Perfluorinated compounds in estuarine and coastal areas of north Bohai Sea, China

Perfluorinated compounds (PFCs) in water, sediment, soil, and biota collected from estuarine and coastal areas of the north Bohai Sea, China, were determined by use of HPLC-MS/MS. Significant concentrations of PFCs were found in water (mean: 18.4 ng/l) and biologic samples (fish: 265 ng/g dw), while concentrations of PFCs in soils and sediments were less. The predominately detected compound was perfluorooctanesulfonate (PFOS), with a maximum concentration of 30.9 ng/l in water and 791 ng/g dw in fish. Concentrations of PFCs were significantly greater in the Liaohe River system than other locations, which suggests point sources in this urbanized and industrialized region. PFOS concentrations in water and biota were both less than the reported threshold concentrations. Detection of PFCs at relatively great concentrations in various environmental matrices from this region suggested that further studies characterizing concentrations of PFCs, their sources and potential risk to both humans and wildlife are needed.     

Spatial distribution of polyfluoroalkyl compounds in dab (Limanda limanda) bile fluids from Iceland and the North Sea

The spatial distribution of polyfluoroalkyl compounds (PFCs) was investigated in dab (Limanda limanda) bile fluids collected from Iceland and the North Sea. Concentrations of various PFCs, including perfluorinated sulfonates (C₄-C₆, C₈ PFSAs), perfluorinated carboxylic acids (C₉-C₁₄ PFCAs) and n-methyl perfluorooctane sulfonamidoethanol (MeFOSE), were quantified. Perfluorooctane sulfonate (PFOS) was the predominant compound with highest concentrations along the Danish and German coast (mean 9.36 ng/g wet weight (ww)). Significantly lower PFOS concentrations were found at the other sampling stations in the North Sea and Iceland (p < 0.01, t-test). Conversely, the spatial distribution of the PFCAs in Iceland and the North Sea was more uniform. The most abundant PFCA was perfluorononanoic acid (PFNA), while the mean concentration decreased with increasing chain length from 4.7 ng/g ww for PFNA to 0.04 ng/g ww for perfluorotetradecanoic acid (PFTeDA). Overall, the different spatial distribution of PFCs indicates different origin of sources and different transportation mechanism.     

Perfluorinated alkyl acids in water, sediment and wildlife from Sydney Harbour and surroundings

Perfluorinated alkyl compounds (PFCs) including perfluorooctane sulphonate (PFOS) and perfluorooctanoate (PFOA) were measured in environmental samples collected from around Homebush Bay, an urban/industrial area in the upper reaches of Sydney Harbour and Parramatta River estuary. Water, surface sediment, Sea Mullet (Mugil cephalus), Sydney Rock Oyster (Saccostrea commercialis) and eggs of two bird species; White Ibis (Threskiornis molucca), and Silver Gull (Larus novaehollandiae) were analysed. In most samples PFOS was the dominant PFC. Geometric mean PFOS concentrations were 33 ng/g ww (wet weight) in gull eggs, 34 ng/g ww in ibis eggs, and 1.8 ng/g ww and 66 ng/g ww in Sea Mullet muscle and liver, respectively. In sediment the PFOS geometric mean was 1.5 ng/g, in water average PFOS and PFOA concentrations ranged from 7.5 to 21 ng/L and 4.2 to 6.4 ng/L, respectively. In oysters perfluorododecanoic acid was most abundant, with a geometric mean of 2.5 ng/g ww.     

Partitioning behavior of perfluorinated compounds between sediment and biota in the Pearl River Delta of South China

Surface sediment and biota were collected from 12 sampling sites – seven along the Pearl River Delta and five along the Hong Kong coastline. Perfluorinated compound (PFC) concentrations were detected using a high-performance-liquid-chromatogram–tandem-mass-spectrometry system. Analytical results indicated that the total PFC concentrations were in the range of 0.15–3.11 ng/g dry weight in sediments, while the total PFC concentrations in oyster and mussel samples were between 0.46–1.96 and 0.66–3.43 ng/g wet weight, respectively. The major types of PFCs detected in the sediment samples were perfluorooctanesulfonic acid (PFOS) and perfluorobutanoic acid (PFBA), with concentrations ranging from low limits of quantification to 0.86 ± 0.12 ng/g dry weight and 1.50 ± 0.26 ng/g dry weight, respectively. In bivalve samples, PFOS was the dominant contaminant with concentrations ranging from 0.25 ± 0.09 to 0.83 ± 0.12 ng/g wet weight in oysters and 0.41 ± 0.14 to 1.47 ± 0.25 ng/g wet weight in mussels. An increase in PFC concentration was found to be correlated with increased human population density in the study areas.     

Distribution and accumulation of organotin species in seawater, sediments and organisms collected from a Taiwan mariculture area

The present study was undertaken to evaluate the distribution and accumulation of tributyltin (TBT) and triphenyltin (TPhT) in seawater, sediments and selected organisms from a cage mariculture area in southern Taiwan, Hsiao Liouchiou Island. Our results show that ΣOTs were found in concentrations as high as 196 ng/L in seawater collected from the sites in Pai-Sa harbor, and up 1040 ng/g dry wt. in sediments dredged from sites within Da-Fu harbor. Also, ΣOTs concentrations of 859 ng/g dry wt. were observed in the liver of cobia (Rachycentron canadum) from mariculture cages. As most published studies have focused on the acute toxicity and bioaccumulation of organotins in mussels, the effects of organotins on cobia and other marine fauna are still poorly understood. This study highlights the significance of ΣBTs accumulation in cobia, as well as in the sediments and seawater surrounding their culture facilities.     

Dioxin-like compounds in sediments from the Daliao River Estuary of Bohai Sea: distribution and their influencing factors

The concentrations, compositional profiles, and potential ecological risk of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs) and polychlorinated naphthalenes (PCNs) in sediments of the Daliao River Estuary were investigated. Total concentrations of PCDD/Fs, PCBs, and PCNs were in the range of 11.3-133.2 ng/kg dry weight (dw), 1 971-37 632 ng/kg dw and 33.1-284.4 ng/kg dw, respectively. The total TEQ values varied from 0.37 to 4.08 ng/kg dw, with the dominant contributions by PCDD/Fs, then by PCBs and PCNs. The spatial distributions of PCDD/Fs, PCBs and PCNs in the river estuary were much related to hydrodynamic conditions. The risk of contamination to the deeper sea was increased in the flood seasons. Moreover, our data confirmed that both organic matter in sediments and molecular properties of dioxin-like compounds were the factors which strongly influenced the partition behavior of these dioxin-like compounds between sediments and water phase in the estuarine zone.     

Polybrominated diphenyl ether congeners in the young-of-the-year bluefish,Pomatomus saltatrix,from several nursery habitats along the US Atlantic coastline

Spatial trends of polybrominated diphenyl ether (PBDE) congeners were examined by using high resolution gas chromatography – low resolution electron impact mass spectrometry (GC-EIMS) in 414 samples of young-of-the-year (YOY) bluefish (Pomatomus saltatrix) collected from a total of 29 nursery habitats along the US Atlantic coastline from Massachusetts to Florida. Of the 26 target PBDE congeners, BDE-47 (4 Br), BDE-100 (5 Br), BDE-49 (4 Br), BDE-99 (5 Br), and BDE-154 (6 Br) were the five most frequently detected congeners in the order of decreasing importance. The sum of the concentrations of five major PBDE congeners, referred to as ΣPBDEs, varied between estuaries and also among samples from a given estuary. ΣPBDEs were lowest in YOY bluefish from Vineyard Sound, Nantucket Sound, Great Bay, Delaware Bay, Lynnhaven Bay, Cape Lookout, and Crescent Beach, with maximum ΣPBDE concentrations below 10 ng/g wet weight. ΣPBDEs in three bluefish samples from Stamford Harbor were detected at relatively high to unusually high concentrations of 69.1, 205, and 561 ng/g wet weight. ΣPBDE values for other Stamford Harbor bluefish were generally low. Highest PBDE concentrations were detected in the vicinity of industrial and urban locations within the New York – New Jersey metropolitan complex. Among them, bluefish from Newark Bay were generally the most contaminated with an average ΣPBDE value of 56.6 ± 30.8 ng/g wet weight. ΣPBDEs in bluefish from Newark Bay were numerically greater than ΣPBDEs in bluefish from all locations, however these differences were not statistically significant. Modest to good correlations between ΣPBDEs and lipids were observed for YOY bluefish from Buzzards Bay, Upper New Bedford Harbor, Lower New Bedford Harbor, Outer New Bedford Harbor, Providence Harbor, Housatonic River, Norwalk Harbor, Little Neck Bay, Newark Bay, Sandy Hook Bay, Great Bay, Delaware Bay, Patuxent River and Crescent Beach. Poor correlations between ΣPBDE and lipids were observed for bluefish from other estuaries. ΣPBDEs were not always correlated with fish length or weight. ΣPBDEs in YOY bluefish along the US Atlantic coastline modestly paralleled ΣPBDEs in mussels and oysters, from not exact but geographically loosely similar locations, reported in the NOAA Mussel Watch Program. A number of researchers who used the high resolution mass spectrometry reported additional PBDE congeners. Although PBDE congeners we report do appear to be the prominent congeners in these studies, it is likely that the comparisons will be skewed in certain instances.     

Assessment of tributyltin contamination in a shipyard area using a mussel transplantation approach

Mussels (Mytilus galloprovincialis) were transplanted to seven stations around a large shipyard for 126 days to evaluate tributyltin (TBT) contamination. Although the application of TBT-based paints to ships is totally banned in Korea, butyltin compounds were found to accumulate in mussels following transplantation. Concentrations of TBT and total butyltins in transplanted mussels near the shipyard were in the range of 40-350 ng Sn/g and 74-530 ng Sn/g on a dry weight basis, respectively. Obviously, low TBT concentrations (6.0-53 ng Sn/gdw) were determined in mussels at four stations outside the shipyard. A negative gradient of TBT concentrations and TBT portion to total butyltin concentrations were found in both the surface water and transplanted mussels according to distance from the shipyard. In addition, TBT concentrations in surface water and transplanted mussels showed significant correlation (r(2) = 0.71; p < 0.001). These results indicate that the shipyard still releases fresh TBT into surrounding waters even after TBT regulation in Korea, and mussel transplantation is useful in evaluating TBT contamination in shipyard area.     

Perfluorinated compounds in the surface waters of Puget Sound,Washington and Clayoquot and Barkley Sounds,British Columbia

Perfluorinated compounds (PFCs) are persistent organic contaminants detected in various environmental matrices including sediment, air, biota, and water. The objectives of this study was to evaluate the occurrence of these contaminants within the surface waters of the Pacific Northwest region and through relative concentrations and ratios, to assess their possible sources. Surface waters were extracted and analyzed by liquid chromatography tandem mass spectrometry (LCMSMS). Perfluoroheptanoic acid (PFHpA), perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) were the most commonly detected PFCs. Total PFC concentrations detected ranged from 1.5 to 41 ng L-1. Surprisingly, levels of PFCs in the more urbanized Puget Sound waters were comparable to those measured from the more rural region of Clayoquot and Barkley Sounds in British Columbia. The ratio of PFHpA/PFOA were also similar between the two regions, suggesting that the burden of PFCs throughout the region results from direct input from regional sources.     

Total body burden and tissue distribution of polyfluorinated compounds in harbor seals (Phoca vitulina) from the German Bight

Total body burden and tissue distribution of polyfluorinated compounds (PFCs) were investigated in harbor seals (Phoca vitulina) from the German Bight in 2007. A total number of 18 individual PFCs from the following groups could be quantified in the different tissues: perfluorinated carboxylic acids (PFCAs) and perfluorinated sulfonates (PFSAs) and their precursors perfluorinated sulfinates (PFSiAs), perfluorinated sulfonamides, and sulfonamido ethanols. Perfluorooctanesulfonate (PFOS) was the predominant compound in all measured seal tissues (up to 1665 ng g⁻¹ wet weight in liver tissue). The dominant PFCAs were perfluorononanoic acid (PFNA) and perfluorodecanoic acid (PFDA), but their concentrations were much lower compared to PFOS. The mean whole body burden in harbor seals of all detected PFCs was estimated to be 2665 ± 1207 μg absolute. The major amount of the total PFCs burden in the bodies was in blood (38%) and liver (36%), followed by muscle (13%), lung (8%), kidney (2%), blubber (2%), heart (1%), brain (1%), thymus (<0.01%) and thyroid (<0.01%). These data suggest large differences in body burden and accumulation pattern of PFCs in marine mammals.     

Perfluorinated compounds in blood of Caretta caretta from the Mediterranean Sea

Perfluorinated compounds (PFCs), widely used for their hydro-oil repellent properties, are almost non-degradable in the environment; there is scientific evidence that indicate bioaccumulation. They represent a threat to many organisms, because they are toxic and are endocrine disruptors. Scientific studies have demonstrated the presence of PFCs in blood and liver samples of fish, turtles, birds and mammals of marine ecosystems in different geographical areas. The aim of this study was to determine the distribution of PFOS and PFOA in blood samples of the marine turtle Caretta caretta, using a minimally invasive sampling procedure. 49 blood samples of marine turtle, taken from several Italian marine turtle rescue centers, were analyzed. While PFOA was never detected, measurable concentrations of PFOS were found in 15 blood samples; the values show a range from 1.14 ng/g to 28.51 ng/g (wet wt.). No differences between groups of samples taken from different areas were found.     

Assessment of perfluorinated compounds (PFCs) in plasma of bottlenose dolphins from two southeast US estuarine areas: relationship with age, sex and geographic locations

Plasma PFCs were measured in 157 bottlenose dolphins (Tursiops truncatus) sampled from two US southeast Atlantic sites (Charleston (CHS), SC and Indian River Lagoon (IRL), FL) during 2003-2005. ∑PFCs, perfluoroalkyl carboxylates (∑PFCAs), perfluoroalkyl sulfonates (∑PFSAs) and individual compounds were significantly higher in CHS dolphins for all age/sex categories compared to IRL dolphins. Highest ∑PFCs concentrations occurred in CHS juvenile dolphins (2340 ng/g w.w.); significantly higher than found in adults (1570 ng/g w.w. males; 1330 ng/g w.w. females). ∑PFCAs were much greater in CHS dolphins (≈ 21%) compared to IRL dolphins (≈ 7%); ∑PFSAs were 79% in CHS dolphins versus 93% in IRL dolphins. PFOS, the dominant compound, averaged 72% and 84%, respectively, in CHS and IRL dolphins. Decreasing PFC levels occurred with age on the bioaccumulation of PFCs in both sites. These observations suggest PFC accumulation in these two dolphin populations are influenced by site-specific exposures with significantly higher levels in CHS dolphins.     

Accumulation of butyltin compounds in cetaceans from Korean coastal waters

Data on the occurrence and accumulation profiles of butyltins (BTs), including tributyltin (TBT), in marine mammals are scarce. This is the first study to investigate residue levels and accumulation patterns of BTs in cetaceans from Korean coastal waters. The total concentrations of BTs (sum of mono- to tri-butyltins) in minke whales (Balaenoptera acutorostrata) and long-beaked common dolphins (Delphinus capensis) ranged from 15.7 to 297 ng/g wet weight (mean: 100 ng/g wet weight) and from 59.0 to 412 ng/g wet weight (mean: 228 ng/g wet weight), respectively. Dibutyltin (DBT) accounted for 63% of the total BTs in all cetacean samples. Significant species-specific differences in BT concentrations, possibly due to the differences in their habitat and diet, were found between the two cetacean species. The concentrations of DBT and TBT in most cetacean samples exceeded the threshold value for cytotoxic effects in cetaceans, implying potentially adverse health risks from exposure to BTs.     

Organochlorines and dioxin-like compounds in green-lipped mussels Perna viridis from Hong Kong mariculture zones

Concentrations of persistent organic pollutants including polychlorinated biphenyls (PCBs), organochlorine (OC) pesticides and dioxin-like compounds were measured in green-lipped mussels, Perna viridis, collected from seven mariculture zones in Hong Kong between September and October in 2002 in order to evaluate the status, spatial distribution and potential sources of pollution in these areas. Concentrations ranged from 300 to 4400 ng/g lipid weight for total OCs and 170–1000 ng/g lipid weight for total PCBs (based on 28 congeners). Relatively smaller DDT concentrations in mussels compared with previous studies suggest reduced discharges of DDTs from nearby regions into Hong Kong waters. Detection of a mixture of HCH isomers in the mussels indicated that Hong Kong waters were predominantly contaminated by technical HCHs rather than lindane. Mussel samples from all sampling locations elicited significant dioxin-like activity in the H4IIE-luc bioassay. The greatest magnitude of dioxin-like response (39 pg TEQ/g wet wt.) was detected in mussels from Ma Wan in the western waters of Hong Kong, which is strongly influenced by the Pearl River discharge. Human health risk assessment was undertaken to evaluate potential risks associated with the consumption of the green-lipped mussels. Risk quotient (RQ) for dioxin-like compounds was greater than unity suggesting that adverse health effects may be associated with high mussel consumption.     

Organochlorines and dioxin-like compounds in green-lipped mussels Perna viridis from Hong Kong mariculture zones

Concentrations of persistent organic pollutants including polychlorinated biphenyls (PCBs), organochlorine (OC) pesticides and dioxin-like compounds were measured in green-lipped mussels, Perna viridis, collected from seven mariculture zones in Hong Kong between September and October in 2002 in order to evaluate the status, spatial distribution and potential sources of pollution in these areas. Concentrations ranged from 300 to 4400 ng/g lipid weight for total OCs and 170–1000 ng/g lipid weight for total PCBs (based on 28 congeners). Relatively smaller DDT concentrations in mussels compared with previous studies suggest reduced discharges of DDTs from nearby regions into Hong Kong waters. Detection of a mixture of HCH isomers in the mussels indicated that Hong Kong waters were predominantly contaminated by technical HCHs rather than lindane. Mussel samples from all sampling locations elicited significant dioxin-like activity in the H4IIE-luc bioassay. The greatest magnitude of dioxin-like response (39 pg TEQ/g wet wt.) was detected in mussels from Ma Wan in the western waters of Hong Kong, which is strongly influenced by the Pearl River discharge. Human health risk assessment was undertaken to evaluate potential risks associated with the consumption of the green-lipped mussels. Risk quotient (RQ) for dioxin-like compounds was greater than unity suggesting that adverse health effects may be associated with high mussel consumption.     

Temporal trend, spatial distribution, and terrestrial sources of PBDEs and PCBs in Masan Bay, Korea

Congener specific determination of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) was carried out in 21 surface sediment samples and a sediment core from Masan Bay, Korea. Among the 40 PBDE congeners targeted only 29 were detectable. PBDE congener profile within sediments was dominated by BDE-209 followed by BDEs-99, -47, -153 and -183, sequentially. In surface sediments, the average ΣPBDEs levels approached that of average ΣPCBs values. However, trends observed in the sediment core suggest that this pattern will alter over time and result in higher surface sediment PBDE concentrations than PCBs in future. Various diffuse and point sources for PBDEs and PCBs were identified in this location. Shipping and other industrial activities were associated with PCB contamination while domestic and industrial waste discharges corresponded with PBDE contamination. The average concentration for PBDEs and PCBs in surface sediments were 5.7, 7.2 ng/g dry weight, respectively.     

Okadaic acid, a causative toxin of diarrhetic shellfish poisoning, in green-lipped mussels Perna viridis from Hong Kong fish culture zones: method development and monitoring

Green-lipped mussels (Perna viridis) were collected from seven fish culture zones (FCZs) in Hong Kong and analyzed for okadaic acid (OA). A conventional HPLC method was modified by incorporating a proteinase K digestion step. Results suggest that a higher recovery (2.5 times higher) of OA was obtained from spiked samples after the addition of 1.08 mg proteinase K in comparison with samples incubated without the proteolytic enzyme. For the hepatopancreas (HP) of individual field-collected mussels, the additional digestion step can enhance OA extraction by 3.1 times. Spatial and temporal variations in OA concentrations in the mussels from various FCZs were investigated. The highest concentration of OA in mussel HP samples was 1164.9 ng/g HP wet wt. With respect to OA concentrations in whole mussel tissues from seven sites and four seasonal samplings, the concentrations were between 70.0 and 131.0 ng/g wet wt., which did not exceed the generally recognized international regulatory criteria (>200 ng/g) for OA.     

Okadaic acid, a causative toxin of diarrhetic shellfish poisoning, in green-lipped mussels Perna viridis from Hong Kong fish culture zones: Method development and monitoring

Green-lipped mussels (Perna viridis) were collected from seven fish culture zones (FCZs) in Hong Kong and analyzed for okadaic acid (OA). A conventional HPLC method was modified by incorporating a proteinase K digestion step. Results suggest that a higher recovery (2.5 times higher) of OA was obtained from spiked samples after the addition of 1.08 mg proteinase K in comparison with samples incubated without the proteolytic enzyme. For the hepatopancreas (HP) of individual field-collected mussels, the additional digestion step can enhance OA extraction by 3.1 times. Spatial and temporal variations in OA concentrations in the mussels from various FCZs were investigated. The highest concentration of OA in mussel HP samples was 1164.9 ng/g HP wet wt. With respect to OA concentrations in whole mussel tissues from seven sites and four seasonal samplings, the concentrations were between 70.0 and 131.0 ng/g wet wt., which did not exceed the generally recognized international regulatory criteria (>200 ng/g) for OA.     

Organochlorine contamination (PCBs, DDTs, HCB, HCHs) in sediments from Cienfuegos bay, Cuba

The spatial distribution of various organochlorinated compounds, e.g. PCBs, DDTs, HCB and HCHs, were investigated in sediments from Cienfuegos bay, Cuba. Their concentrations appeared to be relatively low by global standards and only sediments receiving the impact from the residual waters of the city and thermoelectrical power approached the sediment quality guidelines for PCBs and DDTs. Relatively higher ΣDDT concentrations and high DDT/DDE + DDD ratios in two sites near the outfalls of the city indicated a current DDT usage, probably linked to public health emergencies. These results contribute to the sparse regional database for organochlorinated compounds in the Caribbean marine environment.     

Sources of polyfluoroalkyl compounds in the North Sea, Baltic Sea and Norwegian Sea: Evidence from their spatial distribution in surface water

The spatial distribution of 15 polyfluoroalkyl compounds (PFCs) in surface water was investigated in the North Sea, Baltic Sea and Norwegian Sea. In addition, an interlaboratory comparison of the sampling techniques and analysis was conducted. Highest concentration in the North Sea was found near the coast, whereas the ∑PFC concentration decreased rapidly from 18.4 to 0.07 ng l⁻¹ towards the open North Sea. The river Elbe could identify as a local input source for PFCs into the North Sea, whereas perfluorobutanoic acid (PFBA) was transported into the sampling area with the easterly current. In contrast to the North Sea, the distribution of PFCs in the Baltic Sea was relatively homogenous, where diffuse sources dominated. In general, the composition profile was influenced from local sources caused by human activities, whereas atmospheric depositions of here analysed PFCs were negligible, but it could have possibly an influence on low contaminated sites like the open North Sea or Norwegian Sea.