Bioavailability and effects of sediment-bound TBT in deposit-feeding clams, Scrobicularia plana

Concentrations of tributyltin (TBT), dibutyltin (DBT), inorganic and total tin have been measured in water, sediments and deposit feeding clams, Scrobicularia plana, from 25 estuarine locations in England and Wales, in order to compare the bioavailability of different forms of the element. Abnormally high tin values in Scrobicularia from harbours and areas of high boating activity testify to the high bioaccumulation potential of organotins, notably TBT derived from anti-fouling paints, relative to inorganic tin.Infaunal deposit-feeding bivalves consistently contain higher concentrations of TBT than other benthic organisms indicating that sediments may be an important route for uptake. Significant correlations between sediment TBT values and residues in clams such as S. plana (r = 0·81, p < 0·001) support this hypothesis. Direct evidence of the bioaccumulation of sediment-bound TBT is provided from laboratory experiments in which Scrobicularia were exposed to TBT in water and in sediments, either separately or in combination. The results of these experiments clearly demonstrate a predominantly particulate component for TBT uptake in clams.The kinetics of TBT accumulation and elimination were studied in Scrobicularia exposed to sediments containing 0·3 and 1·0 μg/g TBT (as tin). Equilibrium concentrations in tissue are approached after 40 days.Sediments containing 10 μg/g TBT are acutely toxic to S. plana, although such concentrations are only likely to occur close to dockyards and large marinas. Preliminary laboratory and field observations suggest however, that clam populations could be affected at TBT concentrations in sediments of 0·3 μg/g and possibly lower.     

Embryotoxicity of butyltin compounds to the sea urchin Paracentrotus lividus.

Tributyltin (TBT) has been widely employed in marine anti-fouling paints as a biocide, although it represents a serious risk, particularly in estuarine and coastal water/sediment ecosystems. In this study, the embryotoxic effects of TBT and its degradation products, dibutyltin (DBT) and monobutyltin (MBT), were analyzed during the development of the sea urchin Paracentrotus lividus from post-fertilization to the pluteus stage, to better clarify ecotoxicological impact. The embryotoxicity of butyltins is concentration-dependent and increases proportionally with number of butyl groups. Significant growth reduction was observed at TBT concentrations as low as 0.01 microgram l-1; 1 microgram l-1 was the maximum concentration allowing embryos to reach the pluteus stage at 48 h post-fertilization. Development was blocked at the morula or blastula stage with higher TBT concentrations. DBT and MBT are less toxic: slowed development and a decrease in pluteus size occurred at 10 micrograms l-1 DBT and 0.5 mg l-1 MBT. Effects on both skeletal deposition and blocked embryonic development are suggested to be due to the interference of organotin compounds with intracellular calcium homeostasis.     

The relationship between the copper complexing capacity of sea water and copper toxicity in shrimp zoeae

Mortality of larval coon-stripe shrimp, Pandalus danae, was related to labile copper and the copper complexing capacity of sea water, as measured by differential pulse Anodic Stripping Voltammetry (ASV). In nominal treatments of control, 5 and 10μg/litre Cu which contained less than 1·0μg/litre ASV labile Cu, zoeal development was usually complete. In treatments of 20 and 50μg/litre Cu which contained more than 7·0μg/litre ASV labile Cu, most larvae died while in the first zoeal stage. ASV labile Cu was related to the copper complexing capacity of sea water. Copper toxicity at less than 1·0 μg/litre ASV labile Cu is indicated by moulting delay and apparent Cu accumulation in zoea of the 5 and 10μg/litre Cu nominal treatments.     

厦门西港和闽江口表层沉积物中有机锡含量分布

对1996年10月在闽江口和1999年6月在厦门西港采集的表层沉积物样品中有机锡的含量进行分析,结果表明，TBT、DBT和MBT在所有厦门西港表层沉积物样品中均被检出，除XM21A和XM21B外，其它站位的TBT中Sn元素浓度均低于4.3×10     

Uptake and transformation of C-labelled tributyltin chloride by the dog-whelk, nucella lapillus: Importance of absorption from the diet

The importance of the diet as a source of tributyltin (TBT) in Nucella lapillus was studied using [¹⁴C]tributyltin chloride. In N. lapillus provided with prelabelled mussels, Mytilus edulis, in labelled water (mean 20·5 ng/litre TBT) the rate of accumulation of total ¹⁴C was 2–3 times that in unfed animals. Owing to its degradation in the tissues of both fed and unfed animals, concentrations of [¹⁴C]TBT tended to reach a plateau after only 28 days. However, total concentrations of ¹⁴C were still increasing after 49 days. Under experimental conditions (15°C, ample food, no disturbance) the diet accounted for about 50% of the body burden of TBT in N. lapillus after 49 days exposure: concentration factors (dry tissue/water) for [¹⁴C]TBT in both male and female N. lapillus were similar at about 60 000 in fed and 30 000 in unfed animals. It is concluded that the diet may contribute less than half of the body burden of TBT found in natural populations subjected to life-long exposure.     

Assessing site-specific effects of TBT contamination with mussel growth rates

During nine field transplant tests in San Diego Bay (1987–1990), juvenile mussels were exposed to mean concentrations of tributyltin (TBT) in ambient seawater ranging from 2 to 530 ng liter⁻¹ for 12 weeks under natural conditions. A total of 79 cages with 18 mussels each were monitored at 18 different sites. Growth and seawater TBT concentrations were measured weekly or on alternate weeks (biweekly). Mean growth rates ranged from 17 to 505 mg week⁻¹ (0·2 to 2·5 mm week⁻¹). Accumulation of TBT in mussel tissues was measured at the end of each 12-week test exposure and ranged from 0·1 to 3·2 μg g⁻¹ TBT wet weight. The frequency of the measurements and the integration of chemical and biological measurements improved the accuracy of the assessment over more traditional approaches. Growth was significantly related to seawater and tissue TBT. The statistical relationships with growth effects were used to estimate chemical effect zones for TBT in San Diego Bay. Site-specific differences were distinguished by additional statistical analyses and consideration of environmental significance.     

Chlorination by-products in chlorinated cooling water of some European coastal power stations

Chlorination by-products (CBPs) are formed as a result of the cnlorination of power station cooling water for anti-fouling purposes. Their production was studied at 10 coastal power stations in the UK, France and The Netherlands. Three categories of CBPs were determined: trihalomethanes; haloacetonitriles; and halophenols. Bromoform was the CBP most abundantly present in the effluents of all 10 power stations. At a mean chlorine dosage of 0.5–1.5 mg/litre (as Cl₂) the mean bromoform concentration was 16.32 ± 2.10 μg/litre. The CBP found in second highest concentrations was dibromoacetonitrile (DBAN) with mean concentrations of 1.48 ± 0.56 μg/litre. Other CBPs detected were dibromochloromethane, bromodichloromethane and 2,4,6-trichlorophenol; concentrations of these three compounds were very low (< 1 μg/litre). At those sites at which bromoform was measured in the dispersing effluent plume it was found to behave as a conservative parameter (Significant direct correlation with plume ΔT).     

Butyltin concentrations along the Japanese coast from 1997 to 1999 monitored by Caprella spp. (Crustacea: Amphipoda)

The concentrations of butyltins along the Japanese coastline were investigated from 1997 to 1999, 7 to 9 years after implementation of legislation limiting the use of tributyltin (TBT) in Japan. Seawater was sampled at 0.5 m depth, and Caprella spp. were collected from Sargassum spp. and aquaculture facilities from 18 areas within four broad areas along the coastline of Japan, i.e., the Pacific coast of northern Japan, the coast along the Sea of Japan, Tokyo Bay and adjacent areas, and western Japan. Butyltins (MBT, DBT and TBT) were detected in 32 of the 63 seawater samples with average concentrations of 4.6 ng MBT/l, 4.5 ng DBT/l and 6.8 ng TBT/l, respectively. Butyltin concentrations in seawater from western Japan indicate "hot spots" even in unpopulated areas. Butyltins (MBT, DBT and TBT) were detected in all samples of Caprella spp., varying from 2.3 ng BTs /g wet wt in C. penantis R-type from Tobishima Island in the Sea of Japan to 464 ng BTs /g wet wt in C. decipiens Mayer from Amakusa, western Kyushu. The BT concentrations in Caprella spp. form western Japan were significantly higher than those from other areas, including Tokyo Bay and adjacent areas, where large scale industry and international ports are located. These results indicate that butyltin contamination still remains even in unpopulated areas after the regulation on TBT usage, and that the regulation governing TBT usage since 1990 has not been effective enough to concede recovery of shallow water ecosystems around Japan.     

Sublethal effects of hydrogen sulfide in sediments on the Urchin Lytechinus pictus

Laboratory exposures of the urchin Lytechinus pictus to sediment dosed with varying concentrations of hydrogen sulfide (H₂S), but without elevated organic material, were conducted. Changes in mortality, behavior, growth and gonad production were measured during 49 days' flow through exposures. Hydrogen sulfide concentrations of 165·8 μ liter⁻¹ in pore water caused significant changes in all parameters measured. Concentrations as low as 32·9 μ liter⁻¹ caused significant decreases in wet weight and male gonad production. A concentration of 91·8 μ liter⁻¹ caused the mortality rate to increase 100-fold over control exposures (0·63 μ liter⁻¹). Sublethal effects on growth and gonad production could have been caused by either direct biochemical inhibition by H₂S or secondarily through behavioral modifications. Hydrogen sulfide concentrations above 165·8 μ liter⁻¹ are common near sewage outfalls and could contribute to changes in species composition and sediment toxicity that occur there.     

An experimental marine ecosystem study of the pelagic biogeochemistry of pentachlorophenol

The marine biogeochemistry of pure pentachlorophenol was studied relative to a control treatment at a scale which provided a good model for the pelagic planktonic environment (70 m³ polyethylene bags). Pentachlorophenol that was dispersed at concentrations of 10 and 100 μg/litre showed identical relative rates of decrease over 25 days to concentrations 32·8% and 31·1%, respectively, of the initial concentrations. No bioaccumulation by phytoplankton or zooplankton was observed and pentachlorophenol removal by adsorption (by particulates, zooplankton or the enclosure walls) was insignificant. The log of the pentachlorophenol concentration was significantly correlated to the hours of bright sunshine up to Day 18, after which the photolysis efficiency decreased as the proportion of pentachlorophenol exposed to sunlight decreased. The results imply a long residence time for pentachlorophenol in deeper waters outside the photolysis zone. A persistent reduction in the primary production and production per unit carbon was observed at 100 μg/litre and, when coupled to the reproducible demise of the centric diatom Skeletonema costatum in culture and the spiked enclosures, suggests that pentachlorophenol inhibits phytoplankton growth.     

Long-term effects of tributyltin compounds on the baltic amphipod, Gammarus oceanicus

Amphipod larvae, Gammarus oceanicus, were exposed for 8 weeks to bis(tributyltin) oxide (TBTO) or tributyltin fluoride (TBTF), or for 5 weeks to leachates from tributyltin-containing antibiofouling paints. No larvae survived 8 weeks' exposure to 3 μg/litre TBTO or TBTF. Differential larval survival occurred during exposure to 0·3 gmg/litre of these same compounds. Paint leachates were shown to cause similar toxicity responses at comparable aqueous tributyltin concentrations. An examination of sublethal responses showed slight decreases in growth for larvae exposed to TBTO and to paint leachates, although responses at tributyltin levels below 1 μg/litre were not marked. Whole-animal oxygen consumption rates were not affected by low tributyltin exposure levels. While these studies demonstrate low level toxicity of tributyltins, effects on oxygen consumption and growth do not indicate a mode of action for these compounds.     

Relationships between macroalgal biomass and nutrient concentrations in a hypertrophic area of the Venice Lagoon

Macroalgae biomass and concentrations of nitrogen, phosphorus and chlorophyll a were determined weekly or biweekly in water and sediments, during the spring-summer of 1985 in a hypertrophic area of the lagoon of Venice. Remarkable biomass production (up to 286 g m⁻² day⁻¹, wet weight), was interrupted during three periods of anoxia, when macroalgal decomposition (rate: up to 1000 g m⁻² day⁻¹) released extraordinary amounts of nutrients. Depending on the macroalgae distribution in the water column, the nutrients released in water varied from 3·3 to 19·1 μg-at litre⁻¹ for total inorganic nitrogen and from 1·8 to 2·7 μg-at litre⁻¹ for reactive phosphorus. Most nutrients, however, accumulated in the surficial sediment (up to 0·640 and to 3·06 mg g⁻¹ for P and N respectively) redoubling the amounts already stored under aerobic conditions, Phytoplankton, systematically below 5 mg m⁻³ as Chl. a, sharply increased up to 100 mg m⁻³ only after the release of nutrients in water by anaerobic macroalgal decomposition. During the algal growth periods, the N:P atomic ratio in water decreased to 0·7, suggesting that nitrogen is a growth-limiting factor. This ratio for surficial sediment was between 6·6 and 13·1, similar to that of macroalgae (8·6–12·0).     

Evidence on the interaction of mercury and selenium in the shrimp Palaemon elegans

The interaction of selenium with mercury was studied in the shrimp Palaemon elegans. The release of ²⁰³HgCl₂ (5·0 μg Hg per gramme body weight) from shrimp pretreated with selenium (SeO₂ doses of 1·97, 3·95 and 7·90 μg Se per gramme fresh weight) was significantly decreased compared with the control group to which only 5·0 μg Hg/g had been administered.In the presence of HgCl₂ (5·0 μg Hg per gramme fresh weight) the release of ⁷⁵Se also diminished significantly at the higher stable Se pretreated dose (7·90 μg Se/g) while, at a lower selenium concentration, the release was not statistically different. Analyses for stable Hg and Se confirmed the decrease in rate of selenium loss in the presence of mercury which had been demonstrated with radiotracers.A dose of 7·9 μg Se per gramme fresh weight injected 12 h before exposure of the shrimp to the various mercuric chloride solutions did not produce a significant difference in the 24 h LC₅₀ compared with the group not pretreated with selenium. However, during exposure to mercury at 3·8 mg/litre, the median lethal time (LT₅₀) for the shrimp pretreated for 4 days with sublethal selenium (6·9 and 10·5 mg Se/litre) was delayed (19·2 and 33·2 h) compared with the group which was not pretreated. The results are discussed in relation to the role of selenium in the acutely toxic effects of inorganic mercury.     

Butyltins in marine waters of The Netherlands in 1988 and 1989; Concentrations and effects

Specific effects of tributyltin (TBT) on Crassostrea gigas—valve thickening, and Nucella lapillus—imposex, were measured on local populations, relatively clean unaffected species from England were transferred to the Netherlands and exposed during six weeks to ambient TBT concentrations. Near marinas 50% of the exposed species were sterile after six weeks. In general, no dissolved butyltins were detected in the Rhine and Scheldt estuaries. In 1988 TBT concentrations in marinas ranged from 120 to 4000 ng litre⁻¹. In sediments (fraction <60 μm) and suspended particulate matter TBT concentrations reached up to 1200 ng g⁻¹. TBT concentrations in mussel tissue ranged from <1 to 2300 ng g⁻¹ based on a dry weight. In 1989 concentrations of dissolved TBT ranged from <0·1 to 7200 ng litre⁻¹. In 1989 a seasonal study in the marina of Colijnsplaat showed that dissolved butyltins increased from April to the end of May due to the launching of freshly painted boats, and decreased afterwards.     

绿化修剪草与污水厂污泥混合中温厌氧消化的可行性研究

对城市绿化修剪草与污水厂污泥消化联合处理的可行性进行了研究.选择了10%,20%,30%,40%和50%共5个修剪草与污泥的干基投加比例,试验结果表明,随着修剪草投加量的增加污泥消化系统的产气率亦随之增加,当修剪草投加比例为50%时,消化系统产气率可达348L/kg.TS,与不加修剪草相比,产气率增幅达到30%,修剪草与污水厂污泥消化联合处理是可行的.     

Toxicity of copper to three estuarine bivalves

This paper reports on a study of the toxicity of copper to three species of bivalve of commercial food value, Anadara granosa (Linnaeus), Meretrix casta, Deshayes and Crassostrea madrasensis (Preston) inhibiting the Vellar estuary at Porto Novo (southern India). The LC₅₀ values were estimated as 60 μg Cu/litre for A. granosa, 72 μg Cu/litre for M. casta and 88 μg Cu/litre for C. madrasensis subjected to 96-h static bioassay tests after acclimation for a period of four days in the laboratory. The animals selected for study ranged in length from 29 to 44 mm in A. granosa, from 25 to 42 mm in M. casta and from 31 to 115 mm in C. madrasensis. The experiments were conducted at 25% salinity with pH 8·0 ± 0·1 at a temperature of 27°C ± 0·5°C. The revival rates of bivalves which survived exposure to the LC₅₀ concentrations for the 96-h period (when marked and released in the natural environment) were 67% for A. granosa, and C. madrasensis and 83% for M. casta. The LT₅₀ values for the three bivalves at different concentrations of the metal were also calculated.     

Phosphorus metabolism in anthropogenically transformed lagoon ecosystems: The Comacchio lagoons (Ferrara, Italy)

Inorganic phosphorus dynamics were investigated with the use of ³²P in the hypertrophic Comacchio lagoons (NE Adriatic) during an extremely dense, quasi-permanent bloom of picocyanobacteria. Concentrations of dissolved inorganic phosphate (DIP) in waters of the blooming lagoons were usually near the detection limit (0.01 μmoles·dm⁻³). DIP uptake rates by microplankton at near-ambient concentrations (0.01 to 0.1 μmoles·dm⁻³) were in the range of 9.6 to 16.1 nmoles P·dm⁻³·min⁻¹, and turnover times were 1.5 to 3 min. The turnover time was >40 h in the eutrophic coastal waters of the adjacent Adriatic Sea. The uptake rate of DIP depended on its initial concentration. In water samples artificially enriched with DIP, the uptake rate rose to its maximum of 0.10 to 0.13 μmoles P·dm⁻³·min⁻¹ (or 6 to 7 μmoles·dm⁻³·h⁻¹) when the initial concentration of DIP was elevated to 10 to 20 μmoles·dm⁻³. The potential capacity of microplankton in the water samples to consume and retain DIP was estimated at 25 μmoles·dm⁻³. Specific features are discussed of phosphorus metabolism in the anthropogenically transformed lagoon ecosystem with an anomalous food web with few animals.     

Flux of Reduced Sulfur Gases Along a Salinity Gradient in Louisiana Coastal Marshes

Seasonal and diurnal reduced sulfur gas emissions were measured along a salinity gradient in Louisiana Gulf Coast salt, brackish and freshwater marshes. Reduced sulfur gas emission was strongly associated with habitat and salinity gradient. The dominant emission component was dimethyl sulfide (average: 57·3 μg S m⁻² h⁻¹) in saltmarsh with considerable seasonal (max: 144·03 μg S m⁻² h⁻¹; min: 1·47 μg S m⁻² h⁻¹) and diurnal (max: 83·58 μg S m⁻² h⁻¹; min: 69·59 μg S m⁻² h⁻¹) changes in flux rates. Hydrogen sulfide was dominant (average: 21·2 μg S m⁻² h⁻¹, max: 79·2 μg S m⁻² h⁻¹; min: 5·29 μg S m⁻² h⁻¹) form in brackishmarsh and carbonyl sulfide (average: 1·09 μg S m⁻² h⁻¹; max: 3·42 μg S m⁻² h⁻¹; min: 0·32 μg S m⁻² h⁻¹) was dominant form in freshwater marsh. A greater amount of H₂S was evolved from brackishmarsh (21·22 μg S m⁻² h⁻¹) as compared to the saltmarsh (2·46 μg S m⁻² h⁻¹) and freshwater marsh (0·30 μg S m⁻² h⁻¹). Emission of total reduced sulfur gases decreased with decrease in salinity and distance inland from the coast. Emission of total reduced sulfur gases over the study averaged 73·3 μg S m⁻² h⁻¹ for the saltmarsh, 32·1 μg S m⁻² h⁻¹ for brackishmarsh and 2·76 μg S m⁻² h⁻¹ for the freshwater marsh.     

Acute and chronic toxicity of the rice herbicides thiobencarb and molinate to opossum shrimp (Neomysis mercedis)

Neomysis mercedis were exposed to the rice herbicides molinate and thiobencarb, which have been detected in the Sacramento-San Joaquin Delta. Continuous-flow acute and chronic toxicity studies were performed. For thiobencarb, the 4-, 7- and 14-day LC_sos were 304, 214 and 91 μg/liter, respectively. For molinate, these values were 9910, 2530, and 820 μg/liter, respectively. Mortality stabilized after 18 and 28 days exposure, respectively, for thiobencarb and molinate. The incipient lethal concentrations were 53 and 230 μg/liter, respectively. Joint toxicity studies indicated additive toxicity for the two chemicals. Chronic no observable effects concentrations (NOECs) were estimated at 3·2 and 25·6 μg/liter for thiobencarb and molinate, with measurable effects occurring at 6·2 and 45·2 μg/liter, respectively. Environmental monitoring data suggests that concentrations of these chemicals in the Delta prior to 1985 may have exceeded the threshold for chronic toxicity, under conditions of joint exposure. However, due to continued improvements in pesticide management practices, environmental concentrations decreased to approximately 30 percent of the chronic threshold for joint toxicity by 1988. Baseline data on growth and reproduction relevant to toxicity tests are also presented for this species.     

Acute toxicity of bromochlorinated seawater to selected estuarine species with a comparison to chlorinated seawater toxicity

The acute toxicity of bromochlorinated estuarine water (ca. 20%) was determined for several estuarine organisms. The most sensitive species were oysters (Crassostrea virginica, larvae and juveniles) and copepods (Acartia tonsa) with 48-h LC₅₀'s of 0·10 to 0·21 mg BrCl/litre. Palaemonetes pugio was most tolerant with a 96-h LC₅₀ of 0·70 mg BrCl/litre. The fish species tested (Menidia menidia, Brevoortia tyrannus and Leiostomus xanthurus) all had a 96-h LC₅₀ of 0·21–0·23 mg BrCl/litre.The BrCl toxicity data are compared with Cl₂ toxicity data for the same species. When the LC₅₀'s are expressed as equivalents per litre, BrCl is found to be two to four times less toxic than Cl₂. The ranking of species in terms of sensitivity is the same for both disinfectants.Some data are provided concerning the decay rates of BrCl and Cl₂ in estuarine water. BrCl was found to decay more rapidly than Cl₂ at higher ammonia levels (0·25 mg NH₄-N/litre). The question of chemical speciation is discussed with particular reference to the differential toxicities.