Organotins and imposex in the rock shell, Thais clavigera, from oyster mariculture areas in Taiwan

The amounts of organotin compounds such as butyltins [sigma BTs: tributyl- (TBT), dibutyl- (DBT), monobutyl- (MBT)] and phenyltins [sigma PhTs: triphenyl- (TPhT), diphenyl- (DPhT) and monophenyl- (MPhT)] in rock shells, Thais clavigera, from the northern (Shiangsan), central (Lukang) and southern (Chiku) Taiwan oyster mariculture areas varied with season and location. High values of sigma BTs (mainly TBT) and low values of sigma PhTs (mainly TPhT) were found during winter (January 1999) at Shiangsan, while high amounts of sigma PhTs (mainly TPhT) and low sigma BTs (mainly TBT) were found during summer (August 1998) at Lukang. The snails were also affected by imposex. Imposex at Shiangsan, Lukang and Chiku increased from 67.1, 59.3 and 36.7% in summer to 100, 100 and 80% in winter, respectively. Relative penis size indices similar trend at Chiku site. No male displayed rock shells were found at Shiangsan and Lukang in winter. Linear correlations between pseudopenis length versus TBT (r = 0.7655, P < 0.001), DBT (r = 0.4253, P < 0.05), MBT (r = 0.5865, P < 0.01) and TPhT (r = -0.6160, P < 0.01) were obtained significant. Among 200 samples, significant positive correlations between length (pseudopenis/shell) ratio of female versus TBT (r = 0.6944, P < 0.005) and sigma BTs (r = 0.6413, r < 0.01) were also observed. The weak correlations between length (pseudopenis/shell) ratio of female versus DBT (r = 0.3085) and MBT (r = 0.4240, P < 0.1) and TPhT (-0.4917, P < 0.05; negative correlation) could indicate that DBT, MBT and TPhT have little or no effect on the development of imposex in rock shells.     

Quantification of organotin compounds and determination of imposex in populations of dogwhelks (Nucella lapillus) from Norway

Unintentional effects of the antifouling agent tributyltin (TBT) have been discovered in marine gastropods as the induction of male sex characters in females, known as imposex. The occurrence of imposex in dogwhelks (Nucella lapillus) was investigated in 41 populations sampled in 1993-1995 along the Norwegian coast. A method for quantification of organotin species using gas chromatography and atomic emission detection (GC-AED) was developed. Some degree of imposex occurred in almost all populations of dogwhelks studied, except in four from Northern Norway. The concentration of organotin compounds in the gastropods from the unaffected populations was below the detection limit (7 ng Sn/g d.w.). The concentration of TBT in dogwhelks from affected populations was in the range 48-1096 ng Sn/g d.w. A positive relation between the concentration of TBT in dogwhelks and the degree of imposex was found.     

Development of imposex and accumulation of butyltin in the tropical muricid Thais distinguenda transplanted to a TBT contaminated site

The muricid Thais distinguenda (ca. 1,300 individuals) was collected from a pristine island in the Andaman Sea and tagged prior to translocation to an area of intense shipping activities. A minimum of 50 tagged individuals were recaptured 1, 2, 3, 5, 6, 7, 8 and 12 months after transplantation. The animals were separated into small (< or = 25 mm) and big (>25 mm) specimens based on total shell length and both incidence of imposex and body burden of butyltin (BT) were determined. After 3 months 16.7% of the small size and none of the big size class had developed imposex. After 5 months the incidence of imposex in the big and small size classes increased steadily with time reaching 86.4 and 80%, respectively after 1 year. Time after transplantation was significantly correlated with the incidence of imposex for the big size class (Spearman Rs=1; P=0.008); RPLI (Spearman Rs=1; P=0.008) and VDSI (Spearman Rs=1; P=0.008); and the small size class: incidence of imposex (Spearman Rs=1; P=0.006); RPLI (Spearman Rs=1; P=0.006) and VDSI (Spearman Rs=1: P=0.007). The development of imposex was not significantly related to body size after five months (chi square P<0.001). The body burden of tributyltin was not significantly different between the two size classes (paired t-test ) but the smaller animals had significantly higher concentrations of both dibutyltin (DBT; P<0.005) and monobutyltin (MBT; P<0.001). The use of transplantation experiments in addition to imposex surveys and analysis of body burden of tributyltin (TBT) can enhance the interpretation of the results and understanding of the time scale involved with the development of imposex.     

Kinetics of the development of imposex in transplanted adult dogwhelks, Nucella lapillus

The degree of imposex in dogwhelks, Nucella lapillus (L.), is normally described in terms of a series of vas deferens development stages. The progression of adult female dogwhelks through vas deferens stages 0-5 in response to exposure to tributyltin at 2-128 ng/l has been modelled on the basis of first-order kinetics. Modelling indicated that the half-lives of stages 0, 1 and 2 were from 1-8 weeks and that the half-life of stage 3 was approximately twice as long. The half-life of stage 4 was 90-120 weeks. Half-lives decreased with increasing exposure concentration. The implications of these data for field surveys and transplantation experiments are discussed. Transplanted dogwhelks will not rapidly attain equilibrium with environmental conditions. Experiments will require careful control of exposure period, and preferable supporting chemical data.     

Combined effect of polystyrene plastics and triphenyltin chloride on the green algae Chlorella pyrenoidosa

The combined effect of polystyrene (PS) particles and triphenyltin chloride (TPTCl) to the green algae Chlorella pyrenoidosa was studied. The 96 h IC₅₀ of TPTCl to the green algae C. pyrenoidosa was 30.64 μg/L. The toxicity of PS particles to C. pyrenoidosa was size-dependent, with the 96 h IC₅₀ at 9.10 mg/L for 0.55 μm PS but no toxicity observed for 5.0 μm PS. The exposure to 0.55 μm PS led to damage on structure of algal cells, which could in turn cause inhibition on photosynthesis and population growth of the green algae. TPTCl concentrations in test medium were lowered by 15–19% at presence of 0.55 μm PS particles, indicating a reduced bioavailability of TPTCl. In spite of this reduced bioavailability, the presence of PS increased the toxicity of TPTCl, which might be attributed to facilitated uptake of TPTCl by the green algae after the damage of cell structure. The overall results of the present study provided important information on the effect of PS on the bioavailability and toxicity of TPTCl to phytoplankton species.

     

Occurrence of organotin compounds in water and sediment in Canada

Water and sediment samples from 265 locations across Canada were analyzed for butyltin and methyltin species, and inorganic tin. In 10% of the water samples the highly toxic tributyltin species was found at concentrations which could cause growth retardation upon chronic exposure to a sensitive organism, rainbow trout yolk sac fry. High concentrations of tributyltin were found in some sediments (up to 10 mg Sn/kg dry weight), but the biological availability of sediment-associated tributyltin is unknown. Tributyltin was mainly found in areas of heavy boating and shipping traffic, which is consistent with its use as an antifouling agent in some paints for boats, ships and docks. The methyltin species were found much less frequently in water and sediment than tributyltin and its degradation products.     

Effects of perfluorinated compounds on development of zebrafish embryos

Perfluorinated compounds (PFCs) have been widely used in industrial and consumer products and frequently detected in many environmental media. Potential reproductive effects of perfluorooctanesulfonate (PFOS), perfluorooctanoic acid (PFOA) and perfluorononanoic acid (PFNA) have been reported in mice, rats and water birds. PFOS and PFOA were also confirmed developing toxicants towards zebrafish embryos; however, the reported effect concentrations were contradictory. Polyfluorinated alkylated phosphate ester surfactants (including FC807) are precursor of PFOS and PFOA; however, there is no published information about the effects of FC807 and PFNA on zebrafish embryos. Therefore, this study was conducted to determine the effects of these four PFCs on zebrafish embryos. Normal fertilized zebrafish embryos were selected to be exposed to several concentrations of PFOA, PFNA, PFOS or FC807 in 24-well cell culture plates. A digital camera was used to image morphological anomalies of embryos with a stereomicroscope. Embryos were observed through matching up to 96-h post-fertilization (hpf) and rates of survival and abnormalities recorded. PFCs caused lethality in a concentration-dependent manner with potential toxicity in the order of PFOS > FC807 > PFNA > PFOA based on 72-h LC(50). Forty-eight-hour post-fertilization pericardial edema and 72- or 96-hpf spine crooked malformation were all observed. PFOA, PFNA, PFOS and FC807 all caused structural abnormalities using early stages of development of zebrafish. The PFCs all retarded the development of zebrafish embryos. The toxicity of the PFCs was related to the length of the PFC chain and functional groups.     

Pilot study on the contamination of drinking water by organotin compounds from PVC materials

Raw and treated water samples and tap water samples from four to six houses located on distribution lines where PVC pipe/tubing had been recently installed were collected in five Canadian municipalities for the analysis of organotin compounds. After derivatisation with sodium tetraethylborate the ethylated organotin compounds were extracted with hexane and analysed by gas chromatography-microwave induced plasma atomic emission spectrometry using a wavelength (326.234 nm) specific for tin. Organotin compounds, mainly methyltin and dimethyltin at concentrations ranging respectively from 0.5 to 257 ng Sn/L and from 0.5 to 6.5 ng Sn/L, were detected in samples from ten of the twenty-two houses. No organotin compounds were detected in raw water or treated water leaving the treatment plant, indicating that the organotin compounds were leaching into the water from some component of the distribution system.     

Concentrations of organotin compounds in sediment and clams collected from coastal areas in Vietnam

Levels of butyltin (BT) and phenyltin (PT) compounds were determined in sediments and clam Meretrix spp. collected from north and central coastal areas in Vietnam. Concentrations of TBT in sediments ranged from 0.89 to 34 ng g(-1) dry wt and those in clams ranged from 1.4 to 56 ng g(-1) wet wt. The levels of TBT in sediments and clams from Vietnam were within limits reported from other countries. Further, the TBT level in clams was lower than the tolerable average residue level (TARL) estimated based on tolerable daily intake (TDI). Trace amounts of PTs were also found in both sediment and clam samples. In sediments from north and central Vietnam, the concentrations of TBT were highest in the order of Hue (28 ng g(-1) dry wt), Cua Luc (15 ng g(-1) dry wt), Sam Son (6.3 ng g(-1) dry wt), and Tra Co (5.5 ng g(-1) dry wt). Among the clams from north and central Vietnam, the levels of TBT in clams from Cua Luc were dramatically high at 47 ng g(-1) wet wt. TBT formed the principal butyltin species in sediment at all sites studied. The ratios of TBT in sediment were higher among BT compounds at all study sites. Of total BTs, TBT was the dominant species in clams from almost all sites studied. In spatial distribution, TPT showed a pattern similar to TBT, suggesting the use of TPT as an antifouling paint. The partition coefficient between sediment and calms was calculated. The partition coefficients of TBT and TPT were 2.01 (0.56-5.5) and 9.23 (3.1-20), respectively. These results show that sediment-bound TBT is a source of contamination to clams in addition to dissolved TBT.     

Survey of organotin compounds in rivers and coastal environments in Portugal 1999-2000

In the period from April 1999 to May 2000, organotin pollution, namely butyl and phenyltins, was investigated in coastal and continental waters (46 stations), estuarine sediments (15 stations) and mussels (Mytilus galloprovincialis) (13 stations) throughout Portugal. Sampling points were chosen in areas of specific industrial, agricultural and harbor activities. Butyltins (BTs) were the only tin species identified of which tributyltin (TBT) was found in the whole area. Concentrations of TBT in river water ranged from 3 to 30 ng L(-1) (as Sn), marine sediment ranged from 4 to 12 microg kg(-1) (as Sn), whereas concentrations in mussel tissue ranged from 2.5 to 490 microg kg(-1) (as Sn). Given that some water samples appeared to be contaminated by higher monobutyltin (MBT) and dibutyltin (DBT) concentrations, the role of biological degradation and direct inputs from agricultural and industrial applications areas are discussed. The study compares depleted butyltin pollution in sediments and mussels of the Portuguese coastline associated with antifouling paints with previously reported levels. Inputs in river waters are more related to (i) PVC leaching and (ii) industrial sources, in some cases discharged by municipal wastewaters.     

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.     

Occurrence of PCDD/F, PCB, PBDE, PFAS, and organotin compounds in fish meal, fish oil and fish feed

We analysed polychlorinated dibenzo-p-dioxins and furans (PCDD/F, dioxins), and polychlorinated biphenyls (PCB) in 13 fish meal, five fish oil, and seven fish feed samples. Polybrominated diphenyl ethers (PBDE), organotin compounds (OTC), and perfluoroalkylated substances (PFAS) were analysed in ten fish meal, two fish oil, and two fish feed samples. All measured TEQ concentrations of PCDD/F and PCB were below the maximum levels set by Directive 2002/32/EC. There was no correlation between concentrations of WHOPCDD/F-TEQ and indicator PCB in our samples. The most common congeners among PBDEs were BDE-47 and BDE-100. BDE-209 was present in five fish meals of the ten analysed. Tributyltin (TBT) was the predominant congener in all samples except in three fish meals, where monobutyltin (MBT) was the major congener. Perfluorooctane sulphonate (PFOS) was the predominant congener in six fish meals of the ten analysed. There was large variation in concentrations and congener distributions of the studied compounds between our samples. Our results underline a need to pay special attention to the origin and purity of feed raw material of marine origin.     

Review of measured concentrations of triphenyltin compounds in marine ecosystems and meta-analysis of their risks to humans and the environment

The state of scientific knowledge regarding analytical methods, environmental fate, ecotoxicity and ecological risk of triphenyltin (TPT) compounds in marine ecosystems as well as their exposure and health hazard to humans was reviewed. Since the 1960s, TPT compounds have been commonly applied as biocides for diverse industrial and agricultural purposes. For instance, they are used as active ingredients in antifouling systems on marine vessels and mariculture facilities, and as fungicides in agriculture. Due to their intensive use, contamination of coastal waters by TPT and its products of transformation has become a worldwide problem. The proportion of quantified TPT to total phenyltin compounds in the marine environment provides evidence that TPT is photodegradable in water and sediment but resistant to biotransformation. Concentrations of TPT in marine biota are consistently greater than concentrations in water and sediment, which implies potential of TPT to bioaccumulate. TPT is toxic to both marine plants and animals. The predicted no effect concentration (PNEC) for TPT, as determined by use of the species sensitivity distribution approach, is 0.64 ng L⁻¹. In some parts of the world, concentrations of TPT in seawater exceed the PNEC, indicating that TPT can pose risks to marine life. Although there is negligible risk of TPT to average human consumers, TPT has been detected in blood of Finnish people and the concentration was greater in fishermen who ate more seafood. It is, therefore, advocated to initiate regular monitoring of TPT in blood and breast milk of populations that consume greater amounts of seafood.     

Vertical profile of PCDD/Fs, dioxin-like PCBs, other PCBs, PAHs, chlorobenzenes, DDX, HCHs, organotin compounds and chlorinated ethers in dated sediment/soil cores from flood-plains of the river Elbe, Germany

Concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) and other organic micropollutants were determined in dated sediment/soil cores collected from the flood-plain of the river Elbe near Pevestorf (PT), approximately 125 km upstream of Hamburg, and Heuckenlock (HL) in southeast of Hamburg. Concentrations of PCDD/Fs peaked sharply at PT in the 1950s and at HL at the end of the 1940s. Cluster analyses provide evidence that the region of Bitterfeld-Wolfen (about 350-400 km upstream of Hamburg) could be the source of the PCDD/F contamination existing in the cores PT and HL since the 1940s. Obviously it is caused by sediments of the river Elbe of a similar composition. Whereas the PCDD/Fs, HCHs (hexacyclohexane isomers), DDX (DDT, DDD, DDE), and tetrachlorinated ethers in PT and HL presumably originated predominantly from the Bitterfeld-Wolfen region, organotin compounds in HL and dichlorinated haloethers in HL during the 1940s and 1950s can probably largely be attributed to emissions from the Hamburg region. Although they are separated by a large distance, in both sediment cores PT and HL concentrations and composition patterns of most organic micropollutants analyzed widely match. Inductively it can be concluded that similar contaminations will be found in many of the river bank soils between the Bitterfeld-Wolfen region and Hamburg. Excavation of top soils may uncover highly contaminated materials. Since the dated sediment cores show the variation in contaminants in the Elbe sediments over a defined time period, it is possible to make an approximate assessment of the actual degree of contamination to be expected in areas where in previous decades contaminated dredged sediments from the Elbe and from the Port of Hamburg have been deposited on land and used for building plots or for agricultural purposes.     

贝壳粉对污染土壤中Pb、Zn、Cd的稳定化作用

价廉易得且无二次污染的稳定剂开发是重金属污染土壤稳定化修复的关键。以铅蓄电池污染场地Pb污染土壤(CQ土壤样品)及铅锌冶炼厂周边Pb、Zn、Cd复合污染土壤(ZZ土壤样品)为研究对象,用贝壳粉进行稳定化研究,通过毒性特征浸出测试(TCLP)评价其稳定化效果。X射线衍射(XRD)和X射线荧光光谱(XRF)等分析结果表明,贝壳粉的主要成分为CaCO3。稳定化实验结果表明:贝壳粉在2%(质量分数,下同)~10%的添加量下,CQ土壤样品中Pb的浸出浓度降低22%~62%;ZZ土壤样品中Pb、Zn、Cd的浸出浓度分别降低11%~91%、26%~65%、18%~64%。贝壳粉添加后土壤pH升高可能会使重金属形成氢氧化物沉淀;部分重金属可能会通过离子交换作用形成碳酸盐沉淀。经贝壳粉稳定化后土壤中重金属浸出浓度降低,有效降低了重金属的迁移性,因此贝壳粉可作为稳定剂应用于重金属污染土壤的修复。     

Levels of dioxins, dibenzofurans and selected other chlorinated organic compounds in food from Russia

Food is considered to be the main source of dioxins (PCDDs) and dibenzofurans (PCDFs) for human intake, but there are relatively few publications reporting the levels of dioxins and furans in food samples.^(1–4) Food samples from western to eastern Russia were collected during three recent trips by one of us (AS), and tested for dioxins and dibenzofurans to provide some indication of environmental contamination. The results show that in specific food samples there are more dioxins present than dibenzofurans, but in fish samples the opposite is true. We compare the levels found in Russian food with levels found in samples from other countries, on both wet weight and lipid basis. These Russian samples show ranges similar to but slightly lower than those seen in other industrial countries.     

三氯乙酸与其他有机物在活性炭上的竞争吸附

通过等温吸附实验,考察了三氯乙酸(TCAA)与十二烷基苯磺酸钠(DBS)、腐殖酸(HA)在活性炭(GAC)上的竞争吸附现象。结果表明,GAC对TCAA的吸附符合Langmuir模型,对DBS和HA的吸附均符合Freudlich模型;在GAC上,DBS和HA对TCAA构成竞争吸附,大分子HA阻塞GAC的微孔,使得TCAA与DBS难以进入微孔;GAC对3种物质的吸附能力由大到小依次为DBS、TCAA和HA;离子型表面活性剂DBS憎水性一端与TCAA竞争吸附位,亲水性一端与TCAA形成吸附,使GAC总饱和吸附量有所加大。     

Reuse of walnut shell waste in the development of fired ceramic bricks

Environmental Science and Pollution Research - The development of agricultural waste–doped fired bricks is an important step toward achieving lightweight eco-efficient bricks with improved...