Dissemination patterns and risks impersonated of PAHs contaminated in the surface and subsurface soil

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1 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.

2 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.

3 Avowal Situation

4 History of PAHs 1775: scrotum cancer in London chimney sweeps s: skin cancer : 1922: coal tar induced tumours 1933: Benzo(a)pyrene; 1942: particulate matter 4

5 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

6 PAHs Description

7 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.

8 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

9 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

11 Formed during incomplete burning of Coal Oil Gas Garbage Tobacco Released from : Volcanoes Forest Fires Exhaust

12 Industrial pollution

13 Airborne Fallout to Parking Lots 6% Airborne Fallout to Streets 6% Coal Tar Sealer Washoff 1% Rooftop Runoff 38% Tire Wear 49%

15 Benzo[a]pyrene (BaP)

16 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

17 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

18 Environmental Fate

19 Toxicity of PAHs carcinogenic no toxic effects not even studied mutagenic

20 Health Effects of PAHs

21 Composition of Diesel Exhaust

22 Diesel Exhaust Particles Elemental Carbon (EC) Unburned Fuel PAHs... Dr. John Froines, Director, UCLA Southern California Particulate Center and Supersite Health Effects Institute, 1995

23 How Are We Exposed? Inhalation of air releases Contact with contaminated soil Ingestion of contaminated water or cow s milk

24 How Are We Exposed?

25 Inhalation of PAHs from coal tar sealed pavement

26 PAHs Health Effects

27 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

28 1 1- Release from soil matrix Ingested contaminants? 2- Complexation to organic matter 3- BIOACCESSIBILITY 4- Intestinal absorption 5- Biotransformation 6- BIOAVAILABILITY L I V E R 5 6

29 Urban playground soil sample 25 PAH release estrogenicity µg PAH/L released % EE2 equivalence stomach small intestine colon From: Tom Van de Wiele Univ. of Gent

30 Asthma Epidemic 50 % in Children 100% in Adults

31 Environmental vs. Hereditary Cancer Cancer Etiology Environmental Hereditary

32 Case Study

33 Riyadh capital of Saudi Arabia, Riyadh, Saudi Arabia

34 Riyadh

36 PAHs Methodology Extraction & Cleanup Confirmation Analysis

37 Historical

38 Methodology

40 16 EPA priority PAH pollutants

41 23 PAHs # Compound Rt Target ion Q1 Q2 1 Naphthalene Acenaphthylene Acenaphthene Fluorene Phenanthrene Anthracene Fluoranthene Pyrene Benz[a]anthracene Chrysene Benzo[b+j]fluoranthene Benzo(a)pyrene Benzo[k]fluoranthene methylcholanthrene Dibenz[a,h]acridine Dibenz[a,j]acridine Indeno[1,2,3-cd]pyrene Dibenz[a,h]anthracene H-dibenzo(c,g)carbazole Benzo[ghi]perylene Dibenzo[a.e]pyrene Dibenzo[a,h]pyrene Dibenzo[a,i]pyrene

42 23 PAHs Separation Thermo Scientific TSQ GC-MS system

43 23 PAHs Separation TSQ 8000 GC-MS system

44 23 PAHs and Blank

45 Soil Samples

46 Contour plot Courtesy slide from Jef Focant

47 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

10-15 15-10 -5 g ) (Su 0 5 10 15 Distance (Km) Distance (Km)

sta ce ( ) sta ce ( ace So ) 5 5 sta ce ( t 0 0-5 -5-10 -10-15

48 Distribution of PAHs t/( t y ) (Su t/( ace So ) y ) (Subsu ) sta ce ( ) g ) (Su Distance (Km) Distance (Km) py/( py ace So ) py/( py g ) (Subsu ace So ) ) sta ce ( ) sta ce ( ace So ) 5 5 sta ce ( t Distance (Km) Distance (Km)

49 PAHs Levels in Riyadh Soil

50 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 ± ± ± ± ± ±

51 PAHs in Surface & Subsurface Soil PAHs Compounds Fluoranthene Flt Surface 0-5 cm Subsurface 5-10 cm Max Min Average Max Min Average Pyrene Pyr Benzo(a)pyrene BaP, Benzo(k)fluoranthene BkF Indeno(1,2,3-cd)pyrene IP Benzo (g,h,i) perylene BgP

53 Austin Waterbody PAH Levels 250 Conc. (mg/kg) Sediment measurements typical rdemott@environcorp.com

54 Publications

55 Acknowledgment (NSTIP) MRs. Friederike Jockwer, on behalf of the organizing committee Dr. Milos Korman, Sales Manager Distributers, Chromatography

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