Electrokinetic removal of chromium and copper from contaminated soils by lactic acid enhancement in the catholyte

The electrokinetic removal of chromium and copper from contaminated soils by adding lactic acid in cathode chamber as an enhancing reagent was evaluated. Two sets of duplicate experiments with chromium contaminated kaolinite and with a silty soil sampled from a supeffund site in Califomia of USA and polluted by Cr and Cu, were carried out in a constant current mode. Changes of soil water content and soil pH before and after the electrokinetic experiments, and variations of voltage drop and electroosmosis flow during the treatments were examined. The results indicated that Cr, spiked as Cr(Ⅵ) in the kaolinite, was accumulated mainly in the anode chamber, and some of Cr and metal hydroxides precipitated in the soil sections in contact with the cathode, which significantly increased electrical energy consumption. Treatment of the soil collected from the site showed accumulation of large amounts of Cr and Cu in the anode chamber while none was detected in the cathode one. The results suggested that the two metals either complexed with the injected lactic acid at the cathode or existed as negatively charged complex, and electromigrated toward the anode under a voltage gradient.     

Identification and characterization of the chromium（Ⅵ） responding protein from a newly isolated Ochrobactrum anthropi CTS-325

A Gram-negative, chromium(VI) tolerant and reductive strain CTS-325, isolated from a Chinese chromate plant, was identified as Ochrobactrum anthropi based on its biochemical properties and 16S rDNA sequence analysis. It was able to tolerate up to 10 mmol/L Cr(VI) and completely reduce 1 mmol/L Cr(VI) to Cr(III) within 48 h. When the strain CTS-325 was induced with Cr(VI), a protein increased significantly in the whole cell proteins. Liquid chromatography tandem mass spectrometry (LC-MS/MS) analysis revealed that this protein was a superoxide dismutase (SOD) homology. The measured superoxide dismutase activity was 2694 U/mg after three steps of purification. The SOD catalyzes the dismutation of the superoxide anion (O₂^·−) into hydrogen peroxide and molecular oxygen. This protein is considered to be one of the most important anti-oxidative enzymes for O. anthropi as it allows the bacterium to survive high oxygen stress environments, such as the environment produced during the reduction process of Cr(VI).     

Removal and desorption of chromium in synthetic effluent by a mixed culture in a bioreactor with a magnetic field

Two chromium removal experiments were performed in bioreactors with and without a magnetic field under the same conditions.The release of the chromium present in the biomass was tested in two experiments one with the initial pH of the medium and one with pH 4.0.The objective was to remove Cr(Ⅵ) and total Cr from the effluent,this was carried out by placing biological treatments of synthetic effluent contaminated with 100 mg/L of Cr(Ⅵ) in a bioreactor with neodymium magnets that applied a magnetic field(intensity85.4 mT) to the mixed culture.The removal of Cr(Ⅵ) was approximately 100.0% for the bioreactor with a magnetic field and 93,3% for the bioreactor without a magnetic field for9 hr of recirculation of the synthetic effluent by the bioreactor.The removal of total Cr was61.6% and 48.4%,with and without a magnetic field,respectively;for 24 hr.The desorption of Cr(VI) in the synthetic effluent was 0.05 mg/L,which is below the limit established by Brazilian legislation(0.1 mg/L) for the discharge of effluent containing Cr(Ⅵ) into bodies of water.The results obtained for the removal of chromium in synthetic effluent suggested that there was no significant influence on the viable cell count of the mixed culture.The desorption of Cr(Ⅵ) in synthetic effluent after bioadsorption of chromium by the mixed culture in the process of removal of chromium in bioreactors with and without a magnetic field was not significant in either of the experiments with different initial pHs.     

Kinetics and mechanism of hexavalent chromium removal by basic oxygen furnace slag

Basic oxygen furnace slag(BOFS) has the potential to remove hexavalent chromium(Cr(VI))from wastewater by a redox process due to the presence of minerals containing Fe2+. The effects of the solution p H, initial Cr(VI) concentration, BOFS dosage, BOFS particle size, and temperature on the removal of Cr(VI) was investigated in detail through batch tests. The chemical and mineral compositions of fresh and reacted BOFS were characterized using scanning electron microscope(SEM) equipped with an energy dispersive spectrometer(EDS)system and X-ray diffractometer(XRD). The results show that Cr(VI) in wastewater can be efficiently removed by Fe2+released from BOFS under appropriate acidic conditions. The removal of Cr(VI) by BOFS significantly depended on the parameters mentioned above. The reaction of Cr(VI) with BOFS followed the pseudo-second-order kinetic model. Fe2+responsible for Cr(VI) removal was primarily derived from the dissolution of Fe O and Fe3O4 in BOFS. When H2SO4 was used to adjust the solution acidity, gypsum(Ca SO4·2H2O)could be formed and become an armoring precipitate layer on the BOFS surface, hindering the release of Fe2+and the removal of Cr(VI). Finally, the main mechanism of Cr(VI) removal by BOFS was described using several consecutive reaction steps.     

Bio-immobilization and recovery of chromium using a denitrifying biofilm system: Identification of reaction zone, binding forms and end products

Chromium is an important resource in strategic metals. Different from most studies focusing on the bio-reduction of hexavalent chromium [Cr(VI)], this study aims to achieve the immobilization and recovery of chromium using a sequencing batch biofilm reactor. Results showed that Cr(VI) removal efficiency remained more than 99%, and 97% of reduced Cr(III) was immobilized in the biofilm. Immobilization zone, chromium forms and extracellular polymeric substances composition changes were combined to reveal the mechanism of Cr(VI) reduction and immobilization. The chromium distribution in biofilm demonstrated that intercellular layer was the main active zone with an immobilization amount of 891.70±126.32 mg/g-VSS. The reduced products analysis confirmed that trivalent chromium [Cr(III)] chelated with carboxyl, amino and other functional groups and immobilized in the form of organic Cr(III). The digestion method realized a chromium recovery efficiency of 74.59%. This study provides an alternative method for the bioremediation and resources recovery in chromium polluted wastewater.     

土柱淋洗法修复铬污染土壤的水力梯度优化试验

针对重金属污染土壤的修复,淋洗法是一种比较成熟的方式,但目前研究主要聚焦于淋洗剂的选择,而关于水力停留时间对淋洗效果影响的研究相对较少.水力梯度是影响水力停留时间的重要因素,优化水力梯度能够缩短修复周期,降低淋洗成本,有效提高淋洗效率,为现场淋洗修复工程应用提供参考.本文针对人工制备的不同质地的铬污染土壤进行了土柱淋洗...     

Preparation of cross-linked magnetic chitosan with quaternary ammonium and its application for Cr(VI) and P(V) removal

Pollutants that exist in anionic species are issues of concern in water treatment. Compared to cationic pollutants, the removal of anionic pollutants by adsorption is more difficult because most adsorbents carry predominantly negative charges in neutral and alkaline environments. In this study, a cross-linked chitosan derivative with quaternary ammonium and magnetic properties（QM-chitosan） was prepared and employed to remove chromium（VI） and phosphorus（V）（Cr（VI） and P（V）） from aqueous environments. The QM-chitosan was characterized by Fourier transform infrared spectrometry（FT-IR）,thermogravimetric analysis（TGA）, energy dispersive X-ray（SEM-EDX） and zeta potential.Batch experiments show that QM-chitosan can effectively remove Cr（VI） and P（V）, and the main mechanism was believed to be electrostatic interaction. A pseudosecond-order model was fitted to describe the kinetic processes of Cr（VI） and P（V） removal. The adsorption isotherms of both Cr（VI） and P（V） on the QM-chitosan were well fitted by the Langmuir isotherm equation. The saturated adsorption capacity of P（V）（2.783 mmol/g） was found to be higher than that of Cr（VI）（2.323 mmol/g）, resulting from the size of the H2PO-4ions being smaller than that of the HCr O-4ions. However, the theoretical calculation and experimental results showed that QM-chitosan had a stronger affinity for Cr（VI） than P（V）. The adsorption–desorption of the QM-chitosan was evaluated, and high regeneration rates were demonstrated.     

Screening of leather auxiliaries for their role in toxic hexavalent chromium formation in leather—posing potential health hazards to the users

With increasing concern about the potential health hazards of toxic chemicals in consumer articles such as leather products, many countries importing these articles have introduced stringent stipulation for the permissible levels of such chemicals in these articles. Hexavalent chromium is one such toxic metal ion included in the list of regulated substances. The problem is unique to leather industry as it uses only trivalent chromium based salts in the tanning process but faces the problem of presence of Cr(VI) in the end product. Efforts are being made to understand the reasons for the presence of hexavalent chromium in leather and to devise strategies for eliminating the same in processing. This paper describes our attempt to investigate the role of potential post-tanning (wet finishing) and finishing auxiliaries used in leather processing in the conversion of Cr(III) to Cr(VI) in the chrome-tanned leather. The auxiliaries were also screened for the presence of oxidizing functionality and the amount estimated as persulfate. The study reveals that the auxiliaries suspected of having a role in Cr(VI) formation do have considerable quantities of residual oxidizing functionality capable of converting Cr(III) to Cr(VI). The study with persulfate as the model oxidizing agent confirms the role of oxidizing agents in the formation of quantities of Cr(VI) well above the permissible limit of 3 mg/kg in leather matrix, which basically provides a reducing environment.     

铬渣浸溶Cr(Ⅵ)溶解释放规律研究-以锦州堆场铬渣为例

通过锦州地区铬渣样品静态浸溶实验,测定不同固液比、浸出时间、浸取剂pH及组成、振荡速度、铬渣粒度大小、温度等因素对铬渣中Cr(VI)溶解释放的影响,揭示铬渣中Cr(VI)析出、释放机理。结果显示,稀释作用在不同固液比浸出中起主导作用,随固液比的降低,Cr(VI)浸出浓度逐渐降低,但是Cr(VI)浸出总量却在增加;随着浸出时间的增大,浸出Cr(VI)浓度随之增大;铬渣浸出液碱性很高,在铬渣溶解释放过程中,随酸性增强Cr(VI)溶解量相应增大,体现强的酸中和能力;随着振荡速度增加,Cr(VI)溶解释放速度明显加快;粒径越小,铬酸盐的溶解释放速度越快,溶解作用越充分;铬渣的浸出为吸热反应过程,铬渣溶解度随温度升高而增大。铬渣中Cr(Vl)溶解释放速率服从菲克(Fick)扩散定律。研究结果为铬渣危害的评价、监测及铬渣污染有效防治提供参考。     

Study on activated carbon in chromium-containingwastewater treatment by XPS

Ｓｔｕｄｙｏｎａｃｔｉｖａｔｅｄｃａｒｂｏｎｉｎｃｈｒｏｍｉｕｍ－ｃｏｎｔａｉｎｉｎｇｗａｓｔｅｗａｔｅｒｔｒｅａｔｍｅｎｔｂｙＸＰＳＹａｎｇＪｕｎ；ＷａｎｇＹｕｎｘｉｕ（ＳｈａｎｄｏｎｇＵｎｉｖｅｒｓｉｔｙｏｆＴｅｃｈｎｏｌｏｇｙ，Ｊｉｎａｎ２５０...     

Response of soil catalase activity to chromium contamination

The impact of chromium(III) and (VI) forms on soil catalase activity was presented. The Orthic Podzol, Haplic Phaeozem and Mollic Gleysol from di erent depths were used in the experiment. The soil samples were amended with solution of Cr(III) using CrCl3, and with Cr(VI) using K2Cr2O7 in the concentration range from 0 to 20 mg/kg, whereas the samples without the addition of chromium served as control. Catalase activity was assayed by one of the commonly used spectrophotometric methods. As it was demonstrated in the experiment, both Cr(III) and Cr(VI) have an ability to reduce soil catalase activity. A chromium dosage of 20 mg/kg caused the inhibition of catalase activity and the corresponding contamination levels ranged from 75% to 92% for Cr(III) and 68% to 76% for Cr(VI), with relation to the control. Catalase activity reached maximum in the soil material from surface layers (0–25 cm), typically characterized by the highest content of organic matter creating favorable conditions for microorganisms.     

可渗透反应复合电极法对铬(Ⅵ)污染土壤的电动修复

将Fe0、沸石等活性材料附着在电极上构成可渗透反应复合电极,以Cr(Ⅵ)污染土壤为处理对象,对电动修复过程中可渗透反应复合电极法对土壤pH的控制、Cr的去除效果以及形态变化进行了研究.结果表明,添加可渗透反应材料的复合电极法比单一电极法无论在土壤pH控制还是Cr的去除方面都有明显的改善和提高,其中以在阳极同时添加Fe0和沸石效果最为显著.在施加2 V.cm-1的直流电压,运行5 d后,相比在阳极单纯添加沸石或Fe0可渗透反应层,添加"Fe0+沸石"反应层能在最大程度上减小阳极土壤pH值的波动,可将土壤pH值控制在5.5～8.5范围内,土壤中任意位置Cr(Ⅵ)的去除率可提高到97%以上,土壤中残留的Cr(Ⅲ)更少,可渗透反应层对Cr的截留量可分别提高8倍和1.8倍,并将98%的Cr(Ⅵ)转化为低毒的Cr(Ⅲ).研究结果为开发具有实用意义的可渗透反应复合电极修复技术提供了理论依据.     

风化铬渣与新鲜铬渣中六价铬溶出特性的研究

采用直接淋浸法对风化铬渣及新鲜铬渣进行了六谷铬溶出的条件试验，60min的浸泡时间，80目以下的粒度对渣水比250g/200mL的新渣中Cr(VI)浸出率达69．4％，渣水比250g/200mL,500g/400mL,750g/600mL的风化渣中Cr(VI)的总溶出率分别为70．2％，86．3％，94．0％，其中第一次淋滤溶出率分别达48．1％，70．0％，81．6％，低PH值的淋浸水有利于Cr(VI)的浸出，在PH值为3时溶出率达高峰，Cr（VI）浸出质量比自然条件（近中性）高出14．1％－16．3％，增大管径和降低装置的滤面负荷可提高浸出效果，在直径80mm管径，500g铬渣装填料，滤面负荷9．95g/cm^2时，Cr（VI）溶出率达98．7％，真空抽滤可提高Cr（VI）浸出速率，但降低了滤液中Cr（VI）的浓度和溶出质量，上述试验结果表明了直接淋浸法回收铬渣中六价铬的可行性，并可作为工业化装置的设计参数。     

热活化过硫酸钠耦合甲酸技术研究——处理水溶液中四氯化碳与六价铬污染

以甲酸为活化剂,耦合热活化过硫酸钠技术产生还原性二氧化碳阴离子自由基（CO₂^·-）,从而还原去除水溶液中四氯化碳（CT）和Cr（VI）,考察过硫酸钠和甲酸初始浓度的影响以及复合污染处理效果.结果表明：当过硫酸钠与甲酸浓度均为100mmol/L时,单独CT或Cr（VI）分别在120min、60min内基本完全去除（50℃）,且污染物去除效率随过硫酸钠及甲酸浓度升高而增强.在CT和Cr（VI）复合污染体系中,Cr（VI）的存在能够抑制CT降解,且抑制程度随Cr（VI）初始浓度升高而提高,但Cr（VI）去除率随CT初始浓度增大而升高.加入CO₂^·-猝灭剂（甲基紫精）能够抑制CT降解,但促进Cr（VI）去除,表明有机物的存在能够增强Cr（VI）去除效率.     

没食子酸还原六价铬反应动力学规律研究

实验研究了不同pH值,温度和六价铬初始浓度等条件对没食子酸还原六价铬的反应动力学的影响,分别建立六价铬还原反应速率常数关于氢离子浓度和温度的函数方程.结果表明:pH值 为2.0~5.0时,没食子酸与六价铬发生的氧化还原反应符合准一级动力学反应;而pH值为6时,因[H+]不足,二者的反应不符合准一级动力学反应.在pH值为2.0~5.0时,六价铬反应速率常数(103kobs)分别是是951.6、103.6、17.3和7.5h-1.pH值 为2.5时,温度升高,反应速率常数快速增加;温度为30℃时,没食子酸还原六价铬的反应速率常数分别是温度为20℃和10℃时反应速率常数的1.61倍和3.68倍.不同初始浓度六价铬的反应体系中,六价铬反应速率常数随着反应体系中六价铬与没食子酸初始浓度比值的增加而逐渐减小.利用最小二乘线性回归法和阿伦尼乌斯公式分别建立了六价铬还原反应速率常数关于氢离子浓度和温度的函数方程,为预测和分析没食子酸还原六价铬反应过程中六价铬的反应速率常数和浓度变化情况提供动力学模型参考.     

Kinetics of hexavalent chromium reduction by iron metal

The kinetics of Cr(VI) reduction to Cr(III) by metallic iron (Fe⁰) was studied in batch reactors for a range of reactant concentrations, pH and temperatures. Nearly 86.8% removal efficiency for Cr(VI) was achieved when Fe⁰ concentration was 6 g/L (using commercial iron powder (< 200 mesh) in 120 min). The reduction of hexavalent chromium took place on the surface of the iron particles following pseudo-first order kinetics. The rate of Cr(VI) reduction increased with increasing Fe⁰ addition and temperature but inversely with initial pH. The pseudo-first-order rate coefficients (k _obs) were determined as 0.0024, 0.010, 0.0268 and 0.062 8 min⁻¹ when iron powder dosages were 2, 6, 10 and 14 g/L at 25°C and pH 5.5, respectively. According to the Arrehenius equation, the apparent activation energy of 26.5 kJ/mol and pre-exponential factor of 3 330 min⁻¹ were obtained at the temperature range of 288–308 K. Different Fe⁰ types were compared in this study. The reactivity was in the order starch-stabilized Fe⁰ nanoparticles > Fe⁰ nanoparticles > Fe⁰ powder > Fe⁰ filings. Electrochemical analysis of the reaction process showed that Cr(III) and Fe(III) hydroxides should be the dominant final products.     

Reduced graphene oxide-nano zero value iron (rGO-nZVI) micro-electrolysis accelerating Cr(VI) removal in aquifer

Nanoscale zero-valent iron (nZVI) assembled on graphene oxide (GO) (rGO-nZVI) composites were synthesized by reduction of GO and ferrous ions with potassium borohydride, for use in Cr(VI) removal from aqueous solution. The results showed that the two-dimensional structure of GO could provide a skeleton support for Fe⁰, thus overcoming the bottleneck of aggregation for nZVI. Also, rGO-nZVI would form a ferric-carbon micro-electrolysis system in Cr(VI)-contaminated aquifers, enhancing and accelerating electron transfer, exhibiting high rate and capacity for Cr(VI) removal. The optimum dosage of the applied rGO-nZVI was linearly correlated with the initial Cr(VI) concentration. Characterization of rGO-nZVI before and after reaction with Cr(VI) revealed the process of Cr(VI) removal: rGO-nZVI firstly transferred electrons from Fe⁰ cores via their Fe(II)/Fe(III) shells to the GO sheet; there, negatively charged Cr(VI) received electrons and changed into positively charged Cr(III), which was adsorbed by the negatively charged GO sheet, avoiding the capping and passivating of nZVI. rGO-nZVI formed a good electrically conductive network, and thus had long-term electron releasing properties, which was important for groundwater remediation.     

某铬渣堆场周边土壤地下水Cr~(6+)污染特征研究

通过采集某铬渣堆场周边不同距离、深度的土壤和地下水样品,研究了铬渣堆场周边土壤、地下水中六价铬的分布特征和污染状况,通过数据分析确定了铬渣堆场周边受铬污染的地下水和土壤的范围及污染程度,判断污染边界,为后续场地污染治理提供了基础资料。结果表明:铬渣堆场周边土壤地下水已受到严重铬污染,必须尽快采取有效措施对其进行治理修复,以保证当地的农业生产和人体健康。     

非正规垃圾填埋场土壤和地下水重金属污染特征与评价

为了解非正规垃圾填埋场土壤和地下水重金属污染状况,以江西乱石湾垃圾填埋场周边土壤和地下水为研究对象,对研究区进行采样分析,应用内梅罗综合污染指数法和美国环保局地下水健康风险评价模型对该垃圾填埋场土壤和地下水中重金属污染物进行含量特征分析与评价。结果表明,Cr(Ⅵ)、Cd、Cu、Pb重金属是填埋场土壤中的主要污染物,区域所有采样点的内梅罗综合污染指数平均值为2. 20,说明土壤受中度重金属污染; Cr(Ⅵ)是填埋场地下水的主要污染物,所有采样点的综合污染指数平均值为0. 89,说明地下水总体处于警戒线等级;致癌健康风险值在2. 32×10~(-4)～1. 69×10~(-3)/a之间,是国际委员会推荐值的4. 64～33. 8倍,致癌风险水平为Cr(Ⅵ)NiAsCd;非致癌健康风险值在2. 54×10~(-10)～9. 72×10~(-9)/a之间,致癌类重金属的个人年健康风险值是非致癌类重金属的10~5～10~6倍,说明该区域的致癌风险极大,应引起重视。     

回收电镀废液制取鞣革剂方法的研究

在高浓度的含铬、铜电镀废液中加入亚硫酸钠还原Cr6+为Cr3 +;再加入硫化钠去除铜 ;然后加入氢氧化钠调节pH值使Cr3 +生成氢氧化铬沉淀 ;最后加入一定量硫酸溶解氢氧化铬制成鞣革剂———碱式硫酸铬 ,且出水水质达到国家工业废水排放标准