小清河表层沉积物重污染区重金属赋存形态及风险评价

测定了小清河表层沉积物重污染区间隙水中重金属(Cu、As、Pb、Zn、Cr、Cd和Ni)的质量浓度,采用改进的BCR顺序提取法分析了沉积物中重金属的赋存形态,并分别基于美国水质基准(CCC、CMC)和风险评价编码法(RAC)、潜在生态风险指数法对间隙水和表层沉积物中重金属的毒性及生态风险进行评价.结果表明,小清河沉积物间隙水中的重金属基本不会对水生态系统产生毒性.除As外,表层沉积物中6种重金属的含量显著高于土壤背景值,呈现明显的累积效应.沉积物中Cu、As和Ni主要赋存于残渣态,Pb、Cr主要赋存于可氧化态和残渣态,Zn、Cd以酸可溶解态和可还原态为主.Cd、Zn、Cr和Pb的有效态含量高于残渣态,有较高的二次释放潜力.RAC的评价结果表明,沉积物中Cu、Pb、Cr和As处于无风险到低风险级,Ni处于低风险到中等风险级,Cd处于中等到高风险级,Zn处于中等到极高风险级,不同重金属RAC的平均值依次为CdZnNiAsCuCrPb.潜在生态风险指数法的评价结果表明,沉积物中除Cd有强~很强生态风险外,其他6种重金属均表现为低生态风险,RI值介于136.83~264.83,研究区采样点处于中等~强生态风险.     

北京市4种不同污水处理系统中病原菌变化研究

采用定量PCR技术,对北京市4种不同污水处理系统中大肠杆菌、军团菌和沙门氏菌随工艺及四季的数量变化进行了追踪研究,以评估病原菌的去除效果及污水回用的健康风险.结果发现,大肠杆菌在夏季进水和出水中的浓度分别在107~108copies·m L-1和105copies·m L-1左右;G-A/O系统对大肠杆菌的去除率最高,平均去除率达99.88%.军团菌在4个污水处理系统中进水浓度为104~105copies·m L-1,出水浓度约为104copies·m L-1,其在剩余污泥样品中浓度较高,达到105~106copies·m L-1.沙门氏菌进水浓度较低,为102~103copies·m L-1,且其在多个工艺段样品中未检出.季节变化对于病原菌的去除具有较大影响.研究表明,大肠杆菌在各污水处理系统中均可检出,且其分布具有一定的季节性,夏季的进出水中浓度相对较高;而军团菌和沙门氏菌浓度在各工艺中则并未呈现出明显的季节性变化.G-A/O系统对3种细菌的整体去除效果最为稳定,去除率较高.大肠杆菌在污水处理厂的出水及剩余污泥中浓度仍然较高,此外,冬季出水中也能检测到沙门氏菌的存在,因此,污水处理厂的出水和污泥排放仍存在一定的生态和健康风险.     

污染源半定量化的地下水有机污染风险评价

结合细河沿岸地区水文地质条件及地下水有机污染特征,通过AHP法确定权重,建立DRSIC模型,将评价结果与污染源荷载评价叠加,构建研究区有机污染风险评价模型.并通过研究区有机污染特征检验模型的合理性.结果表明:区内大部分地区有机污染风险中等或低.只有细河沿岸、杨士至于洪区一带污染风险处于高水平.评价结果较好的符合研究区有机污染现状.     

我国生物质气化发电行业综合风险评价

针对我国生物质气化发电行业的现状,总结诸多风险的影响因素,建立了我国生物质气化发电行业综合风险评价体系。该评价体系主要包括5个一级风险影响因素:市场风险、技术风险、安全风险、管理风险、环境风险,每个一级影响因素包括4个二级风险影响因素。由层次分析法获得各个一级影响因素和二级影响因素的权重值,根据所构建的评价集和评分标准,结合模糊综合评价法对我国生物质气化发电行业现状的综合风险等级做定量定性分析。综合风险评价研究结果表明,生物质气化发电行业处于"较高"的风险等级,与实际情况相符。综合风险评价体系的构建合理,所建立的评价方法以及相应对策分析可为决策者提供参考依据。     

苯并芘对稀有鮈鲫的内分泌干扰效应研究

为评价典型有机污染物对长江三峡库区上游特有珍稀鱼类的环境风险,本实验以稀有鮈鲫为对象,研究了低剂量多环芳烃(PAHs)暴露而引起的内分泌干扰效应.将成年稀有鮈鲫暴露于不同浓度(0、0.1、0.3、1.0和3.0μg·L-1)的苯并芘(Ba P)中28 d,测定了体质系数、性激素含量、下丘脑-垂体-性腺(HPG)轴和肝脏中与繁殖相关基因的表达.结果显示:在雌鱼中,Ba P暴露后,睾酮(T)的含量显著升高,雌二醇(E2)的水平显著下降并改变了T/E2的比值;在雄鱼中,T和E2的含量都显著下降.雌雄鱼性激素的改变可能与类固醇合成相关基因(Cyp17、Cyp19a)表达量的改变有关.Ba P暴露显著抑制了雌雄鱼肝脏中卵黄蛋白原(VTG)基因的表达.以上检测到的激素或者基因表达的改变主要发生在高剂量(3.0μg·L-1)Ba P暴露下,而长江上游库区水体中多环芳烃含量较低(100 ng·L-1),因此推测,库区存在的多环芳烃不会对三峡库区上游水体中的鱼类产生内分泌干扰效应.     

Predicted no-effect concentrations for mercury species and ecological risk assessment for mercury pollution in aquatic environment

Mercury(Hg) exists in different chemical forms presenting varied toxic potentials. It is necessary to explore an ecological risk assessment method for different mercury species in aquatic environment. The predicted no-effect concentrations(PNECs) for Hg(Ⅱ) and methyl mercury(Me Hg) in the aqueous phase, calculated using the species sensitivity distribution method and the assessment factor method, were 0.39 and 6.5 × 10-3μg/L, respectively. The partition theory of Hg between sediment and aqueous phases was considered, along with PNECs for the aqueous phase to conduct an ecological risk assessment for Hg in the sediment phase. Two case studies, one in China and one in the Western Black Sea, were conducted using these PNECs. The toxicity of mercury is heavily dependent on their forms,and their potential ecological risk should be respectively evaluated on the basis of mercury species.     

全氟和多氟烷基化合物的环境风险评估研究现状、不确定性与趋势分析

本研究系统梳理了国际学术界关于全氟和多氟烷基化合物(perfluoroalkyl and polyfluoroalkyl substances,PFASs)的术语、范畴和应用物质的界定与变迁,以PFASs的环境危害性评估和暴露评估为重心,综述评析当前关于PFASs环境风险评估研究现状、不确定性和发展趋势.总体上,PFASs风险评估正面临着物质谱系复杂、种类众多、衍生关系复杂、商业秘密及风险不确定的复杂局面.尽管长链PFASs的环境风险已获广泛认可,但以其替代品形式大量涌现的短链PFASs及各类短链氟调聚物的环境危害性、环境行为和暴露风险则尚存很多的不确定性与研究空白,国际社会对于PFASs的风险控制范畴值得商榷.PFASs替代物质的结构和风险信息因商业秘密及市场竞争因素而缺乏公开性和透明度,多数含氟和非氟替代品的环境风险尚有待识别.总之,国际上对PFASs风险评估研究呈现出由以全氟辛烷磺酸类化合物(perfluorooctane sulfonic acid,PFOS)和全氟辛酸类化合物(perfluorooctanoic acid,PFOA)等为代表的长链全氟烷基酸(perfluoroalkyl acids,PFAAs)逐步扩展到短链PFAAs,再扩展到其他非PFAAs的PFASs物种的发展趋势.当前亟待解决及未来将持续研究关注的主要问题:关于短链PFASs的生物累积性和环境迁移性等关键环境危害性的评估指标和方法的优化,以及其环境释放和多介质环境归趋;中性PFASs的环境归趋及其作为短链PFAAs潜在前体物质的转化与贡献;未来PFASs含氟或非氟替代品的风险识别和评估.     

DOM对被动采样技术的影响与应用

主要研究了不同浓度的天然溶解性有机物(DOM)对单片膜被动采样技术的影响.结果表明,DOM的存在会影响膜吸附有机污染物的能力:当lg KOW为3~5时,DOM对膜吸附有机物的影响较小;当lg KOW5.5时,DOM会显著增强膜的吸附能力.同时,通过低密度聚乙烯膜(LDPE)被动采样技术对太子河流域3个表层沉积物的孔隙水进行多环芳烃类(PAHs)和邻苯二甲酸酯类(PAEs)监测.结果表明,所选取的几种目标污染物在各监测点均有不同程度的检出.最后,利用商值法对太子河流域的PAHs和PAEs进行生态风险评价.结果表明,荧蒽超过水生生态基准值,其生态风险较大.     

The effect of alkyl chain length on the degradation of alkylimidazolium- and pyridinium-type ionic liquids in a Fenton-like system

Background, aim, and scope  Ionic liquids are regarded as essentially “green” chemicals because of their insignificant vapor pressure and, hence, are a good alternative to the emissions of toxic conventional volatile solvents. Not only because of their attractive industrial applications, but also due to their very high stability, ionic liquids could soon become persistent contaminants of technological wastewaters and, moreover, break through into natural waters following classical treatment systems. The removal of harmful organic pollutants has forced the development of new methodologies known as advanced oxidation processes (AOPs). Among them, the Fenton and Fenton-like reactions are usually modified by the use of a higher hydrogen peroxide concentration and through different catalysts. The aim of this study was to assess the effect of hydrogen peroxide concentration on degradation rates in a Fenton-like system of alkylimidazolium ionic liquids with alkyl chains of varying length and 3-methyl-N-butylpyridinium chloride. Materials and methods  The ionic liquids were oxidized in dilute aqueous solution in the presence of two different concentrations of hydrogen peroxide. All reactions were performed in the dark to prevent photoreduction of Fe(III). The concentrations of ionic liquids during the process were monitored with high-performance liquid chromatography. Preliminary degradation pathways were studied with the aid of ¹H NMR. Results  Degradation of ionic liquids in this system was quite effective. Increasing the H₂O₂ concentration from 100 to 400 mM improved ionic liquid degradation from 57–84% to 87–100% after 60 min reaction time. Resistance to degradation was weaker, the shorter the alkyl chain. Discussion  The compound omimCl was more resistant to oxidation then other compounds, which suggests that the oxidation rates of imidazolium ionic liquids by OH· are structure-dependent and are correlated with the n-alkyl chain length substituted at the N-1-position. The level of degradation was dependent on the type of head group. Replacing the imidazolium head group with pyridinium increased resistance to degradation. Nonetheless, lengthening the alkyl chain from four to eight carbons lowered the rate of ionic liquid degradation to a greater extent than changing the head group from imidazolium to pyridinium. 1H-NMR spectra show, in the first stage of degradation, that it is likely that radical attack is nonspecific, with any one of the carbon atoms in the ring and the n-alkyl chain being susceptible to attack. Conclusions  The proposed method has proven to be an efficient and reliable method for the degradation of imidazolium ionic liquids by a Fenton-like reagent deteriorated with lengthening n-alkyl substituents and by replacing the imidazolium head group with pyridinium. The enhanced resistance of 1-butyl-3-methylpyridinium chloride when the resistance of imidazolium ionic liquids decreases with increasing H₂O₂ concentration is probably indicative of a change in the degradation mechanism in a vigorous Fenton-like system. H-NMR spectra showed, in the first stage of degradation, that radical attack is nonspecific, with any one of the carbon atoms in the ring and the n-alkyl chain being susceptible to attack. Recommendations and perspectives  Since ionic liquids are now one of the most promising alternative chemicals of the future, the degradation and waste management studies should be integrated into a general development research of these chemicals. In the case of imidazolium and pyridinium ionic liquids that are known to be resistant to bio- or thermal degradation, studies in the field of AOPs should assist the future structural design as well as tailor the technological process of these chemicals     

采油废水中多环芳烃的生态风险评价

先利用C-18固相萃取小柱富集大港油田港东联合处理站污水处理站的采油废水中16种多环芳烃(PAHs,即萘、苊烯、苊、芴、菲、蒽、荧蒽、芘、、苯并[a]蒽、苯并[b]荧蒽、苯并[k]荧蒽、苯并[a]芘、茚并[1,2,3-cd]芘、二苯并[a,h]蒽和苯并[g,h,i]苝),再用气相色谱/质谱(GC/MS)分析测定其浓度,以评价PAHs的去除率和生态风险。结果表明:(1)采油废水经处理后,COD、石油类去除率分别达到82.27%、91.06%;外排水COD、石油类达到《污水综合排放标准》(GB 8978—1996)一级标准要求,优于中国采油废水处理的一般水平。(2)采油废水主要以2、3环的PAHs为主,约占总量的93%以上。(3)苯并[a]芘超过《地表水环境质量标准》(GB 3838—2002)中限值。(4)处理前的采油废水中蒽、菲和苯并[a]芘具有一定的生态风险;处理后的外排水中萘、蒽、菲、荧蒽、苯并[a]芘的暴露浓度(PEC)/预测无效应浓度(PNEC)均小于1,目前尚未对环境造成威胁。但是8种PAHs(苊烯和苯并类PAHs除外)总和表现出较大的毒性,需要引起重视。