SeaNine 211 as antifouling biocide: A coastal pollutant of emerging concern

SeaNine 211, with 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (DCOIT) being the biocidal ingredient, is a widely-used antifouling agent to deter the undesirable biofouling phenomenon. It is commercially promoted as an environmentally acceptable antifoulant mainly due to its claimed rapid degradation in marine environment. However, increasing researches document varying degradative kinetics in different environments, proving that SeaNine 211 is actually not degraded equally fast around the world (half-life between < 1 day and 13.1 days). Large-scale application of SeaNine 211 in antifouling coatings has also caused global contamination of marine environment in various compartments. For example, accumulation of SeaNine 211 is detected as high as 3700 ng/L in Spanish seawater and 281 ng/g dry weight in Korean sediment. Considering that SeaNine 211 is highly toxic against non-target marine organisms, environmental risk assessment finds that most marine organisms are endangered by SeaNine 211 in worst-case scenario. Its endocrine disrupting and reproductive impairing effects at environmentally worst-case concentrations further constitute a long-term threat to the maintenance of population stability. Therefore, in the light of the varying degradability, environmental pollution and high toxicity, especially the endocrine disruption, SeaNine 211 as an antifouling agent is likely to cause non-negligible damages to the marine ecosystem. There is an urgency to perform a systematic ecological risk assessment of SeaNine 211 to prevent the potential impacts on the health of marine environment. A regular monitoring also becomes necessary to place the usage of antifouling biocides under control.     

Thyroid status in juvenile alligators (Alligator mississippiensis) from contaminated and reference sites on Lake Okeechobee, Florida, USA

Exposure to environmental contaminants has been shown to alter normal thyroid function in various wildlife species, including the American alligator (Alligator mississippiensis). Abnormalities in circulating levels of the thyroid hormone thyroxine (T₄) have been reported in juvenile alligators from several contaminated lakes in Florida. To further elucidate these functional thyroid abnormalities, this study examines the structure of thyroids and circulating T₄ concentrations from juvenile alligators collected from three sites of varying contamination on Lake Okeechobee, Florida. The following variables were used to characterize thyroid morphology: epithelial cell height, width and area, percent colloid, and follicle area. These variables were compared among study sites and between genders. No difference was detected in epithelial cell height, epithelial cell area, or follicle area among the sites, whereas significant differences in epithelial cell width (p=0.02) and percent colloid (p=0.008) were found. Animals from the most contaminated site (Belle Glade) had significantly greater epithelial cell widths and significantly less colloid present in their follicles compared to animals from the reference site (West). Gender did not have a significant interaction with site for any variable measured. Thyroxine (T₄) concentrations were elevated in the intermediately contaminated site (Conservation Area 3A) compared to the other sites (p<0.0001). It is proposed that the disruptions seen in Lake Okeechobee alligators are due to disruptions at both the thyroid and extra-thyroidal tissues.     

应用体内和体外方法评价原油水溶性组分和原油污染的地表水对淡水生物的内分泌干扰潜力

目前关于原油对淡水水生脊椎动物内分泌信号的潜在影响的认知有限。本文以非洲爪蟾(爪蟾属,X. laevis)蝌蚪和莫桑比克罗非鱼幼鱼(口孵非鲫属,O. mossambicus)为研究对象,选择风化原油和未风化提炼后的原油这2种原油的水溶性组分(WAFs)进行暴露实验,选择出可作为内分泌信号改变的生物标志物的基因,对其表达进行了研究。此外,将X. laevis蝌蚪暴露于靠近地下石油库的地表水中,对上述基因表达做了定量分析。利用重组酵母对原油、原油水溶性组分和地表水的(抗)雌激素和(抗)雄激素性进行了评价。在X. laevis对2种原油WAFs的响应中,甲状腺激素受体β表达均显著下调,而另一种与甲状腺相关的基因,2型脱碘酶,在O. mossambicus暴露于高浓度的原油WAF时被上调。此外,这2种WAFs都改变了与脂肪生成相关的过氧化物酶体增殖物激活受体γ在X. laevis中的表达。原油和WAFs在体外表现出抗雌激素和抗雄性激素的活性。然而,O. mossambicus雄激素受体2作为唯一一个代表生殖系统的基因,受到WAF暴露的影响显著。在地表水样品中发现了雌激素、抗雌激素和抗雄激素的作用;但是,在暴露于地表水的X. laevis中没有观察到任何基因表达的明显变化。在所用的2种模式生物以及2种原油中,响应各不相同。尽管如此,这些数据提供了证据证明原油污染可能会因内分泌信号转变对淡水鱼和两栖动物的健康造成不利影响。
精选自Truter, J. C., van Wyk, J. H., Oberholster, P. J., Botha, A.-M. and Mokwena, L. M. (2017), An evaluation of the endocrine disruptive potential of crude oil water accommodated fractions and crude oil contaminated surface water to freshwater organisms using in vitroand in vivo approaches. Environmental Toxicology and Chemistry, 36: 1330–1342. doi: 10.1002/etc.3665
详情请见http://onlinelibrary.wiley.com/doi/10.1002/etc.3665/full
     

Microbial transformation of synthetic estrogen 17α-ethinylestradiol

Natural estrogens such as estrone, 17β-estradiol, estriol, and the particularly recalcitrant synthetic estrogen 17α-ethinylestradiol used as oral contraceptive, accumulate in the environment and may give rise to health problems. The processes participating in their removal from soil, wastewater, water-sediments, groundwater-aquifer material, and wastewater or sewage treatment plant effluents may involve the action of bacterial and microbial consortia, and in some cases fungi and algae. This review discusses the different efficiencies of bacterial degradation of 17α-ethinylestradiol under aerobic and anaerobic conditions, the role of sulfate-, nitrate-, and iron-reducing conditions in anaerobic degradation, and the role of sorption. The participation of autotrophic ammonia oxidizing bacteria and heterotrophic bacteria in cometabolic degradation of estrogens, the estrogen-degrading action of ligninolytic fungi and their extracellular enzymes (lignin peroxidase, manganese-dependent peroxidase, versatile peroxidase, laccase), and of algae are discussed in detail.     

水中微量弱极性内分泌干扰物测定方法的研究

使用ENVITM Chrom P固相萃取小柱、双(三甲基硅烷基)三氟乙酰胺(BSTFA)衍生剂及气质联机,系统研究了水中弱极性内分泌干扰物(EDCs)的测定方法.通过正交试验,得到最佳固相萃取条件为:水样流速5 mL/min,洗脱剂为二氯甲烷,洗脱速率0.5 mL/min,洗脱剂体积6 mL.最佳衍生化条件为:BSTFA 100 μL,60 ℃,反应时间30 min.结果表明,双酚A、五氯酚、2,4-二氯苯酚、4-壬基酚、雌二醇、雌三醇、雌酮、炔雌二醇的回收率在82.4%～101.9%,检出限为0.01～0.06 μg/L.     

Reproduction disturbances of Brachionus calyciflorus (rotifer) for the screening of environmental endocrine disrupters

Rotifers and especially the Brachionus calyciflorus species have already shown advantages (e.g. good sensitivity, simplicity, ecological relevance, short generation time) for the chronic toxicity assessment of water pollutants. In this study, the B. calyciflorus three-day test was evaluated on ethinylestradiol, nonylphenol and testosterone for the determination of endocrine disrupting (reproductive) effects. Reproduction (intrinsic rate of population increase) and sex ratio (males/females and mictic females/amictic females) were explored and discussed as suitable endpoints. B. calyciflorus has shown a fair sensitivity to detect reproductive disrupting effects after exposure to ethinylestradiol, nonylphenol and testosterone. Population growth (intrinsic rate of population increase, r) and the ratio ovigerous females/non-ovigerous females are both suitable endpoints, whereas the occurrence of males was not frequent enough to be used as endpoint.     

New potential mammalian lignan metabolites of environmental phytoestrogens

Seven new dibenzylbutyrolactone and six new dibenzylbutanediol lignans were prepared to assist in the identification of a number of potential mammalian metabolites of the endocrine disrupting plant lignans syringaresinol and medioresinol, present in food.     

Roles of membrane and organic fouling layers on the removal of endocrine disrupting chemicals in microfiltration

To understand the adsorption behavior of endocrine disrupting chemicals(EDCs) is important for enhancing the treatment performance and preventing potential secondary pollution caused by EDCs desorption in a microfiltration system. The dynamic adsorption of four representative EDCs, namely estriol(E3), 17β-estradiol(E2), 17α-ethynylestradiol(EE2), and 4-nonylphenol(4-NP) in a microfiltration system was investigated using the Thomas' model.The product of the equilibrium constant and the total adsorption capacity of the membrane,Ka, for E3, E2, EE2, and 4-NP were 4.91, 9.78, 15.6, and 826, respectively, strongly correlating with the compound octanol–water partition coefficient(KOW). Adsorption appeared to be enhanced when organic fouling formed on the surface of membrane, indicating the role of an additional adsorption column for EDCs acted by a fouling layer in microfiltration. Results of a comparison between the Ka values for clean membrane and fouled membrane illustrated that the significant contribution made by fouling layers may be attributed to the foulant layer's hydrophobicity(in the case of calcium humate layer) and thickness(in the case of calcium alginate layer). This study provided a novel perspective to quantitatively analyze the dynamic adsorption behavior of trace pollutants in membrane process.     

Nonylphenols in freshwaters of the hydrologic system of an Italian district: association with human activities and evaluation of human exposure

A sampling campaign for the determination of concentrations of nonylphenol isomers (NPs) in freshwaters and sediments of the hydrologic system of the Rieti district (central Italy) was conducted from 2002 to 2003. Eighteen sampling points, selected on the basis of the different human activities in the vicinity, were monitored; six series of water samples (from June 2002 to February 2003) and one of sediment samples (summer 2002) were analyzed by GC/MS.

There was a direct relationship between concentrations of NPs and the presence of urban or industrial activities near the sampling point. However, concentrations of NPs in water were in the range of <0.1–1.4 μg l⁻¹, and their presence limited to short distances from the sources of contamination. Accumulation factors in sediment samples ranged from 10² to 5 × 10³.     

Determination of estrogenic activity by LYES-assay (yeast estrogen screen-assay assisted by enzymatic digestion with lyticase)

In order to enhance the sensitivity and the speed of the yeast estrogen screen (YES)-assay, which has been established in many laboratories for the determination of estrogenic activity of compounds and environmental samples, the LYES-assay, a modified version of the YES-assay including a digestion step with the enzyme lyticase, was developed. With the LYES-assay the estrogenic activities of natural (17β-estradiol E2 and estrone), synthetic (17-ethinylestradiol EE2) and pharmaceutical estrogens (diethylstilbestrol DES) as well as xenoestrogens (4-nonylphenol NP and five parabens) were determined and compared with the results obtained by other in vitro-assays namely the conventional YES-assay, the E-Screen-assay (MCF-7 breast tumor cell proliferation) and a receptor binding-assay (RB) with human estrogen receptors hER- and hER-β. In the case of E2 the LYES-assay had a significantly lower limit of quantification (LOQ) than the conventional YES-assay and even two orders of magnitude lower than the RB-assay. Compared to the E-Screen-assay the LOQ of the LYES-assay was almost one order of magnitude higher. The time required to perform the LYES-assay was as little as seven hours compared to three to five days for the conventional YES-assay. Thus, the LYES-assay is a very good alternative to existing estrogenic in vitro-assays, since it has a good sensitivity, is cheap and much faster than the other assays.