PCBs and chlorinated pesticides in the atmosphere and aquatic organisms of Ross Island, Antarctica

PCBs, p,p′-DDT, p,p′-DDE and lindane (γ-hexachlorocyclohexane) were monitored in the lower atmosphere of Ross Island, in Antarctica for 2 yr. Geometrical means were 15.2 pg m⁻³ for PCBs, 2.0 pg m⁻³ for p,p′-DDT, 1.0 pg m⁻³ for p,p′-DDE and 25.8 pg m⁻³ for lindane. Atmospheric levels of lindane were positively correlated with temperature, and a significant difference was found between spring-summer and summer-winter concentrations. No season related differences were found for the other chlorinated hydrocarbons, possibly owing to their lower vapour pressure and the cold climate. Periods with increased atmospheric levels of PCBs and DDT compounds were recorded. Lindane, p,p′-DDE and PCBs were present in fish and zooplankton sampled close to Ross Island. Pollutant levels in the zooplankton (on an extractable fat basis) were highest during the Antarctic spring and autumn and were inversely correlated to their fat content.     

Uptake and depuration of PAHs and chlorinated pesticides by semi-permeable membrane devices (SPMDs) and green-lipped mussels (Perna viridis)

Semi-batch seawater experiments were conducted to follow the uptake and release of selected PAHs (anthracene, fluorathene, pyrene and B[a]P) and organochlorine pesticides (-HCH, aldrin, dieldrin, p,p′-DDT) in semi-permeable membrane devices (SPMDs) and green-lipped mussels (Perna viridis). Mathematical models were applied to describe the uptake and elimination curves of the contaminants for SPMDs, and kinetic parameters, such as uptake rate constants, and equilibrium triolein/water partitioning coefficients were calculated. SPMD data showed a good fit to estimate rate constant and partition coefficient equations, but only those contaminants which partitioned mainly in the dissolved phase (-HCH and dieldrin) were well explained for mussels. Poor conformity of the other contaminants indicated mussels uptake by routes other than diffusion, such as ingestion of algae. An apparent equilibrium state was only noted for -HCH in mussels. Aldrin was not detected in mussels in the first few days of exposure, indicating potential metabolism of this compound. B[a]P was not detected in the triolein of SPMDs, which suggests that the membrane may act as a reservoir. Loss of spiked B[a]P from the triolein was evident in a depuration experiment, which may indicate transfer to the membrane. Rate constants for mussels were higher than those for SPMDs, but the reverse was true for partition coefficients. Overall, mussels and SPMDs had similar uptake rates for all compounds in this study, excluding p,p′-DDT and dieldrin. Contaminant elimination took place more rapidly in mussels, implying that SPMDs are better candidates for detecting episodic discharge of organic contaminants.     

Relationships between tissue concentrations of chlorinated hydrocarbons (polychlorinated biphenyls and chlorinated pesticides) and antioxidative responses of marine mussels,Perna viridis

Marine mussels, Perna viridis, were transplanted from a reference site to various polluted sites around Hong Kong. After 30 d of exposure, antioxidative responses in the gills and hepatopancreas and tissue concentrations of chlorinated hydrocarbons [polychlorinated biphenyls (PCBs) and chlorinated pesticides (CPs)] were determined for individual mussels. Glutathione S transferase (GST) and glutathione (GSH) were positively correlated with tissue PCB concentrations. Only one of the enzymatic antioxidants, glutathione peroxidase (GPx), showed significant response to tissue PCB. No significant correlation was found between tissue concentrations of chlorinated hydrocarbons and other enzymatic antioxidants (superoxide dismutase (SOD), catalase (CAT), glutathione reductase (GR) and NADPH DT-diaphorase (DT-d). Oxidative stress, measured as thiobarbituric acid reactive substances, was correlated with chlorinated pesticide concentrations in tissues. This study demonstrated a correlation between GST/GSH and chlorinated hydrocarbons. The apparent lack of correlation between trace organic pollutants and some of the enzymatic antioxidants may be due to the inhibitory effects caused by these chemicals. The above results suggest that more investigations are needed before these enzymes can be used as biomarkers.     

Field accumulative behavior of organochlorine pesticides. The role of crabs and sediment characteristics in coastal environments

The influence of intertidal crab beds on the concentrations of organochlorine (OC) pesticides in sediment was studied in two different coastal environments in Argentina. Samples of male burrowing crabs (Chasmagnathus granulatus) were collected for this study. Our field data showed lower bioaccumulation of OC pesticides in crabs from sediments with a higher total organic carbon (TOC) and higher clay content. Thus, concentrations in crabs depend on the physico-chemical characteristics of the sediment where they live more than on the OC pesticide concentrations in the environment. The distribution patterns in sediment from inside and outside crab burrows were similar for both coastal areas being HCHs  γ-chlordane > p,p′-DDE for San Antonio Bay (SAO), and HCHs > p,p′-DDE  γ-chlordane for Mar Chiquita (MCh) coastal lagoon. OC pesticide concentrations in sediment were significantly lower inside than outside crab burrows, irrespective of the sediment physico-chemical characteristics due to the bioturbation activity of C. granulatus.     

Screening of Mercury and Persistent Organochlorine Pollutants in Long-Finned Pilot Whale (Globicephala melas) in the Faroe Islands

Results of mercury and organochlorine analyses in pooled muscle and blubber samples representing in all 417 long-finned pilot whales (Globicephala melas) sampled in 1997 in the Faroe Islands are presented. The 28 pooled muscle samples from (in all) 9 pods were analysed for total mercury and the same number of pooled blubber samples were analysed for PCB (IUPAC CBs no. 28, 52, 99, 101, 105, 118, 128, 138, 153, 170, 180, 183 and 187), p,p′-DDT and metabolites and o,p′-DDT and metabolites, cis () and trans (γ)-chlordane, cis- and trans-nonachlor, oxychlordane, mirex, hexachlorobenzene, β-HCH and toxaphene (Parlars no. 26 (T2), 32, 50 (T12), 62 (T20) and 69.     

Lysosomal membrane stability and metallothioneins in digestive gland of Mussels (Mytilus galloprovincialis Lam.) as biomarkers in a field study

The lysosomal membrane destabilization and the metallothionein content in the digestive gland cells of mussels (Mytilus galloprovincialis Lam.), collected along the east coast of the North Adriatic (Istrian and Kvarnerine coast, Croatia), were examined over a period of four years (1996–1999). The lysosomal membrane stability, as a biomarker of general stress, showed that the membrane labilization period in mussels from polluted, urban- and industrial-related areas was significantly decreased (p<0.05) when compared to mussels from control, clean sea water sites. In the harbour of Rijeka, the most contaminated site, the lysosomal membrane stability was reduced by more than 70% compared to the control. This method also proved to be a useful biomarker for detection of additional stress caused by short-term hypoxia that occurred once during this study inside the polluted and periodically quite eutrophic Pula Harbour. The concentration of metallothioneins in the mussel digestive gland, as a specific biomarker of exposure to heavy metals, did not reveal significant differences (p<0.05) between sites covered by this study.     

Relationships between tissue concentrations of chlorinated hydrocarbons (polychlorinated biphenyls and chlorinated pesticides) and antioxidative responses of marine mussels, Perna viridis

Marine mussels, Perna viridis, were transplanted from a reference site to various polluted sites around Hong Kong. After 30 d of exposure, antioxidative responses in the gills and hepatopancreas and tissue concentrations of chlorinated hydrocarbons [polychlorinated biphenyls (PCBs) and chlorinated pesticides (CPs)] were determined for individual mussels. Glutathione S transferase (GST) and glutathione (GSH) were positively correlated with tissue PCB concentrations. Only one of the enzymatic antioxidants, glutathione peroxidase (GPx), showed significant response to tissue PCB. No significant correlation was found between tissue concentrations of chlorinated hydrocarbons and other enzymatic antioxidants (superoxide dismutase (SOD), catalase (CAT), glutathione reductase (GR) and NADPH DT-diaphorase (DT-d). Oxidative stress, measured as thiobarbituric acid reactive substances, was correlated with chlorinated pesticide concentrations in tissues. This study demonstrated a correlation between GST/GSH and chlorinated hydrocarbons. The apparent lack of correlation between trace organic pollutants and some of the enzymatic antioxidants may be due to the inhibitory effects caused by these chemicals. The above results suggest that more investigations are needed before these enzymes can be used as biomarkers.     

Persistent organochlorine residues and toxic evaluation of polychlorinated biphenyls in sharks from the Mediterranean Sea (Italy)

Persistent organochlorines such as polychlorinated biphenyls including coplanar congeners, DDT compounds and HCB were measured in different tissues (muscle, liver and eggs) of two Mediterranean shark species: namely Centrophorus granulosus and Squalus blainvillei. The concentrations of organochlorines in the tissues and organs of both species were in the order DDTs>PCBs>HCB. The highest values of DDTs, PCBs and HCB were found in liver followed by eggs and muscle. Among DDTs the compound found in greatest concentration was p,p^′-DDE. The PCB profiles were dominated by congeners 138, 153, and 180. The isomers with higher TEQs values were non- and mono-ortho congeners than di-ortho ones in muscle, liver and eggs of both species. Among the non-ortho, PCB 126 was the major contributing individual to the total TEQs in both species.     

Organochlorine pesticide residues in sediments and biota from the coastal area of Dar es Salaam city,Tanzania

Sediment and biota samples were collected from Msimbazi and Kizinga rivers and from the coastal marine environment of Dar es Salaam during both dry and wet seasons. The samples were analyzed for various organochlorine pesticide residues using GC-ECD and GC-MS. Dieldrin, p,p^′-DDT, p,p^′-DDE, p,p^′-DDD, o,p^′-DDT and γ-HCH were detected at significantly greater concentrations above the method detection limits. Recoveries of pesticide residues ranged 86.5–120% in sediments and 62–102% in biota. The average concentrations of total DDT in sediments for the two seasons were almost the same. Biota samples showed significant difference in levels of residues depending on mode of feeding and age of analyzed biota. p,p^′-DDT to total DDT ratios in all matrices indicated recent use of DDT. The levels of residues in sediments suggest possible adverse effects to humans consuming biota that are directly exposed to the sediments. This effect, which is associated with bio-concentration of residues in the tissues of edible aquatic biota, should not affect wildlife. In spite of concern on the adverse effect to humans posed by pesticide residues in sediments, edible biota from the examined water bodies were found to be safe for human consumption.     

Imposex in Morula Granulata as Bioindicator of Tributyltin (TBT) Contamination in the Dampier Archipelago, Western Australia

This study was undertaken to examine the use of imposex in the tropical neogastropod whelk Morula granulata as bioindicator of tributyltin (TBT) contamination. Samples were collected from sites throughout the Dampier Archipelago; both impact sites close to intensive shipping activity and remote control sites. TBT in this area originates mainly from commercial vessels using the Port of Dampier that are >25 m in length and exempt from legislation controlling the use of TBT in antifouling paints. A field survey was undertaken in July 1997; 100 M. granulata were taken at each of 18 sites with varying vessel activity, and examined for imposex. The level of TBT contamination in the Archipelago was low; ranging from <0.3 to 25 ng Sn l⁻¹ in water,<0.3 to 80 ng Sn g−¹ in oyster tissue (Saccostrea cuccullata – prey of M. granulata), and <0.3 to 33 ng Sn g⁻¹ in whelks. Percentage of imposex in M. granulata ranged from 0% to 57%, and was correlated with distance to vessel activity (r=0.646, p<0.05). The only significant relationship of imposex with butyltin concentrations was with TBT in oysters (r=0.826, p<0.05), and dibutyltin (DBT) in whelks (r=0.783, p<0.05). It is postulated that this is because of interspecies variation in ability to metabolize TBT to DBT and MBT (monobutyltin), as well as induction of imposex in earlier life stages, so that imposex in adults could be a reflection of prior contamination. M. granulata is a suitable bioindicator of TBT contamination in the Dampier Archipelago, which could be used throughout the Indo-Pacific given its abundance in the region.     

Responses of the green-lipped mussel Perna viridis (L.) to suspended solids

Laboratory experiments were conducted to investigate the lethal and sublethal effects of suspended solids on the survival and physiological, behavourial and morphological changes of the green-lipped mussel Perna viridis collected from Tolo Harbour, Hong Kong. Results showed that P. viridis survived in all test conditions of suspended solids from 0 to 1200 mg/l over a period of 96 h. Physiological responses of the green-lipped mussel under 14-d exposure of suspended solids from 0 to 600 mg/l, followed by 14-d recovery in natural seawater, revealed no significant changes (p>0.05) in oxygen consumption and dry gonosomatic index for treatments in different concentrations of suspended solids and exposure time. Changes in clearance rate were only found to be significant (p<0.001) with exposure time. Responses in behavourial and morphological changes of the green-lipped mussel were also studied under similar experimental treatments and exposure time. Byssus production was significantly (p<0.001) related to exposure time. Gill damage, however, was significantly greater in treatments (p<0.001). Present findings suggested that P. viridis could tolerate a high level of suspended solids in the laboratory. There were dose-dependent effects of suspended solids on morphology of gill filaments. Implications of survival and responses of the green-lipped mussel to suspended solids in the marine environment are discussed.     

Chlorinated compounds and polybrominated diphenyl ethers (PBDEs) in mussels (Mytilus galloprovincialis) collected from Apulia Region coasts

This project was carried out to assess the levels and spatial distribution of organochlorine compounds in the coastal marine environment, using mussels as bioindicators to evaluate the coastal water quality. Levels of polychlorobiphenils (PCB), chlorinated pesticides (DDT isomers, HCH isomers, Aldrin, Dieldrin, alfa-Endosulfan, Hexachlorobenzene, Pentachlorobenzene) and polybrominated diphenyl ethers (PBDEs) were determined in tissues from mussels (Mytilus galloprovincialis) collected along the Apulia Region coasts (Mediterranean Sea). Results indicate that contamination by organochlorine compounds is higher in mussels sampled in the Ionian Sea than in those from the Adriatic Sea, with PCB levels up to seven times higher in mussels from Ionian than from the Adriatic Sea. Although PCB levels were above the maximum values indicated by both European Community (EC) and National regulation in several sample sites, the PCB concentrations were particularly high in some stations, suggesting that these locations require a much specific attention. Conversely, results on the mussel contamination by PBDEs highlight their ubiquitous environmental distribution, and underline the need to establish the maximum level for these compounds in foodstuff, according to European Regulations.     

Composition and distribution of organochlorine pesticide residues in surface sediments from the Wu-Shi River Estuary,Taiwan

The contamination of organochlorine pesticides (OCPs) in sediments from the Wu-Shi River estuary was investigated to evaluate the pollution potentials and distribution of OCPs in central Taiwan. A total of 19 sediment samples were collected at five sampling stations along the River estuary. The concentrations of OCPs were in the range of 0.99–14.5 ng/g-dry weight (dw) for ΣHCH (-, β-, γ-, δ-HCH), 0.46–13.4 ng/g-dw for Σcyclodiene and 0.53–11.4 ng/g-dw for ΣDDT (p,p^′-DDD, p,p^′-DDE, p,p^′-DDT). The mean concentrations of ΣHCH, Σcyclodiene and ΣDDT were 3.79, 4.87 and 2.51 ng/g-dw, respectively. The total concentrations of OCPs correspond to 1.73–71.9 μg/g-OC when normalized to TOC contents. Among the organochlorine pesticides, endosulfan sulfate, β-HCH, and p,p^′-DDD were the most dominant compounds in the sediments with the average concentrations of 1.97, 3.43 and 2.08 ng/g, respectively. Also, different contamination patterns among sampling seasons were observed. The measured concentrations of OCPs collected in spring were higher than those in autumn and winter. A linear relationship between sediment characteristics and OCP residues was also demonstrated. The results obtained in this study show that there still exist a variety of organochlorine pesticide residues in the sediments from the near shore of central Taiwan.     

Concentration of polychlorinated biphenyls (PCBs) in beached resin pellets: variability among individual particles and regional differences

Concentrations of polychlorinated biphenyls (PCBs) in beached resin pellets were examined to reveal variability between individual particles and differences among beaches. Fifty-five resin pellets from a beach in Tokyo were individually analyzed for PCBs, and showed concentrations ranging from <28 to 2,300 ng/g. This indicates that concentrations are highly variable between particles. Among several characters, discoloration (e.g., yellowing) had a positive relationship with PCB concentration: discolored pellets contained more PCBs than others on most of the beaches sampled. Given the color-selective ingestion of food by some organisms, this may be ecotoxicologically important. Measurements of samples from 47 beaches in Japan showed regional differences in PCB concentrations in resin pellets consistent with those in mussels. Sporadic high concentrations of PCBs were also found in pellets from remote islands, suggesting that resin pellets could be the dominant route of exposure to the contaminants at remote sites. The similarity of PCB concentrations between resin pellets and mussels suggests a potential use of resin pellets to monitor pollution in seawater.     

The Impact of the Herbicide Diuron on Photosynthesis in Three Species of Tropical Seagrass

The impact and recovery from exposure to the herbicide diuron [DCMU; 3-(3′,4′-dichlorophenyl)-1,1-dimethylurea] was assessed for three tropical seagrasses, maintained in outdoor aquaria over a 10-day period. Photosynthetic stress was detected using chlorophyll a fluorescence, measured with a Diving-PAM (pulse amplitude modulated fluorometer). Exposure to 10 and 100 μg l⁻¹ diuron resulted in a decline in effective quantum yield (ΔF/F_m^′) within 2 h of herbicide exposure in Cymodocea serrulata, Halophila ovalis and Zostera capricorni. Effective quantum yield also declined over the first 24 h of exposure in H. ovalis at even lower diuron concentrations (0.1 and 1.0 μg l⁻¹). Effective quantum yield in H. ovalis and Z. capricorni was significantly depressed at all diuron concentrations (0.1–100 μg l⁻¹) after 5 days exposure, whereas effective quantum yield in C. serrulata was only significantly lower in plants exposed to highest diuron concentrations (10 and 100 μg l⁻¹). Effective quantum yield depression was present 5 days after plants exposed to 10 and 100 μg l⁻¹ diuron were returned to fresh seawater. These results indicate that exposure to herbicide concentrations present in nearshore Queensland sediments present a potential risk to seagrass functioning.     

Levels of organochlorine pesticide residues in some organs of the Ganges perch, Lates calcarifer, from the Ganges-Brahmaputra-Meghna Estuary, Bangladesh

Levels of organochlorine pesticide residues (p,p′ DDT, DDD, DDE, Aldrin, Dieldrin, Lindane, Heptachlor and BHC) were analysed in the dry and wet seasons in four organs (muscle, liver, gut and egg samples) of Ganges Perch, Lates calcarifer, collected during October–November–December, 1996 and May–June–July, 1997 from the Ganges–Brahmaputtra–Meghna estuary. The residues were analysed by using gas-chromatography (GC) in electron capture detector (ECD) mode and were verified by thin layer chromatography (TLC). Among the four organs analysed, the residues were found in the order egg > gut > muscle > liver. The pesticide residues were found in the order ∑DDT > Heptachlor >Dieldrin > Aldrin. Higher levels of residues were found during the dry season due to high lipid content in fishes. A positive correlation was observed between the pesticide residues (∑DDT and ∑OCs) and lipid contents of fish, and the correlation was found to be linear. The concentrations of pesticide residues in muscle, liver and gut were below the FAO/WHO (1993) recommended permissible limit except in eggs.     

Organochlorine pesticides and PCB residues in sediments of Alexandria Harbour,Egypt

Persistent organochlorine compound concentrations were determined for 23 surface sediment samples collected from Alexandria Harbor, Egypt. Total PCB concentrations ranged from 0.9 to 1210 ng/g with four to seven Cl-substituted biphenyls being the most prevalent PCBs congeners. Different PCB congener distribution patterns were observed, probably reflecting different inputs and attenuation at various locations. Total DDT concentrations varied from <0.25 ng/g to 885 ng/g. The ratios of DDTs (2,4^′- and 4,4^′-DDT)/total DDTs (DDTs plus metabolites) in sediment samples from certain sites were 0.86 or higher, indicating little attenuation or recent input of DDT. Total chlordane (the sum of heptachlor and its epoxide, oxy-, γ- and -chlordane and cis+trans-nonachlor) ranged from <0.25 to 44 ng/g with the highest concentration found in the Arsenal Basin. The geographic distributions of PCBs, total DDTs and total chlordane were similar. Chlorinated benzenes (CBs), hexachlorocyclohexanes (HCHs), aldrin, dieldrin, endrin, chloropyrifos, endosulfan, mirex and pentachloroanisole were below detection limits or detected at low concentrations in most of the samples. Sites that were contaminated with high concentrations of organochlorine compounds were associated with dense population and low energy environment. The contamination levels of PCBs, total DDTs and total chlordane were in high range compared to other locations worldwide.     

Biomonitoring with benthic macroalgae and direct assay of heavy metals in seawater of the Oporto coast (northwest Portugal)

The concentrations of dissolved Cd, Cu, Hg and Pb in seawater and algae (Enteromorpha spp. and Porphyra spp.) were determined in parallel on three beaches located in the Oporto coast (Portugal), during 8 successive months, comprising periods of low and high biological productivity. The concentrations of dissolved metals in seawater varied markedly during the sampling period and exhibited seasonality. The concentrations of Cd were high in autumn and winter, but low in spring. The concentrations of Cu and Hg were high in autumn, low in winter and peaked in May. The concentrations of Pb were low in autumn and winter, and also peaked in May. It is likely that biological activity was, at least partially, responsible for the observed seasonal changes. The mean concentrations of dissolved metals in seawater were similar to those reported for polluted and industrialized european coastal areas. Metal concentration factors, calculated month-to-month for each alga, metal and site, varied markedly during the sampling period, indicating that concentration factors based on single or few determinations could be misleading. On the contrary, mean concentration factors (calculated by dividing the mean metal concentration in the algae by the mean metal concentration in seawater) were relatively constant at all three sites, indicating that in the Oporto coast, Enteromorpha spp. can be used to estimate the mean concentration of dissolved Cd, Cu and Hg in seawater, and Porphyra spp., the mean concentration of Cd, Cu and Pb. However, considering that future estimates of the concentrations of these metals in seawater should be based on determinations of the metal contents in Enteromorpha spp. and Porphyra spp. carried out on several occasions spanning a considerable period of time, the use of these algae as monitors of heavy metal pollution can have limited practical advantages over the direct assay of the metals in seawater.     

Polychlorinated biphenyls (PCBs) in a benthic ecosystem in Gwangyang Bay, South Korea

Benthic ecosystem in Gwangyang Bay, a fast developing industrial area with steel production, port container handling, petroleum and other chemical processing in South Korea was studied. The average levels of polychlorinated biphenyls (ΣPCB) in the benthic components were: seawater 2.99 ± 0.13 (ng/L); sediment 294 ± 118 (ng/g TOC); [biota=ng/g lipid] starfish 92; prawn 131 ± 2; mussels 127 ± 22; crab 182 ± 114; clam 187; polychaeta 215; sea cucumber 497 ± 90; squill 603 ± 38; fish 396 ± 159. Levels in the inner bay samples were higher than the outer bay samples suggesting land based pollution. Good correlation (r(2)=0.79; p<0.05) existed between PCB concentration and lipid content indicating partitioning processes in action. PCB signature in the abiotic and biotic components shows enrichment of lower chlorinated congeners emitted by a unique source nearby, viz. steel manufacturing plant.