Triethylenetetramine/hydroxyethyl cellulose-functionalized graphene oxide monoliths for the removal of copper and arsenate ions

Nitrogen-doped graphene oxide monoliths (GOMs) were readily constructed by crosslinking graphene oxide (GO) using triethylenetetramine (TETA) and hydroxyethyl cellulose (HEC). The addition of HEC was beneficial to the formation of a network structure compared to that in the absence of HEC. The generated monoliths have shown various morphologies with different d spacing, layer thickness, and micropore size. Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS) analyses provided evidences for the formation of covalent C–N bonds and some nitrogen-containing heterocyclic composition inside the graphene oxide sheet, indicating that the interaction of GO with the amine crosslinker involved the crosslinking reaction between GO epoxides and amine groups. HEC was also involved in the N-doping reaction via the partial reduction of oxygen in HEC molecules. Analysis of X-ray diffraction (XRD) results indicated that the lattice distance between GO sheets increased after TETA/HEC crosslinking. Thermogravimetric analysis (TGA) confirmed the successful incorporation of crosslinker moieties on the surface of GO sheets. The fabricated GOMs could be used to efficiently adsorb metal ions and arsenate by the introduced polar functional groups on GO sheets and porous structures based on hydrogen bonds, whose morphologies and compositions were confirmed via XRD, scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS).     

硫化物矿床氧化带砷酸盐矿物的地质找矿意义

砷酸盐矿物是主要产出于硫化物矿床氧化带中的次生矿物,在自然界中已发现２５０ 多种,我国目前仅发现该类矿物３８ 种。砷酸盐矿物的生成与原生矿石的矿物成分及其数量、气候条件和介质条件等因素密切相关。毒砂及含砷矿物和黄铜矿、黄铁矿、磁黄铁矿、方铅矿、闪锌矿等硫化物的大量存在是形成砷酸盐矿物的物质基础。该类矿物一般多形成于温湿多雨的热带－ 亚热带气候区域和矿床围岩为碳酸盐岩的弱酸性－ 中性的介质环境中。砷酸盐矿物常是硫化物矿床氧化带发育至末期阶段的重要产物之一,对判断原生矿床的氧化程度和剥蚀深度有一定的指示意义;根据砷酸盐矿物的组合类型可较快速地确定原生矿床（ 体） 的工业类型和找矿方向。根据砷酸盐矿物的形成条件,砷酸盐矿物大量发育的铁帽氧化带一般可作为寻找（ 夕卡岩型） 铜锡多金属硫化物矿床的重要标志。     

砷铁渣中砷酸铁的热力学分析及热分解试验

利用铁盐法处理某铅冶炼工业含砷废水,得到砷质量分数为10%的砷铁渣,物相分析表明砷与铁在渣中以砷酸铁的形态存在。据热力学分析,砷酸铁化合物在1600℃以下不会热分解,表明其热力学性质稳定;而在有添加剂碳的情况下,砷酸铁的热分解温度大大降低。试验结果表明:在1200℃条件下,静态焙烧5h,砷酸铁砷的挥发率在90%以上,铁富集10%以上。     

含砷铜烟尘砷的选择性分离实验

在氮气气氛下,采用低温焙烧的方法对含砷铜烟尘中的砷进行选择性分离,研究了温度、氮气流量和焙烧时间的变化对砷挥发率的影响,用X射线衍射分析、差热-差重分析等方法研究了含砷铜烟尘中砷的挥发规律,并分析了砷挥发过程的动力学。结果表明,含砷铜烟尘中砷的选择性分离应在低温下进行,避免高温下Zn、Pb挥发损失和As_2O_3生成难挥发的砷酸盐。在250℃,氮气流量300mL/min、焙烧120min的条件下,砷的挥发率为95.68%,渣中砷的含量为0.79%,其他有价金属基本不挥发,实现了砷与其他有价金属的选择性分离,砷以初级As_2O_3产品回收,纯度为96.85%。动力学研究表明,在一定范围内,砷的低温选择性挥发过程符合收缩核模型,其表观活化能为19.71kJ/mol,该过程受内扩散控制。     

磷渣基地聚物材料固化砷钙渣的机理

以砷含量为7.63%的砷钙渣为研究对象,利用磷渣基地聚物材料对其进行固化处理,并采用毒性浸出实验考察了砷钙渣及固化体砷毒性浸出特性。结果表明:砷钙渣中砷的毒性浸出浓度可达2 450 mg/L,远超过国家毒性浸出鉴别标准限值(5 mg/L)。考察了不同养护时间、不同p H值(1~12)浸取剂环境下固化体中砷的浸出规律。结果表明:在p H=4~8范围内,砷浸出浓度较小;在酸性(p H4)和碱性(p H8)条件下砷浸出相对较大,但均小于5 mg/L。并考察了固化体中砷形态变化规律,揭示其固化机理。当养护时间为28 d时,固化体中As(Ⅲ)含量由96.3%降至28.8%,其后随着养护时间的变化固化体中As(Ⅲ)含量呈缓慢降低趋势,180 d As(Ⅲ)含量为12.6%,240 d As(Ⅲ)含量为10.8%。磷渣基地聚物固化砷钙渣机理为:磷渣基地聚物材料水化环境和所含的铁氧化物可使高毒性及强迁移性As(Ⅲ)向相对稳定的As(Ⅴ)转化;随时间的变化,磷渣基地聚物材料不断水化,并提供游离Ca2+、Al3+离子,使砷化合物经沉淀反应生成Al-As-O、Ca-As-O难溶性盐,进而降低砷浸出浓度。     

Shewanella sp. O23S as a Driving Agent of a System Utilizing Dissimilatory Arsenate-Reducing Bacteria Responsible for Self-Cleaning of Water Contaminated with Arsenic

The purpose of this study was a detailed characterization of Shewanella sp. O23S, a strain involved in arsenic transformation in ancient gold mine waters contaminated with arsenic and other heavy metals. Physiological analysis of Shewanella sp. O23S showed that it is a facultative anaerobe, capable of growth using arsenate, thiosulfate, nitrate, iron or manganite as a terminal electron acceptor, and lactate or citrate as an electron donor. The strain can grow under anaerobic conditions and utilize arsenate in the respiratory process in a broad range of temperatures (10–37 °C), pH (4–8), salinity (0%–2%), and the presence of heavy metals (Cd, Co, Cr, Cu, Mn, Mo, Se, V and Zn). Under reductive conditions this strain can simultaneously use arsenate and thiosulfate as electron acceptors and produce yellow arsenic (III) sulfide (As₂S₃) precipitate. Simulation of As-removal from water containing arsenate (2.5 mM) and thiosulfate (5 mM) showed 82.5% efficiency after 21 days of incubation at room temperature. Based on the obtained results, we have proposed a model of a microbially mediated system for self-cleaning of mine waters contaminated with arsenic, in which Shewanella sp. O23S is the main driving agent.     

铁铝复合氧化物吸附砷氟性能实验研究

采用共沉淀法制备了复合铁铝氧化物吸附剂,并对其表面ξ电位和砷氟共存时除砷氟性能进行了初步研究。ξ电位表明铁铝复合氧化物pHzpc在9.0附近;铁铝复合氧化物对砷氟共存溶液中As(V)和F-均表现出很强的吸附能力,决定F-的去除率的是铝含量;该吸附剂对砷氟共存溶液As(V)在广谱pH范围内具有很高的去除能力,对F-在pH为6~7之间时去除率最高;砷氟共存溶液中As(V)对F-具有竞争吸附作用。     

铅锌烟尘中铅的物相分析

铅锌烟尘中铅主要以氧化铅、金属铅和砷酸铅的形式存在。实验以云南某铅厂生产的铅锌烟尘为实验原料,利用乙酸、硝酸铜、氢氧化钠、蔗糖和抗坏血酸等化学试剂,使用正交实验和单因素实验方法,设计在多种条件组合下浸出铅锌烟尘中各种成分铅的实验。通过火焰原子吸收光谱法检测浸出液中铅的含量从而得出浸出各组分铅的最佳条件。通过实验得出铅锌烟尘中砷酸铅的质量分数为21.25%,氧化铅质量分数为10.91%,铅的质量分数为2.01%。     

高砷铜精矿浸出液制备砷酸铜及热力学研究

高砷铜精矿浸出液中因含砷较高存在砷害问题,砷回收利用具有重要的意义。研究针对某高砷硫化铜精矿除杂后的浸出液,探讨了以砷酸铜形式综合利用砷的热力学及工艺参数。绘制了Cu-As-H2O系电位-pH图,进行了砷酸铜制备工艺过程的热力学分析,对净化后的某高砷硫化铜精矿浸出液,以氨水为中和剂,当pH=5.0~8.0,温度80~90℃时,制得了CuAs2O4、C4H6As6Cu4O16、Cu5As2O10.5H2O、Cu5As4O15.9H2O、Cu2AsO4OH.3H2O及Cu2AsO4OH 6种不同结构的砷酸铜,沉砷后溶液中砷含量为9.11~35.82 mg/L。     

Anaerobic microbial mobilization and biotransformation of arsenate adsorbed onto activated alumina

Due to the enactment of a stricter drinking water standard for arsenic in the United States, larger quantities of arsenic will be treated resulting in larger volumes of treatment residuals. The current United States Environmental Protection Agency recommendation is to dispose spent adsorbent residuals from arsenic treatment into non-hazardous municipal solid waste (MSW) landfills. The potential of microorganisms to alter the speciation affecting the mobility of arsenic in the disposal environment is therefore a concern. The purpose of this paper was to evaluate the potential of an anaerobic microbial consortium to biologically mobilize arsenate (As(V)) adsorbed onto activated alumina (AA), a common adsorbent used for treating arsenic in drinking water. Three anaerobic columns (0.27 l) packed with 100 g dry weight of AA containing 0.657 mg adsorbed As(V) (expressed as arsenic) per gram dry weight were continuously flushed with synthetic landfill leachate for 257 days. The fully biologically active column was inoculated with methanogenic anaerobic sludge (10 g volatile suspended solids l(-1) column) and was operated with a mixture of volatile fatty acids (VFA) in the feed (2.5 g chemical oxygen demand l(-1) feed). At the end of the experiment, 37% of the arsenic was removed from the column, of which 48% was accounted for by arsenical species identified in the column effluent. The most important form of arsenic eluted was arsenite (As(III)), accounting for nearly all of the identified arsenic in periods of high mobilization. Additionally, two methylated metabolites, methylarsonic acid and dimethylarsinic acid were observed. Mobilization of arsenic is attributed to the biological reduction of As(V) to As(III) since literature data indicates that As(III) is more weakly adsorbed to AA compared to As(V). Batch and continuous assays confirmed that VFA, present in landfill leachates, served as an electron donating substrate supporting enhanced rates of As(V) reduction to As(III). Two control columns, lacking inoculum and/or VFA in the feed displayed low mobilization of arsenic compared to the fully biologically active column. Therefore, leachates generated in MSW landfills could potentially result in the biologically catalyzed mobilization of arsenic from As(V)-laden drinking water residuals.