水体中17种持久性和可迁移有机污染物的检测

持久性和移动性有机污染物 (persistent and mobile organic contaminants, PMOCs) 在环境中降解缓慢,并且可以通过水体循环进行迁移。由于缺乏水体中PMOCs的高效富集和准确测定方法,导致关于PMOCs在水体中存在水平的可靠监测数据较少。通过优化固相萃取条件和高效液相色谱-串联质谱参数,建立了同时检测水中17种PMOCs的分析方法。采用HLB固相萃取柱对水样中的PMOCs进行富集,乙腈和含10 mmol·L⁻¹乙酸铵的水溶液作为流动相进行梯度洗脱,PMOCs检出限为0.04~0.35 ng·L⁻¹,定量限为0.13~1.16 ng·L⁻¹,回收率为65.01%~98.65%。在北京潮白河、广东北江和河北滹沱河进行布点采样,并测定其PMOCs的质量浓度。实验结果表明：17种PMOCs在潮白河、北江和滹沱河中均有检出,其ƩPMOCs平均质量浓度分别为604.69、740.45和505.11 ng·L⁻¹。潮白河地表水中安赛蜜、金刚烷胺和己内酰胺的质量浓度相对较高,分别高达261.75、143.84和153.71 ng·L⁻¹。北江中安赛蜜、磷酸三 (2-氯丙基) 酯和己内酰胺的质量浓度相对较高,分别高达433.14、444.46和108.76 ng·L⁻¹。滹沱河中金刚烷胺、己内酰胺和磷酸三 (2-氯丙基) 酯的质量浓度较高,分别高达218.10、101.14和222.60 ng·L⁻¹。本研究结果可为地表水和地下水水体中PMOCs的检测评价提供参考。     

Organochlorine contaminants in eggs of Common Terns from the Canadian Great Lakes, 1981

To determine if contaminant levels in Common Terns had changed over the last decade, we collected and analyzed eggs from four nesting colonies on the three lower Great Lakes during 1981. DDE and PCBs were detected in every egg from the four colonies. Dieldrin, mirex and trans-nonachlor were detected in more than 45% of the eggs. Seven other organochlorine contaminants (DDD, DDT, hexachlorobenzene, oxychlordane, cis-chlordane, cis-nonachlor and toxaphene) were detected in less than 25% of the eggs. Eggs from the Lake Ontario colony were generally the most heavily contaminated. Comparisons of DDE and PCB data with earlier studies of Common Terns indicated that contaminant levels in eggs from the four sampled colonies, or nearby sites, have decreased by up to 80-90% from 1969-1973 to 1981. Interspecies comparisons showed that Common Tern eggs have lower organochlorine residue levels than eggs of Caspian Terns or Herring Gulls. Dietary variation and migratory status are possible explanations for the differences in residue levels among species. Eggshell thickness, log-PCBs, and log-DDE were not significantly intercorrelated. Elevated contaminant levels in the early 1970s might be at least partly responsible for the decline of the Great Lakes Common Tern population over the past decade. Stabilization of population numbers during the early 1980s suggests that organochlorine pollution levels have been reduced to a point where they are no longer an important factor in the population dynamics of this species on the Great Lakes.     

Formation of mutagenic activity during surface water preozonization and its removal in drinking water treatment

The influence of preozonization, coagulation and double layer filtration on formation and removal of mutagenic activity was studied using XAD-8 extracts collected from neutral and acidic solutions and assaying them in the Salmonella typhimurium microsomal assay.Preozonization of surface water produced direct acting frame shift mutagens which were adsorbed on XAD-8 from neutral solutions. This phenomenon was shown to be dependent on the ozone dose applied. Coagulation with different chemicals and subsequent direct filtration partially reduced the mutagenic activity.     

Quantification of carbamazepine and atrazine and screening of suspect organic contaminants in surface and drinking waters

A new approach for the identification of suspect trace organic contaminants in drinking and surface waters is presented. Samples were initially analyzed using a target determination method for two contamination tracers, carbamazepine (CBZ) and atrazine (ATZ). This method used offline solid-phase extraction and online solid-phase extraction techniques coupled to liquid chromatography-triple quadrupole mass spectrometry to accelerate the sample preparation process and improve method performance. CBZ and ATZ were found respectively in 31% and 56% of the samples, and concentrations were usually <20 ng L⁻¹. These samples were re-analyzed with a similar method on a quadrupole time-of-flight mass spectrometer to identify suspect contaminants by means of exact mass measurements and isotope patterns. A database of 264 common organic contaminants was built and used in conjunction with a Molecular Feature algorithm to identify the presence of these substances in drinking and surface water collected from different sources at various locations across Canada. Several organic contaminants were identified in the samples, but only the presence of caffeine, desethylatrazine, simazine and venlafaxine could be verified by comparison to pure standards. The presence of desethylatrazine was also confirmed by MS/MS experiments. These results suggest that target analysis for tracers of organic contamination may be a helpful tool to prioritize samples which should be further screened for suspect contaminants. This study also shows that the combination of separation techniques (offline and online SPE, LC) contribute to advance the applicability of high-resolution mass spectrometry for the identification of trace organic contaminants by accelerating the preparation step, reducing complexity and increasing analyte concentrations for optimal detection.     

Modeling transport and deposition of contaminants to ecosystems of concern: a case study for the Laurentian Great Lakes

Transfer efficiency (TE) is introduced as a model output that can be used to characterize the relative ability of chemicals to be transported in the environment and deposited to specific target ecosystems. We illustrate this concept by applying the Berkeley-Trent North American contaminant fate model (BETR North America) to identify organic chemicals with properties that result in efficient atmospheric transport and deposition to the Laurentian Great Lakes. By systematically applying the model to hypothetical organic chemicals that span a wide range of environmental partitioning properties, we identify combinations of properties that favor efficient transport and deposition to the Lakes. Five classes of chemicals are identified based on dominant transport and deposition pathways, and specific examples of chemicals in each class are identified and discussed. The role of vegetation in scavenging chemicals from the atmosphere is assessed, and found to have a negligible influence on transfer efficiency to the Great Lakes. Results indicate chemicals with octanol-water (K(ow)) and air-water (K(aw)) partition coefficients in the range of 10(5)-10(7) and 10(-4)-10(-1) combine efficient transport and deposition to the Great Lakes with potential for biaccumulation in the aquatic food web once they are deposited. A method of estimating the time scale for atmospheric transport and deposition process is suggested, and the effects of degrading reactions in the atmosphere and meteorological conditions on transport efficiency of different classes of chemicals are discussed. In total, this approach provides a method of identifying chemicals that are subject to long-range transport and deposition to specific target ecosystems as a result of their partitioning and persistence characteristics. Supported by an appropriate contaminant fate model, the approach can be applied to any target ecosystem of concern.     

水中有机污染物超声强化氧化技术研究进展

超声波技术在化学、环境、制药以及生物等领域有着广阔的应用前景。在降解水中难降解有机污染物方面 ,超声强化氧化技术有一定优势 ,降解效果显著 ,符合绿色环保技术的要求。超声强化氧化技术主要可分为超声空化技术、超声强化化学 (催化 )氧化技术、超声强化电化学 (催化 )氧化技术、超声强化光化学 (催化 )氧化技术、超声 生物降解等几大类 ,本文对各类技术的优缺点进行了评述。     

镀镍漂洗废水中有机物的臭氧氧化处理研究

用臭氧氧化处理镀镍漂洗废水中的有机物,主要考察pH、臭氧投加量、废水初始COD浓度、温度等因素对处理效果的影响,并对反应机理进行初步的探讨.实验结果表明,废水的COD去除率随pH的增大而升高,比较适宜的pH为6～7;适当地增加臭氧投加量有利于提高COD去除率;在一定温度范围(15～35℃)内,提高反应温度有利于废水中有机物的降解;当臭氧投加量为20 mg/(min·L),对于初始COD为56 mg/L、pH 6.5的实际镀镍漂洗废水,在25 ℃的条件下氧化100min,出水COD降至10mg/L,COD去除率达到82%;在臭氧氧化镀镍漂洗废水的反应中,部分有机物的降解是在Ni2 的催化下由臭氧分解生成氧化能力更强的自由基来完成.臭氧氧化可作为镀镍漂洗废水处理回用的预处理工艺.     

混凝技术去除水中新兴污染物的研究进展

常规水处理工艺通常不能完全将水中新兴污染物(ECs)去除,残留的污染物仍然具有相当大的环境风险,如何有效地去除水中痕量新兴污染物是一个亟待解决的难题。本文概述了新兴污染物的来源、种类和危害,并分析了混凝工艺去除新兴污染物的可行性,重点介绍了新兴污染物性质、混凝剂种类和投加量、pH和水中溶解性物质对混凝效果的影响机制,并介绍了混凝与氧化、膜过滤及吸附等工艺的组合集成技术。在此基础上,对未来混凝技术去除新兴污染物的研究方向和发展趋势进行了展望。     

Spatial and temporal trends in surface water and sediment contamination in the Laurentian Great Lakes

Data from recent sediment and surface water surveys have been collated and mapped to illustrate the spatial distribution of contaminants across the entire Great Lakes basin. Information from historical surveys, together with data from surface water monitoring programs in three major connecting channels, has also been collated in order to evaluate temporal trends. In general, Lakes Superior and Michigan exhibited the lowest levels of sediment contamination while Lake Ontario had the highest. Contaminants such as gamma-HCH (lindane) and dieldrin were ubiquitous in surface waters across the entire basin, which was indicative of atmospheric sources. The distribution of other compounds including hexachlorobenzene, octachlorostyrene and mirex indicated the presence of local sources within the watersheds of the connecting channels. Surficial sediment contamination was found to have decreased markedly since the late 1960s and 1970s. Similarly, surface water contamination decreased over the period 1986-1997 with concentrations of dieldrin, hexachlorobenzene, octachlorostyrene and mirex reduced by over 50%. However, the spatial distributions of both sediment and surface water contamination indicate that further effort is warranted in reducing local sources of contaminants, particularly in Lake Ontario.     

The use of XAD-resins for the detection of mutagenic activity in water: II. Studies with drinking water

The combined XAD-4/8-Ames test procedure for concentrating and detecting trace amounts of organic mutagens, as already described for surface water, is shown to be suitable for drinking water as well. DMSO is as effective as acetone in eluting the adsorbed mutagens, and optimal recovery of overall mutagenic activity is observed at a flow rate of 2–4 bed volumes/min. The drinking water of 6 cities in The Netherlands, which prepare their drinking water from the rivers Rhine and Meuse, has been tested for mutagenic activity. Mutagenic activity could be demonstrated in 4 cities. Dose-related responses are observed with concentrates of as little as 500 ml of drinking water and the 4 cities clearly differ with regard to the type of mutations induced (TA 98 or TA 100) and the effect of metabolic activation. The absence of mutagenic activity in drinking water of 2 cities indicates that by a proper combination of treatment processes the organics which are responsible for the detected mutagenic activity in drinking water can be removed to a high degree.     

Transport of organic contaminants through salinity stratified water masses. A microcosm experiment

A salt-wedge stratified microcosm, spiked with 31 target analytes, including PCBs, organochlorine and organophosphorous pesticides, triazines, organophosphate flame retardants and caffeine (an urban wastewater molecular marker), was setup. Compound behaviour was monitored during a four week period, by sampling at six different levels of the water column, in order to understand the transport and loss processes of the different classes of chemical substances. Compound transport from one water body to the other has been positively correlated with diffusion via their molar volume. Target analytes loss has been positively correlated with evaporation via their K(H) and with degradation via their halve-lives. From these two processes, evaporation was found to be predominant using a multiparametric regression.     

Comparison of methods for determination of volatile organic compounds in drinking water

Comparison of four methods including liquid-liquid extraction (LLE), direct aqueous injection (DAI), purge and trap (PAT) and head space (HS) were carried out in this work for determination of volatile organic compounds (VOCs) including trihalomethanes (THMs) in drinking water. This comparison is made especially to show the advantages and disadvantages and specifically the different detection limits (DL) that can be obtained for a given type of analysis. LLE is applicable only for determination of the THMs concentrations, while DAI, PAT, HS methods with different DL each of them are applicable for all VOCs, with PAT to be the most sensitive. Sampling apparatus and procedure for all these methods except of PAT are very simple and easy, but possible disadvantages for LLE and DAI are the low sensitivity and especially the detection only of THMs with LLE.     

活性炭-超滤深度处理工艺对三氯乙醛生成潜能的影响及其对饮用水中有机物的去除

以我国南方某活性炭-超滤深度处理工艺水厂为研究对象,对工艺过程中三氯乙醛生成潜能(CHFP)及相关有机物指标进行为期1年每月1次的监测,以明晰活性炭-超滤深度处理工艺对CHFP及有机物的去除能力。结果表明:原水CHFP均呈现一定的季节性变化趋势,高温季节(5—9月)相对较高,范围为15.50～64.00 μg·L-1,活性炭-超滤深度处理工艺对CHFP 、TOC、CODMn和UV254去除率范围分别为37.42%～69.12%、25.25%～66.71%、27.33%～61.25%和21.80%～72.46%,平均去除率分别为54.51%、39.21%、45.04%和42.91%;混凝沉淀单元在CHFP和有机物指标去除中均起主要作用,炭滤单元对TOC有较好的去除作用,超滤单元对CHFP和CODMn有较好的去除作用。建议水厂设计与运行中将臭氧与活性炭滤池联合使用,以协同去除CHFP和有机物,进一步提高供水水质。     

气相色谱法测定饮水中1,2,3-三氯苯的方法研究

建立了液液萃取-气相色谱法测定饮用水1,2,3-三氯苯的方法。根据测定研究,得出其方法检出限为0.05ug/L,建立的曲线回归系数高于0.995,回收率在91.17%-106.25%之间,符合要求。     

臭氧对饮用水管网中溶解性有机物的影响

利用生物膜环状反应器模拟配水管网系统,将水厂砂滤池出水经过臭氧氧化后投加氯然后进入该模拟管网,另外把水厂砂滤池出水加氯后通入另一模拟管网作为对照实验。通过对两管网出水余氯、总铁、浊度、溶解性有机物(DOC)、以及消毒副产物三卤甲烷(THMs)、卤乙酸(HAAs)生成情况的测定,研究了饮用水臭氧处理对管网出水水质的影响。单因素方差分析结果表明,两管网出水的余氯、总铁、浊度以及THMs、HAAs含量相差不大,但DOC在臭氧氯管网中消耗较多。同时通过高效凝胶色谱(HPSEC), 红外光谱(FTIR)和三维荧光光谱(EEM)表征了不同管网进出水DOC变化,结果表明,臭氧氧化后的管网出水中溶解性有机物荧光光谱中三区富里酸和五区腐植酸荧光峰值(ФⅢ+Ⅴ,n)减小较多,管网出水消毒副产物稍有增加。     

固相微萃取-气相色谱法测定饮用水及其水源水中的氯酚

利用固相微萃取(SPME)-气相色谱法(GC)联用技术测定饮用水及其水源水中的氯酚．优化萃取温度、萃取平衡时间、酸度、离子强度等实验条件．所建方法简便、精确,自来水和太湖水中均检测到氯酚。     

Analysis of 2,3,7,8-Tetrachlorodibenzo-p-dioxin in Great Lakes fish

In fish samples from Lake Ontario and Lake Huron 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) was found at concentrations from 2 to 162 pg/g (ppt) and from 2.5 to 29 ppt respectively. Fish from the other Great Lakes (Lake Superior, Lake Michigan and Lake Erie) generally had no detectable signals for TCDD although a few samples had < 3 ppt.     

Status and changes of water quality in typical near-city zones of three East African Great Lakes in Tanzania

Environmental Science and Pollution Research - Tanzania is the only country bordering all three transboundary East African Great Lakes, i.e., Lake Victoria, Lake Tanganyika, and Lake Nyasa (Lake...     

光电氧化降解饮用水中有机污染物的效能

针对地表水中普遍存在的有机污染物现状和常规水处理工艺无法去除有机污染物的问题,以紫外光电氧化技术为基础,提出了以“分质供水”为目标的末端深度水处理工艺。与单独电解和光解相比,电化学氧化与紫外耦合技术可以将布洛芬、阿特拉津、三氯乙酸、乐果的降解率在15 min内分别提高到92.5%、98.1%、71.0%和94.6%,并且能耗有所降低。电流和光强对光电氧化降解有机污染物有促进作用,但污染物初始质量浓度、Cl⁻、HCO₃⁻和天然有机物(HA)和污染物去除率呈反比关系。在此基础上,以布洛芬为污染物代表,测定了布洛芬的中间产物,并计算了降解中间体的毒性变化,发现光电氧化明显降低了布洛芬的毒性。