Oxidative stress related enzymes in response to chromium (Ⅵ) toxicity in Oxya chinensis ( Orthoptera : Acridoidae)

The toxic effects of Cr(Ⅵ) on antioxidant enzymes of Oxya chinensis(Orthoptera: Acridoidae) were determined. Changes in the activities of the antioxidant enzymes superoxide dismutase(SOD), catalase(CAT), and guaiacol peroxidase(GPx) were measured in O. chinensis insects injected with Cr(Ⅵ). Fifth-nymphs of O. chinensis insects were injected with Cr(Ⅵ) with different concentrations (0, 75, 150, 225, 300, 375, 450 mg/kg of body weight). The results showed that Cr(Ⅵ) led to the change of SOD, CAT, and GPx activities at different concentrations, which revealed that: (1) The oxidative stress of SOD increased with the increase of Cr (Ⅵ)concentration. (2) With the increase of Cr (Ⅵ) concentrations, CAT activities for females increased at lower concentrations, but decreased at higher concentration range, which indicated that antioxidant system of O. chinensis was not influenced by the presence of Cr (Ⅵ). A very similar response to Cr(Ⅵ) effect for males indicated that Cr(Ⅵ) concentrations were not high enough to damage O. chinensis in terms of CAT. (3) The GPx activity for females increased in all treatments, which revealed that the damage power of Cr(Ⅵ)was increased with the increase of Cr(Ⅵ) concentrations in terms of GPx, but the effect was not so remarkable. There was not a consistent trend of GPx activities for males in all treatments of Cr(Ⅵ). Cr(Ⅵ)-induced changes in antioxidant enzymes were different for SOD, CAT and GPx, of which the tendency was that activities generally changed with increase of concentrations of Cr(Ⅵ) suggesting SOD, CAT, and GPx could serve as indices of oxidative stress to some extent.     

Oxidative stress related enzymes in response to chromium (Ⅵ) toxicity in Oxya chinensis ( Orthoptera : Acridoidae)

The toxic effects of Cr（Vl） on antioxidant enzymes of Oxya chinensis（Orthoptera： Acridoidae） were determined. Changes in the activities of the antioxidant enzymes superoxide dismutase（SOD）, catalase（CAT）, and guaiacol peroxidase（GPx） were measured in O. chinensis insects injected with Cr（VI）. Fifth-nymphs of O. chinensis insects were injected with Cr（VI） with different concentrations （0, 75, 150, 225, 300, 375, 450 mg/kg of body weight）. The results showed that Cr（VI） led to the change of SOD, CAT, and GPx activities at different concentrations, which revealed that： （1） The oxidative stress of SOD increased with the increase of Cr （VI） concentration. （2） With the increase of Cr （VI） concentrations, CAT activities for females increased at lower concentrations, but decreased at higher concentration range, which indicated that antioxidant system of O. chinensis was not influenced by the presence of Cr （VI）. A very similar response to Cr（VI） effect for males indicated that Cr（VI） concentrations were not high enough to damage O. chinensis in terms of CAT. （3） The GPx activity for females increased in all treatments, which revealed that the damage power of Cr（VI） was increased with the increase of Cr（Vi） concentrations in terms of GPx, but the effect was not so remarkable. There was not a consistent trend of GPx activities for males in all treatments of Cr（VI）. Cr（VI）-induced changes in antioxidant enzymes were different for SOD, CAT and GPx, of which the tendency was that activities generally changed with increase of concentrations of Cr（VI） suggesting SOD, CAT, and GPx could serve as indices of oxidative stress to some extent.     

铬污染建筑废物清洗剂的筛选

以原海北化工厂的铬污染建筑废物为研究对象,用微波消解、碱消解-共沉淀和改良BCR顺序提取法,研究了不同粒径样品总Cr和Cr(Ⅵ)以及各形态Cr的含量,探讨了6种清洗剂对样品总Cr和Cr(Ⅵ)的清洗效果,最终筛选出合适的清洗剂. 结果表明:粒径对样品总Cr和Cr(Ⅵ)以及各形态Cr含量的影响不显著,对样品总Cr和Cr(Ⅵ)的解吸无影响. 水洗1次后,总Cr和Cr(Ⅵ)的去除率分别为75.24%和77.59%;用6种清洗剂第2次清洗后,柠檬酸、高浓度盐酸和高浓度醋酸对总Cr和Cr(Ⅵ)的去除率最高,均达到94%以上,说明这3种酸可将Cr(Ⅵ)还原为Cr(Ⅲ),从而去除Cr(Ⅵ). 从经济环保角度考虑,宜选择柠檬酸作为二次清洗剂.      

土著微生物修复Cr（Ⅵ）污染土壤还原后有效铬分析及其稳定性的初步实验研究

通过铬（Ⅵ）污染土壤中筛选出的土著微生物对六价铬污染土壤的还原实验结果,对还原前后土壤中有效铬的含量进行了分析,并对还原后土壤进行了不同条件下的暴露,检测了土样中六价铬浸出毒性,结果表明,经过土著微生物还原后的土壤中,水溶性态铬与可交换态铬都得到了显著的降低,而且土壤浸出液中的六价铬也在不断地降低,说明微生物对六价铬的还原不仅能显著降低其毒性,而且还原产物还具有一定的稳定性。     

陈皮对土壤中六价铬的去除效果及机理

获取廉价、易得且环境友好的高效修复药剂是Cr(Ⅵ)污染土壤修复的重要工作之一. 基于室内模拟培养试验,研究了陈皮添加量和土壤中Cr(Ⅵ)初始浓度对Cr(Ⅵ)去除过程的影响,通过Illumina NovaSeq高通量测序技术和X射线近边吸收光谱(XANES)等方法初步探讨了陈皮修复Cr(Ⅵ)污染土壤的机理. 结果表明:当土壤中Cr(Ⅵ)初始浓度为(1 600.13±298.11) mg/kg、Cr(Ⅵ)浸出浓度为(143.20±13.5) mg/L、陈皮添加量为5%时,培养30 d后,土壤中Cr(Ⅵ)浓度及其浸出浓度分别降至(10.07±2.98) mg/kg和(1.02±0.30) mg/L,去除率分别达到99.37%和99.29%. 土壤中Cr(Ⅵ)的去除效率随陈皮添加量的增加而增大,随Cr(Ⅵ)初始浓度的增加而减小,且添加陈皮后土壤中的Cr(Ⅵ)转化为生物有效性较低的Cr(Ⅲ). 此外,陈皮的添加丰富了土壤细菌的营养底物,缓解了Cr(Ⅵ)对细菌生长的抑制作用. 土壤中放线菌门(Actinobacteria)为最优菌门,微杆菌属(Microbacterium)、土壤球菌属(Agrococcus)、链球菌属(Streptococcus)和链霉菌属(Streptomyces) 4种Cr(Ⅵ)还原菌不同程度富集. 研究显示,陈皮能在较短时间内有效降低污染土壤中Cr(Ⅵ)浓度及其浸出浓度,并影响了污染土壤中细菌群落结构及其组成;陈皮去除土壤中Cr(Ⅵ)的机制可能是其在土壤中水解的小分子有机物直接将Cr(Ⅵ)还原为Cr(Ⅲ),以及作为碳源驱动Cr(Ⅵ)还原菌的富集进而间接降低Cr(Ⅵ)的毒性.      

Enhanced remediation of Cr（Ⅵ）-contaminated groundwater by coupling electrokinetics with ZVI/Fe3O4/AC-based permeable reactive barrier

Although widely used in permeation reaction barrier（PRB） for strengthening the removal of various heavy metals, zero-valent iron（ZVI） is limited by various inherent drawbacks, such as easy passivation and poor electron transfer. As a solution, a synergistic system with PRB and electrokinetics（PRB-EK） was established and applied for the efficient removal of Cr（Ⅵ）-contaminated groundwater. As the filling material of PRB, ZVI/Fe₃O₄/activated carbon（ZVI/Fe₃O₄     

富里酸对针铁矿吸附Cr(Ⅵ)的影响机理

为研究复杂三元体系中FA(fulvic acid,富里酸)对针铁矿吸附Cr(Ⅵ)的影响,探究FA对重金属Cr(Ⅵ)在环境中迁移转化的作用机理,通过改变FA的添加顺序及添加量,系统研究了FA存在时Cr(Ⅵ)在针铁矿上的吸附行为.结果表明:不添加FA时,离子强度增大促进了针铁矿对Cr(Ⅵ)的吸附;ρ(FA)为50 mg/L时,离子强度增加会抑制针铁矿对Cr(Ⅵ)的吸附.pH为6.98、离子强度为1.0 mol/L时,针铁矿对Cr(Ⅵ)的吸附量比不添加FA时高11.0%.pH为2.98时,添加FA后针铁矿对Cr(Ⅵ)的吸附量最大,比不添加FA时高31.9%.无论是否添加FA,升温均有利于针铁矿对Cr(Ⅵ)吸附,其吸附机理可能是氢键、偶极间力等作用.FA的添加顺序对Cr(Ⅵ)吸附量的影响表现为后添加FA>先添加FA>同时添加FA>对照.研究显示,FA的存在能显著改变针铁矿对Cr(Ⅵ)的吸附行为.      

氢自养还原菌同步去除水中Cr(Ⅵ)和NO3-

本实验研究了序批式条件下Cr（Ⅵ）和NO₃^-浓度、pH值和H₂含量对于氢自养还原菌同步去除水中Cr（Ⅵ）和NO₃^-的性能及微生物群落的影响.结果表明：系统中存在氢气时,正常活性的氢自养还原菌可实现Cr（Ⅵ）的还原;Cr（Ⅵ）初始浓度不高于2000 μg/L时,Cr（Ⅵ）和NO₃^-的还原速率及氢自养还原菌的活性不会受到Cr（Ⅵ）初始浓度的影响;作为一种优先电子受体,NO₃^-会与Cr（Ⅵ）争夺电子,降低Cr（Ⅵ）的还原速率;氢自养还原菌同步还原Cr（Ⅵ）和NO₃^-的最佳pH值为7.0左右,酸性或碱性环境都会抑制Cr（Ⅵ）还原,且NO₂^-会随着pH值的升高逐渐积累;作为电子供体,H₂是还原Cr（Ⅵ）和NO₃^-的必要条件,但H₂足量后,过量提供H₂不能提高Cr（Ⅵ）和NO₃^-的还原速率.     

聚合多巴胺包覆的磁性微球吸附Cr(Ⅵ)

用聚合多巴胺(PDA)包覆溶剂热法制备Fe_3O_4磁性微球,得到Fe_3O_4@PDA复合材料,并采用红外光谱、扫描电镜、透射电镜对复合材料进行表征。同时,对Fe_3O_4@PDA吸附溶液中六价铬(Cr(Ⅵ))的性能进行研究,考察了溶液pH对其吸附性能的影响。结果表明:Fe_3O_4@PDA在溶液pH为3.0时对Cr(Ⅵ)有较好的吸附性能,其吸附动力学数据符合伪二级动力学方程,等温吸附符合Langmuir吸附模型,最大吸附容量达到108.8 mg/g,热力学实验计算出的吉布斯自由能为负值,表明Cr(Ⅵ)在Fe_3O_4@PDA的吸附为自发过程。     

铬污染场地调查数据评估与暴露浓度估计

针对某铬污染场地调查采样得到的1 269个土壤w(TCr)和w〔Cr(Ⅵ)〕,分别采用检出限替代法和Walsh's Test方法分析了未检出值和潜在的异常值.结果表明,异常值的取舍对数据的统计分析结果影响较大,结合该铬污染场地的实际情况和采样记录,最终保留了潜在异常值. 分别采用Q-Q图示法和假设检验方法探讨了该铬污染场地土壤w(TCr)和w〔Cr(Ⅵ)〕的数据分布形态发现,二者均不符合3种常见的分布形态(即正态分布、对数正态分布和Gamma分布),因此,采用基于切比雪夫不等式的非参数方法计算该铬污染场地调查数据的95%UCL(置信区间上限值),确定w(TCr)和w〔Cr(Ⅵ)〕的暴露值分别为0.285 6%和0.022 7%.      

细菌X07吸附Cr(Ⅵ)的研究

从不同来源的样品中分离出一株吸附Cr(Ⅵ)较强的菌株X07,经鉴定为蜡状芽孢杆菌(Bacillus.cereus)。通过吸附实验探讨了X07死菌体对Cr(Ⅵ)的吸附特性,结果表明,X07死菌体吸附Cr(Ⅵ)的最适pH值为6.0;其吸附Cr(Ⅵ)是一个快速、非温度依赖过程,吸附50min达到饱和,在最初的5min内,吸附量达到最大吸附量的76.8%;菌体浓度的增加有利于对Cr(Ⅵ)的吸附:其吸附等温线符合Langmuir和Freundlich吸附模型,在试验的条件下,对Cr(Ⅵ)的饱和吸附容量为146.9mg/g干菌体。     

水泥窑协同处置Cr污染土壤过程中Cr的化学形态转化

为了对水泥熟料中的水溶性类Cr（Ⅵ）化合物从源头入窑废物控制以达到合理处置铬污染土壤的目的,以生料中Cr（Ⅲ）转化为熟料中Cr（Ⅵ）及水溶性Cr（Ⅵ）转化率为切入点展开探究。采用实验室模拟实验结合现场实验分别对含Cr污染土壤（CCS）中Cr元素煅烧前后质量平衡,Cr（Ⅲ）转化为Cr（Ⅵ）的转化率以及水溶性Cr（Ⅵ）的转化率进行研究。结果发现:Cr总量在煅烧前后基本未发生改变;在模拟煅烧实验中,Cr（Ⅲ）→Cr（Ⅵ）的转化率仅为40%左右,但在现场实验中可达到90%左右;水溶性Cr（Ⅵ）仅在现场实验工况下的熟料中检测到,Cr（Ⅵ）中水溶性Cr（Ⅵ）占比为60%~69%,水溶性Cr（Ⅵ）的转化率为35.40%。水泥产品中的水溶性Cr（Ⅵ）检测结果中复合型硅酸盐水泥中水溶性Cr（Ⅵ）含量低于GB 31893-2015《水泥中水溶性铬（Ⅵ）的限值及测定方法》中的相应限值10 mg/kg。     

Cr(Ⅵ)在Fe(Ⅲ)-柠檬酸盐体系中紫外光还原研究

研究了在紫外光照射下,Fe(Ⅲ)-柠檬酸盐溶液对Cr(Ⅵ)的光还原反应.同时,考察了溶液pH值、Fe(Ⅲ)浓度、柠檬酸盐浓度、Cr(Ⅵ)初始浓度对光还原效率的影响,并分析了光还原反应的动力学.研究结果表明,Fe(Ⅲ)-柠檬酸盐体系能光还原Cr(Ⅵ),在pH为2.0～6.0的范围内,Cr(Ⅵ)的还原率随着溶液初始pH值的降低而增大.当pH值为2.0、Fe(Ⅲ)浓度为10μmol·L-1、柠檬酸盐浓度为250μmol·L-1及Cr(Ⅵ)初始浓度为19.2μmol·L-1时,光照反应8min后Cr(Ⅵ)的最大还原率达到100%,但当pH值增加到6.0时,Cr(Ⅵ)的最大还原率下降到19%;当Cr(Ⅵ)的初始浓度在9.6～96.0μmol·L-1的范围内时,Cr(Ⅵ)光还原反应的初始速率随着Fe(Ⅲ)、柠檬酸盐(cit3)、Cr(Ⅵ)初始-浓度的增加而增加.表观动力学方程为:-dCCr(Ⅵ)/dt=0.1019[Cr(Ⅵ)]0.[Fe(Ⅲ)]0.[cit3]0..536-25     

湿法解毒还原工艺对铬渣中Cr(Ⅵ)的治理特性

以治理铬渣中的Cr(Ⅵ)污染为目的,提出了硫酸浸出-硫酸亚铁还原的铬渣湿法解毒工艺,在对铬渣处理前后的表面形貌进行表征的基础上,探究了不同处理条件下铬渣中Cr(Ⅵ)的处理效果及其修复机理。结果表明:铬渣湿法球磨时间为20 min时,铬渣颗粒98.68%过200目筛,水溶性Cr(Ⅵ)的浸出率可达40.96%;铬渣硫酸添加量为60%,液固比为4∶1,酸溶时间为2.5 h时,Cr(Ⅵ)浸出趋于饱和,此时浸出终点pH为5.8,水溶性和酸溶性Cr(Ⅵ)总浸出率为95.38%;硫酸亚铁添加量为40%时,铬渣中Cr(Ⅵ)含量下降为1.38 mg/kg。铬渣中Cr(Ⅵ)的去除主要与硫酸对含Cr(Ⅵ)矿物的溶解、SO₄2-和CrO₄2-的离子交换以及Fe(Ⅱ)对溶液中Cr(Ⅵ)的还原作用有关。     

稻草秸秆对水中六价铬去除效果的研究

为实现农业废料资源化,解决水体Cr(Ⅵ)污染的问题,研究了稻草秸秆对水中Cr(Ⅵ)的去除效果。实验考察了pH,温度,溶液初始Cr(Ⅵ)浓度以及稻草秸秆粒径大小对吸附效果的影响,进而确定了稻草秸秆去除Cr(Ⅵ)的最佳条件。结果表明,在pH2.0,温度47℃时,稻草秸秆对Cr(Ⅵ)的吸附效果最好,在48h内可将100mg/L的Cr(Ⅵ)完全去除。利用酒石酸对稻草秸秆进行化学改性,研究其对溶液中Cr(Ⅵ)的去除以及溶液pH的变化。Cr(Ⅵ)的去除过程中伴随着Cr(Ⅲ)的出现,说明改性稻草秸秆(TARS)不仅可以将Cr(Ⅵ)从溶液中去除,且还可将其转化成低毒的Cr。溶液pH的上升说明Cr(Ⅵ)的去除需要消耗溶液中的H+。通过RS和TARS对Cr(Ⅵ)的热力学吸附过程的进一步分析,结果表明:RS和TARS对Cr的吸附均较符合Langmuir吸附等温模式,其中TARS的最大吸附容量可以达到5.266mg/g。     

Experimental study on Cr(Ⅵ) reduction by Pseudomonas aeruginosa

Investigation on Cr(Ⅵ) reduction was conducted using Pseudomonas aeruginosa. The study demonstrated that the Cr(Ⅵ) can be effectively reduced to Cr(Ⅲ) by Pseudomonas aeruginosa. The effects of the factors affecting Cr(Ⅵ) reduction rate including carbon source type, pH, initial Cr(Ⅵ) concentration and amount of cells inoculum were thoroughly studied. Malate was found to yield maximum biotransformation, followed by succinate and glucose, with the reduction rate of 60.86%, 43.76% and 28.86% respectively. The optimum pH for Cr(Ⅵ) reduction was 7.0, with reduction efficiency of 61.71% being achieved. With the increase of initial Cr(Ⅵ) concentration, the rate of Cr(Ⅵ) reduction decreased. The reduction was inhibited strongly when the initial Cr(Ⅵ) concentration increased to 157 mg/L. As the amount of cells inoculum increased, the rate of Cr(Ⅵ) reduction also increased. The mechanism of Cr(Ⅵ) reduction and final products were also analysed. The results suggested that the soluble enzymes appear to be responsible for Cr(Ⅵ) reduction by Pseudomonas aeruginosa, and the reduced Cr(Ⅲ) was not precipitated in the form of Cr(OH)3.     

化学改性对BA-3活菌体去除Cr(Ⅵ)的影响作用

通过对BA-3活菌体进行多种化学改性,比较了经化学改性后的BA-3菌体对C(rⅥ)的去除效率。结果表明,所试化学改性均会导致BA-3活菌体一定程度的质量减少;无机酸改性及有机溶剂改性均可较大程度提高菌体的C(rⅥ)去除效率,而无机酸改性、有机溶剂改性及盐改性则对菌体吸附Cr的效率有不同程度的提高作用。菌体表面上的[H+]及[OH-]的分布对于其吸附Cr及还原C(rⅥ)均有重要的影响作用,当溶液中的[H+]浓度增加时,会加快菌体还原Cr(Ⅵ)的速率,并促进菌体对Cr的吸附作用;当溶液中[OH-]增加时,C(rⅥ)的去除速率会相应降低,而菌体对Cr的吸附效果也有所降低。以盐改性时可提高菌体表面可交换阳离子的活性,并促进菌体表面与C(rⅢ)的离子交换,从而在Cr的吸附后期有利于菌体吸附溶液中的C(rⅢ)。此外,菌体的菌丝球结构及其比表面积也会影响其吸附Cr及还原C(rⅥ)的效率。有机溶剂改性可改善菌体的有效表面积,对菌体去除C(rⅥ)及吸附Cr都是有利的。     

Intensification of adsorption process by using the pyrolytic char from waste tires to remove chromium(Ⅵ) from wastewater

Pyrolysis has the potential of transforming waste into valuable recyclable products. Pyrolytic char(PC) is one of the most important products from the pyrolysis of used tires. One of the most significant applications for pyrolytic char recovered is used for the removal of Cr(Ⅵ) in the wastewater effluent to control waste by waste. The surface chemistry properties of surface element distribution / concentration and chemical structure were examined for the pyrolytic char and the commercial activated carbon(CAC) respectively. The results showed that surfaces of PC possesses a large amount of ester and hydrocarbon graft, whereas there are mainly carbon functional components of C-OH, C=O and COOH on the surface of CAC. Therefore the surface electronegativity of PC is lower than that of CAC in the water. The repulsive interactions between the surfaces of PC and the negatively charged Cr(Ⅵ) ion are weaker than that of CAC, which results in an intensification of the adsorption process by the utilization of PC. The adsorption isotherms of Cr(Ⅵ) ion on the two kinds of carbons were determined experimentally. The larger adsorption amount on the PC in the case of Cr(Ⅵ) may be attributed mainly to its special surface micro-chemical environment. The mechanism of the removal Cr(Ⅵ) from aqueous solution was assumed to be the integration of adsorption and redox reaction. The adsorption was the rate-controlled step for Cr(Ⅵ) removal. The adsorption of Cr(Ⅵ) has been identified as pseudo-second- order kinetics. The rate constants of adsorption have been evaluated.     

Fe(Ⅲ)-OH配合物同时引发水中Cr(Ⅵ)光还原和甲基橙光氧化

在250 W照明金属卤化物灯(λ≥313 nm)照射下,Fe(Ⅲ)-OH配合物能同时引发水中Cr(Ⅵ)的光还原和偶氮染料甲基橙的光氧化,并且同时Cr(Ⅵ)光还原和甲基橙光氧化效率都较Fe(Ⅲ)-OH配合物单独作用下的效率有明显提高.在c(Fe(Ⅲ)),c(Cr(Ⅵ))和c(甲基橙)为25～200 μmol/L时,pH=3.0是最佳值;c(Fe(Ⅲ))的增加同时有利于Cr(Ⅵ)光还原和甲基橙光氧化;c(Cr(Ⅵ))为25 μmol/L时,其自身光还原的初始速率最大,甲基橙光氧化反应初始速率则随c(Cr(Ⅵ))和c(甲基橙)的增大而减小.      

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%。