Occurrence and distribution of PAHs in rainwater and urban runoff

OCCURRENCE AND DISTRIBUTION OF PAHs IN RAINWATER AND URBAN RUNOFF ELISABETH RIANAWATI NATIONAL UNIVERSITY OF SINGAPORE 2007 OCCURRENCE AND DISTRIBUTION OF PAHs IN RAINWATER AND URBAN RUNOFF ELISABETH RIANAWATI (B Eng., ITB) A THESIS SUMBITTED FOR THE DEGREE OF MASTER OF ENGINEERING DIVISION OF ENVIRONMENTAL SCIENCE AND ENGINEERING NATIONAL UNIVERSITY OF SINGAPORE 2007 ACKNOWLEGEMENT I would like to express my gratefulness and sincere thanks to Dr R Balasubramanian for his supervision, valuable comments and indispensable support throughout the research period A deep gratitude is dedicated to AUN/Seed-Net JICA who has provided me the opportunity of a lifetime to pursue master degree I also acknowledge the effort of Dr S Karthikeyan, who patiently gave guidance to me during this research The meteorological data were provided by a meteorology lab monitoring of Geography Department in NUS administrated by Matthias Roth I appreciate the assistance of the lab members: Umid M.J, He Jun, Q.T Augustine and especially S.S.W Ellis who provided significant insights in many ways I acknowledge the generous and excellent assistance given by Hannah Foong and S Venkatesa P who personally dealt with the submission procedure while I was away; and to lab officer Sukiantor bin Tokiman and M Sidek who created the best working environment ever Sincere thanks are dedicated to Julia Ho for her competent editorial assistance, to Lilian Lee and N Aini Masruroh who have given immeasurable and substantial help throughout the making of the manuscript Special gratitude is dedicated for my Father and Mother and parents in law for their unceasing love and comfort and for Debora Pujiyanti, whose assistance enabled me able to concentrate fully on the manuscript I cherish the warm care of Han Seo Eun and Hanna Kurniawati; and the constant support of Lina M.Setiowati and Joshua B.N.Situmorang Mostly, I am forever debt to my husband Saut Sagala who has sustained my being and selflessly sacrificed for the completion of this manuscript Lastly, I dedicate this thesis, with all the effort and time invested for it, to my Lord Jesus Christ i TABLE OF CONTENTS Pages ACKNOWLEDGEMENTS i TABLE OF CONTENTS ii SUMMARY vi NOMENCLATURE viii LIST OF TABLES x LIST OF FIGURES xi CHAPTER 1 INTRODUCTION 1.1 Introduction 1.2 Motivation of study 1.3 Objectives and scope 1.4 Structure of the thesis CHAPTER LITERATURE REVIEW 2.1 Introduction 2.2 Physical and Chemical Properties 11 2.3 Environmental Fate of PAHs 12 2.3.1 PAHs in the atmosphere 13 2.3.2 PAHs in the hydrosphere 14 2.4 Sources of PAHs 16 2.4.1 Domestic and residential heating 17 2.4.2 Municipal waste incinerator 17 2.4.3 Petroleum refineries 18 2.4.4 Open burning 18 2.4.5 Traffic related activities 19 2.5 Source Apportionment 20 ii 2.5.1 LMW/HWM relative proportion 20 2.5.2 Ratio of isomer concentration 22 2.5.2.1 Ant/Ant+PA ratio (mass 178) 22 2.5.2.2 Flt/Flt+Pyr ratio (mass 202) 23 2.5.2.3 BaA/BaA+Cyr ratio (mass 228) 23 2.5.2.4 IND/IND+BghiP ratio (mass 276) 25 2.5.2.5 Other mass 26 2.5.3 PAHs profiles 26 2.6 Analytical Techniques 28 2.7 Summary 31 CHAPTER EXPERIMENTAL DETAILS 33 3.1 Background information 33 3.2 Sample Collection and Preservation 34 3.2.1 Collection of Rainwater Samples 34 3.2.2 Collection of Stormwater Samples 35 3.3 Chemical Analysis 36 3.3.1 Standards 36 3.3.2 Instrumentation 37 3.3.2.1 SPME Devices 37 3.3.2.2 Gas Chromatography – Mass Spectroscopy (GC-MS) 37 3.3.2.3 Microwave Assisted Extraction (MAE) 38 3.3.3 Calibration and Recovery Tests 39 3.3.4 Detection Limits 40 3.3.5 Analytical Quality Assurance 41 CHAPTER METHOD DEVELOPMENT OF SOLID PHASE MICROEXTRACTION (SPME) 4.1 Introduction 43 43 iii 4.2 4.3 4.4 Optimization of SPME Parameters 44 4.2.1 Extraction Time 44 4.2.2 Water Temperature 47 4.2.3 Stirring Speed 50 4.2.4 Ionic Strength 52 4.2.5 pH 54 4.2.6 Desorption Time and Carry Over 56 SPME Validation 57 4.3.1 Enrichment Factor 57 4.3.2 Linearity, reproducibility and limit of detection (LOD) 57 4.3.3 Applicability of SPME in Rainwater and Stormwater Samples 61 4.3.3.1 Linearity in sample matrix 61 4.3.3.2 SPME recovery of PAHs 63 Conclusion CHAPTER 65 PAHS OCCURRENCE AND DISTRIBUTION IN RAINWATER 67 5.1 Introduction 67 5.2 PAHs Concentration in Singapore Rainwater 68 5.2.1 Dissolved Phase 68 5.2.2 Particulate Phase 73 5.2.3 Comparison with Studies in Literature 74 5.3 Temporal Variation 76 5.3.1 Rainwater deposition flux 78 5.3.2 Impact of meteorological parameters 82 5.4 Source Apportionment 93 5.4.1 Pearson Correlation Matrix 94 5.4.2 Diagnostic ratio of PAHs isomers 96 5.5 Conclusion 99 iv CHAPTER PAHS OCCURRENCE AND DISTRIBUTION IN STORMWATER 101 6.1 Introduction 101 6.2 PAHs Concentration in Singapore Stormwater 102 6.2.1 Dissolved Phase 102 6.2.2 Particulate Phase 105 6.2.3 Comparison with Studies in Literature 107 6.3 Temporal Variation 110 6.3.1 Stormwater flux 110 6.3.2 Impact of meteorological parameters 112 6.4 Source Apportionment 116 6.4.1 Pearson Correlation Matrix 116 6.4.2 Diagnostic ratio of PAHs isomers 118 6.4.3 PAHs composition 123 6.4.3.1 PAHs profile 123 6.4.3.2 LMW-HMW relative proportion 125 6.5 Conclusion CHAPTER CHAPTER 127 CONCLUSION RECOMMENDATION FOR FURTHER STUDY 128 132 REFERENCES 133 APPENDIX A 163 APPENDIX B 168 APPENDIX C 170 v SUMMARY Polycyclic aromatic hydrocarbons (PAHs) have received considerable attention in scientific communities during the past few decades because of their ubiquitous presences and carcinogenic properties PAHs are formed mainly by thermal decomposition of organic compounds consisting of hydrogen and carbon PAHs are introduced into the environment by natural and anthropogenic sources Natural sources (e.g forest fires and volcanoes) are minor contributors in comparison to the anthropogenic sources (e.g emissions from vehicles, power plants, incinerators, petroleum refineries) In order to fully comprehend the occurrence and distribution of PAHs in Singapore’s water systems, the composition of PAHs in rainwater and stormwater were studied in detail While wet deposition is a main route by which PAHs are removed from the atmosphere, urban runoff is a main pathway by which PAHs are transferred from the geosphere to the hydrosphere The PAHs concentration in Singapore’s rainwater was investigated under a variety of atmospheric conditions from July 2005 to January 2006, whereas stormwater samples were collected during October 2005 to March 2006 Altogether, 40 rain events and 55 storm events were sampled and characterized at the Atmosphere Research Station, NUS, and at the boundary shoulder of Ayer Rajah Expressway (AYE), respectively In order to assess the occurrence and distribution of PAHs in environmental matrices, an organic extraction method, solid phase micro-extraction (SPME), was optimized based on five parameters: extraction time, temperature, salt concentration, pH and stirring speed The optimized SPME method was found to extract PAHs efficiently from rainwater and stormwater dissolved-phase Particulate-bound PAHs were analyzed using microwave assisted extraction (MAE) system, while the chemical analysis utilized gas chromatography coupled with mass spectrometry (GC-MS) The PAHs observed in this study were the 16 priority compounds listed by USEPA (1992): naphthalene (Nap), acenaphthylene (Acy), acenaphthene (Ace), fluorene (Flu), phenanthrene (PA), anthracene (Ant), fluoranthene (Flt), pyrene (Pyr), benz[a]anthracene (BaA), chrysene (Cry), benzo[b]fluoranthene (BbF), vi benzo[k]fluoranthene (BkF), benzo[a]pyrene (BaP), dibenz[a,h]anthracene (DBA), indeno[1,2,3c,d]pyrene (IND) and benzo[g,h,i]perylene (BghiP) The total PAHs concentrations in the dissolved and particulate phase of rainwater were 2,408 ± 899 and 1,847 ± 414 ng/l, respectively Similarly, the concentrations of PAHs in dissolved and particulate phases of stormwater were 1,143 ± 498 ng/l and 8,164 ± 3,063 ng/l, respectively The concentration and composition of PAHs in Singapore’s rainwater and stormwater were compared to those reported for other countries in Europe and North America The dissolved phase of rainwater and stormwater were dominated by low molecular weight (LMW) PAHs, particularly Nap, whereas the particulate phase in both matrices had relatively equal abundance of LMW and high molecular weight (HMW) PAHs The level of PAHs in the particulate phase was higher than of the dissolved phase in stormwater On the other hand, higher level of PAHs was found in the dissolved phase of rainwater compared to those in the particulate phase A temporal variation in the concentration of PAHs was found in the rainwater, which exhibited a peak concentration during the beginning of rain season in October This trend could be due to stronger emissions of PAHs from their corresponding sources in conjunction with the prevailing weather conditions including the intensity of rainfall A comprehensive statistical analysis of the concentrations data indicated that the PAHs measured in Singapore rainwater and stormwater originated from anthropogenic sources, particularly from local traffic related activities vii NOMENCLATURE Abbreviations Ace Acenapthene Acy Acenapthylene Ant Anthracene AYE Ayer Rajah Expressway BaA Benz[a]anthracene BaP Benzo[a]pyrene BbF Benzo[b]fluoranthene BghiP Benzo[g,h,i]perylene BkF Benzo[k]fluoranthene Ca eq Concentration of analyte in aqueous phase at equilibrium Co eq Concentration of analyte in the fiber at equilibrium cp PAHs concentration in precipitation Cyr Chrysene DBA Dibenz[a,h]anthracene Ef Enrichment Factor Fd Precipitation flux Flt Fluoranthene Flu Fluorene FoE Faculty of Engineering GCMS Gas chromatography mass spectrophotometry Hf Heat of formation HMW High molecular weight compounds IND Indeno[1,2,3-c,d]pyrene Koc Organic-aqueous partition coefficient viii Reference DC, for the Office of Transportation and Air Quality; EPA/600/8-90/057F Available from: National Technical Information Service, Springfield, VA; PB2002-107661, and United States of Environmental Protection Agency, USEPA Locating and estimating air emissions from sources of polycyclic organic matter Office of Air Quality Planning and Standards, U.S EPA-454/R-98-014 (1998) USEPA, Methods for the determination of metals in environmental samples, U.S Environmental Protection Agency, Cincinnati (1992) 339 USEPA Results of the Nationwide Urban Runoff Program (1993) Valor, I., Molto´, J.C., Apraiz, D., Font, G Matrix effects on solid-phase micro-extraction of organophosphorus pesticides from water J Chromatogr A 767 (1997), pp 195-203 Van Jaarsveld, J.A.,Van Pul, W.A.J.,De Leeuw,F.A.A.M Modelling transport and deposition of persistent organic pollutants in the European region Atmospheric Environment 31 (1997), pp 1111–1124 Van Metre P.C., B.J Mahler and E.T Furlong, Urban sprawl leaves its PAH signature Environ Sci Technol 34 (2000), pp 4064–4070 Van Metre PC, BJ Mahler, The Contribution of Particles Washed from Rooftops to Contaminant Loading to Urban Streams., Chemosphere 52 (2003) 1727-1741 Van Noort PCM & Wondergem E Scavenging of airborne polycyclic aromatic hydrocarbons by rain Environ Sci Technol, 19 (1985b), pp 1044-1048 157 Reference Van Noort PCM & Wondergem E The isolation of some polynuclear aromatic hydrocarbons from aqueous samples by means of reversed-phase concentrator columns Anal Chim Acta, 172 (1985a), pp 335-340 Venkataraman, C., Friedlander, S.K Source resolution of fine particulate PAHs using a receptor model modified for reactivity Journal of Air and Waste Management Association 44 (1994), pp 1103–1108 Verschueren, K Handbook of Environmental Data on Organic Chemicals, 2nd edition Van N Reinhold Co New York, NY (1983) Vilanova, R.M., Ferna´ndez, P., Martı´nez, C., Grimalt, J Polycyclic aromatic hydrocarbons in remote mountain lake waters Water Res 35 (2001), pp 3916–3926 Vogt NB, Brakstad F, Thrane K Polycyclic aromatic hydrocarbons in soil and air: Statistical analysis and classification by the SIMCA method Environ Sci Technol 21 (1987), pp 35-44 Wakeham S.G., C Schaffner and W Geiger, Polycyclic aromatic hydrocarbons in Recent lake sediments- I Compounds having anthropogenic origins Geochim Cosmochim Acta 44 (1980), pp 403–413 Walker, William, Richard P McNutt and CarolAnn K Maslanka The potential contribution of urban runoff to surface sediments of the Passaic river: sources and chemical characteristics Chemosphere, 38 (1999), 363-377 Walters RW & Luthy RG Liquid/suspended solid phase partitioning of polycyclic aromatic hydrocarbons in coal coking wastewaters Water Res, 18 (1984), pp 795-809 Wang J., C.R Jia, C.K Wong and P.K Wong, Characterisation of polycyclic aromatic hydrocarbons created in lubricating oils, Water Air Soil Pollut 120 (2000), pp 381–396 158 Reference Wang Z., M Fingas, Y.Y Shu, L Sigouin, M Landriault, P Lambert, R Turpin, P Campagna and J Mullin , Quantitative characterization of PAHs in burn residue and soot samples and differentiation of pyrogenic PAHs from petrogenic PAHs—the 1994 Mobile burn study Environ Sci Technol 33 (1999), pp 3100–3109 Wang, Z., Fingas, M., Landriault, M., Sigouin, L., Feng, Y and Mullin, J Using systematic and comparative analytical data to identify the source of an unknown oil on contaminated birds J Chromatogr 775 (1997), pp 251–265 Warman, Kristofer Improved two-dimensional gas chromatographic method for the separation of products from the analytical pyrolysis of coal Journal of Analytical and Applied Pyrolysis, (1984), pp.137-143 Wercinski, Sue Ann and J Pawliszyn Solid Phase Microextraction Theory Book Chapter 1: Wercinski, Sue Ann Solid Phase Microextraction, A Practical Guide New York: Marcel Dekker, Inc (1998), pp 1-26 Westerholm R and Li H A multivariant statistical analysis of fuel-related polycyclic aromatic hydrocarbon emissions from heavy-duty diesel vehicles Environ Sci Technol 28(1994), pp 965-972 Westerholm R N., J Alment, H Li, H Ulf Rannug, K E Egeback and K Gragg, Environ Sci Technol., 25 (1991), pp 332-338 Westerholm R.N., A Christensen, M Törnqvist, L Ehrenberg, U Rannug, M Sjögren, J Rafter, C Soontjens, J Almén and K Grägg , Comparison of exhaust emissions from Swedish Environmental Classified Diesel Fuel (MK1) and European Program on Emissions, Fuels and Engine Technologies (EPEFE) reference fuel: a chemical and biological 159 Reference characterization, with viewpoints on cancer risk Environ Sci Technol 35 (2001), pp 1748– 1754 White JB, Vanderslice RR POM source and ambient concentration data: Review and analysis Washington, D.C U.S Environmental Protection Agency, Office of Research and Development EPA-600/7-80-044 (1980) Wild SR, Berrow ML, McGrath SP Polynuclear aromatic hydrocarbons in crops from longterm field experiments amended with sewage sludge Environ Poll 76 (1992), pp.25-32 Williams PT, Taylor DT Aromatization of tire pyrolysis oil to yield polycyclic aromatic hydrocarbons Fuel 72 (1993), pp 1469-1474 Williams R, Meares J, Brooks L Priority pollutant PAH analysis of incinerator emission particles using HPLC and optimized fluorescence Int J Environ Anal Chem 54 (1994), pp.`:299-314 Williams, P.T., Bartle, K.D., Andrews, G.E The relation between polycyclic aromatic compounds in diesel fuels and exhaust particulates Fuel 65 (1986), 1150–1158 Windsor JG, Hites RA Polycyclic aromatic hydrocarbons in Gulf of Maine sediments and Nova Scotia sils Geochim Cosmochim Acta 43 (1979), pp.27-33 Wise, S.A., Hilpert, L.R., Rebbert, R.E., Sander, L.C., Schantz, M.M., Chesler, S.N., May, W.E Standard reference materials for the determination of the polycyclic aromatic hydrocarbons Fresenius J Anal Chem 332 (1988b), pp 573–582 World Health Organization (WHO) Emissions of Heavy Metal and PAH compounds from Municipal Solid Waste Incinerators Control Technology and Health Effects WHO Regional Office for Europe Copenhagen, Denmark (1988) 160 Reference Yang S.Y.N., Connell D.W., Hawker D.W Polycyclic aromatic hydrocarbons in air soil and vegetation in the vicinity of an urban roadway Sci Total Environ 102 (1991), pp 229-240 Yang, X., and T Peppard, LC-GC, 882 (1995), pp 13s Yunker M.B and R.W Macdonald , Composition and origins of polycyclic aromatic hydrocarbons in the Mackenzie River and on the Beaufort Sea shelf Arctic 48 (1995), pp 118–129 Yunker M.B., F.A McLaughlin, R.W Macdonald, W.J Cretney, B.R Fowler and T.A Smyth, Measurement of natural trace dissolved hydrocarbons by in situ column extraction: an intercomparison of two adsorption resins Anal Chem 61 (1999), pp 1333–1343 Yunker Mark B., Robie W Macdonald, Roxanne Vingarzan, Reginald H Mitchell, Darcy Goyette and Stephanie Sylvestre PAHs in the Fraser River basin: a critical appraisal of PAH ratios as indicators of PAH source and composition Organic Geochemistry, 33 (2002) pp 489-515 Yunker, M.B., Snowdon, L.R., Macdonald, R.W., Smith, J.N., Fowler, M.G., Skibo, D.N., McLaughlin, F.A., Danyushevskaya, A.I., Petrova, V.I., Ivanov, G.I Polycyclic aromatic hydrocarbon composition and potential sources for sediment samples from the Beaufort and Barents Seas Environ Sci Technol 30 (1996), 1310–1320 Zhang X, Christensen ER, Yan L Fluxes of polycyclic aromatic hydrocarbons to Green Bay and Lake Michigan Sediments J Great Lakes Res 19 (1993), pp 429-444 Zhang Z., M.J Yang and J Pawliszyn, Solid-phase microextraction, Anal Chem 66 (1994), pp 844A–853A 161 Reference Zhu L, Baoliang Chen, J Wang, H Shen Pollution survey of polycyclic aromatic hydrocarbons in surface water of Hangzhou, China Chemosphere 56 (2004), pp 1085-1095 162 % to Total PAH 0% 5% 10% 15% 20% 25% 30% 35% Ace Ant Cry IND Fuel Oil Flu Pyr BkF BghiP Urban Dust SRM 1649 Acy Flt BbF DBA Particulate Rainwater Dissolved Particulate Stormwater Dissolved Figure A.1 Comparison of PAHs profile in rainwater and stormwater (dissolved and particulate phase) with PAHs profile from South Carolina (Ngabe et al., 2000) Crankcase Oil Nap PA BaA BaP Appendix A - PAHs profile in rainwater and stormwater - Appendix A Comparison of PAHs profile in the rainwater and Stormwater with those in the literature 163 % to Total PAH 0% 5% 10% 15% 20% 25% 30% 35% 40% Cry BaA BkF Flu Peat Fire BbF Acy IND Ant Dissolved BaP PA BghiP Pyr Rainwater Particulate DBA Flt Particulate Stormwater Dissolved Figure A.2 Comparison of PAHs profile in rainwater and stormwater (dissolved and particulate phase) with PAHs profile incinerator (Lee et al., 2002) and peat combustion (See et al., 2006) Incinerator Ace Nap Appendix A - PAHs profile in rainwater and stormwater - 164 % to Total PAH 0% 10% 20% 30% 40% 50% 60% Tire S1 S3 S5 Gasoline vehicle exhaust S4 Ace Ant Cry IND S8 Flu Pyr BkF BghiP S9 Combustion products Asphaltpavement or except for those in vehicle engines Bitumen S7 Acy Flt BbF DBA Particulate Rainwater Dissolved Particulate Stormwater Dissolved Figure A.3 Comparison of PAHs profiles in rainwater and stormwater (dissolved and particulate phase) with PAHs profile from Tokyo road dust of various origin (n = 189) (Petch et al., 2003) Diesel Vehicle exhaust S2 Nap PA BaA BaP Appendix A - PAHs profile in rainwater and stormwater - 165 % to Total PAH 0% 5% 10% 15% 20% 25% 30% 35% IND BaP BbF PA Street Dust BghiP Cry Flu Source Material Asphalt DBA BaA Acy Sump Sediment BkF Ant Tanker Effluent Particulate Rainwater Dissolved Particulate Stormwater Dissolved Figure A.4 Comparison of PAHs profile in rainwater and storm water (dissolved and particulate phas)e with PAHs profiles from various sources: used crankcase oil (Wang et al., 2000); asphalt (Brandt and De Groot, 2001); urban dust (SRM 1649a) (King, 1997), street dust, sump sediment and tanker effluent (Brown et al., 2005) Urban DustSRM 1649a Pyr Flt Used Crankcase Oil Ace Nap Appendix A - PAHs profile in rainwater and stormwater - 166 % to Total PAH 0% 5% 10% 15% 20% 25% 30% 35% 40% 45% 50% Ace Cry Highway Acy BbF Flu BkF Lake from Highway PA BaP Snow Ant IND concrete pavement Flt DBA Asphalt Pavement Pyr BghiP Particulate Stormwater Dissolved Figure A.5 Comparison of PAHs profile in stormwater dissolved and particulate phase with PAHs profile from Norwegian runoff (EHC,1998) Highway Run-off Nap BaA Appendix A - PAHs profile in rainwater and stormwater - 167 Appendix B - LMW/HMW relative proportion - Appendix B LMW/HMW relative proportion Table C.1 Composition of LMW and HMW PAH in the dissolved and particulate phase of rainwater in comparison with literature data Sample Unit Concentration LMW HMW Composition LMW HMW LMW/HMW Reference Environmental Matrices Air Particulate ng/m3 ng/m3 ng/m3 0.92 0.24 0.05 1.06 2.2 4.1 46% 10% 1% 54% 90% 99% 0.87 0.11 0.01 Kartikeyan et al., 2006 Sern, 2004 Sern, 2004 Singapore rainwater, dissolved ng/l 1,902 506 79% 21% 3.8 This Study Singapore rainwater, particulate ug/g 960 886 52% 48% 1.1 This Study ng/l % 1,017 41 916 41 53% 50% 47% 50% 1.11 1.05 Grynkiewicz et al., 2001 Golomb et al., 2001 % ng/l 53 143 35 52 60% 73% 40% 27% 1.49 2.76 Golomb et al., 2002 Ligocki et al., 1985a ng/l 8.5 27.2 24% 76% 0.31 ng/l 3.1 4.6 40% 60% 0.67 Ligocki et al., 1985b McVeety and Hites, 1988 ng/l ng/l ng/l 149 42,433 1,983 329 21,369 7,093 31% 67% 22% 69% 33% 78% 0.45 1.99 0.28 Levsen et al., 1991 Berglind, 1982 Gjessing et al., 1984 ng/l 4,900 5,648 46% 54% 0.87 Lygren et al., 1984 ng/l % 8,270 30 8,987 52 48% 37% 52% 63% 0.92 0.58 Lygren et al., 1984 Golomb et al., 2001 % 18 65 22% 78% 0.28 Golomb et al., 2002 ng/l 17.6 27.8 39% 61% 0.63 ng/l ug/kg 1,017 2,630 916 20,553 53% 11% 47% 89% 1.11 0.13 Berg and Hjellbrekke, 1988 Grynkiewicz et al., 2001 Metre et al., 2003 ng/l 1,879 2,912 39% 61% 0.65 Berglind, 1982 ng/l 537 606 47% 53% 0.90 This Study ng/l ug/kg % 1,413 275 7% 1,658 1425 92% 46% 16% 7% 54% 84% 93% 0.85 0.19 0.08 This Study Metre et al., 2003 Petch et al., 2003 Singapore (PM2.5) Singapore, NUS Singapore bus terminal Poland Urband Area rainwater New England, Nahant New England, Wolf Neck Portland rainwater Portland, dissolved phase Isle Royale precipitation Germany, Levsen precipitation Snow from highway Lake from Highway Wet Deposition Dry Deposition Bulk Precipitation Stormwater Road Dust Snow from concrete pavement Snow from asphalt pavement New England, Nahant New England, Wolf Neck Finland Poland Urban area Austin, Shoal Creek Norwegia, Highway runoff Singapore, Dissolved phase Singapore, Particulate phase Austin, MoPac roadside Tire 168 Appendix B - LMW/HMW relative proportion - Sample Diesel Vehicle exhaust Gasoline vehicle exhaust Asphalt-pavement or Bitumen Combustion products except for those in vehicle engines Source Material Used Crankcase Oil Urban Dust-SRM 1649a Asphalt Street Dust Sump Sediment Tanker Effluent Crankcase Oil Fuel Oil Urban Dust SRM 1649 Incinerator, Linkoping Incinerator, Gothenburg Incinerator, Stockholm Incinerator, Malmo Peat Fires Incinerators Incinerator, Gaseous Incinerator, Particulate Total Gaseous Particulate Total Unit Concentration LMW HMW Composition LMW HMW LMW/HMW Reference % % % % 30% 50% 30% 11% 70% 50% 70% 89% 30% 50% 30% 11% 70% 50% 70% 89% 0.43 0.43 0.12 Petch et al., 2003 Petch et al., 2003 Petch et al., 2003 Petch et al., 2003 % % 19% 19% 81% 80% 19% 19% 81% 81% 0.23 0.24 Petch et al., 2003 Petch et al., 2003 % 14% 85% 14% 86% 0.16 Petch et al., 2003 % % % % % % % % % ug/kg ug/kg ug/kg ug/kg ng/m3 ng/g ng/g ng/g ng/g ng/g ng/g 55 13 35 18 27 17 62 96 20 2,475 625 457 289 303 1,254 1,260 555 559 46 94 67 84 75 89 38 80 1,114 368 200 190 431 14 21 10 13 23 54% 12% 34% 18% 26% 16% 62% 96% 20% 69% 63% 70% 60% 41% 99% 28% 98% 98% 19% 96% 46% 88% 66% 82% 74% 84% 38% 4% 80% 31% 37% 30% 40% 59% 1% 72% 2% 2% 81% 4% 1.2 0.14 0.52 0.21 0.36 0.19 1.63 24 0.25 2.22 1.7 2.29 1.52 0.7 176 0.38 59 55 0.23 24 Brown et al., 2005 Brown et al., 2005 Brown et al., 2005 Brown et al., 2005 Brown et al., 2005 Brown et al., 2005 Ngabe et al., 2000 Ngabe et al., 2000 Ngabe et al., 2000 Johansson et al., 2003 Johansson et al., 2003 Johansson et al., 2003 Johansson et al., 2003 Wei et al., 2006 Lee et al., 2002 Lee et al., 2003 Lee et al., 2004 Lee et al., 2005 Lee et al., 2006 Lee et al., 2007 169 Appendix C - Regulation on PAHs - Appendix C Regulation on PAHs Table C.1 Regulation on PAHs Agency WHO EPA EPA, Land disposal treatment concentration EPA, water programs EPA, Final rule: Water Quality standards; numeric criteria for priority toxic pollutants; states’ compliance EPA, toxic pollutant standards for point sources that don not use end of pipe biological treatment EPA, toxic pollutant standards for indirect discharge point sources Description European standard for drinking water Limits for exclusion of wastederived residues BaA DBA Waste No F039 Acy Ace/Ant/Flu PA Flt Pyr BaA, Cyr BbF, BkF BaP DBA BghiP Public notification under the SDWA BaP Maximum contaminant levels for organic contaminants (BaP) Human health (10-6 risk for carcinogens); for consumption of (ng/l): Ant BaA, BaP, BbF, BkF, Cyr, DBA, IND Flt Flu Pyr Ace, Acy, Ant, BaA, BkF, Cyr, Flu, PA BaP, Pyr Flt Ace, Ant, Flu, PA Flt Pyr Information Reference WHO, 1971 200 ng/l 40 CFR 266, App VII 0.1 µg/kg 0.007 µg/kg NonWaste wastewater water (µg/kg) (ng/l) 3,400 59,000 4,000 59,000 3,100 59,000 8,200 68,000 8,200 67,000 8,200 59,000 3,400 55,000 8,200 61,000 8,200 55,000 1,500 55,000 2,000 ng/l 200 ng/l 40 CFR 268.43 40 CFR 141.32 40 CFR 141.61 57 FR 60848 Dec 22, 1992 (40 CFR 131) Water and Organisms Organisms only 9,600,000 110,000 2,800 300,000 1,300,000 960,000 31,000 370,000 14,000,000 11,000 47,000 48,000 54,000 19,000 20,000 22,000 58 FR 36872 (40CFT 414.101) 47,000 54,000 48,000 19,000 22,000 20,000 58 FR 36872 40 CFR 170 Appendix C - Regulation on PAHs - Agency EPA OWRS EPA OW EPA Description Ambient water quality criteria for protection of human health Ingestion of water and organisms PAHs Flt Drinking water standards and health advisories Maximum contaminant level goal (BaP) RID (Oral) Ant Ace Flt Flu Pyr Information Reference 414.111 2,8 ng/l 42,000 ng/l 40 CFR 141.50 mg/l IRIS, 1994 300 µg/kg/day 60 µg/kg/day 40 µg/kg/day 40 µg/kg/day 30 µg/kg/day 171 [...]... assess PAHs distribution in rainwater and stormwater; (2) To determine PAHs distribution in rainwater and stormwater; (3) To estimate deposition flux of PAHs from the rainwater ; (4) To study temporal variation of PAH in water samples; (5) To estimate the level of carcinogenic PAHs in dissolved and particulate phase; (6) To investigate the sources of PAHs in the rainwater and stormwater samples using... methods and molecular ratios 4 Chapter 1 – Introduction - Research Objectives: Assessment of the occurrence and distribution of PAHs in rainwater and urban runoff Literature Review Chapter 2 Sampling and Experimental Details Chapter 3 Method development and validation Chapter 4 Database: The level of PAHs in rainwater and urban runoff Level of carcinogenic compounds Temporal Variation Identification of PAHs. .. an urban area in Singapore, which is possibly highly contaminated due to its location being close to an expressway, petroleum refineries, an incinerator, and a sea port The data on PAHs in the rainwater and urban runoff were analyzed further to determine the level of carcinogenic compounds, the existence of temporal variation, and the possible sources of PAHs The levels of PAHs in rainwater and urban. .. strength, and adsorption time The detailed experimental results of the method development are discussed in Chapter 4 The second part of the thesis focuses on the assessment of the occurrence and distribution of PAHs in the rainwater and urban runoff using the analytical method that has been developed in our laboratory The samples used for assessment of PAHs in rainwater and urban runoff were obtained from... concentrations This finding underlines the importance of rainwater in transporting and distributing PAHs in the other compartments of the environment Once PAHs are deposited on the urban landscape by wet or dry deposition, the migration of PAHs occurs by urban runoff, which is formed when precipitation flows over the ground surfaces Urban runoff tends to accumulate and retain PAHs that settle on impervious... between wind direction and monthly PAHs (dissolved and particulate) composition in rainwater, which is classified by increasing C number 90 Frequency distribution of wind direction from August 2005 to January 2006 92 PAHs cross plots for the ratios of IND/IND+BghiP and Flt/Flt+Pyr in the rainwater; the majority of the samples are within the range of petroleum combustion 99 PAHs concentration in stormwater... the stormwater in comparison to data reported in literatures 126 Comparison of PAHs profile in rainwater and stormwater (dissolved and particulate phase) with PAHs profile from South Carolina (Ngabe et al., 2000) 158 Comparison of PAHs profile in rainwater and stormwater (dissolved and particulate phase) with PAHs profile incinerator (Lee et al., 2002) and peat combustion (See et al., 2006) 159 Figure... Comparison of PAHs profiles in rainwater and stormwater (dissolved and particulate phase) with PAHs profile from Tokyo road dust of various origin (n = 189) (Petch et al., 2003) 160 Comparison of PAHs profile in rainwater and storm water (dissolved and particulate phas)e with PAHs profiles from various sources: used crankcase oil (Wang et al., 2000); asphalt (Brandt and De Groot, 2001); urban dust... of ionic strength 53 Figure 4.5 Optimization of pH 55 Figure 4.6 GC-MS chromatogram of PAHs extraction in rainwater (a) and stormwater (b) samples 60 Averaged PAHs composition in dissolved and particulate phase in rainwater (n = 40) 71 Concentration of carcinogenic PAHs in the dissolved and particulate phase of rainwater in comparison in comparison to those from literature; ∑ 6 PAHCARC is the sum of. .. over 50% of the total PAHs in the river originated from a highway runoff The runoff- loading factor per vehicle was as high as 24 mg/kg (Hoffman et al., 1985) However, the relative contribution of urban runoff to adjacent water bodies is site-specific, and dependent heavily on the magnitudes of the wet and dry deposition as well as sources of PAHs in the urban runoff (EHC 202, 1998) 2.4 Sources of PAHs .. .OCCURRENCE AND DISTRIBUTION OF PAHs IN RAINWATER AND URBAN RUNOFF ELISABETH RIANAWATI (B Eng., ITB) A THESIS SUMBITTED FOR THE DEGREE OF MASTER OF ENGINEERING DIVISION OF ENVIRONMENTAL... method to assess PAHs distribution in rainwater and stormwater; (2) To determine PAHs distribution in rainwater and stormwater; (3) To estimate deposition flux of PAHs from the rainwater ; (4) To... methods and molecular ratios Chapter – Introduction - Research Objectives: Assessment of the occurrence and distribution of PAHs in rainwater and urban runoff Literature Review Chapter Sampling and