TBT pollution and effects in molluscs at US Virgin Islands,Caribbean Sea

An almost ubiquitous occurrence of imposex and butyltins in the molluscs from US Virgin Islands gives evidence to a widespread contamination with the antifouling agent tributyltin (TBT), which most likely is related to a relatively intense ship traffic. Three different muricid neogastropod species Thais deltoidea, Thais rustica and Purpura patula all seem to have potential as suitable and sensitive bioindicators for assessing levels and effects of TBT pollution in coastal areas including coral reefs in the Caribbean Sea. However, considerable interspecies differences in especially accumulation potential of butyltins were seen in this study. Furthermore, a high accumulation potential of TBT in the edible gastropod West Indian topshell (Cittarium pica) was found, despite that no signs of imposex were observed in this archaeogastropod species.     

Imposex as a biomonitoring tool for marine pollution by tributyltin: some further observations

Imposex, i.e., the imposition of male sexual characteristics on female neograstropods, has been used worldwide as a bioindicator of pollution by the antifouling agent TBT as well as to assess the related ecological impact. The recent total ban on the use of TBT in the maritime industry has been partly based on the use of such a biomarker. This is mainly based on the assumption that no other pollutant, or environmental stress, is able to induce such a biological response. Nonetheless, several authors had challenged this idea. The present paper will present further field observations on imposex in Hexaplex trunculus from Malta (Central Mediterranean) which may help clarify this issue. Furthermore, the incidence of imposex in this species will be related to body burdens and to the environmental levels of organotins as measured analytically. First histological observations will also be presented which may help clarify the ecological significance of this response in this species. Finally a number of alternative scenarios regarding the relationship between imposex and TBT will be discussed.     

Occurrence and degradation of butyltins and wastewater marker compounds in sediments from Barcelona harbor, Spain

Contamination of Barcelona harbor sediments was assessed by the quantitative determination of butyltins (TBT, DBT and MBT) and surfactant intermediates, namely linear alkylbenzenes (LABs) and nonylphenols (NPs), as markers of urban and industrial wastewater contamination, respectively. Degradation indexes of TBT and LABs were calculated. Tributyltin predominated in the whole area over its degradation products, ranging from 98 to 4702 ng Sn/g. These elevated concentrations reveal a persistent historical contamination and a moderate degradation (BT(deg)). Moreover, the high LAB concentrations (1.2-53.1 microg/g) compared to the relatively low NP levels (3.8-72.0 ng/g) suggest a predominance of urban over industrial wastewater inputs, although a significant correlation (r(2) = 0.82, N = 12, P = 0.001) between LABs and NPs was found. Stormwater runoff and combined sewer overflows (CSO) were likely the most possible sources for both surfactant intermediates. The high degradation index values obtained for LABs could indicate an improvement in the wastewater management reducing its recent discharge into the Barcelona harbor area.     

Butyltins in the sediments of Kochi and Mumbai harbours, west coast of India

Surface sediment samples were collected from various locations in the Mumbai and Kochi harbours, west coast of India, to assess the presence of butyltin compounds. Tributyltin (TBT) and dibutyltin (DBT) varied from 16 to 16,816 ng/g dry wt. and from undetected to 469 ng/g dry wt., respectively, of the sediment in Kochi harbour. In Mumbai harbour, the values of TBT and DBT ranged between 4.5 and 1193 ng/g dry wt. and from undetected to 131 ng/g dry wt. of the sediments, respectively. The concentrations of both TBT and DBT showed strong seasonal variation probably due to the effect of tides and currents. Nevertheless, the levels of butyltin compounds were generally higher at sites influenced by shipping activities such as navigation, dry dock and ship-building activities. The presence of DBT indicates the abiotic or microbiological degradation of TBT. Compared to TBT, DBT was relatively less abundant, suggesting either fresh inputs of TBT and/or less degradation of TBT. The concentrations of TBT showed significant positive relationships with organic carbon and lipid, implying that both lipophilic and ionic interactions were probably involved in controlling the abundance of TBT at these sediments. The observed levels of butyltin compounds are much higher than those required to induce toxic effects on marine organisms, suggesting that these sediments were contaminated with butyltin compounds.     

Environmental levels, toxicity and human exposure to tributyltin (TBT)-contaminated marine environment. a review. b_antizar@hotmail.com

Tributyltin (TBT) is a toxic chemical used for various industrial purposes such as slime control in paper mills, disinfection of circulating industrial cooling waters, antifouling agents, and the preservation of wood. Due to its widespread use as an antifouling agent in boat paints, TBT is a common contaminant of marine and freshwater ecosystems exceeding acute and chronic toxicity levels. TBT is the most significant pesticide in marine and freshwaters in Europe and consequently its environmental level, fate, toxicity and human exposure are of current concern. Thus, the European Union has decided to specifically include TBT compounds in its list of priority compounds in water in order to control its fate in natural systems, due to their toxic, persistent, bioaccumulative and endocrine disruptive characteristics. Additionally, the International Maritime Organization has called for a global treaty that bans the application of TBT-based paints starting 1 of January 2003, and total prohibition by 1 of January 2008. This paper reviews the state of the science regarding TBT, with special attention paid to the environmental levels, toxicity, and human exposure. TBT compounds have been detected in a number of environmental samples. In humans, organotin compounds have been detected in blood and in the liver. As for other persistent organic pollutants, dietary intake is most probably the main route of exposure to TBT compounds for the general population. However, data concerning TBT levels in foodstuffs are scarce. It is concluded that investigations on experimental toxicity, dietary intake, potential human health effects and development of new sustainable technologies to remove TBT compounds are clearly necessary.     

Genotoxic effects of binary mixtures of xenoandrogens (tributyltin, triphenyltin) and a xenoestrogen (ethinylestradiol) in a partial life-cycle test with Zebrafish (Danio rerio)

A partial life-cycle test with the model fish Danio rerio was performed in order to evaluate the genotoxic potential of binary mixtures of xenoandrogenic (tributyltin--TBT; triphenyltin--TPT) and an estrogenic compound (ethinylestradiol--EE2). Five days post-fertilisation larvae were diet-exposed to environmental relevant concentrations of TBT and TPT (25 ng/g-100 ng/g), and water-exposed to ethinylestradiol (3.5 ng/L) for a four-month period; binary mixtures of TBT plus EE2 and TPT plus EE2 were run in parallel. The erythrocytic nuclear abnormalities (ENA) assay in circulating erythrocytes was used to evaluate genotoxicity in the end of the four-month exposure period. A significant increase (p<0.05, Kruskall-Wallis non-parametric ANOVA) in ENA frequency, in comparison with control animals, was observed in those animals exposed to TBT and TPT (the highest doses only), and to EE2 and the binary mixtures, although neither synergistic nor additive effects of the tested compounds were evident. Overall, the results clearly indicate that chronic exposure to low levels of TBT, TPT, EE2 and binary mixtures of TBT plus EE2 and TPT plus EE2 are genotoxic to zebrafish, which may suggest that wild fish populations may be under increased DNA damage in areas contaminated by these endocrine disrupting chemicals.     

Effects of 17alpha-ethinylestradiol on the reproduction of the cladoceran species Ceriodaphnia reticulata and Sida crystallina

Single-species tests allow the assessment of chronical effects of endocrine disruptors on organisms under laboratory conditions. In the current study, three-generation tests with Ceriodaphnia reticulata and Sida crystallina were carried out to examine the influence of the synthetic hormone 17alpha-ethinylestradiol (EE) on the reproduction of these cladoceran species. For each species, six different concentrations (10-500 microg/l EE) and two controls were tested with eight replicates for a duration of 4 weeks. The test was initiated by transferring one neonate individual into a test vessel which was incubated under standardized conditions. Every 2 days, the medium was renewed and life history parameters such as survivorship of the adults and juveniles, clutch size, first appearance and number of produced offspring were investigated. Acute toxicity tests showed that C. reticulata (EC50 (24 h) 1814 microg/l) was more sensitive towards the substance compared to S. crystallina (EC50 (24 h) >4100 microg/l). The juvenile phase of S. crystallina was significantly shorter at concentrations above 100 microg/l EE. For C. reticulata, 17alpha-ethinylestradiol caused a higher mortality of the newly hatched juveniles at EE concentrations above 200 microg/l. No effects were found for mortality of adult animals, birth rate, number of juveniles per female and net reproduction rate of S. crystallina and C. reticulata. Thus, sublethal effects on parental generation exposed to EE lead to disturbances in reproduction and to affection of their offspring. Negative consequences for the population dynamic cannot be excluded, e.g. the decrease of a population.     

Distribution of organotin compounds in the bivalves of the Aegean Sea, Greece

Five bivalve species--Mytilus galloprovinciallis (Mediterranean mussels), Venus gallina (stripped venus), Modiola barbatus L. (bearded horse mussels), Pecten jacobeus (scallops) and Callista chione (hard clams)--were collected from seven areas in Aegean Sea, Greece, between August 2001 and January 2003 and analyzed for organotins (OTs). The concentrations (as geometric means) found were 17.1 ng g-1 for tributyltin (TBT), 18.8 ng g-1 for dibutytltin (DBT), 7.8 ng g-1 for monobutyltin (MBT) and 13.0 ng g-1 for triphenyltin (TPhT) (wet weight), which are at similar or lower levels than those reported worldwide. Studying OTs distribution between different bivalve species, lower concentrations were observed in mediterranean mussels, possibly due to their growth in water column (grown on sea net pens in mussel farms), in contrast to the free-ranging species, collected from fishing grounds. Concentrations of the OTs in the examined bivalves varied seasonally.     

一种基于代表性样点的钉螺密度抽样调查设计方法

抽样设计是钉螺调查的关键环节，直接影响到统计推断的总体精度。目前湖沼型血吸虫病流行区钉螺调查常用的系统抽样设计方法存在样本量大、代表性不强、抽样效率不高等问题。通过对与钉螺空间分布上具有协同变化的环境因子进行模糊聚类分析，寻找可代表钉螺空间分布的代表性样点，提出一种基于代表性样点的抽样设计方法。将本研究设计的方法应用于鄱阳湖区恒湖农场茶叶港草洲的钉螺抽样设计研究，对采集的代表性样点进行误差分析，并将抽样结果与简单随机抽样和系统抽样方法进行精度比较。结果显示：本研究提出的“基于代表性样点的钉螺抽样设计方法（SORS）”明显优于简单随机抽样和系统抽样，抽样绝对误差分别为：0.440 7、1.551 4、3.565 3，相对误差分别为：1.048 1、3.689 7、8.479 6。本研究表明新方法能够获得比现有血防部门的钉螺调查方法更高的估算精度，可为优化湖沼型血吸虫病流行区钉螺调查方法提供借鉴。 关键词： 模糊聚类；抽样设计；代表性样点；钉螺     

Distribution and temporal trends of butyltins monitored by molluscs along the Chinese Bohai coast from 2002 to 2005

Thirteen areas around the Chinese Bohai coast, individuals including ten kinds of bivalves and two kinds of snails were collected during the period of 2002-2005 for the investigation of spatial distribution and temporal variations of butyltin compounds (BTs). BTs including tributyltin (TBT) and its derivates, dibutyltin (DBT) and monobutyltin (MBT) were quantified by gas chromatography/flame photometric detection after extraction and Grignard derivatization. BTs compounds were widely existed in the samples and TBT was the dominant composition, indicating recent TBT input along Bohai coast. As a whole, BTs concentration remained high during the sampling years except a slightly decreased in samples from several sites in 2005. The contamination characteristics of BTs in different sampling sites were analyzed using principal component analysis (PCA) method, and the species specific bioaccumulation of BTs was also identified using cluster analysis.     

Uranium in sediments, mussels (Mytilus sp.) and seawater of the Krka river estuary

The response of an aquatic environment to the decrease of phosphate discharges from a technologically improved transhipment terminal, situated at the Croatian Adriatic coast in the port of Sibenik, has been assessed based on uranium activity and concentration in sediment, seawater and mussels Mytilus sp. The highest 238U activities (485+/-16Bqkg(-1) dry weight) were found in the sediment sample collected from the sampling site closest to the terminal. The maximum concentrations in the sediment samples are above the natural ranges and clearly indicate the harbour activities' influence. The 238U/226Ra activity ratios in sediment samples demonstrate the decreasing trend of phosphate ore input. Mussel samples showed levels of 238U activities in the range from 12.1+/-2.9 to 19.4+/-7.2 Bqkg(-1) dry weight, thus being slightly higher than in normally consumed mussels. Only the seawater, taken just above the bottom sediment at the sampling site closest to the terminal, shows a slightly higher uranium concentration (3.1+/-0.2 microgL(-1)) when compared to the samples taken in upper seawater layers (2.1+/-0.2 microgL(-1)) but is in the range of the concentration level of uranium in natural seawater. Since the transhipment terminal in the port of Sibenik was modernised in 1988, discharge of phosphate ore into the seawater was drastically reduced and, consequently, uranium concentration levels in seawater have decreased. However, enhanced uranium activity levels are still found in deeper sediment layer samples and in mussel.     

An evaluation of mixed species in-situ and ex-situ feeding assays: the altered response of Asellus aquaticus and Gammarus pulex

Mixed species feeding assays were undertaken with pollution sensitive (Gammarus pulex) and tolerant (Asellus aquaticus) macro-invertebrates during August 2003 and April 2004. The purpose of this study was to establish if a test animals' response is comparable during in-situ and ex-situ toxicity tests. Seven test sites were established along an undisclosed stream, which received leachate discharge from an unlined, disused UK landfill site. Sampling points A-B were upstream of the contamination, C was adjacent to the influx and D-G were downstream of the leachate discharge (at 100 m intervals). During the in-situ and ex-situ tests, 2-week-old male laboratory bred A. aquaticus and G. pulex were used as test animals. The animals were transplanted to the seven sampling points for the duration of the in-situ tests, whilst water samples from each site were returned to the laboratory for ex-situ testing. The results show that the animals' mortality and feeding rates followed similar trends during the in-situ and ex-situ tests, however, the animals' response was amplified during the in-situ tests. It was also observed that the effects were greater in April, compared to August that may be attributed to a higher frequency of rainfall during spring, which could have flushed a greater proportion of the contaminant load from the waste mass and as a consequence, higher levels of pollution may have leached into the stream from the landfill site. The study, therefore, concludes that in-situ toxicity tests are a more precise monitoring technique, in comparison to ex-situ assays.     

Persistent organic pollutants in breast milk of mothers residing around an open dumping site in Kolkata,India: Specific dioxin-like PCB levels and fish as a potential source

Concentrations of persistent organic pollutants (POPs) such as polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), polychlorinated biphenyls (PCBs) and organochlorine pesticides were measured in human breast milk collected from mothers residing near an open dumping site and a reference site in Kolkata, India during 2004–2005. POPs were detected in all the human milk samples analyzed, suggesting that residents of Kolkata are widely exposed to these contaminants. Concentrations of dioxin-like PCBs in the samples from the dumping site were significantly higher than in the reference site samples, whereas no such difference was found for PCDDs and PCDFs. In addition, significantly higher concentrations of total PCBs were also observed in the samples from the dumping site than the reference site. Interestingly, concentrations of total and dioxin-like PCBs in the breast milk of mothers from the dumping site significantly increased with the number of years of residence near the dumping site. These results indicate that significant pollution sources of PCBs are present in the dumping site of Kolkata and the residents living around are exposed to relatively higher levels of PCBs. When the residue levels of dioxins and related compounds in fish collected from ponds near the Kolkata dumping site and the reference site were measured, it was found that dioxin-like PCB and TEQ levels in fish from the dumping site were notably higher than those from the reference site. This result indicates that fish is a potential source of PCBs for residents living near the Kolkata dumping site.     

Presence, biotransformation and effects of sulfophenylcarboxylic acids in the benthic fish Solea senegalensis

The presence of linear alkylbenzene sulfonates (LAS) and their degradation intermediates, sulfophenylcarboxylic acids (SPCs), with concentrations up to 100 ppb has been found in surface waters taken from the estuary of the river Guadalete (Cádiz, SW of Spain). Higher concentrations were found at the sampling site located adjacent to the discharge outlet of a wastewater treatment plant (WWTP). The concentrations decreased downstream to a few ppb as a result of dilution, sorption, and degradation processes, which were taking place along the estuary. Once the presence of both xenobiotics was confirmed in the environment, an in vivo assay was conducted to study their biotransformation and effects in the benthic fish Solea senegalensis. A flow-through system was employed, consisting of an exposure phase (120 h) with environmental levels of the surfactant (200, 500 and 800 microg/L of 2?C(10)LAS), followed by a depuration stage (72 h). The generation of SPCs has been quantified during these phases in both water and fish, with LAS biotransformation shown in all cases. The antioxidant enzymes catalase (CAT), glutathione peroxidase (GPX), glutathione reductase (GR), the phase II enzyme glutathione S-transferase (GST), and the phase III acid and alkaline phosphatases (AcP, ALP) were also estimated and utilized as biomarkers.     

Radioecological Studies on the Plankton of the Cooling Water Reservoir of the Beloyarsk Nuclear Power Plant

In the zone of heated water discharge and at the control site of the Beloyarsk Reservoir, the phytoplankton was characterized by dominance of blue-green, green, and pyrrophyte algae, and the zooplankton, by the prevalence of crustaceans over rotifers. The study sites differed in the species and quantitative composition of the dominant complex, but the total abundance and biomass of the phytoplankton in the heated zone and the control site did not differ significantly. In Teplyi Bay, the zooplankton was inhibited, which was manifested in the decrease of its abundance and biomass by four and seven times, respectively, in comparison with the control. Radionuclide concentrations in the plankton of the cooling reservoir in the period between 1986 and 1988 were determined. It was found that radionuclide concentration in the plankton is higher in the zone of heated water discharge than beyond it.     

江苏阳澄湖螺类群落的空间分布格局

2008年1月～2009年10月对江苏阳澄湖螺类群落结构进行了季节调查研究。共采集到螺类4科5属6种,优势种为铜锈环棱螺,次优种为长角涵螺。阳澄湖螺类平均密度为220±47 ind./m2,平均生物量为2331±469 g/m2,螺类密度和生物量在年际和季节间均无明显差异,但群落结构存在显著的空间变化,密度在东湖区和中华绒螯蟹围网养殖区较大、西湖区最小,生物量围网养殖区最高、西湖区最低;铜锈环棱螺密度围网养殖区最高、西湖区最低,长角涵螺密度东湖区最高、围网养殖区次之、入湖河流及其它湖区极低。中华绒螯蟹养殖未导致围网养殖区螺类数量下降,螺类（主要是铜锈环棱螺）的投放可能是该区螺类密度、生物量及铜锈环棱螺所占比例较高的主要原因之一。逐步回归分析表明,水深是影响螺类群落整体密度和生物量空间分布差异的主要因子;典型对应分析（CCA）表明,铜锈环棱螺主要分布在叶绿素a较高的水域,而长角涵螺和纹沼螺则主要分布在透明度较大的地方     

流域气候变化和人类活动对长江径流量影响的辨识

利用1956~2011年的流域气温、降水量、径流量及有关文献所载蒸发量、水库修建、用水量、水土保持等资料,探讨气候变化和人类活动对长江径流量的影响。结果表明：（1）流域气温明显上升,且上升速率大于全球平均上升速率;（2）流域平均降水量下降了约1%,年降水量与年均气温之间无显著相关性;（3）年径流量随降水量频繁振荡,最大和最小值之比达19;（4）太阳净辐射量和风速下降导致流域自然蒸发作用减弱,而水库修建、耗水增多和水土保持等人类活动则使蒸发作用加强。两方面的影响相互削弱;入海年径流量下降1%;（5）流域内分区间存在差异,北域（岷江、嘉陵江和汉江）人类活动的影响居主导地位,径流量下降约15%;中域（金沙江以下干流两翼“未测区”）则以气候变化的影响占优,径流量上升约9%;西域（金沙江流域）径流量减少4%;南域（乌江、洞庭湖和鄱阳湖流域）径流量上升2%。推断今后几十年气候要素仍将主导径流量的年际波动,而南水北调、新建水库、耗水增多和水土保持加强将可能使径流量再下降约10%     

Radioactivity and elemental analysis in the Ruseifa municipal landfill, Jordan

In this study, a low background gamma-ray spectrometer based on a Hyper Pure Germanium detector was used to determine the activity concentrations of natural radionuclides in soil samples from various locations within the Ruseifa municipal landfill in Jordan. The chemical composition of the samples was also determined using a Wavelength Dispersive X-Ray Fluorescence Spectrometer. The maximum and minimum annual outdoor effective doses were found to be 103 and 36muSva(-1) in the old landfill and Abu-Sayaah village, respectively. The annual outdoor effective dose at the recent landfill site was found to be 91muSva(-1). The annual effective dose equivalents from outdoor terrestrial gamma radiation at the old landfill and the recent landfill were higher than the typical worldwide value of 70muSva(-1). Thus, some remediation of the soils on both old and recent landfills should be considered before any development for public activities. This could be achieved by mixing with clean soil from areas which are known to have lower radiation background. The concentration of heavy metals Zn, Cr, and Ba in the three sites included in this study were found to be higher than the background levels in the soil samples of the control area (Abu-Sayaah village). The enrichment factors for the above three elements were calculated and found to be: complex building site: Zn=2.52 and Ba=1.33; old landfill site: Cr=1.88, Zn=3.64, and Ba=1.26; and recent landfill site: Cr=1.57, Zn=2.19, and Ba=1.28. There was a strong negative correlation between the concentrations of the metallic elements (Mg, Al, Mn, Fe and Rb) and the concentrations of Zn, Ba, and Cr. Moreover, a strong positive correlation was found between Zn, Ba, and Cr. Thus these elements were enriched in the solid waste.     

Worldwide occurrence and effects of antifouling paint booster biocides in the aquatic environment: a review

Organic booster biocides were recently introduced as alternatives to organotin compounds in antifouling products, after restrictions imposed on the use of tributyltin (TBT) in 1987. Replacement products are generally based on copper metal oxides and organic biocides. This ban has led to an increase in alternative coating products containing the above biocides. The most commonly used biocides in antifouling paints are: Irgarol 1051, diuron, Sea-nine 211, dichlofluanid, chlorothalonil, zinc pyrithione, TCMS (2,3,3,6-tetrachloro-4-methylsulfonyl) pyridine, TCMTB [2-(thiocyanomethylthio) benzothiazole], and zineb. Since 1993, several studies have demonstrated the presence of these biocides in European coastal environment as a result of their increased use. More recently, the presence of these biocides was also revealed in waters from Japan, United States, Singapore, Australia and Bermuda. This paper reviews the currently available data on the occurrence of these biocides in the aquatic environment. Some data dealing with the environmental fate, partitioning, behaviour and risk assessment of antifouling paint booster biocides are also reported in order to discuss the detected levels of contamination.     

Systematic review of pentachlorophenol occurrence in the environment and in humans in China: Not a negligible health risk due to the re-emergence of schistosomiasis

Pentachlorophenol (PCP) has been widely used for killing snails in areas of China where schistosomiasis is epidemic. With the re-emergence of schistosomiasis, the warranted production and consumption of PCP has inevitably resulted in persistent environmental contamination by it and its impurities, polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). This study aimed to evaluate the contamination status and human burden of PCP and its impurities (PCDD/Fs) in China, considering the previous epidemic and re-emergence of schistosomiasis. We searched studies relevant to PCP occurrence in the environment and in humans in China. Data on snail elimination areas were included to estimate PCP consumption. Relevant publications were analyzed to distinguish PCDD/Fs contamination from PCP usage. PCP contamination was detected ubiquitously in various environmental media and in human samples; environmental levels were generally low, with the exception of some hot spots. In schistosomiasis-epidemic areas, there were significantly higher PCP levels in the environment and in humans than in control areas. Spatial disparities indicated the consistency between serious schistosomiasis epidemic areas and hot spots of PCP contamination. The data suggest an increased trend in PCP contamination of the environment. Specific PCDD/Fs contamination from PCP usage existed even at low environmental levels. The occurrence of PCP in the environment and in humans positively correlated with the epidemic of schistosomiasis. Thyroid-disrupting effects and cancer risk caused by PCP and PCDD/Fs even at low environmental levels in China's schistosomiasis-epidemic areas are of concern.