饮用水中含氮消毒副产物卤代腈(氰)的生成特性与控制研究进展

卤代腈(氰)是水处理过程中产生的一类含氮的氯化消毒副产物。鉴于这种物质有极强的致畸和致突变性,其细胞毒性也远大于三卤甲烷和卤乙酸等常规消毒副产物,因此成为近年来饮用水中颇受关注的含氮消毒副产物种类之一。卤代腈(氰)在水厂出厂水中被大量检出,其质量浓度基本维持在μg/L,而采用氯胺消毒的出厂水中其浓度明显高于自由氯消毒方式。重点对卤代腈(氰)的物质种类、理化特性、遗传毒性、生产机制、检测方法及控制方法进行综述。鉴于多数卤代腈(氰)类消毒副产物均具有含量低、亲水性强等特点,若生成将难以在饮用水处理工艺中有效去除,因此如何有效控制其生成是卤代腈(氰)研究的主要发展方向。     

过硫酸钾去除水中的TCE

以地水中的氯代烃污染物三氯乙烯(TCE)为目标污染物,以过硫酸钾溶液为氧化剂,探讨了不同条件下过硫酸钾对TCE的去除效果。实验结果表明,在40℃,过硫酸钾初始浓度为2.43 g/L条件下,反应2 h后,TCE的去除率就可达到96.8%;过硫酸钾对TCE的去除符合一级反应动力学方程,速率常数(K)为1.3364 h-1,半衰期(t1/2)为0.51 h;过硫酸钾对TCE的去除速率在pH为中性附近时最大,其后无论pH升高或降低去除速率均减小;受温度和pH影响较明显,并且反应温度越高,受pH的影响越明显;随离子强度的增加而减小;反应活化能为119.6 kJ/mol;过硫酸钾溶于水生成过硫酸根离子(S2O28-),S2O28-会进一步生成硫酸根自由基(SO4-.),在碱性条件下,SO4-.与OH-反应会进一步生成羟基自由基(.OH)。过硫酸钾对于TCE的去除主要源自SO4-.和.OH的强氧化性。     

城市污水再生氯消毒过程中HAAs生成及迁移转化

针对城市污水再生处理工艺中卤乙酸类(HAAs)消毒副产物和卤乙酸生成潜能(HAAFP),结合三维荧光光谱,分析HAAs及其前体物的变化规律。结果表明,二级出水经2次加氯过程后,再生出水中的总卤乙酸浓度增加了90%,其中溴代乙酸的增幅最大,占增加量的82%。卤乙酸生成潜能较大的为氯代乙酸类物质,说明水中存在大量的氯代乙酸前体物。从工艺过程来看,总卤乙酸生成潜能与总有机物荧光强度分别下降了32%和28%,表明该再生处理工艺对HAAs前体物有一定的去除作用。     

三氯乙烯好氧生物降解的初步研究

工业溶剂三氯乙烯 (TCE)是地下水污染物中发现的最普遍的氯代化合物。本研究的目的是评价以葡萄糖为初始基质时好氧条件下TCE生物降解的可行性 ,以及以TCE为单一基质时的生物降解情况。微生物培养是在好氧条件下以驯化好的活性污泥作为接种体。实验结果表明 ,在 2 5℃时 ,葡萄糖可以在好氧条件下作为共代谢基质使TCE发生生物降解 ,其一级反应速率常数为 0 32 12d-1,半衰期为 2 16d ;TCE可以作为单一基质发生好氧生物转化 ,其一级反应速率常数为 0 2 6 2 4d-1,半衰期为 2 6 4d ;降解过程中无二氯乙烯 (DCE)和氯乙烯 (VC)等中间产物的形成 ;表明葡萄糖共代谢降解TCE的速率大于TCE作为单一基质的降解速率。     

南方某市饮用水源三氯乙醛生成特性

以我国南方某市饮用水源为研究对象,分析了不同反应条件下的三氯乙醛(CH)生成情况、CH与常规消毒副产物(DBPs)的相关关系及水质指标与CH生成势(CHFP)的相关关系。结果表明,5~35℃温度范围内,CH生成量随着温度的升高而逐渐升高,45℃时,反应约30 h后CH降解速率大于生成速率,生成量逐渐减少;CH生成量随着p H的升高而逐渐降低,当p H=11时,CH已经完全降解;Cl_2∶TOC=1∶1~4∶1(质量比)时,CH的生成量随着加氯量的增加而增加,但是当Cl_2∶TOC4∶1时,CH的生成量基本保持不变。CH与两类常规DBPs(三卤甲烷(THMs)和卤乙酸(HAAs))之间均为正相关关系,且CH与卤乙酸(HAAs)的相关关系更为显著。与UV_(254)和SUVA_(254)相比,CHFP与TOC线性关系更为显著,可以根据原水的TOC来简单预测水体中的CHFP。     

不同共代谢基质下四氯乙烯厌氧生物降解研究

分别用葡萄糖、乳酸盐和醋酸盐作为驯化好的厌氧污泥的共代谢基质 ,对四氯乙烯 ( PCE)的降解进行研究。结果表明 ,PCE是通过还原脱氯发生生物降解的。实验的回归结果表明 ,反应均符合一级动力学方程 ;反应速率常数的大小依次为 k乳酸盐 >k葡萄糖 >k醋酸盐 ;以乳酸盐作为共代谢基质时 ,PCE的降解速率较快 ,在实验条件下乳酸盐是最合适的共代谢基质     

Fe0还原、芬顿氧化及其耦合技术去除染料厂剩余污泥中的AOX

染料废水中含有大量难生物降解的卤代有机物合成中间体,合成卤代有机物在废水的生物处理过程中容易被吸附到剩余污泥中,如不能妥善处理会引起生态健康风险。研究了零价铁还原、芬顿氧化及其组合技术对染料企业剩余污泥中AOX(可吸附有机卤代物)的去除效果,优化了处理条件,解析了去除机理。结果表明,铁粉投加量为5 g·L~(-1),厌氧反应30 d时,零价铁还原对污泥中AOX降解率仅为24.7%;Fe2+投加量0.059 mol·L~(-1),H2O_2投加量0.89 mol·L~(-1),芬顿氧化1.5 h时,污泥中AOX去除率提高至73.7%;投加2 g·L~(-1)的铁粉,还原30 d后再进行芬顿反应,则污泥中AOX去除率可达到90.3%。GC-MS分析结果表明,污泥中的主要AOX物质为2,6-二氯-4-硝基苯胺,该物质经过零价铁还原与芬顿氧化组合工艺处理后,比直接芬顿氧化能得到更有效的去除。     

预氯化及常规工艺对消毒副产物的影响

以天津市某给水厂的水源水为实验对象,通过在实验室规模上模拟的给水处理厂工艺流程,比较了3种不同工艺流程中各单元出水的三卤甲烷(THMs)、卤乙酸(HAAs)和总有机物(TOC)浓度变化,分析了水处理单元工艺和TOC浓度对消毒副产物的影响。结果表明,预氯化生成的三卤甲烷和卤乙酸分别占最终出水中三卤甲烷和卤乙酸浓度的55.7%和66.7%,说明预氯化对出厂水中消毒副产物的产生有显著影响;混凝沉淀和过滤对三卤甲烷的去除率分别为17.2%和19.6%,而卤乙酸在水处理过程中变化不大,仅在过滤之后降低了3.32μg/L,说明过滤对三卤甲烷和卤乙酸均有一定的去除作用,而混凝沉淀仅对三卤甲烷有一定的去除作用;TOC浓度经过水处理工艺后整体呈下降趋势,但分析表明,其浓度对三卤甲烷和卤乙酸的生成影响很小,而氯则是三卤甲烷和卤乙酸生成的重要限制因素。     

Fenton氧化水中间氯硝基苯的动力学与机制研究

结合Fenton氧化反应动力学模型研究了Fenton氧化水中间氯硝基苯(m-ClNB)的影响因素和降解机制.结果表明:(1)反应初始pH、H2O2浓度、Fe2+浓度、污染物初始浓度和反应温度对m-ClNB的降解均有明显影响.在反应初始pH为3.5、m-ClNB初始摩尔浓度为0.444mmol/L、H2O2摩尔浓度为21.55mmol/L、Fe2+摩尔浓度为0.054mmol/L、反应温度为(25土1)℃的条件下,m-ClNB的去除效果较好.(2)建立了Fenton氧化m-ClNB的准一级反应动力学模型,且m-ClNB的降解与该模型拟合良好.基于不同反应温度时的准一级反应速率常数(kap),得到了m-ClNB降解的阿累尼乌斯公式,且活化能为36.51kJ/mol.(3)气相色谱(GC)/质谱(MS)和高效液相色谱(HPLC)/MS分析表明,Fenton氧化m-ClNB的主要产物有4-氯-2-硝基苯酚及其同分异构体、羟基乙酸、草酸、丁二酸、丙二酸、6-氯己酸、乙醛酸、2,2-二羟基丙二酸和2-乙基丙二酸等.     

壳聚糖/磁性生物碳对重金属Cu(Ⅱ)的吸附性能

以丝瓜络为原料制备壳聚糖/磁性生物炭(CMLB),并研究了改性前后的生物炭对重金属Cu(Ⅱ)的吸附性能。结果表明,改性后的生物炭包含γ-Fe_2O_3纳米颗粒,颗粒尺寸均匀,大小一致。CMLB对Cu(Ⅱ)的吸附量为54.68 mg·g~(-1),高于原始生物炭(LB)、磁性生物炭(MLB)的吸附量,且能够达到壳聚糖吸附量的86%。整个吸附过程在18 h达到平衡,在pH=5.8±0.1有较好的吸附效果。吸附反应动力学可采用准二级动力学方程拟合,吸附等温线符合Freundlich模型。CMLB吸附Cu(Ⅱ)的机制下包括离子交换、物理吸附和共沉淀。CMLB材料在处理废水后,利用磁铁可将材料从水中分离。CMLB可作为一种吸附剂有效去除水中的重金属,应用前景广阔。     

Use of diffuse reflectance spectrometry in spot test reactions for quantitative determination of cations in water

Diffuse reflectance spectroscopy can be successfully used for the quantitative determination of small amounts of pollutants like metals. The remission function was found to be linearly proportional to the concentration, when we applied the Kubelka–Munk equation. The color reactions of Cu(II), Co(II), and Ni(II) with dithiooxamide, were realised on filter paper. Reaction between Fe(III) and ammonium thiocyanate was realized on filter paper and gelatine matrix. All measurements were accomplished with a laboratory-constructed reflectometer. We have obtained a calibration curve by plotting the optical density of reflectance A_R vs log of the mol l⁻¹ concentration. Limits of detection at the 10⁻⁴ M level were estimated for all the compounds. Linear dynamic range extend over one order of magnitude and shows the potential of device for the quantitative analysis of environmental pollutants.     

Distribution and sources of polyfluoroalkyl substances (PFAS) in the River Rhine watershed

The concentration profile of 40 polyfluoroalkyl substances (PFAS) in surface water along the River Rhine watershed from the Lake Constance to the North Sea was investigated. The aim of the study was to investigate the influence of point as well as diffuse sources, to estimate fluxes of PFAS into the North Sea and to identify replacement compounds of perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA). In addition, an interlaboratory comparison of the method performance was conducted. The PFAS pattern was dominated by perfluorobutane sulfonate (PFBS) and perfluorobutanoic acid (PFBA) with concentrations up to 181 ng/L and 335 ng/L, respectively, which originated from industrial point sources. Fluxes of ΣPFAS were estimated to be ∼6 tonnes/year which is much higher than previous estimations. Both, the River Rhine and the River Scheldt, seem to act as important sources of PFAS into the North Sea.     

Effect of vegetation in pilot-scale horizontal subsurface flow constructed wetlands treating sulphate rich groundwater contaminated with a low and high chlorinated hydrocarbon

In order to characterize the effect of vegetation on performance of constructed wetlands (CWs) treating low and high chlorinated hydrocarbon, two pilot-scale horizontal subsurface flow (HSSF) CWs (planted with Phragmites australis and unplanted) treating sulphate rich groundwater contaminated with MCB (monochlorobenzene, as a low chlorinated hydrocarbon), (about 10 mg L⁻¹), and PCE (perchloroethylene, as a high chlorinated hydrocarbon), (about 2 mg L⁻¹), were examined. With mean MCB inflow load of 299 mg m⁻² d⁻¹, the removal rate was 58 and 208 mg m⁻² d⁻¹ in the unplanted and planted wetland, respectively, after 4 m from the inlet. PCE was almost completely removed in both wetlands with mean inflow load of 49 mg m⁻² d⁻¹. However, toxic metabolites cis-1,2-DCE (dichloroethene) and VC (vinyl chloride) accumulated in the unplanted wetland; up to 70% and 25% of PCE was dechlorinated to cis-1,2-DCE and VC after 4 m from the inlet, respectively. Because of high sulphate concentration (around 850 mg L⁻¹) in the groundwater, the plant derived organic carbon caused sulphide formation (up to 15 mg L⁻¹) in the planted wetland, which impaired the MCB removal but not statistically significant. The results showed significant enhancement of vegetation on the removal of the low chlorinated hydrocarbon MCB, which is probably due to the fact that aerobic MCB degraders are benefited from the oxygen released by plant roots. Vegetation also stimulated completely dechlorination of PCE due to plant derived organic carbon, which is potentially to provide electron donor for dechlorination process. The plant derived organic carbon also stimulated dissimilatory sulphate reduction, which subsequently have negative effect on MCB removal.     

Polychlorinated dibenzo-p-dioxins and related compounds: the blood levels of young Japanese women.

We investigated PCDDs and related compounds in the blood of young Japanese women, approximately 20 years of age, who had not yet had children, and discussed how the TEQ level of PCDDs and related compounds in their blood may affect the next generation. Means of total TEQ levels were 0.063 pg/g for whole blood basis and 21 pg/g for lipid basis. TEQ of PCDDs, PCDFs and coplanar PCBs accounted for about 43, 34 and 23% of the total TEQ in the whole blood basis, respectively. In the lipid basis, their values were about 44, 34 and 22%, respectively. Previously, we investigated PCDDs and related compounds levels in mother's breast milk, lymphocyte subpopulation and thyroid function of their children, and found negative correlations between the TEQ level of PCDDs and related compounds and CD4+/CD8+, and/or the TEQ level of PCDDs and related compounds and the T₄ level in 36 mothers and children. Of these cases, the average age was approximately 28 years. PCDDs and related compounds may be related to immunopathy, such as atopic dermatitis. The effects of PCDDs and related compounds on babies of young Japanese women are important and must be further evaluated.     

BAT and BEP as instruments for reducing emissions of unintentionally produced POPs and development of guidelines under the stockholm convention

The 6th Intergovernmental Negotiating Committee (INC 6), under the Stockholm Convention on POPs, gave an expert group the mandate to develop guidelines for the application and implementation of best available techniques (BAT) and best environmental practices (BEP) for the prevention and reduction of unintentionally produced and emitted POPs, including polychlorinated dibenzodioxins/-furans (PCDD/Fs), polychlorinated biphenyls (PCBs) and hexachlorobenzene (HCB). Measures to reduce or eliminate the release of these POPs to the environment can be found in Article 5 of the Convention. BAT and BEP are already being applied as emission reduction instruments in a number of industrialised countries and are elements of other major international treaties, e.g. the UN ECE Protocol on POPs and the Marine Convention's OSPAR and HELCOM, and of the EU Directive for Integrated Pollution Prevention and Control (IPPC Directive). Existing concepts are presented and compared with the requirements of the Stockholm Convention. Consequences, perspectives and questions for the future intersessional work of the above-mentioned Expert Group are discussed.     

Reduction in uptake by rice and soybean of aromatic arsenicals from diphenylarsinic acid contaminated soil amended with activated charcoal

Activated charcoal (AC) amendment has been suggested as a promising method to immobilize organic contaminants in soil. We performed pot experiments with rice and soybean grown in agricultural soil polluted by aromatic arsenicals (AAs). The most abundant AA in rice grains and soybean seeds was methylphenylarsinic acid (MPAA). MPAA concentration in rice grains was significantly reduced to 2% and 3% in 0.2% AC treated soil compared to untreated soil in the first year of rice cultivation. In the second year, MPAA concentration in rice grains was significantly reduced to 15% in 0.2% AC treated soil compared to untreated soil. MPAA concentration in soybean seeds was significantly reduced to 44% in 0.2% AC treated soil compared to untreated soil. AC amendment was effective in reducing AAs in rice and soybean.     

Natural attenuation of trichloroethene and its degradation products at a lake-shore site

Subsurface contamination by trichloroethene (TCE) was detected at a Michigan National Priorities List (NPL) site in 1982. The TCE plume resulted from the disposal of spent solvent and other chemicals at an industrial facility located in the eastern shore of Lake Michigan. TCE degradation products of three dichloroethene (DCE) isomers, vinyl chloride (VC) and ethene were present. The plume was depleted of oxygen and methanogenic at certain depths. Transects of the plume were sampled by slotted auger borings the year after the TCE plume was first discovered. Water samples were also taken from lake sediments to a depth of 12 m about 100 m offshore. Later samples were taken along the shoreline of the lake with a hand-driven probe. Later in 1998 water was taken from sediments about 3-m from the shoreline. The average concentration of each chemical and net apparent base coefficient between appropriate pairs of transects between the lower site and lakeshore were calculated. Loss rates were then calculated from an analytical solution of the two-dimensional advective-dispersive-reactive transport equation. Net apparent rate coefficients and a set of coupled reaction rate equations were used to extract the apparent loss coefficients. This study showed the field evidence for natural attenuation of TCE.     

Using a Set of Strategic Indicator Systems as a Decision-making Support Implement for Establishing a Recycling-oriented Society - A Taiwanese Case Study (16 pp)

Background Scope and Aims. To realize the vision of sustainable development (SD) originating from the ‘only one earth’ philosophy, and to integrate the conceptions of ecology and sustainability into the planning and decision-making criteria of urban growth management, the establishment of a recycling-oriented society (ROS) is essential. However, before the above intention can be achieved, it is indispensable to develop a system of strategic indicators for supporting a radical reformation of the urban development plan. Therefore, this study, based on the conception of the new urban development pattern ROS, attempted to carefully choose a sample city in Taiwan for launching a preliminary case study, and furthermore designed and proposed a concise and strategy-oriented assessment indicator system termed ROSAIS. ROSAIS, on the one hand, can act as a compass for understanding resource using efficiency and recycling status during city development and, on the other hand, can serve as an implement supporting decision-making for ROS construction.Methods According to the definition and spirit of ROS, the structure of ROSAIS should clearly represent the relationship between resources and environment in human activities. The eco-efficiency indicator system (EEIS) and environmental symbiosis indicator system (ESIS) can be considered two key sub-indicator systems, and are the necessary components of ROSAIS. EEIS chooses the dominant production sectors in urban economic activities to calculate their eco-efficiency (EE). Separately, for obtaining a consensus regarding the framework of ESIS, the questionnaire approaches and expert consultation, together with the research experience and foundation of current relevant studies and indicator systems, are applied when crucial resource and environmental issues and respective indicators are selected.Results and Discussion The calculation results of EEIS in this case study indicated that among the three dominant production activities (agricultural, fishery, and animal husbandry sector) the fishery sector has the highest EE, which indicates that the fishery activities and resources significantly influence the sustainability of the economic-environmental system of the sample city. Furthermore, according to a consensus achieved in ESIS, local green spaces, resource recovery, energy consumption pattern change, freshwater conservation and greenhouse effect abatement were considered as the five crucial issues influencing how the case study city can develop into an ES-city. The rate of local green spaces, resource recycling, freshwater conservation and the rate of reduction of nonrenewable energy use as well as carbon dioxide (CO2) emissions were used to evaluate the above five issues.Conclusion This case study is unparalleled in Taiwan. Even in Japan, where ROS legislation has been implemented, this kind of study remains in the preliminary stages. Furthermore, when communicating the indicator results, it is essential to provide the context and countermeasures of the crucial issues that are faced. The two sub-indicator systems proposed in this case study could comply completely with the above-mentioned requirements. For example, the EEIS provides information for achieving a balance between environmental burden and economic benefits among dominant production sectors; the ESIS provides information for setting strategies for overcoming the crucial issues faced. Recommendation and Outlook This study recommends that urban planers should consider the construction of the corresponding strategic indicator system to be indispensable, and makes further use of the indicator results related to the environmental education of residents for identifying and promoting participation with ROS, and turning them into implements for supporting urban SD decision-making. Furthermore, a successful indicator system depends on data availability and quality. This study recommends that urban planers should pay considerable attention to constructing relevant data collection channels, databases and the data quality.     

Emissions from soil fumigation in two raised bed production systems tarped with low permeability films

Raised beds are used to produce some high-value annual fruit and vegetable crops such as strawberry in California (CA) and tomato in Florida (FL), USA. Pre-plant soil fumigation is an important tool to control soil-borne pests in the raised beds. However, fumigant emissions have detrimental environmental consequences. Field trials were conducted to evaluate emissions of 1,3-dichloropropene (1,3-D) and chloropicrin (CP) in two different production systems with raised beds covered by different tarps. In the CA trial, InLine (60.8% 1,3-D and 33.3% CP) was drip-applied at 340 kg ha⁻¹ to 5 cm deep in the beds (30 cm high and 107 cm wide) tarped with polyethylene (PE) or virtually impermeable film (VIF). In the FL trial, carbonated Telone C35 (63.4% 1,3-D and 34.7% CP) was shank-applied at 151 kg ha⁻¹ to 20 cm deep in the beds (22 cm high and 76 cm wide) tarped with totally impermeable film (TIF). Emissions from tarped beds relative to furrows were contrary between the two trials. For the CA trial, the emission was 47% of applied 1,3-D and 27% of applied CP from PE tarped beds and 31% of applied 1,3-D and 15% of applied CP from VIF tarped beds, while that from uncovered furrows was <0.4% for both chemicals in both fields. In the FL trial, only 0.1% 1,3-D was emitted from the TIF tarped beds, but 27% was measured from the uncovered furrows. Factors contributing to the differences in emissions were chiefly raised-bed configuration, tarp permeability, fumigant application method, soil properties, soil water content, and fumigant carbonation. The results indicate that strategies for emission reduction must consider the differences in agronomic production systems. Modifying raised bed configuration and fumigant application technique in coarse textured soils with TIF tarping can maximize fumigation efficiency and emission reduction.     

Assessment of Organochlorine Pesticide Residues in Water,Sediment, and Fish of the Songhua River,China

This study examined residual concentrations and associated ecological risks of the organochlorine pesticides (OCPs) hexa- chlorocyclohexane (HCH) and dichloro-diphenyl-trichloroethane (DDT) in water, sediment, and fish of the Songhua River in Zhaoyuan County, China. In June 2012, 10 water, 10 sediment, and 20 fish samples were collected. Residual concentrations of ΣHCH and ΣDDT ranged from 10.0–35.59 ng L^?1 (mean 28.03 ± 11.66 ng L^?1) and 5.12–39.66 ng L^?1 (mean 32.36 ± 11.58 ng L^?1) for water. Residual concentrations of ΣHCH and ΣDDT ranged from 0.52–3.00 ng g^?1 (mean 2.04 ± 0.73 ng g^?1) and 0.34–3.41 ng g^?1 (mean 2.38 ± 0.92 ng g^?1) for sediment. The ratios of α-HCH/γ-HCH were close to 1 at the majority of sampling points, indicating considerable new pollution from the use of lindane. The ratios of p,p′-DDE + p,p′-DDD/ΣDDT were less than 0.5, indicating recent inputs from DDT impurities in dicofol. All HCH and DDT isomers except for p,p′-DDD were detected in fish tissue samples, but the associated ecological risks were estimated to be below levels of concern. The study revealed a historical usage of OCPs in the Zhaoyuan section of the Songhua River and new OCP from the use of lindane and dicofol.