Marine Pollution Bulletin 56 (2008) 14761485

Contents lists available at ScienceDirect

Marine Pollution Bulletin

journal homepage: www.elsevier.com/locate/marpolbul

Agrochemical and polychlorobyphenyl (PCB) residues in the Mekong River delta, Vietnam
Fernando P. Carvalho a,b,*, J.P. Villeneuve b, C. Cattini b, I. Tolosa b, Dao Dinh Thuan c, Dang Duc Nhan d
a

Nuclear and Technological Institute, E.N. 10, P-2685-953 Sacavm, Portugal International Atomic Energy Agency, Marine Environment Laboratories, 4 Quai Antoine 1er, MC 98000, Monaco c Hanoi University of Mining and Geology, Co Nhue, Tu Liem, Hanoi, Viet Nam d Vietnam Atomic Energy Commission, 59, Ly Thuong Kiet, Hanoi, Viet Nam
b

a r t i c l e

i n f o

a b s t r a c t
An environmental survey on pesticide residues and polychlorobyphenyl compounds (PCBs), encompassing more than 70 polar and non-polar compounds quantiable by the techniques used, was performed in the Mekong River delta based on analyses of water, sediment and bivalve mollusc samples. Few polar compounds, such as diazinon and fenotrothion, were detected in water but a high number of non-polar chlorinated compounds, such as DDT, HCH, endosulfan and PCBs, were detected in sediments and biota. The highest concentrations measured were of DDT with an average 6.3 ng g1 dry weight (range 0.32 67 ng g1) in sediments and 38.6 ng g1 (range 5.5123 ng g1) in molluscs soft tissues. Amongst chlorinated compounds, DDT concentrations were followed in decreasing order by those of PCB, endosulfan, hexachlorocyclohexane and chlordane. Residues of organochlorine compounds originate from local usage of agrochemicals although with a likely contribution also of atmospheric deposition of residues (not measured) originated elsewhere. Concentrations of PCB and pesticide residues in the aquatic environment of the Mekong River delta are lower than values reported for other regions of Vietnam and Asia. Nevertheless, current concerns about the effects of chlorinated compounds on public health advise improved control of chemical residue discharges in order to abate environmental contamination. 2008 Elsevier Ltd. All rights reserved.

Keywords: DDT PCB Hexachlorocyclohexane Endosulfan Bioaccumulation Marine molluscs

1. Introduction The Mekong is the third largest river in Asia and the rst in the South East Asia. It ows across China, Laos, Thailand, Cambodia and Vietnam, with a catchments area of about 800,000 km2, 8% of which in Vietnam, and annually discharges 475 km3 of water into the South China Sea (Dudgeon, 1995). In Vietnam, the Mekong River spreads in a wide delta with ramications into many channels draining 20% of the surface of the country. The delta had nine main sea communicating channels, which gave rise to the other name of Mekong, i.e., Cuu Long (nine dragons, in Chinese). The delta of the Mekong is a river borne sedimentary formation, with an average height of 5 m above the sea level, and a surface area of 30,000 km2. The area of the delta is administratively divided in 13 provinces (Long An, Dong Thap, Tien Giang, Ben Tre, Tra Vinh, Vinh Long, An Giang, Can Tho, Hau Giang, Soc Trang, Bac Lieu, Ca Mau and Kien Giang) in which live 16.5 million inhabitants. The Mekong River has a very abundant and diverse aquatic fauna. The populations of many sh species migrate up and down the
* Corresponding author. Address: Nuclear and Technological Institute, E.N. 10, P-2685-953 Sacavm, Portugal. Tel.: +351 219946332; fax: +351 219941995. E-mail address: carvalho@itn.pt (F.P. Carvalho). 0025-326X/$ - see front matter 2008 Elsevier Ltd. All rights reserved. doi:10.1016/j.marpolbul.2008.04.042

river and, with oods, spread over the plains into rice paddies, small ponds, and irrigation and navigation channels. Fish, mollusc and crustaceans are important diet components to the people living in the delta. The annual sh harvest of the lower Mekong basin was estimated at about 500,000 tonnes (Dudgeon, 1995) and aquaculture is a fast growing activity. Rice is the dominant cereal crop in the delta, growing round the year in this region. In 1998, the rice growing area in the Mekong delta has been 3.8 Mha and the rice production yield was 4.19 tonnes ha1 in the same year. Sugar cane is an industrial crop grown mainly in Can Tho, Soc Trang, Tra Vinh and Ben Tre, and occupied an area of 74.5 kha in 1998 (MARD, 1998).Vegetables and fruits are also grown in the region and the Mekong delta became the rst agriculture zone of Vietnam. The traditional rice growing practice is seeding and agrochemicals are currently used. Amongst the compounds used in rice, the most common herbicides and fungicides seem to be 2,4D (2, 4 dichlorophenoxy)acetic acid, atrazine, propiconazole, captan, and isoprothiolane. Amongst the insecticides the common ones are endosulfan, lindane, chlorpyrifos, diazinon, fenobucarb, and fenvalerate. Other and more persistent organochlorine pesticides, available at low price in Asian markets, are likely used also by farmers as crop protection chemicals and for sanitation purposes, especially to control malaria vectors.

F.P. Carvalho et al. / Marine Pollution Bulletin 56 (2008) 14761485

1477

Polychlorinated biphenyls (PCBs) are industrial chlorinated hydrocarbons used as electric insulators in transformers, hydraulic uids and paint additives (Waid, 1987). PCBs became widespread contaminants and are amongst the persistent, bioaccumulative, and toxic synthetic chemicals targeted by international conventions to be phased out (UNEP, 1997). The harmful effects of these chlorinated hydrocarbons on wildlife and on human health are well established (Colborn et al., 1993; Woolcoot et al., 2001; Taylor et al., 2003; Isobe et al., 2007). The amounts of chlorinated hydrocarbons applied in Vietnam are not accurately known. This paper reports the rst eld survey on pesticide and PCB residues carried out in the Mekong delta. 2. Material and methods The eld sampling was performed in mid May 1998, before the beginning of the rainy season. Water, sediment, and biota samples were collected in various sites of the Mekong delta, from the border with Cambodia to the coast of South China Sea (Fig. 1). Water samples were collected in 8 out of 16 sampling stations directly drained into large brown glass bottles previously rinsed with hexane. The bottles with water samples, as well as the sediment and biota samples, were kept in the shade in an ice-chest box used for transportation in the eld. Treatment of the samples was done in the same day of the collection, in the laboratory. The water samples were ltered through clean (pre-combusted) glass bre lters (GF/F, Whatman) using vacuum from a hand-pump. A volume of 500 ml of ltered water was immediately spiked with 200 ng of chlortion used as internal tracer, swirled, and immediately drawn through a solid-phase extraction (SPE) column LiChrolut EN. After passing the water sample the SPE column was dried

with the air ow, packed in aluminium foil and kept in the refrigerator until analysis in the laboratory. This method is described in detail in Tolosa et al. (1999). Briey, a wide variety of compounds of differing hydrophobicity, including organophosphorus, triazines, carbamates, and phtalimides, the compounds sorbed on the column were eluted with ethyl acetate. The volume of the eluate is concentrated to 500 lL and dibenzothiophene added to serve as co-injected standard. The extracts were analysed in a gas chromatograph HP5890 equipped with a ame photometric detector (FPD) for determination of the organophosphorus compounds, and with a nitrogen and phosphorus detector (NPD) for determination of herbicides, using in this case desmetryn as a co-injected standard to monitor variations in NPD response (Tolosa et al., 1999). This method was carefully tested for the recovery of 40 compounds from various water types, with very satisfactory analytical results. An attempt was made to measure apolar organochlorine pesticides in the ltered water, using the same SPE columns. Extracts eluted from the column were injected into a GCMS HP5889 Engine B using negative ion chemical ionisation (NICI), and specically the following compounds were looked for: hexachlorobenzene (HCB), lindane, pp0 -DDE, pp0 -DDT, DDMU, op0 -DDE, op0 -DDD, op0 -DDT, heptachlor, aldrin, dieldrin, endrin, a-endosulfan, b-endosulfan, endosulfan sulphate and PCBs. The same extract was also screened by GCMS with electron impact (EI). Surface sediment samples were collected with a clean stainless steel spatula directly into hexane rinsed glass jars. Sediment samples stored in glass jars were kept frozen until analysis. In the laboratory these samples were freeze dried and sieved through a 250 lm metal sieve in order to remove the coarse fraction, which was always less than 2% in weight of sediment collected.

Fig. 1. Location of the sampling sites (116) in Mekong River delta, South of Vietnam. The map shows the river arms and the dense network of navigation canals (lines).

1478

F.P. Carvalho et al. / Marine Pollution Bulletin 56 (2008) 14761485

Sediment burrowing bivalve molluscs were selected as monitoring species due to the fact that they do not undertake up and down-river migrations and, thus, integrate contamination over time at the same site. Bivalve molluscs were collected by hand from the sediment oor of channels and river arms. It was possible to gather sufcient bivalve molluscs at 13 out of the 16 sampling sites. These sediment-dwelling molluscs, although collected in similar biotopes and occupying similar ecological niches, were not all of the same species. Biological species names are given in Table 1, with the geographic coordinates recorded with a portable GPS at the sampling points. From each site, always more than 20 individuals of bivalve molluscs species available were dissected and soft tissues combined in one sample. The samples of bivalve soft tissues were frozen, freeze dried, and the resulting powder homogenized. About 5 g of dry sediment, and a similar amount of bivalve tissues, were used for analysis of chlorinated hydrocarbons, according to techniques described in detail elsewhere (Villeneuve and Cattini 1986; Villeneuve et al., 1999). Briey, at the beginning of the analysis 25 ng of 2, 4, 5 trichlorobiphenyl were added to each sample as an internal standard for control of the chemical recovery yield. Samples were extracted for 8 h in a Soxhlet apparatus with a mixture of hexane and dichloromethane (1:1) for sediments and with only hexane for biological samples, followed by the clean up of extracts performed on methanol and hexane pre cleaned Florisil columns. From the Florisil column three fractions were eluted for separation of PCBs, HCB, DDE, aldrin (1st fraction), toxaphene, DDD, DDT, HCHs (2nd fraction), and dieldrin, endrin and endosulfans (3rd fraction). Elution solvents used were hexane (1st fraction), hexane/MeCl2 70:30 (2nd fraction) and MeCl2 (3rd fraction). Chromatographic analyses were performed with a gas chromatograph HP 5880A, equipped with a capillary column 25 m long, 0.2 mm internal diameter, coated with SE 54 silica phase, and an electron capture detector (ECD). Chromatographic conditions used were the following: splitless injector 250 C, detector 300 C, oven 70 C (2 min) with a ramp of 3 C/min to 260 C (20 min). This method is currently used in the laboratory in the quantication of 30 organochlorine compounds. Conrmatory analyses were performed with a mass spectrometer HP5889 Engine B using negative ion chemical ionisation (NICI).
Table 1 Sampling stations in the Mekong River delta and bivalve mollusc species collected for analysis Station VN 1 VN 2 VN 3 VN 4 VN 5 VN 6 VN 7 VN VN VN VN 8 9 10 11 Latitude N 1048.1370 1046.5500 1025.0590 1020.3970 1013.3160 1005.3800 1003.1320 0949.4310 0936.7320 0958.1860 0941.0520 0952.7260 1021.7720 0959.6400 1003.1890 1008.8870 Longitude E 10520.4840 10521.5090 10538.6300 10547.6450 10557.1010 10552.2190 10547.3960 10548.5970 10606.8180 10613.3190 10630.4770 10623.8020 10559.7430 10637.9760 10634.3370 10630.3440 Site description Hong Ngu, Mekong River Hong Ngu area, drainage from rice elds Cao Lanh, river near ferry harbour Navigation canal, near houses, fruit trees, no rice Vinh Long, canal Can Tho, canal Can Tho, river mudat, near ferry harbour Phung Hiep, canal Long Phu, canal near river mouth Tra Vinh, canal Duyen Hai, near the mouth of Mekong, shrimp farming area Tra Vinh, canal Canal Ba Tri, at the coast, large marine clams Canal, zone of rice paddies Giong Trom, canal Speciesa 1 1, 2, 3, 4 1, 2 1, 3 2 1, 3 2 5 2 1, 2 6 2 2

Thirteen polychlorobyphenyl congeners (congeners number 44, 49, 52, 101, 105, 118, 128, 138, 149, 153, 170, 180 and 200) were systematically quantied in sediment and biota samples. PCB reP sults are shown as PCB (the sum of 13 congeners), and as commercial mixtures aroclor 1254 and aroclor 1260. Solvents used were of high purity pesticide quality (Burdick and Jackson Labs, Muskegon, MI, USA). Authentic standards of organophosphorous, triazines, and phtalimides of purity >98% were purchased from Riedel-de Han (Seelze, Germany) and organochlorine authentic standards, purity >99%, were purchased from Interchim and Promochem (France). The quality control of the analytical performance for water samples was done through the repeated testing of recovery of compounds added in known amounts to water samples. Quality assurance for chlorinated hydrocarbons (Carvalho et al., 1997) was made with reference materials IAEA-142 (mussel tissue homogenate) and IAEA357 (estuarine sediment), co-analysed with each batch of samples. Concentrations of residues in water samples are expressed in ng L1 and in solid samples in ng g1 on sample dry weight. For sediment and biota samples conversion of concentrations on dry weight to lipid weight can be made using the concentration of hexane extracted lipids in sample materials (HEOM) provided in Tables. Whenever a compound was not detected, the limit of detection (LOD) for the compound is provided (as <LOD value).

3. Results and discussion 3.1. Pesticide residues in water Amongst all the compounds searched for in ltered water samples, only diazinon, fenitrothion, nonylphenol and endosulfan sulphate cyclic were detected. Diazinon was quantied in 6 out of 8 samples, with concentrations ranging from 3.5 to 42.8 ng L1, and non quantiable traces were found in the other two samples (Table 2). Fenitrothion was quantied in 5 out of 8 samples with concentrations ranging from 3.3 to 11.9 ng L1. Traces of a few other compounds, e.g. nonylphenol, caffeine, were detected by GCMS-EI and only endosulfan sulphate cyclic was detected in samples 6, 8 and 9 by GCMS-NICI (Table 2). Non detection of other apolar compounds in ltered waters was not surprising due to the small volume of water samples used and to the low water solubility, and concurrent high octanol-water partition coefcients (Kow) of these compounds, with log Kow values ranging from 3 to 6. The theory and experience shows that these compounds concentrate in the solid phase, particularly in the particulates and lipid fraction of organic matter, being their concentration in the water phase very low (Connell, 1994). Taking into account the low detection limit of this SPE method for a wide range of agrochemicals, 14 ng L1 depending on the compound, it is apparent that usage of these compounds either has been very low in this region or chemical degradation has been very rapid in the conditions of the tropical environment, as shown before in other regions and through experimental research (Pereira and Rostad, 1990; Lacorte et al., 1995; Barcelo and Hennion, 1997; Carvalho et al., 1992; Readman et al., 1993; Kale et al., 1999; Nhan et al., 2002) 3.2. Pesticide residues in sediments and biota Concentrations of organochlorine pesticides in bottom sediments are shown in Table 3. The higher concentrations measured were those of DDT compounds, with DDT displaying an average 6.3 ng g1 (median 1.85 ng g1, range 0.3267 ng g1, n = 16), followed by those of hexacyclochorohexane, HCH averaging 0.14 ng g1 (median 0.02 ng g1, range 0.0030.89 ng g1, n = 14), and those of endosulfans with an average 0.073 ng g1 (median

VN 12 VN 13 VN 14 VN 15 VN 16

a Unionidae Family: 1 Lanceolaria spp., 3 Sinanodonta sp.; Corbiculidae Family: 2 Corbicula spp.; Amblemidae Family: 4 Lamprotula quadrangulosa, 5 Oxynaia micheloti; Veneridae Family: 6 Meretrix lyrata.

F.P. Carvalho et al. / Marine Pollution Bulletin 56 (2008) 14761485 Table 2 Results of analyses of water soluble compounds Compounds Diazinon (ng L ) Fenitrothion (ng L1) Caffeine Nonylphenol Endosulfan sulphate cyclic
1

1479

VN 1 <1 <1

VN 2 6.7 <1

VN 3 3.5 <1

VN 6 42.8 3.3 + +

VN 8 9.7 3.7 +

VN 9 10.0 3.6 + +

VN 11 <1 9.1

VN 13 12.9 11.9 +

Nonylphenol and caffeine were detected by GC/MS/EI and endosulfan sulphate cyclic by GC/MS/NICI.

0.023 ng g1, range 0.0070.49 ng g1, n = 14), and chlordane with an average 0.021 ng g1 (median 0.017 ng g1, range 0.004 0.063 ng g1, n = 13). Other organochlorine pesticides, namely hexachlorobenzene (HCB), heptachlor, and the drins, occurred in concentrations generally lower than 0.01 ng g1. In the soft tissues of molluscs (Table 4) the higher concentrations of organochlorine insecticides were again those of DDT, with an average 38.6 ng g1 (median 18.8 ng g1, range 5.46123 ng g1, n = 13). In decreasing order, the concentrations of DDT were followed by those of endosulfan averaging 0.51 ng g1 (median 0.46 ng g1, range 0.111.3 ng g1, n = 12), chlordane with an average 0.38 ng g1 (median 0.33 ng g1, range 0.0460.91 ng g1, n = 13), and HCH with an average 0.25 ng g1 (median 0.21 ng g1, range 0.080.61 ng g1, n = 12). A few other organochlorine insecticides, such as aldrin and dieldrin, were also present but in concentrations much lower than those for the compounds mentioned above (Table 4). The hydrophobic and liphophilic properties of these chlorinated pesticides have been well documented (Spacie et al., 1995). All compounds listed in Tables 3 and 4 are known to generally accumulate in the lipid fraction of biological tissues and, furthermore, are known as environmentally persistent. Once released in the aquatic environment, compounds such as DDT are rapidly sorbed onto sediment particles and, later, concentration equilibrium in the system is maintained by a slow process of exchanges between, mainly, the sediment pool and biota (Bierman, 1990). In the case of deposit-feeding bivalve molluscs, the bioconcentration of chlorinated hydrocarbons is likely to take place with the ingestion of sediment particles followed by digestion and absorption of sediment associated organic matter. Actually, for compounds such as DDTs in mussels, oysters, and clams it has been reported for several coastal regions that concentrations in biota reect concentrations of the same compounds in sediments (Sericano et al.; 1990; Nhan et al., 1998; Carvalho et al., 2002; Chen et al., 2002; Wei et al., 2006). Plotting the concentration values in bivalve molluscs on concentrations in sediments, a positive correlation, statistically signicant at P < 0.05 (95% condence level), was found for DDT, endosulfan, and PCB (Fig. 2). However, no statistically signicant correlation could be nd (P > 0.60) for chlordanes, lindane, dieldrin, endrin, and HCB, likely because these were present in very low concentrations in sediments. The observed concentration of chlorinated hydrocarbons in molluscs is the balance of accumulation processes and metabolic degradation of compounds and excretion of their water soluble metabolites (Di Giulio et al., 1995). Our results suggest that DDT, specially DDE, and PCB are recalcitrant to biotransformation and, thus, accumulate in tissues with little metabolization. On the other hand, compounds such as endosulfan, HCB and lindane are bioaccumulated but seem to be largely destroyed in the metabolic pathways by enzyme activity (Krishna and Philip, 2008). Destruction of these OC compounds in the aquatic environment may, thus, largely depend upon their cycling through biota and metabolization rather than upon photolysis and hydrolysis in the water column. This interpretation is also underscored with results from experiments using 14C-labelled compounds on the degradation of chlorpyrifos, lindane, and DDT (Carvalho et al., 1992; Kale et al., 1999).

The geographic distribution of concentrations determined in sediments and in molluscs from the Mekong delta clearly shows that the highest DDT concentrations were measured close to villages and towns suggesting use of DDT to control mosquito. Endosulfans were higher in the district of Tra Vinh (total a-, b-endosulfan and endosulfan sulphate amounted to 0.49 ng g1 in sediment) which might be linked to endosulfan usage in sugar cane plantation. This is also the same station where dieldrin or endrin was measured in higher concentrations. In the past, these cyclodiene pesticides were commonly used in sugar cane plantations in other countries. In general, concentrations of DDT in clams increased from station 1, close to Cambodia, to the coast, indicating that the main application of DDT was made in the lower delta, in Vietnam. Concentrations of PCB in clams were also higher in the lower delta than at the border with Cambodia. It may be noticed in all samples that, amongst DDT derivatives, DDE was the most abundant compound accounting to DDT with a decimal fraction of 0.38 0.07 in sediments and 0.45 0.10 in molluscs (Tables 4 and 5). This is generally interpreted as an indication that DDT is not from a recent application (Tolosa et al., 1995; Minh et al., 2007). However, in the conditions of the tropics it may happen that at the moment of usage there is already a signicant amount of DDE present in the commercial mixture available. Furthermore, in the aquatictropical environment and in molluscs, DDT is rapidly transformed into DDE, which in turn, has a longer environmental persistence half-life than the parent compound (Carvalho et al., 1992; Minh et al, 2007). Occurrence of endosulfan in the Mekong delta sediments, in concentrations that generally rank immediately after DDT, indicates that usage of more modern and more expensive crop protection chemicals was accessible to the agriculturalists of this region. Furthermore, the presence of endosulfan compounds in water, sediments and bivalve mollusc tissues conrm the contention that has been made already in other regions about the unexpected environmental persistence of this compound (Carvalho et al., 2002). Results for HCH concentrations in the delta are of the same order of magnitude that those reported for China years after the ban on technical HCH (Li et al., 1998). Worldwide, hexacyclochlorohexanes has been the most used insecticide and China was a main producer and a major user of technical HCH. HCH residues were reported almost everywhere in Asia (Iwata et al., 1994; Monirith et al., 2003). Local usage and deposition of HCH following atmospheric transport from other latitudes might have both occurred in the region of the Mekong delta. However, results from our survey indicated that lindane (pure c HCH) had already replaced technical HCH, at least inland, near Vinh Long (e.g., stations VN 4, VN 5), while at the more coastal stations a- and b-HCH isomers, from technical HCH usage, were still present in sediments and biota (Tables 4 and 5). Interestingly, in mollusc tissues the three HCH isomers were generally detected (Table 5). In these samples lindane (c HCH) in average accounted for a decimal fraction of 0.49 0.20 of HCH, while aHCH and b-HCH accounted for 0.28 0.17 and 0.27 0.15, respectively. As lindane displays a shorter environmental half-life than other HCH isomers (Li et al., 1998), our measurements underscore the interpretation that lindane recently has been more used in

1480

F.P. Carvalho et al. / Marine Pollution Bulletin 56 (2008) 14761485

Table 3 Concentrations (ng g1 dry weight) of chlorinated hydrocarbons in sediment samples of the Mekong Delta, Vietnam Compounds Dry/wet weight HEOM(mg g1) HCB Lindane a-HCH b-HCH RHCH pp0 -DDE pp0 -DDD pp0 -DDT DDMU op0 -DDE op0 -DDD op0 -DDT RDDT Heptachlor Aldrin Dieldrin Endrin cis Chlordane trans Chlordane trans Nonachlor RChlordane a-Endosulfan b-Endosulfan Endosulfan sulphate REndosulfan P PCB Aroclor 1254 Aroclor 1260 Compounds Dry/wet weight HEOM (mg g1) HCB Lindane a-HCH b-HCH R HCH pp0 -DDE pp0 -DDD pp0 -DDT DDMU op0 -DDE op0 -DDD op0 -DDT RDDT Heptachlor Aldrin Dieldrin Endrin cis Chlordane trans Chlordane trans Nonachlor RChlordane a-Endosulfan b-Endosulfan Endosulfan sulphate REndosulfan P PCB Aroclor 1254 Aroclor 1260 Station VN 1 0.75 0.003 0.003 <0.001 <0.002 <0.002 ND 0.11 0.056 0.11 0.013 0.019 0.016 <0.002 0.32 <0.002 <0.003 <0.003 <0.015 <0.002 <0.002 0.007 0.007 <0.002 <0.002 <0.003 ND 0.132 0.088 0.28 Station VN 9 0.42 0.16 0.009 0.004 0.003 <0.002 0.007 0.88 0.76 0.11 0.23 0.010 0.083 <0.002 2.07 <0.002 <0.003 0.010 0.039 <0.002 <0.002 0.005 0.005 0.022 0.006 0.065 0.093 0.354 0.25 0.70 Station VN 2 0.57 0.13 0.013 0.009 <0.002 <0.002 0.009 2.0 1.3 0.094 0.95 0.021 0.15 <0.002 4.52 <0.002 <0.003 0.005 0.022 <0.002 <0.002 <0.003 ND 0.016 0.004 0.039 0.059 0.303 0.13 0.40 Station VN 10 0.41 0.21 0.013 0.005 <0.002 <0.002 0.005 0.53 0.61 0.40 0.15 0.011 0.077 <0.002 1.78 <0.002 <0.003 0.013 0.045 <0.002 <0.002 <0.003 ND 0.038 0.062 0.39 0.49 0.223 0.094 0.25 Station VN 3 0.64 0.11 0.022 0.003 <0.002 <0.002 0.003 0.67 0.38 0.12 0.14 0.007 0.052 <0.002 1.37 <0.002 <0.003 <0.003 0.043 <0.002 <0.002 <0.003 ND 0.005 <0.002 0.020 0.025 0.184 0.15 0.31 Station VN 11 0.44 0.17 0.009 0.005 <0.002 0.008 0.013 0.17 0.16 0.082 0.029 <0.002 0.035 <0.002 0.48 <0.002 <0.003 <0.003 <0.015 0.005 <0.002 <0.003 0.005 0.015 <0.002 <0.003 0.015 0.118 0.073 0.19 Station VN 4 0.56 0.11 0.009 0.89 <0.002 <0.002 0.89 0.99 0.43 0.18 0.20 0.016 0.063 <0.002 1.88 <0.002 <0.003 <0.003 0.014 <0.002 0.008 0.005 0.013 0.004 <0.002 0.006 0.01 0.404 0.19 0.81 Station VN 12 0.51 0.29 0.016 0.015 0.018 0.032 0.065 18 41 3.5 4.2 0.19 0.53 0.069 67.49 <0.002 <0.003 0.007 0.075 <0.002 <0.002 0.017 0.017 0.011 <0.002 0.006 0.017 0.985 1.3 1.2 Station VN 5 0.69 0.082 6.9 0.68 0.009 0.004 0.69 0.86 0.50 1.0 0.19 0.013 0.043 <0.002 2.61 <0.002 <0.003 <0.003 <0.015 <0.002 0.015 0.014 0.029 0.003 <0.002 0.004 0.007 0.621 0.85 0.81 Station VN 13 0.46 0.31 0.013 0.022 0.080 0.032 0.13 2.3 1.7 0.19 0.49 0.059 0.37 <0.002 5.11 <0.002 <0.003 <0.003 0.057 0.038 0.018 0.007 0.063 0.055 0.011 0.073 0.139 2.016 2.0 1.8 Station VN 6 0.56 0.22 0.025 0.012 <0.002 0.006 0.02 0.64 0.79 0.080 0.15 0.012 0.15 <0.002 1.82 <0.002 <0.003 0.012 0.026 <0.002 <0.002 0.015 0.015 0.018 0.006 0.049 0.073 0.275 0.35 0.43 Station VN 14 0.56 0.13 0.006 0.004 0.007 <0.002 0.011 0.13 0.19 0.060 0.024 0.003 0.041 <0.002 0.45 <0.002 <0.003 <0.003 0.091 0.004 0.022 <0.003 0.026 <0.002 <0.002 <0.003 ND 0.106 0.10 0.20 Station VN 7 0.62 0.063 0.009 <0.001 <0.002 <0.002 ND 0.49 0.48 0.070 0.13 0.007 0.065 <0.002 1.24 <0.002 <0.003 0.006 <0.015 <0.002 0.016 0.019 0.035 0.005 <0.002 0.009 0.014 0.276 0.19 0.56 Station VN 15 0.4 0.12 0.007 0.006 0.027 0.007 0.040 2.4 2.6 0.22 0.43 0.042 0.55 <0.002 6.24 <0.002 <0.003 <0.003 0.066 <0.002 0.004 <0.003 0.004 0.014 <0.002 <0.003 0.014 0.169 0.11 0.28 Station VN 8 0.50 0.21 0.013 0.004 <0.002 <0.002 0.004 0.66 0.46 0.18 0.18 0.010 0.070 <0.002 1.56 <0.002 <0.003 0.005 0.017 <0.002 0.005 0.013 0.018 0.029 <0.002 0.026 0.055 0.282 0.27 0.34 Station VN 16 0.37 0.30 0.016 0.013 0.019 0.013 0.045 0.91 0.79 0.22 0.22 0.022 0.14 <0.002 2.30 <0.002 0.011 0.008 0.12 0.014 0.012 0.015 0.041 0.011 <0.002 0.011 0.022 1.348 0.83 2.3

ND: Not detected; HEOM: Hexane extractable organic matter; <0.00x: less than the limit of detection.

the delta than the technical HCH mixture. Another likely source for lindane is atmospheric deposition following transport from neighbour countries in SE Asia, such as Malaysia, where lindane is commonly used in palm tree plantations (Iwata et al, 1994; Monirith et al., 2003; Taylor et al., 2003). 3.3. PCBs in sediments and biota Polychlorobyphenyls (PCBs) were measured in sediment and bivalve samples (Tables 3 and 4). PCB averaged 0.49 ng g1 (median

0.28, range 0.112.0 ng g1, n = 16) in sediments and 6.82 ng g1(median 5.20, range 1.8919.4 ng g1, n = 13) in biota. PCBs determined as commercial mixtures display in sediments the average concentration of 0.44 ng g1 (median 0.19 ng g1, range 0.0732.0 ng g1, n = 16) for aroclor 1254, and 0.68 ng g1(median 0.42 ng g1, range 0.192.3 ng g1, n = 16) for aroclor 1260. In clams the same compounds display average concentrations of 8.5 ng g1 (median 5.6 ng g1, range 1.624 ng g1, n = 13) and 3.8 ng g1 (median 2.6, range 0.389.1 ng g1, respectively). Aroclors are complex mixtures of PCBs, with varying degrees of chlorination, used as

Table 4 Concentrations (ng g1 dry weight) of chlorinated hydrocarbons in bivalve mollusc soft tissues of the Mekong Delta, Vietnam Compounds Dry/wet weight HEOM (mg g1) HCB Lindane a-HCH b-HCH RHCH pp0 -DDE pp0 -DDD pp0 -DDT DDMU op0 -DDE op0 -DDD op0 -DDT RDDT Heptachlor Aldrin Dieldrin Endrin cis Chlordane trans Chlordane trans Nonachlor RChlordane a-Endosulfan b-Endosulfan Endossulphate REndosulfan P PCB Aroclor 1254 Aroclor 1260 Station VN 1 0.24 82 0.10 0.27 0.053 0.096 0.42 7.9 4.0 2.3 0.67 0.080 0.71 0.23 15.89 <0.007 0.16 0.67 0.65 0.013 0.022 0.011 0.046 0.43 <0.007 <0.008 0.43 4.037 5.1 2.3 Station VN 3 0.22 72 0.079 0.14 0.063 0.011 0.21 8.5 5.9 1.1 0.77 0.10 0.64 0.023 17.03 <0.007 0.030 1.4 0.31 0.043 0.050 0.057 0.15 0.30 <0.007 0.019 0.32 5.011 5.1 2.7 Station VN 4 0.30 79 0.053 0.20 0.036 0.042 0.28 25 12 2.7 2.3 0.28 1.2 0.11 43.59 <0.007 0.10 1.1 <0.053 0.12 0.064 0.16 0.34 0.46 0.033 0.024 0.52 8.492 5.6 8.0 Station VN 5 0.26 45 0.045 0.042 0.020 0.018 0.08 5.7 3.4 0.15 0.65 0.063 0.39 <0.002 10.35 <0.007 <0.006 0.12 0.17 0.15 0.037 0.080 0.27 <0.006 0.013 0.11 0.12 5.2 3.1 7.1 Station VN 6 0.17 82 0.057 < 0.005 <0.004 <0.009 ND 11 5.5 0.63 0.91 0.12 0.67 <0.002 18.83 <0.007 0.031 0.44 <0.053 0.19 0.095 0.29 0.58 1.3 <0.007 <0.008 1.3 6.226 7.0 2.6 Station VN 8 0.19 49 0.061 0.039 0.038 <0.009 0.08 6.9 3.9 0.23 0.35 0.052 0.50 <0.002 11.93 <0.007 0.063 <0.008 0.98 0.34 0.30 0.27 0.91 0.70 0.020 <0.008 0.72 2.032 2.8 2.0 Station VN 9 0.22 70 0.19 0.084 0.046 0.072 0.20 30 31 1.3 4.1 0.42 2.6 <0.002 69.42 <0.007 0.57 0.82 2.7 0.21 0.084 0.14 0.43 0.49 <0.007 <0.008 0.49 9.268 13 5.4 Station VN 10 0.13 77 0.15 0.16 0.096 <0.009 0.26 5.9 6.6 2.3 0.91 0.067 0.79 <0.002 16.57 <0.007 <0.006 <0.008 5.1 0.047 0.11 0.17 0.33 0.66 <0.007 <0.008 0.66 3.442 6.1 1.7 Station VN 12 0.19 78 0.11 0.067 0.036 0.062 0.17 38 67 6.3 5.5 0.43 5.8 <0.002 123.03 <0.007 1.7 23 1.7 0.29 0.059 0.15 0.50 0.17 <0.007 0.031 0.20 5.5 9.7 1.5 Station VN 13 0.21 37 0.068 0.012 0.087 0.041 0.14 9.0 9.1 0.61 0.68 0.21 1.1 <0.002 20.7 <0.007 0.026 <0.008 0.40 0.081 0.065 0.18 0.33 0.80 0.018 <0.008 0.82 16.098 24 5.8 Station VN 14 0.23 59 0.067 0.046 0.019 0.093 0.16 1.7 2.6 0.69 0.38 0.030 0.058 <0.002 5.46 <0.007 0.16 0.22 1.1 <0.004 0.007 0.060 0.07 <0.006 <0.007 <0.008 ND 2.044 1.6 1.5 Station VN 15 0.25 64 0.048 0.17 0.27 0.17 0.61 26 41 0.62 4.6 0.19 3.2 <0.002 75.61 <0.007 0.36 0.15 <0.053 <0.004 0.11 0.045 0.16 <0.006 <0.007 0.38 0.38 1.893 5.1 0.38 Station VN 16 0.18 89 F.P. Carvalho et al. / Marine Pollution Bulletin 56 (2008) 14761485 0.097 0.33 0.038 0.066 0.43 28 32 4.9 5.6 0.41 2.5 0.14 73.55 <0.007 0.14 0.29 <0.053 0.39 0.21 0.20 0.80 <0.006 <0.007 0.11 0.11 19.37 22 9.1

ND: Not detected; HEOM: Hexane extractable organic matter; <0.00: less than the limit of detection.

1481

1482

F.P. Carvalho et al. / Marine Pollution Bulletin 56 (2008) 14761485

meretrix (Boon et al., 1989), and other species of marine and freshwater clams (this work), either it is not signicant or does not occur at all. Therefore, the current results conrm low degradation of CBs by bivalves and, as a consequence, CB bioaccumulation and effective food chain transfer of these compounds to man. 3.4. Comparison with other regions of Vietnam Table 5 summarizes data available on organochlorine compounds reported for various regions of Vietnam. Concentration of DDT in sediments of the Mekong delta reported in this study (mean 6.3 ng g1 dry weight) is lower than DDT in sediments of freshwater canals reported for the metropolitan area of Ho Chi Minh City (mean 80 ng g1 dry weight) (Phuong et al, 1998). Concentrations of DDTs in sediments of the Mekong delta are also much lower than those of DDT in Vietnamese soils, 110 ng g1 (Thao et al., 1993), and more comparable to concentrations measured in the Saigon-DongNai river and estuarine sediments at the South of Vietnam (Minh et al., 2007). Concentrations of HCHs, chlordanes and endosulfans in the Mekong delta are also lower than values reported for the Saigon River and Ho Chi Minh City area (Iwata et al., 1994; Minh et al., 2007), but are comparable to concentrations measured in the Hanoi region and in the Red River valley at the North of Vietnam (Nhan et al., 1999). Concentrations of PCBs in Mekong delta sediments, with average 0.49 ng g1 dry weight, are much lower than concentrations reported for freshwater canals in Ho Chi Minh City, averaging 223 ng g1 dry weight (Phuong et al. 1998), and for Hanoi canals with 11 ng g1 dry weight (Nhan et al., 2001). It is interesting to notice that in the South of Vietnam, PCB concentrations in sediments decrease from Ho Chi Minh City canals, to the Saigon-DongNai River system, to the Saigon-DongNai estuary, and are even lower in the Mekong River delta (Table 5). The high PCB concentrations near large cities were attributed to the uncontrolled waste discharge by industries and motor repair workshops (Nhan et al., 2001; Minh et al., 2007). Organochlorine residue concentrations in clams collected for this study are moderate for DDTs and PCBs, and low for HCH especially (Table 5). Values determined for molluscs from the Mekong delta are comparable to results reported for the North of Vietnam (Nhan et al., 1998; Nhan et al., 1999). Furthermore, they are comparable also to PCB and DDT concentrations in shellsh bought in the Ho Chi Minh City market (Kannan et al., 1992). Concentrations determined in sediments and clams (Tables 3 and 4) indicate that Mekong waters owing from the neighbour countries into Vietnam carry minor amounts of DDTs, PCBs and other OCs. In the delta, use of DDT and PCBs increase environmental contaminant levels, especially near towns and villages. Nevertheless, current levels of DDTs and PCBs in sediments and molluscs of the Mekong River delta are not as high as reported for freshwater canals by the metropolitan area of Ho Chi Minh City (Phuong et al., 1998; Minh et al., 2007). 3.5. Comparison with other regions in Asia The most comprehensive monitoring programme of persistent organic pollutants in the coastal marine environment of Asia-Pacic region was the International Mussel Watch (Monirith et al., 2003). However, this programme did not include South of Vietnam and Mekong delta areas. Results of the Mussel Watch programme showed widespread contamination of coastal waters in Asia with DDTs, HCHs, chlordanes and PCBs. Concentrations of DDTs generally rank the highest amongst those of persistent organic pollutants and the higher values were measured at the coast of China, Hong-Kong and Vietnam. Values reported for DDTs in these coastal areas are of the same order of magnitude as those measured in the

Fig. 2. Plot of concentrations of organochlorine pesticides in bivalve tissues on concentrations in sediments. Equations of the best t lines are: RDDT: log y = 0.50(log x) + 1.23; R2 = 0.47; p = 0.009; REndosulfan: log y = 0.40(log x) + 0.16; R2 P = 0.41; p = 0.03; PCB: log y = 0.64(log x) + 1.00; R2 = 0.61; p = 0.002

industrial chemicals. The concentrations of PCBs in sediments are low in comparison with concentrations measured in industrialized countries (Dannenberger and Lerz, 1996). The likely source of PCBs may be the old electric transformers in the cities and oils used in engines and other machinery on board of boats. Indeed, the waterways and uvial navigation are, respectively, the roads and the transportation means more used in the Mekong delta area. Repairs on board are often made on the water and leaks of lubricating oils are frequent. Weapons used during the Indochina War (1961 1975) were suggested as another potential source of PCBs in Vietnam (Thao et al., 1993) but there is no clear evidence for this. Furthermore, in contrast with the distribution of pesticides, PCBs were more evenly distributed reinforcing the impression that PCBs may come from pollution by oils used in boat engines, and thus released everywhere in the canals and river arms. Chlorobiphenyl congeners (CBs) concentrate also in bivalve tissues. A graphic plot (not shown) of all individual CB concentration data in bivalves on the concentration of CBs in sediments, showed a statistically signicant positive correlation (R2 = 0.57, n = 169, P < 0.001). An investigation was made on the pattern of the bioaccumulation of CBs through normalising the molar concentration of each CB with the molar concentration of CB153, a congener known to be recalcitrant to metabolic transformation, using concentration ratios CBx/CB153 (Kannan et al., 1994). A plot of these CB ratios in bivalves against the CB ratios in sediments did not show, however, a signicant modication of the pattern of CB ratios (Fig. 3). CBs of Group I (congener n180) are actually somewhat lower in clams; CBs of Group II (congeners n52, 101 and 149) display the same ratio in sediments and bivalves; CBs of Group III (congeners n105, 118, 128, 138 and 170) and Group IV (congeners n44 and 49) also display similar ratios in both compartments. These results suggest that bivalve molluscs do not have enzymatic capability to metabolise the CB congeners and, thus, are passive accumulators of these contaminants. This is not the case for every aquatic species. Different patterns of CB concentration in biota, and thus differential metabolisation of CB congeners, have been described for plankton, gastropod molluscs, sh, seals, whales, etc. (Boon et al. 1989; Khannan et al., 1989). Results of a research carried out in the area of Hanoi, North of Vietnam, showed that a common freshwater gastropod mollusc (Angulyagra sp.) was able to metabolise some CB congeners (Nhan et al., 2001). However, metabolisation of CBs by bivalve molluscs, including mussels Mytilus edulis (Khannan et al., 1995), North Sea clams Macoma baltica, marine clams Meretrix

F.P. Carvalho et al. / Marine Pollution Bulletin 56 (2008) 14761485 Table 5 Comparison of concentrations (ng g1 dry weight) of organochlorine compounds in various regions of Vietnam Compounds and samples Number of samples 5 10 8 16 13 16 11 6 9 7 16 10 7 1 9 13 2 16 5 10 8 12 5 16 6 9 7 14 9 8 1 9 13 2 16 5 10 8 16 13 15 11 6 9 7 16 9 7 1 9 13 1 16 Average 115 146 56 26 6 2.6 80 37 5.6 1.2 6.3 166 18 36 250 39 192 130 16 2.1 1.8 0.8 8.5 114 <0.05 0.011 0.012 0.14 0.4 7.8 14 0.3 0.25 2.5 9 21 4.2 20 11 6.6 126 223 81 6.8 0.90 0.49 22 14 75 7 6.8 34 50 Median 74 10 27 16 6 1 49 1.8 69 19 19 4 0.8 1.7 0.6 1.8 10 0.02 0.3 1.5 0.21 17 3.3 4.1 4.7 2.2 7.6 162 0.28 7.7 16 5.2 MinMax 19330 0.71300 1.9280 781 310.4 0.412 1.8254 1272 0.2123 0.155.4 0.3267 6864 1224 121550 5.4123 1.355 0.095.7 0.234.0 0.073.1 1.234 0.4790 <0.05 <0.010.03 <0.0050.022 0.0030.89 0.151.16 0.747 0.150.50 0.080.61 5.539 0.612 1.5130 0.740 0.528 0.2630 nd590 46150 0.3322 0.491.2 0.112.0 5.576 5.125 117 1.919 References

1483

RDDT:
Soils (North, Hanoi) Soils (Centre, Binh Tri) Soils (South, Ho Chi Minh) Sediments (North, Red River) Sediments (North, coastal) Sediments (South, Ho Chi Minh, Saigon River) Sediments (South, Ho Chi Minh canals) Sediments (South, Ho Chi Minh canals) Sediments (South, Saigon-DongNai River) Sediments (South, Saigon-DongNai estuary) Sediments (South, Mekong delta) Molluscs (North, Hanoi) Molluscs (North, coastal) Molluscs (South, Ho Chi Minh, Saigon River) Molluscs (North and Centre, coastal) Mollucs (South, Mekong delta) Fish (carp) (North, Hanoi) Fish (various species; several origins) Thao et al. (1993) Thao et al. (1993) Thao et al. (1993) Nhan et al. (1998, 1999, 2001) Nhan et al. (1999) Iwata et al. (1994) Phuong et al. (1998) Minh et al. (2007) Minh et al. (2007) Minh et al. (2007) This work Nhan et al. (1998) Nhan et al. (1999) Kannan et al. (1992) Monirith et al. (2003) This work Thao et al. (1993) Kannan et al. (1992) Thao et al. (1993) Thao et al. (1993) Thao et al. (1993) Nhan et al. (1998, 1999, 2001) Nhan et al. (1999) Iwata et al. (1994) Minh et al. (2007) Minh et al. (2007) Minh et al. (2007) This work Nhan et al. (1998) Nhan et al. (1999) Kannan et al. (1992) Monirith et al. (2003) This work Thao et al. (1993) Kannan et al. (1992) Thao et al. (1993) Thao et al. (1993) Thao et al. (1993) Nhan et al. (1998, 1999, 2001) Nhan et al. (1999) Iwata et al. (1994) Phuong et al. (1998) Minh et al. (2007) Minh et al. (2007) Minh et al. (2007) This work Nhan et al. (1998) Nhan et al. (1999) Kannan et al. (1992) Monirith et al. (2003) This work Thao et al. (1993) Kannan et al. (1992)

RHCH:
Soils (North, Hanoi) Soils (Centre, BinhTri) Soils (South, Ho Chi Minh) Sediments (North, Red River) Sediments (North, coastal) Sediments (South, Ho Chi Minh canals) Sediments (South, Ho Chi Minh canals) Sediments (South, Saigon-DongNai River) Sediments (South, Saigon-DongNai estuary) Sediments (South, Mekong delta) Molluscs (North, Red River) Molluscs (North, coastal) Molluscs (South, Ho Chi Minh) Molluscs (North and Centre, coastal) Molluscs (Mekong delta) Fish (carp) (North, Hanoi) Fish (various species; several origins)

RPCB:
Soils (North, Hanoi) Soils (Centre, Binh Tri) Soils (South, Ho Chi Minh) Sediments (North, Red River) Sediments (North, coastal) Sediments (South, Ho Chi Minh canals) Sediments (South, Ho Chi Minh canals) Sediments (South, Ho Chi Minh canals) Sediments (South, Saigon-DongNai River) Sediments (South, Saigon-DongNai estuary) Sediments (South, Mekong delta) Molluscs (North, Red River) Molluscs (North, coastal) Molluscs (South, Ho Chi Minh) Molluscs (North and Centre, coastal) Molluscs (South, Mekong delta) Fish (carp) (North, Hanoi) Fish (various species; several origins)

Mekong delta and reported herein. On the other hand, HCH concentrations measured in the Mekong delta were generally lower than HCH concentrations measured along the coast of China and India (Chen et al., 2002; Monirith et al., 2003; Yang et al., 2004; Wei et al., 2006).

4. Conclusions A few polar herbicides, fungicides and insecticides, namely diazinon, fenotrothion and endosulfan sulphate cyclic, were detected in water samples from the Mekong River delta. These residues originate in the neighbour rice elds but, in all water

samples the concentration of residues was low, i.e., fairly below acute toxic levels to aquatic biota (Mayer, 1987; Peterson et al., 1994). In most of sediment and biota samples the non-polar hydrophobic chlorinated hydrocarbons, especially DDTs, HCHs, endosulfans, and PCBs, were measured. In particular, the more persistent organochlorine compounds, such as DDTs, were found everywhere in the delta. This is explained by the general occupation of this fertile land and by the dispersal of residues by oods. Some locations displayed high concentrations of DDTs, probably due to recent application for malaria vector control. Concentrations of organochlorine residues, such as DDTs and HCHs, in bivalve molluscs from the Mekong delta are comparable

1484

F.P. Carvalho et al. / Marine Pollution Bulletin 56 (2008) 14761485 Boon, J.P., Eijenraam, F., Everaaarts, J.M., 1989. A structureactivity relationship (SAR) approach towards metabolism of PCBs in marine animals from different trophic levels. Marine Environmental Research 27, 159176. Carvalho, F.P., Fowler, S.W., Readman, J.W., Mee, L.D., 1992. Pesticide residues in tropical coastal lagoons: the use of 14C-labelled compounds to study cycling and fates of agrochemicals. In: Proceedings of the International Symposium on Applications of Isotopes and Radiation in Conservation of the Environment. Karlsruhe, Germany, 913 March 1992. IAEA, Vienna, pp. 637653. Carvalho, F.P., Fowler, S.W., Villeneuve, J.P., Horvat, M., 1997. Pesticide residues in the marine environment and quality assurance of analytical results. In: Proceedings of the International Symposium on Environmental Behaviour of Crop Protection Chemicals, Vienna, Austria, 15 July 1996. IAEA, Vienna, pp. 35 57. Carvalho, F.P., Villeneuve, J.-P., Cattini, C., Tolosa, I., Montenegro-Guilln, S., Lacayo, M., Cruz, A., 2002. Ecological risk assessment of pesticide residues in coastal lagoons of Nicaragua. Journal of Environmental Monitoring 4, 778787. Chen, W., Zhang, L., Xu, L., Wang, X., Hong, L., Hong, H., 2002. Residue levels of HCHs, DDTs and PCBs in shellsh from coastal areas of east Xiamen Island and Minjiang Estuary, China. Marine Pollution Bulletin 45, 385390. Colborn, T., Saal, F.S.V., Soto, A.M., 1993. Developmental effects of endocrinedisrupting chemicals in wildlife and humans. Environmental Health Perspectives 101, 378384. Connell, D.W., 1994. The octanol-water partition coefcient. In: Calow, P. (Ed.), Handbook of Ecotoxicology, vol. 2. Blackwell Scientic Publications, Oxford, pp. 311320. Dannenberger, D., Lerz, A., 1996. Polychlorinated biphenyls (PCB) and organochlorine pesticides in sediments of the baltic and coastal waters of MecklenburgVorpommern. German Journal of Hydrography 48, 526. Di Giulio, R.T., Benson, W.H., Sanders, B.M., Van Veld, P.A., 1995. Biochemical mechanisms: metabolisms adaptation and toxicity. In: Rand, G.M. (Ed.), Fundamentals of Aquatic Toxicology. Taylor & Francis Publications, Washington DC, pp. 523561. Dudgeon, D., 1995. The ecology of rivers and streams in tropical Asia. In: Cushings, C.E., Cummins, K.W., Minshall, G.W. (Eds.), River and Stream Ecosystems, Ecosystems of the World, vol. 22. Elsevier, pp. 615657. Isobe, T., Takada, H., Kanai, M., Tsutumi, S., Isobe, K.O., Boonyatumanod, R., Zakaria, M.P., 2007. Distribution of polycyclic aromatic hydrocarbons (PAHs) and phenolic endocrine disrupting chemicals in South ans Southeast Asian mussels. Environmental Monitoring and Assessment 135, 423440. Iwata, H., Tanabe, S., Sakai, N., Nishimura, A., Tatsukawa, R., 1994. Geographical distribution of persistent organochlorines in air, water and sediments from Asia and Oceania, and their implication for global redistribution from lower latitudes. Environmental Pollution 85, 1533. Kale, S.P., Carvalho, F.P., Raghu, K., Sherkhane, P.D., Pandit, G.G., Mohan Rao, A., Mukherjee, P.K., Murthy, N.B.K., 1999. Studies on degradation of 14Cchlorpyrifos in the marine environment. Chemosphere 39, 969976. Kannan, K., Tanabe, S., Quynh, H.T., Hue, N.D., Tatsukawa, R., 1992. Residue pattern and dietary intake of persistent organochlorine compounds in food stuffs from Vietnam. Archieves of Environmental Contamination and Toxicology 22, 367 374. Kannan, N., Schulz-Bull, D.E., Petrick, G., Duinker, J.C., Macht-Haussman, M., Wasserman, O., 1994. Toxic chlorobiphenyls in adipose tissue and whole blood of an occupationally/accidentally exposed man and the general population. Archives of Environmental Health 49, 375382. Khannan, N., Tanabe, S., Okamoto, T., Tatsukawa, R., Phillips, D.J.H., 1989. Polychlorinated biphenyls (PCBs) in sediments in Hong-Kong: a congenerspecic approach to the study of coplanar PCBs in aquatic systems. Environmental Pollution 62, 223235. Khannan, N., Reusch, T.B.H., Schulz-Bull, D.E., Petrick, G., Duinker, J.C., 1995. Chlorobiphenyls: model compounds for metabolism in food chain organisms and their potential use as ecotoxicological stress indicators by application of the metabolic slope concept. Environmental Science and Technology 29, 1851 1859. Krishna, K.R., Philip, L., 2008. Biodegradation of lindane, methyl parathion and carbofuran by various enriched bacteria isolates. Journal of Environmental Science and Health: Part B 43, 157171. Lacorte, S., Lartiges, S.B., Garrigues, P., Barcelo, D., 1995. Degradation of organophosphorus pesticides and their transformation products in estuarine waters. Environmental Science and Technology 29, 431438. Li, Y.F., Cai, D.J., Singh, A., 1998. Technical hexachlorocyclohexane use trends in China and their impact on the environment. Archieves of Environmental Contamination and Toxicology 35, 688697. MARD (Ministry of Agriculture and Rural Development of Vietnam), 1998. The Agricultural Development in the Mekong delta. Annual Report to the Government. Mayer Jr., F.L., 1987. Acute Toxicity Handbook of Chemicals to Estuarine Organisms. Fl. EPA/600/8-87/017, US Environmental Protection Agency, Gulf Breeze. Minh, N.H., Minh, T., Iwata, H., Kajiwara, N., Kunisue, T., Takahashi, S., Viet, P.H., Tuyen, B.C., Tanabe, S., 2007. Persistent organic pollutants in sediments from Sai Gon-Dong Nai River basin, Vietnam: levels and temporal trends. Archives of Environmental Contamination and Toxicology 52, 458465. Monirith, I., Ueno, D., Takahashi, S., Nakata, H., Sudaryanto, A., Subramanian, A., Karuppiah, S., Ismail, A., Muchtar, M., Zheng, J., Richardson, B.J., Prudente, M., Hue, N.D., Tana, T.S., Tkalin, A.V., Tanabe, S., 2003. Asia-Pacic mussel watch: monitoring contamination of persistent organochlorine compounds in coastal waters of Asian countries. Marine Pollution Bulletin 46, 281300.

Fig. 3. Concentration ratios of CBx/CB153 in bivalve molluscs on concentration ratios of CBx/CB153 in sediments. Different symbols are used for each group of CB congeners: Group I (CB 180), Group II (CBs 52, 101, 109), Group III (CBs 105, 118, 128, 138) and Group IV (CB 49).

to residue concentrations reported for molluscs of Red River and freshwater canals near Hanoi, in the North of Vietnam (Nhan et al., 1999). Those concentrations are, however, lower than concentrations measured in molluscs from the canals of the metropolitan area of Ho Chi Minh City and Saigon River at the South of Vietnam (Phuong et al., 1998) and in mussels collected at the marine coast (Monirith et al., 2003). PCBs are one interesting case because they were detected in all samples from the Mekong delta despite the little industrialization of this region. Nevertheless, in the aquatic environment of the Mekong delta PCBs are present in concentrations lower than those measured in the canals by the Ho Chi Minh City, conrming that the city industries currently are the main source of PCBs. Current levels of DDTs and PCBs in bivalve molluscs from the delta are moderate in comparison with the area of Ho Chi Minh canals. However the generalized consumption of molluscs, as well as of other aquatic biota from the region, renders effective the food chain transfer of contaminants from the aquatic environment to man and raises the problem of human exposure to these xenobiotics with the ingestion of food (Khannan et al., 1995; Nhan et al., 1998; Carvalho et al., 2002). Taking into account that shery products contribute to near half of the Vietnamese dietary intake, appropriate action by regulatory authorities may be needed to reduce contamination levels of the aquatic environment. Acknowledgements Support to this research is gratefully acknowledged. The Vietnam Atomic Energy Commission was supported by the IAEA Research Contract No. 7940/MC. This project was supported by the Swedish International Development Authority (SIDA) through the IAEA. Thanks are also due to Mr. Nguyen Xuan Duc, Institute of Oceanography, Vietnam Academy of Sciences and Technologies, that identied the mollusc species. The International Atomic Energy Agency (IAEA) is grateful for the support provided to its Marine Environment Laboratories by the Government of the Principality of Monaco. References
Barcelo, D., Hennion, M.-C., 1997. Trace determination of pesticides and their residues in water. Techniques and Instrumentation in Analytical Chemistry, vol. 19. Elsevier, Amsterdam. Bierman, V.J., 1990. Equilibrium partitioning and biomagnication of organic chemicals in benthic animals. Environmental Science and Technology 24 , 14071412.

F.P. Carvalho et al. / Marine Pollution Bulletin 56 (2008) 14761485 Nhan, D.D., Am, N.M., Hoi, N.C., van Dieu, L., Carvalho, F.P., Villeneuve, J.P., Cattini, C., 1998. Organochlorine pesticides and PCBs in the Red River Delta, North Vietnam. Marine Pollution Bulletin 36 (9), 742749. Nhan, D.D., Am, N.M., Carvalho, F.P., Villeneuve, J.-P., Cattini, C., 1999. Organochlorine pesticides and PCBs along the coast of North Vietnam. The Science of Total Environment 237/238, 363371. Nhan, D.D., Carvalho, F.P., Am, N.M., Tuan, N.Q., Yen, N.T.H., Villeneuve, J.P., Cattini, C., 2001. Chlorinated pesticides and PCBs in sediments and molluscs from freshwater canals in the Hanoi region. Environmental Pollution 112/3, 311320. Nhan, D.D., Carvalho, F.P., Nam, B.Q., 2002. Fate of 14C-Chlorpyrifos in the tropical estuarine environment. Environmental Technology 23, 12291234. Pereira, W.E., Rostad, C.E., 1990. Occurrence, distributions, and transport of herbicides and their degradation products in the lower Mississippi River and its tributaries. Environmental Science and Technology 24, 14001406. Peterson, H.G., Boutin, C., Martin, P.A., Freemark, K.E., Ruecker, N.J., Moody, M.J., 1994. Aquatic phyto-toxicity of 23 pesticides applied at expected environmental concentrations. Aquatic Toxicology 28, 275292. Phuong, P.K., Son, C. P.N., Sauvain, J.-J., Tarradellas, J., 1998. Contamination by PCBs, DDTs, and heavy metals in sediments of Ho Chi Minh Citys canals, Vietnam. Bulletin in Environmental Contamination and Toxicology 60, 347354. Readman, J.W., Albanis, T.A., Barcelo, D., Galassis, D., Tronczynski, J., Gabrielides, G.P., 1993. Herbicide contamination of Mediterranean estuarine waters: results form a MEDPOL pilot survey. Marine Pollution Bulletin 26, 613619. Sericano, J.L., Atlas, E.L., Wade, T.L., 1990. NOAAs status and trends mussel watch program: chlorinated pesticides and PCBs in oysters (Cassostrea virginica) and sediments from the gulf of Mexico, 19861987. Marine Environmental Research 29, 161203. Spacie, A., McCarty, L.S., Rand, G.M., 1995. Bioaccumulation and bioavailability in multiphase systems. In: Rand, G.M. (Ed.), Fundamentals of Aquatic Toxicology. Taylor & Francis Publications, Washington DC, pp. 493521. Taylor, M.D., Klaine, S.J., Carvalho, F.P., Barcelo, D., Everaarts, J. (Eds.), 2003. Pesticide Residues in Coastal Tropical Ecosystems. Distribution, Fate and Effects. Taylor & Francis Publications, CRC Press, London, p. 576.

1485

Thao, V., Kawano, M., Matsuda, M., Wakimoto, T., Tatsukawa, R., Cau, H., Quynh, H., 1993. Chlorinated hydrocarbon insecticide and polychlorinated biphenyls residues in soils from southern provinces of Vietnam. International Journal of Environmental Analytical Chemistry 50, 147159. Tolosa, I., Bayona, J.M., Albaigs, J., 1995. Spatial and temporal distribution, uxes, and budgets of organochlorinated compounds in northwest Mediterranean sediments. Environmental Science and Technology 29, 25192527. Tolosa, I., Douy, B., Carvalho, F.P., 1999. Comparison of the performance of graphitized carbon black and poly (styrene-divinylbenzene) cartridges for determination of pesticides and industrial phosphates in environmental waters. Journal of Chromatography A 864, 121136. UNEP, 1997. Global Environment Outlook. United Nations Environment Programme, Oxford University Press. Villeneuve, J.P., Cattini, C., 1986. Input of chlorinated hydrocarbons through dry and wet deposition to the Western Mediterranean. Chemosphere 15, 115120. Villeneuve, J.-P., Carvalho, F.P., Cattini, C., 1999. Levels and trends of PCBs, chlorinated pesticides and petroleum hydrocarbons in mussels from the NW Mediterranean coast: comparison of concentrations in 1973/1974 and 1988/ 1989. The Science of the Total Environment 237/238, 5765. Waid, J.S. (Ed.), 1987. PCBs and the Environment. CRC Press Inc., Boca Raton, FL. Wei, S., Lau, R.K.F., Fung, C.N., Zheng, G.J., Lam, J.C.W., Connel, D.W., Fang, Z., Richardson, B.J., Lam, P.K.S., 2006. Trace organic contamination in biota collected from the Pearl River Estuary, China: a preliminary risk assessment. Marine Pollution Bulletin 52, 16821694. Woolcoot, C.G., Aronson, K.J., Hanna, W.M., SenGupta, S.K., McCready, D.R., Sterns, E.E., Miller, A.B., 2001. Organochlorines and breast cancer risk by receptor status, tumor size, and grade (Canada). Cancer Causes and Control 12, 395 404. Yang, R.Q., Yao, Z.W., Jiang, G.B., Zhou, Q.F., Liu, J.Y., 2004. HCH and DDT residues in molluscs from Chinese Bohai coastal sites. Marine Pollution Bulletin 48, 795 805.