异化铁还原对土壤中重金属形态转化及其有效性影响

铁的微生物还原是以Fe(Ⅲ)为末端电子受体在厌氧条件下氧化有机物的产能过程,在生物地球化学循环中起着重要的作用.铁呼吸被认为是地球上最古老的微生物代谢形式,与水体、土壤及沉积物中物质循环息息相关.铁的微生物还原对土壤中重金属形态转化有显著影响,对修复重金属及放射性核素污染的场地有着重要意义.本文综合评述了近年来铁微生物还原研究进展,从生态安全和可持续发展角度,探讨了异化铁还原对重金属的形态改变及重金属污染土壤修复的潜在价值,并对其应用前景进行客观分析.异化铁还原对重金属形态转化的影响机制,可初步归纳为异化铁还原对重金属的氧化还原作用、对重金属的甲基化作用、对重金属的固定作用,其作用机制包含生物过程和化学作用的相互穿插,值得进一步深入研究.     

典型钢铁行业汞排放特征及质量平衡

以重庆市某钢铁企业各工艺单元的进出物料为研究对象,分析样品总汞及各物料中汞的输入输出量,初步探讨钢铁生产各工序汞的排放特性及其质量平衡.结果发现,各工艺输入物料汞含量为2.93~159.11μg·kg~(-1),其中,高炉所用块矿汞含量最高,其次为烧结以及高炉用煤.输出物料中汞含量为3.09~18.13μg·kg~(-1),除尘灰汞含量最高,其次为转炉渣.该钢铁企业自备焦化厂汞输入量和输出量分别为1 346.74 g·d~(-1)±36.95 g·d~(-1)和177.42 g·d~(-1)±13.73 g·d~(-1),焦化工序中的汞主要来源于焦煤的燃烧.钢铁生产过程中烧结工序汞输入量最高,为1 075.27 g·d~(-1)±60.89 g·d~(~(-1)),占钢铁生产总汞带入量的68.06%,其来源主要是铁矿粉.固体输出物料中,烧结工序输出汞量为14.15 g·d~(-1)±0.38 g·d~(-1),占总固体输出量22.61%.经估算,该钢铁企业2013年汞排放量约为553.83 kg,汞排放因子为0.092 g·t~(-1)钢产量.为控制汞排放,钢铁企业应结合生产实际,进一步降低焦化以及烧结工序能耗水平,或提高原料质量,减少汞的输入.     

水中粪大肠菌群测定方法的比较研究分析——酶底物法与多管发酵法

用酶底物法与多管发酵法分别检测地表水和污水同组样品。应用t-检验：成对双样本均值分析的统计方法比较两种检测手段测定结果的相关性。结果表明,酶底物法与多管发酵法用于水中粪大肠菌群检测,测定结果具有强相关性,但统计学意义上有差异。在置信度95%时此差异能被接受。酶底物法操作简便、快速、结果稳定,满足环境监测技术要求,可用以评价水质微生物污染程度。     

DMP和DEP在氧化铁多相体系中的光催化降解

应用水热合成法制备了4种自然界常见的氧化铁:纤铁矿、赤铁矿、针铁矿和磁赤铁矿,选取邻苯二甲酸二甲酯(DMP)和邻苯二甲酸二乙酯(DEP)作为目标物,研究了它们在氧化铁体系中,紫外光和可见光下的降解过程。重点探讨草酸、光源和氧化铁对其光解效率的影响机制,并与其它文献报道的光解体系进行比较。结果显示,如没有草酸的协同作用,目标物很难发生光解;草酸能够显著促进目标物的光解效率,当目标物初始浓度为20 mg/L,紫外光条件下,DMP和DEP反应60 min后的最高降解率可达到98%以上,可见光条件下,反应180min后可达到96%以上。研究体系与其它光解体系比较,绿色、经济的特点显著。     

pH值对零价铁自养反硝化过程的影响

以零价铁和硝酸盐为基质,通过批量实验和连续流发酵罐实验中铁自养反硝化脱氮速率的测定,研究了铁自养反硝化过程pH值的变化以及pH值对零价铁自养反硝化污泥活性的影响.批量实验采用4个添加污泥的反应瓶,初始pH值分别为6.2、6.7、7.5、8.8和一个初始pH为6.7的未添加污泥瓶.结果表明初始pH值6.7时表现出最高氮素脱除速度,其中未添加污泥的批量瓶pH持续上升至10左右,4个不同初始pH添加污泥的批量瓶的pH值后续均集中在7.5~7.8之间,难以凸显不同pH值对反硝化菌的影响.利用能够控制pH值稳定的连续流发酵罐,通过设立6、6.5、7、7.5、8这5个恒定的pH梯度,对微生物不同pH值条件下的适应性和活性进行观察,结果表明在pH为6.5时污泥活性最大,其氮脱除速率达到1.35mg·(L·h)~(-1).     

阿哈水库沉积物-水界面磷、铁、硫高分辨率空间分布特征

选取贵州典型高原亚深水型湖库阿哈水库为研究对象,利用薄膜扩散梯度技术获取夏季分层期不同湖区沉积物-水界面磷、铁、硫的原位、二维高分辨分布信息,并结合水化学及沉积物磷形态分析,探讨了沉积物P-Fe-S分布规律及控制因素.结果表明:沉积物-水界面DGT-P的浓度变化范围0.00~0.43 mg·L~(-1),DGT-Fe的浓度变化范围0.00~2.83 mg·L~(-1),DGT-S的浓度变化范围0.00~0.10 mg·L~(-1).阿哈水库沉积物孔隙水磷、铁、硫浓度在垂向分布上没有显著的相关性,DGT-P、DGT-Fe甚至还呈反向变化,这与很多湖泊的研究结果存在明显差异,其原因可能是阿哈水库沉积物具有很高的Fe/P和Fe/S比值,过剩的Fe导致还原态S以FeS/FeS_2形式沉淀后,P仍然被Fe(Ⅲ)固定在沉积物中.阿哈水库沉积物磷形态以Na OH-SRP和BD-P为主,Na OH-SRP含量变化范围为192~604 mg·kg~(-1),平均值约为392 mg·kg~(-1),BD-P含量变化范围为143~524mg·kg~(-1),平均值约为225 mg·kg~(-1).阿哈水库底层水体长期处于厌氧环境,Fe、S地球化学循环对沉积物内源磷释放起着重要控制作用.     

Decolorization of Methyl Orange by a new clay-supported nanoscale zero-valent iron: Synergetic effect, efficiency optimization and mechanism

In this study, a novel nanoscale zero-valent iron (nZVI) composite material was successfully synthesized using a low-cost natural clay, “Hangjin 2^# clay” (HJ clay) as the support and tested for the decolorization of the azo dye Methyl Orange (MO) in aqueous solution by nZVI particles. According to the characterization and MO decolorization experiments, the sample with 5:1 HJ clay-supported nZVI (HJ/nZVI) mass ratio (HJ-nZVI5) showed the best dispersion and reactivity and the highest MO decolorization efficiency. With the same equivalent Fe⁰ dosage, the HJ-nZVI1 and HJ-nZVI5 samples demonstrated a synergetic effect for the decolorization of MO: their decolorization efficiencies were much higher than that achieved by physical mixing of HJ clay and nZVIs, or the sum of HJ clay and nZVIs alone. The synergetic effect was primarily due to the improved dispersion and more effective utilization of the nZVI particles on/in the composite materials. Higher decolorization efficiency of MO was obtained at larger HJ-nZVI dosage, higher temperature and under N₂ atmosphere, while the MO initial concentration and pH were negatively correlated to the efficiency. HJ clay not only works as a carrier for nZVI nanoparticles, but also contributes to the decolorization through an “adsorption-enhanced reduction” mechanism. The high efficiency of HJ-nZVI for decontamination gives it great potential for use in a variety of remediation applications.     

A zero-valent iron and organic matter mixture enhances herbicide and herbicide degradation product removal in subsurface waters

The pesticide atrazine,its degradation products,and 2,6-dichlorobenzamide(BAM) are persistent in groundwater environment.We studied whether their dissipation can be enhanced with a mixture of a complex carbon source and zero-valent iron(ZVI) called EHC.The application rates were 1.0% and 2.0%(by weight) in subsurface sediments slurries(atrazine 30 mg/L),and 2.0% in 1.5 m pilot-scale sediment columns with groundwater flowing through(atrazine 0.08,desethylatrazine DEA 0.03,BAM 0.02 μg/L).In the slurries under aerobic conditions,atrazine of 0.88 ± 0.14 mg/g of EHC was dissipated chemically,as concentrations did not differ significantly between the slurries and their sterilized controls.No degradation occurred in the slurries under anaerobic conditions.In the pilot-scale columns under water-saturated conditions,atrazine,DEA and BAM were not detected in effluents during 33,64 and 64 days from the beginning of the water flow through EHC columns,respectively,but thereafter traces of compounds could be detected.No atrazine or degradation products(BAM,DEA,deisopropylatrazine,desethyldeisopropylatrazine) could be extracted from the column sediments at the end of the experiment.As a result,the sum of dissipated pesticides was about7.6 μg/g of EHC in columns under water-saturated conditions,and 0.88 mg/g of EHC in slurries under aerobic conditions.EHC can be used to enhance the dissipation of studied pesticides in small quantities,preferentially under aerobic conditions.     

改性纳米零价铁对稻田土壤As污染的修复效能

为实现对稻田土壤As污染的高效修复,通过制备C-NZVI(壳聚糖基稳定化纳米零价铁),分析其对还原态亚砷酸〔As(Ⅲ)〕的吸附动力学和等温吸附特征,阐明典型竞争性阴离子/分子对C-NZVI吸附As(Ⅲ)效率的影响;在此基础上,重点研究淹水和拮抗性肥料对稻土As的强化溶出效应,揭示C-NZVI对稻土液相As的异位吸附去除与原位补充钝化作用.结果表明:准一级动力学和Langmuir等温吸附模型能很好地描述C-NZVI对As(Ⅲ)的吸附过程特征,该材料对As(Ⅲ)的最大吸附量为145.09 mg/g;当竞争性K₂HPO₄、H₃BO₃、Na₂SiO₃和CH₃COOH的摩尔浓度为0.05~0.50 mmol/L时,C-NZVI对As(Ⅲ)的去除率依然高达99%.在对稻田土壤进行淹水和依次施用NH₄H₂PO₄、(NH₄)₂C₂O₄、Na₂SiO₃三种拮抗性肥料条件下,稻土中累积溶出w(水溶态As)(18.1 mg/kg)达到土壤w(As)的30.0%;对强化溶出反应后的淹水稻土进行排水并利用C-NZVI对各步分离获得的含As液相进行异位吸附,As去除率为91.3%~99.8%,该过程使稻土中w(As)减少43.4%~52.6%;进一步利用1%和5%的C-NZVI对强化溶出后的稻土进行补充钝化,可使稻土中w(非专性吸附态As)降低94.7%~100%.研究显示,淹水强化条件下,利用C-NZVI对稻田土壤As污染进行异位去除与原位钝化的联合修复可为有效减控稻田土壤As生物有效性提供有益途径.