Bioconcentration of butyltin compounds by round crucian carp

Bioconcentration factors (BCF) by round crucian carp and partition coefficients between n‐octanol and water (Pow) were measured for dibutyltin, tributyltin and triphenyltin compounds. Pow was 0.97–3.66 for 7 organotin compounds. BCF of tributyltin and triphenyltin compounds was 1.70–2.77 for muscle, 1.70–2.66 for vertebra, 2.05–3.70 for liver and 1.49–3.50 for kidney.     

Effects of Cr(III) organic compounds on Lactobacillus plantarum

Biotransformation of Cr(VI) to less toxic Cr(III) has been known to produce insoluble Cr(III) compounds and soluble Cr(III) organic complexes. However, recent research reports have indicated that Cr(III) organic complexes are relatively stable in the environment. Little has been reported on the fate and toxic effects of Cr(III) organic compounds on organisms. In this study, the toxic effects of the soluble Cr(III) organic complexes [Cr(III) citrate, Cr(III) histidine, Cr(III) lactate and Cr(III) glutamate] to a local strain of Lactobacillus plantarum isolated from sauerkraut was investigated. Growth inhibition, viable cell count and lactic acid inhibition were measured to determine the toxicity potential of the test compounds. The EC₅₀ values of Cr(III) citrate, Cr(III) histidine, Cr(III) lactate, and Cr(III) glutamate, calculated from the percent growth inhibition were found to be 56 mg L^?1, 70 mg L^?1, 81 mg L^?1, and 85 mg L^?1, respectively. Similar trend was observed in the viable cell counts and lactic acid production. Cr(VI) was observed to be more toxic than the Cr(III) organic compounds, while inorganic Cr(III) was the least toxic. The severity seemed to increase with increase in chromium compounds’ concentration. The results showed that Cr(III) citrate was the most toxic Cr(III) organic compound, while Cr(III) glutamate was the least.     

水生生物水质基准研究中轮虫、水螅、涡虫类受试生物的筛选

轮虫、水螅、涡虫是水生生态系统的重要生物类群。因其对水体污染较敏感,所以对水生生物基准研究有重要意义。依据我国生物区系资料及毒性数据丰度,筛选出8种代表性本土轮虫、水螅、涡虫类生物。参照美国水生生物基准技术指南,搜集、筛选了这8种代表性生物的急性毒性数据,通过数据分析,筛选出对各物种毒性最大的污染物,主要包括重金属、农药、有机锡化物、表面活性剂、吡啶胺类杀菌剂。分析污染物的物种敏感度分布,依据累积概率对代表性生物的物种敏感性进行分类,结果为:萼花臂尾轮虫(Brachionus calyciflorus)、绿水螅(Hydra viridissima)、普通水螅(Hydra vulgaris)对重金属铜的累积概率为6.5%、8.5%和10.4%,普通水螅(Hydra vulgaris)对重金属汞的累积概率为6.3%;龟甲轮虫(Keratella cochlearis)和四齿腔轮虫(Lecane quadridentata)对五氯酚钠的累积概率为5.1%和7.6%;褐水螅(Hydra oligactis)和绿水螅(Hydra viridissima)对三丁基氧化锡的累积概率为6.9%和13.8%,萼花臂尾轮虫(Brachionus calyciflorus)对氟啶胺的累积概率为6.7%,日本三角涡虫(Dugesia japonica)对四氯化碳、十二烷基苯磺酸钠的累积概率分别为6.7%和7.1%。上述结果表明:萼花臂尾轮虫、绿水螅对重金属铜敏感;普通水螅对重金属铜和汞敏感;龟甲轮虫和四齿腔轮虫对农药敏感;褐水螅和绿水螅对有机锡化物敏感;萼花臂尾轮虫对吡啶胺类杀菌剂敏感;日本三角涡虫对四氯化碳、表面活性剂敏感。这7种代表性生物可作为相关污染物的水生生物基准受试物种。     

邻苯二甲酸酯类增塑剂的体外细胞毒性评价

邻苯二甲酸酯(Phthalate esters, PAEs)是环境介质中的一类典型的有机污染物。已有研究表明,PAEs具有明显的内分泌干扰毒性,并会对动物和人体的生殖发育与神经系统造成损伤。体外细胞评价模型因具有高通量、测试周期短、成本低和毒性效应易于探明等技术优点,被广泛应用到PAEs毒理学效应的研究中。本文从内分泌干扰毒性、胚胎发育毒性、神经毒性、免疫毒性、遗传毒性以及致癌作用等方面,对PAEs的一些体外细胞毒性评价模型进行了分类和总结,并对其相应的研究进展进行了综述。本文旨在为体外细胞毒性评价模型的有效利用提供借鉴,并对PAEs毒性作用机制的深入研究提供思路和依据。     

Antioxidant enzyme activities of <Emphasis Type="Italic">Microcystis aeruginosa</Emphasis> in response to nonylphenols and degradation of nonylphenols by <Emphasis Type="Italic">M. aeruginosa</Emphasis>

The aim of this study was to examine the effects of chemical nonylphenols (NPs) on the antioxidant system of Microcystis aeruginosa strains. The degradation and sorption of NPs by M. aeruginosa were also evaluated. High concentrations of NPs (1 and 2 mg/l) were found to cause increases in superoxidase dismutase (SOD) and glutathione-S-transferase (GST) activities and in glutathione (GSH) levels. These results suggest that toxic stress manifested by elevated SOD and GST levels and GSH contents may be responsible for the toxicity of NPs to M. aeruginosa and that the algal cells could improve their antioxidant and detoxification ability through the enhancement of enzymatic and nonenzymatic prevention substances. The observed elevations in GSH levels and GST activities were relatively higher than those in SOD activities, indicating that GSH and GST contributed more in eliminating toxic effects than SOD. Low concentrations of NPs (0.05–0.2 mg/l) enhanced cell growth and decreased GST activity in algal cells of M. aeruginosa, suggesting that NPs may have acted as a protecting factor, such as an antioxidant. The larger portion of the NPs (>60%) disappeared after 12 days of incubation, indicating the strong ability of M. aeruginosa to degrade the moderate persistent NP compounds. The sorption ratio of M. aeruginosa after a 12-day exposure to low nominal concentrations of NPs (0.02–0.5 mg/l) was relatively high (>30%). The fact that M. aeruginosa effectively resisted the toxic effects of NPs and strongly degraded these pollutants indicate that M. aeruginosa cells have a strong ability to adapt to variations in environmental conditions and that low and moderate concentrations of organic compounds may favor its survival. Further studies are needed to provide detailed information on the fate of persistent organic pollutants and the survival of algae and to determine the possible role of organic pollutants in the occurrence of water blooms in eutrophic lakes.     

农药类化合物对大型溞的毒性作用模式:与基线毒性化合物比较研究

农药在控制有害生物的同时,对水生生态系统产生较大的毒性效应。本文通过实验获得了25种基线化合物对大型溞的急性毒性数据,并与57种农药类化合物对大型溞的急性毒性数据进行比较研究,同时根据体外浓度LC_(50)、生物富集因子BCF和体内临界浓度CBR的关系,计算了这些化合物在大型溞体内的临界浓度,研究了农药类化合物对大型溞的毒性作用机理。结果表明,基线化合物在大型溞体内的临界浓度log1/CBR值在一个很窄的范围波动,而农药类化合物在大型溞体内的临界浓度log1/CBR值范围广且较高。这说明多数农药类化合物对大型溞为反应性毒性作用模式。其中,除草剂对大型溞的毒性显著低于杀菌剂和杀虫剂对大型溞的毒性。这可能是因为除草剂主要通过干扰植物光合作用、植物激素或植物分子合成发挥毒性效应,从而导致其对大型溞的生理系统难以发生反应性毒性效应。而杀虫剂和杀菌剂主要通过干扰生物神经系统、生殖系统、呼吸作用或大分子合成发挥毒性效应,因此易与大型溞生理系统发生生物化学反应,从而具有较高的毒性效应。本文分别建立了除草剂、杀菌剂和杀虫剂对大型溞的急性毒性QSAR模型。除草剂对大型溞的急性毒性机理较简单,其毒性与化合物疏水性程度和离子化程度有关;而杀菌剂对大型溞的急性毒性主要与化合物的标准生成热和极性表面积有关;杀虫剂对大型溞的急性毒性作用机理较复杂,它们对大型溞的毒性效应与其和生物分子之间的氢键和范德华力有关。     

Population-related toxicity responses to two butyltin compounds by zoeae of the mud crab Rhithropanopeus harrisii

We exposed zoeae of the mud crab Rhithropanopeus harrisii to either bis(tri-n-butyltin) oxide (TBT) or di-n-butyltin dichloride (DBT). Experiments were repeated with zoeae from females collected from the Petaluma River, California in June–August 1983 and 1984 or from Sykes Creek, Florida (USA) in February 1985. Using probit analysis, we calculated LC₅₀ values for exposure lasting the duration of zoeal development. Tributyltin was 54 to 65 times more toxic than dibutyltin, the lower value characterizing the response of Florida zoeae. Increases in duration of zoeal development and reduction of dry weights of megalops, both sublethal responses, were dose-dependent for the two populations. However, zoeae from Florida consistently had shorter duration of zoeal development and higher megalopal weights at metamorphosis, indicating less sensitivity to an identical exposure to either organotin compound. The results of these experiments show that dibutyltin, a putative degradation product of tributyltin, is less toxic than the parent compound. In addition, early life-history stages of two populations may have significantly different responses to xenobiotic stress which, in the case of brachyuran larvae, is evident in a differential reduction of survival and growth and an increase in duration of zoeal development.     

Individual and combined toxicity of some petroleum aromatics to the marine amphipod Elasmopus pectenicrus

Toxicity of 4 components of petroleum oils to the marine amphipod Elasmopus pectenicrus (Bate) has been assessed. Two ephemeral aromatic hydrocarbons, naphthalene (A) and 1, 2, 4-trimethylbenzene (B) were more toxic than two persistent aromatics, o-cresol (C) and o-toluidine (D). The acute toxicity concentrations obtained for individual aromatic compounds were always greater than the actual concentrations found in the water-soluble fractions (WSF) of fuel oils. Results from mixtures of 2 or more components indicated that the LC₅₀ levels were primarily determined by the more toxic substances, A and B. Naphthalene and 1, 2, 4-trimethylbenzene became more toxic to the E. pectenicrus when present in a mixture of more than 2 components, and the toxicity increased with increasing numbers of components present. Synergistic effects, therefore, possibly occur in the whole WSF. No antagonistic effects were observed among the 4 petroleum aromatics.University of Texas, Marine Science Institute Contribution No. 290     

Assessing the toxicity of chemical compounds associated with marine land-based fish farms: The use of mini-scale microalgal toxicity tests

Many chemicals that are currently used in aquaculture have not been evaluated with regard to their specific effects on the aquatic environment. In the present study, the toxic effects of several chemicals associated with land-based marine fish farming activities were assessed using two species of marine microalgae (Phaeodactylum tricornutum and Isochrysis galbana). Mini-scale toxicity tests were performed with six antibiotics (amoxicillin, ampicillin, flumequine, oxytetracycline, streptomycin and sulfadiazine) and two disinfectants (formaldehyde and hypochlorite). Amoxicillin and streptomycin did not exert toxic effects. Sulfadiazine was the most toxic chemical; the EC₅₀ values were 0.11 mg/L and 1.44 mg/L for P. tricornutum and I. galbana respectively. As expected, the disinfectants displayed high toxicity, and P. tricornutum was particularly sensitive to these compounds. Although the differences in microalgal sensitivity depended on the chemical considered, both species were highly sensitive to most of the compounds tested. We recommend the inclusion of mini-scale microalgal toxicity tests in environmental risk assessment (ERA) and environmental monitoring plans because they are cost-effective and rapid.     

Retrospektives Monitoring von Organozinnverbindungen in biologischen Proben aus Nord- und Ostsee – sind die Anwendungsbeschränkungen erfolgreich?

Background, aim, and scope Organotin compounds are used as biocides, plastic additives and catalysts. With respect to environmental effects, tributyltin (TBT) and triphenyltin (TPT) compounds are the most relevant, because of their high aquatic toxicity and endocrine effects on mussels and snails. TBT was mainly used as antifouling agents in coatings of ships and boats. In 1989, Germany banned the application to ships <?25?m length. Finally, in 2003, the use of organotin-based antifoulants within the European Union was completely banned. To verify the effectiveness of the restrictions a retrospective monitoring study was initiated. Material and methods A set of appropriate archived samples was retrieved from the German environmental specimen bank (ESB) comprising standardized pooled samples of eelpout (Zoarces viviparus) muscle tissue and of soft bodies of common mussels (Mytilus edulis) sampled at two locations in the North Sea and one in the Baltic Sea. Analysis of organotin compounds included n-hexane extraction, derivatisation with sodium tetraethyl borate, capillary gas-chromatographic separation and atomic emission detection. Results and Discussion Altogether, time series cover the period 1985 to 2006, including data of an earlier study (Rüdel et al. 2003). Until the late 1990s, TBT remained more or less constant in all samples (e.?g. 17?±?3?ng/g wet weight, ww, in mussels from Jadebay/North Sea). The German ban of TBT-based antifoulings for small ships had no effects on environmental concentrations because large ships dominate in the investigated North Sea regions. After the EU-wide ban of TBT in 2003, however, significant decreases in mussel and fish contamination could be observed. In mussels from Jadebay, TBT concentrations were 14 and 6?ng/g ww in 2004 and 2005, respectively. TBT contamination in eelpout of the same region decreased to about 30 percent of the initial concentrations in 2006. Corresponding decreases were detected for TPT. Declining trends were also found in fish and mussels sampled from a Baltic Sea offshore site. Conclusions The results demonstrate the effectiveness of the legal measures undertaken to control organotin inputs into the aquatic environment. Nevertheless, organotin compounds are still relevant pollutants. Water concentrations calculated from the measured tissue concentrations by using the respective bioconcentration factors are still above the Environmental Quality Standards derived in the context of the Water Framework Directive (0.2?ng/l) and the OSPAR mussel EAC (Environmental Assessment Criteria; 2.4?ng/g ww). Thus adverse effects to marine organisms cannot be excluded. Recommendations and perspectives Further studies should be performed to verify the declining trends. More sensitive analytical methods, e.?g. species-specific isotope dilution analysis, are recommended in order to detect lower environmental concentrations.     

Comparative effects of two antifouling paints on the oyster Crassostrea gigas

The effects of two antifouling paints, one containing organotin compounds, the other copper oxide, were studied from September 1983 to October 1984 on Crassostrea gigas (Thunberg) grown under natural field conditions in the Bay of Arcachon, France. The organotin paint reduced growth rate expressed as weight, length and width, but did not affect shell height; it drastically decreased the dry condition factor and shell density, but did not affect the viability of embryos and larvae from exposed oysters. However, some decrease in larval growth rate was observed. The copper paint had no effect on oyster growth, but lowered the condition factor compared to controls. Neither viability of embryos or larvae nor larval growth were affected by this paint.     

全氟烷基磺酸盐(PFOS)及其替代品对两栖类胚胎的发育毒性

用非洲爪蟾胚胎致畸实验和黑斑蛙胚胎发育毒性实验,比较研究了PFOS及其4种替代品对两栖动物胚胎的发育毒性。结果发现,用调聚法合成的织物三防整理剂和50%的全氟丁基有机铵盐阳离子表面活性剂同PFOS一样对非洲爪蟾胚胎有明显毒性,且织物三防整理剂和表面活性剂的毒性强于PFOS;电解氟化法合成的C4织物及C6织物三防整理剂(以下简称C4及C6织物三防整理剂)对非洲爪蟾胚胎没有明显毒性。与非洲爪蟾不同,PFOS和4种替代品对黑斑蛙胚胎没有明显毒性。结果显示,从生物安全性的角度分析,C4和C6织物三防整理剂可作为PFOS的替代品使用,而织物三防整理剂和表面活性剂的毒性比PFOS大,作为PFOS替代品使用需要慎重考虑。     

有机锡致海洋腹足类性畸变分子机制的研究进展

有机锡作为防污损生物附着添加剂曾被大量使用,在极低浓度下就能诱发腹足类发生性畸变现象,严重危害了海洋生态系统的平衡。虽然三丁基锡已被国际海事组织全球禁用,但目前报道的环境有机锡污染仍然非常严重,而且其致毒机制一直众说纷纭。首先,简述了腹足类性畸变及其在世界各个海域有机锡污染监测中的应用,重点综述了有机锡致海洋腹足类性畸变分子机制的3种假说:脊椎动物类型的类固醇激素假说、神经肽假说以及视黄酸X受体(retinoid X receptor,RXR)假说,另外,结合快速发展的分子生物学技术,探讨了研究腹足类性畸变分子机制的新思路和新方法。     

Genetic toxicology of metal compounds: An examination of appropriate cellular models †

Bacterial systems have not had success predicting metal carcinogenicity. Hypotheses explaining this failure are examined. Using a broad genetic endpoint, λ prophage induction, under sub‐toxic growing conditions, genotoxicity is seen for compounds of chromium, manganese, lead, molybdenum and tungsten. Copper, manganese, arsenic and molybdenum compounds enhanced UV mutagenesis in E. coli WP2.

The toxicity of metal compounds to cultured mammalian cells correlates well with rat oral LD₅₀ values. Whereas insolubility can present problems in bacterial studies, concentrations of metal compounds toxic to mammalian cells can be determined even in the presence of precipitate, and sometimes [Pb(NO₃)₂, BaCl₂ and BeCl₂] occurs only in its presence. PbS and MnS, which are insoluble, are much more toxic than the more soluble compounds Pb(NO₃)₂ and MnCl₂. These results demonstrate the importance of cellular phagocytosis of insoluble metal compounds as a factor in studying the toxicity and genotoxicity of metal compounds.     

Secondary metabolites of the cyanobacterium Microcoleus lyngbyaceus and the sea hare Stylocheilus longicauda: palatability and toxicity

The cyanobacterium Microcoleus lyngbyaceus (Kütz.) Crouan (Lyngbya majuscula Gomont) produces a variety of nitrogen-containing secondary metabolites. M. lyngbyaceus is eaten by the specialist sea hare Stylocheilus longicauda, which sequesters secondary metabolites from its diet and transforms some sequestered metabolites into related compounds. We examined the palatability and toxicity of the metabolites malyngamide A, malyngamide B, and a mixture of majusculamides A and B (from M. lyngbyaceus), and malyngamide B acetate (from S. longicauda, derived from malyngamide B), in order to explore a series of hypotheses about why M. lyngbyaceus produces secondary metabolites and why S. longicauda sequesters and transforms them. All three M. lyngbyaceus metabolites significantly reduced feeding by omnivorous pufferfish (Canthigaster solandri) and crabs (Leptodius spp.). Direct comparisons indicated that neither malyngamide A nor the majusculamide mixture differed significantly in palatability from malyngamide B. The S. longicauda metabolite malyngamide B acetate did not significantly deter feeding by either consumer. Direct comparisons indicated that pufferfish found malyngamide B acetate more palatable than malyngamide B, and that crabs showed a non-significant trend in this direction. Palatability of the metabolites did not correlate with toxicity. Although no significant differences were observed among the M. lyngbyaceus metabolites in their palatability, two toxicity assays consistently ranked malyngamide A more toxic than malyngamide B, which was more toxic than the majusculamide mixture. The majusculamide mixture did not significantly differ in toxicity from malyngamide B acetate, even though the two differed strongly in palatability.     

Tributylzinn auf dem Weg zu den ‘Top of the POPs’?

Two groups of pollutants established during the past years, the impact of which on the eco-system gave cause for concern and legislative reaction: Persistent Organic Pollutants (POPs) and Endocrine Disrupters. At present, only the 12 POPs (‘Dirty Dozen’) are subject to serious international bans as long as they do not belong as well to potential endocrine disrupters, such as the PCDDs/PCDFs (Polychlorinated Dibenzo(p)dioxins and furans). But there are endocrine disrupters which fulfil, the POP-criteria stated in the Stockholm Convention. The organotin compounds are part of them, especially the tributyltin (TBT), since the toxicity increases with increasing alkylation. The present investigations may contribute to the discussion on the POP-potential of TBT on the basis of the results from GfA-internal and literature findings.     

Responses of three mouse species to deterrent chemicals in the monarch butterfly. I. Taste and toxicity tests using artificial diets laced with digitoxin or monocrotaline

Summary Of three common mouse species at the Mexican overwintering sites of the monarch butterfly, onlyPeromyscus melanotis eats monarchs. We hypothesized thatP. aztecus andReithrodontomys sumichrasti reject monarchs because they are more sensitive to the bitter taste and/or toxic effects of the cardiac glycosides (CGs) and pyrrolizidine alkaloids (PAs) in the butterflies. Two-choice preference tests revealed no difference in taste avoidance thresholds to free base and N-oxide forms of the PA, monocrotaline, but very different avoidance thresholds to the CG, digitoxin. Avoidance thresholds forR. sumichrasti andP. aztecus were, in respective order, 1020 and 34 times less than that forP. melanotis. We also tested the toxic sensitivity of juvenile mice by chronically feeding diets containing digitoxin or monocrotaline at concentrations similar to those used in the preference tests. No species developed CG toxicity, but bothP. melanotis andP. aztecus developed moderate PA toxicity (R. sumichrasti was not tested for PA toxicity).P. aztecus grew more slowly and manyP. melanotis had hepatic metabolic lesions. Thus, the three mouse species responded very differently to the taste and toxic properties of CGs and PAs at ecologically relevant concentrations: 1) CGs were taste rejected by all species exceptP. melanotis, while PAs were not; and 2) PAs were toxic, while CGs were not.     

Determination of types of interactions exhibited by binary mixtures of heavy metals tested against the hermit crab,Clibanarius africanus

Single and joint action toxicity of heavy metal compounds (ZnCO₃, CuSO₄ and CdSO₄) were carried out against the hermit crab, Clibanarius africanus in laboratory bioassays. On the basis of 96?h LC₅₀ values, CuSO₄ (96?h LC₅₀?=?0.03?mM) was found to be the most toxic followed by CdSO₄ and ZnCO₃ (96?h LC₅₀?=?0.24?mM) in decreasing order of toxicity. The evaluation of the metal compounds in mixtures of ZnCO₃–CuSO₄, ZnCO₃–CdSO₄ and CdSO₄–CuSO₄ in pre-defined molar ratios revealed that interactions between Zn–Cu and Zn–Cd test mixtures were in conformity with the models of antagonism (reduction in toxicity of constituent metals). The synergistic ratios (S.R.s) and relationship between observed/predicted 96?h LC₅₀ values (relative toxic unit, RTU) were consistently below 1, indicating antagonistic interactions. Analysis using isobolograms also indicated the interactions between the mixture components to be antagonistic. However, with regards to CdSO₄–CuSO₄ test mixtures, the interactions between these metals were mainly in conformity with the model of synergism. The S.R. and RTU values were largely above 1, indicating synergistic interactions. The importance of the joint action evaluations for the management and protection of aquatic ecosystems, particularly in the setting up of water quality criteria was discussed.     

使用底栖和浮游桡足类生物测试评估沉积物修复方案的效果

三丁基锡（TBT）是一种常见于船舶防污涂料中的有机锡化合物。尽管该化学物已于2008年被禁用,但在ports和港口等海上交通区域仍可检出致毒水平（浓度）的TBT。一项补救方案在新西兰的一个港口实施,以将TBT和铜的浓度降低到可接受的（浓度）值。这项研究使用分析化学和桡足类生物测试相结合的方法评估了该方案的有效性。在港口内的三个空间梯度上采集沉积物和水样,并在修复前后测定了有机锡和金属含量。利用底栖和浮游桡足类生物测试估算了沉积物和淘析样品的毒性。虽然底泥样品的急性毒性在修复后减少,但对底栖桡足类的繁殖率仍有影响。本研究所采用的方法有望评估沿海地区修复过程的效果。