Persistent Organic Pollutants (POPs) in Catfish and Sediment from Mekong River: Sources, Occurrences and Risk Assessment

Nguyen Hung Minh (CMES, Postdoctoral), Tu Binh Minh (Faculty of Agriculture, Associate. Professor), Natsuko Kajiwara (CMES, Assistant Professor), Tatsuya Kunisue (CMES, Postdoctoral), Hisato Iwata (CMES, Professor), Shinsuke Tanabe (CMES, Professor), Nguyen Phuc Cam Tu (Faculty of Agriculture, M.S student), Pham Hung Viet (Hanoi National Uni., Professor), Bui Cach Tuyen (Nong Lam University, Professor)

1. Introduction Mekong River is the longest river in southeastern Asia, which flows a distance of almost 4800 km from China through Myanmar, Thailand, Laos, Cambodia and Vietnam. The Mekong River basin with an area of nearly 800 thousand square kilometers is an important habitat for approximately 60 million people. Mekong River delta in South Vietnam, which is inhabited by about 20 million people, is one of the most highly productive agriculture areas in the world. Rice production is major economical activity in Mekong delta contributing half of the rice production in Vietnam - approximately 35 million tons annually. On the other hand, development of agriculture in Mekong delta also raised concerns over environment and biodiversity. For example, intensive use of persistent organic pollutants (POPs) such as organochlorine pesticides and polychlorinated biphenyls (PCBs) may lead to considerable residues in agriculture land, water and sediment. Moreover, relative persistence of such chemicals together with natural processes like evaporation and runoff might enhance their ubiquitous distribution in environment, food chains and eventually in humans. Several of these chemicals are believed to alter normal function of endocrine and reproductive systems in humans and wildlife. Despite this fact, no comprehensive study to evaluate contamination status caused by POPs in this region has been made in recent years. In this study, we collected fish and sediment samples from different locations along Mekong River and determined concentrations of several POPs such as DDTs, HCHs, CHLs, HCB and PCBs. The objectives of this study are to elucidate the recent contamination status of POPs, their pollution sources as well as to assess toxicological risk to the environment. 2. Materials and Methods 2.1. Sample Twenty cage-cultured catfishes (Clarias Gariepinus), five catfishes in pounds near Can Tho dumpsite (hereafter, referred as dumpsite catfishes) and two fishs feeds were collected in 2004. Besides, Twenty four sediment samples were also collected a long Hau River (the biggest branch of Mekong River flowing across South Vietnam) during 2003-2004.
2.2. Chemical analysis All samples were analyzed for chlorine pesticides (DDTs, HCHs, CHLs and HCB) and polychlorinated biphenyls (PCBs). The analytical procedures followed available standard methods which were validated and used in our laboratory. Details of the methods can be found elsewhere in our recent publications.

3. Results and Discussion 3.1. Contamination of POPs in catfishes collected from Mekong River In general, mean concentration of DDTs and PCBs in catfishes was much higher than other pollutants (Table 1), suggesting widespread contamination of these chemicals in aquatic environment of Mekong River. Interestingly, POPs levels in the dumpsite catfishes were significantly higher than those in the cage-cultured catfishes, indicating additional pollution sources to the vicinity of the dumpsite. Leachages and runoff from the dumpsite may be a likely source of POPs to these fishes because recently, municipal wastes dumpsites in Asian developing countries were reported as emerging pollution sources of POPs. In this context, further studies toward POPs exposure of people living nearby Can Tho dumpsite may be needed to assess their possible health risk. Comparison between POPs levels in the feed and those in the cage-cultured catfishes demonstrated significant difference (p<0.05) only for DDTs. In contrast, the dumpsite catfishes contained significantly higher levels of all POPs compared to those in the feeds. This result showed considerable uptake of POPs via the diets in the cage-cultured and dumpsite catfishes. Examination of PCB congeners profile and DDTs composition further suggested the feeds as an important pollution source for the cage-cultured catfishes but not for the dumpsite catfishes (the dumpsite catfishes may uptake more POPs from contaminated pond water).

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Table 1: Concentrations of POPs in catfishes and feeds (ng/g lipid wt) a Catfish (Near dumpsites) Catfish (Cage-cultured) Mean Median Range Mean Range Body length (cm) 32 33 29 - 36 28 27 - 29 Lipid (%) 3.75 3.83 0.674 - 7.18 3.62 3.16 - 4.08 PCBs 7.2** 5.9 0.91 - 27 50 55 - 76 HCB 0.73** 0.73 <0.04 - 1.8 2.6 2.4 - 3.2 0.47* 0.18 <0.2 - 1.5 2.2 0.86 - 5.1 HCHs

Mean 3.49 6.4* 0.37* 0.27* 1.3* 5.4 5.6 8.8 20*

Fish's Feeds Range

3.41 - 3.56 6.3 - 6.6 0.37 - 0.38 0.27 - 0.29 0.95 - 1.7 5.3 - 5.5 4.8 - 6.4 7.4 - 10 18 - 22

CHLs p,p' -DDE p,p' -DDD p,p' -DDT DDTs

a

0.89* 29 19 11 59**

0.41 25 16 9.0 46

nd - 6.3 3.8 - 85 2.3 - 48 1.8 - 34 7.9 - 150

5.7 230 72 87 390

4.2 - 8.2 220 - 310 59 - 130 50 - 270 330 - 700

* p<0.05; ** p <0.001 (indicating significant difference with the dumpsite catfishes) significant difference (p <0.05) between the cage-cultured catfishes and the feeds was only observed for DDTs
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10 Using the fish consumption rate of 50 ** (** p < 0.001; * p < 0.05) 10 g/person/day (FAO-Vietnam, 1999), POPs intake was ** estimated for two groups of people: those consume 10 * * the cage-cultured catfishes (general people G.P) 10 and those consume the dumpsite catfishes (exposed 10 people E.P). In general, intake of DDTs, PCBs, 0 E.P G.P E.P G.P E.P G.P E.P G.P CHLs and HCB in the exposed people was significant DDT intake PCB intake HCB intake CHLs intake higher than the general people by 1 to 2 orders of magnitude (Figure 1). This result perhaps suggests Fig.1: Comparison of POPs intake for the exposed people (E.P) further necessary study toward assessment of human and the general people (G.P) health risk caused by exposure to various pollutant groups that may spread out of the dumpsite. Futher investigation for other pollution groups may be needed. Intake (ng/person/day)
3 2 1 0

3.2. Contamination of POPs in sediments from Mekong River The residue pattern of POPs in the sediment from Mekong River followed the order: DDTs > PCBs > CHLs HCHs HCB (Tab. 2). However, their concentrations varied among the sampling sites, showing higher concentrations in sediments close to urban areas (e.g. Can Tho, Vinh Long), suggesting urban areas as important point sources of DDTs and PCBs to the river. Besides, composition of DDTs with higher proportion of p,p-DDT in sediments close to urban areas may also support this hypothesis.
Table 2: Concentrations (ng/g dry wt) of POPs in sediments from Mekong River, South Vietnam Sample ID PCBs p,p' -DDE 3.7 1.9 2.4 2.1 4.7 7.9 0.80 0.79 0.21 0.17 0.15 0.043 0.31 0.30 0.32 0.74 0.23 0.51 0.21 0.80 0.11 0.32 0.17 0.89 0.14 1.5 0.045 0.54 0.96 1.3 0.22 0.77 0.045-4.7 0.043-7.9 DDTs p,p' -DDD p,p' -DDT 0.79 0.54 1.9 0.98 24 22 0.49 0.56 0.24 2.9 0.041 0.010 0.22 0.16 0.22 0.12 0.24 0.28 0.44 0.38 0.21 0.075 0.23 0.027 0.41 0.23 0.36 0.36 2.1 2.0 0.30 0.32 0.04-24 0.01-22 DDTs 3.2 4.3 54 1.8 3.3 0.095 0.67 1.1 1.1 1.6 0.61 1.2 2.1 1.3 5.5 1.5 0.09-54 t -chlor 0.044 0.062 4.7 0.088 <0.01 <0.01 <0.01 <0.01 0.015 <0.01 0.029 <0.01 <0.01 <0.01 0.35 <0.01 <0.01-4.7 c -chlor 0.039 0.055 3.0 0.034 <0.01 0.014 0.025 0.019 0.014 0.023 0.020 0.025 <0.01 <0.01 0.23 0.022 <0.01-3.0 CHLs t -nona 0.021 0.042 1.4 0.031 <0.01 <0.01 0.017 <0.01 0.016 0.018 0.015 0.021 0.017 <0.01 0.11 0.017 <0.01-1.4 c -nona 0.014 0.021 0.73 0.0091 <0.004 <0.004 <0.004 0.0056 <0.004 0.018 <0.004 <0.004 0.0047 <0.004 0.057 0.0024 <0.004-0.73 CHLs 0.12 0.18 9.9 0.16 0.015 0.020 0.085 0.043 0.042 0.059 0.061 0.075 0.022 <0.04 0.77 0.060 <0.04-9.9 HCB 0.080 0.022 <0.006 0.059 0.0074 <0.006 0.0093 0.0071 0.016 0.012 0.0083 <0.006 0.016 <0.006 0.019 0.0093 <0.006-0.08 HCHs 0.032 <0.02 0.16 <0.02 0.078 <0.02 <0.02 <0.02 <0.02 <0.02 <0.02 0.044 0.000 1.3 0.12 <0.02 <0.02-1.3

CC-1 CC-4 CC-7 * NK-SE Hau-1 * Hau-2 * Hau-3 * Hau-4 * Hau-5 * Hau-6 * Hau-7 * Hau-8* Hau-11 Hau-12 Mean Median Range * indicates mean values of two samples collected at the same sites

t -chlor: trans -chlordane, c -chlor: cis- chlordane, t-nona: trans-nonachlor, c -nona: cis -nonachlor DDTs = p,p' -DDE + p,p' -DDD + p,p' -DDT, CHLs = t -chlor + c -chlor + t -nona + c -nona

Risk assessment for DDTs and PCBs in the sediment was carried out basing on the Canadian Environmental Quality Guideline for freshwater sediments (interim sediment quality guideline - ISQG and probable effect level - PEL). Compared to these criteria for DDE, DDD and DDT (ISQG: 1.42, 3.54, 1.19; PEL: 6.75, 8.51, 4.77 in ng/g dry wt, respectively), some sediments from Mekong River had levels exceeding the guideline values (Table 2). Therefore, continuous monitoring for DDTs contamination in the river sediment is needed. PCBs levels in the sediment are lower than the guideline (ISQG 34.1; PEL 277 ng/g), implying lower toxicological effect caused by PCBs contamination in sediment of Mekong River.

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