等离子光谱法分析黄铁矿的研究

本项工作试图利用等离子光谱分析的特点,制定一个用样量少,分析速度快,分析成本低和测定元素多的黄铁矿单矿物分析方法。由于黄铁矿单矿物中铁的干扰严重,几项易挥发元素的检出限较差,所以还需保持必要的取样量。 实验部分 1.工作条件 光量计:Jarrell—Ash Mark Ⅲ 1160 Plasma ATOMCOMP 雾化器:高盐雾化器,附蠕动泵。     

对我国斑岩型铜(钼)矿床某些元素存在形式的研究

为进一步提高地球化学找矿的地质效果,近四年来,我们在含矿斑岩体上,研究了黄铁矿和岩石中某些元素存在形式,富集矿物和载体矿物,借以了解元素的空间分布规律,确定元素的找矿意义.工作方法一、对矿物中元素存在形式的测定选出纯黄铁矿磨成砂片,在显微镜下检查独立矿物,测定单矿物晶胞参数,使用激光、电子探针和各种分析手段,以及不同溶剂萃取等方法,测定非独立矿物(类质同象和机械混入物).     

等离子体直读光谱法分析单矿物初探

单矿物分析既要求测定主元素,也要求测定痕量元素。矿物中一些痕量元素的分布及其含量变化可以为矿床成因、成矿预测和普查探勘的研究提供有关的科学信息。对单矿物中痕量元素的测定既要求少取样,又要求有高准确度,在这一方面,等离子体直读光谱法相对优于其他分析方法。本文选定黄铁矿及几个主要硫化物单矿物作为研究课题,根据等离子体直读光谱分析原理及其突出优点拟定相对合理的分析步骤以满足工作需要。试验结果表明,本方法可适用于快速分析以铁、铜、铅、锌为基体的多种硫化矿物,以至类似的非硫化矿物。可以预料,等离子体直读光谱技术有可能在单矿物分析领域中发挥更大作用。     

黄铁矿单矿物分析

黄铁矿常规分析多采用单独取样,针对某些元素采用有关分析方法。因而手续较繁琐,需要样品量也大。为了简化分析流程,减少样品用量,经试验拟定了黄铁矿单矿物系统分析流程。其特点是在一分称样中通过阳离子交换树脂分离,使阴阳离子分成两部分。在含阴离子溶液中可测定硫、砷、硒、磷等元素;在含阳离子溶液中可测定铁、铜、锌、镉、钴、镍、锰、锢、钙、镁等元素。解决了黄铁矿单矿物主要项目的测定。 试剂及装置     

激光剥蚀电感耦合等离子体质谱-电子探针分析白山堂铜矿中的黄铁矿成分

通过激光剥蚀电感耦合等离子体质谱(LA-ICP-MS)获得被测物相中痕量元素的丰度值是目前原位分析矿物物相的技术之一。黄铁矿作为斑岩铜矿中的重要矿物,其主量、微量元素的特征能为成矿过程提供重要信息。本文建立了应用LA-ICP-MS测定黄铁矿微区微量元素组成、电子探针(EMPA)测定主量元素的方法,并将该方法应用到白山堂斑岩铜矿区。LA-ICP-MS实验采用60μm的激光束对分析样品进行斑点式剥蚀,以氦气作载气,重复频率5 Hz,激光能量约6 J/cm~2;单点分析时间60 s,分析数据以Fe作内标,用MASS-1黄铁矿标样进行校正,多数元素分析精度好于10%。针对黄铁矿与毒砂光学性质相似,容易混淆的问题,可以利用二者物理性质的差异进行区分。测试结果显示:矿区黄铁矿的主量元素呈亏硫高铁的特征,指示其为热液成因;微量元素特征表明其形成深度为中部,属与火山作用有关的中低温热液型黄铁矿。此结论对白山堂铜矿的成因类型、成矿流体来源等提供了相应的证据,对矿区的勘查具有理论指导意义。     

等离子体直读光谱法分析以Pb、Zn、Cu、Fe为基体的硫化矿物的研究

近年来地质科研工作对单矿物分析提出了新的任务。除主、次元素外,还要求测定微量元素。地质科学工作者已把微量元素研究作为探索矿床成因的主要手段之一。本文继黄铁矿分析之后,试图把等离子体直读光谱分析技术的应用扩大到其他硫化矿单矿物的分析领域。具体实验包括闪锌矿、方铅矿和黄铜矿。     

苏州富铌钽花岗岩的物质组成及钽的赋存状态研究

苏州富含铌钽花岗岩 (A型 )由富黑云母花岗岩和富钠长石花岗岩组成。主要副矿物为铌钽铁矿、锆石、细晶石、磷钇矿、黄玉和黄铁矿。钽元素主要形成铌钽铁矿系列单矿物 ,少量分散于长石、石英、黑云母、黄铁矿及萤石中     

河南元岭金矿黄铁矿和方铅矿的微量元素特征及其意义

本文研究了元岭金矿含金单矿物黄铁矿和方铅矿的一般特点和微量元素及其变化规律，并发现：黄铁矿和方铝矿微量元素含量由早至晚的变化显示出亲石元素→亲石铁族元素→亲硫铁族元素→高温亲硫元素→低温亲硫元素逐次富集的过程，这与围岩蚀变和成矿溶液的变化惊人地相似，热液演化在岩石和矿物中的表现一致，金富集发生在铁族和亲硫元素交代之间或亲硫元素交代的早期     

黄铁矿单矿物分析

黄铁矿常规分析多采用单独取样,针对某些元素采用有关分析方法。因而手续较繁琐,需要样品量也大。为了简化分析流程,减少样品用量,经试验拟定了黄铁矿单矿物系统分析流程。其特点是在一分称样中通过阳离子交换树脂分离,使阴阳离子分成两部分。在含阴离子溶液中可测定硫、砷、硒、磷等元素;在含阳离子溶液中可测定铁、铜、     

浙江某金银矿床黃铁矿的穆斯堡尔谱参数及其地质意义

本文根据黄铁矿及有关矿物的晶体结构和穆斯堡尔谱参数的特点、对浙江某金银矿床及有关矿床的黄铁矿中杂质元素含量及其对黄铁矿结构与穆斯堡尔谱参数的影响,得出黄铁矿的四极分裂值QS的变化主要由黄铁矿中呈类质同象存在的杂质元素的含量不同所致的结论。由于黄铁矿中这些杂质元素的含量具有指示矿床成因、矿化阶段、矿床分带以及矿物组合的意义,因而黄铁矿的穆斯堡尔谱参数也就具有这些方面的意义,这可作为黄铁矿的一个新的标型特征并可在矿床的找寻、评价和勘探工作中应用。     

柱子淋洗模拟研究磷酸铁膜抑制黄铁矿氧化效果

自然室温条件下用柱子淋洗模拟研究了接氧化亚铁硫杆菌（Ｔｈｉｏｂａｃｉｌｌｕｓ ｆｅｒｒｏｏｘｉｄａｎｓ,简称Ｔ．Ｆ菌）时磷酸铁膜抑制黄铁矿氧化的效果。试验结果首次指出：用ＫＨ２ＰＯ４与Ｈ２Ｏ２淋洗黄铁矿,在其表面形成的磷酸铁膜不能抑制黄铁矿的生物氧化,反而在一定程度上加速其氧化进程。经包膜后的黄铁矿矿石柱子间歇循环淋洗一年后的收集液中ＳＯ４＾２－累积量高达３３７５６．１ｍｇ;为对照组的１．６倍,是     

The iron-coating role on the oxidation kinetics of a pyritic sludge doped with fly ash

The present study examines the processes that control the oxidation attenuation of a pyrite-rich sludge (72 wt% pyrite) from the Iberian Pyrite Belt by the buffer capacity of a fly ash from Los Barrios power station (S Spain), using saturated column experiments. In addition, in order to understand the behaviour of both materials inside these experiments, a fly-ash leaching test and flow-through experiments with pyritic sludge were carried out. The fly-ash leaching test showed that after leaching this material with a slightly acid solution (Millipore MQ water; pH 5.6) the pH raised up to 10.2 and that the metals released by the fly-ash dissolution did not increase significantly the metal concentrations in the output solutions. The flow-through experiments with the pyritic sludge were performed at pH 9, 22 °C and O₂ partial pressure of 0.21 atm, to calculate the dissolution rate of this residue simulating the fly-ash addition. In the experiments Fe bearing oxyhydroxides precipitated as the sludge dissolved. In two non-stirred experiments the iron precipitates formed Fe-coatings on the pyrite surfaces preventing the interaction between the oxidizing agents and the pyrite grains, halting pyrite oxidation (this process is known as pyrite microencapsulation), whereas in two stirred experiments, stirring hindered the iron precipitates to coat the pyrite grains. Thus, based on the release of S (aqueous sulphate) the steady-state pyritic sludge dissolution rate obtained was 9.0 ± 0.2 × ⁻¹¹ mol m⁻² s⁻¹.In the saturated column experiments, the sludge dissolution was examined at acidic and basic pH at 22 °C and oxygen-saturated atmosphere. In a saturated column experiment filled with the pyritic sludge, pyrite oxidation occurred favourably at pH approx. 3.7. As the leachates of the fly ash yielded high basic pH, in another saturated column, consisting of an initial thick layer of fly-ash material and a layer of pyritic sludge, the pyrite dissolution took place at pH approx. 10.45. In this experiment, iron was depleted completely from the solution and attenuation of the sludge oxidation was produced in this conditions. The attenuation was likely promoted by precipitation of iron-bearing phases upon the pyritic surface forming Fe-coatings (of ferrihydrite and/or Fe(III) amorphous phases) that halted the pyrite oxidation (as in non-stirred flow-through experiments). Results suggest that buffering capacity of fly ash can be used to attenuate the pyrite-rich sludge oxidation.     

Immobilization of copper under an acid leach of colloidal pyrite waste rocks by a fixed-bed column

Colloidal pyrite waste rocks (CPWR) which are mainly composed of colloidal pyrite and siderite widely deposit in sulfide mines in the middle and lower reaches of the Yangtze River belt, China, especially in Tongling City, Anhui Province, China. In this paper, a fixed-bed column was used to investigate the weathering and oxidation of CPWR and its role in immobilizing low-concentration Cu (10 mg L^?1) under weakly acidic leach (pH = 5.0). The experimental results indicated that the breakthrough capacity was around 14.0 mg Cu g^?1 CPWR when Cu²⁺ breakthrough concentration was 0.5 mg L^?1. Sequential extraction of Cu and dithionite–citrate–bicarbonate extraction of free iron in the used CPWR after the column breakthrough indicated that Cu removal by CPWR consisted of the following processes: oxidation of pyrite and dissolution of siderite in CPWR, ferrous oxidation, and adsorption of Cu on ferric (hydr)oxides. This study shows the potential application of CPWR as an effective sorbent for the removal of low-concentration Cu from acid mine drainage.     

Particulate sulfur species in the water column of the Cariaco Basin

The biogeochemistry of iron sulfide minerals in the water column of the Cariaco Basin was investigated in November 2007 (non-upwelling season) and May 2008 (upwelling season) as part of the on-going CARIACO (CArbon Retention In A Colored Ocean) time series project. The concentrations of particulate sulfur species, specifically acid volatile sulfur (AVS), greigite, pyrite, and particulate elemental sulfur, were determined at high resolution near the O₂/H₂S interface. In November 2007, AVS was low throughout the water column, with the highest concentration at the depth where sulfide was first detected (260 m) and with a second peak at 500 m. Greigite, pyrite, and particulate elemental sulfur showed distinct concentration maxima near the interface. In May 2008, AVS was not detected in the water column. Maxima for greigite, pyrite, and particulate elemental sulfur were again observed near the interface. We also studied the iron sulfide flux using sediment trap materials collected at the Cariaco station. Pyrite comprised 0.2-0.4% of the total particulate flux in the anoxic water column, with a flux of 0.5-1.6 mg S m⁻² d⁻¹.Consistent with the water column concentration profiles for iron sulfide minerals, the sulfur isotope composition of particulate sulfur found in deep anoxic traps was similar to that of dissolved sulfide near the O₂/H₂S interface. We conclude that pyrite is formed mainly within the redoxcline where sulfur cycling imparts a distinct isotopic signature compared to dissolved sulfide in the deep anoxic water. This conclusion is consistent with our previous study of sulfur species and chemoautotrophic production, which suggests that reaction of sulfide with reactive iron is an important pathway for sulfide oxidation and sulfur intermediate formation near the interface. Pyrite and elemental sulfur distributions favor a pathway of pyrite formation via the reaction of FeS with polysulfides or particulate elemental sulfur near the interface. A comparison of thermodynamic predictions with actual concentration profiles for iron sulfides leads us to argue that microbes may mediate this precipitation.     

Pyrite geochemistry in the Toarcian Posidonia Shale of south‐west Germany: Evidence for contrasting trace‐element patterns of diagenetic and syngenetic pyrites

Authigenic pyrite grains from a section of the Lower Toarcian Posidonia Shale were analysed for their trace‐element contents and sulphur‐isotope compositions. The resulting data are used to evaluate the relationship between depositional conditions and pyrite trace‐element composition. By using factor analysis, trace‐elements in pyrite may be assigned to four groups: (i) heavy metals (including Cu, Ni, Co, Pb, Bi and Tl); (ii) oxyanionic elements (As, Mo and Sb); (iii) elements partitioned in sub‐microscopic sphalerite inclusions (Zn and Cd); and (iv) elements related to organic or silicate impurities (Ga and V). Results indicate that trace‐element contents in pyrite depend on the site and mechanism of pyrite formation, with characteristic features being observed for diagenetic and syngenetic pyrites. Diagenetic pyrite formed within anoxic sediments generally has a high heavy metals content, and the degree of pyritization of these elements increases with increasing oxygen deficiency, similar to the degree of pyritization of reactive Fe. The highest gradient in the increase of the degree of trace element pyritization with bottom‐water oxygenation was found for the elements Ni < Cu < Mo = As < Tl. In contrast, syngenetic pyrite formed within a euxinic water column typically is enriched in As, Mo and Sb, but is low in heavy metals, and the geochemical variation reflects changes in sea water composition.     

胶东焦家金成矿带2420~3206 m垂深金矿物和黄铁矿微量元素特征

在胶东莱州吴一村地区完成的3266.06 m深钻,是目前焦家金成矿带最深见矿钻孔,研究钻孔揭露的深部矿石中金矿物及黄铁矿微量元素特征,对探讨深部成矿作用演化具有重要意义。笔者采取深钻中2420~3206 m垂深的岩（矿）芯样品进行了详细的岩相学和矿相学研究,结合扫描电镜和电子探针微区分析,研究了矿石中金矿物的赋存状态和成分。对不同成矿阶段形成的黄铁矿进行了LA-ICPMS微量元素分析。研究结果表明,深部矿石中载金矿物主要为黄铁矿,其次为石英、黄铜矿、方铅矿,可见金主要以自然金和银金矿的形式存在,以晶隙金和裂隙金为主,其次为包体金。与浅部金矿床比较,深部金的成色较高。黄铁矿分为6种类型,第Ⅰ成矿阶段形成富Co型黄铁矿Py1,第Ⅱ成矿阶段形成富Ni型黄铁矿Py2a和Py2b,第Ⅲ成矿阶段形成富Au、As型黄铁矿Py3a和富Au、Ag、Pb、Bi型黄铁矿Py3b,第Ⅳ成矿阶段形成贫微量元素黄铁矿Py4。其中,Py1和Py2a发生强烈破碎,裂隙表面对热液中的Au络合物产生吸附作用,对金沉淀富集起重要作用。黄铁矿中Co、Ni、As等微量元素主要以类质同象形式赋存,而Au、Ag、Cu、Pb、Zn、Bi等主要以纳米级、微米级矿物包体形式赋存。Pb+Bi、Cu+Pb+Zn、Te+Bi与Au+Ag呈明显正相关,而Au与As相关性较差。黄铁矿中Co、Ni含量较低,而Au+Ag+As或Au+Ag+Pb+Bi+Cu含量较高指示成矿有利。另外,黄铁矿中Co、Ni含量较高,并且破碎强烈,成矿相关元素含量较高也指示成矿有利。     

Soft X-ray spectroscopic studies of the reaction of fractured pyrite surfaces with Cr(VI)-containing aqueous solutions

We have used synchrotron-based soft X-ray core-level photoemission and adsorption spectroscopies to study the reaction of aqueous sodium chromate solutions with freshly fractured pyrite surfaces. Pyrite surfaces were reacted with 50 μM sodium chromate solution at pH 7 for reaction times between 1 min and 37 hr. Additional experiments were performed at pH 2 and pH 4 with 50 μM sodium chromate solutions and at pH 7 with 5 mM solutions. At chromate concentrations of 50 μM, all chromium present on the pyrite surface was in the form of Cr(III), while at 5 mM, both Cr(III) and Cr(VI) were present at the pyrite surface. Minor quantities of oxidized sulfur species (sulfate, sulfite, and zero-valent sulfur) were identified as reaction products on the pyrite surface. The amount of oxidized sulfur species observed on the surface was greater when pyrite was reacted with 5 mM Cr(VI) solutions because the rate of chromium deposition exceeded the rate of dissolution of pyrite oxidation products, effectively trapping Cr(VI) and oxidized sulfur species in an overlayer of iron(III)-containing Cr(III)-hydroxide. This work shows that pyrite, an extremely cheap and readily available waste material, may be suitable for the removal of hexavalent chromium from acidic to circumneutral waste streams. The reduced chromium ultimately forms a coating on the pyrite surface, which passivates the pyrite surface towards further oxidation.     

The effect of As, Co, and Ni impurities on pyrite oxidation kinetics: Batch and flow-through reactor experiments with synthetic pyrite

Pyrite samples synthesized with As, Co, or Ni impurities and without added impurities were oxidized in batch and mixed flow-through reactors in the presence of 1 mM ferric iron, at pH 2. Six samples from each dopant population were used to provide a statistically robust comparison; two natural samples from Leadville, CO (major impurities Pb, As, Bi, Ag, Zn) and Elba, Italy (Co, As) were also included. In each experiment, three reaction progress variables were monitored: ferric iron, ferrous iron, and sulfate. The pyrite samples with impurities have average oxidation rates that are faster than the undoped samples, with As- and Co-doped pyrite having the highest rates. As, Co, and Ni were released to solution in accordance with their concentrations in the solid samples. As concentrations in the batch reactor experiments tended to remain constant, in contrast to Co and Ni, which increased over time. Initial rates, calculated from the batch reactor experiments, were faster than the steady-state rates calculated from the mixed flow-through reactor experiments. Apparent rates calculated using sulfate were faster than apparent rates calculated using ferric and ferrous iron, reflecting oxidation of ferrous iron in solution by dissolved oxygen. The results imply that impurities in pyrite do contribute to its reactivity, in agreement with studies using electrochemical methods. Oxidation rate differences among pyrite samples with different impurities are probably too small to warrant explicit consideration in environmental modeling applications, but are important to understanding pyrite oxidation mechanisms and semiconducting properties.     

金在黄铁矿表面沉淀机理的实验研究

为了研究金在黄铁矿表面沉淀的机理,于室温、常压,在氯化物溶液中进行了黄铁矿粉末吸附金的实验。在不同pH的溶液中,黄铁矿均可吸附金,而且pH值明显地影响吸附速率。扫描电镜观察表明,反应后黄铁矿粒表面有金晶体形成。XPS研究得知,黄铁矿光片与含金氯化物溶液反应后表面有A⁰存在;硫在反应初期为S⁰、S₂O₃^2-,随后转变为SO₄^2-,而铁成为Fe³⁺.黄铁矿中的Fe²⁺和S₂^2-是溶液中金的还原剂。金在黄铁矿表面沉淀可能涉及吸附、还原和晶体生长等过程。     

Coupled Reactive Transport Modeling of Redox Processes in a Nitrate-Polluted Sandy Aquifer

The reactive transport modeling of a complicated suite of reactions apparent in the aquifer during the application of N-containing fertilizers is reported. The unconfined sandy aquifer can be subdivided into an oxic zone which contains groundwater with oxygen and nitrate and an anoxic zone characterized by elevated iron and sulfate concentrations in groundwater. Oxygen and nitrate are being reduced by pyrite and organic matter that commonly apparent in the aquifer. The oxidation of pyrite is modeled using the local equilibrium approach, whereas decomposition of organic matter, with the adoption of kinetic approach. The system is buffered by dissolution of aluminum and iron oxides. The modeling process is a two-step procedure. First, the processes are modeled in the one-dimensional (1D) column using PHREEQC code. Subsequently, the calibrated and verified data were copied and used in two-dimensional (2D) PHAST model. Prior to the performance of reactive transport modeling operations with PHAST, a reliable flow model was executed. Finally, predictions are made for the distribution of water chemistry for the year 2008. Model predicts that sulfate derived from the ongoing pyrite oxidation is reduced by the dissolved organic carbon at the higher depth and forms pyrite by the reaction with iron. The results of this study highlight the importance of understanding the interplay between the transport and chemical reactions that occur during the input of nitrate to the aquifer. Reactive transport modeling incorporating the use of a newly developed code PHAST have proved to be a powerful tool for analyzing and quantifying such interactions.