International Pellet Watch: Global monitoring of persistent organic pollutants (POPs) in coastal waters. 1. Initial phase data on PCBs, DDTs, and HCHs

Samples of polyethylene pellets were collected at 30 beaches from 17 countries and analyzed for organochlorine compounds. PCB concentrations in the pellets were highest on US coasts, followed by western Europe and Japan, and were lower in tropical Asia, southern Africa and Australia. This spatial pattern reflected regional differences in the usage of PCBs and was positively correlated with data from Mussel Watch, another monitoring approach. DDTs showed high concentrations on the US west coast and in Vietnam. In Vietnam, DDT was predominant over its metabolites (DDE and DDD), suggesting the principal source may be current usage of the pesticide for malaria control. High concentrations of pesticide HCHs were detected in the pellets from southern Africa, suggesting current usage of the pesticides in southern Africa. This study demonstrates the utility and feasibility of the International Pellet Watch approach to monitor POPs at a global scale.     

Increasing levels and biomagnification of persistent organic pollutants (POPs) in Antarctic biota

Representatives of the Antarctic food web (krill, cephalopod, fish, penguin, seal) of the area around Elephant Island and from the Weddell Sea were analysed for the most recalcitrant organochlorine compounds. Due to sorption of the compounds to sinking particles and accumulation in sediments, two benthic fish species (Gobionotothen gibberifrons, Chaenocephalus aceratus) feeding on benthos invertebrates and fish reflected significantly increasing concentrations within a decade (1987-1996), while a benthopelagic species (Champsocephalus gunnari) feeding on krill did not. In the pelagic food chain, lipid normalised concentrations of all compounds increased from Antarctic krill to fish proving that biomagnification of highly lipophilic pollutants (log octanol-water partition coefficient>5) occurs in water-breathing animals. As top predators Weddell and southern elephant seals (Leptonychotes weddellii, Mirounga leonina) biomagnified the persistent organic pollutants relative to krill 30-160 fold with the exception of hexachlorobenzene, the levels of which were lower than in fish indicating its intense specific elimination.     

Diffuse pollution by persistent organic pollutants as measured in plastic pellets sampled from various beaches in Greece

Plastic pellets found stranded on beaches are hydrophobic organic materials and thus, they are a favourable medium for persistent organic pollutants to absorb to. In the present study, plastic pellets are used to determine the diffuse pollution of selected Greek beaches. Samples of pellets were taken from these beaches and were analyzed for PCBs, DDTs, HCHs, and PAHs. The observed differences among pellets from various sampling sites are related to the pollution occurring at each site. Plastic pellets collected in Saronikos Gulf beaches demonstrate much higher pollutant loading than the ones collected in a remote island or close to an agricultural area. Based on data collected in this study and the International Pellet Watch program, pollution in Saronikos Gulf, Greece, is comparable to other heavily industrialized places of the world. The present study demonstrates the potential of pellet watch to be utilized as a detailed-scale monitoring tool within a single country.     

Persistent organic pollutants (POPs) in a small, herbivorous, arctic marine zooplankton (Calanus hyperboreus): trends from April to July and the influence of lipids and trophic transfer

Samples of Calanus hyperboreus, a herbivorous copepod, were collected (n = 20) between April and July 1998, and water samples (n = 6) were collected in May 1998, in the Northwater Polynya (NOW) to examine persistent organic pollutants (POPs) in a high Arctic marine zooplankton. Lipid content (dry weight) doubled, water content (r2 = 0.88) and delta15N (r2 = 0.54) significantly decreased, and delta13C significantly increased (r2 = 0.30) in the C. hyperboreus over the collection period allowing an examination of the role of these variables in POP dynamics in this small pelagic zooplankton. The rank and concentrations of POP groups in C. hyperboreus over the entire sampling was sum of PCB (30.1 +/- 4.03 ng/g, dry weight) > sum of HCH (11.8 +/- 3.23) > sum of DDT (4.74 +/- 0.74), sum of CHLOR (4.44 +/- 1.0) > sum of CIBz (2.42 +/- 0.18), although these rankings varied considerably over the summer. The alpha- and gamma-HCH and lower chlorinated PCB congeners were the most common POPs in C. hyperboreus. The relationship between bioconcentration factor (BCF) and octanol-water partition coefficient (Kow) observed for the C. hyperboreus was linear and near 1:1 (slope = 0.72) for POPs with a log Kow between 3 and 6 but curvilinear when hydrophobic POPs (log Kow > 6) were included. Concentrations of sum of HCH. Sum of CHLOR and sum of CIBz increased over the sampling period, but no change in sum of PCB or sum of DDT was observed. After removing the effects of time, the variables lipid content, water content, delta15N and delta13C did not describe POP concentrations in C. hyperboreus. These results suggest that hydrophobic POP (log Kow = 3.86.0) concentrations in zooplankton are likely to reflect water concentrations and that POPs do not biomagnify in C. hyperboreus or likely in other small, herbivorous zooplankton.     

Bioaccumulation and enantiomeric profiling of organochlorine pesticides and persistent organic pollutants in the killer whale (Orcinus orca) from British and Irish waters

Concentrations and enantiomeric profiles for a range of organochlorine compounds are reported in blubber samples from a number of individual killer whales (Orcinus orca) from British and Irish waters. Elevated contaminant levels and enriched isotopic ratios were determined in one individual whale sampled in the Scottish Western Isles compared to the others suggesting marine mammal based dietary influences. The potential application of isotopic ratios to model contaminant uptake, enantioselective enrichment and accumulation is demonstrated. Data are presented which provide information on enantioselective enrichment factors (EFs) for o,p'-DDT, alpha-HCH and toxaphene congeners CHB26 and CHB 50. This dataset further improves the current database on reported levels of a number of contaminants and provides additional background information on potential metabolic processes in killer whales from British and Irish waters.     

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.     

Evaluation of in situ and remote sensing sampling methods for SPM concentrations, Belgian continental shelf (southern North Sea)

Large sets of suspended particulate matter (SPM) concentration data from in situ and remote sensing (moderate resolution imaging spectroradiometer, MODIS) samplings in the Belgian nearshore area (southern North Sea) are combined in order to evaluate their heterogeneity and the sampling techniques. In situ SPM concentration measurements are from a vessel (tidal cycle) and from a tripod. During the tidal cycle measurements, vertical profiles of SPM concentration have been collected; these profiles have been used as a link between satellite surface and near-bed tripod SPM concentrations. In situ time series at fixed locations using a tripod are excellent witnesses of SPM concentrations under all weather conditions and may catch SPM concentration variability with a much finer scale. The heterogeneity has been statistically assessed by comparing the SPM concentration frequency distributions. Tidal cycle, tripod and MODIS datasets have different distributions and represent a different subpopulation of the whole SPM concentrations population. The differences between the datasets are related to meteorological conditions during the measurements; to near-bed SPM concentration dynamics, which are partially uncoupled from processes higher up in the water column; to the sampling methods or schemes and to measurement uncertainties. In order to explain the differences between the datasets, the tripod data have been subsampled using wave height conditions and satellite and tidal cycle sampling schemes. It was found that satellites and low-frequent tidal cycle measurements are biased towards good weather condition or spring–summer seasons (satellite). The data show that the mean surface SPM concentration derived from satellite data is slightly lower than from in situ tidal cycle measurements, whereas it is significantly lower than the mean SPM concentration interpolated to the water surface from the tripod measurements. This is explained by the errors arising from the interpolation along the vertical profiles, but also by the fact that satellite-measured signal saturates in the visible band used to retrieve SPM concentration in very turbid waters.     

A review of pollutants in the sea-surface microlayer (SML): a unique habitat for marine organisms

Boundary layers between different environmental compartments represent critical interfaces for biological, chemical and physical processes. The sea-surface microlayer (uppermost 1-1000 microm layer) forms the boundary layer interface between the atmosphere and ocean. Environmental processes are controlled by the SML, and it is known to play a key role in the global distribution of anthropogenic pollutants. Due to its unique chemical composition, the upper organic film of the SML represents both a sink and a source for a range of pollutants including chlorinated hydrocarbons, organotin compounds, petroleum hydrocarbons, polycyclic aromatic hydrocarbons (PAH) and heavy metals. These pollutants can be enriched in the SML by up to 500 times relative to concentrations occurring in the underlying bulk water column. The SML is also a unique ecosystem, serving as an important habitat for fish eggs and larvae. Concentration ranges and enrichment factors of pollutants in the SML in different areas of the world's oceans have been critically reviewed, together with available toxicity data for marine biota found within the SML. Overall, the SML is highly contaminated in many urban and industrialized areas of the world, resulting in severe ecotoxicological impacts. Such impacts may lead to drastic effects on the marine food web and to fishery recruitment in coastal waters. Studies of the toxicity of fish eggs and larvae exposed to the SML contaminants have shown that the SML in polluted areas leads to significantly higher rates of mortality and abnormality of fish embryos and larvae.     

Photoproduction of hydrogen peroxide in aqueous solution from model compounds for chromophoric dissolved organic matter (CDOM)

To explore whether quinone moieties are important in chromophoric dissolved organic matter (CDOM) photochemistry in natural waters, hydrogen peroxide (H₂O₂) production and associated optical property changes were measured in aqueous solutions irradiated with a Xenon lamp for CDOM model compounds (dihydroquinone, benzoquinone, anthraquinone, napthoquinone, ubiquinone, humic acid HA, fulvic acid FA). All compounds produced H₂O₂ with concentrations ranging from 15 to 500 μM. Production rates were higher for HA vs. FA (1.32 vs. 0.176 mM h⁻¹); values ranged from 6.99 to 0.137 mM h⁻¹ for quinones. Apparent quantum yields (Θ_app; measure of photochemical production efficiency) were higher for HA vs. FA (0.113 vs. 0.016) and ranged from 0.0018 to 0.083 for quinones. Dihydroquinone, the reduced form of benzoquinone, had a higher production rate and efficiency than its oxidized form. Post-irradiation, quinone compounds had absorption spectra similar to HA and FA and 3D-excitation–emission matrix fluorescence spectra (EEMs) with fluorescent peaks in regions associated with CDOM.     

Regional variations in trace element concentrations in tissues of black tiger shrimp Penaeus monodon (Decapoda: Penaeidae) from South Vietnam

The goal of the present study was to examine the specific bioaccumulation of 22 trace elements in muscle, exoskeleton and hepatopancreas of black tiger shrimp Penaeus monodon from the Mekong River Delta (MRD), and the South Key Economic Zone (SKEZ), South Vietnam. The general tendency in most trace element concentrations among different tissues were hepatopancreas > exoskeleton > muscle. Comparisons of trace element levels in tissues between the two regions showed that concentrations of Se in muscle and As in all three tissues were higher in SKEZ; whereas in MRD, the higher concentrations of most elements such as Mn, Cu, Cd, Ba, Hg, were observed in tissues. These geographical variations in trace element levels may reflect the differences in human activities between the two regions of South Vietnam. The target hazard quotient (THQ) values for trace elements (<1) indicate that local residents are not exposed to potential health risks via the consumption of shrimp.     

Regional variations in trace element concentrations in tissues of black tiger shrimp Penaeus monodon (Decapoda: Penaeidae) from South Vietnam

The goal of the present study was to examine the specific bioaccumulation of 22 trace elements in muscle, exoskeleton and hepatopancreas of black tiger shrimp Penaeus monodon from the Mekong River Delta (MRD), and the South Key Economic Zone (SKEZ), South Vietnam. The general tendency in most trace element concentrations among different tissues were hepatopancreas>exoskeleton>muscle. Comparisons of trace element levels in tissues between the two regions showed that concentrations of Se in muscle and As in all three tissues were higher in SKEZ; whereas in MRD, the higher concentrations of most elements such as Mn, Cu, Cd, Ba, Hg, were observed in tissues. These geographical variations in trace element levels may reflect the differences in human activities between the two regions of South Vietnam. The target hazard quotient (THQ) values for trace elements (<1) indicate that local residents are not exposed to potential health risks via the consumption of shrimp.     

Monitoring of organic contaminants in sediments from the Korean coast: Spatial distribution and temporal trends (2001-2007)

Spatial and temporal trends of organic contaminants in sediments along the Korean coast were estimated through a nationwide environmental monitoring program from 2001 to 2007. The concentrations of organic contaminants in sediments along the Korean coast were relatively low or moderate compared with foreign studies. The mean detection frequencies of organic contaminants during the seven years were highest for PAHs and PCDD/Fs, followed by PCBs, DDTs, TBT and HCHs in decreasing order. Based on published sediment quality guidelines, the ecological risks of persistent organic pollutants in sediments along the Korean coast were low, despite exceedances of the ERL at 2-6 sites for DDTs, and the TEL at 9-18 sites for PCDD/Fs. Nonparametric tests to assess temporal trends revealed significant decreasing trends for PCBs and PCDD/Fs at four and three sites, respectively (p < 0.05). These results reflect the effects of regulations on the use of those contaminants.     

Regional variations in trace element concentrations in tissues of black tiger shrimp Penaeus monodon (Decapoda: Penaeidae) from South Vietnam

The goal of the present study was to examine the specific bioaccumulation of 22 trace elements in muscle, exoskeleton and hepatopancreas of black tiger shrimp Penaeus monodon from the Mekong River Delta (MRD), and the South Key Economic Zone (SKEZ), South Vietnam. The general tendency in most trace element concentrations among different tissues were hepatopancreas > exoskeleton > muscle. Comparisons of trace element levels in tissues between the two regions showed that concentrations of Se in muscle and As in all three tissues were higher in SKEZ; whereas in MRD, the higher concentrations of most elements such as Mn, Cu, Cd, Ba, Hg, were observed in tissues. These geographical variations in trace element levels may reflect the differences in human activities between the two regions of South Vietnam. The target hazard quotient (THQ) values for trace elements (<1) indicate that local residents are not exposed to potential health risks via the consumption of shrimp.     

Polychlorinated biphenyl (PCB) concentrations and congener composition in masu salmon from Japan: A study of all 209 PCB congeners by high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS)

We collected two subspecies of masu salmon: Oncorhynchus masou masou from four localities (southern Sea of Japan northward to Hokkaido) and O. masou ishikawae from upstream from Ise Bay close to a heavy industrial area. All 209 PCB congeners were analyzed using HRGC/HRMS. PCA ordination of congener concentrations divided data into three groups: (i) ssp. masou from Hokkaido, (ii) ssp. masou from the other regions and (iii) ssp. ishikawae. The highest ∑ PCB concentration (40.39 ng/wet wt) was in ssp. ishikawae followed by ssp. masou from southern waters; however the TEQ_{dioxin-like PCBs} was highest in ssp. masou from southern water (1.96 pg-TEQ_{dioxin-like PCBs}/g wet wt.) due to the high proportion of congener #126 in its complement (#126 has the highest toxic equivalency factor among congeners). There is likely a contamination source offshore in the southern Sea of Japan and/or along the migratory route of ssp. masou.     

Reconstruction of pollution history of organic contaminants in the upper Gulf of Thailand by using sediment cores: first report from Tropical Asia Core (TACO) project

This paper reports the first reconstruction of a pollution history in tropical Asia from sediment cores. Four sediment core samples were collected from an offshore transect in the upper Gulf of Thailand and were analyzed for organic micropollutants. The cores were dated by measurement of (137)Cs and geochronometric molecular markers (linear alkylbenzenes, LABs; and tetrapropylene-type alkylbenzenes, TABs). Polychlorinated biphenyl (PCB) concentrations showed a subsurface maximum in layers corresponding to the 1970s, indicating the effectiveness of regulation of PCBs in Thailand. LAB concentrations increased over time, indicating the increase in input of sewage into the Gulf during the last 30 years. Hopanes, biomarkers of petroleum pollution, also increased over time, indicating that the inputs of automobile-derived hydrocarbons to the coastal zone has been increasing owing to the increased number of cars in Thailand since the 1950s. Polycyclic aromatic hydrocarbons (PAHs) increased in the layers corresponding to the 1950s and 1960s, probably because of the increased inputs of automobile-derived PAHs. PAH concentrations in the upper layers corresponding to the 1970s and later remained constant or increased. The absence of a subsurface maximum of PAHs contrasts with results observed in industrialized countries. This can be explained by the facts that the Thai economy did not depend on coal as an energy source in the 1960s and that economic growth has continued since the 1970s to the present. The deposition flux of PAHs and hopanes showed a dramatic offshore decrease, whereas that of LABs was uniform.     

Dependence of eelgrass (Zostera marina) light requirements on sediment organic matter in Massachusetts coastal bays: Implications for remediation and restoration

Using a calibrated bio-optical model we determined that the optical water quality conditions in several nitrogen-impaired embayments and in one unimpaired system were within the range of values known to support eelgrass growth. We also used the model to identify a range of light requirements for eelgrass (Zostera marina). Higher eelgrass light requirements, expressed as a percentage of surface-incident irradiance, corresponded with higher sediment organic matter content. These results corroborated findings by previous studies which indicate a generalized relationship: seagrasses growing in turbid conditions with poorer water and sediment quality have higher light requirements than those growing in less degraded conditions. The mechanistic reason for the variation in light requirements is still not completely explained and cannot be attributed to a single independent variable. Varying light requirement have important implications for eelgrass protection and should be considered when setting restoration targets for eelgrass in water quality and nitrogen remediation programs.     

Variations of O/O in plants from temperate peat bogs (Switzerland): implications for paleoclimatic studies

Despite the great potential of peat bogs as climatic archives, to date only few studies have focused on the climatic controls on cellulose isotopic composition in modern bog plants. This study attempts to calibrate plant-climate relationships by sampling a set of modern plant species (both vascular plants and mosses) and bog surface waters along an altitude transect in Switzerland. Isotopic analyses of water samples show that the δ¹⁸O-values of surface bog waters follow the trend of precipitation despite significant scatter in the data set. Detailed sampling of surface waters within one bog shows that δ¹⁸O-values vary widely and are closely related to the micro-topography of the bog surface. More enriched ¹⁸O/¹⁶O ratios in water samples collected from small raised hummocks than the ones collected from hollows are documented in both horizontal and vertical profiles. A δ¹⁸O-δD plot indicates that the process leading to the isotopic enrichment of the uppermost surface waters is evaporation, greater above Sphagnum covered hummocks than above open pools. To investigate the implications of such high variability of source water for plant α-cellulose δ¹⁸O-values, a detailed study of both surface water and α-cellulose δ¹⁸O-values within one site is conducted. The large δ¹⁸O variability observed in surface waters is found to be considerably smoothed in α-cellulose (by a factor of 5-10 depending on the plant species). This indicates that the water used by plant photosynthetic processes reflects the isotopic composition of the average annual precipitation. This points to a source water level for plants of a few decimeters where the variations are smaller than at the air-water interface. The response of the α-cellulose δ¹⁸O to the environmental gradient along the altitude transect varies considerably from species to species. For most of the species studied, the δ¹⁸O-values decrease with altitude, following the trends of δ¹⁸O-values in precipitation and in surface water samples. Some species, the cotton sedge Eriophorum vaginatum and the moss Sphagnum capillifolium, show statistically significant δ¹⁸O relationships to an altitude of −1.8‰/km and −2.9‰/km respectively. However, some other plant species, Calluna vulgaris, Vaccinium uliginosum, Andromeda poliflora, Carex pauciflora, Sphagnum cuspidatum and Sphagnum magellanicum, do not, or only partially, reflect changes in climatic parameters associated with an altitude increase. Furthermore, changes in relative humidity, which are not correlated with altitude, are found to explain a large part of the variability in δ¹⁸O-values for the sedge Carex pauciflora and the moss Sphagnum cuspidatum. Therefore, this study confirms the importance of species-specific studies when interpreting ¹⁸O/¹⁶O ratios of macrofossils along a fossil peat sequence as a record of past climate changes. Our study allows to extend the mechanistic model that isotopically links source water and cellulose to the physiological specificities of sedges and mosses. A comparison of the modeled and calculated net biological fractionation factors for Eriophorum vaginatum and Sphagnum capillifolium reveals that these two species appear to have a more homogeneous leaf reservoir than trees.