Bioaccumulation surveillance in Milford Haven Waterway.

Biomonitoring of contaminants (metals, organotins, polyaromatic hydrocarbons (PAHs), PCBs) was undertaken in Milford Haven Waterway (MHW) and a reference site in the Tywi Estuary (St Ishmael/Ferryside) during 2007-2008. Bioindicator species encompassed various uptake routes-Fucus vesiculosus (dissolved contaminants); Littorina littorea (grazer); Mytilus edulis and Cerastoderma edule (suspension feeders); and Hediste (=Nereis) diversicolor (sediments). Differences in feeding and habitat preference have subtle implications for bioaccumulation trends though, with few exceptions, contaminant burdens in MHW were higher than the Tywi reference site, reflecting inputs. Elevated metal concentrations were observed at some MHW sites, whilst As and Se (molluscs and seaweed) were consistently at the higher end of the UK range. However, for most metals, distributions in MH biota were not exceptional. Several metal-species combinations indicated increases in bioavailability upstream, which may reflect the influence of geogenic/land-based sources-perhaps enhanced by lower salinity. TBT levels in MH mussels were below OSPAR toxicity thresholds and in the Tywi were close to zero. Phenyltins were not accumulated appreciably in M. edulis, whereas some H. diversicolor populations appear subjected to localized (historical) sources. PAHs in H. diversicolor were distributed evenly across most of MHW, although acenaphthene, fluoranthene, pyrene, benzo(a)anthracene and chrysene were highest at one site near the mouth; naphthalenes in H. diversicolor were enriched in the mid-upper Haven (a pattern seen in M. edulis for most PAHs). Whilst PAH (and PCB) concentrations in MH mussels were mostly above reference and OSPAR backgrounds, they are unlikely to exceed ecotoxicological thresholds. Bivalve Condition indices (CI) were highest at the Tywi reference site and at the seaward end of MH, decreasing upstream-giving rise to several significant (negative) relationships between CI and body burdens. Despite the possible influence of salinity gradient as a complicating factor, multivariate analysis indicated that a combination of contaminants could influence the pattern in condition (and the biomarkers metallothionein and TOSC). Integrating bioaccumulation data with biological and biochemical endpoints is seen as a useful way to discriminate environmental quality of moderately contaminated areas such as MHW and to prioritise cause and effect investigations.

Ecotoxicity of the degradation products of triphenylborane pyridine (TPBP) antifouling agent.

Triphenylborane pyridine (TPBP) is an alternative to organotin antifouling compounds. This work aimed to identify the unknown Peak #1, and to evaluate the ecotoxicity of TPBP and its degradation products. Peak #1 was produced from TPBP dissolved in acetonitrile under UV-A photolysis using a high-pressure mercury lamp. The Peak #1 fraction was purified using two-step column chromatography from a TPBP-acetonitrile solution. The major compound of the fraction was identified as being biphenyl from the 1H NMR and 13C NMR spectra. The ecotoxicity of four degradation products (diphenylborane hydroxide, phenylborane dihydroxide, phenol, and biphenyl) and TPBP towards two marine planktons were assessed. The 48 h LC(50) values of the crustacean, Artemia salina, were 0.13 mg L(-1) for TPBP, 14 mg L(-1) for biphenyl, 17 mg L(-1) for phenol, and > 50 mg L(-1) for the other degradation products. The 72 h EC(50) values of the diatom, Skeletonema costatum, were 0.0022 mg L(-1) for TPBP, 1.2 mg L(-1) for biphenyl, and > 2 mg L(-1) for the other degradation products. Thus, the ecotoxicity of biphenyl and the other degradation products were not high compared to the parent compound, TPBP.

Accumulation of organotin compounds in tissues and organs of stranded whales along the coasts of Thailand.

Concentrations of butyltin (BT) and phenyltin (PT) compounds were measured in organs and tissues of five species of whales (Bride's whale [Balaenoptera edeni], false killer whale [Pseudorca crassidens], pygmy sperm whale [Kogia breviceps], short-finned pilot whale [Globicephala macrorhynchus], and sperm whale [Physeter macrocephalus]) found stranded on the coasts of Thailand. The mean concentrations of BTs in various whales were in the range of 0.157 to 1.03 mg kg(-1 )wet weight, which were higher levels than the reported concentrations in whales from other countries. PT concentrations were also detected in the range of 0.022 to 1.14 mg kg(-1) wet weight. The concentrations of BTs and PTs in whales were higher than those in mussels from the coastal area of Thailand. Concentrations of tributyltin (TBT) and triphenyltin (TPT) compounds in whale organs and tissues were also compared, and it was found that TBT concentrations were generally higher in liver and lower in lung. TPT concentrations were higher in liver and blubber and lower in lung. Ratios of TBT degradation products in whale liver, namely monobutyltin (MBT) and dibutyltin (DBT), were higher than the ratios of TBT. TPTs in liver were found to be dominant among PTs. The patterns of BTs and PTs in false killer whale liver were different from those in the other whales by cluster analysis. Their concentrations in false killer whales were the highest among all whales in this study. False killer whales feed on squid and large pelagic fish containing higher concentrations of organotin (OT) compounds, so the differences in patterns and concentrations of OTs in liver between false killer whales and the other whales may be caused by difference in diet.

Distribution of organotin compounds in tissues of mussels Mytilus edulis and clams Mya arenaria.

Concentrations and composition of butyltin (BT) and phenyltin (PT) compounds were compared in tissues of mussels Mytilus edulis and clams Mya arenaria collected from the Mersey Estuary. Tributyltin (TBT) concentrations were consistently highest in digestive gland and low in muscular tissues such as siphons (Mya) and adductor muscle (Mytilus). Lowest concentrations were found in the periostracum surrounding the siphons of Mya. Ratios of monobutyltin (MBT), dibutyltin (DBT) and TBT to total BT content of Mytilus tissues were in the ranges 25-34%, 21-28% and 44-51%, respectively. Much higher proportions of TBT:total BT were characteristic of Mya (>80% in the digestive gland, remaining tissue and gonad) implying that slow degradation rates account for the relatively high levels of TBT in this species. TPT was the only phenyltin compound detected (albeit at relatively low levels), and, like TBT, was present in highest concentrations in the digestive gland of clams--suggesting an important dietary component in the accumulation of OTs in these bivalves.

Applicability of micellar electrokinetic chromatography to the analysis of estrogens in water.

Estrone, beta-estradiol and ethynylestradiol spiked in water were extracted using solid-phase extraction (SPE) and then directly determined by micellar electrokinetic chromatography (MEKC) with online concentration (sweeping). A 350 mL original sample volume (10 nM each) was concentrated to 1 mL using SPE, and ca. 240 nL of this solution was injected onto an MEKC capillary column. After sweeping, the estrogen related compounds were detected using a commercial absorbance detection system with an LOD of 0.16-0.30 nM in the original sample.

Accumulation of butyltin and phenyltin compounds in various fish species.

Concentrations of organotins (OTs) were measured in the muscle of 11 species of fishes from the Port of Osaka and Yodo River, Japan. Tributytin (TBT) and triphenyltin (TPT) compounds were detected in the range of 0.011-0.182 mg/kg wet weight and < 0.001-0.130 mg/kg wet weight, respectively. Concentrations of TBT were higher than those of TPT in the muscle of fish. Concentrations of OTs in fish from sea areas were higher than those from rivers, and the ratios of TBT to total butyltins (BTs) in fish from sea areas were also higher than those from rivers. A similar trend was found for TPT. Logarithm of bioconcentration factor (BCF) of TBT in fish was in the range of 2.7-3.9. No sex differences in TBT and TPT concentrations in Japanese sea perch were observed, and the concentrations of TBT and TPT were not related to total length of fish. No correlation was also observed between the concentration of TBT or TPT and lipid content. The concentrations of BTs and phenyltins (PTs) in organs and tissues of three fish species were determined. TBT was higher concentration in liver, brain, and muscle of white croaker and yellowtail. The ratios of TBT to the total BTs were 30-40%, and the ratios of TPT to total PTs in these fishes were greater than 50% of the total PT concentrations.

Organotin compounds in water, sediment, and biological samples from the port of osaka, japan

Butyltin (Bts) and phenyltin compounds (Pts) were measured in water, sediment, plankton, and mussels collected from eight stations in the harbor area of the Port of Osaka in 1996, and were compared with those of Otsuchi Bay. The levels of tributyltin (TBT) compounds in all samples from the Port of Osaka were slightly high in marinas and mooring areas of small and medium-hull vessels. Of total Bts, the ratio of TBT was under 50% in water and was dominant in sediment, plankton, and mussels. Triphenyltin (TPT) compounds in water were not detected. TPT was present at lower levels than TBT in sediment, plankton, and mussels. Of total Pts, monophenyltin (MPT) compounds and diphenyltin (DPT) compounds represented a high proportion in sediment, while TPT was dominant in plankton and mussels. The concentrations of TBT in water from the Port of Osaka were lower than those from Otsuchi Bay, however TBT concentrations in sediment, plankton, and mussels from the Port of Osaka were higher than those from Otsuchi Bay. The difference of TBT concentration among stations in the Port of Osaka was slight. In contrast, the levels of TBT in Otsuchi Bay were markedly higher at a station near the shipyard. Though TPT in water from the Port of Osaka was not detected, trace amounts of TPT was found in seawater from Otsuchi Bay. The levels and detected frequencies of TPT in sediment, plankton, and mussels from the Port of Osaka were lower than in those from Otsuchi Bay. The partition coefficients of Bts to sediment, plankton, and mussels from the Port of Osaka were higher than those of dibutyltin (DBT) compounds and MBT and those of TBT to plankton and mussels were higher than those in sediment. The partition coefficients of TBT to sediment and biological samples from the Port of Osaka were higher level than those in Otsuchi Bay.

Contamination of butyltin and phenyltin compounds in the marine environment of Otsuchi Bay, Japan.

Butyltin (BT) and phenyltin (PT) compounds were measured in seawater, sediment, and biological samples collected from coastal areas of Otsuchi Bay, Japan. Tributyltin (TBT) compounds in seawater, sediment, plankton, mussels, scallops and fish were in the range of 0.008-0.074 microg liter(-1), 0.01-0.64 mg (kg dry wt)(-1), 0.24-9.8 mg (kg dry wt)(-1), 0.04-0.18 mg (kg wet wt)(-1), 0.10-0.13 mg (kg wet wt)(-1) and 0.01-0.02 mg (kg wet wt)(-1), respectively. Trace amount of PTs were found in seawater. The highest concentrations of TBT and triphenyltin (TPT) were found near a shipyard. Triorganotin compounds were more dominant than their metabolites. A positive correlation was observed between the concentrations of TBT and TPT in the mussels. Concentrations of TBT and TPT in mussels were high in the upper intertidal zone, and decreased toward the water.

Separation of naphthalene and flavone derivatives by micellar electrokinetic chromatography with double- and triple-chain surfactants.

Three surfactants, p-bis(2-dodecyloxymethyl-3-oxa-6-sodiosulfonatohexyloxy)benz ene (BDSB) having two sulfonate groups and two lipophilic chains, disodium 10-dodecanoyl-5,15-bis(dodecyloxymethyl)-10-aza-4,7,13,16-tetra oxa-1,19-nonadecanedisulfonate (DDBTN) having two sulfonate groups and three lipophilic chains and disodium 4,11-bis(dodecyloxymethyl)-3,6,9,12-tetraoxa-1,14-tetrade canedionate (DBTT) having two carboxylate groups and two lipophilic chains, were used in micellar electrokinetic chromatography (MEKC). Eight naphthalene derivatives were baseline separated at 10 mM BDSB or 5 mM DBTT, and five flavone derivatives at 5 mM BDSB, DDBTN or DBTT. The elution order of the naphthalene derivatives in MEKC with BDSB was identical with that with DDBTN. However, this elution order was different from that found with DBTT. In the case of the flavone derivatives, BDSB, DDBTN and DBTT produced the identical elution order. These double- and triple-chain surfactants exhibited different selectivity when compared with widely used sodium dodecyl sulfate.