合成施威特曼石吸附Cu^2＋和Pb^2＋的实验研究

施威特曼石普遍存在于含大量SO42-的酸矿水中,其表面吸附的SO42-使得该矿物具有强吸附重金属离子的能力,可用于处理重金属离子污染。实验通过在不同浓度Cu2＋溶液中合成施威特曼石时发现,Cu2＋与施威特曼石的共沉淀量较低,FTIR分析表明Cu2＋与施威特曼石的羟基发生反应。开展施威特曼石吸附Pb2＋的实验,结果表明施威特曼石对Pb2＋的吸附符合Langmuir模型,施威特曼石吸附Cu2＋和Pb2＋后出现1545.4 cm-1和1435.0 cm-1（Cu2＋）两个吸收峰,可能是施威特曼石孔道表面形成了三元配合物。在241×10-6的初始浓度（与尾矿孔隙水的Pb2＋含量相近）下有61.4%的Pb2＋去除率,显示了较好的环境修复价值。     

Eu3+水合离子在纳米二氧化硅表面的吸附与结构

采用发射光谱研究了不同pH和不同Eu初始浓度条件下,Eu在纳米二氧化硅-水界面的吸附特征。研究发现,当pH低时,Eu在纳米二氧化硅表面的吸附很少,随着pH的增加,Eu在纳米二氧化硅表面的吸附急剧增加,当出〉6时,几乎所有Eu都被吸附。研究同时表明,吸附在纳米二氧化硅与水界面的Eu离子种类也取决于pH值：当pH〈5时,吸附的Eu主要为Eu^3＋水合离子,当pH〉5时,吸附的Eu主要为Eu（CO3）^＋,甚至Eu（CO3）2^-离子。吸附的机理除了静电吸引外,更重要的是这些离子与纳米二氧化硅表面形成化学键,即表面化学吸附。     

蒙脱石中Cu2+的吸附态研究

对在ＰＨ≤４．５、痕量浓度条件下吸附了Ｃu＾２＋的蒙脱石的Ｘ射线衍射（ＸＲＤ）进 行了研究。该蒙脱石的ｄ（００１）由原始蒙脱石的１．４７９ｎｍ变为１．５２３ｎｍ,说明水合铜离子置换了蒙脱石的层间阳离子;在该蒙脱石的ＥＰＲ谱中记录到了ｇ＝２．０７、ｇ ＝２．１４精细结构线和ｇ为约２．７～２．２超精细结构线三组有关Ｃu＾２＋ 的信号,说明其中的Ｃu＾２＋有三种不同的结构状态。同时,该蒙脱石热处理产物的ＥＰ     

Fe^2＋浓度对Acidithiobacillus ferrooxidans耐铜性的影响

嗜酸性氧化亚铁硫杆菌（Acidithiobacillus ferrooxidans）是铜矿生物冶金中应用最广泛的微生物之一。但在冶金过程中淋滤出来的Cu2＋等重金属逐渐积累,达到一定的浓度后就会抑制A.ferrooxidans的生长,从而降低冶金的效率。本文着重研究了Fe2＋初始浓度对A.ferrooxidans耐铜性的影响。实验中ρ（Cu2＋）变化范围为0～5.0 g/L。结果表明,当ρ0（Fe2＋）为6.7 g/L时,A.ferrooxidans仅在Cu2＋为0～0.4 g/L的体系中能显著地氧化Fe2＋进行生长;当Cu2＋≥0.5 g/L时,A.ferrooxidans生长完全受到抑制。将ρ0（Fe2＋）增加到8.9 g/L,A.ferroox-idans在0.5、1.0、2.0和3.0 g/L Cu2＋的培养基中也能明显氧化Fe2＋,并最终将其完全氧化,Cu2＋对A.ferrooxidans生长抑制作用仅出现在4.0和5.0 g/L Cu2＋的体系中。因此提高体系中亚铁离子的浓度能提高菌体对Cu2＋的耐受力。研究结果对铜矿的生物冶金具有重要意义。     

贵阳市大气总悬浮颗粒物（TSP）中水溶性无机离子的化学特性及季节变化特征

2005年1月到12月,在贵阳市区采集TSP样品,分析了其主要水溶性无机离子的化学性质及其季节变化规律。结果显示,TSP浓度年均值为106.60μg／m^3;各离子摩尔浓度的大小顺序为：SO4^2-＞NH4^＋＞Ca^2＋＞NO3^-＞K^＋＞Na^＋＞C^-＞Mg^2＋＞F^-。TSP及其组分存在明显的季节变化,TSP、Cl^-、SO4^2-、NO3^-、NH4^＋、K^＋、Na^＋、Ca^＋和Mg^2＋浓度的冬／夏比值分别为1.29、5.23、1.35、2.37、1.73、1.22、1.84、1.23和1.02。影响TSP、Ca^2＋、Mg^2＋和F^＋的气象参数主要是相对湿度和风速,影响SO4^2-、NO3^-、NH4^＋,和Cl^-的是温度。TSP大多呈微酸性,可能是高含量的SO4^2-所致。NH4^＋与SO4^2-的相关性最好（R为0.85）,NH^＋与SO4^2-的摩尔比值为0.8,说明NH4^＋主要以（NH4）2SO4的形式存在。     

硫化物吸附金属离子的实验研究──Ⅰ类型

合成ＰｂＳ、ＺｎＳ对金属离子Ａｇ＋、Ｃｕ（２＋）、Ｃｄ（２＋）、Ｚｎ（２＋）、Ｆｅ（２＋）、Ｍｎ（２＋）、Ｍｇ（２＋）、Ｓｂ（３＋）和Ｂｉ（３＋）的吸附等温线（５０℃）研究表明，其可分为Ａ、Ｂ、Ｃ三类：Ａ类，线性型，即吸附量随吸附离子浓度增加而呈线性上升，并表现出百分之百吸附，属于此类的吸附有ＰｂＳ对Ａｇ＋、Ｃｕ（２＋）离子吸附和ＺｎＳ对Ａｇ＋、Ｃｕ（２＋）、Ｃｄ（２＋）离子的吸附；Ｂ类，朗谬尔型，即随吸附离子的浓度增加，吸附量逐趋向一饱和值，属于此类的有ＰｂＳ对Ｆｅ（２＋）、Ｓｂ（３＋）、Ｂｉ（３＋）等离子及ＺｎＳ对Ｆｅ（２＋）、Ｍｎ（２＋）、Ｍｇ（２＋）等离子的吸附；Ｃ类，反朗谬尔型，即吸附量随吸附离子浓度增加而呈非线性增加。属此类吸附的有ＰｂＳ对Ｚｎ（２＋）、Ｃｄ（２＋）等离子的吸附。合成ＰｂＳ、ＺｎＳ对金属离子的吸附量与天然方铅矿和闪锌矿中微量元素含量可类比，这意味着吸附作用可能在硫化物矿物微量元素形成过程中起着重要的作用。     

微藻矿化去除Pb2+的研究

藻类作为水体中的初级生产力,通过生物积累、生物矿化等生理功能与环境中的重金属相互作用、对重金属地球生 物化学循环起到关键作用。为了探讨藻类生物矿化去除水体中重金属的现象,文中研究了淡水微藻FZUL-321对Pb2+的去除 及矿化。结果表明：微藻FZUL-321对Pb2+有较强的去除能力,且是一个快速去除的过程。随着Pb2+浓度增大,该微藻对Pb2+ 的去除效果也增大。在弱酸性条件下（pH5.0）,其去除Pb2+的效果较好。如在Pb2+初始浓度为100mg/L,pH5.0,去除时间 为40min,此时Pb2+的去除量为423.2×10-3干重。原子力显微镜（AFM）对细胞表面的形貌进行观察,发现微藻FZUL-321与 Pb2+作用后,细胞形貌和尺寸变化较大,如细胞褶皱并塌陷,细胞表面变得粗糙等。傅里叶红外光谱（FT-IR）结果表明藻 细胞表面的羧基、氨基和磷酸基团等官能团参与前期Pb2+的吸附沉淀。最终,通过一系列生化作用,微藻FZUL-321将离子 态的Pb2+矿化,X射线衍射（XRD）分析显示,矿化产物为Pb5(PO4)3OH。     

方解石表面Cd2+与Pb2+类质同象的AFM研究

 借助原位液槽原子力显微镜（in situ AFM）的观察,通过Cd2+,Pb2+替代方解石最外层晶格Ca2+生长模式的实验研究, 探讨了Cd2+与Pb2+作用下方解石表面溶解与结晶行为。在液体反应槽中,分别将含不饱和Cd2+与Pb2+溶液流经方解石{101 _ 4}解理面,结果发现:（1）Cd2+的存在不影响方解石沿<4_41> 晶向台阶的溶解,而Pb2+的存在则强烈阻碍了方解石沿<441>+晶向台阶的溶解;（2）停止输入溶液含Cd2+,Pb2+溶液后,随着方解石表面与溶液达到平衡,溶解过程逐渐转变为结晶过程。结果显示在Cd2+存在时,单分子生长层具有方解石原有的定向性,而在Pb2+存在时的生长则不具任何定向性。尽管有此差异, 但（Ca,Cd）CO3 和（Ca,Pb）CO3 固溶体都受控于单分子层外延生长这一结晶机理。 　　含Cd2+和Pb2+溶液对方解石溶解动力学的作用与选择性吸附的阳离子半径大小、吸附复合体的几何形状及其结晶学取 向有关。Cd2+离子倾向于优先进入更狭小的<4_41>- 晶向的微台阶上,而Pb2+则倾向于形成扭曲的八面体络合物吸附在更开 阔的<4_41>+ 晶向台阶上。因此,Pb2+存在下方解石表面生长方向无序可认为是白铅矿和方解石结构差异的原因。     

沸石的活化处理及其对铅、钴的吸附性研究

通过对沸石的活化方法和其基本物化性能（主要包括化学成分、阳离子交换容量、密度、比表面积、孔径、渗透系数及热稳定性）及Pb^2＋,Co^2＋离子的吸附性能的初步研究认识到：1）经过酸化并经热处理后的沸石的阳离子交换容量（CEC）明显高于未经处理的原土;2）通过实验得出粒度为100目的天然沸石经酸活化处理后在300C下热活化,1．5h后测得离子交换量为最佳;3）沸石的密度为1．789g／cm^3;渗透系数为0．087cm／s（20℃）;体积平均粒径为13μm;比表面积为190．67m^2／g,平均孔径为102．27nm;4）沸石对重金属离子的吸附实验表明沸石对重金属离子Pb^2＋的吸附性能优于Co^2＋,20min时Pb^2＋和Co^2＋的吸附比（Rd）分别为20238．8ml／g及63．8ml／g;Pb^2＋和Co^2＋去除率分别为99．50％和40．00％。     

溶液介质条件对重金属离子与石英表面反应的影响

实验研究表明,随着溶液ＰＨ值的升高石芟夺Ｃｕ＾２＋、Ｐｂ＾２＿、Ｃｄ＾２＋等重金属离子的吸附量和表面吸附覆盖率逐渐增大,而表面反应产物的结合开矿相应地出现由单核化合物、多核化合物〖ＳＯＣｕ４（ＯＨ）３＾４＋〗,直至表面沉淀（ＳＯＨ…Ｃｕ（ＯＨ）２（ｓ）〗。随着温度升高,石英对Ｃｕ＾２＋、Ｐｂ＾２＋、Ｃｄ＾２＋等重金属离子的吸附量逐渐减是随着溶液离子强度的增大,石英对Ｃｕ＾２＋离子的吸附量和表面离了     

Simultaneous removal and measurement of sulfide on the basis of turn-on fluorimetry

Hydrogen sulfide is a flammable and poisonous gas pollutant often emitted to air as a by-product of water supply, chemical, petroleum and coal industries. It can be transferred into sulfur dioxide in the air under some meteorologic conditions. Herein, a novel functional copper complex is reported which can selectively absorb hydrogen sulfide and subsequently release a highly fluorescent molecule. The copper complex is functionalized with a benzoxadiazole moiety as a fluorescence reporter, and the copper center serves as the recognition and binding site for sulfide. The application of the copper complex has been demonstrated for sensitive and selective measurement of hydrogen sulfide on the basis of “turn-on” fluorescence method, and the limit of detection is determined to be 0.1 μM. Other relevant anionic ions such as bisulfite, sulfate and mercapto compounds showed no interference for the detection of sulfide. These results suggest that the compound and method can be potentially applied for on-site measurement and effective removal of sulfide from environment.     

七一冰川消融末期融水化学日变化特征

2006年9月1-8日在祁连山七一冰川作用区水文总控点逐时采集河水样, 并分析水样的主要可溶离子含量、电导率以及pH, 研究冰川作用区水化学组成日变化特征. 结果表明: 消融末期河水中pH的平均值约为7.60, 与离子浓度时间变化过程一致, 说明是偏碱性物质的输入增加了融水中化学物质的含量;SO~(2-)_4, Ca~(2+)分别是浓度最大的阴、阳离子, 属于SO~(2-)_4+HCO~-_3-Ca~(2+)+Mg~(2+)型水. 河水中可溶性离子浓度日变化过程具有不对称性, 表现为快速降低和缓慢的增加过程, 与流量变化呈显著反相关, Pearson相关说明流量是冰川区水化学特征随时间变化的控制性因素;阳离子通量计算显示, 在七一冰川区达54.7 t·km~(-2)·a~(-1), 其日变化过程与流量正相关, 与离子浓度成反相关, 说明径流量也是控制离子通量的主要因素.     

电气石微粉吸附水体中金属离子及其机理分析

研究了电气石微粉吸附水中Cu2＋、Pb2＋、Zn2＋的过程,讨论了吸附时间、粒度、用量和pH值等因素对吸附效果的影响,分析了电气石对含Cu2＋、Pb2＋、Zn2＋废水的吸附机理。电气石加工成超细粉体时,表面产生大量的不饱和键,在溶液中与水配位,使水发生解离生成羟基化表面,将重金属离子吸附到晶体负极,使局部金属离子浓度增高与电气石表面羟基离解而产生的氢氧根离子发生反应,形成各种沉淀或碱式盐析出,直到溶液中各种离子浓度达到平衡时为止。提出了凡是氢氧化物难溶于水的金属离子,理论上都可以使用电气石微粉进行吸附净化处理的观点。研究结果表明,电气石微粉对Cu2＋、Pb2＋、Zn2＋有较好的吸附效果。     

Thin layer molecularly imprinted composite membranes for selective separation of erythromycin from water

Molecularly imprinted composite membranes for selective binding of erythromycin were synthesized by UV initiated photo-copolymerization using polysulfone ultrafiltration (PSF) membranes as porous supports. The thin imprinted layers deposited on the surface of the support membranes were formed by copolymerization of acrylic acid (AA) as functional monomer and ethylene glycol dimethacrylate (EGDMA) as cross-linker in the presence of erythromycin as template molecule in acetonitrile solution. Fourier transform infrared spectroscopy (FT-IR) was used to study the binding mechanism between the imprinted sites and the template. Scanning electron microscope (SEM) was utilized to visualize surface and cross-sections of membranes to gain better understanding in the analysis of imprinted layers deposited on PSF support membranes. The modification degrees for imprinted and nonimprinted membranes are 2.04 and 2.15 mg/cm², respectively. Static equilibrium binding and recognition properties of the imprinted and nonimprinted membranes to erythromycin (EM) and its analogue roxithromycin (RM) in aqueous system were tested. The results showed that saturated binding capacity of imprinted membranes to erythromycin was about 0.185 mg/cm², nearly eight times that of nonimprinted ones, and the selectivity factor of αEM/RM was 3.24. The results of this study implied that the synthesized molecularly imprinted composite membranes could be used as selective separation materials for erythromycin enrichment from water.     

Selective flocculation of hematite in the hematite-quartz-ferric ion-polyacrylic acid system. Part 1, activation and deactivation of quartz

This investigation has shown that quartz can be activated for polyacrylic acid adsorption by hydrolyzing metal cations, similar to activation in flotation. Detailed experiments on activation phenomena with ferric ions have been performed. The flocculation of activated quartz can be prevented by suitable additions of disodium EDTA, sodium hexametaphosphate or potassium fluoride. Selective flocculation of hematite with polyacrylic acid from a hematite/quartz mixture can be achieved in the pH range 3 to 9, but the process is not selective in the presence of ferric ions. Suitable additions of EDTA or KF are particularly successful in preventing quartz activation by ferric ions and the facilitating selective flocculation of hematite in artificial mixtures of quartz and hematite.     

无机水化学离子在实验流域降雨径流过程中的响应及其示踪意义

为研究无机水化学离子在降雨径流示踪中的可能性,在实验流域实测降雨、地面径流、壤中流、地下水径流过程和流域内17个测孔的地下水过程中,施测了Na+,K+,Ca2+,Mg2+,Cl-,SO₄2-,HCO₃-+CO₃2-,NO₃-,F-,NH₄-,PO₄2-,SiO₂和pH,EC,18O的同步过程,还施测了少数土壤水水样。结果是:①在Ca2+与Cl-/SO₄2-和EC与Na+/(Na++Ca2+)的关系中以及除NO₃-,NH₄-,PO₄2-外的所有离子,都可识别出上述各种径流组分;②径流离子过程均与降雨离子过程相仿,随径流组分从地面到地下而渐趋坦化;③除个例外,离子浓度过程均以降雨为最小并从地面径流到地下水径流渐次增大;④降雨和地下水离子过程表现为径流离子过程的两端元;⑤在降雨和各径流组分中,18O过程与大部分离子过程有一定的同步性。从以上结果认为,降雨并不是流域径流离子输出的主要来源,然而却是形成它的主要控制因素。此外,有关试验结果还对应用Cl-进行地下水补给的估算方法提出了问题。     

Characterization of hydrogeochemical process and evaluation of water quality of seven geothermal springs,Bakreswar, India

A study was conducted in seven geothermal springs located in Bakreswar, District Birbhum, West Bengal, India, in order to assess numerous geochemical processes which were responsible for chemical composition of thermal and mineralized water. The study area lies over the Sone, Narmada, and Tapti lineament of Precambrian Chotanagpur Gneissic Complex. Water chemistry has been carried out based on reaction stoichiometry and geo-statistical tools to identify geochemical process. Piper and Gibbs diagram suggest that the spring water belongs to Ca²⁺-Mg²⁺-HCO₃^??+?CO₃^2? water type and are controlled by rock dominance. Dissolution and precipitation of calcite, dolomite, gypsum, and fluorite minerals were identified as principle source of major ions in seven geothermal spring water. Principle component analyses revealed that major ions of spring water are derived from geogenic processes such as weathering, dissolution, and precipitation of various minerals. Overall results suggest that major ions of the spring’s water are derived from natural origin because no evidence of anthropogenic sources was observed during the study period. This study has also revealed that water quality of spring’s water is not suitable for drinking purposes and quite suitable for irrigation because of high abundance of Na⁺, K⁺, Cl^?, and HCO₃^? ions.     

人工神经网络在水文水资源中的应用

人工神经网络理论被广泛地应用于水文水资源领域中各种问题的研究,依问题性质不同将其划分为4大类:(1)分类和识别问题;(2)预测预报问题;(3)优化计算问题;(4)基于神经网络的专家系统研制与开发问题,对人工神经网络在水文水资源中的应用现状作了较全面的介绍。还指出了目前应用中存在的主要问题以及今后的研究方向。     

Chemical evolution of a gas-capped deep aquifer,southwest of Iran

The Kangan Aquifer (KA) is located below a gas reservoir in the crest of the Kangan Anticline, southwest of Iran. This aquifer is composed of Permo-Triassic limestone, dolomite, sandstone, anhydrite and shale. It is characterized by a total dissolved solid of about 332,000 mg/L and Na–Ca–Cl-type water. A previous study showed that the source of the KA waters is evaporated seawater. Chemical evolution of the KA is the main objective of this study. The major, minor and trace element concentrations of the KA waters were measured. The chemical evolution of KA waters occurred by three different processes: evaporation of seawater, water–rock and water–gas interactions. Due to the seawater evaporation process, the concentration of all ions in the KA waters increased up to saturation levels. In comparison to the evaporated seawater, the higher concentrations of Ca, Li, Sr, I, Mn and B and lower concentrations of Mg, SO₄ and Na and no changes in concentrations of Cl and K ions are observed in the KA waters. Based on the chemical evolution after seawater evaporation, the KA waters are classified into four groups: (1) no evolution (Cl, K ions), (2) water–rock interaction (Na, Ca, Mg, Li and Sr ions), (3) water–gas interaction (SO₄ and I ions) and (4) both water–rock and water–gas interactions (Mn and B ions). The chemical evolution processes of the KA waters include dolomitization, precipitation, ion exchange and recrystallization in water–rock interaction. Bacterial reduction and diagenesis of organic material in water–gas interaction also occur. A new type of chart, Ca_excess versus Mg_deficit, is proposed to evaluate the dolomitization process.     

塔里木盆地哈得逊油田石炭系地层水化学特征及成因

塔里木盆地哈得逊油田石炭系地层水化学分析结果表明,地层水是以阴阳离子分别为Cl-和(Na++K+)为主的CaCl2型水,具有高矿化度特征(112～291 g/L)。地层水的钠氯系数均值为0.78,脱硫酸系数均值为0.23,Schoeller碱交换指数(IBE)均值为128。地层水化学参数在平面上相对变化不大,在剖面上随深度的增加,HCO3-、SO42-含量具有减小的趋势,而其他离子变化相对较小,表明研究区内的地层水形成于深部封闭环境条件下。地层水化学分析表明,该区地层水经历了强烈的阳离子交替吸附和水岩相互作用。(铁)白云石化作用导致了Ca2+的富集和Mg2+的亏损,形成了现今的地层水离子分布特征。石炭系地层水在构造反转油气藏调整时期一直处于相对封闭的流体动力环境中,这种环境有利于油气的聚集与保存。