Dissemination patterns and risks impersonated of PAHs contaminated in the surface and subsurface soil Mohamed H. EL-Saeid Professor King Saud University, Riyadh, Kingdom of Saudi Arabia 4/29/2015
Pollution exterminates more than ailments PAHs are a type of organic compounds that are produced when complex organic substances are exposed to incomplete combustion or high-pressure processes. PAHs in the environment are found primarily in soil, sediment and oily substances, as opposed to in water or air. However, they are also a component of concern in particulate matter suspended in air. Why PAHs: known carcinogens & chronic PAH toxicity may lead to increased risk for cancer such as skin, lung, bladder, liver & stomach cancer Around the world 40% of death due to environment pollution problem and major PAHs are one of the major contributors.
Avowal Situation
History of PAHs 1775: scrotum cancer in London chimney sweeps. 1880 s: skin cancer 1915-18: 1922: coal tar induced tumours 1933: Benzo(a)pyrene; 1942: particulate matter 4
1949: B(a)p 1952: B(a)P f 1954: ambient particulates 1970s: organic extracts of ambient and primary combustion particles nitro-pah and oxy-pah 5
PAHs Description
The main pathway of carcinogenesis is through PAH metabolite interaction with DNA. travel quickly into cells. CYP450 enzymes them more water soluble. genetic damage before they can be removed.
Sources of PAHs chain food Source % Heating, power production 51 Industrial producers 20 Incineration & open burning 28 Vehicles 1 B(a)P in foodstuffs μg/kg Charcoal broiled steak 8 Margarine 1-36 Sausages 4-50 Roasted coffee 1-13 Toast 0.5
Emissions From Biomass Burning Particulate Matter CO, NO X, SO 2, O 3 Resin acids PAHs and alkyl PAHs Anhydrosugars, e.g. levoglucosan PCDD and PCDF Alkyl amides and nitriles Many others Methoxyphenols
Formed during incomplete burning of Coal Oil Gas Garbage Tobacco Released from : Volcanoes Forest Fires Exhaust
Industrial pollution
Airborne Fallout to Parking Lots 6% Airborne Fallout to Streets 6% Coal Tar Sealer Washoff 1% Rooftop Runoff 38% Tire Wear 49%
Benzo[a]pyrene (BaP)
Environmental Fate Usually enter air when released to the environment, often attaching to particles in air. Can be transported far from their sources. Do not dissolve in water but stick to soil or sediment to be found at the bottom of lakes. Some can be transported into groundwater. Higher concentrations in urban areas than rural areas PAHs are quite persistent in the environment and can bioaccumulate PAHs break down by photolysis and chemical reaction over days and weeks Microorganisms also break down PAHs over time
Environmental Fate PAHs can breakdown by reacting with sunlight and other chemicals (OH radicals) in the air over days to weeks Besides B(a)P, other PAHs are emitted or formed in the atmosphere which account for additional mutagenicity. Gas-phase reactions can convert volatile PAHs to nitro- PAHs and nitro-pah lactones, which are strong "direct-acting" mutagens The presence of nitro-pah lactones formed in the atmosphere contributes significantly to the mutagenicity of ambient air Several reaction products of B(a)P and ozone are strong mutagens a major contributor has been identified as benzo[a]pyrene-4,5-oxide, an animal metabolite, which is a strong direct mutagen
Environmental Fate
Toxicity of PAHs carcinogenic no toxic effects not even studied mutagenic
Health Effects of PAHs
Composition of Diesel Exhaust
Diesel Exhaust Particles Elemental Carbon (EC) Unburned Fuel PAHs... Dr. John Froines, Director, UCLA Southern California Particulate Center and Supersite Health Effects Institute, 1995
How Are We Exposed? Inhalation of air releases Contact with contaminated soil Ingestion of contaminated water or cow s milk
How Are We Exposed?
Inhalation of PAHs from coal tar sealed pavement
PAHs Health Effects
lung cancer In the United States, incidence of lung cancer has decreased significantly by 1.8% per year from 1991 to 2005 among men. increased significantly by 0.5% per year from 1991 to 2005 among women. CDC site on lung cancer http://www.cdc.gov/cancer/lung/
1 1- Release from soil matrix Ingested contaminants? 2- Complexation to organic matter 3- BIOACCESSIBILITY 4- Intestinal absorption 5- Biotransformation 6- BIOAVAILABILITY 2 3 4 L I V E R 5 6
Urban playground soil sample 25 PAH release estrogenicity µg PAH/L released % EE2 equivalence 20 15 10 5 0 stomach small intestine colon From: Tom Van de Wiele Univ. of Gent
Asthma Epidemic 50 % in Children 100% in Adults
Environmental vs. Hereditary Cancer 100 85 80 60 40 20 0 15 Cancer Etiology Environmental Hereditary
Case Study
Riyadh capital of Saudi Arabia, Riyadh, Saudi Arabia
Riyadh
PAHs Methodology Extraction & Cleanup Confirmation Analysis
Historical
Methodology
16 EPA priority PAH pollutants
23 PAHs # Compound Rt Target ion Q1 Q2 1 Naphthalene 8.46 128 129 127 2 Acenaphthylene 12.13 152 153 151 3 Acenaphthene 12.55 154 153 152 4 Fluorene 13.79 166 165 163 5 Phenanthrene 16.07 178 176 179 6 Anthracene 16.19 178 176 179 7 Fluoranthene 18.90 202 200 203 8 Pyrene 19.43 202 200 203 9 Benz[a]anthracene 22.32 228 229 226 10 Chrysene 22.40 228 226 229 11 Benzo[b+j]fluoranthene 24.74 252 253 250 12 Benzo(a)pyrene 24.78 252 253 250 13 Benzo[k]fluoranthene 25.38 252 253 250 14 3-methylcholanthrene 26.10 268 269 266 15 Dibenz[a,h]acridine 27.22 279 280 278 16 Dibenz[a,j]acridine 27.32 279 280 278 17 Indeno[1,2,3-cd]pyrene 27.69 276 277 274 18 Dibenz[a,h]anthracene 27.77 278 276 279 19 7H-dibenzo(c,g)carbazole 28.17 267 265 268 20 Benzo[ghi]perylene 28.30 276 277 274 21 Dibenzo[a.e]pyrene 32.41 302 303 300 22 Dibenzo[a,h]pyrene 32.77 302 303 300 23 Dibenzo[a,i]pyrene 32.95 302 303 300
23 PAHs Separation Thermo Scientific TSQ GC-MS system
23 PAHs Separation TSQ 8000 GC-MS system
23 PAHs and Blank
Soil Samples
Contour plot Courtesy slide from Jef Focant
Contour plot Shade surface plot Courtesy slide from Jef Focant
Distribution of PAHs t/( t y ) (Su t/( ace So ) 15 15 10 10 y ) (Subsu ) sta ce ( ) 0 0-5 -5-10 -10-15 -15-15 -10-5 5 0 10-15 15-10 -5 g ) (Su 0 5 10 15 Distance (Km) Distance (Km) py/( py ace So ) py/( py 15 10 5 5 g ) (Subsu ace So ) ) 15 10 sta ce ( ) sta ce ( ace So ) 5 5 sta ce ( t 0 0-5 -5-10 -10-15 -15-15 -10-5 0 Distance (Km) 5 10 15-15 -10-5 0 Distance (Km) 5 10 15
PAHs Levels in Riyadh Soil
Results PAHs RT (min) Recovery% SD LOD LOQ Fluoranthene Flt Pyrene Pyr Benzo(a)pyrene BaP, Benzo(k)fluoranthene BkF Indeno(1,2,3-cd)pyrene IP Benzo (g,h,i) perylene BgP 18.899 19.423 24.728 25.376 27.688 28.302 98.89 ±2.46 7.391 0.301 103.53 ±2.36 7.077 0.325 96.43 ±2.44 7.306 0.997 96.64 ±3.75 6.237 1.124 99.04 ±8.14 4.423 3.890 97.16 ±7.87 5.611 1.302
PAHs in Surface & Subsurface Soil PAHs Compounds Fluoranthene Flt Surface 0-5 cm Subsurface 5-10 cm Max Min Average Max Min Average 129.9 2 75.52 172.3 2 70.69 Pyrene Pyr 189.9 2 87.95 211.9 2 75.97 Benzo(a)pyrene BaP, 112.6 3.7 10.64 112.6 3.9 17.91 Benzo(k)fluoranthene BkF 166 2 18.07 185.2 2 25.42 Indeno(1,2,3-cd)pyrene IP Benzo (g,h,i) perylene BgP 311.4 4.4 22.11 559.9 3.6 30.60 373.9 2 74.64 371.4 10.3 68.22
Austin Waterbody PAH Levels 250 Conc. (mg/kg) 200 150 100 50 0 Sediment measurements typical rdemott@environcorp.com
Publications
Acknowledgment (NSTIP) MRs. Friederike Jockwer, on behalf of the organizing committee Dr. Milos Korman, Sales Manager Distributers, Chromatography