Study on the photocatalytic reduction of dichromate and photocatalytic oxidation of dichlorvos

In this paper, dichromate and dichlorvos are selected as the deputies of inorganic and organic pollutants, respectively, and TiO2/beads is used as a photocatalyst. The effects of various parameters, such as the amount of the photocatalyst, H2O2 concentration, metal ions, anions, pH value, and organic compounds on the photocatalytic reduction of dichromate and photocatalytic oxidation of dichlorvos are studied. From the studies, the differences of the parameters effect on the photocatalytic degradation of organic and inorganic pollutants are obtained. The results show that the optimum amount of the photocatalyst used is 6.0 g cm(-3) for the photocatalytic reactions. With the addition of a small amount of H2O2, the photocatalytic reduction of dichromate is inhibited while the photocatalytic oxidation of dichlorvos is accelerated. With the addition of trace amounts of Fe3+ or Cu2+, both the reactions are accelerated, and with the addition of Zn2+ and Na+, no obvious effects on the reactions are observed. Acidic solution is favorable for the photocatalytic reduction of dichromate; and acidic and alkaline solutions are favorable for the photocatalytic oxidation of dichlorvos. Adding SO4(2-), the photocatalytic oxidation is accelerated and adding Cl- the reaction is inhibited; and with the addition of trace amounts of SO4(2-), Cl- and NO3-, no obvious effects on the photocatalytic reduction of dichromate are observed. With the addition of methanol and toluene, the photocatalytic reduction of dichromate is accelerated, and the photocatalytic oxidation of dichlorvos is inhibited. The possible roles of the additives on the reactions are also discussed.     

污泥堆肥施用于草坪草栽培：Zn和Cu的分布特征

为了探索污泥堆肥中重金属在土壤一植物系统中的积累与转移特性,通过温室盆栽实验,分析了污泥堆肥对草坪草高羊茅、黑麦草和白三叶生物量积累的情况,研究了污泥堆肥中Zn和Cu在植物和土壤中的分布特征。结果表明,污泥堆肥施用可以有效促进3种草坪草的积累生物量,在0～6kg／m2的污泥堆肥施用量范围内,草坪草的生物量积累随着施用量的增加而提高。土壤中Zn和Cu的含量随污泥堆肥施加量的增加而增大,85％以上的Zn和Cu残留在土壤中。污泥堆肥中的Zn和Cu均可以被植物吸收,随着污泥堆肥施用量的增加,草坪草对Zn和Cu的吸收量增大,但当污泥堆肥施用量超过一定阈值时,草坪草吸收zn和cu不再增加,甚至减少;对于不同的草坪草,这一阈值有所不同。植物对zn和cu的吸收量只占土壤中zn和cu减少量的5％左右。根据生物富集系数（BCF）的计算结果推测,污泥堆肥的施用对土壤环境的影响大于对植物体内累积zn和Cu的影响。     

市政污泥热解特性及含碳官能团演化过程分析

我国市政污泥年产量大,研究其热解机理和碳形态转化可为实现污泥无害化和资源化提供理论基础。采用热重、动力学拟合、红外光谱 (FTIR) 、X射线光电子能谱 (XPS) 等检测和分析方法,对市政污泥热解特性、活化能变化和含碳官能团进行分析。结果表明：市政污泥热解过程中含碳官能团的生成在不同的阶段存在差异,进一步采用Kissinger-Akahira-Sunose (KAS) 法、Flynn-Wall-Ozawa (FWO) 法和Friedman法进行动力学分析,其活化能结果显示在转化率为0.40~0.70时,市政污泥热解速率加快,污泥中含碳官能团加速发生热解转化。FTIR和XPS结果表明,在400 ℃以下时,醇羟基的分解是导致污泥结构中羟基减少的主要原因。在400 ℃时,酚羟基和C=O键相对质量分数最多,而在500 ℃时,羧基和C-O键相对质量分数最高。C=C键和C-N键随温度升高持续减少,C-C结构则先减少后增加,在500 ℃时相对质量分数最低,而芳香结构随温度的上升持续增加。在400~600 ℃内,污泥残炭的含碳氧官能团较多,吸附性和稳定性较高。本研究结果可为市政污泥热解机理及碳形态转化提供参考。     

我国土壤环境管理名录制度实施中的问题分析和对策

我国污染地块土壤环境管理的基本制度包括疑似污染地块名单制度、污染地块名录制度、建设用地土壤污染风险管控和修复名录制度。分析了3项制度的主要内容和执行现状,提出了实施中存在的6个问题,阐述了6个方面的对策建议。分析认为,目前疑似污染地块名单和污染地块名录制度未明确“退出”程序和要求;制度的实际执行情况与管理办法的要求不一致;各地纳入疑似污染地块名单的地块数量明显偏少;信息公开的渠道与内容未做统一要求;初步调查报告的编制和评审要求在现行技术规范中缺乏足够阐述;风险管控和修复名录制度对工程实施的变更程序、是否明确设置工程设计环节等未做出明确规定。最后,提出在污染地块环境管理办法修订过程中应增加“退出”疑似污染地块名单和污染地块名录的条件和要求、信息公开渠道与内容,明确由项目业主单位自行确定是否开展工程设计,将疑似污染地块名录的制定和信息公开责任调升为市级生态环境主管部门负责,并细化《建设用地土壤环境调查评估技术指南》中的初步调查布点要求和采样深度要求,加快省级风险评估报告和效果评估报告评审细则文件的制定等建议,以期为我国土壤环境管理部门提供决策参考。     

新疆油田含油污泥破乳-离心脱水工艺优化

针对新疆油田含油污泥成分复杂、油水分离困难、处理难度大的特性,基于破乳剂、絮凝剂和助剂的油水高效破乳、絮体混凝沉降和助剂骨架强化脱水作用,使用复合调理剂对其进行了处理;并采用响应曲面法研究了破乳剂复配比例、温度、絮凝剂质量浓度对破乳脱水效果的影响。结果表明,各因素影响程度排序为：温度>破乳剂比例>絮凝剂质量浓度。高温有利于污泥脱水的主要原因是,高温有助于降低体系粘度、提升水滴流动性、推动水滴热运动,进而辅助水滴的团聚,最终实现油水分离。在最佳操作条件下(破乳剂NP-9∶SDBS为9∶1且质量浓度为4 g·L⁻¹、温度51 ℃、絮凝剂质量浓度为16 mg·L⁻¹、生石灰加量为1%)进行含油污泥破乳离心分离脱水,脱水率可达92.55%。SEM观察结果表明,复配破乳剂通过改变油泥的堆积方式、增加泥块的疏松程度、增大泥块的孔洞来提高油泥的脱水性能。本研究结果可以为含油污泥减量化处理的现场应用提供参考。     

Natural formation and degradation of chloroacetic acids and volatile organochlorines in forest soil--challenges to understanding

- DOI: http:/dx.doi.org/10.1065/espr2005.06.262 Goal, Scope and Background The anthropogenic environmental emissions of chloroacetic acids and volatile organochlorines have been under scrutiny in recent years because the two compound groups are suspected to contribute to forest dieback and stratospheric ozone destruction, respectively. The two organochlorine groups are linked because the atmospheric photochemical oxidation of some volatile organochlorine compounds is one source of phytotoxic chloroacetic acids in the environment. Moreover, both groups are produced in higher amounts by natural chlorination of organic matter, e.g. by soil microorganisms, marine macroalgae and salt lake bacteria, and show similar metabolism pathways. Elucidating the origin and fate of these organohalogens is necessary to implement actions to counteract environmental problems caused by these compounds. Main Features While the anthropogenic sources of chloroacetic acids and volatile organochlorines are relatively well-known and within human control, knowledge of relevant natural processes is scarce and fragmented. This article reviews current knowledge on natural formation and degradation processes of chloroacetic acids and volatile organochlorines in forest soils, with particular emphasis on processes in the rhizosphere, and discusses future studies necessary to understand the role of forest soils in the formation and degradation of these compounds. Results and Discussion Reviewing the present knowledge of the natural formation and degradation processes of chloroacetic acids and volatile organochlorines in forest soil has revealed gaps in knowledge regarding the actual mechanisms behind these processes. In particular, there remains insufficient quantification of reliable budgets and rates of formation and degradation of chloroacetic acids and volatile organochlorines in forest soil (both biotic and abiotic processes) to evaluate the strength of forest ecosystems regarding the emission and uptake of chloroacetic acids and volatile organochlorines, both on a regional scale and on a global scale. Conclusion It is concluded that the overall role of forest soil as a source and/or sink for chloroacetic acids and volatile organochlorines is still unclear; the available laboratory and field data reveal only bits of the puzzle. Detailed knowledge of the natural degradation and formation processes in forest soil is important to evaluate the strength of forest ecosystems for the emission and uptake of chloroacetic acids and volatile organochlorines, both on a regional scale and on a global scale. Recommendation and Perspective As the natural formation and degradation processes of chloroacetic acids and volatile organochlorines in forest soil can be influenced by human activities, evaluation of the extent of this influence will help to identify what future actions are needed to reduce human influences and thus prevent further damage to the environment and to human health caused by these compounds.     

基于NIR混合废塑料识别仪分选效率的模型

通过对近红外光谱（NIRS）识别分选混合废塑料的过程建立数学模型,将经过预处理的废塑料在传送带上的分布分为密集区和稀疏区两大类。以降低分选时间,提高分选效率为研究目的,对影响分选效率的因素进行分析,如分选机所能承受物料密集度上限值θ以及传送带的传输速度V等因素。比较不同θ和V的组合对总分选时间T的影响,通过数值计算并验证,求得最优组合解。研究结果表明：θ的大小影响密集区和稀疏区的面积在总面积中占有量的变化;分选总时间T在θ和V共同变化过程中存在极小值。     

Study of fractionation and potential mobility of metal in sludge from pyrite mining and affected river sediments: changes in mobility over time and use of artificial ageing as a tool in environmental impact assessment

Sludge from mining exploitation can be a source of land and water contamination in the adjacent zone. Accidents such as the break of waste mining pools in the Aznalcollar Mine (Seville, Spain) in 1998 produce important ecological disasters. In this work is presented a study of the evolution of aqua regia leachable concentration and mobility of metals in sediment samples of Guadiamar River basin from the accident date up to 2001. The application of BCR standard extraction procedures provides valuable information about the mobility and toxicity of the spill and the metal mobility in Guadiamar River polluted sediments. As a rule, themobility of several metals in the initial sludge (sulphides) is low, except for copper. Otherwise, the results of aqua regia leachable concentration and mobility of metal obtained for sediments samples indicate that the cleaning and inertisation works carried out in the zone have been adequate but insufficient, being the metal levels observed in the zone are higher than natural levels. To establish the initial impact of the spill and the mobility changes with time, mineralogical composition of the pyritic sludge and its evolution after the natural weathering and after the induction, of accelerated ageing processes by light and temperature was studied in the laboratory. Oxidation of initial sulphides to sulphates was observed. Both environmental and laboratory oxidation of the metallic sulphides increase the mobility of all metals, especially of copper, zinc and lead. The proposed laboratory procedure allows to predict the changes in mobility and therefore in toxicity that can occur at short or long term after exposure of sludge at environ-mental conditions. The mobility results in sludge and sediment samples are interpreted in terms of the mineral composition of the samples.     

重金属和抗生素胁迫对亚硝酸盐氧化菌及硝化菌群活性的影响

重金属和抗生素广泛存在工业废水、养殖水体中,对硝化细菌活性有不同程度的影响。为研究重金属和抗生素胁迫对亚硝酸盐氧化菌(nitrite-oxidizing bacteria,NOB)及硝化菌群活性的影响,采集珠江水样富集硝化菌群并分离纯化NOB,研究了不同浓度重金属离子(Cu²⁺、Zn²⁺、Cd²⁺、Mn²⁺、Cr⁶⁺)和抗生素(卡那霉素、氨苄青霉素、链霉素、盐酸四环素)对NOB亚硝酸盐氧化活性的影响,揭示了不同重金属和抗生素胁迫对NOB及硝化菌群富集物活性的影响。结果表明：第15代富集培养的硝化菌群中Nitrosomonas丰度由0.11%升高至10.04%,Nitrobacter丰度由0.014%上升到2.104%;经鉴定,分离纯化的NOB菌株与Nitrobacter winogradskyi相似性为99.58%;NOB的亚硝酸盐氧化活性随重金属离子、抗生素浓度升高而下降;在初始NOB量相等情况下,与NOB组相比,硝化菌群富集物实验组在重金属或抗生素胁迫下,亚硝酸盐氧化速率更快,稳定性更高,对重金属和抗生素的抗逆性更强,对于处理含氮废水的实际应用潜力更大。该研究结果可为NOB的研究和在工业、养殖业水体净化的开发应用提供参考。     

稻秆负荷与pH对稻秆厌氧发酵产酸系统启动过程的影响

为探讨稻秆负荷（即稻秆VS/污泥VSS）与发酵pH对稻秆厌氧发酵产酸系统启动过程产挥发性脂肪酸（VFAs）效果的影响,利用厌氧搅拌罐反应系统考察在不同的稻秆负荷（0.556、0.945、1.334和1.724 g/g）和不同的发酵pH（8.0、9.0和10.0）启动运行条件下的产酸性能,并分析了系统启动过程产酸与稻秆主要成分降解之间的关系。实验结果表明,VFAs浓度随稻秆负荷提高而增大,随发酵pH的升高而降低;发酵18 d时,发酵pH为9.0时,稻秆负荷1.334 g/g的产酸效果最好,VFAs浓度与稻秆产酸量分别为4 385.10 mg/L和2.19 gVFAs/g稻秆,此时半纤维素、纤维素和酸性洗涤木质素降解率分别为32.69%、22.53%和6.40%;稻秆负荷为0.945 g/g条件下,VFAs浓度在pH为8.0时达到最高值4 409.51 mg/L,此时稻秆降解量也最多,半纤维素、纤维素和酸性洗涤木质素降解率分别为28.60%、47.32%和22.69%。研究表明,稻秆负荷与发酵pH通过影响稻秆半纤维素、纤维素和木质素的降解影响稻秆厌氧发酵产酸的进程和效果。     

Development of continental scale multimedia contaminant fate models: integrating GIS

The incentives and approaches for modelling chemical fate at a continental scale are discussed and reviewed. It is suggested that a multi-media model consisting of some 20-30 regions, each of which contains typically seven environmental compartments represents a reasonable compromise between the issues of the need for detailed resolution, avoidance of excessive data demands and inherent complexity and transparency. Strategies adopted in compiling the Berkley-Trent (BETR) model for North America are discussed and used to illustrate the issues of selecting appropriate number and nature of segments, treatment of air and water flows and the acquisition of environmental data. It is suggested that GIS software can play a valuable role in gathering and processing such data and in the display and interpretation of the results of the model assessment. The BETR model will be a useful tool for describing the nature of persistence and long-range transport of chemicals of concern in the North American environment.     

钢铁厂露天堆料场挡风抑尘墙效果的数值模拟

对某钢铁厂露天堆料场设置挡风抑尘墙进行数值模拟研究,通过对动力阴影区覆盖面积的考察,分析了自然风速、墙高、墙开孔率及墙后建构筑物对挡风抑尘墙的挡风抑尘效果的影响.该钢铁厂露天堆料场设置防风抑尘墙的最佳几何尺寸是:墙长(L)为500 m,墙厚(d)为5 mm,墙高(H)为15～20 m,墙开孔率(k)为0.2～0.3,在主导风风速达到10 m/s以上的大风天气能够形成有效覆盖整个料场的动力阴影区,再配以合适的喷雾洒水或喷洒化学抑尘剂等其他抑尘手段就能够非常有效地抑制料场扬尘.     

氧化/吸附/混凝协同工艺处理焦化废水生物处理出水的过程及效果分析

针对焦化废水生物处理出水中继续存在多种有机污染物而影响达标及存在安全隐患的现状,基于废水中有机物的物理化学特性,构建了氧化/吸附/混凝的深度处理过程。在NaC lO投加量为40 mg/L,AC投加量为500 mg/L,PFS投加量为300 mg/L,反应时间为0.5 h,以及pH为7.0的最佳条件下,先氧化后吸附混凝,该过程可以实现COD去除率为75%以上,色度去除率80%以上,处理后的水样其COD值与色度值分别下降到60 mg/L及20倍以下;通过GC/MS方法分析处理前后水样中的有机物组分,发现水样中大部分单环芳香族化合物和多环芳香族化合物,部分含氮杂环化学物、有机氯化物以及溴化物被去除,但是,长链烷烃和部分芳香烃继续保留。研究结果证明了氧化/吸附/混凝协同工艺的效果与焦化废水生物出水中有机污染物的分子结构、存在形态形成构效关系,催化作用与氧化作用的协同是获得高效去除率的关键。     

固定污染源污水排放口及监测点位规范设置技术

为规范我国固定污染源污水排放口及监测点位设置,以保障污水样品采集和流量监测的准确性与代表性,在调研与查阅国内外技术文献的基础上,总结了我国现有固定污染源污水排放口和监测点位设置中存在的主要问题,探讨了国内外相关标准规定的缺陷和不足;基于保障实际监测工作需要和便于监督管理的原则,兼顾流量监测的准确性、样品采集的代表性与监测人员采样安全考虑,探讨了排污单位污水排放口与监测点位数量、位置设置技术。结果表明：排污单位不得通过暗管排放污水,应在厂界10 m以内设置1个污水总排放口和1个雨水总排放口及监测点位,排放第1类污染物及其他有毒有害或需优先控制的污染物指标时需同时在车间或车间处理设施出口设置排放口和监测点位;污水日排放量超过50 t·d⁻¹的排放口应按国家标准规范要求选择修建或安装适宜的标准化量水堰槽;其他排放口应修建满足污水采样监测和流量监测、长度不少于3 m的顺直排水明渠及高度不少于0.1 m的垂直跌水落差;通过压力管道排放污水时,应修建长度不少于15倍管径且需时刻满管的直管段,以安装管道流量计和取样阀门。排污单位须设置污水排放口环境保护图形标志与监测点位信息标志,制定污水排放口和监测点位的保障监测安全的防护措施及日常维护和管理的规定。污水排放口和监测点位的有关构筑物及相关设施应作为环境保护设施的组成部分,与主体工程“同时设计、同时施工、同时投产和使用”,且应作为建设项目竣工环境保护验收的必要条件。相关研究结果可为污水排放口和监测点位规范化整治提供技术依据,并为保证污水采样、监测与监管的安全有效实施提供技术保障。     

pH和有机质对铬渣污染土壤中Cr赋存形态的影响

选用3种不同的铬渣污染土壤作为试验样,通过调节其pH和有机质含量,并采用碱消解-共沉淀法和改良BCR顺序提取法,研究了pH和有机质含量对土壤中铬的价态及形态的影响。结果表明,总体上Cr(Ⅵ)含量随pH降低和有机质投加量增大而减小,Cr(Ⅲ)则增加,但土1各水平间差异均显著(F8.89),土2和土3只有部分水平间差异显著。同时,随pH降低和有机质投加量增大,酸可提取态Cr含量减小,可氧化态Cr增加,可还原态略有增加,表明酸性条件和有机质有利于Cr(Ⅵ)的还原和酸可提取态Cr向可还原态和可氧化态Cr的转化。     

电絮凝对电厂循环冷却水中硬度的去除

以某电厂冷却塔循环冷却水为处理对象,利用电絮凝法,以铝板为牺牲阳极去除水中的Ca²⁺和Mg²⁺,分别考察了电絮凝过程中不同电流密度、电解时间、溶液初始pH、阳极极板数量对总硬度去除率的影响。结果表明：增加电流密度、延长电解时间有利于Ca²⁺和Mg²⁺的去除;当电流密度为10 mA·cm⁻²,电解时间为90 min时,Ca²⁺和Mg²⁺去除率分别达到93.5%和95.8%,总硬度去除率为94.6%;相对于酸性和中性条件,碱性条件更有利于Ca²⁺和Mg²⁺的去除,当初始pH为10时,Ca²⁺和Mg²⁺去除率分别达到85.4%和97.7%,总硬度去除率为93.5%;随极板数量的增加,Ca²⁺和总硬度去除率均有所提高;投加Na₂CO₃有利于Ca²⁺和总硬度的去除。上述结果可为进一步提高电絮凝过程中总硬度的去除率提供参考。     

堆肥污泥施用于杨树后土壤理化性质及土壤污染风险

污泥可作为一种土壤改良剂应用于树木,特别是杨树。采用田间实验,探讨堆肥污泥施用于杨树后的土壤理化性质和土壤污染风险,以期为污泥的合理利用提供科学依据。通过2年的田间实验研究了不同堆肥污泥用量对土壤营养成分和重金属污染的影响,实验设置4个处理：对照、低量、中量和高量。结果表明,随着污泥用量的增加,土壤营养成分和重金属的质量分数均有所提高,而且堆肥污泥可显著降低土壤pH,高量污泥可使土壤碱性降为中性。污泥累计施用后,除了低量对K、Na、Cd 和Pb质量分数影响不显著外,污泥处理均对土壤营养成分和重金属的质量分数影响显著;中量和高量污泥处理使土壤有机质增加1.2和1.6倍,有效氮增加1.2和1.9倍,N、P及K质量分数分别增加2.7和2.9倍、2.8和4.3倍及0.6和0.7倍。土壤中Cu、Zn、Ni、Cr、Hg和Pb质量分数均没有超出我国农用地土壤污染风险筛选值和管制值范围(GB 15618-2018);Cd质量分数超过了土壤污染风险筛选值,但也远低于土壤污染风险管制值。本研究可为将堆肥污泥作为土壤改良剂应用于杨树提供参考。     

我国污染地块安全开发利用模式与安全性评价方法

随着对污染地块安全开发利用认识的不断深入,污染地块安全开发利用模式及开发利用的安全性评价日益受到重视。从广义和狭义2个层面分别阐述了污染地块安全开发利用模式的含义,并重点对“四分”总体修复策略和“五个特性”技术策略共同构成的狭义层面上的安全开发利用模式进行了阐释,分析了影响模式选择的5个影响因素。在此基础上,构建出一套包含5个一级指标、10个二级指标的污染地块开发利用“安全性”评价指标体系,提出了各指标的评价方法。本研究旨在提出对我国在污染地块安全开发利用模式及安全性评价方法开展深入研究,并为污染地块修复技术的比选和评价、开展修复（管控）工程的评价提供参考,进而推动我国污染地块的绿色可持续发展。     

长三角示范区饮用水水源水质安全与实体性制度协同立法

在对长三角生态绿色一体化发展示范区(以下简称示范区)饮用水水源保护所涉立法和实务部门进行广泛调研的基础上,研究和探讨了示范区饮用水水源的立法现状与水质状况、水质安全问题的主要成因、协同立法的理论基础和有利条件,并就协同立法的形式选择和核心内容提出了具体建议.研究发现,水质安全与相关实体性制度的构建是示范区饮用水水源保护...     

Assessing the health risk of reuse of bottom ash in road paving

Although the reuse of bottom ash has been favored gradually, reflected on regulations and researches, the associated risk is still an issue of great concern. This study quantified the health risks from multimedia transport and multi-pathway exposure to the concerned chemicals as a result of reusing bottom ash in road paving with consideration of various application scenarios. In particular, the using duration of the pavement was taken into consideration because movement of chemicals in the soils and groundwater would affect the subsequent exposure and risk. By using soil and groundwater transport modeling linked to food chain exposure assessment and incorporating the Monte Carlo method, the study identified Cr as the crucial toxicant and ingestion of drinking water and vegetables as the key exposure pathways. Furthermore, control of the using duration of road pavement is an essential factor of management and regulations to minimize the leaching of the hazardous constituents into the groundwater and subsequent contamination of food chain.