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

Thank you for listening.