1. Xinhong Wang 1, Heyang Li 2, Yusheng Zhang 2 1. Environmental Science Research Center, Xiamen University, Xiamen, 361005, P.R.China 2. Third Institute of Oceanography, State Oceanic Administration, Xiamen, 361005, China Reconstruction of Contamination History for PAHs and Organochlorine Pesticides in the Marine Sediment Cores from Andaman sea, Malaysia

2. PAHs and OCs are hydrophobic, potentially toxic and persistent pollutants, which are ubiquitous in the environment. Once produced, they enter the environment through air transportation or stream pathway and accumulate in the sediment eventually. The profile of organic pollutants concentrations in an undisturbed sediment core can be used as temporal indicator to study the trends of the past and present variations of their inflow and usage.

3. Malaysia is a major producer of primary commodities; Malaysia has a dominant world position in rubber, palm oil and cocoa; Concomitant with the emphasis on agricultural development in the 1960’s and 1970’s. Develop history: emphasis on agricultural development in the 1960’s and 1970’s, pollution from the agro-based industries accounted for approximately 90% of the industrial pollution load and was the largest source of water pollution during a period when there were inadequate provisions for regulating the discharge of effluents (Abdul Rani Abdullah,1995).

4. The wide use and spread of pesticides has resulted in detrimental effects on aquatic resources. The 2004 Indian Oceanic Tsunami has caused considerable changes in the marine ecosystem by polluting the marine environment with high turbidity and damaging the coastal zones.

5. Objectives To reconstruct the usage history of PAHs and OCs. To trace the sources of pollution. To compare the concentrations and variations of PAHs and OCs in sediment cores to evaluate the influence of Tsunami on the sediment.

6. Sampling WC02 KM24 Sediment Rate : WC02 0.5 cm/ year covered the past 100 years. KM24 0.76 cm/year and covered the past 80 years.

7. PAHs and OCs analysis 16 PAHs: Naphthalene (Na); Acenaphthylene (Ace), Acenaphthene (Acen), Fluorene (Flu), Phenanthrene (Phen), Anthracene (An); Fluoranthene (Fluo), Pyrene (Py), Benzo(a)Anthracene (BaA), Chrysene (Chry); Benzo(b)Fluoranthene (B(b)FA), Benzo(k)Fluoranthene (B(k)FA), Benzo(a)Pyrene (B(a)P), Dibenz(a,h)Anthracene (DiBaA); Indeno(1,2,3-cd)Pyrene (Indeo), Benzo(ghi)Perylene (B(ghi)P). 25 or 17 organochloriated pesticides (α-HCH 、 HCB 、 β- HCH 、 γ-HCH 、 δ-HCH 、 Heptachlor 、 Aldrin 、 Isodrin 、 Heptachlor epoxide A 、 oxychlordane 、 Heptachlor epoxide B 、 Chlordane A 、 OP‘-DDE 、 Endosulfate Ⅰ、 Chlordane B 、 Dieldrin 、 PP'-DDE 、 OP'- DDD 、 Endrin 、 Endosulfate Ⅱ、 PP'-DDD 、 OP'-DDT 、 PP'-DDT 、 Methoxychlone 、 Mirex)

8. 15.0020.0025.0030.0035.0040.0045.0050.0055.0060.0065.0070.00 50000 100000 150000 200000 250000 300000 350000 400000 450000 500000 550000 600000 650000 700000 Time--> Abundance TIC: SSIM.D 13.78 13.86 22.84 23.92 24.11 27.56 34.13 34.29 34.60 43.14 44.66 54.01 54.12 54.29 61.71 61.89 63.68 64.09 70.41 70.76 71.70 10.0012.0014.0016.0018.0020.0022.0024.0026.0028.00 1e+07 2e+07 3e+07 4e+07 5e+07 6e+07 7e+07 8e+07 9e+07 1e+08 1.1e+08 1.2e+08 1.3e+08 1.4e+08 1.5e+08 Time Response_ WOCLSTD.D\ECD1B 10.85 12.27 13.50 14.54 15.10 16.28 17.66 19.38 20.86 21.97 22.17 22.85 23.30 23.96 24.14 24.56 25.16 25.50 27.02 PAHs were performed on an Agilent 6890 GC – MSD using an HP-5 MS column (30 m * 0.25 mm * 0.25 mm). OCs were performed by Agilent 5890 GC － ECD using an HP-5 column (60m × 0.32 mm × 0.25 μm ).

9. PAHs: Agilent 6890 GC-5973 MSD operating in selective ion monitoring mode using an HP-5 MS column (30 m * 0.25 mm * 0.25 mm ). Samples were injected in splitless mode with the injector temperature at 280 ℃. Helium was used as carrier gas at a flow rate of 1 mL /min. Oven start at 90 ℃ with 1 min hold, ramp to 160 ℃ at 15 ℃ /min, and then to 290 ℃ at 8 ℃ /min with a final hold of 8 min. OCs : Agilent5890 GC － ECD using an HP-5 column (60m × 0.32 mm × 0.25 μm ) ； High purity nitrogen was used as carrier gas; Samples were injected in splitless mode ； The injector and detector temperature was 250 ℃ and 320 ℃, respectively. Oven start at 90 ℃ with 1min hold ， rampt to 210 ℃ at the rate of 10 ℃ /min with 1min hold ； and then to 230 ℃ at 1 ℃ /min with 10 min hold ； finally, it increased to 250 ℃ at 1 ℃ /min.

10. QA/QC Deuterated PAH compounds (naphthalene-d8, acenaphthene-d10, phenathrene-d10, chrysene-d12 and perylene-d12), as well as PCB166 、 PCB209 、 2,4,5,6- tetrachlore-oxyl-dioxin were used for surrogates and internal standards, which were spiked in the samples prior to extraction for quantifications. The recoveries of PAHs ranged from 65% to 125% and from 50.4% to 124% for OCs.

11. Figure 1. PAHs variations in sediment cores. WC02 KM24 Phenathrene was prevalent component in most samples, accounting for 8 ～ 36%. WC02: 13.25 to 60.11 (the mean 18.09 ) ng/g; KM24: 24.39 to 327.40 (the mean 78.24) ng/g. PAHs

12. That means that the environment at these area were not impacted by human activity heavily and PAHs contamination was not much seriously. In some degree, it is impact by anthropogenic activities at KM24. SitesTotal PAHs In the WorldBohai60.3-2076.5 ng/g Macau321-3112 ng/g Pearl River estuary59-330 ng/g Mediterranean Sea50-1798 ng/g Tokyo Bay225-5967μg/g Boston Harbour in America57000 ng/g the adjacent areaThailand20-120 ng/g Bengal25-1081 ng/g This studyWC02:13.25 to 60.11 (mean 18.09 ) ng/g KM24:24.39 to 327.40 ( mean 78.24) ng/g Table 1 Comparison of PAHs contamination with other sites in the World

13. Figure 3. Depth profile of PAH concentrations in sediment core-KM24

14. Figure 4. Depth profile of PAH concentrations in sediment core-WC02

15. Anthropogenic PAHs originate mainly from combustion of biomass and fossil fuels and oil spillage. Isomeric ratios of PAHs are classical indices for apportioning sources of PAHs in the environment. Sources of PAHs Indeo/(Indeo t BgP) < 0.2, and Fluo/(Fluo t Py) < 0.4 implies petrogenic PAHs, while ratios of both greater than Indeo/(Indeo t BgP) > 0.5, Fluo/(Fluo t Py) > 0.5 suggest PAHs origin from combustion of coal and biomass. 0.2 0.4 implies PAHs originate from petroleum (vehicle fuels and crude oil) combustion.

16. WC02 Petro genic Uncom plete combus tion Petro genic Mixture Petro genic Combu stion Uncomplete combustion Coal and fossile combustion

17. Petrogenic Coal and biomass combustion Petrogenic incomplete combustion Coal and biomass combustion Mixture Combustion KM24 Petrogenic incomplete combustion

18. KM24 WC02 Figure 7. OCs variations in sediment cores. WC02: 0.11 to 111.04 (the mean 16.60 ) ng/g; KM24: 23.13 ～ 216.57 (the mean 66.71) ng/g. OCs

19. ∑HCHs ： 0.57 ～ 24.36 ng/g(mean5.79 ng/g) ， 2.21% ～ 29.73% of total organochlorine pesticides ； ∑DDTs ： 0.99 ～ 52.99 ng/g (mean 6.34 ng/g), 1.92% ～ 29.62% (mean 7.52%) ， with a peak at 5 ～ 6 cm (the year of 2001). Figure 8. Component of HCHs and DDTs in sediment core-KM24

20. ∑HCHs ： 0.22 ～ 54.86 ng/g ； ∑DDTs ： 0 ～ 18.20 ng/g ， with a peak at 5 ～ 6 cm (the year of 2001). Garma-HCH and p,p’-DDT were dominant in WC02. Figure 9. Component of HCHs in sediment core-WC02

21. Total OCs level were generally lower below the depth of 20cm ( <10 ng/g ) compare with the uper layer (more than 100 ng/g )of the sediment cores. From 20cm to 8cm (1980s-2000s), the concentrations of OCs especially for HCHs varied slightly from 18-50cm, the variation of total OCs include HCHs and DDTs did not show significantly difference. Figure 10. Vertical variations of OCP concentrations in sediment core-KM24.

22. OCs changed very slightly below 10cm before the year of 1990s. From 6cm to the surface, the sum of OC compounds showed changeable, which also indicated that OCs begin input to the sea after 1990s. Figure 11. Depth profile of OCs concentrations in sediment core-WC02

23. Conclusion Sedimentary records of PAHs and DDTs in Malaysia sea reflected the economic development in Malaysia over one hundred years. 1. There could be find the environment background of PAHs in this area before 1980s in core KM24 and before 1920s in core WC02. 2. KM24 were contaminated by PAHs more serious than that in WC02, which indicates the impact of human activities especially for sewage discharge and ship activities in the marine coastal environment. 3. Sediments originate predominantly from combustion of coal and biomass, or the mixture. 4. Based on the vertical distribution of OCs in the sediment cores, it were found that manufactured pollutants input the sea mainly after 1980s. The total OCs still increase, DDTs concentration decreased in recent ten to twenty years. 5. The results can not really evaluate the impact of Indian Ocean Tsunami on the sediment from Malaysis for the limit data and suitable samples in these area.

24. Thank You!