矿石中硫的测定—EDTA分离容量法

矿石中硫的测定以重量法较为准确,燃烧法较为快速,但均需较特殊设备。在例行容量测定中,由于干扰元素较多,难于得到满意的结果。为了适应地质野外化验工作的需要,我们采用逆王水(或碱熔)分解样品,把矿石中的硫氧化成SO_4~(2-),在2％的硝酸介质中,用EDTA络合Pb~(2+)、Sr~(2+)、Ca~(2+)等干扰元素,然后加入Ba~(2+),使生成BaSO_4沉淀,经过滤分离大多数干扰元素后,用EDTA法测定Ba~(2+),换算出硫的含量。此法适于测定2％以上的硫。我们曾对十个矿种的样品进行过测定,得到了满意的结果。     

容量法测定水样中硫酸根

本文对EDTA滴定过量Pb间接测定SO_4~(2-)的方法作了改进。加入乙醇抑制PbSO_4沉淀的溶解,使滴定不需分离沉淀而直接进行。用六次甲基四胺调节控制pH为5.2—5.4,可避免大量共存Ca~(2+)、Mg~(2+)的干扰。改进后的方法简单、快速,准确度和精密度均好,可适用SO_4~(2-)含量高于1mg/L的天然水分析。     

浅海Mg~(2+)和SO_4~(2-)对微生物诱导形成锰碳酸盐的影响

为了模拟浅海环境下锰氧化物微生物还原作用诱导碳酸盐沉淀的过程,选取最常见的锰氧化物-水钠锰矿(K_(0.33)Mn_7O_(14)·7H_2O)为研究对象,在不同种类与浓度盐离子(Mg~(2+)、SO_4~(2-))存在条件下开展异化锰还原菌Dietzia cercidiphylli 45-1b好氧还原水钠锰矿的实验研究.通过测试体系蛋白、Mn~(2+)等离子浓度变化,利用X射线衍射(XRD)和X射线吸收谱(XAS)表征反应前后矿物结构变化,来探讨不同初始Mg~(2+)和SO_4~(2-)浓度对于菌株45-1b还原水钠锰矿及诱导碳酸盐矿物沉淀的影响.结果显示体系pH值在4天内从7.0迅速上升至9.3,Mn~(2+)浓度在2天内迅速上升至166μmol/L,随后迅速下降至8μmol/L(第4天),其好氧还原产物为菱锰矿(MnCO3),且其产生量随Mg~(2+)浓度的升高而降低,随SO_4~(2-)浓度的升高而升高.上述实验结果表明好氧环境下菌株45-1b能够利用乙酸为电子供体,水钠锰矿为电子受体还原水钠锰矿释放Mn~(2+),最终转化有机碳为无机碳酸盐矿物菱锰矿.Mg~(2+)通过影响微生物生长和菱锰矿成核对水钠锰矿的还原及菱锰矿沉淀产生抑制作用,而SO_4~(2-)可以缓解Mg~(2+)的抑制作用并促进水钠锰矿的还原及菱锰矿沉淀.     

离子色谱法同时测定地质样品中氟氯磷硫

本文研究了离子色谱同时测定地质样品中F~-、Cl~-、PO_4~(3-)、SO_4~(2-)的前处理过程,选择了色谱测定最佳条件。在Na_2CO_3全熔的样品溶液中,加入(NH_4)_2CO_3使Si、Al随大多数金属离子同时沉淀;再用预处理柱除去熔剂引入的大量Na~+及CO_3~(2-)消除其干扰;并在流出液中补加相应试剂与淋洗液相匹配,实现了多种地质样品中F~-、Cl~-、PO_4~(3-)和SO_4~(2-)的测定。方法检出限(3s,μg/ml)分别为F~-0.05、Cl~-0.1、PO_4~(3-)0.3、SO_4~(2-)0.5。测定范围为F~-0.05—3μg/ml,Cl~-0.1—6μg/ml,PO_4~(3-)0.3 —30μg/ml,SO_4~(2-)0.5—30μg/ml。     

马尾松针叶组织硫酸盐和叶水氧同位素对针叶硫酸盐来源的示踪研究

为探讨植物组织中硫酸盐的来源,在贵州和云南两省部分地区采集了马尾松针叶样品,并测定了其针叶组织中硫酸盐和叶水的氧同位组成。结果显示,所有采样点的针叶δ~(18)O_(SO_4~(2-))值均比大气硫酸盐δ~(18)O_(SO_4~(2-))值显著偏负,说明马尾松针叶中的硫酸盐并不直接来源于叶片吸收的大气硫酸盐。其中,晋宁山区(背景区)的针叶δ~(18)O_(SO_4~(2-))与土壤δ~(18)O_(SO_4~(2-))相近,表明该区针叶硫酸盐主要由根部吸收土壤硫酸盐补给。而在城市地区,土壤δ~(18)O_(SO_4~(2-))值和针叶δ~(18)O_(SO_4~(2-))值有较大差异,且叶水δ~(18)O_(H_2O)值与针叶硫酸盐δ~(18)O_(SO_4~(2-))值呈显著正相关,表明城市地区的针叶硫酸盐主要来源于大气SO_2在叶肉中氧化。两个点污染源(昆明钢铁厂和曲靖火电厂)附近针叶中δ~(18)O_(SO_4~(2-))值都随着与工厂距离的变大而趋于偏负,说明污染源附近针叶吸收了来自工厂烟道排放的原生硫酸盐。     

柳林泉域岩溶水中SO_4~(2-)的来源探讨

SO_4~(2-)浓度偏高是晋西柳林泉域岩溶水的主要特色之一,判断SO_4~(2-)来源对于理解岩溶水的水文地球化学过程具有重要意义。在分析区域地质、水文地质条件及岩溶水中SO_4~(2-)浓度空间分布特征的基础上,利用化学计量学法、同位素质量平衡模型和Rayleigh蒸馏模型,分析了岩溶水中SO_4~(2-)的主要来源,计算了不同来源的SO_4~(2-)所占的比例和滞流区岩溶水中SO_4~(2-)的还原比例。结果显示,石膏的溶解和黄铁矿的氧化是柳林泉域岩溶水中SO_4~(2-)的主要来源,排泄区岩溶水中石膏溶解来源的SO_4~(2-)所占比例介于73%~88%之间,平均为81%;黄铁矿氧化来源的SO_4~(2-)占比12%~27%,平均为19%。滞流区发生了硫酸盐的还原作用,约有9%~15%的SO_4~(2-)被脱硫细菌还原为H2S气体,且越靠近西部边界,还原反应所消耗的SO_4~(2-)比例越高。     

乳化剂OP存在下硫酸钡浊度法测定天然水中硫酸根

水质分析中,硫酸钡比浊法是测定水中SO_4~(2-)的经典方法之一。此方法由于浊度不够稳定,对分析条件要求较为严格,因而分析结果的准确度和精密度不理想。本文在原方法基础上引入乳化剂OP后,分析条件大为改善,吸光度在60min内基本稳定,SO_4~(2-)含量在2～20μg/ml范围内与吸光度呈线性关系。改进后的方法稳定性好,操作简便快速,应用于天然水中SO_4~(2-)的测定及进行加标回收实验,结果令人满意。 1 实验方法     

汾阳地区不同类型地下水SO_4~(2-)、δ~(34)S的特征及影响因素

本文对山西晋中盆地西南汾阳地区北侧裸露岩溶区的岩溶泉和浅井、南侧覆盖岩溶区的深井和第四系孔隙水井及石膏矿水的水化学成分、硫同位素组成进行了测试分析。结果显示:北侧裸露岩溶区的岩溶泉水和浅井δ~(34)S值的范围为4.53%0~6.42%0,SO_4~(2-)含量范围为0.12~0.62mmol/L,表明SO_4~(2-)主要来源于大气降水,受石膏溶解和居民活动影响小;南侧覆盖岩溶区的深井δ~(34)S值的范围为8.73‰~19.35‰,SO_4~(2-)含量范围为0.20~2.35mmol/L,SO_4~(2-)主要来源于石膏夹层的溶解和FeS_2的氧化。第四系孔隙水δ~(34)S值的范围为9.46‰~11.05‰,SO_4~(2-)含量范围为0.19~1.96mmoL/L,SO_4~(2-)主要来源于人为污染;石膏矿水δ~(34)S值为19.28‰,SO_4~(2-)含量为5.62mmol/L,SO_4~(2-)主要来源于石膏层的溶解。因此,应用SO_4~(2-)和δ~(34)S值可以很好的分析地下水中硫酸盐的来源,这为北方岩溶地下水资源的开发与保护研究提供了重要的手段。     

重庆温塘峡背斜地表水-地下水-浅层地热水中硫同位素的环境指示意义研究

稳定同位素硫广泛用于示踪地下水、地表水的来源、物质组成以及水-岩作用过程。不同条件下,不同的水体中,硫同位素具有不同的环境指示意义。通过对位于我国西南川东平行岭谷区温塘峡背斜地区地表水(嘉陵江水)、矿坑水、岩溶地下河水(青木关地下河)、岩溶区浅层地下热水(北温泉水和青木关温泉水)的水化学及δ~(34)S-SO_4~(2-)的值的研究,发现嘉陵江水和姜家泉水的水化学组成显示出碳酸盐岩化学风化的特征,浅层地下热水的水化学组成反映了硫酸盐岩化学风化的特征,砂岩矿坑水既没有体现碳酸盐岩的风化也没有体现硫酸盐岩的风化。各水体的SO_4~(2-)含量与δ~(34)S-SO_4~(2-)的值揭示不同水体中硫具有不同的环境来源。嘉陵江水中的SO_4~(2-)含量与δ~(34)S-SO_4~(2-)的值表明其水的来源主要是流经地区的地表水和雨水;研究区砂岩矿坑水中SO_4~(2-)含量与δ34 SSO_4~(2-)的值表明其水是由原有矿坑水、雨水以及地表水组成;青木关岩溶地下河水中SO_4~(2-)含量与δ~(34)S-SO_4~(2-)的值表明青木关岩溶地下河水主要受到岩层、降雨以及农业活动和生活污水的影响;而浅层地下热水中SO_4~(2-)含量与δ~(34)S-SO_4~(2-)的值的示踪则反应了地下热水的储水层的水-岩作用主要是石膏的溶解。     

宜昌市PM_(10)水溶性无机组分与硫酸盐的δ~(34)S值变化特征

利用TH-150中流量颗粒物采样器,在2012年12月至2013年3月采集了宜昌市PM_(10)样品,测试了水溶性无机离子和硫酸盐硫同位素组成。研究显示,宜昌市PM_(10)主要的水溶性无机离子有SO_4~(2-)、NO_3~-、NH_4~+、Na~+、Ca~(2+),二次离子(SO_4~(2-)+NO_3~-+NH_4~+)的含量与总水溶性无机离子质量浓度比值超过70%,说明宜昌市大气二次污染严重;无机离子冬季以(NH_4)_2SO_4、NH_4NO_3、Ca SO4和Na_2SO_4为主,春季则以NH_4NO_3、Ca SO4、Na_2SO_4为主。冬季白天PM_(10)中硫酸盐δ~(34)S值为2.8‰~4.7‰,夜间为2.9‰~4.8‰;春季白天为1.5‰~4.7‰,夜间为1.7‰~4.0‰,昼夜变化不明显,春季比冬季偏负。研究结果表明,宜昌市PM_(10)的来源主要有燃煤、机动车尾气、道路二次扬尘,春季还受农业活动和生物源释放影响。     

闪锌矿分析

闪锌矿的主要成分是锌(67％)和硫(32％),同时伴生有有色,分散元素要求分析。本文采用阳离子树脂交换分步淋洗,对砷、硒、碲、锗、锌、铜、镉、钴、镍和铁等元素进行分离与测定。 在盐酸介质中砷、硒和锗很容易与各种阳离子分离,碲的分配系数文献没作介     

峨眉山地区大气漂尘化学组成研究

为了揭示峨眉山大气漂尘的化学特征，研究小组分别在1998，1999，2000年使用小型大气采样器进行采样，并测得样品中含有水溶性化学成分（Na^ ,K^ ,Mg^2 ,Ca^2 ,SO4^2-,NO3^-,NH4^ 和Cl^-)和酸溶性化学成分（Pb和Zn)。这一地区三年的大气成分与1990年的相似，而且峨眉山的Na^ ,Cl^-,SO4^2-,NO3^-,Ca^2 ,NH4^ ，Pb和Zn浓度分别比日本山形县鹤岗的要高出4－15，3－19，3－5，3－6，13－23，4－7，11－28和10－23倍之多。     

上海某厂区土壤和地下水环境质量评估

对上海某地老厂区土壤和地下水采样、检测,表明土壤重金属元素Cd、As,Pb的含量符合国家《土壤环境质量标准（GB15618-1995）》的一级标准要求,Hg、V、Cu的含量明显受到了污染,Mg、Cd、As、Zn、Pb、Be等金属元素含量水平与本地区的土壤环境背景水平相吻合;地下水中pH、NO3^-,-N,Zn属《地下水质量标准》（GBl4848-93）Ⅰ类,Cl^-和NH3^＋-N属V类,地下水对混凝土无腐蚀性,对钢筋有弱腐蚀性。     

气相色谱法测定陨石中超微量铑

采用金属螯合物气相色谱分析微量和超微量金属元素是气相色谱领域中一种行之有效的方法。Ross等报导了此法对贵金属元素铑的定量测定也具有很高的灵敏度。国内关于采用金属螯合物气相色谱法测定铑的研究工作尚无报导。本工作以三氟乙酰丙酮的苯溶液为螯合萃取     

X射线荧光光谱测定荧光粉中硅铁锌钴

采用溶液法配制标准,粉末直接制备样饼,用SRS300型X射线荧光光谱仪测定彩色荧光粉中的SiO2、Fe2O3、Co、Zn组分含量,取得较满意的结果,与已知含量样品比较,所测组分的结果基本相符。精密度检验SiO2、Fe2O3、Co、Zn的RSD均<3%(n=10)。     

Effects of Soil Composition on Zn Speciation in Drainage Waters from Agricultural Soils

The influence of Zn speciation on Zn transport by drainage from different soils to surface water is examined in a stream catchment in an agricultural area. Drainage waters were collected from two types of soils, a mineral soil (MS) and a soil rich in organic matter (OS) by means of artificial drainage pipes. The speciation of dissolved Zn in the stream and the drainage waters was determined using ligand-exchange and voltammetry. About 50–95% of dissolved Zn is bound in strong complexes, and the free Zn²⁺ ion concentration is in the range of 1–16% of dissolved Zn. A substantial part of Zn is present in weaker organic or inorganic complexes. The simulated Zn speciation using the WHAM VI model is compared to the determined speciation. Free Zn²⁺ concentrations predicted by the WHAM VI model are generally higher than the analytically determined free Zn²⁺, but are mostly within the same order of magnitude. Effects of different soil organic matter content on Zn speciation and transport are discussed. Zn speciation in the drainage at the OS site is influenced by the distribution of organic matter between the solid and solution phase. The abundant organic Zn complexes in solution contribute to facilitate Zn transport from soil into surface waters, through the drainage at the OS site. Drainage from the OS site contributes about twice as much Zn input to the receiving water as the MS soil, as related to specific area. The mineral soil contains much lower organic matter, and a part of Zn bound with inorganic phases can hardly be released by dissolved organic ligands, leading to much higher Zn retention at the MS site.     

NK8310螯合树脂分离富集地质样品中痕量金银铂钯及其测定

研究了硫脲螯合树脂（NK8310）分类富集地质样品中痕量Au、Ag、Pt和Pd的实验条件。在φ=10％的王水介质中，[AuCI4]^-、[AgCI2]^-、[PtCI6]^2-和[PdCI4]^2-定量吸附于树脂上并与大量贱金属分离；用5g/L硫脲－0.12mol/L HCI溶液洗脱Au、Ag、Pt和Pd，回收率为97％－104％。用硫镍矿管理样以及国家一级标准物质进行分析验证，分析结果与推荐值及标准值吻合，表明NK8310螯合树脂适用于地质样品中Au、Ag、Pt和Pd的分离富集。     

The nature of Cu bonding to natural organic matter

Copper biogeochemistry is largely controlled by its bonding to natural organic matter (NOM) for reasons not well understood. Using XANES and EXAFS spectroscopy, along with supporting thermodynamic equilibrium calculations and structural and steric considerations, we show evidence at pH 4.5 and 5.5 for a five-membered Cu(malate)₂-like ring chelate at 100-300 ppm Cu concentration, and a six-membered Cu(malonate))_1-2-like ring chelate at higher concentration. A “structure fingerprint” is defined for the 5.0-7.0 Å⁻¹ EXAFS region which is indicative of the ring size and number (i.e., mono- vs. bis-chelate), and the distance and bonding of axial oxygens (O_ax) perpendicular to the chelate plane formed by the four equatorial oxygens (O_eq) at 1.94 Å. The stronger malate-type chelate is a C₄ dicarboxylate, and the weaker malonate-type chelate a C₃ dicarboxylate. The malate-type chelate owes its superior binding strength to an -OH for -H substitution on the α carbon, thus offering additional binding possibilities. The two new model structures are consistent with the majority of carboxyl groups being clustered and α-OH substitutions common in NOM, as shown by recent infrared and NMR studies. The high affinity of NOM for Cu(II) is explained by the abundance and geometrical fit of the two types of structures to the size of the equatorial plane of Cu(II). The weaker binding abilities of functionalized aromatic rings also is explained, as malate-type and malonate-type structures are present only on aliphatic chains. For example, salicylate is a monocarboxylate which forms an unfavorable six-membered chelate, because the OH substitution is in the β position. Similarly, phthalate is a dicarboxylate forming a highly strained seven-membered chelate.Five-membered Cu(II) chelates can be anchored by a thiol α-SH substituent instead of an alcohol α-OH, as in thio-carboxylic acids. This type of chelate is seldom present in NOM, but forms rapidly when Cu(II) is photoreduced to Cu(I) at room temperature under the X-ray beam. When the sample is wet, exposure to the beam can reduce Cu(II) to Cu(0). Chelates with an α-amino substituent were not detected, suggesting that malate-like α-OH dicarboxylates are stronger ligands than amino acids at acidic pH, in agreement with the strong electronegativity of the COOH clusters. However, aminocarboxylate Cu(II) chelates may form after saturation of the strongest sites or at circumneutral pH, and could be observed in NOM fractions enriched in proteinaceous material. Overall, our results support the following propositions:

(1)

The most stable Cu-NOM chelates at acidic pH are formed with closely-spaced carboxyl groups and hydroxyl donors in the α-position; oxalate-type ring chelates are not observed.

(2)

Cu(II) bonds the four equatorial oxygens to the heuristic distance of 1.94 ± 0.01 Å, compared to 1.97 Å in water. This shortening increases the ligand field strength, and hence the covalency of the Cu-O_eq bond and stability of the chelate.

(3)

The chelate is further stabilized by the bonding of axial oxygens with intra- or inter-molecular carboxyl groups.

(4)

Steric hindrances in NOM are the main reason for the absence of Cu-Cu interactions, which otherwise are common in carboxylate coordination complexes.

     

天然铁锰氧化物及氢氧化物环境矿物学研究

带有表面电荷及含有变价元素的天然铁锰氧化物及氢氧化物具有良好的表面吸附与氧化还原等化学活性。在不同介质条件下 ,它们能不同程度地表现出对Cr6+,Pb2 +,Hg2 +,Cd2 +,As3 +,Cu2 +,Zn2 +,Co2 +,Ni2 +等重金属离子有吸附作用和对NO-3 ,PO3 -4 ,F-,S2 -等阴离子有吸附作用与氧化作用 ,并对苯酚、乙烷、乙烯、合成有机酸等有机物具有吸附和转化降解作用 ,还对CO2 ,NOx 和SO2 等具有分解转化作用。利用这些矿物的环境属性治理水体、土壤及大气污染的方法 ,具有成本低、效果好、无二次污染及有用金属可回收利用等优点 ,展现出广阔的环境矿物学研究与应用前景。     

Quantitative Zn speciation in a contaminated dredged sediment by μ-PIXE, μ-SXRF, EXAFS spectroscopy and principal component analysis

Dredging and disposal of sediments onto agricultural soils is a common practice in industrial and urban areas that can be hazardous to the environment when the sediments contain heavy metals. This chemical hazard can be assessed by evaluating the mobility and speciation of metals after sediment deposition. In this study, the speciation of Zn in the coarse (500 to 2000 μm) and fine (<2 μm) fractions of a contaminated sediment dredged from a ship canal in northern France and deposited on an agricultural soil was determined by physical analytical techniques on raw and chemically treated samples. Zn partitioning between coexisting mineral phases and its chemical associations were first determined by micro-particle-induced X-ray emission and micro-synchrotron-based X-ray radiation fluorescence. Zn-containing mineral species were then identified by X-ray diffraction and powder and polarized extended X-ray absorption fine structure spectroscopy (EXAFS). The number, nature, and proportion of Zn species were obtained by a coupled principal component analysis (PCA) and least squares fitting (LSF) procedure, applied herein for the first time to qualitatively (number and nature of species) and quantitatively (relative proportion of species) speciate a metal in a natural system.The coarse fraction consists of slag grains originating from nearby Zn smelters. In this fraction, Zn is primarily present as sphalerite (ZnS) and to a lesser extent as willemite (Zn₂SiO₄), Zn-containing ferric (oxyhydr)oxides, and zincite (ZnO). In the fine fraction, ZnS and Zn-containing Fe (oxyhydr)oxides are the major forms, and Zn-containing phyllosilicate is the minor species. Weathering of ZnS, Zn₂SiO₄, and ZnO under oxidizing conditions after the sediment disposal accounts for the uptake of Zn by Fe (oxyhydr)oxides and phyllosilicates. Two geochemical processes can explain the retention of Zn by secondary minerals: uptake on preexisting minerals and precipitation with dissolved Fe and Si. The second process likely occurs because dissolved Zn and Si are supersaturated with respect to Zn phyllosilicate. EXAFS spectroscopy, in combination with PCA and LSF, is shown to be a meaningful approach to quantitatively determining the speciation of trace elements in sediments and soils.