Shewanella oneidensis MR-1对Cr(VI)的还原及其影响因素

在实验室纯培养条件下,探讨厌氧体系中Shewanella oneidensis MR-1对Cr（VI）的还原能力,采用扫描电镜（SEM）-能谱（EDS）、X射线光电子能谱（XPS）等方法进行表征.结果表明,S.oneidensis MR-1介导下不同浓度Cr（VI）的生物转化与微生物对铬的耐受特性密切相关,低浓度Cr（VI）对其生长影响不大,高浓度时细菌生长则受到抑制,进而抑制Cr（VI）的还原率;菌株对Cr（VI）的还原作用随着接种菌悬液量的增加而增强;菌株最适生长pH值为中性,弱碱性环境比酸性环境更有利于菌株对Cr（VI）的还原;增加Fe（Ⅲ）的量会加快Cr（VI）完全还原的速率.通过SEM-EDS和XPS分析,在对Cr（VI）进行处理5d后,菌体表面有Cr（VI）和Cr（Ⅲ）两种形态存在,证实S.oneidensis MR-1在对Cr（VI）进行还原的同时也伴有少量的吸附作用.微生物还原为环境中Cr（VI）的去除以及解毒提供了一种有效的方法.     

嗜根寡养单胞菌DSM14405T对高浓度Cr(Ⅵ)的抗性及其还原特性分析

为了寻找植物-微生物联合治理Cr（VI）污染的合适微生物,分析了一株植物根际促生菌——嗜根寡养单胞菌DSM 14405^T（Stenotrophomonas rhizophila DSM 14405^T）对不同浓度Cr（VI）的还原能力、Cr（VI）还原最适培养条件、对连续投加Cr（VI）的还原能力及高浓度Cr（VI）处理不同时间的转录组变化.结果表明,嗜根寡养单胞菌DSM 14405^T在24 h内对10、50、200和500 mg·L^-1 Cr（VI）的还原率分别为100%、92.4%、26.2%和16.5%,且在30℃、pH=7.5、转速180 r·min^-1条件下培养能最经济、高效地还原Cr（VI）.该菌能在64 h内完全还原2次所投加的50 mg·L^-1的Cr（VI）,第3次投加后仅能还原55.2%左右.比较转录组学分析可得,200 mg·L^-1Cr（VI）作用下,嗜根寡养单胞菌DSM 14405^T细胞表现出显著的抗性.具体表现为：大幅度上调胞内消除有毒自由基的相关基因、DNA修复相关基因以防止DNA因自由基受损,同时下调细胞组分及蛋白代谢等与细胞抗性相关性低的通路.并且,随着Cr（VI）的还原和细胞对环境的适应,Cr（VI）抗性相关基因及通路的调节在长时暴露中明显少于短时暴露.本研究为Cr（VI）污染的原位植物-微生物联合治理提供了可选菌株和理论依据.     

菌株Enterobacter sp. L6异化Fe(III)还原及Cr(VI)还原的性质分析

Cr（VI）是一种毒性极强的重金属,利用微生物还原Cr（VI）为Cr（III）是解决Cr（VI）污染的一条有效途径。菌株Enterobacter sp. L6是一株分离自海洋沉积物中的异化铁还原细菌。接种时细胞密度A₆₀₀为（0.25±0.03）,培养12 h,A₆₀₀达到（1.04±0.05）,累积产生Fe（II）浓度为（0.80±0.03）mmol/L;随着培养时间的延长,细胞密度A₆₀₀和累积产生Fe（II）浓度开始下降;培养36 h时,细胞密度A₆₀₀为（0.81±0.04）,累积Fe（II）浓度（0.63±0.01）mmol/L。在厌氧培养过程中,菌株L6细胞生长与异化还原Fe（III）性质存在明显的偶联关系。利用菌株L6的异化铁还原性质还原Cr（VI）的实验结果表明,在Cr（VI）浓度0～24 mg/L范围内,异化铁还原细菌L6都能进行细胞生长并还原Cr（VI）。Cr（VI）浓度为4、8和12 mg/L时,菌株L6对Cr（VI）还原率可达到100%,当Cr（VI）浓度为16 mg/L时,Cr（VI）还原率是参比[未添加Fe（III）]的2.11倍。Cr（VI）浓度为20、24 mg/L时,仍能够还原Cr（VI）。以Fe（III）为电子受体的异化铁还原细菌能明显提高Cr（VI）还原率,这为利用微生物修复Cr（VI）污染提供实验数据支持。     

乙基黄药对施氏矿物吸附Cr（Ⅵ）的影响研究

选矿药剂在矿产资源开发中被大量使用,环境中残留的选矿药剂及其衍生物对重金属的迁移、转化等环境行为产生重要影响.施氏矿物是广泛存在于酸性矿山废水中的一种典型的羟基硫酸盐铁矿物,对重金属具有明显的吸附作用.然而,浮选药剂对施氏矿物富集重金属的影响有待深入研究.本研究采用快速化学法合成施氏矿物,通过批量吸附实验法系统探究典型浮选药剂乙基黄药存在条件下,反应体系pH、接触时间、浮选药剂浓度、Cr（VI）初始浓度等因素对施氏矿物吸附Cr（VI）的影响规律.结果表明：在酸性条件下,乙基黄原酸钠抑制施氏矿物对Cr（Ⅵ）的吸附作用;在碱性条件下,乙基黄原酸钠对施氏矿物吸附Cr（Ⅵ）具有明显的促进作用.在初始pH条件为8.5时,施氏矿物对Cr（VI）的最大去除容量达到56.96 mg?g^-1,与最佳条件下施氏矿物对Cr（VI）的吸附容量 （40.4 mg?g^-1） 相比,吸附容量提升了41%.乙基黄原酸钠存在条件下施氏矿物对Cr（Ⅵ）的吸附符合准二级动力学,表明该吸附过程以化学吸附机制为主.在Cr（VI）的吸附过程中,黄原酸基将Cr（Ⅵ）还原为Cr（Ⅲ）,从而增强了了施氏矿物在碱性条件下对Cr（VI）的去除能力.研究结果表明乙基黄药的存在能够显著影响施氏矿物对Cr（VI）的吸附过程及吸附机制.     

不同pH值和O2条件下硝酸改性生物炭去除六价铬机理

为改善生物炭对Cr（VI）的去除性能并探究溶液初始pH值和O₂对生物炭的氧化还原活性物质（RAMs,即含氧官能团和环境持久性自由基 （EPFRs））还原Cr（VI）的影响,用硝酸（HNO₃）改性玉米秸秆生物炭（NBC）,采用电子扫描显微镜-能谱仪（SEM-EDX）、比表面积及孔隙测定仪（BET）、Zeta电位仪和红外光谱仪（FTIR）分析生物炭性质,通过X射线光电子能谱仪（XPS）、Boehm滴定和电子顺磁共振波谱仪（EPR）测定生物炭RAMs含量变化.结果表明,HNO₃改性增加了生物炭的比表面积、总孔体积、含氧官能团和表面电位,从而能更有效地去除Cr（VI）（在pH 2.0时去除率达到100%,其表面吸附的铬89.12%被还原为Cr（III））.动力学实验表明,NBC可以直接还原Cr（VI）,也可以通过还原O₂产生的?O₂^-间接还原Cr（VI）;直接还原途径占主导地位,间接还原途径对Cr（VI）的还原贡献率随着pH值的升高而增加.此外,酸性条件下含氧官能团（—OH和C—O—C）是还原反应的主要电子供体,而中性条件下EPFRs主导还原.因此,HNO₃改性提高了生物炭对Cr（VI）的去除能力,NBC可以通过直接途径和间接途径还原Cr（VI）,并且在不同pH值下通过不同电子供体主导NBC还原Cr（VI）的过程.     

真菌对磺胺二甲氧嘧啶降解过程的转录组分析及差异表达基因的功能分析

采用黄孢原毛平革菌降解磺胺二甲氧嘧啶（SDM）,4 d后SDM的去除率达74%,降解速率达3.24 mg·L^-1·d^-1.采用Illumina高通量测序平台对降解SDM后的菌株与对照组菌株进行测序,通过GO和KEGG富集分析,得到的差异表达基因能显著富集到与降解相关的“氧化还原酶活性”途径,及与应激反应有关的“ABC转运体”路径.通过对高表达高上调的差异表达基因的筛选与分析,得到了耐受和降解SDM的功能基因.水通道蛋白、ABC转运蛋白及甲基转运酶基因等在黄孢原毛平革菌对环境的耐受中起到重要的作用.乙醇氧化酶、细胞色素P450和糖苷水解酶等在黄孢原毛平革菌对SDM的降解中起着关键的作用.本文从转录组水平分析了SDM的降解机制,为黄孢原毛平革菌在环境修复中的应用提供一定的参考.     

1株海洋产电菌Shewanella XMS-1的特性分析

以厦门湾海水中的底泥为接种物筛选得到1株具有电化学活性的菌株XMS-1,研究该菌株相关特性及其在环境污染控制中的应用。根据菌株的形态、生理生化性质及16S rRNA基因测序的结果确定其种属,并用以构建微生物燃料电池,研究该菌株的产电性能,以及对典型重金属污染物Cr （Ⅵ）的还原能力。菌株XMS-1经鉴定属于Shewanella属,当MFC中接种初始浓度OD₆₀₀为0.3时可获得最大功率密度18 mW/m2、电流密度243 mA/m2,细菌能够在pH为7~8和NaCl含量为0~6%条件下实现对Cr （Ⅵ）的还原。XMS-1该菌株能在较宽的pH和较高的盐度条件下高效还原Cr（Ⅵ）,并且具备良好的电化学活性,为微生物直接处理含盐工业废水和实现海水资源化利用提供了新的研究思路和数据参考。     

紫外活化甲酸产二氧化碳阴离子自由基还原Cr (VI)的研究

研究高效还原技术是去除废水中Cr（VI）的有效手段,本研究提出了一种新颖有前景的基于紫外（UV）活化甲酸（HCOOH）产还原性二氧化碳阴离子自由基（CO₂^•;-）去除Cr（VI）的方法.通过对比UV、HCOOH、UV/HCOOH三种体系对Cr（VI）还原效率和电子自旋共振（EPR）对体系中自由基的检测研究了其活化原理和还原机制.结果表明UV能显著活化HCOOH产生CO₂^•-（α_H=19.08G,α_N=15.86G,g=2.0036）.此外,试验考察了主要影响因素对Cr（VI）去除效果的影响,包括初始Cr（VI）浓度、甲酸投加量、初始pH值、反应温度、有机污染物以及水中常见阴离子.结果显示当甲酸浓度为40mmol/L,Cr（VI）初始浓度为10mg/L,反应时间在60min内,UV/HCOOH体系对Cr（VI）的去除率能达到100%.在酸性条件下（pH≤3.5）能显著促进Cr（VI）的还原,且Cr（VI）去除效率随着初始HCOOH浓度和反应温度升高而增加.进一步研究表明,该体系下NO₃^-对Cr（VI）的还原有着显著的促进作用,而Cl^-、HCO₃^-和对硝基苯酚（pNP）则有抑制作用.不同温度下Cr（VI）去除率与时间关系的拟合结果表明,当反应时间t³;40min,UV/HCOOH体系去除Cr（VI）过程遵循准一级反应动力学,根据不同温度下对应的反应速率常数k,结合阿伦尼乌斯方程,计算求得准一级反应的活化能为15.9kJ/mol.     

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.     

基于PMS的Cr(VI)-染料复合废水协同处理效果及机理

通过投加过一硫酸盐（PMS）探讨其协同处理偶氮染料金橙Ⅱ（AO7）及Cr（VI）的可行性、影响因素及机理.结果表明,体系可以在有效去除AO7的同时降低Cr（VI）浓度,120min时降解率分别达到97.9%及22.1%;随着初始pH值降低AO7降解及Cr（VI）去除效率逐渐升高;AO7的降解主要是由于Cl^-与PMS反应产生的氧化性物质HClO以及PMS投加创造的酸性条件使得Cr（VI）具有强氧化性的共同作用,其中起主导作用的是HClO;Cr（VI）的转化是由于自身与AO7发生氧化还原反应导致.本研究可以为复合污染废水的处理提供理论依据.     

硫酸根离子强化零价铁去除Cr(Ⅵ)的试验研究

普通零价铁去除Cr（VI）的反应活性较低且Cr（VI）会导致零价铁较快钝化.通过连续流实验,研究了硫酸根离子提高零价铁去除水中Cr（Ⅵ）的可行性与反应机理.实验结果表明,在未加入硫酸根离子时,运行5.5h后柱子出水总铬及Cr（VI）已开始超出饮用水标准.而在加入1~3mmol/L SO₄^2-后,出水总铬及Cr（VI）持续降低,并最终降至饮用水水质标准以下且稳定运行长达240h以上.XPS分析结果表明,还原作用是零价铁除Cr（Ⅵ）的主要机理,硫酸根离子加速了零价铁的腐蚀进而促进了Cr（VI）的去除.     

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.     

草酸改性杨树叶对六价铬的吸附性能

利用草酸改性杨树叶为试验材料,对溶液中六价铬进行吸附去除。试验结果表明:当p H=2,吸附剂剂量为0.3 g,反应时间为120 min时,该材料对50 m L浓度为50 mg/L含铬废水的去除率达99.1%;伪二级动力学方程能较好地拟合该材料对Cr(VI)的吸附动力学过程,揭示其吸附主要是离子交换吸附;Langmuir方程能较好模拟该材料对Cr(VI)的等温吸附过程,表明其吸附主要是单分子层吸附,最大吸附量为40.91 mg/g。热力学研究表明,Cr(VI)在该材料表面的吸附是一个自发、吸热的物理吸附过程。     

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 Fe~0,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 r GO-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:r GO-nZVI firstly transferred electrons from Fe~0 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.     

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.     

Electrochemical reduction of Cr(VI) in the presence of sodium alginate and its application in water purification

Chromium (Cr) is used in many manufacturing processes, and its release into natural waters is a major environmental problem today. Low concentrations of Cr(VI) are toxic to human health and living organisms due to the carcinogenic and mutagenic nature of this mineral. This work examined the conversion of Cr(VI) to Cr(III) via electrochemical reduction using gold electrode in an acidic sodium alginate (SA) solution and subsequent removal of the produced Cr(III)-SA by the polymer-enhanced ultrafiltration (PEUF) technique. A solution of SA in nitric acid was used both as an electrolytic medium during the voltammetric measurements and bulk electrolysis and as an extracting agent during the PEUF technique. The electroanalysis of Cr(VI) was performed by linear sweep voltammetry in the presence of acidic SA solution to study its voltammetric behavior as a function of the Cr(VI) concentration, pH, presence of Cr(III), SA concentration and scan rate. In addition, the quantitative reduction of Cr(VI) to Cr(III) was studied through the bulk electrolysis technique.The results showed efficient reduction with well-defined peaks at approximately 0.3 V vs. Ag/AgCl, using a gold working electrode. As the pH increased, the reduction signal strongly decreased until its disappearance. The optimum SA concentration was 10 mmol/L, and it was observed that the presence of Cr(III) did not interfere in the Cr(VI) electroanalysis. Through the quantitative reduction by bulk electrolysis in the presence of acidic SA solution, it was possible to reduce all Cr(VI) to Cr(III) followed by its removal via PEUF.