Simultaneous determination of brominated phenols in soils

Brominated phenols （BPs）, a widely used group of emerging flame retardants, are important environmental contaminants and exhibit endocrine disrupting potential. Method for simultaneous determination of tetrabromobisphenol A （TBBPA）, tribromophenol （TBP）, dibromophenols （DBPs） and monobromophenols （MBPs） in soils using gas chromatography-mass spectrometry analysis （GC/MS） was successfully developed. Cleanup methods for soil extracts including several solid-phase extraction cartridges and different elution solvents were compared and optimized. Florisil cartridge with dichloromethane as the elution reagent was selected for sample cleanup owing to its high and reproducible recoveries of the target analytes in soils. Derivatization conditions were tested and the optimal conditions were obtained with 20 μL silylation reagent at room temperature. The chromatographic separation was optimized with different columns and DB-XLB column was selected for its excellent separation of the analytes. The limits of detection for the target compounds were from 0.04 to 0.19 ng/g. Mean recoveries of the compounds from spiked soils exceeded 84% with a good reproducibility, excepting that the recovery of 2-bromophenol was relatively poor （lower than 55%） due to its instability. The developed method was applied to the determination of the BPs in the soils collected from e-waste sites. The contents of BPs in the soils were at ng/g levels with TBBPA and TBP the most frequently detected. To our knowledge, this is the first report for the simultaneous determination of TBBPA, TBP, DBPs and MBPs in soils.     

新污染物多环芳烃衍生物的来源、分布与光化学行为

环境中多环芳烃衍生物(SPAHs)来源广泛,具有“三致”效应,毒性与PAHs母体相当甚至高于母体,是一类具有较高风险的新型有机污染物.大气和表层水体等环境介质中,光化学降解是其重要的消减方式.在梳理文献的基础上,发现SPAHs在来源、分布、行为和风险研究方面与传统污染物PAHs相比有了新的突破.通过总结新污染物SPAHs的环境分布特征与光化学行为研究的最新进展,介绍了3类SPAHs的来源和形成机制,重点评述了不同环境介质中的存在状况与分布特征,讨论了水、冰等介质中SPAHs光化学转化动力学、反应路径以及影响因素,最后对SPAHs的环境行为和风险研究进行了展望.     

沈阳市典型城市河流优先控制污染物筛选及生态环境风险评估

细河和蒲河接纳了沈阳市工业废水的排放,水体中有毒、有害污染物不容忽视.为了明确河流中优先控制污染物,评价实际暴露水平下优先控制污染物对该水系生态环境的风险,选择细河和蒲河表层水为研究对象,开展了平水期、丰水期和枯水期的采样及有机污染物的检测分析;通过改进的潜在危害指数法对水体中检出的52种有机污染物打分排序,筛选了优先控制污染物;将效应评价外推法与商值法结合评价了优先控制污染物的生态环境风险.结果表明:52种有机污染物在细河中检出的平均质量浓度范围为9.20×10-6~1.37×10-1 mg/L,在蒲河中检出的平均质量浓度范围为4.30×10-6~3.03×10-2 mg/L.细河或蒲河中这些污染物的危害指数总分值（R）在22分以上的分别有12和13种,其中,PAEs（酞酸酯类）占6种,苯酚类污染物占4种.在细河中,DBP（邻苯二甲酸二丁酯）、苯酚、对甲基苯酚、2,4-二甲基苯酚和2,4,6-三甲基苯酚的R_q（风险商）>1,表明这些污染物存在较大的生态环境风险;在蒲河中,DBP、DEHP[邻苯二甲酸二（2-乙基己基）酯]和苯酚的R_q>1,表明这些污染物存在较高生态环境风险水平.研究显示,在细河、蒲河中PAEs和苯酚类有机物为优先控制污染物,其中部分优先控制污染物具有较高的生态环境风险,可为该流域有毒、有害物污染控制方案的制定提供参考和指导.      

取代脲类除草剂光催化降解动力学比较

为研究取代脲类除草剂在TiO₂光催化降解过程中的动力学规律,以非草隆、异丙隆和利谷隆3种取代脲类除草剂为研究对象,通过Langmuir-Hinshelwood动力学模型对其TiO₂光催化降解动力学进行模拟,并系统探讨了催化剂用量、C₀(取代脲类除草剂的初始浓度)、溶液pH、温度、ROSs(活性氧物种)和电子捕获剂等的影响. 结果表明:非草隆、异丙隆和利谷隆的TiO₂光催化降解均符合假一级动力学模型,其动力学常数分别为0.082 8、0.068 7和0.095 4 min-1;取代脲类除草剂分子中的芳香环和脲桥上的取代基对降解速率常数的大小有明显的影响. ROSs试验表明,非草隆、异丙隆和利谷隆光催化降解过程中分别有91.6%、95.5%和86.8%的贡献来自·OH;而光生空穴和其他ROSs的贡献相对较小,并且电子捕获剂BrO₃-和S₂O₈2-对取代脲类除草剂的降解动力学有显著的促进作用.      

水中痕量酚类的分离富集及色谱分析

本文综述了近十年来水中重要有机污柒物—酚类化合物的分离富集技术,以及色谱法(GC法和HPLC法)分析。     

协同-络合萃取法回收含酚废水中的酚类

在现有的各种回收处理高浓度含酚废水的方法中,溶剂萃取法最为有效.但现有常用脱酚萃取剂分别存在着萃取效能低等诸多缺点,萃残液中一般尚存有几十至几百mg·l~(-1)的酚类,本文提出了协同-络合萃取法,并按该法原理研制了HC-1—HC-4四类新型协同-络合萃取剂.其中HC-3和HC-4对苯酚稀溶液的萃取平衡常数分别为K_((?)C-3)=612.4和K_((?)C-4)=483.7,单级萃取可将两组中高浓度的含酚废水中酚浓度降至10mg·l~(-1)以厂,脱酚率>99%.该法为一步脱酚达标提供了可能性.     

Na~+-K~+-ATP酶活力与取代芳烃分子结构的相关性

本文应用环境毒理学和生物化学原理,检测了38种取代芳烃类化合物对水生生物金鱼(Carassias auratus)肝细胞内Na~+-K~+-ATP三磷酸腺苷酶(ATPase)活力的影响,给出了Na~+-K~+-ATP酶活力(A)值与取代芳烃分子结构的相关性方程.     

Experimental design of Fenton and photo-Fenton reactions for the treatment of cellulose bleaching effluents

Multivariate experimental design was applied to the treatment of a cellulose conventional bleaching effluent in order to evaluate the use of the Fenton reagent under solar light irradiation. The effluent was characterised by the general parameters total organic carbon (TOC), chemical oxygen demand and color, and it was analysed for chlorinated low molecular weight compounds using GC–MS. The main parameters that govern the complex reactive system: Fe(II) and H₂O₂ initial concentration, and temperature were simultaneously studied. Factorial experimental design allowed to assign the weight of each variable in the TOC removal after 15 min of reaction. Temperature had an important effect in the organic matter degradation, especially when the ratio of Fenton reagents was not properly chosen. Fenton reagent under solar irradiation proved to be highly effective for these types of wastewaters. A 90% TOC reduction was achieved in only 15 min of treatment. In addition, the GC–MS analysis showed the elimination of the chlorinated organic compounds initially detected in the studied bleaching effluents.     

MCF-7细胞评价老龄渗滤液经IME-Fenton处理后酚类提取物的雌激素效应

成分复杂的垃圾渗滤液经处理后,研究其中残留的极低浓度的酚类环境内分泌干扰物的雌激素效应及其对生态环境的毒性作用具有非常重要的实际价值.本文选择对雌激素敏感的MCF-7人类乳腺癌细胞进行体外培养,将老龄渗滤液原液、经过内部微电解(IME)和内部微电解结合芬顿试剂(IME-Fenton)处理后的渗滤液酚类提取液稀释10~107倍,采用MTT法测定MCF-7细胞的增殖和细胞划痕损伤实验评价渗滤液中酚类物质的雌激素效应,并探讨了活性炭在反应中对酚类物质的去除效果.结果表明,渗滤液中酚类提取物对MCF-7细胞增殖在浸染72 h后达到最大;与渗滤液原液相比,渗滤液经IME和IME-Fenton处理后,最大增殖效应分别下降了85%和110%,酚类提取物减缓了MCF-7细胞的迁移速度;活性炭对渗滤液中酚的吸附主要发生在反应前30 min,渗滤液经活性炭吸附后的酚类提取物稀释10~107倍仍表现出细胞毒性.渗滤液经IME-Fenton处理后降低了酚类物质进入环境引起的危害,MCF-7细胞增殖和细胞划痕也为检测浓度低至10-15g·L-1的酚类雌激素提供新方法.     

4-AAP两波段光度洁同时测定水中酚类和芳胺

在ＰＨ为５．５的ＨＣｌ－（ＣＨ２）５Ｎ．介质中,铁氰化钾和过二硫酸铵存在下,用４－氨基安替吡啉（４－ＡＡＰ）两波段光度法可同时测定污水中０．１—３０ｍｇ／Ｌ的酚类和０．００８—３．０ｍｇ／Ｌ的芳胺．水样不需要预镏和萃取操作,石油类及０．３ｍｇ／ｔ以下的硫化物不于扰测定,Ｃｕ２＋、Ｆｅ３十的干扰可用ＥＤＴＡ掩蔽消除．酚类和芳胺的水样加标回收率酚类为９８％－１０５％,芳胺为９５％－１０５研究了１０种酚和１３种芳胺的测定灵敏度．