*ADAM PAWEŁCZYK **FRANTIŠEK BOŽEK *KAZIMIERZ GRABAS *BARBARA KOŁWZAN *CZESŁAW MORA
[email protected]
*Wroclaw University of Technology, Poland **University of Defence, Brno, Czech Republic
UAA Seminar „Anthropogenic pollutants in the Environment„ UNIVERSITY OF ALASKA ANCHORAGE Anchorage, September 24-th, 2014
640.000 inhabitants 134.000 students 113 bridges
-34.400 students -over 4.000 staff, half of which are academics -12 faculties
Faculty of Architecture Faculty of Civil Engineering Faculty of Chemistry Faculty of Electronics Faculty of Electrical Engineering Faculty of Geoengineering, Mining and Geology Faculty of Environmental Engineering
Faculty of Computer Science and Management Faculty of Mechanical and Power Engineering Faculty of Mechanical Engineering Faculty of Fundamental Problems of Technology Faculty of Microsystem Electronics and Photonics Department of Fundamental Studies
• • • • • • • •
Introduction What are the petroleum products? Toxicity
Examples of environment contamination Health risk abatement by environment remediation Bioremediation Conclusions References
Materials derived from crude oil (petroleum) as it is processed in oil refineries by fractional distillation or cracking The most known - Asphalt, Diesel fuel, Fuel oils, Gasoline, Jet fuel, Kerosene, Liquified petroleum gas (LPG), Lubricating oils, Paraffin wax, Tar. The largest share of oil products is used as "energy carriers", i.e. various grades of fuel oil and gasoline. Fuels include or can be blended to give gasoline, jet fuel, diesel fuel, heating oil, and heavier fuel oils.
Heavier (less volatile) fractions can also be used to produce asphalt, paraffin wax, lubricating and other heavy oils. Petroleum products are complex mixtures of many hydrocarbons of different chemical – physical properties and toxicological character.
World consumption of refined petroleum products 87,600,000 (barrels per day)
• emissions from the engine exhaust of a motor vehicles, rolling stock, aircrafts • accidental release • intentional discharges of sludges from oil tankers, disposal of oilcontaining waste water from ships • leaks from storage facilities and pipelines, etc.
Typical hydrocarbon composition of JP-4 fuel
concentrations in % (mass fraction)
1,2,3-Trimethylbenzene
1,2,4-Trimethylbenzene
the three isomers exhibit different toxicity for rats
1,3,5-Trimethylbenzene
Carcinogen Classification (US EPA)
Reference Dose RfD mg/(kgday)
Reference Concentration RfC mg/m3
Inhalation Unit Risk IUR µg-1m3
CSF mg/kg-day
Benzene
Group A (human carcinogen)
4.0 x10-3 (oral)
3x10-2 (inhal)
2.2 x 10-6 to 7.8 x 10-6
1.5 x10-2 (oral)
Toluene
Group 3 (not classifiable as to its carcinogenicity in humans) (IARC)
8.0 x10-2 (oral)
5 (inhal)
?
?
D (not classifiable as to human carcinogenicity)
0.1 (oral)
1 (inhal)
?
?
Xylene isomers (o-, m-, p-) mixture
?
0.2 (oral)
0.1 (inhal)
?
?
2-Methylnaphthalene
?
4.0 x10-3 (oral)
?
?
?
Naphthalene
Group C (possible human carcinogen) (EPA IRIS)
2.0 x10-2 (oral)
3x10-3 (inhal)
?
?
Compound
Ethylbenzene
(EPA IRIS)
(EPA IRIS)
(classification of the Integrated Risk Information System EPA IRIS & International Agency for Research on Cancer IARC) The interpretation of inhalation unit risk: if unit risk = 1.2 x 10-2 per µg/ m3 in air, 1.2 excess cancer cases are expected to develop per 100 people if exposed daily for a lifetime to 1 µg of the chemical in 1 cubic meter of air
Health effects Component
Toxic effects to humans
Benzene
Known human carcinogen (group A), affecting central nervous system, causing depression, irregular heart rhythm etc.
Xylenes
Abdominal pain, vomiting; central nervous system effects; heart and liver damage; bone marrow damage
Toluene
Mutagenic, adverse effects of central nervous system, depression, respiratory irritation, liver, kidney damage
Ethylbenzene
Narcosis, central nervous system effects, skin and eye irritation
Naphtalene
Possible human carcinogen (group C). Abdominal pain, jaundice, renal failure, optical neuritis and corneal damage
Polycyclic aromatic hydrocarbons (PAHs)
Diverse degrees of toxicity, several of which possess potential carcinogenic, mutagenic, and teratogenic properties
Chicago O'Hare International Airport
219 volatile compounds in the air around Chicago's O'Hare International Airport have been detected
78 of these chemicals were at "increased levels" The estimated resulting cancer risk for people living near the airport was five times higher than the regional average, proving how dangerous it can be to live near an airport
SOURCE: SKOLNICK
S. R., Exposing Airports' Poison Circles, Earth Island Journal, Winter 2000-2001. Vol. 15, No. 4.
11
Seattle
The average life expectancy was found to be 70.4 years in an area of Seattle which surrounds King County International Airport (a rate comparable to that of many developing countries) Seattle's average life expectancy was 76.0 years.
Mortality rates for all causes of death were found to be 48% higher in King County
SOURCE :
SEATTLE - King County Department of Public Health Report (1997), http://www.areco.org/FuelEssay.pdf
12
quality of water intended for human consumption Benzene
µg/L
1
Total polyaromatic hydrocarbons
µg/L
0.1
soil and earth quality standards (mg/kg dry matter) Soil quality standard
Contaminant
Group A
(residential areas)
Group B
(agricultural areas)
Group C
(industrial areas)
Automotive fuel (C6 – C12)
1
1 - 275
50 - 750
Mineral oil (C12 – C35)
30
50 - 1000
1000 - 3000
Benzene
0.05
0.1 – 25
3 - 150
Ethylbenzene
0.05
0.1 – 70
10 - 250
Toluene
0.05
0.1 - 75
5 - 230
Xylene
0.05
0.1 – 35
5 - 150
Styrene
0.1
0.1 – 5
2 - 100
Total aromatic hydrocarbons
0.1
0.1 – 75
10 - 250
A Chinese man drinks Gasoline regularly
http://seriousfacts.com/chinese-man-drinks-gasoline-regularly/
- 6 firing grounds - 59 towns and garrisons, 15 airfields, a naval station, 11 harbour docks, 14 loading platforms, 7,913 buildings
70,794 ha (708 km2) of grounds in Northern and Western
Military staff – at its peak the number of soldiers was about 300,000. A garrison in the town Legnica was composed of 50 thousands people (together with a Russian civilian personnel)
Sweden Lithuania
The Soviet 4-th Air Army occupied 13 airfields in Poland
Danmark
Russia Gdańsk
Germany
Szczecin
Poznań
Belarus
Warsaw Łódź Lublin
Wroclaw
Czech Republic
Cracow Ukraine Slovakia
View of the „Bagicz” airfield
CCCP
UK Germany Czechoslovakia
France
Evaluation of Environmental Damages
Heavily devastated environment in the abandoned airbases including fuel storage, plane refuelling stations, plane heating slabs Costs of liquidation of the ecological damages: 5,220,000,000 PLN ($ 2,300,000,000) (according to the assesment of the General Inspector for Environment Protection)
Former airbase „Kluczewo”
Surface of the floating fuel
200 350 m2
Thickness of the floating fuel layer
up to 1 m
Cubature of the fuel saturated grounds 197 655 m3 Volume of the free fuel
x 60
59 296 m3
physical and chemical methods - pumping out the petroleum products from water-bearing layer - desorption of pollutants from water to air - extraction of pollutants with organic solvents - adsorption and flotation with coal dust - electrolytical decontamination, - burning the polluted ground, etc.
biological methods (bioremediation)
28
Bioremediation
Use of any organisms to remove pollutants. The bioremediation techniques are classified as in situ or ex situ.
In situ bioremediation involves treating the contaminated material at the site. Ex situ involves removal of the contaminated material to be treated elsewhere.
29
In-situ method
Piezometers
Ex situ method
Where do we have the bacteria from?
sampling
repeated passages
inspection for pathogens
application
multiplication
certification
control of pH, temp., N, P microorganisms
fuel
(inoculum)
heating
to sprayer
air
bioreactor
blower
Hygienic certificate issued by the National Institute of Hygiene
Reconnaissance
– collecting ground samples
37
38
4 zdjęcia
39
40
Application of microorganisms to the ground
The ground after remediation process
Brzeg
Bagicz
5 000,00 4 000,00 3 000,00 2 000,00 1 000,00
r
t Se p
te
m be
us Au g
ly Ju
e Ju n
ay M
il Ap r
ar ch
0,00
M
TPH mg/kg d.m.
6 000,00
month
Former „Bagicz” air base The original concentration of hydrocarbons in the ground was 2800 – 7250 mg/kg of dry matter Average concentration of the petroleum products after the remediation process according to PN-C-04643 standard was 3 - 15 mg/kg dry matter
• Results from this study suggested that the polluted soil can be a source of active bacteria strains able to degrade the petroleum hydrocarbons. • The ex-situ bioremediation of soil by biopile method carried out involving closed water circulation system was very successful thanks to the use of indigenous strains of bacteria, adapted to the type of pollutants present in the soil. • The bioremediation of soil polluted by petroleum products carried out by biopile method assured elimination of over 90% of pollutants during only few months. The final concentration of pollutants was lowest in the surface layer of piles. This can be associated with better accessibility of air to bacteria capable of degrading hydrocarbons.
Bagicz Warsaw – Arkadia Shopping Center under construction The former polluted areas now
Bagicz
Kluczewo Brzeg
Warsaw – Arkadia Shopping Center, now
Projects • Former Soviet airbase “Bagicz” at the Baltic seaside (North Poland). Petroleum products. Ex situ method. Amount of ground cleaned: 800 m3. • Former Soviet airbase “Szprotawa” . (South-West Poland). Petroleum products. In situ method. Area of 16,8 hectares of ground cleaned. • Fuel storage station in Zielona Góra. Ex situ method. Amount of ground cleaned: 960 m3. • Former Soviet airbase “Brzeg” (South West Poland). Ex situ method. Amount of ground cleaned: 1000 m3. • Military airbase in Wroclaw (South West Poland). Ex situ method. Amount of ground cleaned: 1000 m3. • Railway transshipment station in Warsaw Ground contaminated with toluene, xylene and ethylbenzene. Ex situ method. Amount of ground cleaned: 7000m3. • Military airbase “Królewo Malborskie” (North Poland). The project is being realized recently. Aviation fuel. Ex situ method. Total amount of ground to be cleaned: 9000 m3.
The team
K. Grabas, M. Steininger, I. Pawlak, B. Kołwzan, A. Pawełczyk
ALEXANDER M., 1994, Biodegradation and bioremediation, Academic Press. a Division of Harcout Brace & Company ENVIRONMENTAL PROTECTION AGENCY (EPA ), Exposure Assessment, http://cfpub.epa.gov/ncea/iris/index.cfm?fuseaction=iris.showSubstanceList ENVIRONMENTAL PROTECTION AGENCY (EPAa), 1986, Risk Assessment for Carcinogens, http://www.epa.gov/ttnatw01/toxsource/carcinogens.html GRABAS K., PAWEŁCZYK A., KOŁWZAN B., STEININGER M., 2010, System for remediation of grounds contaminated with hydrocarbons, No. 207080 B1, 29.10.2010 KOŁWZAN B., GRABAS K., ADAMIAK W., PAWEŁCZYK A., 2006, Introduction to environmental microbiology, Publ. House of Wrocław University of Technology ŁEBKOWSKA M., 1996, Wykorzystanie mikroorganizmów do biodegradacji produktów naftowych w srodowisku glebowym, Gaz, Woda i Technika Sanitarna, 3, 117–118 MINISTRY OF HEALTH CARE, (MHC 2007), Poland, Decree from 29/03/2007 on requirements for water quality intended for human consumption, Dz.U. No. 61, item 417 MINISTRY OF ENVIRONMENT, (ME 2002), Poland, Decree from 9/09/2002 on soil and earth quality standards, Dz.U. No. 165, item 1358 & 1359 PAWEŁCZYK A., GRABAS K., KOŁWZAN B., 2001, Question of water-ground environment pollution at former airbases in Bagicz, Brzeg and Kluczewo, Environment Protection., ed. by B. Kozłowska, Publ. House Techn. Univ. Łódź, pp. IX 1–12 PAWEŁCZYK A., GRABAS K., KOŁWZAN B., STEININGER M., 2003, Remediation of grounds at the former Soviet military airfields contaminated by petroleum products, Proc. of 2nd European Bioremediation Conference, Technical University of Crete, Chania, Greece, 184–187 RISK ASSESSMENT INFORMATION SYSTEM (RAIS), http://rais.ornl.gov SAILLENFAIT A.M. et al, Developmental Toxicity of Two Trimethylbenzene Isomers, Mesitylene and Pseudocumene in Rats Following Inhalation Exposure, Food and Chemical Toxicology, vol. 43, issue 7, july 2005, pp 1055–1063 SEATTLE - King County Department of Public Health Report (1997), http://www.areco.org/FuelEssay.pdf SKOLNICK S. R., Exposing Airports' Poison Circles, Earth Island Journal, Winter 2000-2001. Vol. 15, No. 4. http://www.areco.org/ExpAir.pdf SMITH, J. H. ; HARPER, J. C. ; JABER, H., Analysis and environmental fate of Air Force distillate and high density fuels, Technical report SRI International (1981), Air Force Engineering and Services Center, Tyndall Air Force Base, MENLO PARK CA FL. ESL-TR-81-54, pp 150 WINKELMAN G., 1992, Microbial degradation of natural products, ed. by G. Winkelman, VCH Verlags- gesellschaft mbH, Weinheim, New York, Basel, Cambridge ZIÓŁKOWSKA A., WYSZKOWSKI M., 2010, Toxicity of Petroleum Substances to Microorganisms and Plants, Ecological Chemistry and Engineering, Vol. 17, No. 1
