FATESCOMARC Riverine transport of polycyclic aromatic hydrocarbons from

FATES-COMARC Riverine transport of polycyclic aromatic hydrocarbons from Kaoping River (Taiwan) to coastal ocean Chon-Lin Lee 1*, Bing-Sian Lin 1, and James T. Liu 2 1 1 Department of Marine Environment and Engineering 2 Institute of Marine Geology and Chemistry National Sun Yat-sen University

FATES-COMARC Introduction What are Polycyclic Aromatic Hydrocarbons (PAHs)? Hydrophobic Organic Compounds (HOC) Persistent Organic Pollutants (POPs) 2

Ring structure of PAHs Naphthalene Acenaphthylene Phenanthrene Fluoranthene Benzo(b)fluoranthene 3 Acenaphthene Pyrene Fluorene Anthracene Benzo(a)anthracene Benzo(k)fluoranthene Dibenz(a, h)anthracene FATES-COMARC Chrysene Benzo(a)pyrene Benzo(g, h, i)perylene Indeno(1, 2, 3 -cd)pryene

FATES-COMARC Introduction Why PAHs? Suspect carcinogens Endocrine disruptors Bioaccumulation Source identification 4

FATES-COMARC Pyrogenic sources Petrogenic sources Industrial emission Vehicles emission Open-burning emission Oil spill Industrial waste PAHs in environment Diagenetic source Retene 5 Diagenesis of biogenic precursors Perylene

Source identification Alkyl- phenanthrenes Anthracene FATES-COMARC CH 3 Fluorene Benzo(a)anthracene Benzo(g, h, i)perylene Phenanthrene Acenaphthene Naphthalene Pyrene Indeno(1, 2, 3 -cd)pryene 6 Benzo(a)pyrene Fluoranthene Chrysene

FATES-COMARC PC 3 vs PC 4 0 Upcanyon 270 Downcanyon 180 T 4 KP 90 Downcanyon heading samples Gasoline vehicle Up-canyon source heading sample Oil source 7 M-D Fang, W-K Chang, C-L Lee, James T. Liu, 2009, J. Mar. Syst. (76) 457 -467

FATES-COMARC PCA score plot – PC 1 versus PC 2 8 M-D Fang, W-K Chang, C-L Lee, James T. Liu, 2009, J. Mar. Syst. (76) 457 -467

FATES-COMARC Fate of anthropogenic HOCs and fluvial particles? N. Shelf Outer Shelf 9 Canyon S. Shelf

Objectives FATES-COMARC • To estimate the annual fluvial discharges of polycyclic aromatic hydrocarbons and particulate organic carbons from Gaoping River • To deploy PAH diagnostic ratios and statistical tools (e. g. principal component analysis) for source recognition 10

Sampling Map FATES-COMARC From： NOV 06 To： NOV 07 11

Methods (2) liquid-liquid extraction FATES-COMARC (3) rotary evaporation (1) Soxhlet extraction (5) GC-MS (4) Clean up 12 M-D Fang, F-C Ko, J. E. Baker, C-L Lee, 2008, Sci. Total Environ. (407) 548 -565

FATES-COMARC PAH concentrations (ng/L) 13

FATES-COMARC Particulate PAHs(ng/L) VS TSP 14

FATES-COMARC Particulate PAHs(ng/g) VS POC R=0. 584 15

FATES-COMARC Source Identification Pyrogenic 16 Petrogenic

May 07 Dry season Sampling Precipitation 17 FATES-COMARC Wet season

FATES-COMARC PC 1 score plot Pyrogenic source PC 1 scores Petrogenic source M-D Fang, P-C Hsieh, F-C Ko, J. E. Baker, C-L Lee, 2007, Mar. Pollut. Bull. (54), 18 1179 -1189. & J-J Jiang, C-L Lee, M-D Fang, James T. Liu, Mar. Pollut. Bull. In Press

HCA cluster • Canyon and Southern shelf Ⅰ • Northern shelf • Wet season • Canyon and Southern shelf Ⅱ • Dry season 19 • Straw burning FATES-COMARC

FATES-COMARC HCA Compositional pattern CH 3 S S Methyl-PAHs Pyrogenic 20

PCA Loading S Mixed Sources Petroleum CH 3 S pyrolysis 21 FATES-COMARC

FATES-COMARC River Suspended Particles Between wet and dry season：Mixed Sources Coastal Surface Sediments 22

FATES-COMARC Unburned Petroleum Petrogenic pyrogenic Pyrogenic 23 Diesel oil Biomass/petroleum combustion

Estimate PAHs Flux Krosa typhoon Typhoon: Aug : Pabuk, Wutip, Sepat sampling Sep : Wipha Oct : Flux: Krosa 4. 3 ton/year Total Nov : Mitag Wet season : 99. 0% Krosa typhoon: Particulate phase : 12. 8% Dissolved phase : 24 6. 7% FATES-COMARC

FATES-COMARC 25

Summary Sources PAH concentration Dissolved phase Particulate phase 26 Wet season petrogenic 85 - 196 ng/L 13 - 41 ng/L 160 - 592 ng/L 397 -1144 ng/g FATES-COMARC Dry season pyrogenic 200 - 515 ng/L 57 - 152 ng/L 12 - 49 ng/L 790 -1797 ng/g

Summary Sediment discharge 18. 7 MT/year organic carbon discharge 95 k. T/year PAH fluvial discharge 4. 3 ton/year Wet season Dissolved phase 85. 4 % Particulate phase 99. 7 % FATES-COMARC Dry season 14. 6 % 0. 3 % Wet season Dissolved phase Particulate phase Typhoon 48. 1 % 67. 0 % 27

Acknowledgements FATES-COMARC • National Science Council for funding support • Prof. H-L Lin for the precious samples 28

FATES-COMARC Thank you and your comments are welcomed 29