Residue levels of HCHs,DDTs and PCBs in shellfish from coastal areas of east Xiamen Island and Minjiang Estuary,China

Shellfish samples were collected from the coastal cultivating areas of east Xiamen Island and Minjing Estuary, China and analyzed for hexachlorocyclohexanes (HCHs), DDTs and polychlorinated biphenyls (PCBs) by GC. Concentration ranges of HCHs, DDTs and PCBs in the coastal area of east Xiamen Island were 0.18–345, 75.2–2143 and ND-23 ng g⁻¹ dry wt., respectively; those for Minjiang Estuary were ND-5.07, 21.5–2396 and ND-6.78 ng g⁻¹ dry wt., respectively. The results showed that the organochlorines were evidently accumulated in marine bivalve molluscs, particularly in oyster. The concentrations of organocholorine pollutants in shellfish samples varied with the sampling locations, the season of collection and organism species, but were generally higher than those in the sediments. The concentrations of DDTs in the shellfish were high as compared with HCHs and PCBs, so that DDTs can be considered as the typical organochlorines in the survey areas. The residue levels and compositions of HCHs, DDTs and PCBs are discussed.     

Geographical distribution and accumulation features of organochlorine residues in bivalves from coastal areas of South Korea

As a part of Mussel Watch Program in Korea, the contamination levels and accumulation features of polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) were assessed for 82 bivalve samples collected from 66 sites along the entire coast of Korea. The dry weight based ∑PCBs and ∑OCPs ranged from 4.4 ng g⁻¹ to 422.0 ng g⁻¹ (geometric MEAN=36.9 ng g⁻¹) and from 9.95 ng g⁻¹ to 131.37 (34.88) ng g⁻¹, respectively. PCB was predominant in Korean coast, followed by DDTs, HCHs, and Chlordanes. From the observed log normal distribution of PCB and each OCP, low- and high-levels were defined as geometric mean ±1 S.D., respectively. The levels at the sites near urban and/or industrial areas often exceeded the high-levels and the spatial distributions of ∑DDTs and ∑CHLs were correlated with that of ∑PCBs, indicating terrestrial input pathways. Even distribution of ∑HCHs suggested a possibility of atmospheric input pathway of HCHs. The observed isomer ratios of DDTs, HCHs, and CHLs indicated that aging has occurred.     

PAH contamination of western Irish Sea sediments

Concentrations of the sum of 15 PAHs in 22 surficial sediment samples from the western Irish Sea ranged from below 100 ng g⁻¹ in sandy sediments to a maximum of 1422 ng g⁻¹ in the centre of the mud basin. The concentrations are typical of coastal shelf sediments, but greater than those observed for aquatic sediments remote from known anthropogenic sources. Organic C and the % sediment <15 μm were positively correlated with ΣPAH. ΣPAH was normalised to organic C and particle size (i.e. expressed as ΣPAH/C^org and ΣPAH/%<15 μm) and significant relationships were still observed with organic C and %<15 μm. The results are discussed in the context of using organic C to normalise concentrations of PAHs to assess contamination levels in sediments.     

Tin and organotin in water, sediments, and benthic organisms of Poole Harbour

Tributyltin (TBT) concentrations in waters of Poole Harbour ranged between 2–139 ng l⁻¹ (as Sn) and increased to 234–646 ng l⁻¹ within marinas. Seasonal trends in contamination coincided with boat usage patterns and peaked during summer months. A combination of poor tidal flushing and removal of TBT to particulates restricts high levels of contamination to areas closest to marinas and moorings; TBT concentrations in benthic sediments decreased from 0.52 μg g⁻¹ near such sites to 0.02 μg g⁻¹ at the harbour mouth. Organotin accumulations in several benthic invertebrates including polychaetes (Nereis diversicolor), snails (Littorina littorea) and clams (Scrobicularia plana, Mya arenaria) reflect the distribution of contamination in the environment, though concentration factors (relative to water) vary considerably between species and were highest in sediment dwelling clams, notably Mya (1.3×10⁵). Compared to organotins, biological availability of inorganic tin is low.

Levels of TBT in parts of Poole Harbour exceed Environmental Quality Targets designed to protect marine life and may be responsible for poor recruitment, particularly in bivalves, at heavily contaminated sites.     

Levels and patterns of polychlorinated dibenzo-p-dioxins, dibenzofurans and biphenyls in surface sediments from the western Baltic Sea (Arkona Basin) and the Oder River estuarine system

Surface sediment samples were collected from the western Baltic Sea (Arkona Basin) and the Oder River estuarine system in May and August 1995 and analysed for polychlorinated dibenzo-p-dioxins, dibenzofurans and biphenyls. Contents of PCDF (sum) and PCDD (sum) varied from 2.5 to 820.0 pg g⁻¹ dw and from 12.7 to 2991.0 pg g⁻¹ dw, respectively. PCB contents (sum of 23 congeners) ranged between < 130.0 and 16267.0 pg g⁻¹ dw. Only slight variations in PCDF/D and PCB contents on dry weight basis were found between the Oder River estuarine system and the open Baltic Sea. TOC-normalization of the data showed an approximately homogen PCDF/D distribution in the study area. The distribution pattern for PCDF/D and PCB may be attributed to high sediment dynamics combined with transport processes from the temporary sedimentation basin (Oderhaff) to the deeper parts of the Baltic Sea.     

A case study on fuel oil contamination in a mangrove swamp in Hong Kong

Mangroves commonly found along tropical and subtropical coastlines are susceptible to oil pollution. In December 2000, around 500 1 m tall Kandelia candel saplings at the age of 3–5 years old located at the foreshore region of Sheung Pak Nai swamp, Hong Kong SAR, were found to be damaged by oil pollution. More than 80% of the saplings were either dead or washed away and leaving less than 5% healthy saplings with dense green leaves. Elevated concentrations of light n-alkanes (ranging from n-C₁₄ to n-C₂₀), pristane and phytane were recorded in surface sediments collected in December 2000. The ratio between light and total n-alkanes was 0.4. The total petroleum hydrocarbons (60–80 μg g⁻¹ TPH) and unresolved complex mixtures (60–70 μg g⁻¹ UCM) were higher than the background values of other mangrove sediments in Hong Kong, which were 40 and 20 μg g⁻¹, respectively. In certain root zone sediments, TPH concentrations were above 1000 μg g⁻¹. These results suggest that surface sediments in Sheung Pak Nai were contaminated by petroleum oil, most likely by illegal discharge of fuel oil which occurred between 1998 and 2002. One year later, in December 2001, unhealthy saplings had recovered and re-grown. The concentrations of TPH and UCM in sediments declined to around 40 μg g⁻¹, pristane and phytane dropped by 80%, and the ratio of light to total n-alkanes was 0.15, suggesting that residual oil in sediments was weathered leading to a remarkable recovery of the unhealthy saplings.     

Mathematical modeling of PCB bioaccumulation in Perna viridis

In the present work, we built a mathematical model of polychlorinated biphenyl (PCB) bioaccumulation in Perna viridis, namely, a one-compartment model with a time dependent incorporation rate R (μg g⁻¹ lipid per ppb water per day), with positive substrate cooperativity as the underlying physical mechanism. The temporal change of the PCB concentration Q (μg g⁻¹ lipid) in the soft tissues of the mussel depends on the competition of the input rate RW and the output rate kQ, where W is the concentration of PCB in water (ppb water) and k is the elimination rate (per day). From our experimental data, k=0.181±0.017 d⁻¹. The critical concentration in water W_c for positive substrate cooperativity was found to be 2.4 ppb. Below W_c, R is a constant. For a water concentration of 0.5 ppb Aroclor 1254, R=24.0±2.4 μg g⁻¹ lipid ppb⁻¹ d⁻¹. Above W_c, positive substrate cooperativity comes into effect and R becomes a function of time and dependent on the concentration Q in a form R=γQ/(Q+δ). This is the case for a water concentration of 5 ppb Aroclor 1254, where γ=15.1 μg g⁻¹ lipid ppb⁻¹ d¹ and δ≈200 μg g⁻¹ lipid. From this model, the uptake is exponentially increasing when the PCB concentration in the mussel is small compared to 200 μg g⁻¹ lipid, and hyperbolically increasing when the concentration is large compared to 200 μg g⁻¹ lipid, which are consistent with the experimental data. The model is useful for understanding the true processes taking place during the bioaccumulation and for risk assessment with higher confidence. Future experimental data which challenge the present model are anticipated and in fact desirable for improvement and perfection of the model.     

Distribution and Fate of Organochlorine Pollutants in the Pearl River Estuary

Samples of surface sediment and suspended particulate matter (SPM) were collected from the Pearl River estuary, China, and the distribution and concentration of hexachlorocyclohexanes (HCHs), DDTs and polychlorinated biphenyls (PCBs) were extensively studied. The concentration ranges of HCHs, DDTs and PCBs in the sediments were 0.28–1.23 ng g⁻¹, 1.36–8.99 ng g⁻¹ and 0.18–1.82 ng g⁻¹, respectively. The concentrations of HCHs, DDTs and PCBs in the SPM varied both with the sampling locations and the season of collection. Higher concentrations were recorded in the SPM as compared with sediments. The distribution pattern of such organochlorine compounds (OCs), in the Pearl River estuary, showed that sources were some major river mouths and input from Shenzhen Bay. The concentrations of OCs were, however, low as compared with other estuaries and seas. The environmental fate of the OCs during estuarine mixing was determined, in part, by physicochemical and biochemical properties. The absorption and sedimentation of SPM were also considered important factors. Marine sediments may, therefore, be regarded as an important reservoir of hydrophobic and persistent OCs.     

The potential role of mucus in the depuration of copper from the mussels Perna viridis (L.) and Septifer virgatus (Wiegmann)

Experiments were conducted to measure the mucus secretion rate in two common mussels in Hong Kong, Perna viridis (L.) and Septifer virgatus (Wiegmann), when chronically exposed to Cu (50 μg l⁻¹). After a 3-month exposure period, the mucus production rate of P. viridis at 25°C in the metal treatment was 2.65 times that of the control (10.7 vs 4.0 mg g⁻¹ dry wt h⁻¹), while S. virgatus showed a 1.85 times difference (4.41 vs 2.38 mg g⁻¹ dry wt h⁻¹). Mucus secretion by P. viridis under acute Cu exposure (0.5 mg l⁻¹) was significantly higher in the metal treatment than the control (13.43 vs 9.16 mg g⁻¹ dry flesh wt). Metal contents of the mucus secreted was about 18 times those in the control and 6 times in the soft tissues. Therefore, mucus appears to be an effective agent for Cu depuration in the mussel. The significance of these results to the local distribution and abundance of the mussels is discussed.     

Organochlorines in Hong Kong Fish

Muscle samples from 15 species of fish (n=1) purchased from markets in Hong Kong and 10 liver samples of tilapia (Tilapia mossambica) collected from the Shing Mun River were analysed for organochlorines (polychlorinated biphenyls, ΣDDTs, hexachlorobenzene, hexachlorocyclohexanes, chlordanes, mirex and dieldrin). Polychlorinated biphenyls (PCBs) were detected in 15 market fish samples but the levels were very low (around 1 ng g⁻¹). PCB levels in tilapia livers collected from Tai Wai (29.3–65.1 ng g⁻¹) were higher than those from Fo Tan (3.5–23.2 ng g⁻¹) suggesting that there may be some local point soucres. ΣDDTs were detected in all samples, ranging from 3.3 to 75.6 ng g⁻¹ in the market fish and from 7.1 to 88.8 ng g⁻¹ in tilapia. The DDE/DDT ratios in the market fish (0.12–0.75) showed higher variability than those of tilapia (0.30–0.46), suggesting that some of the market fish may have been collected from areas where DDT was recently used. Results of this preliminary study show that organochlorine levels in Hong Kong market fish are low and do not cause any concern for human consumption. An on-going monitoring program, however, is recommended.     

Toxic effects of copper on larval development of the barnacle Balanus amphitrite

Experiments were conducted to assess the effects of copper on larval development in the barnacle Balanus amphitrite. In the first experiment, we compared the sensitivity of three naupliar stages to copper stress. Molting inhibition occurred at copper concentrations ranging from 32 μg l⁻¹ in nauplius II to 128 g l⁻¹ in nauplius VI. EC₅₀ for molting ranged from 97 μg l⁻¹ in nauplius II to 129 g l⁻¹ in nauplius VI. Decreased survival occurred at 128 μg Cu l⁻¹ in all of the naupliar stages tested, with LC₅₀ ranging from 145 in nauplius II to 213 μg l⁻¹ in nauplius VI. In the second experiment, we examined effects of copper on the development from nauplius II to cyprid. The larvae reached cypris stage only in treatments of 16 μg Cu l⁻¹. Our study therefore showed that molting was a more sensitive endpoint than survival, nauplius II was the most sensitive naupliar stage, and that whole larval development assay was more sensitive than assays using a particular larval stage. The results were discussed with respect to the use of this species in toxicity tests.     

Persistent organochlorine residues in green mussels from coastal waters of South India

Green mussels (Perna viridis) collected from nine locations along the South Indian coast were used as bioindicator to assess the organochlorine contamination (HCHs, DDTs, and PCBs) in the coastal environment of South India. Concentrations of ΣHCH and ΣDDT were found to be similar, ranging from 3 to 39 ng g⁻¹ on wet wt basis. On the other hand, PCB levels were apparently lower, varying from <1.0 to 7.1 ng g⁻¹ wet wt. The residue pattern of organochlorines in mussels are principally similar to those in Indian human samples, reported earlier. The coastal marine pollution by HCH in India ranks among the highly contaminated areas in the world.     

Pesticides in Sediments From Queensland Irrigation Channels and Drains

Pesticide concentration in sediment from irrigation areas can provide information required to assess exposure and fate of these chemicals in freshwater ecosystems and their likely impacts to the marine environment. In this study, 103 sediment samples collected from irrigation channels and drains in 11 agricultural areas of Queensland were analysed for a series of past and presently used pesticides including various organochlorines, synthetic pyrethroids, benzoyl ureas, triazines and organophosphates. The most often detected compounds were endosulphans (, β and/or endosulphan sulphate) which were detectable in 78 of the 103 samples and levels ranged from below the limit of quantification (0.1 ng g⁻¹ dw) up to 840 ng g⁻¹ dw. DDT and its metabolites were the second most often detected pesticide investigated (74 of the 103 samples) with concentrations up to 240 ng g⁻¹ dw of ∑DDTs. Mean ∑endosulphan and ∑DDT concentrations were 1–2 orders of magnitude higher in sediments from the irrigation areas which are dominated by cotton cultivation compared to those which are dominated by sugarcane cultivation. In contrast to these insecticides, the herbicides diuron, atrazine and ametryn were the compounds which were most often detected in sediments from irrigation drains in sugarcane areas with maximum concentrations in areas of 120, 70 and 130 ng g⁻¹ dw, respectively. In particular during flood events, when light is limiting, transport of these photosynthesis inhibiting herbicides from the sugarcane cultivation areas to the marine environment may result in additional stress of marine plants.     

Intermittent exposure to reduced oxygen levels affects prey size selection and consumption in swimming crab Thalamita danae Stimpson

Portunid crabs Thalamita danae (carapace width: 46–56 mm) were exposed to low oxygen level (4.0 mg O₂ l⁻¹) and hypoxia (1.5 mg O₂ l⁻¹) for 6 h each day with three size classes (large: 15.0–19.9 mm, medium: 10.0–14.9 mm, small: 5.0–9.9 mm) of mussels Brachidontes variabilis offered as food. Consumption rate, prey size preference, and prey handling including breaking time, handling time, eating time and prey value, were studied during the time the crabs were exposed to reduced oxygen levels and results were compared with the crabs maintained at high oxygen level (8.0 mg O₂ l⁻¹) throughout the experiment. Consumption of mussels from all size classes was significantly higher at high oxygen level than at reduced oxygen levels. No mussel size preference was observed for crabs exposed to 4.0 or 8.0 mg O₂ l⁻¹ but those crabs exposed to 1.5 mg O₂ l⁻¹ preferred medium mussels. Both breaking time and handling time increased with mussel size but did not vary with oxygen level. Prey value of each mussel consumed (mg dry wt eaten crab⁻¹ s⁻¹) was calculated by dividing the estimated dry weight of the mussel by the observed handling time. Mean prey value varied significantly with mussel size, with values obtained for large mussels being higher than small mussels at 4.0 and 8.0 mg O₂ l⁻¹; the effect of oxygen level, however, was insignificant. In view of portunid crabs as major predators of mussels, results may help explain dominance of mussels in eutrophic harbours in Hong Kong.     

Fate of polycyclic aromatic hydrocarbon (PAH) contamination in a mangrove swamp in Hong Kong following an oil spill

The fate of polycyclic aromatic hydrocarbon (PAH) contamination in a mangrove swamp (Yi O) in Hong Kong after an oil spill accident was investigated. The concentrations and profiles of PAHs in surface sediments collected from five quadrats (each of 10 m×10 m) covering different degrees of oil contamination and the most contaminated mangrove leaves were examined in December 2000 (30 days after the accident) and March 2001 (126 days later). The concentrations of total PAHs in surface sediments ranged from 138 to 2135 ng g⁻¹, and PAHs concentrations decreased with time. In the most contaminated sediments, total PAHs dropped from 2135 (30 days) to 1196 ng g⁻¹ (120 days), and the decrease was smaller in less contaminated sediments. The percentage reduction in sediment PAHs over three months (44%) was less significant than that in contaminated leaves (85%), indicating PAH in or on leaves disappeared more rapidly. The PAH profiles were very similar in sediments collected from quadrats Q1 and Q2 with benzo[a]anthracene and pyrene being the most abundant PAH compounds, but were different in the other three quadrats. The proportion of the light molecular weight PAHs to total PAHs increased after three months, especially phenanthrene. Results suggest that physical and photo-chemical weathering (tidal washing and photo-oxidation) of crude oil in surface sediments and on plant leaves were important processes in the first few months after the oil spill. The PAH contamination in Yi O swamp came from both petrogenic and pyrolytic sources. The petrogenic characteristic in the most contaminated sediment was confirmed with high values of phenanthrene to anthracene ratio (>10) and low values of fluoranthene to pyrene ratio (0.3–0.4).     

Aliphatic and aromatic hydrocarbons in marine biota and coastal sediments from the Gulf and the Gulf of Oman

The composition and spatial distribution of aliphatic and polycyclic aromatic hydrocarbons (PAHs) were investigated in biota and coastal sediments from four countries surrounding the Gulf (Bahrain, Qatar, United Arab Emirates and Oman). The levels of total petroleum hydrocarbons (TPH), aliphatic unresolved mixture and PAHs in sediments and biota were relatively low compared to world-wide locations reported to be chronically contaminated by oil. Only in the case of the sediments collected near the BAPCO oil refinery in Bahrain, having concentrations of 779 μg g⁻¹ total petroleum hydrocarbon equivalents and 6.6 μg g⁻¹ ∑PAHs, can they be categorized as chronically contaminated. Some evidence of oil contamination was also apparent in sediments and bivalves around Akkah Head and Abu Dhabi in the UAE, and near Mirbat in Oman. Contaminant patterns in sediments and biota indicated that the PAHs were mainly from fossil sources, with the exception of the high PAH concentrations in sediments near the BAPCO refinery that contained substantial concentrations of carcinogenic PAH combustion products.     

Mesocosm experiments for evaluating the biological efficacy of ozone treatment of marine ballast water

Ballast water is a major pathway for the transfer of non-indigenous species in aquatic environments. The objectives of this study were to determine the ability of ozone to reduce the numbers of a spectrum of marine organisms collected from Puget Sound, Washington in replicated mesocosm (280 l) experiments, and estimate the minimum ozone concentrations as measured by total residual oxidant (TRO) required to reduce organism densities. Ozone treatment was effective in removing bacteria, phytoplankton, and mesozooplankton with initial TRO concentrations of 2–5 mg l⁻¹ as Br₂. Persistence of TRO resulted in an extended period of toxicity and cumulative mortality. TRO decay allowed bacteria populations to multiply when TRO levels fell below 0.5–1.0 mg l⁻¹ as Br₂. Phytoplankton chlorophyll a concentrations were rapidly reduced by ozone treatment and did not increase in any treatments or controls because of lack of light. Overall mesozooplankton viability was rapidly reduced by 90–99% in treatment TRO levels above 1.85 mg l⁻¹ as Br₂. Our study outlines novel protocols that can be used for testing different potential ballast water treatment systems in replicated and controlled mesocosm experiments.     

Hydrocarbon and coprostanol levels in seawater, sea-ice algae and sediments near Davis station in eastern Antarctica: A regional survey and preliminary results for a field fuel spill experiment

A survey of hydrocarbons and the sterol coprostanol, together with a hydrocarbon degradation experiment, was conducted in a coastal marine environment in East Antarctica. Aliphatic hydrocarbon levels in sea-ice algae were 1.9–12.5 mg m⁻² and in seawater particulate matter 0.07–0.17 μg l⁻¹. Sea-ice algae contained the diatom biomarker, the highly branched isoprenoid (ip) diene ipC_25:2, and Southern Ocean seawater particulate matter samples were distinguished from near shore samples by the presence of nC_21:6. Sea-ice algae and seawater particulate matter samples showed a predominance of even chain n-alkanes. Hydrocarbon levels in sediment samples from anoxic fjord basins were high (45–48 μg g⁻¹) compared to a sub-tidal marine sample (0.7 μg g⁻¹), and were predominantly of bacterial origin. Contaminants detected were linear alkyl benzenes in sewage effluent from Davis station, and polycyclic aromatic hydrocarbons (PAH) which were present in very low levels (parts per trillion) throughout the environment. High levels of 2,6-dimethylnaphthalene were found in anoxic sediment from Ellis Fjord and may arise from a novel bacterial source. Coprostanol concentrations in sediments ranged from 67 to 1280 ng g⁻¹. A dual origin is proposed from marine mammalian faeces and, at several sites, from conversion of algal-derived sterols by anaerobic bacteria. Future studies examining the impact of human sewage from scientific bases or other ventures should use care in interpreting results when such high baseline values, from marine mammalian input, may occur naturally around the Antarctic coast. The potential exists, however, for the technique to distinguish between human and mammalian inputs through measurement of the coprostanol to epicoprostanol ratio, particularly if undertaken with appropriate comparative sampling. Results for a hydrocarbon degradation experiment where a light fuel was applied to an Antarctic beach, showed loss of up to 99% of the fuel within 2 months, mainly by volatilization.     

Measurement of soluble reactive phosphorus concentration profiles and fluxes in river-bed sediments using DET gel probes

DET (diffusive equilibrium in thin films) gel probes were used for sampling river-bed sediment porewaters, to characterise in situ soluble reactive phosphorus (SRP) concentration profiles and fluxes. DET probes were deployed in three contrasting rural streams: (1) a headwater ‘pristine’ stream, with minimal P inputs from low intensity grassland and no point sources, (2) an intensively cultivated arable catchment, and (3) a stream subject to high P loadings from sewage effluent and intensive arable farming. The DET results showed highly enriched porewater SRP concentrations of between ca. 400 and 5000 μg-P l⁻¹ in the sewage-impacted stream. In contrast, the arable and pristine streams had porewater SRP concentrations <70 μg-P l⁻¹ and <20 μg-P l⁻¹, respectively. Porewater SRP concentration profiles in both the sewage-impacted and arable-impacted streams showed well-defined vertical structure, indicating internal sources and sinks of SRP within the sediment. However, there was little variability in porewater SRP concentrations in the pristine stream. The DET porewater profiles indicated net diffusion of SRP (a) from the overlying river water into the surface sediment and (b) from subsurface sediment upwards towards the sediment–water interface. A mass balance for the sewage-impacted site showed that the influx of SRP into the surface sediments from the overlying river water was small (ca. 1% of the daily river SRP load). The DET results indicated that, in the arable and sewage-impacted streams, the surface ‘cap’ of fine sediment may play an important role in inhibiting upward movement of SRP from subsurface porewaters into the overlying river water, under steady-state, low-flow conditions.     

Polychlorinated biphenyls in the Brisbane River estuary, Australia

The concentrations of PCBs in water, sediments, fish (6 species), crustacea (3 species), molluscs (1 species), polychaetes (mixed species) and birds (1 species) from the Brisbane River estuary were determined. Levels were comparable to other similar situations elsewhere. No relationship was found between trophic class and PCB concentration although pelicans at the highest trophic level examined exhibited the highest muscle tissue concentration (i.e., 15.7 mg kg⁻¹ on a wet weight basis). The pattern of distribution of PCBs within body tissues of fish was closely related to lipid content.