave less covered with salt (Fig. 2‐3).
Fig (2‐1): Mesopotamian Marshes, southern Iraq. 21
Chapter Two: Material and methods
N
Fig. (2‐2): The seventeen study stations in Al‐Hawizeh Marsh (2006). Water inputs: St.1: Al‐Adil, St.2: Al‐Adil Old, St.3: Al‐Zubair, St. 4: Abu Kassaf, and St.5: Al‐Musharah. Water outlets: St.6 (Al‐Kassarah), and St.7 (Al‐Sweeb). Open water marsh stations: St.8, 9 (Ad1, and Ad2), St.10 (Sod.N), St. 11, 12 (UmNj1, and 2), and St.13 (Bed). Shallow Marshes stations: St. 14(UmWd), St.15 (Sod.S), St.16 (Maj), and St.17 (LesEj).
22
Chapter Two: Material and methods
N Al‐Hawizeh Marsh
Central Marsh
Al‐Hammar Marsh
Fig. (2‐3): The study stations of three marshes (Central, Al‐Hammar, and Al‐Hawizeh Marshes) monitoring (2006). 23
Chapter Two: Material and methods
Table (2‐1): The Geographical positions of the studied sites (GPS). Co‐ordinates Stations (St.)
Al‐Hawizeh
Input stations Outlet stations Open water marshes
Shallow marshes Central Marsh
St.1 St.2 St.3 St.4 St.5 St.6 St.7 St.8 St.9 St.10 St.11 St.12 St.13 St.14 St.15 St.16 St.17
Al‐Hammar Marsh
Location
Al‐Adel Old Al‐Adel Al‐Zubair Um Al‐Toos (Abu‐Khassaf) Al‐Musharah Al‐Kassarah Al‐Swayib Al‐Adaim 1 Al‐Adaim 2 Al‐Soda north UmNj1 UmNj2 Al‐Baidah Um Al‐Wared Al‐Souda south Majnoon Lissan Ejerda Beginning Al‐Baghdadia Middle Al‐Baghdadia Al‐Nagarah Al‐Burgah
Latitude (North) ˚ ׳ ״ 31 34 5.6 31 34 3.8 31 38 47 31 37 0.5 31 40 48 31 21 39 30 58 5.6 31 41 30 31 41 30 31 40 23 31 36 0 31 36 0 31 21 28 31 34 12 31 24 54 31 8 18 31 17 21 31 1 20 31 2 9 30 40 1.9 30 41 14.1
Longitude (Eeast) ˚ ׳ ״ 47 30 3.9 47 30 1.1 47 35 15 47 33 7.7 47 37 23 47 26 57 47 29 28 47 44 0 47 25 0.7 47 40 0.3 47 35 20 47 39 16 47 38 58 47 31 7.3 47 36 43 47 35 0 47 34 38 47 2 15 47 2 9.3 47 38 39 47 35 26
24
Chapter Two: Material and methods
2‐2. Material and methods To prevent contamination of tools, instruments and other materials, which may come in contact with the sample, only high density polyethylene, Teflon or other plastic materials of high purity were used. Only borosilicate glass (pyrex) or Teflon laboratory ware were used soft glass and their commercial grade glass are often contain quantities of Pb and other impurities (FAO, 1983). Samples must be protected from contamination effect by keeping containers sealed until processing and minimizing the time of atmospheric contact. All glass wares were carefully cleaned with detergent, tap water then soaked in 10‐20 % v/v nitric acids/water for at least 24 hours and rinsed with deionized distilled water as final step (Riley & Chester, 1981). 2‐2‐1. Sample collection strategy: The sampling was monthly to monitoring three marshes (for investigated the first aim of this study), starting in Jan – Dec 2006. To investigated the other aims of this study, the strategy of sampling was depends on the fluctuation of discharge of water, so the 1st trips was at high discharge month (May 2006), then the 2nd trips in Aug. 2006, while the last trips were in Dec 2006 (look at table 2‐2) 2‐2‐2. General Sampling Procedures: Water samples were collected in 20‐litre container, sediment samples were collected in 1000 ml polyethylene containers, snail samples were collected in 500 ml polyethylene containers, and Potamogeton plant samples in 2 kg polyethylene bags. All sediment and water samples were immediately sealed and cooled upon collection. The samples were returned to the Laboratories for analysis. 2‐2‐2‐1. Water: Surface water samples were collected, from six stations in Al‐Hammar, Central Marsh, and Al‐Hawizeh Marshes, and from 17 stations from Al‐Hawizeh Marsh (to focusing study on this marsh with more details). In each location water sample of about 20L was collected by Van Dorn water sampler (from 30 ‐ 50 cm depth) (Riley & Taylor, 1968; and WASC, 2002). 2‐2‐2‐2. Sediments: Sediment samples were collected using an Ekman Grab sampler (15.2×15.2 cm). After retrieval of the sampler, the water was allowed to drain off, avoiding, disturbing the surface layer of the samples preserved using nylon zipper‐sealed bags (17.7*20.3 cm). As soon as the samples were retrieved, placed in an ice box until reaching the lab they placed in plastic container (1000ml) before freezing at ‐20°C (ICARDA, 1996). Before analysis, the sediment samples were thawed before drying in an oven at 50 °C for over night, grind finely in an agate mortar and sieved through a 63 µm plastic sieve. 2‐2‐2‐3. Sub‐merged plant samples: For investigated this study, chosen potamogeton perfoliatus plant (Fig: 2‐4) because it was dominant at all study sites. 25
Chapter Two: Material and methods
Table (2‐2): The sampling Program of the study (2006): Project Period
Type of samples
For general monitoring of three Mesopotamian Marshes (Central, Al‐Hammar, and Al‐Hawizeh Marshes)
Monthly Started in Jan(2006) until Dec. (2006)
Dissolved Phase
The study of Al‐Hawizeh Marsh as case study
May (2006), Aug.(2006), and Dec.(2006)
Sediments(residual + exchangeable),dissolved, Particulates(residual + exchangeable),benthos, and plants
2‐2‐2‐4. Snail samples: One species were collected, namely Bellamya (Viviparus) bengalensis (Fig: 2‐5), from each stations composite sample consisted of at least 10 uniform size.
Fig (2‐4): Potamogeton perfoliatus plant image.
26
Chapter Two: Material and methods
Fig (2‐5): Bellamya (Viviparus) bengalensis Snails image. 2‐2‐3. Field measurements: Water temperature (WT:°C), Salinity (Sal: ppt), Electrical Conductivity (EC: µs/cm), Total dissolved solids (TDS: mg/L), Dissolved oxygen (DO: mg/L), and pH were measured in each station using a Multi‐parameter (Multi 340i meter, Table 2‐3). The device was calibrated before the use. Water turbidity (NTU) was measured in the field by turbidity meter type WTW (TURB 355 IR) (Table: 2‐3). 2‐2‐4. Water discharge: Water discharge (m3/sec) was determined only at the river sites (input and outlet stations of Al‐Hawizeh Marsh). A flow meter was used in the field to measure water velocity, depth, and the cross section of each site to calculate water flow then discharge according to Bartram & Ballance (1996). The Procedure for measuring Water Flow and Discharge were: 1. Measure the horizontal distance (b1) from reference point (0) on bank to the point where the water meets the bank, point 1 (Fig: 2‐6) 2.Measure the horizontal distance (b2)from reference point 0 to vertical line 2. 3. Measure the channel depth (d2) at vertical line 2. 4. With the current meter, make the measurements necessary to determine the mean velocity (V2) at vertical line 2. 5. Repeat steps 2, 3 and 4 at all the vertical lines across the width of each site (Fig: 2‐6) 27
Chapter Two: Material and methods
The computation for water flow is based on the assumption that the average velocity measured at a vertical line is valid for a rectangle that extends half of the distance to the verticals on each side of it, as well as throughout the depth at the vertical. Thus, in Fig.(2‐6), the mean velocity (V2) would apply to a rectangle bounded by the dashed line p, r, s, and t. The area of this rectangle is: a2 = (b3‐b1/2)*d2 And the flow through it will be: Q2 = a2*V2 Similarly, the velocity 3 applies to the rectangle s, w, z, y and the flow through it will be: Q3 = (b4‐b2/2)*d3*V3 The flow across the whole cross‐section will be: QT = Q1 + Q2 + Q3 ... Q(n ‐ r) + Qn In the example of Fig.(2‐6) 3.1, n = 8. The discharges in the small triangles at each end of the cross‐section, Q1 and Qn, will be zero since the depths at points 1 and 8 are zero.
Fig.(2‐6): Cross‐section of a stream divided into vertical sections for measurement of Water Flow and Discharge (Bartram and Ballance, 1996). 28
Chapter Two: Material and methods
2‐2‐5. Total Suspended Solid (TSS): The total suspended solids that were retained by the filtration process were measured gravimetrically using a Sartorius balance according to the method described in APHA (1998). However, filters were dried in an oven for 3 hours. 2‐2‐6. Total Hardness (TH), Ca2+, and Mg2+,HCO3‐, Cl‐, SO42‐ Concentration: HCO3‐, Cl‐, TH, Ca2+, and Mg2+ (mg/L), were determined by titration methods while SO42‐ determined by photometric method depends on outlined in Standard Methods (APHA, 1998). 2‐2‐7. Sediment Analyses: The sediments were dried at 45 °C for approximately 3 days and ground up using an agate mortar and then passed through a 63µm mesh sieve. The methods used by the International Center for the Agricultural Researches (ICARDA, 1996) were followed to analyze the sediment samples. 2‐2‐7‐1. Sediments EC and pH: For measuring of pH and EC in the sediments, inserted an electrode of the pH and EC meter to 3 cm in the suspension that was above the sediment after collecting it in polyethylene container and take the readings after 30 seconds (KLI, 1998). 2‐2‐7‐2. Total Organic Carbon and Total Organic Matter (TOC% & TOM%): To determined TOC% and TOM% in this study, the method depended on organic matter oxidation by potassium dichromate, it used (according to ICARDA, 1996). 2‐2‐7‐3. Grain size analysis (%): For grain size analysis used the equipments that in table (3‐2). Depend on the hydrometer method (Bouyoucos, 1936). 2‐2‐8. Heavy Metals: 2‐2‐8‐1. Analysis method: ICP‐MS (Inductively Coupled Plasma Mass Spectroscopy, standards for elements were used in specimen analysis. High‐purity deionized water purified with a Milli‐Q analytical‐ reagent‐grade water purification system (Millipore Elix 3 and Milli‐Q Academic Gradient A‐ 10) was used for preparation of reagents and standards. High‐quality concentrated (70% w/v) nitric acid, hydrogen peroxide (35%), hydrofluoric acid (48%), percloric acid (65%), and hydrochloric acid (38%) were also used. Samples, standards, and final volumes were measured by mass in all cases. The standard solutions to make the calibration were prepared from a stock solution of 1000 mg/L (provided from Alfa Aesar a Johnson Matthey Company/ Germany) by successive dilutions with Milli‐ Q water. The use of glass material was avoided to eliminate possible contamination from this material. Volumetric polyethylene material and micropipets with tips of plastic were used. 29
Chapter Two: Material and methods
2‐2‐8‐2. Dissolved Phase: In each station water sample of about 20 L was collected directly by Van Dorn water sampler (30‐ 50 cm depth) and mixed it in polyethylene container as pool samples. In lab (and some samples at field), these samples were filtered as soon as possible through pre‐ washed and pre‐weighted (0.45µm pore size) Millipore membrane filters. The filtrate is considered as dissolved while those retained as particulates. After filtration of samples through 0.45 µm membrane filter, the chelating ion‐exchange pre‐concentration procedure was used to per‐concentrate the dissolved heavy metals from about 20 L of water surface where the concentration of the metal is considerably low for reliable direct measurement. Using 1.5 cm diameter ion exchange column was filled to depth 12 cm with the chelating chelex‐100 resin. 50‐100 Mesh Sodium form (that supplied from BIO‐RAD Company) (Riley & Taylor, 1968 ; and WASC, 2002). The resin was packed freshly and cleaned before use by passing 50 ml of 2N HNO3, there 100 ml of deionized water, and 50 ml NH4OH, before finally 100 ml flushing with deionized water. The filtered water samples were allowed to pass through the chelex‐100 column with a flow rate of about 60 drops/min (Alfred, N., and Hercules, Dr., 2000). The column was then washed with 200 ml deionized water and the washing was rejected the bounded heavy metals were eluted using 50 ml of 2N HNO3 followed by 10 ml deionized water ,the elutes were collected in 50 ml cleaned tightly stopper polyethylene vials to be ready for subsequent analysis of the metals. The blank solution was prepared by adding 4 ml 2N HNO3 to 96 ml deionized water, the prepared solution allowed to pass through the recently regenerated chelex‐100 (Riley &Taylor, 1968). 2‐2‐8‐3. Particulate metals Phase: 2‐2‐8‐3‐1. Exchangeable metals: After filtration, the filters were dried in oven at 60 °C for 6 hours until dry and weighting each dried filter to get the values of the total suspended matter, the exchangeable heavy metals were extracted by using 25 ml 0.5N HCl for over night with Sonicator, the solution was centrifuged at 5000 rpm for 20 minute, the supernatant was filtered using pre‐cleaned filter paper (Watman No. 1) to remove some of suspended matter. The filtrate was decanted in to 50 ml plastic volumetric flask this step was repeated twice and all supernatant were combined and the final volume was made up to 50 ml with deionized water (Chester & Voutsinou, 1981). 2‐2‐8‐3‐2. Residual metals: The residual of HMs in particulate matter was extracted according to Sturgen, et al. (1982). The residue from the above mentioned steps was washed by 20 ml deionized water centrifuge for 30 minutes to clean precipitate from acids. Then samples were digested with mixture of 1:1 concentration HCL: HNO3 acids in propylene vessels in a block digester. Vessels will be closed by glass bulb at all times in order to eliminate contamination from airborne particles and to eliminate loss of potentially volatile analytic. The digestion was further proceeded with 1:1 mixture of concentrated HClO4 and HF acids again digestion. The residue was dissolved in 50 ml of 0.5 HCl, and then made up to 50 ml deionized water. All samples were stored in 50 ml plastic bottles. 2‐2‐8‐4 Sediments:
30
Chapter Two: Material and methods
After retrieval of the sampler, the water was allowed to drain off, avoiding disturbing the surface layer of samples. Before analysis, the sediment samples were thawed before drying in an oven at 50°C for over night, grind finely in an agate mortar and sieved through a 63 µm plastic sieve. 2‐2‐8‐4‐1 Exchangeable metals: Heavy metals analysis was on 0.5 g of the fraction of the sediment. The exchangeable heavy metals were extracted according to the method of Chester and Voutsinou (1981) which mentioned above (2‐1). All samples were stored in 50 ml plastic bottles. 2‐2‐8‐4‐2 Residual metals: The residual heavy metals were extracted according to Sturgen, et al. (1982) procedure, that mentioned before in section (3‐8‐3‐2). All samples were stored in 50 ml plastic bottles. 2‐2‐8‐5 Plant samples: The sampled plants were rinsed thoroughly with warm deionized water (Orson, et al., 1992), and then dried them with Vacuum Freeze Dryer. After drying, grind with an agate mortar and sieved through a 63 µm sieve, to be ready for digestion before analysis. The plants digested with hydrochloric–nitric–hydrofluoric – perchloric acids (30 + 10 + 10 + 5 ml/g sample) in the cups were covered and placed on the steel block which was closed tightly by glass bulb at a temperature of 300 °C, the samples allowed to predigest at room temperature over nigh. Finally the sample transferred to 50 ml volumetric flask, then, the samples were cooled at room temperature, and completed to 50 ml by 0.5N HCl. All samples were stored in 50 ml plastic bottles, then, the heavy metals were determined by the same analytical methods used for water samples (Kamal, et al., 2004). 2‐2‐8‐6. Snail samples: Each samples dried by vacuum freeze dryer and ground prior to analysis then grind with an agate mortar and sieved through a 63 µm sieve, to be ready for digestion before analysis. The analysis was carried out according to USEPA (1992), and FAO (1994). In this procedure, an exact 0.2 g weight of dry sample in propylene vessels in a block digester. Vessels would be closed at all times in order to eliminate contamination from airborne particles and to eliminate loss of potentially volatile analytic. The digestion occurred by add 10 ml of mixture of ultra‐pure nitric acid, hydrochloric acid, and hydrogen peroxide. The samples allowed predigesting at room temperature over nigh, then cooled at room temperature, after that they completed to 50 ml with 0.5N HCl. All samples were stored in 50 ml plastic bottles. 2‐2‐9. The laboratories of did this work: In Marin Science Center/ University of Basra (some physiochemical analysis), University of Kufa (digestion the samples), and University of Waterloo /Canada (sediments analysis and final preparation of samples), the samples were prepared for analysis. Sample must be colorless, transparent, odorless, single phase, and haven’t turbidity (5 6 extremely contaminated >4‐5 5 strongly to extremely contaminated >3‐4 4 strongly contaminated >2‐3 3 moderately to strongly contaminated >1‐2 2 moderately contaminated >0‐1 1 uncontaminated to moderately contaminated Hammar Marsh> Al‐Hawizeh Marsh; Co, Pb, & Zn were: Hammar marsh> Central Marsh> Al‐Hawizeh Marsh; Cr was: Al‐Hawizeh Marsh> Central Marsh> Hammar Marsh; Cu was: Hammar> Al‐Hawizeh Marsh> Central Marsh; and Fe was: Central Marsh> Al‐Hawizeh Marsh> Hammar Marsh. 84
Chapter Four: Discussion
The correlations among heavy metals concentrations and studied physio‐chemicals parameters are illustrated in the Annex (1) Table (2). The correlations among temperature & TDS with all studied heavy metals was positive and that agree with above reasons of seasonal variations of heavy metals (high concentration in summer and low in spring), while the other parameters (pH, DO, TH, Ca+2, and Mg+2) have negative correlations with HMs. The solubility of trace metals in surface waters is predominately controlled by the water pH, the type and concentration of ligands on which the metal could adsorb, and the oxidation state of the mineral components and the redox environment of the system. Many metals are dissolved at low pH and that elevated metals concentrations have been measured in waters of rivers and lakes (Hakanason, 1999), so the solubility of metals are changed with any change in pH (Odum, 2000). During hot summer months there are a lot of organisms are death and DO is decline then anaerobic conditions usually result, the rate at which the oxygen is depleted depends on the ambient temperature (Mitsch & Gosselink, 2000), the microbial anaerobic formation of organic matter reduced pH of wetland soil to 4.3 and increased the solubility of heavy metals by 60‐fold due to the increased presence of H+, and the metal‐chelating and humic‐molecule fragmenting properties of carboxylic acids (Gramss, et al., 2003). The correlations among most HMs were strongly positive, that’s means they came from same source in Mesopotamian Marshes, Al‐Taee (1999), and Mansour & Sidky (2003) mentioned to similar correlation in Euphrates River and Egyptian respectively. 4‐2 The load of HMs in Al‐ Hawizeh Marsh: Hydrologic conditions are extremely important for the maintenance of marshes structure and function; hydrologic conditions affect many abiotic factors including sediments anaerobiosis, nutrient availability, and physiochemical features (Mitsch and Gosselink, 2000). So we can summarize the effects of hydrologic regime on the marshes as the following points: 1. Chemicals availability is significantly influenced by hydrologic conditions in marsh environments (Hussein and Rabenhorst, 2002). 2. Primary productivity and other ecosystem functions in the marshes are often enhanced by following conditions and pulsing hydroperiod and are often depressed by stagnant conditions (Mason, 1969; and Al‐Kinzawi , 2007). 3. Accumulation of organic materials in marshes is controlled by hydrology through its influence on primary productivity, decompositions, and export of particulate organic matter (Mitsch and Gosselink, 2000; and Al‐Saffar, 2006). 4. For effective water pollution control and management there is a need for a clear understanding of the inputs (loads), distribution and fate of contaminants, including trace metals from land‐based sources into aquatic ecosystems. In particular, the quantities and qualities need to be considered together with the distribution pathways fate and the effects on biota (Zoller, 1984).
85
Chapter Four: Discussion
The outlet discharges were more than input discharges, the lowest input discharge was during Aug because of the ground water recharge, evaporation, & transpiration processes, and decrease the levels of waters that coming from Euphrates and Tigress River, in summer the Dams were closed to save the water during the desecrated season for that reason a vary little amount of water were releases. , while the highest values of discharge was during Dec because of: the Dams were open during the ice melt season the water discharge were increased, precipitation, and less temperature (less evaporation). This results was agree with Al‐Furat Center (1988, & 2003), and Rasheed (2008). The total outlet water discharge were more than input water discharge, because of there were another uncounted water amounts were coming from ground water discharge, precipitation, and some waters amount are coming from Iranian side (we can omit it because the Iranian government completed the built of a dams along them side to converted the water way to Iranian ground side, Rasheed, 2008). So we can say that Al‐Hawizeh Marsh conceder as source of water supplied Tigris and Shatt Al‐Arab Rivers through Al‐Kassara and Al‐Swabe streams respectively. The input of chemicals to Marshes occur through geologic, biologic, anthropogenic, and hydrologic pathways, the geologic input from weathering of parent rock, biologic inputs include photosynthetic uptake of chemicals & biotic transport of chemicals, also chemicals inputs to marshes are generally dominated by hydrologic inputs and finally human influences have caused significant changes in the chemical cycling in many wetlands types (Schlesinger, 1991; Reddy & D’Angelo, 1994; Stumm & Morgan, 1996; and NRCS, 1998 ). The marshes play an important role in determining the water quality of streams and are generally considered to act as a sink for many reactive species, and several studies have shown that wetlands are very effective in removing HMs from polluted waters (Qian, et al., 1999; and Yang, et al., 2008). However, retention of chemical constituents varies seasonally and is affected by hydrologic and biogeochemical processes including water source, mineral weathering, dissolved organic matter, suspended particulates matter, redox status, precipitation, dissolution, adsorption, and seasonal events. Relatively little is known about the influence of these factors on trace element cycling in wetland‐influenced streams (Kerr, et al., 2008) Wetlands serve as sources, sinks, or transformers of chemicals, depending on the wetland type, the hydrologic conditions, and the length of time the wetland has been subjected to chemical loadings, when wetlands serve as sinks for certain chemicals, the long term sustainability of that situation depend on the hydrologic and geomorphic conditions, the spatial and temporal distribution of chemicals in the wetland, and the ecosystem succession. Wetlands can become saturated in certain chemicals after a number of years, particularly if loading rates are high (Mitsch and Gosselink, 2000). A wetland is considered a sink if it has a net retention of an element or a specific form of that element, that is, if the inputs are greater than the outputs. If a wetland exports more of an element or material to a downstream or adjacent ecosystem than would occur without that wetland, it’s considered a source. If a wetland transforms a chemical 86
Chapter Four: Discussion
from (like dissolved to particulate) but doesn’t change the amount going into or out of the wetland, it’s considered to be a transformer (Mitsch and Gosselink, 2007). The sedimentations (traps by an aquatic macrophyts or physically sedimentation) and consumptions (by aquatic plants, phytoplankton, and other aquatic organisms) of HMs lead to sinking of some amounts of elements while the others will transformer out of the Marsh. Al‐Hawizeh Marsh was source of some elements (Cr, Fe, Mn, Co, & Ni), that was depended on the forms of elements (marsh can be sinks for an inorganic form and source of an organic form of same elements, Mitsch and Gosselink, 2007), anthropogenic activity (agriculture, industrial wastes, and military stocks that came from the Iraq‐Iranian war), and weather. This result was agree with Klopatek (1974), Nixon & Lee (1986), Spieles and Mitsch (2000, and Franc, et al.(2005). Part of the interest in the source‐ sink‐ transformer question was stimulated by studies that hypothesized the importance of marshes as sources of heavy metals for adjacent streams, the studies that suggested the importance of wetlands as sinking for certain chemicals. Marsh can be sinks for an inorganic form and source of an organic form of same elements. The two concepts of one wetland being a source and a sink for heavy metals are not mutually exclusive. When compared the results of present study with Elbaz‐Poulichet, et al. (2001) study in Mediterranean Basin, we found that in Mediterranean Basin were much more than in this in input and outlet case, but it was sinking for some metals and source for others and that agree with present study (Table: 4‐1). Table (4‐1): Comparative of HMs load in present study and in Mediterranean Basin (Ton/ Month) (Elbaz‐Pouichet, et al., 2001) Element As Cd Co Ni Pb Zn Cu Fe Mn
Present study(Ton/Month) Total metal In Total metal Out 11.78 4.41 0.22 0.20 0.45 0.52 2.72 2.89 7.38 5.40 52.92 35.75 1.82 1.13 210.24 268.50 21.52 26.47
In Mediterranean Basin (Ton/ Month) Dissolved metals input Dissolved metals output 25.00 7525.00 33.75 35.00 33.33 26.25 991.67 825.00 137.08 92.50 1779.17 1216.67 566.67 429.17 2675.00 370.83 804.17 559.58
87
Chapter Four: Discussion
4‐3 The relationship between heavy metals concentrations and water/sediment quality in Al‐Hawizeh Marsh: 4‐3‐1 Water quality: According to Mitsch and Gosselink (2000), When we want restoration of destroyed wetland we must compare this wetland with the original lost wetland or with reference wetland. As we compare the results with reference wetland (wet stations), we must mention before while studing site description chapter that the Al‐Hawizeh Marsh is subdivided in to three parts: completely dried, semidried, and wet parts. In general, the WT, TSS, TH, Ca2+, Mg2+, and Cl‐ values were in completely dried stations > semidried stations > wet stations; EC, salinity, turbidity, TDS, HCO3‐, & SO42‐ values were completely dried stations > wet stations > semidried stations; pH & DO were in semidried stations > wet stations > completely dried stations. The plant’s cover, water discharge, depth, and latitude were different among the stations, the wet stations and semi dried is more plants cover, more water discharge, more depth, and they occupy northern part of Al‐Hawizeh Marsh (Rasheed, 2008), so the temperature was at completely dried more than other stations. In restoration of semidried marshes, the growth in the early years are so fast with high diversity (specially: merged, submerged, floating plants; phyto and zoo planktons) until get the climax communities, while the completely dried want more time than semidried to succession (Mitsch and Gosselink, 2000), that was agree with the study results about turbidity, dissolved oxygen and pH values (the dominant communities were producers , that causes increasing of dissolved oxygen and decreasing carbon dioxide, by photosynthesis processes, leading to decreasing of carboxylic acid and increasing pH values (Wetzel, 2001). Before rehabilitation of completely dried parts of Al‐Hawizeh Marsh the sediment was Sabkah (In some cases water stands on the surface giving the impression of ponds or lakes, usually the water table is very close to the ground surface, the salinity of the sabkha groundwater ranges between 50‐585 g.L‐1 in different places, solute chemistry indicates Na and Mg as the major cations and Cl‐ and SO4‐2 as the major anions, other ions such as Ca+2, K+, CO3‐, and HCO3‐ exist in varying proportions besides B‐, NO3‐ and F‐, The texture of sabkhas soils ranges from sandy to sandy‐clay‐loam at various places with ability to liquefy, the sabkah soils are darkness color, and high humidity, most of the areas adjacent to sabkhas are heavily degraded (Ajmal Khan, et al., 2006; IMET, 2006; Gateaa, 2006; and Rasheed, 2008), when water is gained to the marshes (during restoration processes) all of these salts, elements, organic matter return to the water column (re‐suspended and/or re‐dissolved), these chemicals plus inflow chemicals that also contribute to change of water quality of the dried and semidried stations (must don’t forget the human activities in these regions e.g. agriculture, oil extraction processes, and activities of Iraqi Iranian armies in this lands). Semidried parts were not completely destroyed, also seed bank, hydrologic (surface of land topography), and biologic regimes are more constant than completely dried, so these stations take a better water and sediment quality than completely dried these results were agree with Tahir, et al. (2008) and Al‐Saad, et al. (2008). 88
Chapter Four: Discussion
4‐3‐2 Sediments quality: 4‐3‐2‐1 Soil texture: As was expected the most widespread grain size in the sediments of Al‐Hawizeh Marsh was the silt ‐ clay fraction. The highest percentage, clay‐ silt is more than ten times higher than the lowest, sand. The silt ‐ clay fraction consists of particles less than 63µm in diameter. The study recorded that the clay was more percentage at the southern parts of Al‐Hawizeh Marsh (completely dried part), because of the particles of clay is so fine, the water flow was so slow with a weak vegetation cover at these stations, so most of the heavy particles were sinking (salts then silts) while the lighter molecules (clays) will stay hanging in the water column a long time so it has ability to transported as colloidal forms to far places than others(it wants more time to sitting), this results were matching with Bradl (2005); and Rasheed (2008). According to Al‐Badran (2006), Mesopotamian Marshes beds are mainly covered by recent loose sediments, vary in texture, color and mineral composition from one site to another, however, Aqrawi and Evans (1994) have been classified these beds into three main layer types, from top to bottom: 1. A surface organic‐rich sand silty layer. This layer is thin it does not exceed 7cm in depth. Naturally, this layer contains all the organic remains of plants and its color ranges from black to dark gray or olive. 2. A shelly clayey silt layer with mollusk shells, the depth of this layer is 7‐30cm. 3. A silty clay or/and clay basal layer, its depth is more than 30cm, the fine sand and coarse silt fraction, this ideal succession varies from site to site and it is possible to find two of these layers only. The results of the present study showed that there is dissimilarity for Sediment texture bin all of the study stations, these results were within the range that was detected to Sothern Iraqi marshes region, and this identical with Al‐Annei et al. (2000); Al‐Hussainy (2005); Al‐Badran (2006); Al‐Kinzawi (2007); and Rasheed (2008). 4‐3‐2‐2 pH value The pH values in surface water were more than sediment’s water, the relatively lower Sediment pH in relation to Water pH values agreed with the findings of Al‐Saffar (2006) that the pH usually does not show large variations with depth, but occasionally, the pH is somewhat lower near the bottom than near the surface. Wide variety of factors may have an effect on the Sediment pH, these include water temperature, water bodies with higher temperatures tend to reduce pH values (Heinz Center, 2002), due to the higher decomposition and humic acid release, However, lower solubility of CO2 in higher temperatures can neutralize it (Taha, 1991). As well as, Low‐oxygen conditions due to respiration can also lead to the release of toxic hydrogen sulfate from the sediment and can cause an increasing in aquatic carbon dioxide and changes in pH levels, adding to the stress of any organism that cannot escape (Joyce, 2000). Low Sediment pH during summer is determined largely by both sulfate reduction and oxidation of reaction byproducts of organic matter digenesis, such as oxidation of hydrogen sulfide (Sanders, 2003), this was agree with present study (Sediment pH was elevated during Dec & May 89
Chapter Four: Discussion
and decreasing during Aug, this agree with Al‐Saffar, 2006; Al‐Kinzawi, 2007; and Tahir, et al., 2008 ). The lowest pH values were in completely dried stations (The mean values of pH was fluctuated between 6.52‐7.46), and this was fit with Al‐Saffar (2006); and Tahir, et al. (2008). 4‐3‐2‐3 Electrical conductivity: The results of the present study showed that the sediment electrical conductivity values were at high levels in Aug while the low values were in Dec and May; this agrees with Al‐Saffar (2006) and Al‐kinzawi (2007) studies. Electrical conductivity are affected by many factors, they are affected primarily by the geology of the area through which the water flows and the presence of naturally occurring salts (Behar and Cheo, 2004); it is temperature sensitive and increases with increasing temperature (Horne and Goldman, 1994); whereas the high temperature lead to evaporation the water, so that the water levels be declined and the dissolved ions are concentrated (Adamus et al., 2001), the water electrical conductivity reflect on sediment electrical conductivity (Hammer and Hesltine, 1988; Al‐Essa, 2004). Therefore, this study showed that the sediment electrical conductivity could be increased considerably when the water electrical conductivity increased. The highest EC was in completely dried stations, we mentioned to the dried and semi dried stations and how they became sabkah before rehabilitation in 5‐3‐1 section, after rehabilitation most of salts and ions dissolved in pore sediment water lead to increasing in electrical conductivity, and this results was match with Tahir, et al. (2008). 4‐3‐2‐4 TOC and TOM % Organic matter and carbon are an important source and storage for nutritious components, which are required for growth of plants. Whereas during its degradation, carbon dioxide is released to the atmosphere, which enters in photosynthesis and plays important role in nitrogen changing, phosphorous and trace elements which are present in the organic mater to formula which is easier to up‐take by plants, and its main source is waste of human, animals as well as plants (Wardrop and Brooks, 1998; and Al‐Badran, 2006). The variations in TOM & TOC values among all of three stations, in the present study explained, that the reference stations (Ad1 & Ad 2) had organic mater percentage five times more than completely dried stations, that might be due to the density of vegetation cover for emergent plants, that leads to accumulation of plants litter and other organic maters (Sanchez‐Carrillo et al., 2001). The variations in TOM & TOC percentage at this study showed that the high percentages were at Aug, that might be because of the rise of temperature and increasing active of micro organisms which decomposes the died parts from plants and animals, while the low percentages were at May when the temperature is low and the active of decomposers is declined. Dissolved oxygen levels are an important factor in organic matter processing. Depressed dissolved oxygen concentrations could slow decomposition, and increase retention of detritus (Bass and Potts, 2001). On May, the decrease in TOM was probably due to the consumption by the organisms (e.g. benthic) 90
Chapter Four: Discussion
rather than the decomposition processes and the associated increased temperature and decreased dissolved oxygen levels. Temperature regimes control the rates of important biological processes, such as those involving organic matter decomposition, and consequently, accumulation of peat in the wetlands (DeBusk, 1999; Bass and Potts, 2001). The preservation of organic matter in sediments is inversely related to temperature (Sahagian and Melack, 1996). In case of high water temperature such as observed during Aug, the decomposition rate of organic substances increases, leading to the reduction of dissolved oxygen in the water column (Bij de Vaate and Pavluk, 2004). The water flow reduction may be partly responsible for the increased deposition of organic matter. On the other hand, higher water flow contributed to low retention of TOM (Bis, et al., 2000) and organic matter is processed during higher water flow into successively smaller (and more transportable) particle sizes (Lorenz, et al., 1997; and Galas & Dumnicka, 2003). However, submerged aquatic vegetation beds with high shoot density can play an indirect role in settlement of organic and inorganic particles through reducing water flow (Gallegos, 2004). Finer sediments generally adsorb more organic matter (Rodrigues, et al., 2001) from close to zero up to about 50% organic matter by weight (Wetzel, 2001) and provide more surface area for microbial attachment; however, fine sediments can also become depleted of oxygen (Poulton, et al., 2004). Therefore, sediments of mud or clay were suggested to be rich in organic detritus. These results agreed with Al‐Essa (2004); Al‐Saffar (2006); Al‐Badran (2006); and Tahir, et al. (2008)). 4‐3‐3 Heavy metals: Water pollution by trace metals is an important factor in both geochemical cycling of metals and in environmental health (Kabata –Pendias and Pendias, 1992). The existence of heavy metals in aquatic environments has led to serious concerns about their influence on plant and animal life. Metal nutritional requirements (Cu, Zn etc.) differ substantially between species or elements, and optimum ranges of concentrations are generally narrow severe unbalances on metal proportions caused by exposure to elevated concentrations can cause death for organisms. Other elements (Pb, Cd, etc.) exhibit extreme toxicity even at trace levels (Nicolau, et al., 2006). All heavy metals exist in surface waters in colloidal, particulate, and dissolved phases (Osmond, et al., 1995). 4‐3‐3‐1 Dissolved phase: The behavior of metals in natural waters is a function of the substrate sediment composition, the suspended sediment composition, and the water chemistry (Osmond, et al., 1995). During their transport, the trace metals undergo numerous changes in their speciation due to dissolution, precipitation, sorption and complexation phenomena (Dassenakis, et al., 1997; Akcay, et al., 2003) which affect their behavior and bioavailability (Nicolau, et al., 2006). The mean concentrations of the HMs in the dried stations were more than that in the wet stations, HMs in Mesopotamian Marshes are easily influenced by environmental factors such as surface runoff, groundwater, dissolution from sediment, deposition from the atmosphere and anthropogenic pollutants (Al‐Saad, et al., 2008). 91
Chapter Four: Discussion
The highest values of dissolved heavy metals were during Dec (hot period), and lowest values were during May (spring). Temperature impacts the rates of metabolism and growth of aquatic organisms, rate of plants' photosynthesis, solubility of oxygen in river water, and organisms' sensitivity to disease, parasites, and toxic materials. With increasing of temperature during spring months (May), plants grow and die faster during the late hot summer months (Aug), leaving behind matter that requires oxygen for decomposition, this seasonal variation was agree with Papafilippaki, et al. (2008). Trace elements where are accumulated to phytoplankton may become soluble during the decay of plants (Kabata – Pendias and Pendias, 1992). The seasonal variation of the water temperature in Al‐Hawizeh Marsh may influence the variability of the studied metals indirectly via biological activity (decay of aquatic plant and phytoplankton) or due to possible decrease of dissolved oxygen which related to redox potential decrease. In May period the intense melting cause an increase in the input discharge flow, producing a dilution of the contaminants. During the mixing of large volumes of non contaminated runoff water, the pH increases and the sulphate and metal content decrease. When the discharge inflow decreases during Aug period, the concentrations of contaminants begin to recover, reaching maxima in the summer due to sulphide‐ oxidising bacterial activity increasing with the temperature, and simultaneously, a concentrating effect of the dissolved pollutants occurs in the water due to water evaporation (Olias, et al., 2004), and that was agree with the correlations (r= 0.149, p >0.05) among DO, SO42‐, & WT with studied HMs (Annex 2 Table 8) . The solubility of HMs in surface water is predominately controlled by the water pH. A lower pH increases the competition between metal and hydrogen ions for binding sites. A decrease in pH may also dissolve metal‐carbonate complexes, releasing free metal ions into the water column. Although the pH decrease was low in Al‐Hawizeh Marsh it may play a significant role in the dissolved metal increase in the warm period. A decreased redox potential, as is often seen under oxygen deficient conditions, will change the composition of metal complexes and release the metal ions into the overlying water (Osmond, et al., 1995), so the correlations among the pH with all studied heavy metals were positive (r= 0.149, p >0.05) except with Cd and Mn (Annex: 2 Table: 8). According to statistical analysis (ANOVA), the study investigated that spatial and temporal variance among the stations and the period of study (the linear relationships between the studied physicochemical parameters and the dissolved metals of the sampling site of Al‐Hawizeh Marsh water on hot and cold period) (Annex:2 Table: 9). All of studied HMs were more than Iraqi limitation of river water quality except Se was non‐detectable, this result was disagree with Adam, et al. (2007). Generally, values recorded for HMs in the dissolved phase of water from Southern Iraqi marsh lands were higher than those reported for nearby sites such as Euphrates river (Al‐Taee, 1999; and Salman, 2006), Shatt Al‐Arab estuary (Abaychi and DouAble, 1985, Al‐Khafaji, 1996; Mahmood, 2008), which explained on the basis of high potential source of HM pollution in the Marsh lands, and agree with Al‐Shawi (2006). This study revealed that most of marshland waters in southern Iraq are suffering from pollution by heavy. 92
Chapter Four: Discussion
4‐3‐3‐2 Particulate phase: the low levels of some HMs in the study area attributed to the removing of these metals by many ways such as adsorption by particulate matter, precipitation deposition and removal by organism, Morris (1978) has reported that the degree of accumulation of HMs on the surface of the water divided or portioning finally into suspended matter, bed sediments or living organisms. On filtration, species passing through a filter with pore diameter of (0.45 µm) are commonly denoted as dissolved, while those retain as particulate. The former includes free ions of elements or organic and inorganic chemical compound the later divided into biotic (zooplankton, phytoplankton, bacteria, fungi etc) and abiotic includes clays, silts, feldspars, quarts, etc (Riley and Chester, 1981). Metals enter into a number of reactions, including complexation, precipitation and adsorption in the environment. These reactions affect their mobility and bioviability, however, adsorption could be the first step in the ultimate removal of metals from water (Allen, 1993). In this study, the particulate phase was divided into two main groups these are: exchangeable and residual. The highest values of exchangeable and residual heavy metals were in the wet and semidried stations, while the lowest values were in the completely dried stations, and there were spatial and temporal changes in the HM concentrations among the study stations & among the period of sampling (Annex: 2 Table: 9). For the variation particulate metals there are two factors affecting metals concentrations: runoff input during high discharge periods, and phytoplankton activity during low discharge periods. This shift in the source of suspended particulate matter causes an increase in the metals concentrations during dry season. In the dissolved fraction was related with soil leaching during high discharge periods, as well as the re‐suspension of fine bottom sediments and associated pore water ( Salomao and Ovalle, 2000) , and this agree with present study. The correlations of most exchangeable and residual heavy metals were negative with all water quality, (Annex: 2, Table: 10 & 11). Metal solubility, distribution and adsorption in different media such as soil, sludge, river sediment, and ground water were investigated by several researchers. These researches indicated that environmental factors such as pH, dissolved organic matter, metals competition, adsorbent characteristics and the like might affect the metal adsorption (Apak, et al., 1999; Simposon, et al., 2004; Srivastava, et al., 2005; Qian, et al., 2006; and Wang, et al., 2006 ). In general, higher pH showed higher metal adsorption (Watmough, et al., 2005; and Wang, et al., 2006). Metal adsorption also increased as the dissolved organic compounds increased (Christensen & Christensen, 2000)]. Metal distribution was affected by the co‐existing metals and different types of anions such as OH‐, CO3‐, SO42‐, Cl‐, NH3–H+, HCO31−, etc. (Martinez & Motto., 2000; Nierop, et al., 2002; Ma & Tobin, 2003; Srivastava, et al., 2005; and Wang, et al., 2006). Among the reported investigations, the correlations were agreed with the results of this study. 93
Chapter Four: Discussion
Metal solubility and adsorption can also be affected by the stepwise formation constants and functional groups such as carboxylic acids (Christensen & Christensen, 2000); sulf‐hydryl groups, amino, carboxylate, imidazole and hydroxyl radicals of enzymes and other proteins (Ren, Frymier, 2003); amines, sulfate groups and carboxylic groups (Peiffer, et al., 1994) and seven groups such as mercapto groups, uptake inside bacterial cells, carboxlic groups, phosphate and the like (Becker & Peiffer 1997). It was further noted that metal could be adsorbed in dissolved organic matter such as humic and fulvic acids (Christensen & Christensen, 2000) or solid matrix such as waste and sludge (Erses, et al., 2005; Wang, et al., 2006; and Fiol, et al., 2006). Thus, the metal adsorption constant (stability constant of metal–matrix complex) with detailed continuation research could be used to explain the metal adsorption scenarios in different environmental conditions such as pH, dissolved organic matter, adsorbent characteristics, and metal ions competition. In addition, these results can provide the baseline information of heavy metal levels for risk limitation in the Mesopotamian Marshes. In present study found that heavy metals concentrations in the particulate phase is much more than dissolved phase, this may be due to the considerable variations in partitioning between water and particulate matter. However, the concentrations of HMs in particulate matter mostly depend on many factors such as wastewater discharge, seasonal loads, and the nature of basin (Nolting, 1986). 4‐3‐3‐3 HEAVY METALS IN SEDIMENT Metal speciation can provide information concerning the complex interactions among dissolved, particulate, sedimentary and biological component in aquatic environment (El‐Rayis, 1990). A large portion of HMs that are introduced in different aquatic environments are precipitated as sparingly soluble metal component which are immobilized in particulate and finally accumulated in the sediments, so sediments act as an archive for many pollutants (Al‐Khafaji,1996). Sediments are usually regarded as the ultimate sink of HMs discharged into the environment, therefore the analysis of HMs in sediments offers a more convenient and more accurate means of detecting and assessing the degree of pollution (FAO, 1994). The distribution of metals in the sediment is complex phenomenon. The adsorption of metals suspended matter and subsequent sedimentation, removes these pollutants from the water column. Enrchment of the sediment with metals may cause their transportation to the ground water release of accumulated metals to water column and consequent accumulation by aquatic organisms (Abdelmoneim, et al., 1994). In the present study, HMs in sediments were subdivided into exchangeable and residual phase. Exchangeable HMs are those incorporated into the sediment from aqueos solution by processes such as adsorption and organic complextion. Exchangeable HMs include those originated from polluted water, whereas, residual HMs are defined as those HMs, which are, located in lattice structures of the components minerals (Agemain and Chau, 1976). 94
Chapter Four: Discussion
Much of analytical showing less concentration polluted in sediments with grain size increasing at they think because decreasing in surface area to weight, and they have been found dissolved and particulate organic materials are be complex compound with elements by exchangeable and chemicals reactions (Millward, 1995; and El‐Rayis, et al., 1997). In present study there were a positive correlations between increasing of HMs concentration and grain size and that was agree with Al‐Abdali, et al. (1996), and Hassan (2007), and disagree with Al‐Taee (1999), and Salman (2006). The statistical analysis (ANOVA at F: 0.05) showed that there were a significanct difference among stations for all studied metals during the period of study(Annex:2 Table:9), that was corresponded with Al‐Saa’don (2002) In Shatt Al‐Arab River and Khor Al‐Zubair, and Hassan (2007) in Shatt Al‐Arab River. The distribution of HMs between exchangeable and residual phase of sediment is the result of a number of processes like hydrochemical condition (temperature, salinity, pH, redox potential …..etc), (Al‐Khafaji, 1996). The concentrations of most HMs were in the residual more than them in exchangeable form and that was matching with Al‐Edanee, et al. (1991). Water level fluctuations may have beneficial effects in sediments of which the buffer capacity is large enough to prevent acidification as a result of oxidation of reduced sulphur compounds. Oxidation of such sediments will result in net nitrogen losses and a decrease of the phosphate availability. Desiccation of sediments with high oxidizable sulphur contents, however, might lead to reactions that resemble those observed in acid sulphate soils. Extreme acidification might occur resulting in the mobilisation of high concentrations of potentially toxic metals. Dissolution of oxidized metals at very low pH will also result in the release of previously adsorbed phosphate. In freshwater systems, high concentrations of reduced sulphur will especially accumulate in reductive and iron‐rich sediments which are fed by sulphate‐enriched groundwater and which almost never fall dry (Smolders, et al., 2006). Iraqi natural waters are mildly basic. In the Tigris, Euphrates, and Shatt Al‐Arab Rivers seasonal variations were observed with the lower values during the winter and spring and higher values during summer and fall (IMET and IF, 2005), and values typically ranged from 7.5 to 8.5 (Saad and Antoine 1978). Considering the range of Water pH and Sediment pH in Al‐Hawizeh Marsh along the study period it was almost within the optimal range (6.5 to 8.5). There were negative significant correlations (r=0.149, p>0.05) between pH and all exchangeable residual metals (except exchangeable Cd, Cr, & Mo they have positive correlation with pH; and residual Mo), while exchangeable As, Mn, Zn were haven’t significant correlation with pH. (Annex: 2 Table: 11). Low pH can reduce mineralization rates and contribute to organic matter accumulation (WASC, 2002), Increasing the bioavailability of toxic chemicals from the sediment (Cherry, et al., 2000; Freeman, 2000), and that affecting on the solubility of HMsheavy metals in water (Lazaridou‐ Dimitriadou, et al., 2004) and the concentrations of total dissolved solids (WASC, 2002). EC affected postively (positive correlation) on all exchangeable metals except Mn it was haven’t significant correlation with EC; and with residual Cd, Mn, & Mo; while it affected negativly on concentration of residual Co, Zn, Cr, & Fe. (Annex: 2 Table: 11). 95
Chapter Four: Discussion
Metals entering wetlands will bind to the negatively ionized surface of clay particles, or precipitate as inorganic compounds (metal oxides, hydroxides, and carbonates), or form a complex with humic materials depending on pH. (Sheldon et al., 2003). TOM% and TOC% have same effcting correlation values with studied metals. They have significant negative correlatin with exchangeable As, Co, Cu, Se, Pb, Cr, & Fe; and with residual Mo; while the residual Cu, Pb, Zn, Cr, & Fe were have significant positive correlation with TOM% & TOC% (Annex: 2 Table: 12). This results were agree with Al‐ Saa’don (2002) & Hassan (2007) and not matching with Al‐Taee (1999) & Salman (2006). In dry summer, wetlands may become subject to desiccation and oxidation processes may affect sediment top layers Smolders et al. (2006), and that was agree with the present study, whereas, there were significance differences among the period of sampling for all studied metals except Cd, Ni, Cu, & Mn (Annex: 2 Table: 9). Knowlge of the concentration and distribution of HMs in sediments can play a key role in detecting sources of pollution in aquatic systems (Forstner and Wittman, 1983), many studies in different region from the world have been used the sediments of the wetland as indicator for pollution (Syrovetnik, et al., 2007). Hassan (2007) showed that the concentrations of Pb and Cd in the Shatt Al‐Arab River sediments were higher than the Iraqi standards limitation and WHO, while the present study found that (According to Igeo in Annex: 2 Table: 13) Al‐Hwaizeh Marsh is suffering from strongly polluted with: As in South Al‐Soda station; Co in Um‐El.Nia'j2 station; Mo in all stations except Um Al‐Wared, South Al‐Soda, & Lesan Ejerda station. The study recorded the moderately to strongly polluted for: As in Al‐Adaim1, Al‐Adaim2, Um‐ El.Nia'j1, Lesan Ejerda, & Majnon stations; Cd was in Um‐El.Nia'j1 & South Al‐Soda; Co & Mo were just in Um Al‐Wared station; Pb was just in Um‐El.Nia'j1 station; Zn was in Al‐ Adaim1, Um‐El.Nia'j2, North Al‐Soda, Um Al‐Wared, Lesan Ejerda, & Majnon stations; Fe was in all stations except Um‐El.Nia'j1 station; and Mn was in all stations except Um‐ El.Nia'j2 station. The unpoluted to modrerat values of: As was in North Al‐Soda, Um Al‐ Wared, & Al‐Baidah stations; Cd was in Al‐Adaim1, Al‐Adaim2, Um‐El.Nia'j2, Lesan Ejerda, North Al‐Soda, Um Al‐Wared, Al‐Baidah & Majnon stations; Co was in just North Al‐Soda station; Mo was in South Al‐Soda, & Lesan Ejerda; Ni was just in Um Al‐Wared; Pb was in Al‐Adaim1, Al‐Adaim2, Um‐El.Nia'j2, Lesan Ejerda, south Al‐Soda, North Al‐ Soda, Um Al‐Wared, & Majnon stations; and Mn was just in Um‐El.Nia'j2 station. Finally the Um‐El.Nia'j2 station was unpolluted with As metal; all stations were unpolluted with Co (except Um‐El.Nia'j2, Um Al‐Wared, & Northg Al‐Soda stations), Cr, Ni (except Um Al‐ Wared station), Se, & Cu, while just Um Al‐Wared & Al‐Baidah stations were unpolluted with Pb metal. 4‐4 Can Bellamya (Viviparus) bengalensis snails and Potamogeton perfoliatus plant be used as bio‐indicators to indicate the presence of heavy metals in the Mesopotamian marshes? We discussed the results of heavy metals in dissolved, particulates (exchangeable & residual), and sediments (exchangeable & residual), then discussed the correlations of them with water and sediments quality in section : (4‐3‐2), so in this part, the study 96
Chapter Four: Discussion
going to go to discussed the results of heavy metals in tissues of one of aquatic dominant species submerged plant (Potamogeton perfoliatus), and one of the dominant benthos species (Bellamya (Viviparus) bengalensis) in all Al‐Hawizeh study sites, and find the correlations of the elements in all (dissolved, particulates, sediments, plant, and snail), to suggested whether that the chosen snail and plant were accumulated or not for the different heavy metals, then answer the question: Can choose this plant and snail as bio‐indicator or not? 4‐4‐1 Potamogeton perfoliatus (P. perfoliatus) submerged plants as bioindicator: Different wetland plant species differ, however, in their abilities to take up and accumulate various HMs in their tissues (Rai, et al., 1995). Submerged species have been found to accumulate relatively high HMs concentrations when compared with emergent species (Kara, 2005). The ability of plants to accumulate and eliminate heavy metals in relation to their concentrations in ambient led to the observed variations in metal concentrations in plants. The results showed higher concentration of heavy metals in sediment than in plants, these results were agreed with Awad, et al. (2008). Aquatic plants are known in accumulating metals from their environment (Outridge & Noller, 1991; and Ali & Soltan, 1999) and affect metal fluxes rough those ecosystems (Jackson, et al., 1994; and St‐ Cyr, et al., 1994). The concentrations of metals in aquatic plants were more than in the associated water, this results were agree with Albers and Camardese (1993); Al‐ Taee(1999); Al‐Adrise(2002); Al‐Haidarey(2003); Salman(2006); and Al‐Bayati(2008). In Iraq there were numerous researcher used the aquatic plant as bioindicator for HMs pollution (Abaychi and Al‐Obaidy, 1987; Ibrahim, 1993; Sabri, et al., 2001; Al‐Saadi, et al., 2002; Algam, 2002 ; Salman, 2006), while in the Mesopotamian Marshes : Al‐ Saad, et al., (1994) studied the distribution and concentrations of HMs in aquatic plants of Al‐Hammar Marshes, they found that the concentrations of Fe, Mn, Pb, Ni, and Zn in plants studies were lower than the baseline concentrations, while those for Cd, Cr, and V were relatively higher; Awad and Mahdi (2005) studied a heavy metals in aquatic plants from different regions of southern Iraqi marshes (Amara & Basrah). The results show that the heavy metals content of plants have wide different concentration ranges which reveals that these plants concentrate and accumulate these metals from their environment ( water and sediment); Awad, et al. (2008) analyzed a heavy metals (Cd, Pb, Cu, Zn, Mn and Fe) in six species of aquatic plant (P. Crispus , P. nodosus, Ceratophyllum demersum, Salvinia natans, Potamogeton pectinatans, Salicornia herbaceal, and Vallisneria spiralis) and sediments of Al‐Hawizeh and Al‐Hammar marshes. Significant differences were observed in heavy metals concentrations in plants samples for dried, semi dried and wet stations (the concentrations of metals were in completely dried > semidried > permanently wet), the dried stations have a lot of heavy metals concentrated in sediments, after rehabilitations the heavy metals were re‐influx and gaining to the water column, the fast growing of a biota because of found a lot of nutrients lead to uptake the metals then it's accumulating in plants and animals. The BCF values of all elements were more than BSF values (Annex: 3 Table: 3), this result 97
Chapter Four: Discussion
comes agree with all that above bout the ability of Potamogeton perfoliatus to accumulate of heavy metals. The metal uptake in plants varies. It’s well established that metal aqueous chemistry (i.e., metal speciation, free ion concentration, and metals‐ metal interaction) is critical in controlling heavy metal uptake and toxicity to aquatic organisms (Campbell, 1995). In nutrient enriched environments, the bioavailable fraction of metals may be reduced as a result of binding to nutrient anions. The uptake of heavy metals in plants may also be affected by competition, since nutrient cations complete with the metals for uptake sites (Greger, 1999). Thus, the uptake of the studied metals may decrease with increasing external nutrients to toxic heavy metal ratio. On other hand in Mesopotamian Marshes, a generous availability of nutrients promotes plant growth (Hassan, 1988; and Al‐Kinzawi, 2007), which in turn creates an increasing number of uptake sites for metals in plants, this may increase the uptake (Ekvall and Greger, 2002) and metal concentrations in plants may be expected to either increase, decrease, or sty constant, depending on the relative responses of metal uptake and growth rate. 4‐4‐2 Bellamya (Viviparus) bengalensis Snail as Bioindicators : Viviparus bengalensis (V. bengalensis) snail has been used frequently as bioindicator organisms. Two important advantages of V. bengalensis over most other freshwater organisms for biomonitoring are their large size and limited mobility, in addition, they are abundant in many types of freshwater environments and are relatively easy to collected and identify (Jamil, 2001). V. bengalensis can function as collector‐gatherer, consuming algae growing on any submerged surface, and scraper, utilizing fine particulate organic matter and the bacteria and other microorganisms therein and also filter feed on suspended matter, competing with the clams and mussels. (Voshell, 2002; and Al‐Saffar, 2006) As we mentioned in accumulation of heavy metals in P. perfoliatus, case the dried stations snails were have more concentrations than other stations. AS illustrated in Annex (3) Table (4), there were a positive significant correlation plant As (P As) and snails As (VAs), sediment’s exchangeable As (SEAs) and sediment residual’s As (SRAs)with particulate residual’s (PRAs), while there were a negative significant correlation between particulate exchangeable As and the snail’s As. The correlations were positive significant: plant’s Cd (PCd)& Snail’s Cd (VCd), dissolved Cd (DCd)& residual particulate’s (RPCd), and negative correlation between particulate exchangeable Cd (PECd)& snail’s Cd (VCd)forms (Annex: 3 Table: 5). The dissolved Co phase (DCo) has positive significant correlations with plant’s and snail’s Co (PCo & VCo), while there were negative correlations among snail’s, particulate exchangeable (PECo), and plant’s Co (PCo) (Annex: 3 Table: 6). All the correlations of plant’s Cr (PCr) with other Cr phases were negative except with sediments exchangeable Cr (SECr) was positive insignificant correlation, the strongest correlations were with exchangeable particulate Cr (EPCr) form and residual particulate form, while the snails had a negative correlation with residual particulate Cr (RPCr) and negative correlation with dissolved & sediment residual Cr (Annex: 3 Table: 7). 98
Chapter Four: Discussion
As illustrated in Annex (3) Table (8), there were no significant correlations among the phases of Se. All the correlations among plants Pb form and other Pb forms were insignificant, except with snail’s Pb form it was positive significant, and there was a positive significant between the dissolved and sediment residual Pb forms (Annex: 3 Table: 9). As illustrated in Annex (3) Table (10) the snail’s Zn form had a negative correlations with all other forms of Zn, while the plant’s Zn form had a positive correlations with sediment exchangeable & dissolved Zn forms, and had a negative significant correlations with snail’s, residual particulate, exchangeable particulate, and sediment residual Zn forms, there were a positive significant correlations among sediments residual, residual particulate, and exchangeable particulate Zn forms. The snail’s Ni form had a positive significant correlation with all the other forms of Ni except residual particulate Ni form it had negative insignificant correlation, while the plant’s Ni form had just positive significant with snails and exchangeable Ni forms (Annex: 3 Table: 11). The plant’s Mn form had a negative significant with the sediment & dissolved Mn forms, and insignificant correlation with other forms of Mn, while the snail’s Mn had a negative correlation with all the other forms of Mn, except sediment residual Mn it was positive. There were positive significant correlations among sediment exchangeable, particulate exchangeable & dissolved Mn forms (Annex: 3 Table: 12). All the Mo forms had positive correlations with the plant’s form, except sediment residual Mo form it was had a negative significant correlation, while all they were had positive correlations with the snail’s Mo form except residual particulate Mo form it was had a negative significant correlation (Annex: 3 Table: 13). It is important that a biomonitor strongly accumulate the contaminant of interest and that the tissue contaminant concentrations be directly proportional to average ambient bioavailable contaminant concentrations. For many organic contaminates, relatively simple correlations have been determined (e‐g. fugacity/hydrophobicity constants) that hold over a range of environmental conditions (Clark, et al., 1990). However, the development of "simple" correlations for metal has been more difficult. Metal bioavailability and metal accumulation by biota change in response to environmental conditions and from one species to another. Interpreting tissue metal concentrations in the aquatic environment requires an understanding of the factors that influence metal availability and determine metal accumulation (Please go to comment 118 its same references). The availability of a metal is determined by its speciation which may be very sensitive to changing environmental conditions (e.g. pH, presence of natural inorganic and organic ligands). Reactions affecting metal speciation may occur within organisms, on their surface, in solution, and on the surface of particles, making understanding metal behavior difficult. The availability of metals will be a function of both the source of metal exposure (dissolved or particulate phase) and the geochemical processes that control metal availability within each phase. Metal accumulation is also affected by individual biological characteristics and aspects of organism’s physiology. Individual biological 99
Chapter Four: Discussion
characteristics that determine organism response to metal exposure typically include aspects of growth and reproduction, as well as behavior. There were insignificant correlation among plant’s Fe and other forms of Fe, while there were a positive correlation among the snail’s Fe form and all the other forms of Fe except with the sediment exchangeable form, and there was a positive correlation between the residual particulate Fe form and exchangeable particulate Fe form (Annex: 3 Table: 14). As illustrated in Annex (3) Table (15) the correlation among snail’s , plant’s, & dissolved form of the Cu forms were positive significant, and there were a negative significant correlation among snail’s, exchangeable particulate, and residual particulate Cu forms. For the correlation among different forms of HMs in this work, we can say that the Potamogeton perfoliatus was not considered to be a good bioindicator for Cr contamination in all form (water, particulates, and sediments); however, this species could be used as an indicator of As (in dissolved phase), Cd (in dissolved phase), Co (in dissolved and sediment exchangeable phase), Pb (in dissolved phase), Zn (in dissolved and sediment exchangeable phase), Ni (in dissolved, sediment exchangeable, and particulate phase), Mn (in exchangeable particulate phase), Mo (in dissolved, sediment exchangeable, and particulate exchangeable & residuals phase), Fe (in dissolved phase), and Cu (in dissolved and sediment exchangeable phase) contamination. Finally we can say that the Potamogeton perfoliatus is good indicator for heavy metals in water and sediments. The correlation among different forms of HMs in this work we can say that the V. bengalensis was not considered to be a bioindicator for Cadmium, Lead, Cooper, and Zinc contamination in Sediment, however, this species could be used as a good bioindicator of As, Co, Cr, Ni, Mo, & Fe in sediments, and a good indicator of As, Co, Cr, Pb, Ni, Mo, and Cu in water column. The reactivity of the metal determines the extent of the reaction of the metal with surface cellular sites, and hence its bioavailability. In order for a metal to be accumulated by an organism, a metal must first interact with and/or cross a cell membrane (Campbell and Tessier, 1996). This interaction takes place with the free metal ion or a metal ligand complex as the reactive species, and results in the formation of metal‐X‐cell surface complex, where X‐cell is a cellular ligand present at the ce11 surface. Assuming the concentration of free ‐X‐cell sites remains approximately constant, the biological response (accumulation, toxicity, etc.) will vary as a function of concentration of metal ions. In the case where a metal complex reacts at the cell surface, the reaction must be accompanied by the loss of ligand. Thus, the idea that the free hydrated metal ion is the only bioavailable species is a misconception, since no single species in a solution can be considered more (or less) available than another (Campbell, 1995). There are a number of key assumptions surrounding the flam involving the biological surface and the kinetics of metal‐organism interactions. If the dissolved phase is the primary exposure vector, the metal concentrations in the molluscs should be correlated with the fee‐metal ion concentration in the ambient water or its surrogate. The review by Campbell and Tessier (1996) of bioassays and field 100
Chapter Four: Discussion
surveys of indigenous benthic organisms supports the idea that benthic organisms respond to the free‐metal ion concentration in the ambient water in or near the surficial sediments, that were agree with the study results that were the significant correlations with dissolved and exchangeable forms of metals while the correlations with other part were insignificant or negative. For field studies, the geochemical gradient (metal bioavailability) has been defined in terms of the free‐metal ion (as estimated from sediment‐water equilibria) or the ratio of sorbed metal to sorbent (related to the free‐ metal ion concentration). The free metal ion concentration is a function of both the total aqueous metal present and the quantity and nature of Ligands present in the water. Consequently, it is not surprising that the free metal ion concentration can vary widely among systems as does the biological response it causes (Campbell and Tessier. 1996). The BCF values for all elements were more than BSF values; this result comes agree with P. perfoliatus. The BCF of Cu, Fe, As, and Zn in V. bengalensis were more values than P. perfoliatus, that mean the ability of this snails to accumulated of these metals more than P. perfoliatus, however the ability of P. perfoliatus plant to accumulation of other elements were more than snails (Annex: 3 Table: 3). Metals in contaminated sediments are thought to be taken up by aquatic life in two ways: indirectly (by partitioning of the metals into the ambient water, followed by their assimilation from the aqueous phase), and directly (by digestion of the sediments and assimilation of the metals from the gut), (Campbell and Tessier, 1996). In the past there has been considerable debate over which of the above pathways is of greater significance in terms of metal exposure in snails (Luoma et al., 1992, and Phillips & Rainbow, 1993). There were positive correlations between concentrations of HMs in V. bengalensis and P. perfoliatus, that's mean they up‐taking these metals from same sources, the sediments considered act as an archive for many organic materials that coming from death of organisms (plants and animals), (Griethuysen, et al., 2005; Gregg et al., 2005; and Ahmet, et al., 2005 ), then accumulation in benthic fauna that feed on sediments (Hare, et al., 1994) and through food chain transfer (Luoma, et al., 1992; Lemly 1993; and MacFarlane, et al.,2006). Finally there were significant spatial and temporal differences among the study stations and among the periods of sampling (Annex: 2 Table: 10)
101
Conclusions & Recommendations
The Conclusions and Recommendations 102
Conclusions & Recommendations
1‐ Conclusions 1. The highest concentrations of the studied HMs were recorded during the summer months, while the lowest values were recorded in the spring months, except the Selenium element was no detection concentrations. 2. All the HMs was exceeds than Iraqi limitations for freshwater quality, except As, Se, and Cu were in the range of Iraqi limitations. 3. Al‐Hawizeh Marsh was sinking for: 63%As, 38% Cu, 33% Zn , 30% Mo, 27% Pb, & 8 % Cd; transformer to 93% Cd 73% Pb, 70%Mo, 68% Zn, 62% Cu, & 37% As; and source for 42% Cr, 28% Fe , 23%Mn, 15%Co, & 6% Ni. 4. The WT, TSS, TH, Ca+2, Mg+2, and Cl‐ values were in completely dried stations > semidried stations > wet stations; EC, salinity, turbidity, TDS, HCO‐3, & SO4‐2 values were in completely dried stations > wet stations > semidried stations; pH & DO were in semidried stations > wet stations > completely dried stations. 5. The clay was more percentage at the southern parts of Al‐Hawizeh Marsh (completely dried part). 6. The high percentages of TOM & TOC% were in Aug. while the low percentages were in May. 7. The mean concentrations of the HMs in the dried stations were more than that in the wet stations 8. There were spatial and temporal variance among the stations and the period of study (the linear relationships between the studied physicochemical parameters and the dissolved metals of the sampling site of Al‐Hawizeh Marsh water on hot and cold periods). 9. The highest values of exchangeable and residual heavy metals in Particulates were in the wet and semidried stations, while the lowest values were in the completely dried stations. 10. There were spatial and temporal changes in the HM concentrations in particulate phase among the study stations & among the period of sampling. 11. The HM concentrations in the particulates phase are much more than dissolved phase. 12. There were positive correlations between increasing of HMs concentration and grain size 13. The sediments of Al‐Hwaizeh Marshes is suffering from strongly polluted with: As in South Al‐Soda station; Co in Um‐El.Nia'j2 station; Mo in all stations. 14. The sediments of Al‐Hwaizeh Marshes is suffering from moderately to strongly polluted for: As in Al‐Adaim1, Al‐Adaim2, Um‐El.Nia'j1, Lesan Ejerda, & Majnon stations; Cd was in Um‐El.Nia'j1 & South Al‐Soda; Co & Mo were just in Um Al‐ Wared station; Pb was just in Um‐El.Nia'j1 station; Zn was in Al‐Adaim1, Um‐ El.Nia'j2, North Al‐Soda, Um Al‐Wared, Lesan Ejerda, & Majnon stations; Fe was in all stations; and Mn was in all stations. 15. The sediments of Al‐Hwaizeh Marshes is unpoluted to modrerat values of: As was in North Al‐Soda, Um Al‐Wared, & Al‐Baidah stations; Cd was in Al‐Adaim1, 103
Conclusions & Recommendations
Al‐Adaim2, Um‐El.Nia'j2, Lesan Ejerda, North Al‐Soda, Um Al‐Wared, Al‐Baidah & Majnon stations; Co was in just North Al‐Soda station; Mo was in South Al‐ Soda, & Lesan Ejerda; Ni was just in Um Al‐Wared; Pb was in Al‐Adaim1, Al‐ Adaim2, Um‐El.Nia'j2, Lesan Ejerda, south Al‐Soda, North Al‐Soda, Um Al‐Wared, & Majnon stations; and Mn was just in Um‐El.Nia'j2 station. 16. The Um‐El.Nia'j2 station was unpolluted with As metal; all stations were unpolluted with Co, Se, & Cu, while just Um Al‐Wared & Al‐Baidah stations were unpolluted with Pb metal. 17. The concentrations of HMs in Potamogeton perfoliatus plant were in completely dried > semidried > permanently wet. 18. Potamogeton perfoliatus was not considered to be a good bioindicator for Cr in all phases, and it’s good indicator for others in water and sediments. 19. The V. bengalensis was not considered to be a good bioindicator for Cd, Pb, Cu, and Zn, and its a good bioindicator of As, Co, Cr, Ni, Mo, & Fe in sediments, and a good bioindicator of As, Co, Cr, Pb, Ni, Mo, and Cu in water column. 20. The BCF values for all elements were more than BSF values. 21. HMs in V. bengalensis and P. perfoliatus, comes from same sources. 2‐ Recommendations 1. Scientific groups must form for monitoring damages of environmental change and for their effect in the environment. 2. Preparing a database of the biological and physico‐chemical variables of the Iraqi marshes. 3. Using other aquatic macrophyte and macro invertebrate species in a long‐term biomonitoring program for the Iraqi marshes. 4. Continues monitoring programs should be formulated and conducted to ensure that HMs remine under the baseline levels. 5. Restoration of other up marshes (like Ibn Najem Marsh) to get better water quality in the down Marshes. 6. Increasing the amount of water which is reached the Iraqi marshes by Euphrates and Tigris Rivers to reflood the areas which still dried. 104
105
Annexes
Annexes
106
Annexes
Annex (1) Table (1): The mean, median, standard deviation (Std.Dev), standard error (Std. Err), size of sample, minimum (Min), and maximum (Max) of studied physio‐chemical parameter of the three Mesopotamian Marshes during the study period (2006).
WT Sal EC DO pH TDS TSS TH Mg 2 Ca2 Mean 21.5292 1.2475 2791.86 6.3338 7.7665 1720 26.0791 636.33 111.1462 87.293 Median 23.75 1.4 2800 6.4 7.71 1708 20.5 530 104.2 70.09 Std.Dev 7.0103 0.6304 1569.38 3.0067 0.497 692.7 27.5332 294.25 49.3687 51.6046 Std.Err 0.8262 0.0743 184.953 0.3543 0.059 81.64 3.2448 34.677 5.8182 6.0817 Size 72 72 72 72 72 72 72 74 74 74 Min 11.2 0.2 952 0.13 6.5 575 2 200 24.3 19.44 Max 33 2.6 9720 13.26 8.8 3308 173.95 1480 248.5 238.14
Table (2): The correlations among heavy metals concentrations and studied physio‐chemicals parameters in the three Mesopotamian Marshes (r= 0.11, p >0.05). As Cd Co Cr Mo Ni
0.5482 0.5632 0.642 0.6019 0.4875 0.5975
0.1697 0.2645 ‐0.0346 ‐0.1073 0.2086 0.1384
0.0657 0.1658 ‐0.0195 ‐0.0702 0.1611 0.0732
‐0.0174 ‐0.0901 ‐0.1551 ‐0.2037 ‐0.1925 ‐0.2186
0.1561 0.3959 0.2832 0.3957 0.5734 0.5634
Pb Zn Cu Fe Mn
0.6089 0.4824 0.4613 0.4343 0.4562 WT
0.0025 0.1364 ‐0.2892 ‐0.0553 0.2007 Sal
‐0.0059 0.041 ‐0.2456 ‐0.0939 0.0902 EC
‐0.098 0.0092 ‐0.181 0.0062 0.0377 pH
0.2746 0.0865 0.2186 0.1635 0.1354 TDS
‐0.0741 0.1772 0.1212 0.3004 0.3006 0.2859
‐0.0078 ‐0.0368 ‐0.0586 ‐0.0728 ‐0.0241 ‐0.0386
‐0.4706 ‐0.4978 ‐0.2945 ‐0.2892 ‐0.3722 ‐0.318
‐0.0011 ‐0.0413 ‐0.0418 ‐0.0559 ‐0.0323 ‐0.0364
‐0.0131 ‐0.0331 ‐0.0718 ‐0.0861 ‐0.0172 ‐0.0403
0.1716 ‐0.0566 ‐0.1294 ‐0.0206 0.0915 ‐0.0585 0.2794 ‐0.0434 0.0247 ‐0.019 TSS TH
‐0.453 ‐0.4572 ‐0.146 ‐0.1939 ‐0.4496 DO
‐0.0426 ‐0.0154 ‐0.0312 ‐0.0334 ‐0.0169 Ca
‐0.0676 ‐0.0247 ‐0.0803 ‐0.0512 ‐0.0206 Mg
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Annexes
Annex (2)
Mean Median
TSS 30 4.8
TH 637 500
Ca+ 144 120
Mg+ 53.7 53.4
HCO3ֿ 205.2 207.43
Clֿ 305 284
SO4 ²ֿ 296 272
Tur 48.7 35
Sal 0.8 0.69
EC 1665 1444
pH 8 8
WT 23 27
DO 7.26 7.41
TDS 2481 1118
Std.Dev
66
528
76.05
18.1
54.28
101
118
39
0.38
551
0.3
8.9
2.47
2271
Std.Err
9
74
10.65
2.53
7.68
14.21
16.54
6
0.05
77
0.05
1.2
0.35
318.04
Min
0.3
380
60.10
24.3
102
149
144
0.88
0.30
1027
7.23
10
1.36
490.00
Max
323
4118
408
996
361
567
725
131
2.3
3477
8.7
34
12.7
9895
Table (2): The mean, median, standard deviation (Std.Dev), standard error (Std. Err), minimum (Min), and maximum (Max) of some sediments quality during (2006) in Al‐Hawizeh Marsh.
Mean Median Std.Dev Std.Err Min Max
pH 7.1961 7.195 0.4321 0.0605 6.01 8.2
Ec (ds/m = 1000 ms/cm) 2.3055 2.435 0.6012 0.0842 1.11 3.28
TOC 2.5196 2.015 1.9731 0.2763 0.07 7.78
TOM 5.7966 4.645 4.5374 0.6354 0.161 17.894
Table (1): The mean, median, standard deviation (Std.Dev), standard error (Std. Err), minimum (Min), and maximum (Max) of water quality parameter during (2006) in Al‐Hawizeh Marsh.
108
Annexes
Table (3): The mean, median, standard deviation (Std.Dev), standard error (Std. Err), minimum (Min), and maximum (Max) of Stations Ad1
Ad2
UmNj1
UmNj2
N. Sod
Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max
As 0.021 0.021 0.016 0.009 0.006 0.037 0.013 0.015 0.007 0.004 0.006 0.020 0.022 0.020 0.018 0.011 0.005 0.041 0.020 0.023 0.011 0.006 0.009 0.029 0.019 0.019 0.010 0.006 0.009 0.028
Cd 0.050 0.042 0.042 0.024 0.013 0.096 0.024 0.026 0.006 0.003 0.017 0.028 0.029 0.038 0.015 0.009 0.011 0.038 0.038 0.042 0.011 0.007 0.025 0.046 0.042 0.041 0.025 0.014 0.018 0.067
Co 0.011 0.010 0.005 0.003 0.007 0.017 0.008 0.008 0.000 0.000 0.008 0.009 0.007 0.009 0.002 0.001 0.005 0.009 0.009 0.009 0.001 0.001 0.007 0.010 0.011 0.010 0.003 0.002 0.008 0.014
Cr 0.248 0.228 0.080 0.046 0.180 0.337 0.182 0.184 0.008 0.005 0.173 0.189 0.207 0.202 0.044 0.025 0.166 0.253 0.213 0.207 0.044 0.026 0.173 0.261 0.170 0.174 0.009 0.005 0.161 0.177
Mo 0.119 0.122 0.101 0.058 0.017 0.217 0.039 0.019 0.042 0.024 0.011 0.087 0.262 0.122 0.337 0.195 0.019 0.647 0.647 0.070 1.042 0.602 0.021 1.850 0.093 0.035 0.121 0.070 0.012 0.232
Ni 0.321 0.294 0.085 0.049 0.253 0.415 0.213 0.225 0.083 0.048 0.125 0.290 0.270 0.272 0.054 0.031 0.215 0.324 0.272 0.269 0.084 0.048 0.190 0.357 0.255 0.259 0.040 0.023 0.214 0.292
Pb 0.034 0.039 0.009 0.005 0.023 0.039 0.036 0.038 0.016 0.009 0.019 0.050 0.045 0.042 0.008 0.004 0.040 0.054 0.042 0.046 0.007 0.004 0.035 0.047 0.047 0.046 0.005 0.003 0.042 0.053
Zn 4.411 3.595 1.706 0.985 3.267 6.373 2.060 1.961 0.467 0.270 1.651 2.568 2.096 2.194 0.318 0.184 1.739 2.353 2.194 2.046 0.685 0.396 1.595 2.941 4.726 4.093 2.473 1.428 2.632 7.454
Cu 0.226 0.250 0.109 0.063 0.108 0.321 0.200 0.200 0.029 0.017 0.171 0.230 0.253 0.247 0.121 0.070 0.134 0.377 0.247 0.255 0.091 0.052 0.153 0.333 0.340 0.317 0.156 0.090 0.198 0.506
Fe 1.968 1.826 0.911 0.526 1.136 2.941 1.874 1.821 0.502 0.290 1.401 2.401 1.706 1.659 0.624 0.361 1.107 2.353 1.659 1.730 0.165 0.095 1.471 1.778 1.662 1.662 0.659 0.381 1.003 2.322
Mn 0.181 0.184 0.027 0.016 0.153 0.207 1.155 0.998 0.625 0.361 0.624 1.844 0.081 0.098 0.038 0.022 0.037 0.107 0.098 0.072 0.053 0.030 0.062 0.158 0.669 0.531 0.243 0.140 0.526 0.950
dissolved HMs (ppm) during (2006) in Al‐Hawizeh Marsh.
109
Annexes
Stations UmWd
Bed
S. Sod
LesEj
Maj.
Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max
As 0.0995 0.0668 0.0666 0.0384 0.0556 0.1761 0.0288 0.0336 0.0137 7.92E‐03 0.0134 0.0395 0.0332 0.04 0.0211 0.0122 9.52E‐03 0.05 0.035 0.0363 0.0176 0.0102 0.0168 0.052 0.0387 0.0421 0.0312 0.018 5.95E‐03 0.0681
Cd 0.038 0.0369 0.0195 0.0113 0.019 0.058 0.0408 0.0374 0.0252 0.0146 0.0174 0.0675 0.2913 0.1896 0.3419 0.1974 0.0117 0.6725 0.0496 0.0391 0.0311 0.018 0.025 0.0846 0.0326 0.0382 0.0139 8.00E‐03 0.0168 0.0428
Co 0.0114 0.0105 5.82E‐03 3.36E‐03 6.01E‐03 0.0176 0.0138 0.0121 5.20E‐03 3.00E‐03 9.61E‐03 0.0196 0.0124 0.012 5.55E‐03 3.20E‐03 7.05E‐03 0.0181 0.0149 0.0142 4.44E‐03 2.57E‐03 0.0109 0.0197 0.0143 0.0133 4.92E‐03 2.84E‐03 9.90E‐03 0.0196
Cr 0.1333 0.1338 0.022 0.0127 0.1111 0.1551 0.1386 0.1475 0.0375 0.0216 0.0975 0.1709 0.2368 0.2135 0.0664 0.0383 0.1853 0.3118 0.1853 0.174 0.0723 0.0418 0.1193 0.2626 0.3055 0.2438 0.1253 0.0723 0.223 0.4496
Mo 0.0951 0.1179 0.052 0.03 0.0356 0.1318 0.0391 0.0392 0.0254 0.0147 0.0136 0.0644 0.0494 0.0661 0.0328 0.0189 0.0116 0.0705 0.1392 0.121 0.1035 0.0597 0.0461 0.2506 0.0575 0.0486 0.019 0.011 0.0445 0.0793
Ni 0.5425 0.4292 0.2072 0.1196 0.4167 0.7817 0.3652 0.3499 0.0666 0.0384 0.3077 0.4381 0.3 0.3358 0.0815 0.047 0.2068 0.3575 0.4506 0.4219 0.1196 0.0691 0.348 0.582 0.5318 0.4998 0.0863 0.0498 0.4661 0.6295
Pb 0.044 0.0419 6.31E‐03 3.64E‐03 0.039 0.0511 0.044 0.0424 5.88E‐03 3.40E‐03 0.0391 0.0506 0.0603 0.053 0.0159 9.17E‐03 0.0493 0.0785 0.1404 0.1185 0.1106 0.0639 0.0423 0.2603 0.05 0.048 8.01E‐03 4.62E‐03 0.0432 0.0588
Zn 9.0067 6.6366 7.6928 4.4414 2.7778 17.6056 4.971 4.8236 1.427 0.8239 3.6235 6.466 2.7336 2.5 1.1005 0.6354 1.7687 3.9322 6.1371 5.5859 3.719 2.1472 2.7245 10.101 7.421 6.5515 1.6269 0.9393 6.4137 9.2979
Cu 0.5201 0.4079 0.3092 0.1785 0.2827 0.8697 0.2761 0.2932 0.1236 0.0714 0.1449 0.3904 0.5316 0.4592 0.4714 0.2721 0.1007 1.035 0.5888 0.5564 0.4423 0.2554 0.1635 1.0464 0.3138 0.3665 0.1418 0.0818 0.1533 0.4217
Fe 3.6831 2.9392 2.0355 1.1752 2.1242 5.9859 2.0965 2.2099 0.9301 0.537 1.1148 2.9647 2.5953 2.587 0.1507 0.087 2.449 2.75 1.8645 2.0451 0.3662 0.2114 1.443 2.1053 2.291 2.3445 1.2234 0.7063 1.0417 3.4867
Mn 0.3559 0.4452 0.1628 0.094 0.1679 0.4544 0.8745 0.8765 0.0584 0.0337 0.8152 0.9319 0.2887 0.3368 0.1677 0.0968 0.1023 0.4272 0.2309 0.2674 0.0743 0.0429 0.1454 0.28 0.2831 0.2257 0.1011 0.0584 0.2238 0.3998
Table (3) Continued.
110
Annexes
Table (4): The mean, median, standard deviation (Std.Dev), standard error (Std. Err), minimum (Min), and maximum (Max) Stations Ad1
Ad2
UmNj1
UmNj2
N. Sod
Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max
As Cd 414.3655 53.4408 758.8235 52.0322 487.1371 38.9712 344.458 22.5001 69.9076 15.193 758.8235 93.0973 142.1365 4.6948 170.3842 4.6948 116.7163 0.8763 67.3862 0.5059 13.8889 3.8186 242.1365 5.5711 250.107 8.3126 213.8889 5.7705 222.6408 4.5769 128.5417 2.6425 47.7958 5.5711 488.6364 13.5964 4.1013 8.9507 3.1566 7.0554 4.4571 3.47E+00 2.5733 2.00E+00 0.1923 6.8413 8.9551 12.9553 22.1216 10.9374 17.4262 11.1659 21.5166 1.0471 12.4226 0.6046 3.3403 9.7949 45.5981 11.8514
Co 28.7744 31.7647 24.0397 13.8793 3.3794 51.1791 2.6431 2.6431 0.8931 0.5156 1.75 3.5362 11.1918 3.5227 14.8449 8.5707 1.75 28.3026 2.1848 1.5215 1.4145 0.8167 1.2239 3.8091 3.0866 2.9112 0.8039 0.4641 2.385 3.9638
Cr 93.3704 78.0153 29.1705 16.8416 75.0848 127.011 37.1712 37.0047 13.2509 7.6504 24.0044 50.5046 89.3983 94.257 36.5409 21.0969 50.6711 123.2667 35.8625 34.9135 20.501 11.8362 15.8524 56.8214 24.6213 27.0407 11.0872 6.4012 12.5242 34.2989
Mo 22.0878 17.7249 19.5263 11.2735 5.112 43.4264 22.3206 23.2357 16.4158 9.4777 5.4664 38.2598 79.6596 85.0673 64.1665 37.0465 12.9604 140.9511 10.2152 8.6181 3.8547 2.2255 7.4158 14.6118 460.3096 660.6243 376.9956 217.6585 25.4416 694.8628
Ni Pb 20.4575 68.0461 21.8292 63.1487 6.2857 17.5115 3.6291 10.1103 13.5992 53.5047 25.9442 87.4849 26.1403 81.6902 16.7692 105.1859 24.7443 49.4606 14.2861 28.5561 7.4503 24.8611 54.2015 115.0235 30.484 55.3893 31.6116 67.6596 12.616 39.1573 7.2838 22.6075 17.342 11.5663 42.4983 86.942 27.2084 67.2096 23.8799 36.6919 14.8679 54.2719 8.584 31.3339 14.287 35.0665 43.4585 129.8703 134.8934 26.1315 148.0285 27.7036 38.012 7.2045 21.9462 4.1595 92.0559 18.2708 164.5959 32.42
Zn 34062.0659 1568.6274 56638.6979 32700.3675 1155.205 99462.3653 21398.1912 30389.1453 17582.0977 10151.0289 1138.761 32666.6673 19697.6404 7497.376 27003.6524 15590.566 946.9697 50648.5755 30965.8623 31186.869 30707.2832 17728.8582 148.6722 61562.0456 21367.0434 25545.0834 19146.1847 11054.0549 476.8433 38079.2035
Cu 76.6032 52.4915 72.927 42.1044 18.7855 158.5326 74.8467 67.2354 30.2545 17.4674 49.1246 108.18 90.9233 90.96 34.1691 19.7275 56.7358 125.0739 123.891 122.348 18.6634 10.7753 106.047 143.278 49.6851 48.8024 11.5677 6.6786 38.584 61.6688
Fe 12569.84 14694.88 3689.539 2130.156 8309.532 14705.11 30989 30989 22309.45 12880.37 8679.545 53298.45 34840.45 22106.26 36124.85 20856.69 6807.182 75607.91 6997.946 4719.29 5959.242 3440.57 2514.253 13760.29 3258.657 3677.146 1917.762 1107.22 1166.207 4932.616
Mn 18779.02 20061.19 12695.04 7329.482 5491.551 30784.31 20202.34 12060.24 23670.28 13666.04 1677.778 46869.01 17297.46 7954.545 20133.19 11623.9 3533.138 40404.68 7203.894 1622.736 9969.293 5755.774 1275.253 18713.69 7118.253 7877.304 3478.406 2008.258 3323.002 10154.45
of exchangeable HMs in the particulate (ppm) during (2006) in Al‐Hawizeh Marsh.
111
Annexes
Stations UmWd
Bed
S. Sod
LesEj
Maj.
Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max
As 21.3322 3.1992 33.2301 19.1854 1.1133 59.6841 24.7131 26.8237 19.5621 11.2942 4.1812 43.1343 44.4808 5.6264 68.5778 39.5934 4.153 123.6631 31.516 32.0358 27.1928 15.6997 4.0671 58.4452 122.9099 123.6066 77.7566 44.8928 44.8073 200.3158
Cd 3.6908 1.197 4.6976 2.7121 0.7661 9.1094 13.8045 4.7179 16.7196 9.6531 3.5958 33.0998 3.576 2.4919 3.5712 2.0618 0.6726 7.5636 4.3945 4.2365 1.5137 8.74E‐01 2.9661 5.9811 4.9928 2.8075 4.76E+00 2.75E+00 1.7171 10.4538
Co 3.686 4.2656 1.2035 0.6948 2.3024 4.49 3.4156 3.8099 1.4309 0.8262 1.8288 4.608 2.3318 2.373 1.4677 0.8474 0.844 3.7785 2.1878 2.04 0.9827 0.5674 1.2873 3.2361 7.9564 7.4321 1.9985 1.1538 6.2723 10.1648
Cr 8.1511 8.1105 2.9058 1.6776 5.2659 11.077 30.4889 33.8644 12.1461 7.0126 17.012 40.5902 25.5991 31.443 21.7641 12.5655 1.5097 43.8448 11.8645 10.5628 2.3616 1.3635 10.4401 14.5905 16.315 15.0235 4.2698 2.4652 12.84 21.0815
Mo 92.5999 110.9153 77.4657 44.7248 7.6178 159.2665 40.6943 33.487 33.0281 19.0688 11.865 76.731 34.6366 4.4255 55.2045 31.8724 1.1315 98.353 20.0119 21.2979 17.7955 10.2742 1.6083 37.1295 113.4791 105.7127 28.6321 16.5307 89.5314 145.1932
Ni 16.0453 16.3675 6.406 3.6985 9.4843 22.2842 191.346 184.5129 124.9371 72.1325 69.9658 319.5595 106.1136 39.447 127.2922 73.4922 26.0011 252.8928 9.9952 10.3167 5.9767 3.4506 3.8643 15.8047 44.8485 44.2812 10.7252 6.1922 34.4181 55.846
Pb 10.2244 13.5544 5.8763 3.3927 3.4394 13.6794 156.8426 108.1624 117.5445 67.8643 71.4587 290.9069 38.9353 32.3209 50.4168 29.1082 ‐7.8478 92.3329 17.858 15.8257 11.926 6.8855 7.0787 30.6695 122.0535 91.5278 58.9781 34.051 84.595 190.0379
Zn 5859.5492 3985.7705 5505.4249 3178.5586 1535.6004 12057.2768 10084.7218 8117.0437 5750.9301 3320.301 5575.895 16561.2268 7518.1555 5345.0862 8400.4261 4849.9883 417.7808 16791.5996 6105.5502 3773.5195 6792.9482 3921.9105 785.7833 13757.3476 2511.8514 1423.7325 2372.5526 1369.7939 878.5264 5233.2955
Cu 29.312 32.886 16.3779 9.4558 11.4422 43.6078 10.4891 14.709 8.4861 4.8994 0.7203 16.038 45.3285 58.1472 25.1434 14.5166 16.3592 61.4791 62.3876 38.1435 68.3032 39.4349 9.5134 139.5058 26.4906 30.6279 7.178 4.1442 18.2022 30.6419
Fe 1310.976 1961.82 1127.317 650.8566 9.2628 1961.845 10723.81 13928.74 6599.394 3810.162 3133.997 15108.69 3132.583 1864.469 2720.581 1570.728 1277.569 6255.711 1723.86 1741.901 96.7754 55.8733 1619.334 1810.345 3167.756 2832.655 843.918 487.2363 2542.856 4127.757
Mn 646.7916 580.1157 370.2517 213.7649 314.4083 1045.851 4916.969 5944.115 4255.62 2456.983 241.783 8565.01 380.592 225.6016 302.0076 174.3642 187.5469 728.6275 1532.754 1446.144 1131.17 653.0815 447.379 2704.74 1308.979 1199.291 587.4687 339.1752 784.0848 1943.56
Table (4) Continued.
112
Annexes
Table (5): The mean, median, standard deviation (Std.Dev), standard error (Std. Err), minimum (Min), and maximum Stations Ad1
Ad2
UmNj1
UmNj2
N. Sod
Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max
As 10292 15244 8634 4985 323 15310 8077 190 13683 7900 165 23877 13834 229 23614 13633 172 41101 74 68 61 35 17 139 1685 204 2670 1542 83 4767
Cd 36 33 13 7 26 51 42 35 21 12 25 65 109 109 60 35 49 169 15 13 9 5 8 25 29 23 17 10 15 48
Co 30 37 13 8 15 38 32 35 15 8 17 46 88 106 77 44 3 154 10 10 3 2 7 13 17 18 2 1 15 18
Cr 652 267 753 435 170 1520 813 896 561 324 215 1327 672 541 254 147 510 965 332 297 315 182 35 663 611 589 544 314 78 1165
Mo 213 272 103 59 95 273 1484 92 2454 1417 43 4317 4709 697 7512 4337 55 13376 40 48 16 9 21 51 69 75 18 11 48 83
Ni 163 160 15 8 149 178 188 188 31 18 156 219 250 271 145 84 96 383 55 73 32 18 18 74 124 122 79 46 46 204
Pb 2406 3305 1567 905 597 3317 2150 680 2598 1500 621 5150 4427 5235 3802 2195 285 7760 478 215 554 320 104 1115 501 397 348 201 217 889
Zn 1079819 991544 1125945 650065 610 2247303 102765 40287 142132 82060 2574 265435 749815 1090599 630068 363770 22749 1136097 58058 64726 54547 31492 483 108963 120161 121258 72558 41892 47060 192164
Cu 230 189 75 43 184 317 200 200 126 73 75 326 306 284 91 53 227 406 80 78 46 26 35 126 103 103 47 27 56 150
Fe 40939 38872 7634 4407 34551 49393 53930 55592 24208 13976 28934 77263 78399 107942 54485 31457 15523 111732 14539 15367 2140 1235 12109 16142 22678 27179 9052 5226 12258 28597
Mn 3175 3698 944 545 2085 3742 9979 13329 6942 4008 1997 14610 3599 4910 2584 1492 622 5266 789 741 153 88 666 960 2530 1348 2709 1564 612 5629
(Max) of residual HMs in the particulate (ppm) during (2006) in Al‐Hawizeh Marsh.
113
Annexes
Stations UmWd
Bed
S. Sod
LesEj
Maj.
Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max
As 1119 57 1886 1089 4 3297 353 168 407 235 70 819 20891 20942 8620 4977 12246 29485 3832 4832 3373 1948 71 6592 9227 9227 9221 5324 7 18448
Cd 32 2 53 30 1 93 30 30 18 11 12 48 98 101 12 7 86 109 16 16 1 0 16 17 20 20 17 10 3 38
Co 10 4 13 7 2 25 12 12 3 2 8 15 46 53 33 19 10 74 16 20 9 5 6 23 48 48 45 26 3 94
Cr 90 18 131 76 12 241 312 303 33 19 284 348 237 246 139 80 94 372 235 145 161 93 138 421 179 179 129 75 50 309
Mo 21 10 27 16 2 53 1372 68 2292 1323 29 4018 129 127 63 36 67 193 72 93 47 27 17 105 223 223 219 127 4 443
Ni 55 18 69 40 12 135 109 118 38 22 67 143 160 168 49 28 107 204 71 71 6 4 65 78 170 170 149 86 21 318
Pb 227 20 370 214 5 654 247 125 217 125 119 498 2124 2385 1405 811 607 3380 1083 1083 841 485 242 1923 2322 2322 2295 1325 27 4617
Zn 66972 5037 110020 63520 1880 194000 251628 208353 214988 124123 61569 484961 131274 19607 196523 113463 16026 358191 117981 117981 56348 32533 61633 174329 48312 48312 40246 23236 8066 88558
Cu 49 28 60 34 3 116 93 107 36 21 53 120 138 138 0 0 137 138 81 81 28 16 53 109 119 119 99 57 20 219
Fe 12540 3135 16770 9682 2584 31903 22093 25261 5631 3251 15591 25426 35200 41385 21025 12139 11776 52438 17409 17409 4592 2651 12817 22001 39156 39156 34356 19836 4800 73512
Mn 1085 387 1507 870 54 2815 1939 2606 1398 807 333 2879 1088 1218 794 458 238 1810 1591 1591 1075 621 516 2666 1938 1938 1796 1037 143 3734
Table (5) Continued.
114
Annexes
Table (6): The mean, median, standard deviation (Std.Dev), standard error (Std. Err), minimum (Min), and maximum Stations Ad1
Ad2
UmNj1
UmNj2
N. Sod
Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max
As Cd ‐ 0.3144 ‐ 0.3144 ‐ 0.0265 ‐ 0.0153 ‐ 0.2879 ‐ 0.3409 0.9235 0.1831 1.2568 0.1831 0.5956 3.05E‐03 0.3439 1.76E‐03 0.2359 0.18 1.2778 0.1861 1.3442 0.3022 0.8273 0.3022 0.9407 0.1702 0.5431 0.0982 0.7753 0.132 2.43 0.4723 0.5279 0.1037 0.2769 0.1301 0.6792 0.077 0.3921 0.0445 0.01 0.017 1.2969 0.1641 2.2556 0.2009 2.2485 0.2008 0.2575 0.046 0.1487 0.0266 2.0017 0.155 2.5167 0.247
Co 0.6933 0.6933 0.0584 0.0337 0.6348 0.7517 2.9317 3.265 0.6251 0.3609 2.2106 3.3194 4.5144 4.5144 1.4644 0.8455 3.05 5.9788 2.0188 1.749 1.3645 0.7878 0.8094 3.498 6.1453 4.3833 3.2891 1.899 4.1124 9.94
Cr 1.1604 1.3645 0.4699 0.2713 0.623 1.4937 5.1075 6.1075 1.8215 1.0516 3.0051 6.21 8.5931 8.5931 2.5431 1.4683 6.05 11.1362 0.8147 0.132 1.2771 0.7373 0.0241 2.2881 6.5758 7.2433 2.098 1.2113 4.2252 8.2588
Mo 5579.8822 866.9935 8922.6581 5151.4991 1.8865 15870.7665 7222.1269 5832.8215 8007.4424 4623.099 0.2459 15833.3133 0.2878 0.2878 0.2152 0.1243 0.0725 0.503 12276.6534 12159.9806 5165.9784 2982.579 7169.9997 17499.98 6035.6666 946.3899 9645.3261 5568.7316 0.8667 17159.7433
Ni 3.5624 3.5674 0.3359 0.1939 3.224 3.8957 19.1585 20.4918 2.6108 1.5073 16.1503 20.8333 22.8417 22.8417 2.3683 1.3673 20.4735 25.21 4.3948 5.8378 3.4078 1.9675 0.503 6.8438 54.4645 36.3905 38.4942 22.2246 28.3333 98.6696
Pb 1.2208 1.2208 0.1046 0.0604 1.1162 1.3254 3.6822 3.6822 0.0617 0.0356 3.6205 3.7439 7.6239 7.6239 3.9539 2.2828 3.67 11.5778 11.8767 8.44 11.9903 6.9226 1.98 25.21 9.7586 4.5362 10.5425 6.0867 2.8467 21.8929
Se ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ 3.67 ‐ ‐ ‐ 3.67 3.67 3.4599 ‐ ‐ ‐ 3.4599 3.4599
Zn 11.6033 11.3039 0.5783 0.3339 11.236 12.2699 11.8634 8.3333 6.2329 3.5986 8.1967 19.0601 17.9856 17.9856 6.1744 3.5648 11.8112 24.16 10.6233 8.115 10.2308 5.9067 1.88 21.875 13.6013 16.2722 9.6812 5.5895 2.8649 21.6667
Cu 4.2607 4.8174 1.3662 0.7888 2.7041 5.2607 7.0929 7.7596 1.2683 0.7323 5.6302 7.8889 10.8094 10.8094 3.4094 1.9684 7.4 14.2187 3.05 3.05 1.9656 1.1349 1.0844 5.0156 5.857 4.9667 3.5316 2.039 2.8557 9.7485
Fe 208.7321 224.7191 46.757 26.9952 156.0784 245.3988 837.9782 971.3115 245.0935 141.5048 555.123 987.5 3219.424 3219.424 2283.424 1318.336 936 5502.849 355.275 523.8375 302.4982 174.6474 6.05 535.9375 1290.409 1582.84 1150.688 664.3498 21.7212 2266.667
Mn 212.0454 224.6991 41.1463 23.7558 166.0584 245.3788 478.6685 452.7578 51.4409 29.6994 445.3352 537.9126 435.2318 435.2318 211.2318 121.9547 224 646.4636 50.6783 22.5675 67.0122 38.6895 2.3 127.1675 242.3962 246.6467 6.0111 4.2505 238.1457 246.6467
(Max) of exchangeable HMs in the sediments (ppm) during (2006) in Al‐Hawizeh Marsh.
115
Annexes
Stations UmWd
Bed
S. Sod
LesEj
Maj.
Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max
As 0.9412 0.9412 0.9096 0.5251 0.0316 1.8507 2.1083 2.1167 0.0431 0.0249 2.0617 2.1466 1.8385 2.6399 1.5108 0.8722 0.0959 2.7798 1.7833 1.9969 0.4774 0.2756 1.2365 2.1167 1.5758 1.5758 0.1576 0.091 1.4182 1.7333
Cd 0.2676 0.2676 0.1585 0.0915 0.1092 0.4261 0.153 0.1575 0.0115 6.63E‐03 0.14 0.1617 0.1684 0.1712 5.03E‐03 2.90E‐03 0.1626 0.1714 0.1383 0.1525 0.0328 0.0189 0.1008 0.1617 0.3758 0.3758 0.0376 0.0217 0.3382 0.4133
Co 12.1035 10.003 7.1679 4.1384 6.2206 20.087 5.4804 3.6667 3.2244 1.8616 3.5714 9.2032 3.8021 4.5979 1.5941 0.9203 1.9668 4.8417 8.4377 3.6667 8.4441 4.8752 3.4591 18.1874 3.8333 3.8333 0.3833 0.2213 3.45 4.2167
Cr 4.5038 1.3635 6.4173 3.705 0.2615 11.8865 8.0811 8.0705 0.1073 0.062 7.9795 8.1933 6.0683 7.5999 3.0104 1.7381 2.6 8.0049 9.1933 8.1933 2.1483 1.2403 7.7273 11.6594 11.9448 11.9448 1.1985 0.6919 10.7464 13.1433
Mo 2361.4565 136.0699 3972.7509 2293.6688 0.1765 6948.1232 6564.5425 49.507 11326.1611 6539.1621 1.2833 19642.8371 11.5466 0.9573 18.3829 10.6134 0.9091 32.7733 0.95 1.2107 0.5157 0.2978 0.356 1.2833 18030.283 18030.283 18029.3997 10409.2788 0.8833 36059.6827
Ni 39.6316 30.3734 17.9192 10.3457 28.2353 60.286 20.1333 20.1299 0.5317 0.307 19.6032 20.6667 25.1969 29.7203 9.233 5.3307 14.5745 31.296 19 19.4969 1.9628 1.1332 16.8365 20.6667 29.3939 29.3939 2.9394 1.6971 26.4545 32.3333
Pb 17.5862 18.5601 10.5208 6.0742 6.6124 27.5862 2.054 2.4313 0.7108 0.4104 1.2341 2.4967 3.1982 3.1464 0.2412 0.1393 2.987 3.4611 2.1633 2.3542 0.4595 0.2653 1.6391 2.4967 3.283 3.283 0.3303 0.1907 2.9527 3.6133
Se 6.4599 ‐ ‐ ‐ 6.4599 6.4599 ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐
Zn 17.6471 17.6471 17.1787 9.9181 0.4684 34.8257 10.3926 10 0.9143 0.5279 9.7403 11.4377 21.5049 22.7273 3.2177 1.8577 17.8551 23.9323 10 10 3.3929 1.9589 6.6071 13.3929 13.6364 13.6364 1.3636 0.7873 12.2727 15
Cu 18.0882 18.0882 12.0106 6.9344 6.0776 30.0989 6.9845 6.4667 1.0458 0.6038 6.2987 8.1881 5.3499 5.354 0.1382 0.0798 5.2098 5.486 5.6573 6.1006 1.1001 0.6352 4.4047 6.4667 8.5303 8.5303 0.853 0.4925 7.6773 9.3833
Fe 2147.059 2282.506 2071.048 1195.72 11.6123 4147.059 2047.174 2857.143 1469.385 848.3498 351.0443 2933.333 1770.123 2377.622 1163.1 671.5163 429.0635 2503.682 2264.525 2767.296 1018.009 587.7475 1092.945 2933.333 3212.121 3212.121 321.2121 185.4519 2890.909 3533.334
Mn 444.0976 ‐‐ Indefinite 0 444.0976 444.0976 219.5753 254.8501 67.07 38.7229 142.229 261.6467 351.785 272.4395 149.4683 86.2956 258.7213 524.1944 216.9037 246.8354 65.0928 37.5814 142.229 261.6467 224.2224 224.2224 22.4242 12.9466 201.7982 246.6467
Table (6) Continued.
116
Annexes
Ad1
Ad2
UmNj1
UmNj2
N. Sod
Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max
As 300 300 8 5 292 309 284 284 10 6 274 295 295 295 34 20 261 329 312 312 4 2 308 316 386 386 287 166 99 673
Cd 47 47 17 10 31 64 97 97 23 14 74 121 84 84 54 31 30 138 57 57 31 18 26 88 111 91 46 27 79 164
Co 14 14 12 7 2 26 25 25 16 9 9 41 16 14 10 6 6 26 16 16 4 2 12 20 40 33 17 10 27 58
Cr 1413 1413 13 8 1400 1427 1991 1991 585 338 1405 2576 1650 1650 317 183 1333 1967 1492 1492 210 121 1282 1701 2202 2202 1867 1078 335 4070
Mo 88 88 9 5 79 98 138 138 84 48 54 222 94 94 29 16 65 122 108 108 17 10 91 125 142 142 24 14 117 166
Ni 166 166 36 21 129 202 235 235 118 68 116 353 164 164 4 2 160 168 166 166 1 1 165 167 419 386 153 88 285 587
Pb 555 555 290 167 265 846 932 932 706 408 226 1638 489 489 8 5 481 497 485 485 91 53 393 576 1326 752 1347 777 361 2864
Zn 2089966 2089966 1223330 706290 866636 3313296 521260 398337 412316 238051 184384 981058 1942989 1942989 1491260 860979 451729 3434249 966905 1081912 671202 387519 245630 1573172 363519 363519 194949 112554 168569 558468
Cu 294 294 7 4 287 302 356 337 125 72 242 490 389 389 205 119 184 594 286 286 57 33 229 344 916 1098 564 325 284 1367
Fe 32132 32132 29983 17311 2149 62115 83394 83394 70065 40452 13329 153460 26552 26552 16075 9281 10477 42627 34589 34589 2082 1202 32507 36671 75880 51378 55587 32093 36753 139509
Mn 1939 1939 1292 746 647 3232 1229 443 1533 885 248 2996 1816 1127 1247 720 1064 3256 2160 2160 436 252 1724 2596 10639 10639 7682 4435 2957 18321
Table (7): The mean, median, standard deviation (Std.Dev), standard error (Std. Err), minimum (Min), and maximum (Max) of residual HMs in the sediments (ppm) during (2006) in Al‐Hawizeh Marsh.
117
Annexes
Stations
UmWd
Bed
S. Sod
LesEj
Maj.
Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max
As 438 541 322 186 77 695 85 85 58 34 27 143 384 190 404 233 113 848 530 530 436 252 93 966 211 64 310 179 2 568
Cd 88 81 91 53 0 182 13 8 15 8 1 29 86 56 61 35 47 156 128 128 126 73 1 254 90 85 93 54 0 185
Co 22 22 22 13 0 44 10 10 7 4 3 17 12 13 4 2 8 15 46 46 23 13 23 69 7 9 5 3 1 10
Cr 1750 847 2163 1249 186 4219 98 98 1 0 98 99 276 163 262 151 90 576 3136 3136 3025 1747 111 6161 108 78 111 64 15 231
Mo 146 114 60 35 108 215 246 246 27 16 218 273 306 257 231 133 104 558 217 245 78 45 129 277 348 249 221 128 193 601
Ni 288 193 257 148 93 579 92 92 9 5 83 101 99 91 63 37 39 165 486 486 387 223 99 873 160 119 106 61 81 281
Pb 519 54 838 484 16 1487 8 7 7 4 3 16 341 74 521 301 8 941 1808 1808 1795 1036 13 3602 448 19 758 437 2 1323
Zn 251259 26740 412166 237964 99 726938 92 92 34 20 58 126 185399 735 320430 185000 63 555399 460994 460994 460909 266106 85 921903 179333 454 310195 179091 31 537515
Cu 199 47 280 162 28 522 25 26 3 2 21 28 84 22 113 65 15 214 825 825 774 447 52 1599 52 62 31 18 18 77
Fe 35092 3412 55646 32127 2519 99344 14224 14224 5857 3382 8367 20081 11592 10194 6089 3516 6323 18258 95444 95444 70408 40650 25035 165852 9105 9743 7340 4238 1467 16105
Mn 7142 376 11916 6880 149 20902 134 153 46 27 81 167 303 300 66 38 238 369 3841 3841 3499 2020 342 7340 748 428 826 477 129 1686
Table (7) Continued.
118
Annexes
Table (8): The correlations among HM concentrations in dissolved phase and physio‐chemicals parameters in Al‐Hawizeh Marsh As Cd Co Ni Mn Cu Pb Zn Cr Mo Fe
‐0.5441 ‐0.0812 0.5183 0.0692 ‐0.2063 ‐0.155 0.3937 ‐0.0538 0.7314 0.0268 ‐0.6012 WT
‐0.2884 0.2075 0.7803 0.2693 ‐0.1661 0.3088 0.7128 0.1053 0.5383 ‐0.2818 ‐0.3081 EC
‐0.2324 0.1212 0.8025 0.2844 ‐0.1389 0.4046 0.8498 0.1367 0.3192 ‐0.2379 ‐0.2997 Sal
0.5056 ‐0.5163 0.1365 0.6935 ‐0.6016 0.2971 0.294 0.6001 0.0891 0.338 0.2913 pH
0.7271 ‐0.233 0.3853 0.6106 0.2865 0.48 0.0218 0.8234 ‐0.5626 ‐0.4731 0.6683 Tur.
0.22 ‐0.2179 0.5729 0.6905 ‐0.1056 ‐0.0433 ‐0.0631 0.5669 0.5169 ‐0.2987 0.217 TSS
‐0.1941 0.0965 0.7785 0.282 ‐0.0668 0.4067 0.8541 0.1236 0.2091 ‐0.2735 ‐0.2561 TDS
‐0.1281 0.4199 0.6617 0.1447 0.0291 0.3912 0.5707 ‐0.0412 0.0441 ‐0.0083 ‐0.1096 TH
‐0.1824 0.6835 0.5706 ‐0.0055 ‐0.0015 0.4912 0.6061 ‐0.1856 0.082 ‐0.1691 ‐0.1078 Ca+2
‐0.2966 0.2262 0.3745 0.1389 ‐0.4489 0.0505 0.4145 ‐0.1548 0.6803 0.3548 ‐0.2931 Mg+2
‐0.182 0.3817 ‐0.1673 ‐0.4997 0.3176 ‐0.0358 ‐0.1512 ‐0.334 ‐0.3362 ‐0.3558 ‐0.043 HCO3‐
‐0.2484 ‐0.0368 0.7059 0.345 ‐0.2527 0.2459 0.7159 0.1758 0.5422 ‐0.0663 ‐0.3397 Cl‐
0.2073 0.2442 0.9001 0.6002 ‐0.0612 0.596 0.6554 0.4709 0.1971 ‐0.5204 0.2175 SO4‐2
0.4003 ‐0.6629 0.2257 0.6319 ‐0.498 0.153 0.2644 0.6027 ‐0.0398 0.1851 0.1702 DO
Table (9): The HM analysis of variance (ANOVA, F values at r=0.05) of Al‐Hawizeh Marsh stations and seasons (2006). Phase of HMs Sediments Dissolved Particulate Plants Snails
As
Cd
Co
Cr
Mo
Ni
Pb
Zn
Cu
Fe
Mn
F (stations) F (season) F (stations) F (season) F (stations) F (season) F (stations) F (season) F (stations) F (season)
1.46354 0.09889 3.67558 5.40827 1.90368 4.57006 0.84026 ‐7.42867 3.20879 16.3751
0.81274 ‐0.36649 1.68781 1.58981 2.69285 ‐1.9075 1.14187 1.35421 5.12007 19.4736
2.96751 0.94410 1.83595 7.25898 4.27238 7.14641 2.66205 ‐4.35552 5.49104 9.47229
1.71729 0.08903 1.29235 ‐3.07499 4.78666 0.57202 4.85766 ‐7.88474 1.48662 ‐8.19483
1.31004 2.68252 0.85216 1.23369 1.12303 2.83764 0.66981 1.84159 3.99077 10.0110
0.76512 ‐0.24262 2.53928 ‐2.77135 4.78666 0.57202 4.40703 ‐5.8809 4.29047 ‐2.18966
1.43470 2.11169 2.11991 0.53879 2.81179 7.37317 3.02467 ‐4.3741 3.80365 24.9362
2.56646 ‐0.21722 1.64861 ‐0.54861 2.01500 1.16158 0.74195 ‐6.70634 1.93998 ‐5.2965
2.31916 ‐0.42896 1.75699 8.47092 2.53951 ‐4.03419 0.76726 ‐7.71365 3.10027 1.63324
1.38693 ‐0.32521 1.30140 0.76533 4.76444 3.03446 2.591083 2.49415 5.93674 ‐6.7706
1.38102 0.2208 5.30658 ‐1.7572 2.15409 2.57156 1.16494 ‐7.3563 4.96187 ‐5.8319
during (2006) (r= 0.149, p >0.05).
119
Annexes
Table (10): The correlations among particulate HM concentrations in exchangeable phase and physio‐chemicals parameters in Al‐ As Cd Co Ni Cu Mn Pb Zn Cr Mo Fe
0.0906 0.0164 0.0835 0.0431 0.0334 ‐0.1382 0.3955 ‐0.1139 ‐0.0679 0.1183 ‐0.2092 WT
‐0.0689 ‐0.1679 ‐0.0975 ‐0.028 ‐0.1932 ‐0.3765 0.1881 ‐0.4716 ‐0.3084 ‐0.1456 ‐0.3399 EC
‐0.1516 ‐0.1816 ‐0.1648 ‐0.029 ‐0.1775 ‐0.3919 0.1127 ‐0.4765 ‐0.3351 ‐0.2072 ‐0.3389 Sal
‐0.0993 ‐0.2751 ‐0.0413 ‐0.6558 0.0641 ‐0.3396 ‐0.2648 ‐0.3257 ‐0.2577 ‐0.0825 ‐0.2587 pH
‐0.4878 ‐0.228 ‐0.3078 0.1257 ‐0.7154 ‐0.5488 ‐0.2471 ‐0.4965 ‐0.658 0.3548 ‐0.5969 Tur.
‐0.0598 ‐0.24 ‐0.0168 ‐0.0034 ‐0.5773 ‐0.4573 0.5175 ‐0.6125 ‐0.374 ‐0.0025 ‐0.3168 TSS
‐0.1385 ‐0.1824 ‐0.1735 ‐0.0364 ‐0.1944 ‐0.339 0.1359 ‐0.4907 ‐0.3047 ‐0.3327 ‐0.2386 TDS
‐0.5538 ‐0.3999 ‐0.5255 0.3319 ‐0.2384 ‐0.5937 0.2673 ‐0.4948 ‐0.5004 ‐0.3752 ‐0.3983 TH
‐0.4108 ‐0.3592 ‐0.4443 0.298 ‐0.1874 ‐0.4812 0.0816 ‐0.4673 ‐0.3629 ‐0.3545 ‐0.2794 Ca +2
0.0086 ‐0.1031 ‐0.0182 ‐0.2833 0.2773 ‐0.2286 0.263 ‐0.1399 ‐0.1028 ‐0.5287 ‐0.1921 Mg+2
0.3302 0.5711 0.3564 0.3275 ‐0.0002 0.4113 ‐0.155 0.4214 0.4324 0.0145 0.1825 HCO3‐
‐0.1155 ‐0.2291 ‐0.1343 ‐0.1724 ‐0.0729 ‐0.3789 0.1738 ‐0.4283 ‐0.3477 ‐0.1138 ‐0.3453 Cl‐
‐0.2286 ‐0.2479 ‐0.193 ‐0.0669 ‐0.5317 ‐0.6012 0.0686 ‐0.7395 ‐0.5462 ‐0.321 ‐0.5166 SO4‐2
0.1001 0.0449 0.208 ‐0.4325 ‐0.0578 ‐0.1773 ‐0.1015 ‐0.2017 ‐0.0182 ‐0.0426 ‐0.1699 DO
Table (11): The correlations among particulate HM concentrations in residual phase and physio‐chemicals parameters in Al‐ Hawizeh Marsh during (2006) (r= 0.149, p >0.05). As Cd Co Ni Cu Mn Pb Zn Cr Mo Fe
0.156 ‐0.3447 0.2607 0.253 ‐0.0943 0.0518 0.2774 ‐0.0895 ‐0.0131 ‐0.1763 0.1301 WT
0.2848 ‐0.2154 0.167 0.0969 ‐0.1333 ‐0.1073 0.1957 ‐0.2246 ‐0.2682 ‐0.2772 ‐0.0059 Ec
0.1167 ‐0.2775 0.017 ‐0.0661 ‐0.1709 ‐0.1897 0.0604 ‐0.2191 ‐0.2958 ‐0.2415 ‐0.1266 Sal
‐0.3344 ‐0.3681 0.0198 ‐0.3272 ‐0.3869 ‐0.2748 ‐0.0172 ‐0.1819 ‐0.4939 ‐0.0476 ‐0.1851 pH
‐0.6116 ‐0.4825 ‐0.6664 ‐0.6409 ‐0.2929 ‐0.7452 ‐0.75 ‐0.4357 ‐0.5121 ‐0.4972 ‐0.7039 Tur.
0.0048 ‐0.3341 0.2178 0.1143 ‐0.2328 ‐0.2281 0.0992 ‐0.3143 ‐0.5158 ‐0.1498 0.0136 TSS
0.0961 ‐0.2377 0 ‐0.0736 ‐0.0991 ‐0.1596 0.0573 ‐0.1822 ‐0.2818 ‐0.1473 ‐0.1013 TDS
0.0265 ‐0.1245 ‐0.2114 ‐0.3065 ‐0.3602 ‐0.4573 ‐0.2727 ‐0.4832 ‐0.5115 ‐0.2591 ‐0.3733 TH
0.3472 0.2051 ‐0.0005 ‐0.0926 ‐0.2466 ‐0.2316 ‐0.0462 ‐0.3412 ‐0.3614 ‐0.1591 ‐0.1644 Ca +2
0.3135 ‐0.1585 0.2008 0.0302 ‐0.1905 ‐0.0318 0.2601 ‐0.1632 ‐0.2931 ‐0.2334 0.0303 Mg+2
0.2117 0.3484 ‐0.1684 0.1079 0.2341 0.2939 ‐0.0415 0.5278 0.456 0.0035 0.0509 HCO3‐
0.0913 ‐0.3956 0.1185 ‐0.0025 ‐0.1642 ‐0.177 0.1444 ‐0.2944 ‐0.2997 ‐0.2733 ‐0.0608 Cl‐
0.1252 ‐0.2625 ‐0.1192 ‐0.214 ‐0.2436 ‐0.3995 ‐0.105 ‐0.3433 ‐0.592 ‐0.4336 ‐0.2918 SO4‐2
‐0.4434 ‐0.3988 ‐0.0315 ‐0.2712 ‐0.3915 ‐0.1475 ‐0.0362 0.1401 ‐0.3404 0.0934 ‐0.1531 DO
Hawizeh Marsh during (2006) (r= 0.149, p >0.05).
120
Annexes
Exchangeable
Residual
As
Cd
Co
Ni
Mn
Cu
Se
Pb
Zn
Cr
Mo
Fe
pH
0.129
0.178
‐0.300
‐0.243
‐0.077
‐0.215
‐0.523
‐0.600
0.021
0.311
0.297
0.132
EC
0.438
0.522
0.229
0.788
0.029
0.326
0.304
0.298
0.327
0.474
0.471
0.498
TOC %
‐0.337
‐0.023
‐0.572
‐0.140
0.054
‐0.443
‐0.186
‐0.211
‐0.117
‐0.501
‐0.030
‐0.725
TOM %
‐0.336
‐0.022
‐0.572
‐0.140
0.054
‐0.443
‐0.186
‐0.211
‐0.117
‐0.500
‐0.029
‐0.725
pH
0.422
‐0.256
‐0.491
‐0.477
‐0.634
‐0.570
‐
‐0.349
‐0.353
‐0.643
0.751
‐0.423
EC
‐0.048
0.204
‐0.152
0.025
0.394
‐0.089
‐
‐0.139
‐0.468
‐0.354
0.435
‐0.314
TOC %
0.023
0.016
0.123
0.002
0.101
0.316
‐
0.176
0.533
0.211
‐0.519
0.322
TOM %
0.023
0.016
0.123
0.002
0.101
0.316
‐
0.176
0.533
0.211
‐0.519
0.322
Table (13): The geochemical index of studied HMs in Al‐Hawizeh Marsh during the study period (2006). As Cd Co Cr Mo Ni Pb Se Zn Cu Fe Mn
Adaim 1 2.722 1.913 0.013 0.639 3.167 0.266 1.904 ‐ 3.928 0.494 2.836 2.509
Adaim 2 2.617 1.967 0.069 0.737 3.344 0.362 1.856 ‐ 2.906 0.441 2.960 2.998
Um‐Nia'j1 2.851 2.386 0.488 0.657 3.077 0.482 2.170 ‐ 3.769 0.625 3.134 2.585
Um‐Nia'j2 0.585 1.534 3.766 0.346 3.495 ‐0.180 1.213 0.133 2.658 0.044 2.395 1.903
N. Soda 1.937 1.808 1.068 0.614 3.190 0.720 1.231 0.108 2.974 0.161 2.601 2.409
Um Al‐Wared 1.759 1.853 2.048 ‐0.199 2.782 1.086 0.911 0.379 2.721 ‐0.049 2.389 2.070
Al‐Baida 1.260 1.829 0.174 0.329 3.304 0.158 0.920 ‐ 3.295 0.126 2.605 2.313
S. Al‐Soda 3.030 2.341 0.216 0.210 1.553 0.312 1.851 ‐ 3.013 0.280 2.790 2.137
Lissan Ejerdah 2.294 1.563 0.186 0.211 1.265 0.002 1.558 ‐ 2.966 0.064 2.516 2.236
Majnoon 2.675 1.661 0.241 0.105 3.666 0.345 1.889 ‐ 2.579 0.232 2.849 2.314
Table (12): The correlations among sediment HM concentrations and some sediment parameters in Al‐Hawizeh Marsh during (2006) (r= 0.149, p >0.05).
121
Annexes
Annex (3)
Stations
Ad1
Ad2
UmNj1
UmNj2
N. Sod
Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max
As 0.11 0.14 0.08 0.05 0.02 0.17 0.11 0.15 0.08 0.05 0.02 0.17 1.53 2.24 1.28 0.74 0.04 2.30 1.57 2.29 1.32 0.76 0.05 2.38 1.38 1.80 1.19 0.68 0.04 2.29
Cd 2.03 2.41 0.70 0.40 1.22 2.45 2.38 2.65 0.98 0.57 1.29 3.19 1.77 2.09 0.72 0.42 0.95 2.27 1.85 2.19 0.76 0.44 0.98 2.38 2.90 3.63 1.34 0.77 1.35 3.72
Co 4.53 5.18 1.22 0.71 3.12 5.29 5.11 5.24 0.88 0.51 4.17 5.91 5.87 6.00 1.59 0.92 4.22 7.39 7.49 7.48 2.13 1.23 5.36 9.62 8.80 10.00 2.20 1.27 6.26 10.14
Cr 16.71 17.54 2.91 1.68 13.48 19.13 17.66 18.42 2.11 1.22 15.27 19.28 18.05 18.73 1.68 0.97 16.14 19.30 18.36 18.91 1.31 0.76 16.87 19.30 28.82 28.65 2.76 1.59 26.14 31.66
Mo 5.22 5.69 1.56 0.90 3.48 6.49 4.78 5.20 1.33 0.77 3.29 5.85 9.75 10.40 3.34 1.93 6.13 12.70 10.10 10.48 3.76 2.17 6.17 13.66 11.41 12.51 3.83 2.21 7.15 14.57
Ni 16.92 18.13 3.81 2.20 12.65 19.98 17.87 18.81 3.36 1.94 14.14 20.65 23.44 23.35 2.50 1.45 20.99 25.99 24.88 24.40 2.51 1.45 22.65 27.59 20.11 21.10 2.80 1.61 16.96 22.29
Pb 2.27 1.97 1.27 0.73 1.17 3.66 3.31 4.00 1.28 0.74 1.84 4.10 6.56 7.46 3.26 1.88 2.95 9.27 6.74 7.67 3.19 1.84 3.19 9.37 5.38 5.38 3.20 1.85 2.18 8.57
Se ‐ ‐ ‐‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ 2.94 3.01 0.10 0.07 2.87 3.01 3.13 3.27 0.19 0.14 2.99 3.27 ‐ ‐ ‐ ‐ ‐ ‐
Zn 26.54 25.86 2.66 1.54 24.29 29.48 36.48 35.79 2.69 1.55 34.20 39.45 37.77 36.86 2.38 1.38 35.97 40.47 35.90 35.72 2.19 1.26 33.81 38.17 53.22 58.51 12.67 7.31 38.77 62.38
Cu 7.81 7.37 0.93 0.53 7.19 8.88 11.85 10.20 5.21 3.01 7.67 17.69 15.62 18.61 6.52 3.76 8.15 20.11 18.08 19.47 7.47 4.31 10.02 24.76 22.94 24.69 5.40 3.12 16.89 27.25
Fe 177.67 186.00 16.20 9.35 159.00 188.00 199.00 198.00 33.51 19.35 166.00 233.00 209.67 200.00 45.28 26.14 170.00 259.00 235.00 218.00 33.87 19.55 213.00 274.00 460.83 477.00 59.91 34.59 394.50 511.00
Mn 1268.67 1137.00 424.12 244.86 926.00 1743.00 1392.67 1240.00 556.92 321.54 928.00 2010.00 1965.67 1937.00 192.61 111.20 1789.00 2171.00 2035.00 2001.00 165.64 95.63 1889.00 2215.00 613.92 634.00 106.31 61.38 499.00 708.75
Table (1): The mean, median, standard deviation (Std.Dev), standard error (Std. Err), Min, and Max of HMs in the tissues of Potamogeton perfoliatu plant (ppm) during (2006) in Al‐Hawizeh Marsh.
122
Annexes
Stations UmWd
Bed
S. Sod
LesEj
Maj.
Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max
As 2.19 2.41 2.03 1.17 0.05 4.11 0.16 0.18 0.13 0.07 0.03 0.28 1.17 1.71 0.98 0.57 0.03 1.76 2.35 2.57 2.18 1.26 0.07 4.42 2.52 2.73 2.33 1.35 0.08 4.73
Cd 3.35 3.87 1.79 1.03 1.36 4.82 6.34 7.75 3.44 1.99 2.42 8.85 5.42 6.65 3.48 2.01 1.49 8.12 5.82 6.88 3.44 1.98 1.98 8.60 4.59 5.77 2.81 1.62 1.38 6.63
Co 11.75 12.94 4.43 2.56 6.85 15.45 14.55 17.54 6.40 3.70 7.20 18.91 16.26 20.12 7.69 4.44 7.40 21.25 16.52 20.28 7.90 4.56 7.44 21.84 16.92 20.59 7.54 4.35 8.25 21.92
Cr 30.62 32.15 3.66 2.11 26.45 33.27 26.70 26.12 1.32 0.76 25.78 28.21 27.64 28.44 1.53 0.88 25.88 28.61 19.50 20.00 1.34 0.78 17.98 20.52 23.76 24.30 1.19 0.69 22.40 24.58
Mo 10.59 11.77 3.84 2.21 6.30 13.69 10.92 12.00 3.54 2.04 6.97 13.79 6.23 7.37 2.14 1.24 3.76 7.56 6.73 7.59 2.29 1.32 4.13 8.46 8.43 7.92 2.68 1.55 6.05 11.33
Ni 21.21 22.21 2.75 1.59 18.11 23.32 44.79 46.66 12.00 6.93 31.97 55.75 34.94 36.49 10.42 6.01 23.83 44.49 42.24 43.27 13.16 7.60 28.60 54.86 21.80 22.31 2.88 1.67 18.70 24.40
Pb 3.40 4.06 1.27 0.74 1.93 4.20 4.91 4.27 3.17 1.83 2.11 8.36 7.33 8.55 2.92 1.69 3.99 9.44 5.88 6.11 3.26 1.88 2.51 9.01 6.20 6.84 3.40 1.96 2.53 9.24
Se 2.58 ‐ ‐ 0.00 2.58 2.58 2.55 2.82 0.38 0.27 2.28 2.82 2.64 2.94 0.42 0.30 2.35 2.94 2.73 2.94 0.30 0.21 2.51 2.94 2.88 3.00 0.18 0.12 2.75 3.00
Zn 61.23 68.35 17.34 10.01 41.47 73.87 39.08 38.01 2.09 1.21 37.75 41.49 49.24 48.34 11.88 6.86 37.83 61.54 33.01 33.47 2.94 1.70 29.87 35.69 33.53 33.60 2.32 1.34 31.19 35.82
Cu 23.20 25.40 5.54 3.20 16.90 27.30 24.91 26.51 4.36 2.52 19.98 28.26 20.22 22.13 6.30 3.64 13.18 25.35 21.47 22.67 5.62 3.24 15.35 26.38 21.97 23.54 5.95 3.43 15.40 26.98
Fe 501.00 507.00 16.82 9.71 482.00 514.00 153.22 169.00 31.46 18.16 117.00 173.67 157.81 171.00 25.87 14.94 128.00 174.42 268.33 268.00 11.50 6.64 257.00 280.00 400.00 400.00 93.00 53.69 307.00 493.00
Mn 674.00 680.00 81.17 46.86 590.00 752.00 696.67 694.00 71.04 41.01 627.00 769.00 2223.00 2019.00 379.62 219.17 1989.00 2661.00 816.00 816.00 68.00 39.26 748.00 884.00 898.00 862.00 89.60 51.73 832.00 1000.00
Table (1)Continued.
123
Annexes
Table (2): The mean, median, standard deviation (Std.Dev), standard error (Std. Err), Min, and Max of HMs in the tissues of stations Ad1
Ad2
UmNj1
UmNj2
N. Sod
Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max
As 3.60 3.51 0.56 0.32 3.10 4.20 4.09 4.08 0.83 0.48 3.27 4.92 4.35 4.13 0.77 0.44 3.72 5.20 5.18 5.12 0.81 0.47 4.40 6.02 6.26 6.41 0.78 0.45 5.42 6.96
Cd 0.11 0.09 0.07 0.04 0.05 0.19 0.12 0.10 0.07 0.04 0.06 0.20 0.13 0.10 0.07 0.04 0.09 0.21 0.15 0.14 0.06 0.04 0.09 0.22 0.16 0.16 0.06 0.04 0.10 0.22
Co 1.32 1.22 0.44 0.25 0.95 1.80 1.46 1.45 0.48 0.28 0.99 1.95 1.59 1.64 0.45 0.26 1.11 2.00 2.19 1.95 0.43 0.25 1.93 2.69 3.90 3.90 0.80 0.46 3.10 4.70
Cr 4.81 4.82 0.19 0.11 4.63 5.00 5.21 5.38 0.43 0.25 4.72 5.52 15.25 15.25 1.84 1.06 13.42 17.09 15.17 15.42 2.06 1.19 13.00 17.10 5.34 5.40 0.40 0.23 4.91 5.71
Mo 0.67 0.64 0.22 0.13 0.47 0.90 0.76 0.82 0.18 0.10 0.57 0.91 0.89 0.85 0.29 0.17 0.62 1.20 1.13 0.99 0.34 0.19 0.88 1.51 0.95 0.90 0.35 0.20 0.63 1.32
Ni 9.66 9.87 0.48 0.28 9.12 10.00 9.83 10.10 0.53 0.30 9.22 10.16 10.45 10.31 1.10 0.64 9.43 11.62 11.61 11.82 2.07 1.19 9.45 13.58 37.03 36.79 3.75 2.16 33.42 40.90
Pb 0.54 0.50 0.15 0.08 0.42 0.70 0.76 0.76 0.11 0.07 0.65 0.88 1.74 1.69 0.44 0.26 1.31 2.20 1.70 1.91 0.63 0.36 1.00 2.20 0.85 0.88 0.10 0.06 0.74 0.94
Se ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐
Zn 179.33 181.00 21.55 12.44 157.00 200.00 181.67 185.00 20.21 11.67 160.00 200.00 206.33 190.00 30.92 17.85 187.00 242.00 234.67 224.00 41.05 23.70 200.00 280.00 245.67 227.00 47.82 27.61 210.00 300.00
Cu 108.67 110.00 8.08 4.67 100.00 116.00 112.00 116.00 10.58 6.11 100.00 120.00 115.67 120.00 11.15 6.44 103.00 124.00 144.33 153.00 33.84 19.54 107.00 173.00 154.33 156.00 23.54 13.59 130.00 177.00
Fe 1033.33 1000.00 142.95 82.53 910.00 1190.00 1233.33 1110.00 231.16 133.46 1090.00 1500.00 1400.00 1390.00 105.36 60.83 1300.00 1510.00 1603.33 1560.00 111.50 64.38 1520.00 1730.00 3550.00 3160.00 728.08 420.36 3100.00 4390.00
Mn 115.38 114.00 8.15 4.71 108.00 124.13 128.81 120.00 17.01 9.82 118.00 148.42 168.33 174.00 28.92 16.70 137.00 194.00 179.67 180.00 19.50 11.26 160.00 199.00 190.67 185.00 26.95 15.56 167.00 220.00
Viviparus bengalensis snails (ppm) during (2006) in Al‐Hawizeh Marsh.
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Stations UmWd
Bed
S. Sod
LesEj
Maj.
Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max Mean Median Std.Dev Std.Err Min Max
As 6.45 6.44 0.69 0.40 5.76 7.15 5.56 5.36 0.68 0.39 5.00 6.32 5.83 5.68 0.52 0.30 5.40 6.41 5.97 6.03 0.82 0.47 5.12 6.75 6.12 6.35 0.92 0.53 5.10 6.90
Cd 0.20 0.21 0.04 0.02 0.16 0.24 0.18 0.17 0.04 0.03 0.13 0.22 0.18 0.19 0.05 0.03 0.13 0.23 0.18 0.20 0.07 0.04 0.10 0.23 0.23 0.21 0.06 0.03 0.18 0.29
Co 2.65 2.17 0.97 0.56 2.01 3.76 3.30 2.99 0.62 0.36 2.90 4.02 3.35 3.53 0.85 0.49 2.42 4.10 3.32 3.58 1.01 0.59 2.20 4.17 3.64 3.72 0.61 0.35 3.00 4.22
Cr 6.26 5.95 1.11 0.64 5.33 7.48 14.61 14.58 2.21 1.28 12.41 16.83 15.58 15.00 1.23 0.71 14.75 17.00 15.96 15.43 1.40 0.81 14.91 17.55 19.26 19.13 2.02 1.17 17.31 21.35
Mo 0.98 0.91 0.39 0.22 0.64 1.40 1.03 0.94 0.35 0.20 0.73 1.43 1.04 0.97 0.38 0.22 0.71 1.45 1.04 0.98 0.40 0.23 0.69 1.47 1.12 0.98 0.33 0.19 0.87 1.50
Ni 23.17 26.53 10.90 6.29 11.00 32.00 29.91 27.51 4.24 2.45 27.42 34.81 31.21 31.42 5.67 3.28 25.44 36.78 31.49 31.78 7.92 4.57 23.43 39.25 34.94 34.17 4.83 2.79 30.55 40.11
Pb 1.02 1.03 0.21 0.12 0.81 1.22 1.29 1.07 0.63 0.36 0.81 2.00 1.59 1.54 0.41 0.24 1.21 2.02 2.03 2.00 0.32 0.18 1.73 2.37 2.24 2.11 0.41 0.24 1.92 2.70
Se 2.52 ‐ ‐ ‐ 2.52 2.52 3.30 ‐ ‐ ‐ 3.30 3.30 3.40 ‐ ‐ ‐ 3.40 3.40 3.42 ‐ ‐ 0.00 3.42 3.42 2.60 ‐ ‐ ‐ 2.60 2.60
Zn 270.67 264.00 37.45 21.62 237.00 311.00 267.67 270.00 48.54 28.03 218.00 315.00 272.67 280.00 51.39 29.67 218.00 320.00 286.97 286.00 47.46 27.40 240.00 334.91 294.33 290.00 45.65 26.36 251.00 342.00
Cu 164.67 161.00 13.87 8.01 153.00 180.00 165.33 165.00 17.50 10.11 148.00 183.00 162.67 165.00 22.59 13.04 139.00 184.00 172.33 165.00 14.47 8.35 163.00 189.00 175.67 174.00 13.58 7.84 163.00 190.00
Fe 4026.67 4050.00 455.45 262.95 3560.00 4470.00 4280.00 4280.00 280.00 161.66 4000.00 4560.00 4006.67 4300.00 782.39 451.71 3120.00 4600.00 4376.67 4310.00 305.51 176.38 4110.00 4710.00 4710.00 4900.00 512.15 295.69 4130.00 5100.00
Mn 212.00 200.00 20.78 12.00 200.00 236.00 217.67 207.00 26.65 15.39 198.00 248.00 212.33 214.00 38.53 22.24 173.00 250.00 222.33 215.00 26.76 15.45 200.00 252.00 235.00 215.00 35.51 20.50 214.00 276.00
Table (2) Continued.
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Table (3): The bio‐concentration Factor (BCF), and Bio Sedimentation Factor (BSF) of HMs in P. perfoliatus plant and V. bengalensis snails studied stations during (2006). Dissolved Average
Sediment Average
Cu Fe As Se Cd Pb Co Zn Cr Ni Mn Mo
0.34972 2.14004 0.03306 0 0.0635 0.05426 0.01128242 4.57566 0.20203 0.35211 0.4217 0.15399
175.153525 21767.74347 500.1154474 4.529933333 40.197475 348.684455 12.836575 348092.7441 708.962135 125.655995 1641.2729 2995.72505
Snails Average Plant Average 147.56667 3022 5.34045 1.5236 0.16283 1.37717 2.67151 243.99701 11.74571 22.93223 188.21817 0.9626
18.80864 276.25278 1.30877 2.778257143 3.64448 5.19812 10.77896 40.60001 22.78273 26.82119 1258.35835 8.41577
plant 0.107384 0.012691 0.002617 0.613311 0.090664 0.014908 0.839707 0.000117 0.032135 0.213449 0.766697 0.002809
Snails 0.842499 0.138829 0.010678 0.33634 0.004051 0.00395 0.208117 0.000701 0.016567 0.1825 0.114678 0.000321
BCF plant 53.782 129.0877 39.58772 0 57.39339 95.80022 955.3766 8.873039 112.769 76.17276 2984.013 54.65141
Snails 421.9566 1412.123 161.5381 0 2.564252 25.38094 236.7852 53.32499 58.13844 65.12803 446.3319 6.251055
HMs
BSF
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VAs PAs DAs PEAs RPAs SEAs SRAs
1 0.6655 0.5753 ‐0.7948 ‐0.1912 0.6364 0.2775 VAs
1 0.495 ‐0.4086 ‐0.1468 0.2578 ‐0.0575 PAs
1 ‐0.2884 ‐0.1591 0.0365 0.0521 DAs
1 0.3608 ‐0.4884 ‐0.2358 PEAs
1 0.2017 0.7487 RPAs
Table (4): The correlations among different phases of water sediments and biota of Arsenic (As) in Al‐Hawizeh Marsh during (2006) (r= 0.149, p >0.05).
1 0.3617 SEAs
1 SRAs
Table (5): The correlations among different phases of water sediments and biota of Cadmium (Cd) in Al‐Hawizeh Marsh during (2006) (r= 0.149, p >0.05). VCd PCd DCd PECd RPCd SECd SRCd
1 0.5482 0.0636 ‐0.5919 ‐0.2583 0.315 0.1988 VCd
1 0.3243 ‐0.3438 ‐0.1225 ‐0.2773 ‐0.0463 PCd
1 ‐0.1089 0.6293 ‐0.2453 0.0401 DCd
1 ‐0.0446 0.2299 ‐0.4766 PECd
1 0.0354 ‐0.0406 RPCd
1 0.025 SECd
1 SRCd
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Table (6): The correlations among different phases of water sediments and biota of Cobalt (Co) in Al‐Hawizeh Marsh during (2006) (r= 0.149, p >0.05). 1 ‐0.4489 0.8671 0.8547 ‐0.0419 ‐0.1339 0.3951 PCo
1 ‐0.1011 ‐0.5186 ‐0.2759 0.2913 ‐0.3919 PECo
1 0.7574 0.0776 ‐0.3134 0.341 DCo
1 0.1751 ‐0.2816 0.4031 VCo
1 ‐0.3524 0.4701 SRCo
1 ‐0.2033 RPCo
PCo PECo DCo VCo SRCo RPCo SECo
1 SECo
Table (7): The correlations among different phases of water sediments and biota of Chrome (Cr) in Al‐Hawizeh Marsh during (2006) (r= 0.149, p >0.05). PCr VCr DCr PECr SECr RPCr SRCr
1 ‐0.0063 ‐0.2526 ‐0.641 0.2568 ‐0.5989 ‐0.3799 PCr
1 0.4548 ‐0.1571 0.4687 ‐0.5104 ‐0.4305 VCr
1 0.191 0.1546 ‐0.084 ‐0.4793 DCr
1 ‐0.203 0.6979 0.0794 PECr
1 ‐0.1496 ‐0.1632 SECr
1 0.3709 RPCr
1 SRCr
Table (8): The correlations among different phases of water sediments and biota of Selenium (Se) in Al‐Hawizeh Marsh during (2006) (r= 0.149, p >0.05). PSe SESe VSe
1 0.1133 0.4337 PSe
1 ‐0.1548 SESe
1 VSe
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(2006) (r= 0.149, p >0.05). PPb 1 VPb 0.8082 PEPb ‐0.0719 DPb 0.2942 RPPb 0.1462 SEPb 0.0398 SRPb ‐0.1561 PPb
1 0.1125 0.4822 0.1703 ‐0.0373 ‐0.0598 VPb
1 ‐0.3757 0.0494 ‐0.4171 ‐0.4879 PEPb
1 ‐0.1235 ‐0.2626 0.6491 DPb
1 ‐0.366 ‐0.1611 RPPb
Table (9): The correlations among different phases of water sediments and biota of Lead (Pb) in Al‐Hawizeh Marsh during
1 ‐0.0601 SEPb
1 SRPb
Table (10): The correlations among different phases of water sediments and biota of Zinc (Zn) in Al‐Hawizeh Marsh during (2006) (r= 0.149, p >0.05). PZn VZn DZn RPZn SEZn PEZn SRZn
1 ‐0.5688 0.2899 ‐0.4513 0.605 ‐0.4528 ‐0.524 PZn
1 ‐0.1187 ‐0.0682 ‐0.1753 ‐0.1356 ‐0.1813 VZn
1 ‐0.213 ‐0.0933 ‐0.5603 ‐0.3988 DZn
1 0.0441 0.4696 0.8779 RPZn
1 ‐0.4435 ‐0.0754 SEZn
1 0.6896 PEZn
1 SRZn
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Table (11): The correlations among different phases of water sediments and biota of Nickel (Ni) in Al‐Hawizeh Marsh during SRNi PNi RPNi SENi VNi PENi DNi
1 ‐0.0186 ‐0.3462 0.4159 0.2594 ‐0.2282 0.2099 SRNi
1 ‐0.2633 ‐0.041 0.5103 0.4966 0.1693 PNi
1 0.0741 ‐0.2309 0.0089 ‐0.3546 RPNi
1 0.6544 0.3999 0.2726 SENi
1 0.5993 0.4907 VNi
(2006) (r= 0.149, p >0.05).
1 ‐0.1513 PENi
1 DNi
Table (12): The correlations among different phases of water sediments and biota of Manganese (Mn) in Al‐Hawizeh Marsh during (2006) (r= 0.149, p >0.05). RPMn SRMn SEMn EPMn DMn VMn PMn
1 ‐0.1337 0.5511 0.741 0.7076 ‐0.6441 ‐0.0639 RPMn
1 ‐0.0028 ‐0.1314 0.0781 0.2666 ‐0.5565 SRMn
1 0.2803 0.3664 ‐0.1483 0.01 SEMn
1 0.2133 ‐0.9056 0.1562 EPMn
1 ‐0.2108 ‐0.4125 DMn
1 ‐0.2242 VMn
1 PMn
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Table (13): The correlations among different phases of water sediments and biota of Molybdenum (Mo) in Al‐Hawizeh Marsh PEMo DMo RPMo SEMo SRMo PMo VMo
1 ‐0.2172 ‐0.0525 0.0461 ‐0.0366 0.4764 0.0026 PEMo
1 0.0412 0.3209 ‐0.5025 0.4117 0.3692 DMo
1 ‐0.3519 ‐0.3748 0.1597 ‐0.3286 RPMo
1 0.1143 0.1733 0.301 SEMo
during (2006) (r= 0.149, p >0.05).
1 ‐0.2014 0.5209 SRMo
1 0.4901 PMo
1 VMo
Table (14): The correlations among different phases of water sediments and biota of Iron (Fe) in Al‐Hawizeh Marsh during (2006) (r= 0.149, p >0.05). EPFe RPFe PFe VFe SEFe SRFe DFe
1 0.8663 1 ‐0.3987 ‐0.368 1 ‐0.1616 ‐0.0056 ‐0.2208 1 0.1668 0.4341 0.238 0.451 1 0.1357 ‐0.121 0.1902 ‐0.4408 ‐0.2787 1 ‐0.4418 ‐0.3081 0.3949 ‐0.1575 0.2206 ‐0.3285 EPFe RPFe PFe VFe SEFe SRFe
1 DFe
131
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DCu PECu RPCu SECu SRCu VCu PCu
1 ‐0.4856 ‐0.4802 0.2168 0.0514 0.7109 0.5814 DCu
1 0.2921 ‐0.4048 0.2483 ‐0.589 ‐0.5479 PECu
1 0.0684 0.0156 ‐0.797 ‐0.6913 RPCu
1 ‐0.1193 0.0767 0.2568 SECu
Table (15): The correlations among different phases of water sediments and biota of Cooper (Cu) in Al‐Hawizeh Marsh during (2006) (r= 0.149, p >0.05).
1 ‐0.123 ‐0.0176 SRCu
1 0.9016 VCu
1 PCu
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اﻟﺨﻼﺻﺔ: ت ﺑِﻴﺌﻴًﺎ ﺖ هﺬﻩ اﻟﻤﺴﺘﻨﻘﻌﺎ ِ ﺣﻄّﻤ ْ ﺗﻌﺪ اهﻮار وادي اﻟﺮاﻓﺪﻳﻦ ﻣﻦ اﻗﺪم ﻣﻨﺎﻃﻖ اﻻراﺿﻲ اﻟﺮﻃﺒﺔ اﻟﻄﺒﻴﻌﻴﺔ ﻓﻲ اﻟﻌﺎﻟﻢ ُ . ﻓﻲ ﺑﺪاﻳﺔ ﻋﺎم 1990ﻣﻦ ﺧﻼل ﺗﺤﻮﻳﻞ ﻣﺠﺎري اﻟﻤﻴﺎﻩ وﺑﻨﺎء اﻟﻌﺪﻳﺪ ﻣﻦ اﻟﺴﺪود ﻣﻤﺎ ادى اﻟﻰ ﺟﻔﺎف اﻏﻠﺐ ﻣﺴﺎﺣﺎﺗﻬﺎ .و ﻓﻲ ﻋﺎم 2003ﺗﻢ ﻏﻤﺮ وآﺴﺮ اﻟﺴﺪود اﻟﺘﺮاﺑﻴﺔ ﻓﻲ ﻣﺤﺎوﻟﺔ ﻻﻋﺎدة اﻻﻏﻤﺎر و ﺗﺎهﻴﻞ هﺬﻩ اﻻهﻮار ، وﻋﻠﻴﻪ ﻓﻤﻦ اﻟﻤﻬﻢ ﻣﺮاﻗﺒﺔ اﻟﺘﻐﻴﺮات اﻟﺘﻲ ﺗﺤﺪث ﻓﻲ ﻧﻮﻋﻴﺔ هﺬﻩ اﻟﻤﻴﺎﻩ اﻟﻔﻴﺰﻳﺎﺋﻴﺔ واﻟﻜﻴﻤﻴﺎﺋﻴﺔ واﻟﺒﺎﻳﻮﻟﻮﺟﻴﺔ . ن اﻟﺜﻘﻴﻠ ِﺔ ف اﻟﻜﺜﻴﺮ ﺣﻮل اﻟﻤﻌﺎد ِ اﻟﻤﻌﺎدن اﻟﺜﻘﻴﻠﺔ ﻟَﻬﺎ أهﻤﻴﺔ ﺑﻴﺌﻴّﺔ آﺒﻴﺮة ﺑﺴﺒﺐ اﻟﺴﻤﻴﺔ واﻟﺴﻠﻮك اﻟﺘﺮاآﻤﻲ و ﻧﺤﻦ ﻻ َﻧﻌْﺮ ُ ﺐ اﻹﻋﺎدةَ ،و هﻜﺬا ﻓﻤﻦ اﻟﻤُﻬ ِﻢ َﻓﻬْﻢ اﻟﺘﻮزﻳ ِﻊ و اﻟﺤﻤﻞ و اﻟﻤﻮازﻧﺔ ﻓﻲ هﺬا اﻟﻨﻈﺎم اﻟﺒﻴﺌﻲ اﻟﻐﻴﺮ ﻣﺴﺘﻘﺮ .ﺑﺴﺒﺐ ﺗﻌﺎﻗ ِ واﻟﺘﺮاآﻢ اﻟﺤﻴﻮي ﻟﻠﻤﻌﺎدن اﻟﺜﻘﻴﻠﺔ ﻓﻲ اﻟﻨﻈﺎم اﻟﺒﻴﺌﻲ ﻻهﻮار وادي اﻟﺮاﻓﺪﻳﻦ ﺑﻌﺪ إﻋﺎد ِة اﻟﺘﺄهﻴﻞ وأﻋﺎد ِة اﻟﻤﺎ ِء .ﻟﺬا ﺟﺎءت اﻟﺪراﺳﺔ اﻟﺤﺎﻟﻴﺔ ﻟﻐﺮض :اﺟﺮاء دراﺳﺔ اوﻟﻴﺔ ﻋﺎﻣﺔ ﺣﻮل ﺗﺮاآﻴ ِﺰ اﻟﻤﻌﺎد ِ ن اﻟﺜﻘﻴﻠ ِﺔ ) Asو Cdو Crو Coو Cuو Moو Mnو Znو Pbو Seو Feو ( Ni ﺑﺎﺧﺬ ﻋﻴﻨﺎت ﺷﻬﺮﻳﺎ وﻗﻴﺎس ﺑﻌﺾ اﻟﺼﻔﺎت اﻟﻔﻴﺰﻳﺎﺋﻴﺔ واﻟﻜﻴﻤﻴﺎﺋﻴﺔ ﻟﻠﻤﻴﺎﻩ ﻣﻦ ﺳﺖ ﻣﺤﻄﺎت) هﻮر اﻟﺤﻤﺎر :ﻣﺤﻄﺘﻲ اﻟﺒﺮآﺔ واﻟﻨﻜﺎرة ،و هﻮر اﻟﺤﻮﻳﺰة :ﻣﺤﻄﺘﻲ ام اﻟﻮرد وام اﻟﻨﻌﺎج ،و اﻻهﻮار اﻟﻤﺮآﺰﻳﺔ :ﻣﺤﻄﺘﻲ ﺑﺪاﻳﺔ اﻟﺒﻐﺪادﻳﺔ و وﺳﻂ اﻟﺒﻐﺪادﻳﺔ( .ﻟﻤﺮاﻗﺒﺔ اﻟﺤﻤﻞ اﻟﺸﻬﺮي واﻟﺴﻨﻮي ﻟﻜﻞ ﻋﻨﺼﺮ ﻓﻲ هﻮر اﻟﺤﻮﻳﺰة ﻟﺘﺤﺪﻳﺪ ﻓﻴﻤﺎ اذا آﺎﻧﺖ اﻻهﻮار اﻟﻌﺮاﻗﻴﺔ ﺗﻌﻤﻞ آﻤﺮﺳﺐ أو ﺗﻌﺘﺒﺮ ﻣﺼﺪر أو هﻲ ﻣﺠﺮد وﺳﻂ ﻻﺗﺎﺛﻴﺮ ﻟﻪ ﻓﻲ زﻳﺎدة أو ﺗﻘﻠﻴﻞ اﻟﺤﻤﻞ اﻟﺸﻬﺮي واﻟﺴﻨﻮي ﻟﻠﻤﻌﺎدن اﻟﺜﻘﻴﻠﺔ وﺑﺎﻟﺘﺎﻟﻲ ﻣﺪى ﺗﺎﺛﻴﺮهﺎ ﻋﻠﻰ ﻧﻮﻋﻴﺔ اﻟﻤﻴﺎﻩ اﻟﺨﺎرﺟﺔ ﻣﻨﻬﺎ ،ﻣﻦ ﺧﻼل اﺧﺬ ﺳﺒﻊ ﻣﺤﻄﺎت ﺗﻮزﻋﺖ آﺎﻻﺗﻲ :ﺧﻤﺲ ﻣﺤﻄﺎت ﻓﻲ ﻣﺪاﺧﻞ هﻮر اﻟﺤﻮﻳﺰة اﻟﺨﻤﺲ)اﻟﻌﺪل اﻟﻘﺪﻳﻢ و اﻟﻌﺪل و اﺑﻮ ﺧﺼﺎف و اﻟﻤﺸﺮح و اﻟﺰﺑﻴﺮ ( وﻣﺤﻄﺘﻴﻦ ﺗﻤﺜﻼن ﻣﺨﺎرج اﻟﻤﻴﺎﻩ ﻣﻦ هﻮر اﻟﺤﻮﻳﺰة )اﻟﻜﺴﺎرة واﻟﺴﻮﻳﺐ( .و ﻟﻐﺮض ﺗﻮﺿﻴﺢ ﻓﻴﻤﺎ اذا آﺎﻧﺖ هﻨﺎك ﻋﻼﻗﺔ ﻣﺎ ﺑﻴﻦ ﺗﺮاآﻴﺰ اﻟﻌﻨﺎﺻﺮ اﻟﺜﻘﻴﻠﺔ ﺑﺎﺷﻜﺎﻟﻬﺎ اﻟﻤﺨﺘﻠﻔﺔ ﻣﻊ ﺻﻔﺎت اﻟﻤﺎء واﻟﺮواﺳﺐ وﻣﻘﺎرﻧﺔ اﻟﻤﻨﺎﻃﻖ اﻟﺘﻲ ﺗﻌﺮﺿﺖ ﻟﻠﺘﺠﻔﻴﻒ ﻣﻊ اﻟﻤﻨﺎﻃﻖ اﻟﻐﻴﺮ ﻣﺘﻌﺮﺿﺔ ﻟﻠﺘﺠﻔﻴﻒ ،ﺗﻢ اﺧﺘﻴﺎر ﻋﺸﺮة ﻣﺤﻄﺎت ﻓﻲ هﻮر اﻟﺤﻮﻳﺰﻩ هﻲ اﻟﻌﻈﻴﻢ 1واﻟﻌﻈﻴﻢ ) 2ﻣﺤﻄﺎت ﻏﻴﺮ ﻣﺘﻌﺮﺿﺔ ﻟﻠﺘﺠﻔﻴﻒ( و اﻟﺴﻮدة اﻟﺸﻤﺎﻟﻴﺔ وام اﻟﻨﻌﺎج 1وام اﻟﻨﻌﺎج ) 2ﻣﻨﺎﻃﻖ ﺷﺒﺔ ﺟﺎﻓﺔ( و ام اﻟﻮرد واﻟﺴﻮدة اﻟﺠﻨﻮﺑﻴﺔ وﻟﺴﺎن ﻋﺠﻴﺮدة و ﻣﺠﻨﻮن و اﻟﺒﻴﻀﺔ ) ﺟﻔﺖ ﺗﻤﺎﻣﺎ( .و ﻟﻤﺘﺎﺑﻌﺔ ﺳﻠﻮك وﺣﺮآﺔ اﻟﻤﻌﺎدن اﻟﺜﻘﻴﻠﺔ ﻓﻲ رواﺳﺐ و وﻋﻤﻮد اﻟﻤﺎء و ﻧﺒﺎت اﻟــ Potamogeton perfoliatusو ﺣﻠﺰون اﻟـ Viviparus bengalensisوﺗﻘﺮﻳﺮ ﻓﻴﻤﺎ اذا ﺑﺎﻻﻣﻜﺎن اﺳﺘﺨﺪام هﺬﻩ اﻟﻜﺎﺋﻨﺎت آﺪﻟﻴﻞ ﺣﻴﻮي ﻋﻠﻰ اﻟﺘﻠﻮث ام ﻻ . ﺖ ﻓﻲ اﺷﻬﺮ اﻟﺮﺑﻴﻊ ، ﺳﺠّﻠ ْ ﺖ ﻓﻲ اﺷﻬﺮ اﻟﺼﻴﻒ ،ﺑﻴﻨﻤﺎ اﻟ ِﻘﻴَﻢ اﻷوﻃﺄ ُ ﺳﺠّﻠ ْ ن اﻟﺘﺮاآﻴﺰ اﻷﻋﻠﻰ ُ ﺞ ﺑﺄ ّ اوﺿﺤﺖ اﻟﻨَﺘﺎ ِﺋ َ ﻣﺎﻋﺪا ﻋﻨﺼﺮ اﻟﺴﻴﻠﻴﻨﻴﻮم )ﺗﺮاآﻴﺰﻩ ﻏﻴﺮ ﻣﺤﺴﻮﺳﺔ( و آﺎن ﺗﺮاآﻴﺰ اﻟﻌﻨﺎﺻﺮ اﻟﻤﻘﺎﺳﺔ اﻋﻠﻰ ﻣﻦ اﻟﻤﺤﺪدات اﻟﻌﺮاﻗﻴﺔ ﻟﻠﻤﻴﺎﻩ اﻟﻌﺬﺑﺔ ﻋﺪا ﻋﻨﺼﺮي اﻟـﻨﺤﺎس و اﻻرﺳﻨﻚ . ﺑﻴﻨﺖ اﻟﻨﺘﺎﺋﺞ ان هﻮر اﻟﺤﻮﻳﺰة آﺎن ﻣﺮﺳﺒﺎ ﻟــ % 63 :ارﺳﻨﻚ و % 38ﻧﺤﺎس و % 33 زﻧﻚ و % 30 ﻣﻮﻟﺒﻴﺪﻳﻮم و % 27 رﺻﺎص و % 8آﺎدﻣﻴﻮم و ﻧﺎﻗﻼ ً ﻟـ % 93آﺎدﻣﻴﻮم و %73رﺻﺎص و ،و% 70 ﻣﻮﻟﺒﻴﺪﻳﻮم و %68 زﻧﻚ و %62 ﻧﺤﺎس و % 37ارﺳﻨﻚ وﻣﺼﺪر ﻟـ %42 :آﺮوم و %28ﺣﺪﻳﺪ و %23 ﻣﻨﻐﻨﻴﺰ و %15 آﻮﺑﻠﺖ و 6%ﻧﻴﻜﻞ. ﺖ ﻓﻲ اوﺿﺤﺖ اﻟﻨﺘﺎﺋﺞ ان ﻗﻴﻢ درﺟﺔ اﻟﺤﺮارة و اﻟﻤﻮاد اﻟﻌﺎﻟﻘﺔ اﻟﻜﻠﻴﺔ و اﻟﻌﺴﺮة اﻟﻜﻠﻴﺔ واﻟﻜﺎﻟﺴﻴﻮم واﻟﻤﻐﻨﺴﻴﻮم آَﺎﻧ ْ ﺠﻔﱠﻔ ِﺔ ﺗﻤﺎﻣًﺎ< ﻣﺤﻄﺎت ﺷﺒﻪ اﻟﺠﺎﻓﺔ< اﻟﻤﺤﻄﺎت اﻟﻐﻴﺮ ﻣﻌﺮﺿﺔ ﻟﻠﺘﺤﻔﻴﻒ .؛و آﺎﻧﺖ ﻗﻴﻢ اﻟﺘﻮﺻﻴﻠﻴﺔ ت اﻟ ُﻤ َ اﻟﻤﺤﻄﺎ ِ ﺠﻔﱠﻔ ِﺔ ﺗﻤﺎﻣًﺎ