occurrence and distribution of oxygenated polycyclic...
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Occurrence and Distribution of Oxygenated Polycyclic Aromatic Hydrocarbons (Oxy-PAHs) in Soils of an Australian Industrial City Oluyoye IDOWU Global Centre for Environmental Remediation (GCER) University of Newcastle, Australia
Presentation Outline
Introduction Methods Results References
Introduction
Polycyclic AromaticCompounds (PACs)
Oxygenated PAHs
Oxy-PAHs
Aromatic CompoundsPolycyclic Aromatic
Hydrocarbons (PAHs)
Other Polycyclic
Nitrated PAHs (NPAHs)
N/S/O heterocycles
Polar Polycyclic Aromatic Compounds
(POLAR PACs)
Not Only PAHs…
Greater mobility and
bioavailability…
Biogenic Sources
Pyrogenic Sources
Petrogenic Sources
Organic Matter
Mineral Fraction
Surface SorptionDiffusion
into pores
Diffusion of more hydrophobic polar PAHs into rubbery and
glassy soil organic matter (Non-bioavailable fraction)
Microbial Degradation
SOIL
Volatilisation
Leaching of less hydrophobic/bioavailable polar PAHs into sub-soil and underground water
Particulate Matter deposition on plant
leaves and soil
Atmospheric gas and particulate matter partitioning
Plant uptake of bioavailable polar PAHs
Increased environmental and human health risk?
Idowu et al., 2019a
Direct toxic effects…
Idowu et al., 2019a
• Skin and lungs• Gastrointestinal tractAbsorption
• Cells• TissuesDistribution
Storage • Kidneys, liver and adipose tissues• Spleen adrenal glands and ovary
Metabolism To increase contaminant polarity and facilitate excretion
Excretion
Indirect toxic effects
(Homocyclicand Heterocyclic
PAHs)
Direct toxic effects (Oxy-PAHs and N-
PAHs)
Final stage of the elimination process of polar and non polar PAHs from the body
Oxidative Protein Damage
DNA DamageLipid
PeroxidationDNA Adducts
Formation
Direct toxic effects (Oxy-PAHs and
N-PAHs)
Indirect toxic effects
(Homocyclic and Heterocyclic PAHs)
Soil sampling Locations
Methodology
Idowu et al., 2019b
Exhaustive Extraction
Soil Sampling
Fractionation and Clean-up
GC/MS Analysis
Consult Idowu et al., 2019b for detailed methodology
RESULTS AND DISCUSSION
Physicochemical Properties of Representative Soils
Percent contribution of PAHs and oxy-PAHs to total concentrations per land use
Industrial Smoking area Recreational Residential0
20
40
60
80
100
Perc
ent C
ontri
butio
n to
∑13
PAH
s
Land use
I(CD)P D(AH)A B(A)P B(B/K)F CHRY B(A)A PYR FLUA ANTH PHEN FLU ACEN ACENY
Industrial Smoking area Residential Recreational0
20
40
60
80
100
Per
cent
Con
tribu
tion
to ∑
7oxy
-PA
Hs
Land use
1,4-NQ 9-FLO9,10-ANQ 2-MAQ 2-EAQ2,3-DMAQ7H-BANT
Concentrations(µg/g) of oxy/parent PAHs in Newcastle soils
∑7oxy-PAHs ∑13PAHs
Industrial 3.9 94.5
Recreational 1.5 20.5
Smoking 0.6 4.7
Residential 3.1 5.4
Concentration profile of oxy/parent PAHs
Reported occurrence levels of oxy-PAHs (mean concentrations ng/g d.w.) Analyte This study Other studies Industrial
soil Smoking zone soil
Residential soil
Recreational soil
1,4-NQ
705
163
1193
703
6.9 (U)4, 0.5(U)6, 2720 (S)7
9-FLO 783 289 1990 572 3.7(A)4, 603.8(U)8, 8992(I)9 26000(G)5, 9.4(U)6, 4990 (S)7
9,10-ANQ 525 39.1 329 73.5 7.1(A)4, 56.8(G)9, 24000(G)5 35.6(U)10, 12.2 (U)6, 14100 (S)7
2-EAQ 181 39.7 47.4 37.1 2-MAQ 137 49.8 5.85 31.9 5500 (G)9, 7.3(U)6 2,3-DMAQ 156 36.5 4.79 23.9 7H-BANT 1436 26.6 79.4 74.3 11.2(U)9, 18000 (G)5, 12.6(U)6
Conclusion • Concentrations of oxy-PAHs in soils were much lower than that of
parent PAHs across all the land uses. • Analysed soil concentrations of oxy-PAHs were comparatively higher
than concentrations from agricultural, urban and industrial areas of other parts of the world.
• Analysed soil concentrations of oxy-PAHs were lower than concentrations in historically contaminated soils such as former gaswork and superfund sites.
• High oxy-PAH concentrations in soils across land uses may have high implications from the perspective of human health risks.
References
1.Idowu, O.; Semple, K. T.; Ramadass, K.; O'Connor, W.; Hansbro, P.; Thavamani, P., Beyond the obvious: Environmental health implications of polar polycyclic aromatic hydrocarbons. Environ. Int. 2019a, 543-557. 2.Idowu, O.; Semple, K. T.; Ramadass, K.; O'Connor, W.; Hansbro, P.; Thavamani, P., Analysis of polycyclic aromatic compounds (PACs) in soils of an industrial heritage city of Australia. Sci. Total Environ. 2019b 3.Cai, C.; Li, J.; Wu, D.; Wang, X.; Tsang, D. C. W.; Li, X.; Sun, J.; Zhu, L.; Shen, H.; Tao, S.; Liu, W., Spatial distribution, emission source and health risk of parent PAHs and derivatives in surface soils from the Yangtze River Delta, eastern China. Chemosphere 2017, 178, 301-308. 4.Sun, Z.; Zhu, Y.; Zhuo, S.; Liu, W.; Zeng, E. Y.; Wang, X.; Xing, B.; Tao, S., Occurrence of nitro- and oxy-PAHs in agricultural soils in eastern China and excess lifetime cancer risks from human exposure through soil ingestion. Environ. Int. 2017, 108, 261-270. 5.Wei, C.; Bandowe, B. A. M.; Han, Y.; Cao, J.; Zhan, C.; Wilcke, W., Polycyclic aromatic hydrocarbons (PAHs) and their derivatives (alkyl-PAHs, oxygenated-PAHs, nitrated-PAHs and azaarenes) in urban road dusts from Xi'an, Central China. Chemosphere 2015, 134, 512-520. 6.Musa Bandowe, B. A.; Wei, C.; Han, Y.; Cao, J.; Zhan, C.; Wilcke, W., Polycyclic aromatic compounds (PAHs, oxygenated PAHs, nitrated PAHs and azaarenes) in soils from China and their relationship with geographic location, land use and soil carbon fractions. Sci. Total Environ. 2019, 690, 1268-1276. 7.Trine, L. S. D.; Davis, E. L.; Roper, C.; Truong, L.; Tanguay, R. L.; Simonich, S. L. M., Formation of PAH Derivatives and Increased Developmental Toxicity during Steam Enhanced Extraction Remediation of Creosote Contaminated Superfund Soil. Environ. Sci. Technol. 2019, 53, (8), 4460-4469. 8.Arp, H. P. H.; Lundstedt, S.; Josefsson, S.; Cornelissen, G.; Enell, A.; Allard, A. S.; Kleja, D. B., Native oxy-PAHs, N-PACs, and PAHs in historically contaminated soils from Sweden, Belgium, and France: Their soil-porewater partitioning behavior, bioaccumulation in Enchytraeus crypticus, and bioavailability. Environ. Sci. Technol. 2014, 48, (19), 11187-11195. 9.Lundstedt, S. Analysis of PAHs and their transformations products in contaminated soil and remedial processes. Doctoral thesis, comprehensive summary, Kemi, Umeå, 2003. 10.Niederer, M., Determination of polycyclic aromatic hydrocarbons and substitutes (Nitro-, Oxy-PAHs) in urban soil and airborne particulate by GC-MS and NCI-MS/MS. Environ. Sci. Pollut. Res. 1998, 5, (4), 209.
Acknowledgement
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