Sulfur speciation and associated trace metals (Fe,Cu) in the pore waters of Great Marsh,Delaware

The pore waters of sediments from a salt marsh along the Delaware estuary have been analyzed for sulfur species and associated trace metals. Since the sediment interface is usually in contact with the atmosphere, the sulfur species are dependent on the production of hydrogen sulfide by sulfate reduction and subsequent oxidation by diffusing oxygen. The most important species observed are hydrogen sulfide, polysulfide ions and thiosulfate. Secondary reactions of hydrogen sulfide and polysulfides with decomposing organic matter yield significant concentrations of both thiols and organic polysulfides. Upon isolation of the sediment from the atmosphere due to tidal inundation, bacterial sulfate reduction becomes the dominant process. This results in the reduction of the polysulfides in agreement with thermodynamic predictions, and suggests that the redox couple sulfide/polysulfide is a good redox indicator under such reducing environments.The concentrations of trace elements Cu and Fe in the pore waters are mainly controlled by sulfide formation. Calculations show that copper is strongly complexed probably with organo-sulfur ligands. Iron might be complexed as such sulfur species to a much lesser extent than copper.     

Examination and Refinement of the Determination of Aqueous Hydrogen Sulfide by the Methylene Blue Method

The accurate and precise measurement of total sulfide has been of major interest for well over a century. The most commonly used method involves the formation of a methylene blue?Csulfide complex and spectrophotometric measurement of its concentration. The study presented herein compares the two most commonly used methods as outlined in Standard Methods for the Examination of Water and Wastewater (in APHA, Standard methods for the examination of water and wastewater, Washington, 1960) and by Cline (Limnol Oceanogr 14:454?C458, 1969). In addition, this study clarifies the existing confusion of Cline??s reagent preparation procedure, as it is apparent that various interpretations exist among research groups regarding reagent preparation. After evaluating both methods with respect to precision and accuracy, detection limit, sample storage time, and ease of use, the method outlined in Cline was determined to be superior. Furthermore, we suggest that the reagent concentration has to be optimized depending on the range of sulfide concentrations to increase the accuracy and precision of the method.     

Removal of hydrogen sulfide by zinc oxide nanoparticles in drilling fluid

Hydrogen sulfide is a very dangerous, toxic and corrosive gas. It can diffuse into drilling fluid from formations during drilling of gas and oil wells. Hydrogen sulfide should be removed from this fluid to reduce the environmental pollution, protect the health of drilling workers and prevent corrosion of pipelines and equipments. In this research nano zinc oxide with 14–25 nm particle size and 44–56 m2/g specific surface area was synthesized by spray pyrolysis method. The synthesized nanoparticles were used to remove hydrogen sulfide from water based drilling fluid. The efficiency of these nanoparticles in the removal of hydrogen sulfide from drilling mud were evaluated and compared with that of bulk zinc oxide. The obtained results show that synthesized zinc oxide nanoparticles are completely able to remove hydrogen sulfide from water based drilling mud in just 15 min., whereas bulk zinc oxide is able to remove 2.5% of hydrogen sulfide in as long as 90 min. under the same operating conditions.     

Spectrophotometric determination of hydrogen sulfide in environmental samples using sodium 1,2-naphthoquinone-4-sulfonate and response surface methodology

A simple spectrophotometric method for determination of hydrogen sulfide in wastewater and hot spring samples was developed. The method is based on the reaction between hydrogen sulfide and sodium 1,2-naphthoquinone-4-sulfonate (NQS). The effect of various experimental factors on the reaction between hydrogen sulfide and NQS was investigated and optimized using central composite design. The optimal values of the factors were 5.00 × 10^?4 mol L^?1 for concentration of NQS and 1.00 × 10^?2 mol L^?1 for concentration of hydrochloric acid. The wavelength of the maximum absorption of the reaction product was 320 nm. Constructed calibration curve for hydrogen sulfide determination was linear in the range of 0.5–20.0 mg L^?1 with the detection limit of 0.16 mg L^?1. The method was free from interferences. Percent relative errors below 2 % were obtained for determination of hydrogen sulfide in environmental samples.     

煤矿水平孔复杂地质模型方位电磁波响应数值模拟

煤岩界面的预先、精准识别是实现煤矿巷道自动化掘进和煤矿智能化的关键技术之一,方位电磁波仪器探测距离较大,能够分辨岩性界面和界面方位,在油田测井中已取得成功应用,但在煤矿领域应用较少。为了研究方位电磁波测井在煤矿复杂三维(3D)模型中的探测性能,使用有限元数值模拟方法,考察了方位电磁波测井在煤矿测量环境中,不同发射频率和源距时受钻孔内流体的影响,以及采空区和起伏地层边界对方位电磁波测量的影响。结果表明:对于煤矿测井中的常见情况——孔中流体为空气时,方位电磁波响应受钻孔的影响较小;方位电磁波测量信号能够反映地层界面的起伏变化,其探测能力与发射频率、源距有关;方位电磁波响应对低阻采空区较敏感,但在高频发射时可以利用相位差信号实现对高阻采空区的探测。方位电磁波方法为煤矿井下水平孔煤岩界面和采空区测量提供了一种新技术手段,具有较大的应用潜力。      

The use of sulfur to extract hydrogen from coal

The world's recoverable coal reserves contain about 3 × 10¹⁰ tons of hydrogen. The reaction of sulfur vapor with medium-volatile bituminous coal produces hydrogen sulfide in yields up to 97% (based on sulfur), and utilizes 70–75% of the hydrogen from the coal. The conversion of hydrogen sulfide to hydrogen can be effected through commercially proven processes; several laboratory-scale processes could also be scaled up for future use. The solid by-product of the coal–sulfur reaction meets or exceeds specifications for fixed carbon, ash, and friability of conventional metallurgical coke, though produced at lower temperatures than typical by-product coke ovens. A conceptual process is presented in which sulfur is converted to hydrogen sulfide by reaction with coal, the hydrogen sulfide in turn is converted to the desired hydrogen and to sulfur, and the sulfur is recycled through the reactor. The by-product is a good quality coke, but may also have other applications as a carbon material.     

Geochemical Evidences for Possible Absence of Cu-Sulfide Deposits in the Deccan Volcanic Province,India

Continental flood basalt provinces (CFBs) are important hosts for large-scale Cu-sulfide deposits. However, sulfide mineralization is yet to be discovered, if any, in the end-Cretaceous Deccan volcanic province, India. In the present study, geochemical evidences for the possible absence of Cu-sulfide deposits associated with the Deccan basalts by analyzing and comparing the geochemistries of the Deccan and Siberian CFBs are provided. The Fe-rich nature and high fO₂ conditions did not favour sulfide saturation at any stage of magma evolution in the Deccan province. Crustal contamination of the Deccan magmas also did not increase the sulfur budget. The most contaminated basalts of Bushe and Poladpur formations of the Deccan province do not show any depletion in the copper contents compared to other formations. In the absence of sulfide saturation, copper behaved as an incompatible element in the Deccan magmas in contrast to the Siberian basalts, in which copper behaved as a compatible element during magma evolution due to sulfide saturation consequently formed world-class copper sulfide deposits. It is demonstrated that the lithosphere- and asthenosphere-derived Deccan magmas have similar Cu abundances thereby suggesting that the Cu-sulfide deposits associated with the CFBs are process-controlled rather than source-controlled. Although Cu-sulfide deposits may not have formed, the geochemical patterns suggest favourable conditions for native copper mineralization in the Deccan volcanic province. In the present study, a set of geochemical proxies that can be utilized as preliminary exploration tools for Cu-sulfide mineralization in the CFBs is proposed.     

电感耦合等离子体发射光谱法测定地热水中的硫化物

地热水中的硫化物(H_2S、HS~-和S~(2-))通常受到硫酸根、亚硫酸根、硫代硫酸根等硫元素的共存干扰,并且硫化物具有热、光、氧不稳定性,在水样保存、前处理、标准溶液配制等环节影响着测试的准确度和精密度。本文在现场采集的地热水水样中加入乙酸锌及氢氧化钠,使硫化物形成硫化锌沉淀而与溶液分离,将此沉淀溶于双氧水和逆王水,使低价态的S2-氧化成稳定的SO_4~(2-),选择易于纯化且性质稳定的硫酸钠配制硫标准储备液,以182.624 nm谱线作为硫元素分析谱线,应用电感耦合等离子体发射光谱法测定出地热水样中的硫化物含量。硫的浓度在0.1~100 mg/L范围内与其发射强度呈线性(相关系数为0.9994);方法检出限为0.009 mg/L,相对标准偏差(n=11)低于1.80%,实际水样中硫化物的加标回收率介于99.0%~103.0%。与前人相关测试方法相比,本方法的技术指标具有优势。     

液液萃取电感耦合等离子体光谱法测定碳酸盐岩中的单质硫

建立了碳酸盐岩样品中单质硫的分析方法,此法以正己烷为萃取剂,在180.7 nm和182.0 nm波长下用电感耦合等离子体光谱法(ICP-AES)测定国家标准物质GBW(E)07108和碳酸盐岩样品。正己烷萃取碳酸盐岩中单质硫的回收率在90%～110%之间;每个样品测定7次,相对标准偏差(RSD)<5.0%。结果表明,此法满足实验要求,可用于大批量碳酸盐岩样品中单质硫的测定。      

新疆铜镍硫化物矿床的基本地质特点

作者从矿化岩带、含矿岩体和矿床特点三个层次,概括地阐述了新疆铜镍硫化物矿床成生的地质条件、基本特点,成因及矿模式;用归纳对比法,突出地探讨了新疆槽区铜镍硫化物矿床的分布规律.     

综合物探技术在北京山前平原隐伏断层探测中的应用

复杂地质隐伏断层探测是地球物理勘测难点之一。本文介绍了高密度电法、浅层地震反射波法、可控源音频大地电磁测深法在北京山前平原隐伏断层综合探测的应用。在北京山前平原复杂地形条件下,综合物探技术方法对隐伏断层的探测具有可靠和成果直观的特点。     

氢化物发生-原子荧光光谱法测定铜矿石中的砷锑铋

样品经王水溶矿分解,在氨水存在下,以Fe3+作共沉淀剂分离铜后,用氢化物发生-原子荧光光谱法测定铜矿石中的砷、锑、铋。方法检出限为砷0.19μg/g、锑0.052μg/g、铋0.049μg/g;精密度(RSD,n=10)为砷5.87%、锑7.58%、铋2.42%。     

Efficient separation of zinc from zinc containing copper sulfide concentrate by chemical leaching

As the most abundant copper containing resource and zinc containing resource, chalcopyrite and sphalerite/marmatite commonly coexist as Cu-Zn mixed ores in deposits. However, it is difficult to completely separate sphalerite and chalcopyrite by flotation, thus resulting in the existence of zinc impurity in copper concentrate. Sphalerite/marmatite existed in copper sulfide concentrate as impurity may lead to severe damage of the smelting equipment, and cause the waste of copper and Zn resources, it will also decrease of the sale price of copper concentrates. Therefore, the deep separation of zinc from zinc bearing copper sulfide concentrate is of great significance. In this work, selective chemical leaching was developed to efficiently remove zinc from zinc containing copper sulfide concentrate. Under the optimal condition (i.e., sulfuric acid concentration exceed 100 g/L, temperature of 80 °C, pulp density of 10%, leaching time of 48 h), over 85% Zn was extracted into the leaching solution together with only about 10% Cu and Fe, according to the leaching experiment. Leaching slurry had good solid-liquid separation characteristics, and zinc can be further effectively recovered from the leaching solution. According to X-ray diffraction (XRD) and scanning electron microscope/energy dispersive spectrometer (SEM/EDS) analysis, chalcopyrite was the main mineralogical phase in the residues, which can be regarded as high quality copper concentrate for metallurgy. Accordingly, a new process for deep and efficient separation of Cu-Zn mixed ores has been proposed.     

X射线荧光光谱微区分析在铜矿物类质同象鉴定中的应用

铜矿物种类繁多,赋存状态各异,成分复杂,由于共生矿物和伴生矿物的存在,增加了传统岩矿鉴定工作的难度。特别是铜矿物间存在的类质同象现象(黝铜矿和砷黝铜矿)和铜矿物与其他矿物间(磁黄铁矿和方黄铜矿)存在镜下光学特征相似的现象,应用偏光或反光显微镜难以给铜矿物准确定名。本文应用具有微区分析功能的X射线荧光光谱仪扫描铜矿物标本谱图,通过选择测量条件、测量方式和干扰校正模型(谱线重叠和基体效应)建立了类质同象物相的鉴定方法。该方法具有较高的精密度和准确度,对黄铜矿标本进行12次测定,S、Fe、Cu的相对标准偏差(RSD)分别为0.74%、0.86%、0.18%;对铜矿物标准样品进行单次测定,待测元素的测量结果与推荐值的相对误差均小于6%。该方法可准确甄别出黝铜矿与含银砷黝铜矿、磁黄铁矿与方黄铜矿;测量效率高,能够提供主量元素和主要伴生元素的二维或三维图像,直观地呈现矿物的分布情况,为铜矿物的准确定名和矿物的综合利用提供了有价值的信息。     

机载电磁测量系统及应用效果——以云南金平地区寻找铜镍矿为例

金平地块位于扬子克拉通西南缘,该地区岩浆熔离型铜镍硫化物型矿床产于与二叠系峨眉山玄武岩有成因联系的基性-超基性侵入岩体中,赋矿围岩及矿石的物性特征与其它非含矿岩石具有明显的差异,对航测所获得的特定频率(900 Hz)电磁异常及磁异常进行分析,结合地面地质检查和物化探测量工作,对有望成矿潜力区进行快速远景评价.     

A rapid x-ray fluorescence procedure applicable to exploration geochemistry

A rapid X-ray fluorescence method is described for the analysis of all elements heavier than iron. It is based upon the measurement of a peak and background, while primary scattered radiation is used to correct or compensate for matrix effects. About 15 analyses per man hour can be made on individual samples for such elements as Th, Nb, Ta and W, which are normally difficult to determine by other techniques. Lower limits of detection of about 50 ppm are routinely obtained, and even lower limits of detection (e.g., 20 ppm) can be obtained should these be necessary by increasing the counting time (from 20 to 40 seconds).     

发射光谱法测定化探样品中的铜、铅、锌元素

本法以氧化铝、焦硫酸钾、氟化钠、石墨粉的混合物为缓冲剂,锗为内标元素,一次取样,用垂直电极发射光谱法,同时测定铜、铅、锌元素.方法检出限,精密度及准确度均能满足化探样品的要求.并提供了一个简便、快速、成本低的光谱分析方法.     

矿用钻孔超声流量自适应检测技术

为了更好地实现煤矿井下瓦斯抽采钻孔端流量监测,针对管路内介质成分复杂、纯净度差、稳定性差等因素对抽采流量参数测量准确性影响的问题,提出以时差法为测量原理,以双阈值比较法为检测方法,设计了一套矿用钻孔超声流量自适应检测系统。通过分析影响双阈值比较法测量准确性的关键问题出发,设计了检测系统的总体方案,并对其中激励信号放大电路、接收信号调理电路及由峰值检波电路与增益控制电路构成的自适应电路几项关键模块进行了详细地介绍,叙述了检测系统运行软件的工作流程。通过工况环境适应能力测试与准确度性能检验,对检测系统的功能与性能进行了检验,检验结果表明,该系统能够适应瓦斯抽采钻孔管路内的工况需求,实现高精度的气体流量测量。      

Silikatische Kupferlagerstätten in Nordchile

The formation of isolated silicateous copper deposits is controlled by two main conditions:

1. oversaturation of groundwaters in silica
2. lateral inflow of copper bearing and slightly acid solutions originating from the oxidation of primary sulfide deposits.

The basic copper silicate chrysocolla is formed by chemisorption of copper ions by disilicic acid with a net-like structure. Under favourable conditions copper silicate deposits are formed which contain up to several million tons of copper as for example the La Exotica deposit in Northern Chile. The copper values of these deposits sometimes exceed those of the primary sulfide deposits. Thus, the oxidation of sulfide deposits, the migration of copper bearing solutions and the chemisorption of copper ions by the disilicic acid can result in workable new copper concentrations originating from sulfide protores. High concentrations of silica in groundwaters and thus the chemisorption of copper ions by the disilicic acid as an ore forming process is restricted to arid or semiarid regions. Therefore it is proposed to call such deposits arid silicateous infiltration deposits. Infiltration deposits are related to weathering processes. “They comprise products of weathering by which valuable substances were leached from the host rocks, migrated in groundwaters and were redeposited in other neighbouring rocks” (Smirnov, 1970, p. 324).     

刚果（金）如瓦西铜-钴矿床表生成矿过程及其勘探意义

中非成矿带刚果（金）如瓦西（Ruashi）铜-钴矿床经历了表生成矿作用,但其研究薄弱。在野外地质调查、室内矿物学观察和矿山生产勘探的基础上,对如瓦西铜-钴矿床的表生分带组构与次生富集规律进行研究。结果表明,该矿床原生矿体由黄铜矿、斑铜矿、硫铜钴矿等含铜硫化物矿物组成,矿石品位铜在1%~2%、钴在0.1%~0.3%范围内。矿床在近地表发生表生氧化作用后,上部形成了氧化带,可进一步划分为3个亚带：（1）完全氧化亚带;（2）淋滤亚带;（3）次生氧化物富集亚带。上部完全氧化亚带发育富钴氧化物堆积体“矿帽”（钴品位在1%~3%,部分可达12%）,淋滤亚带几乎不含铜、钴金属矿物,次生富集氧化物亚带由孔雀石、硅孔雀石、蓝铜矿、胆矾、水胆矾等氧化物矿物和碳酸盐矿物组成,矿石品位铜在5%~10%、钴在0.8%~1.0%范围内,相对原生矿石富集了3~5倍。下部为次生硫化物富集带,出现蓝铜矿、辉铜矿等次生硫化物矿物,矿石品位铜在3%~5%、钴在0.3%~0.8%范围内,相对原生硫化矿富集了1~3倍。综合分析认为,如瓦西铜-钴矿床表生成矿作用受岩石地层、地质构造和地下水等因素的控制,次生富集作用明显提高了矿石品位和矿床开发价值,形成了氧化物富铜-钴矿、硫化物富铜-钴矿和碳酸盐岩接触带附近的氧化物富铜矿及黑色富钴矿等类型的高-特高品位矿体。经勘探验证,在矿区深边部新揭露高品位矿石资源量256万吨,平均品位铜为3.68%、钴为0.44%,可采储量143万吨,平均品位铜为3.53%、钴为0.32%。该研究可为矿区及区域同类型矿山硫化矿演化成氧化矿的表生富集过程及深边部找矿预测提供科学依据。