还原——固液法镀铬废水处理后Cr(Ⅵ)反弹成因与防治对策

从化学热力学和电化学理论出发,结合目前普遍采用的还原-固体分离法处理含铬废水工艺步骤,对固-液分离后的上清液和沉降污泥Cr(Ⅵ)含量以及Cr(Ⅲ)-Cr (Ⅵ)之间的形态转化相关性进行研究和分析,进而提醒人们要特别注意控制含铬污水中铬反弹及全过程处理的完整性。     

煤矸石酸雨淋滤特征的研究

本文对重庆中梁山煤矸石在自然酸度和模拟酸雨下静态态及动态淋溶特征进行了研究。结果表明,淋出液成弱碱性,其中的铅、锌、铬、镍、铜和铁等元素的浓度均超过了水综合排放标准和地面水环境质量标准规定的阈值;在模拟酸雨中上述离子的溶出能力强于在于蒸溜水中;温度升高时各元素及总离子的淋出量增大。     

Cr(Ⅵ)/亚硫酸钠体系快速氧化活性蓝4的动力学研究

亚硫酸钠还原法是目前处理含Cr(Ⅵ)废水的常用方法之一,在Cr(Ⅵ)/亚硫酸钠体系中加入染料活性蓝4时,Cr(Ⅵ)被还原去除的同时,活性蓝4也会被快速氧化。初始p H为4.0时,100μmol/L Cr(Ⅵ)与1 mmol/L亚硫酸钠可在3.5min内快速氧化20μmol/L活性蓝4,Cr(Ⅵ)的剩余浓度也低于其排放标准。提高亚硫酸钠浓度至3mmol/L时,活性蓝4在12s内被完全氧化。对活性蓝4的氧化动力学进行假一级拟合,其速率常数随p H降低而升高,p H由6.0降低至3.5时,速率常数由0.000 6 s-1升高至0.012 9 s-1。在较高的亚硫酸钠浓度和较酸性环境下,Cr(Ⅵ)和亚硫酸钠之间的反应加快,产生中间态活性氧化剂的速率提高,使得Cr(Ⅵ)/亚硫酸钠体系降解活性蓝4的效果更优。该体系通过Cr(Ⅵ)和亚硫酸钠之间的反应,首先产生了亚硫酸根自由基SO·-3,在氧气的作用下,SO·-3经过一系列反应产生了二级自由基,即高活性的硫酸根自由基SO·-4和羟基自由基·OH,这两种自由基作为体系中的中间态活性氧化剂,实现了对活性蓝4的氧化。     

含Cr（Ⅵ）废水生物处理技术及其影响因素

本文综述了微生物还原处理含价铬的废水的研究进展。讨论了影响微生物还原Cr(Ⅵ）因素包括生物体密度、初始Cr（Ⅵ）的浓度、碳源、pH、温度、溶解氧、氧化还原电位、含氧阴离子和金属离子。微生物还原Cr（Ⅵ）技术作为一种富有创新的研究应用于Cr（Ⅵ）污染的环境恢复。     

木屑分离铬（Ⅵ）的应用研究

探讨了木屑分离格（Ⅵ）的条件，研究了酸度。温度、吸附时间及铬（Ⅲ）与某些离子对木屑分离铬（Ⅵ）的影响。结果表明，木屑对铬（Ⅵ）具有高选择性吸附特性，用木屑可成功地处理环境中含Ｃｒ（Ⅵ）水样，有效地降低水质中Ｃｒ（Ⅵ）的浓度，因此可以降低Ｃｒ（Ⅵ）对环境产生的污染程度，以便最终消除铬的污染。     

木屑分离铬（VI）的应用研究

探讨了木屑分离铬（ＶＩ）的条件，研究了酸度，温度、吸附时间及铬（Ⅲ）与某些离子对木屑分离铬（Ⅵ）的影响。结果表明，木屑对铬（Ⅵ）具有高选择性吸附性，用木悄可成功地处理环境中含Ｃｒ（Ⅵ）水样，有效地降低水质中Ｃｒ（Ⅵ）浓度，因此可以降低Ｃｒ（Ⅵ）对环境产生的污染程度，以便最终消除铬的污染。     

新安江-钱塘江流域水环境健康风险评价研究

本文采用美国环境保护署推荐的水环境健康风险评价模型,对新安江—钱塘江流域水体通过饮水途径导致的人体健康风险进行评价。结果表明:水环境质量监测的11项污染物浓度均符合或优于地表水三类标准。对人体有健康风险的有毒污染物主要是化学致癌物Cr(Ⅵ);非致癌物中氨氮的健康风险最大;个人化学致癌物年总风险远大于非致癌物年总风险;2014年新安江—钱塘江流域的三都大桥断面、西区、闸口、七堡断面的水环境健康个人总年风险均超过国际辐射防护委员会推荐的标准,分别超标0.03、0.69、0.20、0.23倍,其主要原因是这些断面的Cr(Ⅵ)的风险略高。因此,加强对化学致癌物Cr(Ⅵ)的管控,是降低水环境健康风险的有效途径。     

铁-空气燃料电池体系用于还原固定Cr(Ⅵ)

采用了由铁阳极和空气阴极构成的单室铁-空气原电池(IAFC)替代传统的EC法还原固定Cr (Ⅵ),并且通过实验研究了电解质浓度、溶液pH值和气体氛围对Cr (Ⅵ)去除的影响。实验结果表明,随着溶液的pH值从6.0降低到3.0,Cr (Ⅵ)的去除速率逐步提高,并伴随着功率密度从1 040 mW/m~2升高到2 880 mW/m~2。此外,将Na_2SO_4浓度从0.01 mol/L提高到0.1 mol/L,也促进了Cr (Ⅵ)的去除。     

混凝处理皮革废水研究

利用混凝剂对皮革废水进行处理，包括综合废水、铬鞣液及加碱处理后铬鞣液。对三种无机混凝剂和十种有机混凝剂进行了初步筛选。结果表明，混凝处理对三种废水均有一定作用，最适用于综合废水，而铬鞣液直接混凝效果不佳。最佳混凝剂为PAM(分子量900x10^4—1200x10^4)40mg／L Al2(S04)3 1000mg／L，色度能完全去除，对SS、COD、Cr的去除率也较高。     

锰改性活性炭对Cr(Ⅵ)的吸附研究

Cr(Ⅵ)是一种高毒性重金属.为了探究炭质材料对水中六价铬的吸附行为,首次尝试用不同浓度的锰离子溶液对颗粒活性炭进行改性,研究了包括pH、温度、投加量和Cr(Ⅵ)初始浓度对原活性炭和改性活性炭的对比实验.结果表明在相同的条件下锰离子改性可以增加活性炭对Cr(Ⅵ)的吸附容量,溶液pH、温度、投加量和初始浓度对CKⅥ)的去除率有很大影响.活性炭对Cr(Ⅵ)的吸附等温线与Langrmuir模型有更好的线性相关性.     

Leachability of dissolved chromium in asphalt and concrete surfacing materials

Leachate metal pollutant concentrations produced from different asphalt and concrete pavement surfacing materials were measured under controlled laboratory conditions. The results showed that, in general, the concentrations of most metal pollutants were below the reporting limits. However, dissolved chromium was detected in leachate from concrete (but not asphalt) specimens and more strongly in the early-time leachate samples. As the leaching continued, the concentration of Cr decreased to below or close to the reporting limit. The source of the chromium in concrete pavement was found to be cement. The concentration of total Cr produced from leachate of different cement coming from different sources that was purchased from retail distributors ranged from 124 to 641 μg/L. This result indicates that the potential leachability of dissolved Cr from concrete pavement materials can be reduced through source control. The results also showed that the leachability of dissolved Cr in hardened pavement materials was substantially reduced. For example, the concentration of dissolved Cr measured in actual highway runoff was found to be much lower than the Cr concentration produced from leachate of both open and dense graded concrete pavement specimens under controlled laboratory study. It was concluded that pavement materials are not the source of pollutants of concern in roadway runoff; rather most pollutants in roadway surface runoff are generated from other road-use or land-use sources, or from (wet or dry) atmospheric deposition.     

The influence of biochar and black carbon on reduction and bioavailability of chromate in soils

The widespread use of chromium (Cr) has a deleterious impact on the environment. A number of pathways, both biotic and abiotic in character, determine the fate and speciation of Cr in soils. Chromium exists in two predominant species in the environment: trivalent [(Cr(III)] and hexavalent [Cr(VI)]. Of these two forms, Cr(III) is nontoxic and is strongly bound to soil particles, whereas Cr(VI) is more toxic and soluble and readily leaches into groundwater. The toxicity of Cr(VI) can be mitigated by reducing it to Cr(III) species. The objective of this study was to examine the effect of organic carbon sources on the reduction, microbial respiration, and phytoavailability of Cr(VI) in soils. Organic carbon sources, such as black carbon (BC) and biochar, were tested for their potential in reducing Cr(VI) in acidic and alkaline contaminated soils. An alkaline soil was selected to monitor the phytotoxicity of Cr(VI) in sunflower plant. Our results showed that using BC resulted in greater reduction of Cr(VI) in soils compared with biochar. This is attributed to the differences in dissolved organic carbon and functional groups that provide electrons for the reduction of Cr(VI). When increasing levels of Cr were added to soils, both microbial respiration and plant growth decreased. The application of BC was more effective than biochar in increasing the microbial population and in mitigating the phytotoxicity of Cr(VI). The net benefit of BC emerged as an increase in plant biomass and a decrease in Cr concentration in plant tissue. Consequently, it was concluded that BC is a potential reducing amendment in mitigating Cr(VI) toxicity in soil and plants.     

Effects of organic amendments on the reduction and phytoavailability of chromate in mineral soil

In this study, seven organic amendments (biosolid compost, farm yard manure, fish manure, horse manure, spent mushroom, pig manure, and poultry manure) were investigated for their effects on the reduction of hexavalent chromium [chromate, Cr(VI)] in a mineral soil (Manawatu sandy soil) low in organic matter content. Addition of organic amendments enhanced the rate of reduction of Cr(VI) to Cr(III) in the soil. At the same level of total organic carbon addition, there was a significant difference in the extent of Cr(VI) reduction among the soils treated with organic amendments. There was, however, a significant positive linear relationship between the extent of Cr(VI) reduction and the amount of dissolved organic carbon in the soil. The effect of biosolid compost on the uptake of Cr(VI) from the soil, treated with various levels of Cr(VI) (0-1200 mg Cr kg(-1) soil), was examined with mustard (Brassica juncea L.) plants. Increasing addition of Cr(VI) increased Cr concentration in plants, resulting in decreased plant growth (i.e., phytotoxicity). Addition of the biosolid compost was effective in reducing the phytotoxicity of Cr(VI). The redistribution of Cr(VI) in various soil components was evaluated by a sequential fractionation scheme. In the unamended soil, the concentration of Cr was higher in the organic-bound, oxide-bound, and residual fractions than in the soluble and exchangeable fractions. Addition of organic amendments also decreased the concentration of the soluble and exchangeable fractions but especially increased the organic-bound fraction in soil.     

Evaluation of hexavalent chromium removal in a continuous biological filter with the use of central composite design (CCD)

Hexavalent chromium is frequently found in industrial effluents as a result of the industrial applications of this compound and its anti-corrosive features. However, hexavalent chromium is extremely toxic, and its discharge in water is regulated, with a maximum limit of 0.1 mg/L in accordance with legislation established by CONAMA-Brazil (no. 397, April 3, 2008). To achieve lower discharge values, it is necessary to reduce from Cr(VI) to Cr(III), which is less toxic, and an economic alternative involves biological removal of this compound. Residence time distributions (RTDs) were measured to evaluate the behavior of actual biofilter operation conditions in a biofilter flow. The medium residence time distributions used were 8 and 24 h (recommended by the legislation). To optimize this process, a central composite design was used, considering the initial chromium concentration and pH as the independent variables and the removal of hexavalent chromium as the response. The boundary curves and surface response showed optimal behavior at 3.94 mg/L [Cr(0)] and a pH of 6.2. The removal process of hexavalent chromium is mathematically described by the Michaelis-Menten kinetic model. This model appropriately represents the variation of chromium concentration along the bioreactor.     

Low-temperature chromium(VI) biotransformation in soil with varying electron acceptors

Effective and low-cost strategies for remediating chromium (Cr)-contaminated soil are needed. Chromium(VI) leaching from contaminated soil into ground water and surface water threatens water supplies and the environment. This study tested indigenous Cr(VI) microbial transformation in batch systems at 10 degrees C in the presence of various electron acceptors. The effects of carbon addition, spiked Cr(VI), and mixing highly contaminated soil with less contaminated soil were investigated. The results indicated that Cr(VI) can be biotransformed in the presence of different electron acceptors including oxygen, nitrate, sulfate, and iron. Sugar addition had the greatest effect on enhancing Cr(VI) removal. Less dissolved organic carbon (DOC) was consumed per amount of Cr(VI) transformed under anaerobic conditions [0.8-93 mg DOC/mg Cr(VI)] compared with aerobic conditions [1.4-265 mg DOC/mg Cr(VI)]. Toxicity of high concentrations (< 160 mg/L) of spiked Cr(VI) were not evident. At Cr(VI) concentrations > 40 mg/L, aerobic conditions promoted faster Cr(VI) reduction than anaerobic conditions with nitrate or sulfate present. Biotransformation of Cr(VI) in highly contaminated soil (22,000 mg Cr/kg) was facilitated by mixing with less-contaminated soil. The study results provide a framework for evaluating indigenous Cr(VI) microbial transformation and enhance the ability to develop strategies for soil treatment.     

涂铁石英砂吸附水中Cr（Ⅵ）的研究

采用静态吸附和动态过滤的试验方法研究了涂铁石英砂（IOCS）滤料对水中Cr（Ⅵ）的去除，并探讨其吸附机理。研究结果表明，Cr（Ⅵ）在IOCS上的吸附平衡符合Langmuir吸附模型。经氧化铁改性滤料表面电位带正电荷，对水中的Cr（Ⅵ）有良好的去除效果。pH值对Cr（Ⅵ）的去除影响较大，随着溶液的pH值升高，滤料表面电位减小，Cr（Ⅵ）的吸附率也减小。IOCS滤料去除Cr（Ⅵ）机理主要为静电吸附。     

光催化还原法处理含cr（Ⅵ）废水的研究

采用自制TiO2作为光催化剂,利用光催化-混凝联合处理含Cr（Ⅵ）废水,研究了废水的pH值、催化剂用量、反应时间、有机物和混凝剂种类对含Cr（Ⅵ）废水中Cr（Ⅵ）去除率的影响。结果表明,在添加EDTA,pH值为1,紫外灯120min左右,二氧化钛加入量为0．4g,采用FeCl3和PAM作为混凝剂时,Cr（Ⅵ）的去除效率最好。     

Leaching mechanisms of Cr(VI) from chromite ore processing residue

Batch leaching tests, qualitative and quantitative x-ray powder diffraction (XRPD) analyses, and geochemical modeling were used to investigate the leaching mechanisms of Cr(VI) from chromite ore processing residue (COPR) samples obtained from an urban area in Hudson County, New Jersey. The pH of the leaching solutions was adjusted to cover a wide range between 1 and 12.5. The concentration levels for total chromium (Cr) and Cr(VI) in the leaching solutions were virtually identical for pH values >5. For pH values <5, the concentration of total Cr exceeded that of Cr(VI) with the difference between the two attributed to Cr(III). Geochemical modeling results indicated that the solubility of Cr(VI) is controlled by Cr(VI)-hydrocalumite and Cr(VI)-ettringite at pH >10.5 and by adsorption at pH <8. However, experimental results suggested that Cr(VI) solubility is controlled partially by Cr(VI)-hydrocalumite at pH >10.5 and by hydrotalcites at pH >8 in addition to adsorption of anionic chromate species onto inherently present metal oxides and hydroxides at pH <8. As pH decreased to <10, most of the Cr(VI) bearing minerals become unstable and their dissolution contributes to the increase in Cr(VI) concentration in the leachate solution. At low pH ( <1.5), Cr(III) solid phases and the oxides responsible for Cr(VI) adsorption dissolve and release Cr(III) and Cr(VI) into solution.     

DISSOLVED HEAVY METALS IN SHALLOW GROUND WATER IN A SOUTHEASTERN MICHIGAN URBAN WATERSHED1

ABSTRACT: The occurrence of dissolved heavy metal concentrations in shallow ground water were measured at 126 sites within an urban watershed in southeastern Michigan. A total of 1,140 samples were collected from the first saturated zone, and the mean concentrations of 11 heavy metals (arsenic, barium, cadmium, chromium, copper, lead, mercury, nickel, selenium, silver, and zinc) were obtained and compared to their corresponding mean concentrations within surface soil. The results suggest that former and current land use processes have resulted in significant adverse impacts on the study region. Levels of Cr 20 to 30 times the maximum contaminant level (MCL) have been detected in the ground water beneath industrial sites. In addition, Cd and Pb have been found at levels exceeding their MCLs where surface soils are clay‐rich, and in sandy soils at more than 10 times their MCLs. The high levels of Cr in ground water strongly suggest that the chromium is in a hexavalent form, and this likelihood is supported by current studies. Given the hydraulic connection between the watershed's surface waters and the Great Lakes, these findings raise significant ecological and public health concerns.