水中内分泌干扰物-壬基酚的去除研究进展

壬基酚是一种内分泌干扰物,主要来源于NPEO,能通过生物富集作用进入生物体内并造成危害。当前检测水样中壬基酚的主要方法是采用GC—MS,预处理采用固相萃取。研究表明自来水厂的常规处理工艺对于壬基酚的去除有限;而活性炭、有机蒙脱土吸附等物理方法,超声声化、电化学氧化、光分解等化学方法可有效降解水中的壬基酚。     

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.     

壬基酚在活性污泥系统中的去除研究进展

壬基酚是一种持久性有毒的内分泌干扰物,它会对生物系统产生有害影响。本文介绍了壬基酚的来源、物化性质、化学结构、城市污水处理厂和实验系统中的迁移转化及去除,以及壬基酚在活性污泥分离的菌种中的降解。最后分析了目前研究中存在的问题并提出了相应的解决方法。     

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.     

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.     

Synthesis of core-shell magnetic molecular imprinted polymer by the surface RAFT polymerization for the fast and selective removal of endocrine disrupting chemicals from aqueous solutions

In this study, we present a general protocol for the making of surface-imprinted core-shell magnetic beads via reversible addition-fragmentation chain transfer (RAFT) polymerization using RAFT agent functionalized iron oxide nanoparticles as the chain transfer agent. The resulting composites were characterized by X-ray diffraction (XRD) and Fourier transform infrared (FT-IR) analysis, thermogravimetric analysis (TGA), vibrating sample magnetometer (VSM), and scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The surface-imprinted magnetic beads were demonstrated with a homogeneous polymer films (thickness of about 22 nm), spherical shape, and exhibited magnetic property (Ms = 0.41 mA m² g⁻¹) and thermal stability. Rebinding experiments were carried out to determine the specific binding capacity and selective recognition. The as-synthesized surface-imprinted core-shell magnetic beads showed outstanding affinity and selectivity towards bisphenol A over structurally related compounds, and easily reach the magnetic separation under an external magnetic field. In addition, the resulting composites reusability without obviously deterioration in performance was demonstrated at least five repeated cycles.     

Alkylphenol oxidation with a laccase from a white-rot fungus: effects of culture induction and of ABTS used as a mediator

We investigated the potential of the laccase from the white-rot fungus Marasmius quercophilus to transform certain alkylphenols (p-nonylphenol, p-octylphenol and p-t-octylphenol). We tested the reactivity of this enzyme under different conditions: in liquid cultures and using the partially purified laccase with and without 2,2′-azino-bis-3-ehtylbenzothiazoline-6-sulfonicacid (ABTS) as a mediator. The percentage of p-t-octylphenol disappearance in liquid cultures was 69.0 ± 1.5% and 81 ± 5% after a 8-d or 15-d incubation, respectively, with p-nonylphenol, these percentages were 62 ± 4% and 91 ± 6% and with p-octylphenol 37 ± 3% and 65 ± 1% after a 15-d and a 21-d incubations, respectively. Induced pre-cultures were also used to inoculate the liquid cultures to enhance p-octylphenol transformation: the percentages of disappearance were 91.0 ± 0.5% and 97 ± 1% after a 8-d and a 15-d incubation, respectively. Mass spectrometry analysis showed that the products of oxidation of p-octylphenol were dimers with a mass of 411 m/z. Furthermore, we identified a purple compound (m/z 476) formed when ABTS was added to the reaction medium with the purified laccase. This result confirms that, in complex environments such as soils or litters where many molecules can interact with the enzyme substrate or the product of oxidation, laccase activities and those of other phenoloxidases should not be measured with ABTS.     

Assessment of bisphenol A released from reusable plastic, aluminium and stainless steel water bottles

Bisphenol A (BPA) is a ubiquitous high volume industrial chemical that is an estrogen and an environmental endocrine disrupting chemical. Bisphenol A is used extensively in the production of consumer goods, polycarbonate plastics, epoxy resins and coatings used to line metallic food and beverage cans. There is great concern regarding the possible harmful effects from exposures that result from BPA leaching into foods and beverages from packaging or storage containers. The objective of this study was to independently assess whether BPA contamination of water was occurring from different types of reusable drinking bottles marketed as alternatives to BPA-containing polycarbonate plastics. Using a sensitive and quantitative BPA-specific competitive enzyme-linked immunosorbent assay we evaluated whether BPA migrated into water stored in polycarbonate or copolyester plastic bottles, and different lined or unlined metallic reusable water bottles. At room temperature the concentration of BPA migrating from polycarbonate bottles ranged from 0.2 to 0.3 mg L⁻¹. Under identical conditions BPA migration from aluminium bottles lined with epoxy-based resins was variable depending on manufacturer ranging from 0.08 to 1.9 mg L⁻¹. Boiling water significantly increased migration of BPA from the epoxy lined bottles. No detectable BPA contamination was observed in water stored in bottles made from Tritan™ copolyester plastic, uncoated stainless steel, or aluminium lined with EcoCare™. The results from this study demonstrate that when used according to manufacturers’ recommendations reusable water bottles constructed from “BPA-free” alternative materials are suitable for consumption of beverages free of BPA contamination.