Arch. Environ. Contam. Toxicol. 50, 153–165 (2006) DOI: 10.1007/s00244-005-7001-1 Organochlorine Insecticides in Mudflats of Hong Kong, China H. L. Wong,1 J. P. Giesy,1,2 P. K. S. Lam1 1 Department of Biology and Chemistry, City University of Hong Kong, Tat Chee Avenue, Kowloon, Hong Kong Zoology Department, National Food Safety and Toxicology Center and Center for Integrative Toxicology, Michigan State University, East Lansing, Michigan 48824-1311, USA 2 Received: 4 January 2005 /Accepted: 14 May 2005 Abstract. Organochlorine (OC) insecticides were measured in different environmental compartments (including seawater, sediment, and biota) at six sites within the Mai Po Marshes Nature Reserve (MPMNR) and at one site in A Chau (AC) in Hong Kong in June 2002 (wet season) and January 2003 (dry season). MPMNR is a Wetland of International Importance (Ramsar site) situated in the western part of Hong Kong, whereas AC is a relatively remote island in Starling Inlet on the eastern side of the New Territories of Hong Kong. Generally, concentrations of OC insecticides in water, sediment, and biota were greater at MPMNR than at AC. Hexachlorobenzene, dichloro-diphenyl-trichloroethane, and hexachlorocyclohexanes were detected in all samples collected from MPMNR. Preliminary risk assessments were performed by comparing the measured concentrations of OCs in different environmental compartments with the corresponding guidelines promulgated by various environmental protection authorities. Concentrations of some OCs in sediments from certain locations in MPMNR were consistently greater than their corresponding sediment guideline values. These results suggest that the sediment OC concentrations in the sediments of MPMNR might pose a risk to aquatic organisms. Despite this, concentrations of OCs in biota samples were much lower than the relevant guideline values promulgated by government agencies to protect the health of human consumers. It is postulated that the management practices adopted at MPMNR have been effective in limiting the bioaccumulation window (duration) for OCs. This situation may have been aided by a frequent exchange of water between the tidal shrimp ponds at MPMNR and the open sea, again attributable to management practices. The low-cost maintenance practices adopted at MPMNR may potentially be applicable to wetlands in other southeastern Asian countries, thus allowing sustainable fishery production and wildlife conservation. Organochlorine (OC) insecticides have been widely used in China. Although most applications have ceased, the residues of OC insecticides still persist in many environmental compartCorrespondence to: P. K. S. Lam; email: bhpksl@cityu.edu.hk ments in the southern region of China. In the Pearl River Delta, it has been estimated that OC pesticide use was approximately 76,000 to 100,000 tons/y from 1972 to 1982 (Hua and Shan 1996). These OC insecticides, which have leached into the Pearl River (Zhang et al. 2002), have resulted in relatively great historical concentrations in water birds and sediments from the mudflats and mangrove stands at the Mai Po and Inner Deep Bay (ID) Ramsar sites of Hong Kong (Liang et al. 1999; Zheng et al. 2000; Connell et al. 2003). Discharge from the highly polluted Shenzhen River and its catchment is another source of pollution to Deep Bay (Hong Kong Environmental Protection Department 2003). These compounds are classified by the United Nations Environment Program as being of ‘‘great concern’’ because of their persistence, toxicity, and wide distribution in the southeast Asian region (United Nations Environmental Programme [UNEP] 2003). Because of the positioning of the ecologically important Ramsar site near the heavily industrialized area of southern China and the fact that China is a signatory to the Stockholm Convention, it was necessary to prepare an inventory of the current status of contamination at the site. Situated within the Mai Po and ID Ramsar sites, the Mai Po Marshes Nature Reserve (MPMNR) occupies an area of 380 ha and is composed of five main wetland habitat types: mangroves, fishponds (FPs), reed beds, mudflats, and intertidal shrimp ponds. Intertidal shrimp ponds (or gei wais [GWs]) are established with flooding at selected high tides through regulation by a single sluice, which facilitates the material exchange with the open sea area. The central area of a GW is mainly covered by mangroves and reeds and is an important habitat for water birds. To counter pollution stress, the management authority of the MPMNR—the World Wildlife Fund for Nature Hong Kong (WWFHK)—performs various lowcost traditional practices to maintain the habitat. The present study was conducted to determine the current status of OC contamination and assess the efficiency of these low-cost management practices, especially regarding their potential for decreasing hazards to humans who might consume fish from these areas. In addition, preliminary risk assessment was conducted by comparing the measured OC concentrations in water, sediment, and fish with relevant guidelines promulgated by various jurisdictions to estimate the potential ecologic risk of OCs to wildlife at MPMNR. H. L. Wong et al. 154 Fig. 1. Map showing the Mai Po and AC study sites. Sampling locations in the Mai Po area: 1 = FPs; 2 = GWs; 3 = the gate of GWs; 4 = MM; 5. mudflat near the NB; 6. ID. Dotted lines represent the tidal flushing direction. FPs = fishponds; GWs = gei wais; NB = near the bird-watching blind; ID = Inner Deep Bay; MM = middle part of the mangrove. Materials and Methods Seawater, sediment, and biota (including polychaetes, shrimp, and fish) were collected from six sites in MPMNR and one site in A Chau (AC) in June 2002 and January 2003 (Fig. 1 and Table 1). The sampling periods corresponded to the wet and dry seasons as defined by the Hong Kong Observatory based on rainfall records (Hong Kong Observatory 2003). The six sampling sites in MPMNR were selected to represent different hydrological characteristics. The outer part of the Mai Po marshes (i.e., ID [location no. 6] and near the bird-watching blind [NB; location no. 5]; Fig. 1) is heavily influenced by tidal flushing, whereas the inner part (i.e., location nos. 1 through 4) is predominantly affected by artificial flushing of GW water. Two seawater samples were analyzed from each site. No water samples were collected from ID during the dry season. Four surface sediment samples were collected with a stainless steel grab. Large objects such as leaves, rubbish, and rocks were removed by hand. Twenty g sediments were weighed and freeze-dried for subsequent OC analysis. Dichlorodiphenyl-trichloroethane and its metabolites (DDTs), hexachlorocyclohexanes (HCHs a, b, and c), and 11 cyclodiene insecticides— including chlordanes (a and c), endosulfans (I and II), aldrin, dieldrin, endrin, heptachlor, kepone, methoxychlor, and mirex—were measured using previously described methods (Khim et al. 1999; Snyder et al. 2001). Concentrations of OC insecticides were measured in composite samples of surface sediments. Dried samples were weighed and then ground with a precleaned mortar and pestle. Total organic carbon (TOC) was determined using a Perkin Elmer 2400 Series II CHNS/O analyzer (Perkin Elmer, CT) after acidification for carbonate removal (National Oceanic and Atmospheric Administration 1993). Biota samples (n = 5) were collected from the Mai Po mudflat (near the NB and GWs) and AC. Polychaetes, shrimp, and fish were collected from both sites subject to their availability. The shrimp (Metapenaeus ensis) from Mai Po were only available for collection during the wet season. Mudskippers (Boleophthalmus boddaerti) were collected from the mudflat near NB in both the wet and dry season. Three fish species— Mugil cephalus (flathead mullet), Mylio macrocephalus (black porgy), and Tilapia zilla (redbelly tilapia)—were collected from GWs during the wet season. Two unidentified species of Gobiidae and the bivalve Cyclina orientalis were collected from AC in both seasons. Shrimp (Acetes spp.) and other species of fish were collected from AC during the wet season only (Table 1). For the analysis of biota samples, whole-body tissues were completely homogenized, and 20 g homogenized tissue was used for OC determination. The samples were freeze-dried and mixed with 3x volume precleaned sodium sulfate. Dried samples were Soxhlet extracted for 16 hours using 400 mL distilled 75% dichloromethane (Tedia) with hexane (LabScan, Thailand). Sediment extracts were treated with activated copper to remove sulfur. All extracts were concentrated to 1 mL by rotary evaporation at approximately 40C. Twenty L seawater was filtered through precleaned 0.5-lm glass fiber filters (GC-50; Toyo, Japan). The filters were Soxhlet extracted in a manner similar to that for sediments. The remaining filtrates were extracted three times with 1 L dichloromethane. The lipid contents of biotic samples were determined gravimetrically. Extracts were passed through 10 to 12 g activated Florisil (60- to 100-mesh size; Sigma) for the removal of impurities and fractionation (Khim et al. 1999). Polychlorinated biphenyls (PCBs), dichlorodiphenyldichloroethane (DDDs), dichlorodiphenyldichloroethylene (DDEs), and a- and bHCHs were eluted in fraction 1 by 80 to 100 mL hexane. Other OC pesticides and PCB 169 were eluted in fraction 2 by 100 mL dichloromethane and hexane (1:4). The extracts were concentrated by rotary evaporation and blow-down with high-purity nitrogen gas. OC insecticides were quantified using a Hewlett Packard 5890 series II gas chromatograph equipped with an 63Ni electron-capture detector. A fused silica capillary column (60 m · 0.25 mm diameter) coated with DB-5MS (J &W Scientific, Folsom, CA) at 0.25-lm film thickness was used. The column oven was programmed from an initial temperature of 100C with a 3-minute hold time to 210C at a rate of 25C/min and then ramped at a rate of 1C/min to 270C with a final hold time of 60 minutes. The injector and detector temperatures were maintained at 250C and 280C, respectively. Accuracy and precision were determined by use of matrix spikes, matrix spike duplicates, and analysis of standard reference materials (SRM-2978, National Institute of Standards and Technology). Method detection limits (MDLs) were determined as the concentrations of spiked standards in various environmental samples that give rise to a peak with a signalto-noise ratio of 3 (United States Environmental Protection Agency [USEPA] 1996). Procedural blanks were included to check for potential contamination. Statistical Analysis and Calculations Concentrations in sediment and biota samples were compared among locations and seasons using nonparametric Mann-Whitney U and 155 Organochlorine Insecticides In Mudflats of Hong Kong, China Table 1. Details of samples collected from Mai Po and AC during 2002 and 2003 Location and matrix N Collection date Body length (cm) Mai Po (wet season) Seawater Plankton Sediment Polychaetes Shrimp Mudskipper 2 2 4 4 4 4 6/15/2002 6/15/2002 6/15/2002 6/16-18/2002 6/17/2002 6/20/2002 NA NA NA 0.5–6.1 12.3–13.5 12.1–12.9 20.0 20.0 20.0 20.0 9.4 13.4 € € € € € € 0.1 L 0.1 L 0.01 g 0.01 g 1.3 g 1.5 g Collected in six sampling points Filter 20 L seawater with 63-lm pore size net Collected in six sampling points Scientific name: unknown (pooled sample) Scientific name: Metapenaeus ensis Scientific name: Boleophthalmus boddaerti Mai Po (dry season) Seawater Plankton Sediment Polychaetes Mullet Black porgy Redbelly tilapia Mudskipper 2 2 4 4 4 4 4 4 1/15/2003 1/15/2003 1/15/2003 1/14-19/2003 1/19/2003 1/19/2003 1/19/2003 1/14/2003 NA NA NA 0.5–5.0 37.9–39.0 19.5–26.1 21.8–23.5 12.1–13.6 20.0 € 20.0 € 20.0 € 20.0 € 20.0 € 20.0 € 20.0 € 15.7€ 0.1 L 0.1 L 0.01 g 0.01 g 0.03 g 0.02 g 0.02 g 1.4 g Collected in five sampling points Filter 20 L seawater with 63-lm pore size net Collected in six sampling points AC (wet season) Seawater Plankton Sediment Polychaetes Clam Shrimp Gobiidae sp. A Gobiidae sp. B Shortnose ponyfish 2 2 4 4 4 4 4 4 4 6/23/2002 1/15/2003 6/23/2002 6/23–30/2002 6/24/2002 6/23–27/2002 6/23–27/2002 6/23–27/2002 6/23–27/2002 NA NA NA 0.5–3.2 6.5–7.5 NA 11.9–12.5 12.5–14.2 3.0–4.0 20.0 20.0 20.0 20.0 7.5 20.0 12.8 10.8 20.0 0.1 L 0.1 L 0.01 g 0.01 g 1.3 g 0.01 g 1.7 g 1.2 g 0.01 g Hawaiian Islands silverside 4 6/23–27/2002 1.5–2.0 20.0 € 0.01 g Reeve's shad Konoshiro gizzard shad 4 4 6/23–27/2002 6/23–27/2002 6.2–8.5 10.5–12.7 8.6 € 1.3 g 10.4 € 1.8 g 2 2 4 4 4 4 4 1/20/2003 1/15/2003 1/20/2003 1/20–31/2003 1/22/2003 1/20–25/2003 1/20–25/2003 NA NA NA 0.5–2.5 5.4–8.5 8.3–9.6 10.5–11.3 20 20 20 20 6.1 10.7 12.4 AC (dry season) Seawater Plankton Sediment Polychaetes Clam Gobiidae sp. A Gobiidae sp. B Volume or WW € € € € € € € € € € € € € € € € 0.1 L 0.1 L 0.01 g 0.01 g 1.9 g 2.3 g 1.6 g Remarks Scientific Scientific Scientific Scientific name: name: name: name: Mugil cephalus Mylio macrocephalus Tilapia zilla Boleophthalmus boddaerti Filter 20 L seawater with 63-lm pore size net Scientific name: unknown (pooled sample) Scientific name: Cyclina orientalis Scientific name: Acetes spp. (pooled sample) Scientific name: Unknown Scientific name: Unknown Scientific name: Leiognathus brevirostris (pooled sample) Scientific name: Atherinomorus insularum (pooled sample) Scientific name: Tenualosa reevesii Scientific name: Konosirus punctatus Filter 20 L seawater with 63-lm pore size net Scientific Scientific Scientific Scientific name: name: name: name: Unknown (pooled sample) Cyclina orientalis Unknown Unknown AC = A Chau. NA = Not applicable. Kruskal-Wallis tests because of failure in normality and homogeneity of variance tests (Sigmastat 3.0; SPSS, Chicago, IL). Hierarchical cluster analysis was applied to classify the relationship of concentrations among different sites with different seasons for sediment and biota samples (Systat 11.0; Systat). To facilitate comparisons of OC concentrations in different matrices with environmental guidelines, sediment concentrations were expressed on a dry-weight (dw) basis. The organic carbon–normalized values were calculated based on concentrations on a dw basis and the corresponding TOC values listed in Table 4. Concentrations of biota samples were expressed on a wetweight basis. The lipid-normalized values were calculated based on concentrations on a wet weight basis and the corresponding lipid weights listed in Table 5. Preliminary Risk Assessment Preliminary risk assessments were performed by comparing the measured concentrations of OCs in different compartments with the corresponding guidelines from various environmental protection authorities. Typical and worst-case risk quotients were estimated by calculating the ratios of the means and the highest concentrations of OCs to their corresponding guideline values, respectively (Tables 4 and 5) (DHHS 1994; USEPA 1995a, 1995b, 1995c, 2004; Environmental Canada 2002; Ontario Ministry of Environment and Energy 1997; ZHB 1999). Results and Discussion Extraction Efficiency and Recoveries External standards of OC pesticides—100 ng/L, 20 ng/g dw, and 20 ng/g dw—were added to water, sediment, and biota samples, respectively. OC pesticides had recoveries ranging from 90% to 102% in sediment and biotic samples. The average recoveries of chlordanes, DDTs, endosulfans, aldrin, H. L. Wong et al. 156 Table 2. Comparison of measured and listed OC insecticide concentrations (ng/g dw) in SRM2978 OC insecticides Measured values c-chlordane o,pÕ-DDD p,pÕ-DDD o,pÕ-DDE p,pÕ-DDE o,pÕ-DDT p,pÕ-DDT a-chlordane Endrin 11.38 4.4 37.5 10.5 38.8 9.2 3.9 14.6 5.3 € € € € € € € € € 0.83a 0.6 1.5 1.0 2.3 1.6 0.3 0.9 0.7 Listed values 8.9 3.9 38.3 7.6 39.4 7.7 4.3 13.9 4.8 € € € € € € € € € Mean deviation (%) 0.84 2.0 2.7 1.6 4.3 1.9 0.4 1.0 0.3 +28 +13 )2 +38 )2 +19 )9 +5 +10 a Mean € SD. DDD = dichloro-diphenyl-dichloroethane. DDE = dichloro-diphenyl-dichloroethylene. DDT = Dichloro-diphenyl-trichloroethane. OC = Organochlorine. SRM = Standard reference material. dieldrin, endrin, and HCHs were >90%, and the recoveries of heptachlor, mirex, kepone, and methoxychlor were 75% to 85% in seawater samples. The MDLs of chlordanes, DDTs, endosulfans, aldrin, dieldrin, endrin, and HCHs in seawater were 0.01 to 0.5 ng/L. The MDLs of the other OCs in seawater were 1 ng/L. The MDLs of OCs in sediment and biota samples were 0.01 to 0.05 and 0.01 to 0.1 ng/g dw, respectively. Concentrations were not corrected for recoveries. The measured and listed values of standard reference material (SRM) 2978 are listed in Table 2. Most of the measured values were in close agreement with the listed values except for c-chlordane and o,p-DDE, for which the measured concentrations were higher than the listed values. c-chlordane and o,p-DDE (10 lg/L) were spiked into different environmental matrices— including particulates in water, sediments, and all biota species (n = 4)—to act as a supplementary test. The recoveries of cchlordane and o,p-DDE were 86.5% to 105.3% and 75.2% to 106.8%, respectively. Spatial and Temporal Variations of OC Concentrations OCs were detected in most samples analyzed (Tables 3, 4, and 5). In general, DDTs were the predominant contaminants in most samples. Cyclodienes, hexachlorobenzene (HCB), and HCHs showed a large variation in concentrations in various species and among sampling locations. Generally, concentrations of OC pesticides in water, sediment, and biota were greater at MPMNR than at AC (Tables 3, 4, and 5). Sediments from MPMNR contained finer particles and greater TOC contents than those from AC (Table 4). Concentrations of total DDTs and total HCHs in water samples from all of the sampling sites (Table 3) were relatively small compared with the no-hazard levels for surface waters (1000 ng/L for DDTs and 5000 ng/L for HCHs) as promulgated by the State Environmental Protection Administration of China (ZHB 1999). Sediments from MPMNR (total OC insecticides = 7.0 to 96 ng/g dw) were generally more contaminated than those from AC (3.4 to 5.7 ng/g dw). In MPMNR, GWs, the mudflat (near NB), and ID were most contaminated in terms of DDTs, HCB, HCHs, and cyclodienes (Fig. 2 and Table 4). Concentrations of OCs were lower in areas with strong tidal and artificial flushing. Concentrations of OC residues in fish from MPMNR (15 to 55 ng/g ww) were generally higher than those from AC (1.1 to 3.6 ng/g ww) (Fig. 3). Concentrations of OC pesticides in plankton samples were all less than those of MDLs. No significant temporal variations in concentrations of OC insecticides in seawater were observed (Kruskal-Wallis test p >0.05) except for HCHs. Among the OC insecticides, HCB occurred at the greatest concentrations in both seasons (wet season = 0.05 to 0.61 ng/L and dry season = 0.14 to 0.34 ng/ L), with the greatest concentrations found in GWs. Concentrations of OCs in sediments varied among sampling sites (Table 4 and Fig. 2). Concentrations of HCB in the water samples from FPs were twice as great during the dry compared with the wet season. The spatial patterns were dissimilar for different insecticides, with HCHs and cyclodienes showing marked variations between the dry and wet seasons (Fig. 3). DDTs. Concentrations of total DDTs in the sediments ranged from 1.4 to 19 ng/g dw (dry season) to 2.0 to 31 ng/g dw (wet season). DDT concentrations varied with sampling locations in MPMNR and were generally greater than those at AC (1.4 and 2.0 ng/g dw) (Table 4). GWs, ID, and FPs were classified as a different group from the middle part of the mangrove (MM) and AC by cluster analysis (Fig. 2). DDT levels recorded in this study were comparable with the concentration ranges found in surface sediments from the Pearl River Delta (38.3 € 1.7 ng/g dw; Zhang et al. 2002), Daya Bay (0.14 to 20.7 ng/g; Zhou et al. 2001), and Lake Tai (0.33 to 1.8 ng/g dw) and Shanghai (13 to 33 ng/g dw) (Nakata et al. 2005). DDEs were the dominant DDT metabolites in the sediments from both MPMNR and AC. Ratios of (DDDs + DDEs)/total DDTs in the surface sediments collected from MPMNR were generally close to unity (Fig. 4), and approximately half of the DDTs were metabolic products. In this study, the proportion of DDEs and DDDs relative to total DDTs were greater than those in samples collected from various Chinese estuaries during the 1980 s (DDDs + DDEs)/total DDTs = 0.5 to 1) (Fu et al. 2001; Mai et al. 2002) and 2001 (0.81) (Nakata et al. 2005). Specifically, the proportion of p,pÕ-DDE was larger in the inner part of GWs at Mai Po, where there was relatively little tidal flushing compared with the outer areas (NB and ID) (Table 3). Although the ratios (close to unity) recorded in this study might suggest that a great proportion of the existing DDTs were related to historical input rather than fresh discharge, the substantial amount of DDTs found in seawater still pointed to the possible existence of fresh sources of DDTs (Table 3). Higher concentrations of DDTs were detected in the biological samples from the MPMNR compared with AC. Concentrations of total DDTs ranged from 7.9 to 12.9 ng/g ww in fish and from 0.1 to 6.9 ng/g ww in other biota samples from MPMNR (Table 5). These levels were similar to the concentration range (3.9 to 76 ng/g ww) reported for Hong Kong fishes (Chan et al. 1999). Cluster analysis classified the mudskipper (Boleophthalmus boddaerti) as a separate group from other species in GWs within the same season (Fig. 4). Compared with MPMNR, lower concentrations were found in 0.010 0.005 0.013 0.024 0.014 € € € € 0.018 0.018 0.002 0.111 € 0.012 € € € € € AC = A Chau. FP = Fishpond. GW = Gei wai. HCB = Hexachlorobenzene. HCH = Hexachlorocyclohexane. ID = Inner Deep Bay. MDLs = Method detection limits. MM = Middle part of the mangrove. NB = Mudflat near Bird-watching blind. NG = Gate of geiwai. ND = Samples with concentrations less than the MDLs. OC = Organochlorine. € 0.012 € 0.005 € 0.052 € 0.012 € 0.022 29.5 ND ND ND ND 0.021 0.012 0.080 0.067 0.084 ND ND 0.036 ND ND 0.029 0.041 0.092 0.341 ND ND ND ND Salinity (psu) Aldrin a-chlordane c-chlordane o,pÕ-DDD p,pÕ-DDD o,pÕ-DDE p,pÕ-DDE o,pÕ-DDT p,pÕ-DDT Dieldrin Endrin Endosulfan I Endosulfan II Endosulfan sulfate a-HCH b-HCH c-HCH HCB Heptachlor Kepone Methoxylor Mirex 5.9 ND ND ND ND ND 0.009 0.085 ND 0.247 ND ND 0.041 ND ND ND ND ND 0.271 ND ND ND ND GW Insecticides and salinity FP Dry season 30.4 ND ND ND ND 0.016 0.012 0.080 0.067 0.092 ND ND 0.028 ND ND ND 0.009 0.153 0.332 ND ND ND ND NG 0.003 0.005 0.013 0.024 0.007 € .003 € 0.011 € 0.153 € 0.006 € € € € € 33.4 ND ND ND ND 0.008 ND 0.064 ND 0.046 ND ND 0.032 ND ND 0.015 0.009 0.153 0.222 ND ND ND ND MM € € € € 0.010 0.003 0.011 0.160 € 0.003 € 0.008 € 0.006 € 0.002 34.1 ND ND ND ND 0.048 ND 0.062 0.017 0.020 ND ND 0.012 ND ND 0.040 0.026 0.020 0.137 ND ND ND ND NB € € € € 0.002 0.014 0.021 0.057 € 0.001 € 0.003 € 0.024 € 0.016 € 0.004 35 0.122 ND ND ND 0.010 0.001 0.117 0.041 0.030 ND ND ND ND ND ND ND ND 0.121 ND ND ND ND AC 5.3 € 0.052 ND ND ND 0.068 € 0.001 0.086 € 0.001 0.080 € 0.023 0.130 € 0.009 0.030 € 0.004 0.102 ND ND 0.058 ND ND 0.081 0.020 0.096 € 0.015 0.407 ND ND ND ND FP 0.022 0.045 0.005 0.045 0.019 0.007 € € € € 0.007 0.011 0.022 0.073 € 0.007 € € € € € € Wet season 8.1 ND ND ND 0.142 0.072 0.054 0.459 0.013 0.214 ND ND 0.091 ND ND 0.052 0.024 0.085 0.608 ND ND ND ND GW 0.059 0.014 0.002 0.020 .011 0.012 € € € € 0.001 0.003 0.003 0.020 € 0.036 € € € € € € 10.2 ND ND ND 0.053 0.118 0.077 0.098 0.017 0.097 ND ND 0.053 ND ND 0.086 0.012 0.080 0.356 ND ND ND ND NG 0.084 0.054 0.084 0.162 0.044 0.107 € € € € 0.076 0.028 0.111 0.458 € 0.063 € € € € € € Table 3. Concentrations (ng/L € SD) of OC insecticides and salinity in water samples from Mai Po and AC during the dry and wet seasons 18.3 ND ND ND ND 0.010 ND 0.023 0.009 0.053 ND ND 0.059 ND ND 0.042 0.008 0.048 0.165 ND ND ND ND MM € € € € 0.029 0.011 0.002 0.108 € 0.004 € 0.023 € 0.012 € 0.008 € 0.001 18.3 ND ND ND ND 0.034 0.005 0.023 0.004 0.067 ND ND 0.039 ND ND 0.031 0.009 0.049 0.047 ND ND ND ND NB 0.013 0.001 0.017 0.005 0.017 € € € € 0.011 0.012 0.044 0.030 € 0.020 € € € € € 20.0 0.053 ND ND 0.016 0.026 0.043 0.084 0.004 0.073 ND ND 0.054 ND ND 0.095 0.015 0.081 0.372 ND ND ND ND ID 30 € 0.020 0.022 ND ND € 0.015 ND € 0.006 ND € 0.001 ND € 0.001 ND € 0.002 ND € 0.006 0.041 ND ND € 0.066 ND ND € 0.008 0.006 € 0.011 0.006 € 0.015 0.066 € 0.174 0.065 ND ND ND ND AC € € € € 0.008 0.001 0.015 0.047 € 0.009 € 0.014 1900c — 2a 2.26b 2.26b 1.22b 1.22b 2.07b 2.07b 1.19b 1.19b Wet season TOC (% dw) Aldrin a-chlordane c-chlordane o,pÕ-DDD p,pÕ-DDD o,pÕ-DDE p,pÕ-DDE o,pÕ-DDT p,pÕ-DDT 0.32b 0.32b 0.32b 22e 6d — 2a 2.26b 2.26b 1.22b 1.22b 2.07b 2.07b 1.19b 1.19b 0.72b 4200c (ng/g TOC) 290c (ng/g TOC) 1400c (ng/g TOC) Endosulfan sulfate a-HCH b-HCH c-HCH HCB Heptachlor Kepone Methoxylor Mirex Endosulfan II Endosulfan I TOC (% dw) Aldrin a-chlordane c-chlordane o,pÕ-DDD p,pÕ-DDD o,pÕ-DDE p,pÕ-DDE o,pÕ-DDT p,pÕ-DDT Dieldrin Endrin Dry season TEL/SQAL/ AET-L/LEL/ ISQG (ng/g) (2.05) (17.00) (0.15) (0.88) (3.73) (1.85) (0.87) (0.21) (1.37) (17.94) (1.87) (0.35) (1.95) 0.01 (0.10) 0.29 (10.03) 0.11 (1.33) 0.01 (0.13) 1.12–1.23 1.83 € 0.08 ND ND ND ND 1.30 € 0.06 12.93 € 5.10 1.68 € 0.14 0.33 € 0.03 0.11 € ND 0.09 € 9.97 € 1.17 € ND ND ND 0.25 € 0.07 (0.35) 0.96 € 0.09 (1.08) ND 1.05–1.18 ND ND 0.76 € 0.07 0.19 € 0.03 ND 1.87 € 0.16 16.02 € 0.75 0.78 € 0.07 0.12 € 0.02 3.29 € 0.35 1.73 € 0.08 FP (2.34) (28.01) (3.81) (1.32) (10.71) (6.94) (1.29) (9.62) (5.33) (0.96) (4.52) (2.54) (2.27) (1.42) (5.16) (17.22) (5.82) (1.25) 0.99 (24.94) 0.07 (1.02) 0.05 (0.64) 0.02 (0.91) 1.09–1.14 0.81 € 0.12 4.47 € 0.07 2.40 € 0.14 1.97 € 0.21 1.25 € 0.11 5.07 € 0.09 16.39 € 0.87 5.38 € 0.31 1.21 € 0.04 0.58 € 0.89 € ND 24.12 € 0.93 € ND ND ND 0.15 € 0.12 (0.29) 2.59 € 0.07 (2.67) 0.80 € 0.07 (0.88) 1.10–1.25 1.24 € 0.04 9.47 € 0.12 5.17 € 0.18 ND ND 2.28 € 0.06 25.38 € 3.81 3.55 € 0.19 1.29 € 0.03 10.49 € 0.21 6.73 € 0.16 GW 0.13 0.02 0.01 0.67 0.03 0.05 0.56 (1.94) (0.33) (0.29) (15.54) (0.19) (0.65) (12.23) 1.05–1.17 ND 1.92 € 0.06 (2.01) ND ND ND ND 0.33 € 0.08 (0.41) ND ND 1.76 € 0.30 € 0.28 € 14.93 € 0.16 € 0.59 € 11.50 € ND 1.15 € 0.03 (1.17) 2.86 € 0.09 (2.97) 2.59 € 0.09 (2.67) 1.22–1.48 ND ND 1.64 € 0.10 (1.72) 0.43 € 0.01(0.44) ND 2.83 € 0.48 (3.51) 9.92 € 0.30 (10.34) ND ND 0.86 € 0.01 (0.87) 0.12 € 0.08 (0.20) NG (2.19) (0.11) (2.02) (0.09) 0.01 (0.06) 0.16 (4.49) 0.09 (0.87) 0.04 (0.15) 0.04 (0.70) 1.18–1.28 ND ND ND ND ND ND 3.20 € 0.28 (3.55) ND ND 0.10 € 0.65 € ND 0.05 € 4.35 € 0.76 € ND ND 0.22 € 0.02 (0.24) ND 0.15 € 0.06 (0.19) 1.12–1.59 ND 0.09 € 0.01 ND 1.99 € 0.04 ND ND ND 2.18 € 0.13 0.10 € 0.02 ND ND MM (1.72) (3.47) (4.08) (1.09) (2.76) (1.36) (5.17) (3.09) (0.90) 0.24 0.04 0.15 0.38 0.05 0.01 0.93–1.14 ND 6.79 € 0.12 4.31 € 0.32 1.13 € 0.11 1.27 € 0.11 4.55 € 0.35 10.17 € 0.33 6.66 € 0.21 5.45 € 0.27 2.52 € 0.54 € 2.32 € 7.46 € 1.09 € 0.20 € ND ND (6.91) (4.73) (1.25) (1.38) (4.96) (10.63) (6.92) (5.66) (2.87) (0.57) (2.53) (8.00) (1.15) (0.20) 0.32 € 0.18 (0.58) ND 0.15 € 0.04 (0.19) 0.84–1.06 ND 4.53 € 0.59 2.43 € 0.53 0.80 € 0.08 ND 1.48 € 0.28 3.15 € 0.30 3.52 € 0.46 1.06 € 0.04 2.70 € 0.05 1.24 € 0.09 NB (2.06) (3.60) (2.24) (0.88) (1.05) (7.08) (8.60) (5.60) (4.77) (2.27) (2.80) € € € € € € € € 0.51 0.35 0.05 0.90 0.04 0.10 0.01 0.02 0.56–0.6 0.60 € 0.21 1.99 € 0.02 2.43 € 0.48 0.74 € 0.11 1.40 € 0.29 4.04 € 1.12 7.09 € 0.49 0.35 € 0.12 3.25 € 0.16 5.49 1.29 1.80 10.67 2.37 0.32 0.50 0.31 (0.81) (2.01) (3.09) (0.90) (1.79) (5.49) (7.75) (0.52) (3.47) (6.00) (1.46) (1.85) (11.87) (2.41) (0.47) (0.51) (34) 0.12 € 0.07 (0.21) 0.63 € 0.04 (0.66) ND 0.67–0.85 1.93 € 0.10 3.52 € 0.06 1.91 € 0.24 0.82 € 0.08 1.02 € 0.03 6.71 € 0.46 8.02 € 0.39 5.37 € 0.39 4.07 € 0.53 2.18 € 0.11 1.83 € 0.68 ID 0.57–0.85 0.36 € 0.36 (0.86) ND ND ND ND ND 2.04 € 0.26 (2.37) ND ND 0.41 € 0.05 (0.46) ND ND 1.48 € 0.16 (1.64) ND ND ND ND 0.08 € 0.05 (0.13) ND ND 0.27–0.53 ND ND ND ND ND ND 1.40 € 0.06 (2.00) ND ND ND ND AC Table 4. Concentrations (ng/g dw) of OC pesticides in sediment samples in dry and wet seasonsa Concentrations are reported as mean € standard derivation. Maximum concentrations are given in parentheses. Locations are abbreviated as fish pond (FP); gei wai (GW); the gate of the gei wai (NG); middle part of the mangrove (MM); mudflat near the bird watching blind (NB); Inner Deep Bay (ID). Typical and worst-case risk quotients larger than unity are in bold. 1900c 2.20 € 1.31 € 0.85 € 8.01 € ND ND ND ND 0.32b 0.32b 0.32b 22e 6d € € € € € 2.09 2.87 1.14 0.46 0.19 0.72b 4200c (ng/g TOC) 290c (ng/g TOC) 1400c (ng/g TOC) FP 0.04 0.06 0.06 0.22 0.09 0.18 0.09 0.09 0.09 (2.23) (1.37) (0.91) (8.16) (2.16) (3.01) (1.25) (0.59) (0.30) € € € € € 0.95 € 2.22 € 1.47 € 20.73 € 1.26 € ND ND ND 3.90 1.64 0.39 1.73 0.41 GW 0.05 0.25 0.11 0.82 0.08 0.23 0.09 0.07 0.27 0.03 (1.01) (2.48) (1.57) (21.69) (1.34) (4.16) (1.77) (0.45) (2.03) (0.49) 0.44 € 0.03 (0.47) ND ND 3.76 € 0.20 (3.99) ND ND ND ND ND ND ND 0.44 € 0.02 (0.47) ND NG € € € € € 0.01 0.04 0.09 0.06 0.10 (0.17) (0.69) (0.19) (0.58) (1.79) 1.11 € 0.09 (1.23) ND ND 3.93 € 0.21 (4.16) ND 0.65 € 0.06 (0.68) ND ND 0.17 0.64 0.15 0.49 1.67 MM € € € € € 5.43 € 1.53 € 2.01 € 1.47 € 2.28 € 0.10 € ND ND 2.00 2.33 0.06 0.80 0.51 NB 0.34 0.15 0.21 0.24 0.21 0.01 0.10 0.18 0.02 0.09 0.04 (5.79) (1.70) (2.20) (1.72) (2.51) (0.10) (2.20) (2.57) (0.08) (0.92) (0.55) € € € € € 3.07 € 2.30 € 1.26 € 14.46 € ND ND 0.38 € 0.36 € 1.57 1.82 0.22 0.45 0.34 ID (3.36) (2.49) (1.81) (17.55) (1.80) (2.80) (0.50) (0.60) (0.36) 0.20 (0.63) 0.14 (0.52) 0.21 0.23 0.38 2.80 0.27 0.69 0.21 0.16 0.02 d Canadian ND ND ND 3.25 € 0.05 (3.30) ND ND ND ND ND ND ND ND 0.04 € 0.03 (0.07) AC Used at contaminated sites sediments-LEL (ng/g); b USEPA threshold effects levels (TEL) (ng/g); c USEPA sediment quality advisory levels (SQAL ng/g Total organic carbon (TOC)); Interim Sediment Quality Guideline (ISQG) (ng/g); e USEPA apparent effects threshold-low (AET-L) (ng/g). AC = A Chau. FP = Fishpond. GW = Gei wai. HCB = Hexachlorobenzene. HCH = Hexachlorocyclohexane. ID = Inner Deep Bay. MDLs = Method detection limits. MM = Middle part of the mangrove. NB = Bird watching blind. NB = Mudflat near NB. ND = Samples with concentrations less than the MDLs. OC = Organochlorine. TOC = Total organic carbon. a Dieldrin Endrin Endosulfan I Endosulfan II Endosulfan sulfate a-HCH b-HCH c-HCH HCB Heptachlor Kepone Methoxylor Mirex Wet season TEL/SQAL/ AET-L/LEL/ ISQG (ng/g) Table 4. Continued 100 300 300 300 3000 300 300 300 ND ND ND 8.36 0.33 0.02 0.72 0.13 0.33 0.22 ND 33.8 0.68 ND ND 0.3 ND ND ND 0.8 0.02 0.004 1.4 0.01 0.05 0.1 € 1 0.04 € 0.70 € 0.64 € € € € € € € ND 9.6 € 0.4 ND ND 2.78 € 0.1 ND ND 0.19 € 0.02 8.81 € 0.2 0.69 € 0.1 0.21 € 0.03 0.13 € 0.01 0.12 € 0.03 0.61 € 0.01 0.23 € 0.08 ND 18.38 € 0.61 1.42 € 0.1 ND ND 0.31 € 0.04 0.08 € 0.01 ND ND ND ND 0.78 ND ND ND 8.41 0.32 0.02 0.34 0.31 0.29 0.39 ND 3.82 ND ND ND 0.04 ND ND ND 0.8 0.02 0.01 0.02 0.04 0.05 0.1 € 0.02 € 0.2 € € € € € € € € 0.1 0.37 € 0.71 € 2.81 € ND ND 1.60 € 11.19 € ND 0.06 € ND ND 0.81 € 0.43 € 0.08 € 9.82 € 0.05 € 0.19 € 0.05 € 0.10 € ND ND ND 0.05 0.02 0.01 0.57 0.01 0.01 0.01 0.01 0.01 0.09 0.64 0.02 0.04 0.17 0.38 € 0.72 € 2.75 € ND ND 0.78 € 9.59 € 1.43 € 0.71 € ND 30.32 € 0.39 € 0.38 € 2.34 € 9.61 € 0.23 € 0.44 € ND 0.49 € ND ND ND 0.43 0.24 0.32 0.23 0.50 7.04 0.21 0.33 0.72 6.51 1.10 0.49 0.33 0.04 1.63 0.02 0.27 0.31 ND 0.17 1.43 0.17 0.04 0.12 ND 0.11 0.11 0.07 ND 1.17 0.01 0.04 0.12 0.05 0.06 ND ND 0.05 0.38 0.04 0.01 0.03 € € € € € € 0.31 0.03 0.01 0.03 0.02 0.02 € 0.02 € 0.03 € 0.09 € € € € € € 0.01 € 0.07 € 0.09 0.01 0.12 0.16 ND 0.10 0.97 0.05 0.01 0.05 0.01 0.05 0.07 0.12 0.03 0.79 ND 0.05 0.08 0.05 0.04 ND ND Risk for carcinogenicity is considered significant if the risk quotient is greater than 10-5 by comparing OC concentrations with relevant USEPA guideline values. D = Dry. FDA = Food and Drug Administration. MDLs = Method detection limits. ND = Sample with concentrations less than the MDLs. OC = Organochlorine. US EPA = United States Environmental Protection Agency. W = Wet. a Aldrin 320 a-chlordane 650 c-chlordane 650 o,p'-DDD p,p'-DDD o,p'-DDE p,p'-DDE o,p'-DDT p,p'-DDT Dieldrin Endosulfan I 65000 Endosulfan II 65000 Endosulfan sulfate Endrin HCB 8600 a-HCH b-HCH c-HCH Heptachlor 5400 Kepone Methoxylor Mirex 2200 Mai Po biota € € € € € € € € € € € € € € € 0.01 0.01 0.01 0.01 0.01 0.19 0.01 0.01 0.01 0.01 0.02 0.1 0.02 0.01 0.16 € 0.01 € 0.02 € 0.03 ND ND 0.74 0.29 ND ND 8.17 0.33 0.07 2.41 0.33 0.31 0.04 ND 3.30 0.09 ND ND 0.04 0.38 0.14 0.04 1.17 0.01 0.01 0.32 0.04 0.03 0.05 € € € € 0.01 0.03 0.01 0.01 € 0.42 € 0.01 € € € € € € € € 0.08 € 0.57 US EPA FDA guidance noncancer action/tolerance Boleophthalmus Boleophthalmus Metapenaeus hazard level level Mugil cephalus Mylio macrocephalus Tilipia zillia boddaerti (W) boddaerti (D) Polychaetes (W) Polychaetes (D) ensis (D) Table 5. Concentrations of OC insecticides (ng/g ww € SDs) in the biota from Mai Po and AC in the dry and wet seasonsa 160 H. L. Wong et al. ND 0.04 € 0.01 300 300 300 100 5400 2200 b-HCH c-HCH Heptachlor Kepone Methoxylor Mirex ND ND ND ND 0.03 € 0.04 a-HCH 0.3 € 0.02 0.2 € 0.4 ND ND 0.1 € 0.03 0.1 € 0.02 0.1 € 0.03 0.2 € 0.04 ND 0.13 € 0.04 ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND 0.1 € 0.02 ND 0.1 € 0.02 0.02 € 0.02 0.1 € 0.02 ND 0.1 € 0.1 0.7 € 0.03 0.3 € 0.02 0.4 € 0.4 0.1 0.1 0.03 0.03 0.02 0.1 0.5 € 0.1 3000 € € € € € € 0.01 € 0.02 0.1 € 0.02 0.1 0.1 € 0.03 0.1 € 0.02 0.1 0.1 € 0.02 0.02 € 0.02 0.1 0.1 € 0.04 0.1 € 0.03 0.1 0.1 € 0.02 0.1 0.1 € 0.01 0.1 € 0.1 0.1 0.03 € 0.03 0.1 € 0.1 0.02 € 0.02 0.04 € 0.05 0.05 € 0.04 0.01 € 0.01 o,p'-DDT p,p'-DDT Dieldrin Endosulfan I 65000 Endosulfan II 65000 Endosulfan sulfate Endrin HCB 8600 0.13 € 0.05 ND 0.04 € 0.03 0.08 € 0.03 ND 0.53 € 0.03 ND 0.13 € 0.05 0.02 € 0.01 0.11 € 0.02 0.02 € 0.01 ND ND ND ND ND ND ND 0.2 € 0.03 0.1 € 0.01 0.1 € 0.01 0.04 € 0.01 ND 0.1 € 0.01 0.04 € 0.03 0.1 € 0.1 0.1 € 0.02 1.09 € 0.45 0.3 € 0.2 0.1 € 0.02 0.3 € 0.2 0.7 € 0.01 ND 0.1 € 0.03 0.1 € 0.02 0.1 € 0.1 0.1 € 0.01 0.1 € 0.01 0.1 € 0.02 0.1 € 0.1 ND ND ND 0.02 € 0.03 ND 0.1 € 0.01 0.1 € 0.01 0.1 € 0.01 0.04 € 0.02 0.2 € 0.1 ND 0.3 € 0.2 0.2 € 0.02 0.1 € 0.02 ND ND p,p'-DDD o,p'-DDE p,p'-DDE 300 300 300 € € € € 0.05 0.03 0.01 0.16 € € € € 0.07 0.04 0.02 0.04 € 0.09 ND 2.87 € 0.23 0.12 € 0.03 0.08 € 0.05 0.13 € 0.03 0.27 € 0.14 ND ND 0.15 ND 0.31 0.14 0.03 0.05 0.05 € 0.04 1.42 € 0.21 0.10 € 0.01 0.08 0.04 0.12 0.62 0.04 € 0.01 ND 0.86 € 0.09 0.03 € 0.02 0.14 € 0.12 0.02 € 0.02 ND ND ND ND ND ND ND ND 0.97 € 0.72 ND 0.04 € 0.01 ND ND 0.57 € 1.06 € € € € 0.11 0.12 0.01 0.08 € € € € 0.10 0.10 0.03 0.03 € 0.08 ND 3.21 € 0.88 0.11 € 0.02 0.13 € 0.11 0.07 € 0.03 0.23 € 0.11 ND ND 0.17 ND 0.09 0.18 0.04 0.05 0.04 € 0.04 0.71 € 0.42 0.10 € 0.07 0.13 0.16 0.11 0.07 0.08 € 0.02 0.04 € 0.01 ND 0.06 € 0.01 ND ND ND ND ND ND 0.17 € 0.01 ND ND ND ND ND ND ND ND ND ND ND 0.06 € 0.01 ND ND ND ND 0.41 € 0.03 ND ND ND 0.20 € 0.01 ND ND ND ND ND 0.01 € 0.01 ND ND ND ND ND ND ND 0.05 0.27 ND € 0.05 € 0.07 ND ND ND ND ND ND ND ND ND ND ND ND 1.22 0.65 0.20 € 0.12 € 0.07 € 0.08 ND ND ND ND ND ND ND ND ND ND 0.08 € 0.03 ND ND ND ND ND ND 0.49 0.34 0.11 € 0.17 € 0.20 € 0.05 ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND FDA US EPA guidance Noncancer action/ Atheri Cyclina Cyclina Poly Poly hazard tolerance Hyporhamphus Konosirus Tenualosa nomorus Leiognathus Gobiddae spp. Gobiddae spp. Gobiddae spp. Gobiddae spp. orientalis orientalis chaetes chaetes Acetes level level quoyi punctatus reevesii insularum brevirostris A (D) A (W) B (D) B (W) (D) (W) (W) (D) spp. Aldrin 320 a-chlordane 650 g-chlordane 650 o,p'-DDD AC biota Table 5B. 162 H. L. Wong et al. Fig. 2. Cluster analysis of concentrations of total DDTs, HCHs, cyclodienes, and HCB in sediments. Separate groups are clustered by linked lines. DDTs = dichloro-diphenyl-trichloroethane and its metabolites; HCB = hexachlorobenzene; HCHs = hexachlorocyclohexanes. fish (0.39 to 2.6 ng/g ww) and other biota samples (0.02 to 0.2 ng/g ww) from AC. Although large-scale application of DDTs has been banned in China for >20 years, the long half-lives and potential ecological impacts of these chemicals still warrant continuous monitoring. The occurrence of detectable concentrations of DDTs in the water column in this area (Luo et al. 2004) indicated that some fresh inputs might still be present. HCB. Measurable concentrations of HCB were found in all environmental compartments at MPMNR and AC. The greatest concentrations of HCB were observed in sediments from GWs (>20 ng/g dw), and these were greater than those from other locations in MPMNR during both seasons (Fig. 3). Overall, HCB contamination was found to be higher in the samples from GWs, ID, and FPs in MPMNR (0.05 to 24 and 1.5 to 21 ng/g dw during the dry and wet seasons, respectively) than AC (1.5 and 3.3 ng/g dw during the dry and wet seasons, respectively). These values were comparable with concentrations recently reported from Lake Tai (0.1 to 3.2 ng/g dw) (Nakata et al. 2005). In addition, detectable levels of HCB were found in fish and other biota samples, possibly reflecting consistent contamination by HCB in MPMNR and AC. In general, cluster analysis classified fish collected from MPMNR as a distinct group containing higher concentrations of HCB (Concentration less than the method detection limit [ND] to 33.8 ng/g ww) compared with fish from AC (ND to 0.7 ng/g ww) (Table 5). The relatively great concentrations of HCB recorded in this study might be related to its intense use in the heavily industrialized Pearl River Delta. These chemicals might conceivably be transported to the study areas by water and tidal currents and aerial deposition (Louie et al. 2004; Wong et al. 2004). HCB concentrations in the Mai Po sediments were similar to those in other estuaries near urban and industrial areas (Lee et al. 2000; UNEP 2002; United Nations University 2003). It should be noted that HCB is still being used in various industrial processes in China and has been detected in various locations in China (Wu et al. 1999; Kunisue et al. 2003; Nakata et al. 2005). HCHs. Low concentrations of HCHs in mixture form were found in both biota and abiotic samples from the study areas. The concentrations of HCHs in sediments were comparable with or higher than those reported in Xiamen Harbour (<0.01 to 0.15 ng/g dw; Zhou et al. 2000) and Daya Bay (0.32 to 4.16 ng/g; Zhou et al. 2001), but they were lower than the historical concentrations in the Pear River Estuary (42 to 101 ng/g; Wu et al. 1999) in China. The spatial and temporal Organochlorine Insecticides In Mudflats of Hong Kong, China 163 Fig. 3. Cluster analysis of concentration of total DDTs, HCHs, cyclodienes, and HCB in fish. Separate groups are clustered by linked lines. DDTs = dichloro-diphenyl-trichloroethane and its metabolites; HCB = hexachlorobenzene; HCHs = hexachlorocyclohexanes. variations of HCHs were less marked than other OCs as shown in Figure 3. Concentrations of total HCHs in biota samples were similar for both MPMNR and AC (Fig. 4), which were apparently lower than those reported for biota from India, where technical HCH is still being used (Kannan et al. 1995; Pandit et al. 2002). The sum of a- and b-HCH accounted for >50% of total HCHs in sediments from MPMNR (Table 4). In general, the b- and c-isomers were dominant in samples collected from AC. The ratios of aHCH to c-HCH in the abiotic and biotic samples from MPMNR were generally greater than unity (Fig. 3), which might indicate the greater use of HCH mixtures than lindane (Willet et al. 1998). In samples from ID, which experienced the greatest tidal flushing, a-HCH was the predominant isomer. b-HCH, with the slowest degradation rate in sediments, tended to accumulate in areas with relatively low flushing rates such as GWs (Willet et al. 1998). In general, the relatively small concentrations of b-HCH observed probably reflected the decreasing use of technical HCHs and lindane in the Pearl River Delta area. Cyclodienes. Concentrations of cyclodienes were greater in sediment and fish samples from MPMNR compared with AC (Tables 4 and 5). Sediments from GWs were the most con- Fig. 4. The relationship between (DDDs + DDEs)/total DDTs and DDDs/DDEs in sediments from AC and Mai Po. Points where DDT levels are below the detection limit are omitted. AC = A Chau; D = dry season; DDTs = dichloro-diphenyl-trichloroethane and its metabolites; FP = fishponds; HCB = hexachlorobenzene; HCHs = hexachlorocyclohexanes; ID = Inner Deep Bay; GW = gei wais; MM = middle part of the mangrove; NB = mudflat near the bird-watching blind; NG = the gate of GW; W = wet season. H. L. Wong et al. 164 taminated for cyclodienes (38 and 17 ng/g dw during the dry and wet seasons, respectively). GW samples formed a distinct group relative to other locations based on cluster analysis, especially during the dry season (Fig. 2). Approximately 20% to 40% of cyclodienes detected in MPMNR were aldrin, dieldrin, and endrin (Table 4). Chlordanes were detectable (ND to 11.2 ng/g dw) in some sampling locations at MPMNR. Endosulfans accounted for 5% to 20% of the cyclodienes measured in sediments. This result is consistent with previous data reported for the Pearl River Delta area (Mai et al. 2002). Low concentrations of endosulfans (<0.1 ng/L) were commonly found in seawater samples from MPMNR. Concentrations of cyclodienes varied considerably with different biota species collected from MPMNR. For example, fish (2.0 to 13 ng/g ww) were more contaminated by cyclodienes than other animals (0.05 to 3.4 ng/g ww). Chlordanes and dieldrin were important contaminants among the cyclodienes in biota samples from MPMNR (Fig. 4c). The levels of cyclodienes in fish from MPMNR were close to the concentrations in fish from tropical Asian countries (Kannan et al. 1995). Lower concentrations of cyclodienes were generally detected in various environmental compartments at AC compared with those at MPMNR, except seawater (Tables 3, 4, and 5). The compositions of cyclodienes were dissimilar for the two study areas, and this might be related to differences in input sources (Fig. 4). Preliminary Risk Assessment Recoveries for OCs in water samples in this study were generally between 80% and 90%. Concentrations reported in this study were not corrected for recoveries. However, even if the concentrations were corrected for recoveries (data not shown), they were still below the acceptable levels promulgated by various environmental protection authorities (e.g., ZHB 1999; USEPA 2002). Thus, it could be concluded that the risks related to OC concentrations in seawater at the two study sites were low. Concentrations of p,pÕ-DDE, a-HCH, b-HCH, chlordanes, and heptachlor in sediments from GWs and ID were consistently greater than their corresponding sediment guideline values under both typical and worst-case scenarios (Table 4). These results suggest that the concentrations of OC insecticides in the sediments of the Mai Po area did pose a risk to aquatic life, especially sediment-dwelling organisms. Although concentrations of a number of OCs in the Mai Po sediments were greater than their corresponding sediment guideline values, concentrations of OCs in biota samples were much lower than the relevant guideline values promulgated by government agencies to protect the health of human consumers (Table 5). It is worth noting that GWs at MPMNR have been managed by WWFHK for >20 years according to a standard procedure. Principally, GWs are completely drained twice a year, and fish are removed. The GWs are restocked with fingerlings after the drain-down process. This operation may have the overall effect of decreasing the concentrations of toxic contaminants in the fish tissues by limiting the bioaccumulation window (duration) for OCs, thus decreasing the risk of exposure to these toxic contaminants by way of fish consumption. During shrimp harvesting from GWs during the wet season, the sluice gates are opened, and water is allowed to flush out during low tides on a regular basis (>100 times/y). The strong flushing currents create an upwelling force between the surface sediments and water, which may increase the amount of particle-bound OCs in the water being flushed out of GWs. During high tide on the same day, GWs are reflooded to allow recolonization by juvenile shrimp (Cha et al. 1997). These operations allow an efficient and regular circulation and exchange of water between GWs and the open sea during a prolonged period, and this may potentially be effective in decreasing the accumulation of OCs in biota tissues. We speculate that the current low-cost maintenance practices adopted by WWFHK may be effective in decreasing the potential hazards caused by OC contamination in MPMNR. Such an approach may potentially be applicable to wetlands in other locations, e.g., in other southeastern Asian countries, thus allowing sustainable fishery production and wildlife conservation. In theory, it may be possible to decrease the quantity of insecticides accumulated in GWs by periodic removal of the contaminated sediments. However, such operations may exacerbate the resuspension of sediment particles and increase the concentrations of OCs in the water column. This could worsen the situation, particularly if water circulation is restricted. Further studies will need to be carried out to examine and ascertain the relative merits of these management options. Acknowledgments. This study was supported by a Central Allocation Grant (Grant No. 8730020) awarded by the Research Grants Council, Hong Kong; and the Area of Excellence Scheme under the University Grants Committee of the Hong Kong Special Administration Region, China (Project No. AoE/P-04/2004). 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