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).     

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.     

Exposure-response of Cr(III)-organic complexes to Saccharomyces cerevisiae

Hexavalent chromium [Cr(VI)] bioreduction produces soluble Cr(III)-organic complexes. The Cr(III)-organic complexes are relatively stable once they are formed, and no data about their toxicity were reported. Therefore, this study aims to investigate the bioavailability and toxicity of the soluble Cr(III)-organic complexes. Saccharomyces cerevisiae L-1 wild type yeast strain was chosen as the model organism and Cr(III)-citrate was selected as the representative compound of the Cr(III)-organic complexes. The short-term chronic aquatic toxicity tests of the Cr(III)-citrate was explored by measuring growth inhibition, direct viable cell count, dry biomass, biosorption, and the amount of CO₂ production. Cr(III)-citrate exerted a toxicity of 51 mg/L with an EC ₅₀, which was calculated from the percent growth inhibition. These toxicity data would be helpful to define the toxic potential of the organo-chromium-III compounds in the environment.     

铬胁迫对3种草本植物生长及铬积累的影响

为了阐明铬胁迫对白花三叶草（Trifolium repens）、高羊茅（Festuca arundinacea）、紫花苜蓿（Medicago sativa）3种草本植物的毒害机制,为铬污染土壤植物修复提供理论依据,采用盆栽试验,在土壤中添加不同浓度的铬[Cr（Ⅵ）]（K2Cr2O7为0、100、200、300和400 mg.kg-1）,研究重金属铬对3种草本植物生长、生理特性、重金属铬累积与分布的影响.结果表明,白花三叶草、高羊茅和紫花苜蓿的平均耐性指数分别为62.5、48.3和36.33.在铬浓度为400 mg.kg-1处理条件下,白花三叶草和高羊茅叶绿素含量、SOD和POD活性分别为对照的57.14%、51.51%、35.76%和63.27%、52.96%、41.36%,而紫花苜蓿无法生存.在铬胁迫下,3种草本植物的株高、根长、地上（下）部干重均表现降低,其降低大小顺序为紫花苜蓿〉高羊茅〉白花三叶草,但MDA含量增加,并且紫花苜蓿增加幅度最大,高羊茅次之,白花三叶草最小.三者对铬的耐受性表现为白花三叶草〉高羊茅〉紫花苜蓿.3种草本植物叶片积累的铬主要贮存于细胞壁,其次是细胞质,而在叶绿体和线粒体中含量较低.叶绿体和线粒体中铬含量与叶绿素、MDA含量、SOD和POD活性存在明显的相关性.随着铬浓度增加,3种草本植物叶片亚细胞组分中铬含量增加,并且总是紫花苜蓿〉高羊茅〉白花三叶草.当铬处理浓度为300 mg.kg-1时,与白花三叶草、高羊茅相比,紫花苜蓿叶片富集铬浓度最高,达51.44 mg.kg-1,其中分配于叶绿体（19.09%）和线粒体（18.04%）中铬的比例也明显较高.白花三叶草、高羊茅和紫花苜蓿地上部和地下部富集系数平均值分别为1.22、1.54;1.16、1.44和1.26、1.62,转运系数平均值分别为0.78、0.78和0.74.在重金属铬污染土壤治理中,白花三叶草和高羊茅有一定的潜在应用价值.     

阴极pH控制对电动修复Cr(Ⅵ)污染高岭土影响研究

试验选用重铬酸钾作为污染物,配制高岭土中Cr(Ⅵ)初始质量分数为100mg/kg和500mg/kg。试验研究了对阴极电解产生的OH-的控制对电动修复效率的影响以及不同的控制方式对电动修复效率的影响。试验结果表明:对阴极电解产生的pH进行控制可以明显提高Cr(Ⅵ)去除效率;多种控制方式中,以盐酸的中和控制最为有效,可使去除效率达到90.8%,但引起的土壤酸化问题应当进一步进行研究。     

Flower-, wire-, and sheet-like MnO2-deposited diatomites: Highly efficient absorbents for the removal of Cr(VI)

Flower-, wire-, and sheet-like MnO₂-deposited diatomites have been prepared using a hydrothermal method with Mn(Ac)₂, KMnO₄ and/or MnSO₄ as Mn source and diatomite as support. Physical properties of the materials were characterized by means of numerous analytical techniques, and their behaviors in the adsorption of chromium(VI) were evaluated. It is shown that the MnO₂-deposited diatomite samples with different morphologies possessed high surface areas and abundant surface hydroxyl groups (especially the wire-like MnO₂/diatomite sample). Thewire-like MnO₂/diatomite sample showed the best performance in the removal of Cr(VI), giving the maximum Cr(VI) adsorption capacity of 101 mg/g.     

难溶态Cr (Ⅵ)对重度铬污染土壤淋洗还原修复效果的影响

通过对某铬渣堆场的重度铬污染土壤进行解吸动力学和难溶态Cr (Ⅵ)还原实验,揭示限制重度铬污染土壤有效修复的关键因素。结果表明:室温下,采用柠檬酸淋洗可显著降低土壤中难溶态Cr (Ⅵ)浓度,将淋洗温度提高至90℃,可进一步显著降低难溶态Cr (Ⅵ)浓度。淋洗后土样中难溶态Cr (Ⅵ)浓度越低,其还原效果越好。供试土样经柠檬酸高温淋洗+FeSO₄高温还原工艺修复后,Cr (Ⅵ)浓度从(1813.2±59.8) mg/kg降至(99.1±8.8) mg/kg。此外,淋洗实验中柠檬酸对难溶态Cr (Ⅵ)的还原可忽略不计;土样中残留的柠檬酸对土壤Cr (Ⅵ)的检测结果无显著影响。研究证明了难溶态Cr (Ⅵ)的还原效果是重度铬污染土壤修复的关键限制因素,结果可为铬污染土壤修复工艺研发提供参考。     

Elimination of a pollution associated with chromic acid during the electro-deposition of Cr(III) using appropriate anodic and membrane materials in a double film bath

A method using trivalent chromium has been used to replace hexavalent chromium for the electro-deposition of chromium. Using a tri-chamber bath system various anodic materials and membranes were evaluated to minimize the production of environmentally and health damaging chromic acid. By measuring the absorbance of Cr(VI) at 640 nm, the results indicate that the use of a titanium plated ruthenium (Ti-Ru) anode produces the least amount of chromic acid byproduct compared to lead-gold alloy and graphite anodes. The concentration of Cr(VI) in the immediate vicinity of the Ti-Ru anode decreased from 0.389 mg/L to 0 during a 40-min deposition period. The use of a Nafion^TM quaternary cation exchange membrane portioning the buffer and anode selectively prevented Cr(III) from entering the anode compartment whilst allowing the migration of H⁺ to maintain overall voltaic continuity. It has been demonstrated that the use of a Ti-Ru anode with a Nafion^TM membrane can eliminate the production of chromic acid associated with the electro-deposition of chromium plate thereby preventing its health damaging exposure to plant operators and preventing discharge of Cr(VI) into the environment. Addition of a surfactant improved current efficiency by 34.7%.     

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.     

制革行业土壤铬污染特征及其影响因素

为了解制革场地土壤Cr(Ⅵ)污染情况和分布特征,选取我国3种典型制革企业用地的土壤和污泥样品,分析了制革行业土壤铬污染特征。结果表明:调查的Ⅰ型制革企业场地土壤Cr(Ⅵ)含量最高为48 mg/kg,超过GB 36600—2018《土壤环境质量建设用地土壤污染风险管控标准(试行)》筛选值,存在环境风险。调查的Ⅱ型制革企业环保设施完善,场地土壤Cr(Ⅵ)含量低于GB 36600—2018筛选值,土壤Cr(Ⅵ)环境风险低。Ⅱ型制革企业危险废物暂存间污泥总铬含量高达85377 mg/kg, Cr(Ⅵ)含量最高为1455 mg/kg。调查的Ⅲ型制革企业场地泥土混合物总铬含量为1564~28000 mg/kg, Cr(Ⅵ)含量最高为250 mg/kg,相较于Ⅰ型和Ⅱ型制革企业场地,受到严重污染。总体上,制革企业用地土壤铬污染物以Cr(Ⅲ)形态为主,Cr(Ⅵ)形态占比少,不足1%。     

Flower-, wire-, and sheet-like MnO2-deposited diatomites: Highly efficient absorbents for the removal of Cr(VI)

Flower-, wire-, and sheet-like MnO₂-deposited diatomites have been prepared using a hydrothermal method with Mn(Ac)₂, KMnO₄ and/or MnSO₄ as Mn source and diatomite as support. Physical properties of the materials were characterized by means of numerous analytical techniques, and their behaviors in the adsorption of chromium(VI) were evaluated. It is shown that the MnO₂-deposited diatomite samples with different morphologies possessed high surface areas and abundant surface hydroxyl groups (especially the wire-like MnO₂/diatomite sample). The wire-like MnO₂/diatomite sample showed the best performance in the removal of Cr(VI), giving the maximum Cr(VI) adsorption capacity of 101 mg/g.     

Simultaneous removal of Cu(II) and Cr(VI) by Mg–Al–Cl layered double hydroxide and mechanism insight

Mg–Al–Cl layered double hydroxide (Cl-LDH) was prepared to simultaneously remove Cu(II) and Cr(VI) from aqueous solution. The coexisting Cu(II) (20 mg/L) and Cr(VI) (40 mg/L) were completely removed within 30 min by Cl-LDH in a dosage of 2.0 g/L; the removal rate of Cu(II) was accelerated in the presence of Cr(VI). Moreover, compared with the adsorption of single Cu(II) or Cr(VI), the adsorption capacities of Cl-LDH for Cu(II) and Cr(VI) can be improved by 81.05% and 49.56%, respectively, in the case of coexisting Cu(II) (200 mg/L) and Cr(VI) (400 mg/L). The affecting factors (such as solution initial pH, adsorbent dosage, and contact time) have been systematically investigated. Besides, the changes of pH values and the concentrations of Mg²⁺ and Al³⁺ in relevant solutions were monitored. To get the underlying mechanism, the Cl-LDH samples before and after adsorption were thoroughly characterized by X-ray powder diffraction, transmission electron microscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. On the basis of these analyses, a possible mechanism was proposed. The coadsorption process involves anion exchange of Cr(VI) with Cl⁻ in Cl-LDH interlayer, isomorphic substitution of Mg²⁺ with Cu²⁺, formation of Cu₂Cl(OH)₃ precipitation, and the adsorption of Cr(VI) by Cu₂Cl(OH)₃. This work provides a new insight into simultaneous removal of heavy metal cations and anions from wastewater by Cl-LDH.     

沼渣协同硫酸亚铁修复Cr(Ⅵ)污染土壤

通过稳定化实验、连续提取实验及植物毒性实验,研究了沼渣对硫酸亚铁稳定化Cr （Ⅵ）污染土壤的促进效果与机制.结果表明,沼渣协同硫酸亚铁对土壤中Cr （VI）有良好的稳定化效果.最佳的修复条件为：n（Fe）/n（Cr）=3∶1,含水率为35%,沼渣投加量为4.5%,反应时间为12 d,此时Cr （VI）稳定化效率为99.85%,残余六价铬含量为1.49 mg·kg^-1,满足《土壤环境质量建设用地土壤污染风险管控标准》（GB 36600—2018）第二类用地筛选值5.7 mg·kg^-1的限值要求.由连续提取实验结果可知,沼渣+硫酸亚铁稳定化处理后酸溶态铬含量显著降低,而可还原态、可氧化态和残渣态铬含量明显增加.风险分析进一步表明,沼渣+硫酸亚铁稳定化处理后铬的风险等级由非常高风险降至低风险.植物毒性分析可知,沼渣+硫酸亚铁稳定化处理植物毒性显著降低.微生物多样性和群落结构分析可知,沼渣+硫酸亚铁稳定化处理后土壤中细菌群落的丰度和多样性均明显增加.     

Removal of hexavalent chromium from contaminated waters by ultrasound-assisted aqueous solution ball milling

Batch mode experiments were conducted to study the removal of hexavalent chromium(Cr(Ⅵ)) from aqueous solutions using ultrasound-assisted aqueous solution ball milling.The results show that the reduction rate of Cr(Ⅵ) by ultrasound-assisted aqueous solution ball milling was significantly faster than that by ball milling or ultrasound treatment alone,and an initial Cr(Ⅵ) concentration of 166 mg/L could be decreased to 0.35 mg/L at 120 min.The decisive factors, including initial concentration of Cr(Ⅵ), p H value, ultrasonic frequency and filling gas, were studied. It was found that the optimal ultrasonic frequency for ultrasound-assisted aqueous solution ball milling device was 20 k Hz, and the rate of Cr(Ⅵ)reduction as a function of filling gas followed the order: Ar air N_2 O_2. Samples were characterized by X-ray diffraction, fluorescence measurements, atomic absorption and the diphenylcarbazide colorimetric method. The Cr(Ⅵ) transformed into a precipitate that could be removed from the contaminated water, after which the water could be reused.     

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.     

Nano-sized Fe2O3/Fe3O4 facilitate anaerobic transformation of hexavalent chromium in soil–water systems

The purpose of this study is to investigate the effects of nano-sized or submicro Fe_2O_3/Fe_3O_4 on the bioreduction of hexavalent chromium(Cr(VI)) and to evaluate the effects of nano-sized Fe_2O_3/Fe_3O_4 on the microbial communities from the anaerobic flooding soil.The results indicated that the net decreases upon Cr(VI) concentration from biotic soil samples amended with nano-sized Fe_2O_3(317.1 ± 2.1 mg/L) and Fe_3O_4(324.0 ± 22.2 mg/L) within21 days,which were approximately 2-fold of Cr(VI) concentration released from blank control assays(117.1 ± 5.6 mg/L).Furthermore,the results of denaturing gradient gel electrophoresis(DGGE) and high-throughput sequencing indicated a greater variety of microbes within the microbial community in amendments with nano-sized Fe_2O_3/Fe_3O_4 than the control assays.Especially,Proteobacteria occupied a predominant status on the phylum level within the indigenous microbial communities from chromium-contaminated soils.Besides,some partial decrease of soluble Cr(VI) in abiotic nano-sized Fe_2O_3/Fe_3O_4 amendments was responsible for the adsorption of nano-sized Fe_2O_3/Fe_3O_4 to soluble Cr(VI).Hence,the presence of nano-sized Fe_2O_3/Fe_3O_4 could largely facilitate the mobilization and biotransformation of Cr(VI) from flooding soils by adsorption and bio-mediated processes.     

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。     

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.     

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.     

A meta-analysis of heavy metals pollution in farmland and urban soils in China over the past 20 years

A total of 713 research papers about field monitor experiments of heavy metals in farmland and urban soils in China, published from 2000 to 2019, were obtained. A meta-analysis was conducted to evaluate the level of China's heavy metal pollution in soils, mainly focusing on eight heavy metals. It was found that the average concentrations of cadmium (Cd), lead (Pb), zinc (Zn), copper (Cu), mercury (Hg), chromium (Cr), nickel (Ni), and arsenic (As) in China were 0.19, 30.74, 85.86, 25.81, 0.074, 67.37, 27.77 and 8.89 mg/kg, respectively. Compared with the background value (0.097 mg/kg), the Cd content showed a twofold (0.19 mg/kg) rise in farmland soils and a threefold (0.29 mg/kg) rise in urban soils. The decreasing order of the mean I_geo was Cd (1.77) > Pb (0.62) > Zn (0.60) > Cu (0.58) > Hg (0.57) > Cr (0.54) > Ni (0.47) > As (0.28). Nearly 33.54% and 44.65% of sites in farmland and urban soils were polluted with Cd. The average concentrations of eight heavy metals were not sensitive change in recent two decades in farmland and urban soils. The average P_n values for urban (2.52) and farmland (2.15) soils showed that heavy metal pollution in urban soils was more serious than that in farmland, and the middle Yangtze River regions, where industrial activity dominates, were the most polluted. The meta-analysis comprehensively evaluated the current pollution situation of soil heavy metal, and provided important basis for soil management and environment prevention in China.