生物难降解有机污染物的治理对策

针对废水中难降解化学合成有机污染物的种类和数量不断增加，生物处理出水达标困难的现状，总结了国内外的经验和研究成果，对现有处理装置改造提出了若干建议，并介绍了几种国外废水处理新技术。     

农业化学品投入状况及其对环境的影响

农业生产中,农业化学品的大量使用产生了明显的负外部性影响,尤其是农业的面源污染问题随化肥、农药投入的增加而不断加剧。通过统计分析方法,对农业化学品投入数量及区域分布特征、农业化学品投入存在的问题及其所造成的面源污染问题进行分析。结果表明:化肥和农药总投入不断增加,其中河南、山东、江苏、安徽、湖北和湖南6省投入总额接近全国的一半;农业化学品使用存在过量投入、投入结构失衡和施肥施药技术落后等问题;农业化学投入品的过量使用造成的环境污染问题正不断加剧,农业面源污染排放对污染总量的贡献率不断上升。最后提出了相关政策建议,包括加强农业面源污染控制的政策框架和配套制度建设、推广成熟的化肥农药施用技术和加强农业环保教育。     

采油用油田化学剂对鱼类的急性毒性实验研究

以白鲢鱼为实验生物,采用半静态实验方法,研究了几种油田化学剂的半致死浓度和安全浓度。研究表明:防膨剂、杀菌剂K、杀菌剂L、清蜡剂、四氟硼酸、酸化缓蚀剂、阻垢剂、阻垢缓蚀剂、缓蚀阻垢剂和破乳剂的96h半致死浓度LC50值分别为0.68、1.6、9.3、25、123、510、620、3240、4570、7410mg/L。根据化学物质对鱼类毒性物质分级标准,防膨剂属于剧毒物质;杀菌剂K、杀菌剂L和清蜡剂属于高毒物质;四氟硼酸、酸化缓蚀剂和阻垢剂属于中毒物质;阻垢缓蚀剂、缓蚀阻垢剂和破乳剂属于低毒物质。这几种油田化学剂的安全浓度为0.068～741mg/L。此研究可为评价油田化学剂对水生生物的影响,制定废水排放浓度标准提供依据。     

Bioanalytical characterisation of multiple endocrine- and dioxin-like activities in sediments from reference and impacted small rivers

A comprehensive evaluation of organic contamination was performed in sediments sampled in two reference and three impacted small streams where endocrine disruptive (ED) effects in fish have been evidenced. The approach combined quantitative chemical analyses of more than 50 ED chemicals (EDCs) and a battery of in vitro bioassays allowing the quantification of receptor-mediated activities, namely estrogen (ER), androgen (AR), dioxin (AhR) and pregnane X (PXR) receptors. At the most impacted sites, chemical analyses showed the presence of natural estrogens, organochlorine pesticides, parabens, polycyclic aromatic hydrocarbons (16 PAHs), bisphenol A and alkylphenols, while synthetic steroids, myco-estrogens and phyto-estrogens were not detected. Determination of toxic-equivalent amounts showed that 28-96% of estrogenic activities in bioassays (0.2-6.3 ng/g 17β-estradiol equivalents) were explained by 17β-estradiol and estrone. PAHs were major contributors (20-60%) to the total dioxin-like activities. Interestingly, high PXR and (anti)AR activities were detected; however, the targeted analysed compounds could not explain the measured biological activities. This study highlighted the presence of multiple organic EDCs in French river sediments subjected to mixed diffuse pollution, and argues for the need to further identify AR and PXR active compounds in the aquatic environment.     

Distribution and bioaccumulation of steroidal and phenolic endocrine disrupting chemicals in wild fish species from Dianchi Lake, China

The distribution and bioaccumulation of steroidal and phenolic endocrine disrupting chemicals (EDCs) were studied in various tissues of wild fish species from Dianchi Lake, China. In muscle tissue, 4-tert-octylphenol, 4-cumylphenol, 4-nonlyphenol and bisphenol A were detected in fish from each sampling site, with maximal concentrations of 4.6, 4.4, 18.9 and 83.5 ng/g dry weight (dw), respectively. Steroids (estrone, 17β-estradiol 17α-ethynylestradiol and estriol) were found at lower levels (<11.3 ng/g dw) and less frequently in muscle samples. The highest concentrations of steroids and phenols were found in liver, followed by those in gill and the lowest concentration was found in muscle. The field bioconcentration factors (BCFs) of phenols were calculated in fish species ranged from 18 to 97. Moreover, the measured tissue concentrations were utilized in order to estimate water concentration of steroids (4.4-18.0 ng/L). These results showed that steroidal and phenolic EDCs were likely ubiquitous contaminants in wild fish.     

Use of fugacity model to analyze temperature-dependent removal of micro-contaminants in sewage treatment plants

Effluents from sewage treatment plants (STPs) are known to contain residual micro-contaminants including endocrine disrupting chemicals (EDCs) despite the utilization of various removal processes. Temperature alters the efficacy of removal processes; however, experimental measurements of EDC removal at various temperatures are limited. Extrapolation of EDC behavior over a wide temperature range is possible using available physicochemical property data followed by the correction of temperature dependency. A level II fugacity-based STP model was employed by inputting parameters obtained from the literature and estimated by the US EPA’s Estimations Programs Interface (EPI) including EPI’s BIOWIN for temperature-dependent biodegradation half-lives. EDC removals in a three-stage activated sludge system were modeled under various temperatures and hydraulic retention times (HRTs) for representative compounds of various properties. Sensitivity analysis indicates that temperature plays a significant role in the model outcomes. Increasing temperature considerably enhances the removal of β-estradiol, ethinyestradiol, bisphenol, phenol, and tetrachloroethylene, but not testosterone with the highest biodegradation rate. The shortcomings of BIOWIN were mitigated by the correction of highly temperature-dependent biodegradation rates using the Arrhenius equation. The model predicts well the effects of operating temperature and HRTs on the removal via volatilization, adsorption, and biodegradation. The model also reveals that an impractically long HRT is needed to achieve a high EDC removal. The STP model along with temperature corrections is able to provide some useful insight into the different patterns of STP performance, and useful operational considerations relevant to EDC removal at winter low temperatures.     

Part V—sorption of pharmaceuticals and personal care products

Background, aim, and scope  Pharmaceuticals and personal care products (PPCPs) including antibiotics, endocrine-disrupting chemicals, and veterinary pharmaceuticals are emerging pollutants, and their environmental risk was not emphasized until a decade ago. These compounds have been reported to cause adverse impacts on wildlife and human. However, compared to the studies on hydrophobic organic contaminants (HOCs) whose sorption characteristics is reviewed in Part IV of this review series, information on PPCPs is very limited. Thus, a summary of recent research progress on PPCP sorption in soils or sediments is necessary to clarify research requirements and directions. Main features  We reviewed the research progress on PPCP sorption in soils or sediments highlighting PPCP sorption different from that of HOCs. Special function of humic substances (HSs) on PPCP behavior is summarized according to several features of PPCP–soil or sediment interaction. In addition, we discussed the behavior of xenobiotic chemicals in a three-phase system (dissolved organic matter (DOM)–mineral–water). The complexity of three-phase systems was also discussed. Results  Nonideal sorption of PPCPs in soils or sediments is generally reported, and PPCP sorption behavior is relatively a more complicated process compared to HOC sorption, such as the contribution of inorganic fractions, fast degradation and metabolite sorption, and species-specific sorption mechanism. Thus, mechanistic studies are urgently needed for a better understanding of their environmental risk and for pollution control. Discussion  Recent research progress on nonideal sorption has not been incorporated into fate modeling of xenobiotic chemicals. A major reason is the complexity of the three-phase system. First of all, lack of knowledge in describing DOM fractionation after adsorption by mineral particles is one of the major restrictions for an accurate prediction of xenobiotic chemical behavior in the presence of DOM. Secondly, no explicit mathematical relationship between HS chemical–physical properties, and their sorption characteristics has been proposed. Last but not least, nonlinear interactions could exponentially increase the complexity and uncertainties of environmental fate models for xenobiotics. Discussion on proper simplification of fate modeling in the framework of nonlinear interactions is still unavailable. Conclusions  Although the methodologies and concepts for studying HOC environmental fate could be adopted for PPCP study, their differences should be highly understood. Prediction of PPCP environmental behavior needs to combine contributions from various fractions of soils or sediments and the sorption of their metabolites and different species. Recommendations and perspectives  More detailed studies on PPCP sorption in separated soil or sediment fractions are needed in order to propose a model predicting PPCP sorption in soils or sediments based on soil or sediment properties. The information on sorption of PPCP metabolites and species and the competition between them is still not enough to be incorporated into any predictive models.     

Sulfate removal from waste chemicals by precipitation

Chemical oxidation using Fenton's reagent has proven to be a viable alternative to the oxidative destruction of organic pollutants in mixed waste chemicals, but the sulfate concentration in the treated liquor was still above the acceptable limits for effluent discharge. In this paper, the feasibility of sulfate removal from complex laboratory wastewaters using barium and calcium precipitation was investigated. The process was applied to different wastewater cases (two composite samples generated in different periods) in order to study the effect of the wastewater composition on the sulfate precipitation. The experiments were performed with raw and oxidized wastewater samples, and carried out according to the following steps: (1) evaluate the pH effect upon sulfate precipitation on raw wastewaters at pH range of 2-8; (2) conduct sulfate precipitation experiments on raw and oxidized wastewaters; and (3) characterize the precipitate yielded. At a concentration of 80 g L(-1), barium precipitation achieved a sulfate removal up to 61.4% while calcium precipitation provided over 99% sulfate removal in raw and oxidized wastewaters and for both samples. Calcium precipitation was chosen to be performed after Fenton's oxidation; hence this process configuration favors the production of higher quality precipitates. The results showed that, when dried at 105 degrees C, the precipitate is composed of hemidrate and anhydrous calcium sulfate ( approximately 99.8%) and trace metals ( approximately 0.2%: Fe, Cr, Mn, Co, Ag, Mg, K, Na), what makes it suitable for reuse in innumerous processes.     

化学品危险性鉴别分类研究的现状与展望

从对GHS(化学品分类及标记全球协调制度)化学品危险性鉴别分类的分析出发,归纳和总结了联合国、欧盟、美国以及中国的化学品危险性鉴别分类研究现状;提出化学品危险性鉴别分类是获取化学品安全信息、评估化学品的固有危险性的重要手段;给出化学品危险性鉴别分类试验必须满足OECD(经济合作与发展组织)的各项标准和准则;对化学品危险性鉴别分类的应用前景及未来工作进行评述和展望;指出为化学品安全管理、事故应急救援、事故调查及做好基础数据的积累是今后研究工作的努力方向;提出了借鉴GHS,REACH(化学品注册、评估、许可和限制)等先进化学品安全监管法规,对完善我国的化学品安全监管制度,化学品鉴别分类标准的重要现实意义。     

我国危险化学品事故统计分析及对策研究

基于2005—2008年我国发生的1565起危险化学品事故,从事故发生时间、发生地点、发生环节等方面分析事故的致因、特点以及规律,可以发现:近3年来我国危险化学品事故呈逐渐下降趋势;石化产业大省是危险化学品事故高发省份;每年3—8月是危险化学品事故高发时期;每天上午10点和下午3点是危险化学品事故高发时间;生产、运输、储存是危险化学品产业链六大环节中的事故高发环节。根据统计结果分析,指出我国危险化学品安全管理存在的问题,并提出预防和减少危险化学品事故的对策。