重庆长河碥煤矿晚三叠世2号煤中微量元素的赋存状态

为了探讨煤中微量元素的赋存状态和地质成因,本文运用电离耦合等离子体质谱(ICP-MS)、电离耦合等离子体原子发射光谱(ICP-AES)、X射线荧光光谱(XRF)、冷原子吸收光谱(CV-AAS)、离子选择性电极法(ISE)、逐级化学提取试验(SCEE)等,研究了重庆长河碥矿晚三叠世须家河组2号煤层中微量元素的含量、赋存特征及其影响因素.发现该煤层中As(12.9 μg/g)、Cu(125 μg/g)、Cr(72 μg/g)、Ni(63 μg/g)、Pb(111 μg/g)等元素富集;逐级化学提取结果显示,煤层中Pb主要赋存在低温热液成因的黄铁矿脉中;Cr主要存在于粘土矿物中,Cr可能与陆源碎屑供给有关;Cu不仅与粘土矿物有关,也与煤中黄铁矿有关.表明低温热液流体和陆源碎屑供给对该煤中主要微量有害元素的含量和赋存特征起了决定作用.     

山西省阳泉新景煤矿15煤微量元素的富集及沉积环境研究

在对山西省阳泉矿区中新景煤田15号煤层采集的30个煤样进行ICP-MS微量元素含量分析测试的基础上,讨论了新景矿15号煤层剖面上Li、Be、Sc、Cu、Ba、Sr、Rb、U、Th和Pb微量元素的分布和富集特征,发现15号煤中Li富集,Be,Sc,Rb亏损。通过计算Sr/Ba、Sr/Cu和U/Th比值作为判断成煤环境的地球化学指标,分析新景矿15号煤层的成煤环境。     

硫同位素在地球化学异常成因研究中的应用

地球化学异常成因研究是评价其成矿前景、矿化类型的基础资料。本文借鉴稳定同位素示踪成矿物质来源的原理和方法,将硫同位素引入到地球化学异常成因研究中,通过对乌奴格吐山和垦山试验区Cu矿化体、Cu异常地段硫同位素组成特征的研究,发现在乌奴格吐山试验区Cu矿化及Cu异常地段硫的来源是一致的,表明应用硫同位素组成特征判断地球化学异常成因是可行的;对比发现,垦山试验区Cu异常地段硫同位素值较乌奴格吐山试验区偏高,推断该Cu异常是由后期热液作用形成的,由此针对该异常的地质找矿及工作部署应该围绕热液矿床进行。     

新疆-甘肃-内蒙古衔接区Cu和W地球化学异常及找矿意义

对新疆-甘肃-内蒙古衔接区的1：20万地球化学数据研究结果表明,该区Cu地球化学异常主要与基性、超基性岩和斑岩体有关,成矿元素组合为Co-Zn-Cr—Ni—Cu;W地球化学异常主要与中酸性岩有关,成矿元素组合为W—Sn—Bi。区内主要铜、钨矿床和新发现的矿床（点）均有相应元素区域异常显示,表明地球化学异常在本区具有重要指示意义。在全区确定了4个Cu地球化学省、5个W地球化学省、15个Cu区域异常和17个W区域异常,其中上马崖一铜山Cu地球化学省、黄山-梧桐窝子-葫芦北Cu地球化学异常带、土屋-赤湖Cu区域异常、大狐狸山Cu地球化学省、鹰嘴红山W地球化学省、古堡泉-柳园W地球化学省、英姿山W区域异常具有重要的找矿意义。     

新疆—甘肃—内蒙古衔接区Cu和W 地球化学异常及找矿意义

对新疆—甘肃—内蒙古衔接区的1∶20万地球化学数据研究结果表明,该区Cu地球化学异常主要与基性、超基性岩和斑岩体有关,成矿元素组合为Co-Zn-Cr-Ni-Cu;W地球化学异常主要与中酸性岩有关,成矿元素组合为W-Sn-Bi。区内主要铜、钨矿床和新发现的矿床（点）均有相应元素区域异常显示,表明地球化学异常在本区具有重要指示意义。在全区确定了4个Cu地球化学省、5个W地球化学省、15个Cu区域异常和17个W区域异常,其中上马崖—铜山Cu地球化学省、黄山—梧桐窝子—葫芦北Cu地球化学异常带、土屋—赤湖Cu区域异常、大狐狸山Cu地球化学省、鹰嘴红山W地球化学省、古堡泉—柳园W地球化学省、英姿山W区域异常具有重要的找矿意义。     

鄂尔多斯盆地北部地区延安组煤层自燃烧变产物及其特征

煤层自燃是世界范围内普遍存在的一种地质现象,但针对煤层自燃形成的产物尚缺乏系统研究。我国鄂尔多斯盆地北部地区延安组煤层在地史时期普遍发生自燃,研究中主要针对该地区的煤层自燃烧变产物的特征进行系统分析。结果表明,煤层烧变产物包括烧变残留煤、煤灰、烧变岩三类,其纵向和横向剖面上具有明显的分带规律,对其岩石物理学、地球化学等特征分析显示较原岩(煤、泥岩、砂岩)发生了不同程度的变化,可将其看成一类特殊的变质岩类。     

黔西晴隆矿区晚二叠世煤地球化学变异的地质成因

运用仪器中子活化分析(INAA)、电离耦合等离子体质谱(ICP—MS)、电离耦合等离子体原子发射光谱(ICP—AES)、X射线荧光光谱(XRF)、冷原子吸收光谱(CVAAS)、离子选择性电极法(ISE)、逐级化学提取试验(SCEE)等,结合带能谱仪的扫描电镜(SEMEDX)和MPV—Ⅲ显微镜下观察的煤岩学特征的分析,对贵州晴隆矿区上二叠统含煤岩系8号煤层中微量元素的含量和赋存特征及其影响因素进行了研究。发现该煤层中Cu(263.4μg／g)、Cr(154．2μg／g)、Hg(0．86／μg／g)、Mo(82．47μg／g)、Ni(63．3μg／g)、Pb(200．4／μg／g)、Se(4．25／μg／g)、U(154．8／μg／g)、Zn(214．6／μg／g)和Zr(754．3μg／g)等元素异常富集;而As和F的含量不高,其含量分别为1．58／μg／g和83．4μg／g。逐级化学提取结果显示,该煤层中Hg、Mo、Ni、Pb、Se和Zn元素主要赋存在低温热液成因的黄铁矿脉中;Cr、U和Zr主要存在于粘土矿物中,其中Cr和Zr可能与康滇古陆陆源碎屑供给有关;Cu不仅与粘土矿物有关,而且也和煤中黄铁矿有关。表明低温热液流体和陆源碎屑供给对该煤中主要微量有害元素的含量和赋存特征起了决定作用。     

长江中下游地区铜地球化学块体物质来源及其对铜矿集区形成的制约

本文从成矿物质供应角度入手,来剖析长江中下游地区大型矿床/矿集区的成因。研究区内共圈定出5个Cu地球化学块体,区内所有已发现的Cu矿集区和绝大多数已发现的大型Cu矿均位于Cu地球化学块体范围内。根据前人获得的研究区典型成矿岩体的Sr-Nd、Hf同位素及成矿岩体中继承锆石年龄,推断研究区产出有矿集区中Cu地球化学块体内巨量的Cu元素主要来源于富集岩石圈地幔,并有少量地壳物质的贡献。正是由于长江中下游地区存在规模巨大的Cu地球化学块体,这些块体能够提供区域成矿带所需的巨量的成矿物质,从而使得该区经历了长期的构造活动、岩浆作用和成矿作用后形成了数量众多的铜矿床。     

类芽孢杆菌对铜陵新桥矿区土壤中Cu化学形态的影响

采用Tessier五步连续提取法和红外光谱技术,研究类芽孢杆菌对铜陵新桥矿区重金属污染土壤中Cu化学形态的影响,初步探讨了Cu形态变化的机理。结果表明,不同投入量的类芽孢杆菌接种到土壤培养一周后,土壤溶液pH值降低,土壤中可交换态、有机结合态Cu含量增加,碳酸盐结合态、铁锰氧化物结合态和残渣态Cu的含量降低。土壤中可交换态、铁锰氧化物结合态和残渣态Cu含量的变化主要受土壤溶液的pH值控制;有机结合态升高主要与类芽孢杆菌菌数及其代谢产生的低分子量有机酸有关。类芽孢杆菌可以改变矿区土壤中Cu的化学形态,影响Cu的生物有效性。     

玄武岩及硫化物淋洗过程Cu同位素分馏实验

<正>作为重要的过渡族金属元素和营养元素,Cu的地球化学循环对海洋生命演化非常重要[1]。而海洋中的Cu大多来自大陆风化输入,因此研究风化过程的Cu同位素分馏行为至关重要。岩石风化过程会释放金属离子进入水体,进而影响金属离子在水圈和岩石圈的地球化学循环过程,研究风化过程Cu同位素分馏情况能够更好地应用Cu同位素解释自然环境中Cu同位素变化及其循环过程。前人主要集中研究酸性条件下的含Cu硫化物淋洗过程中Cu同位素变化[2-5],但含Cu硫化物中的Cu只占硅酸岩总Cu中的     

Cu(II) adsorption at the calcite-water interface in the presence of natural organic matter: Kinetic studies and molecular-scale characterization

We have characterized the adsorption of Suwannee River humic acid (SRHA) and Cu(II) on calcite from preequilibrated solutions at pH 8.25. Sorption isotherms of SRHA on calcite follow Langmuir-type behavior at SRHA concentrations less than 15 mg C L⁻¹, whereas non-Langmuirian uptake becomes evident at concentrations greater than 15 mg C L⁻¹. The adsorption of SRHA on calcite is rapid and mostly irreversible, with corresponding changes in electrostatic properties. At pH 8.25, Cu(II) uptake by calcite in the presence of dissolved SRHA decreases with increasing dissolved SRHA concentration, suggesting that formation of Cu-SRHA aqueous complexes is the primary factor controlling Cu(II) sorption at the calcite surface under the conditions of our experiments. We also observed that surface-bound SRHA has little influence on Cu(II) uptake by calcite, suggesting that Cu(II) coordinates to calcite surface sites rather than to surface-bound SRHA.Cu K-edge X-ray absorption near edge structure (XANES) and extended X-ray absorption fine-structure (EXAFS) spectroscopic results show that the local coordination of Cu adsorbed at the calcite surface is very similar in the presence and absence of SRHA. Ca backscatterers at ∼3.90 Å indicate that Cu(II) forms tetragonally distorted inner-sphere adsorption complexes in both binary and ternary systems. Subtle differences in the XANES and EXAFS between binary sorption samples and ternary sorption samples, however, prevent us from ruling out the formation of ternary Cu-SRHA surface complexes. Our findings demonstrate that SRHA plays an important role in controlling the fate and transport of Cu(II) in calcite-bearing systems.     

宁镇中段矽卡岩的石榴子石与成矿关系研究

宁镇中段铜多金属矿床与矽卡岩、尤以石榴子石矽卡岩关系密切,故从矿物学角度研究该区矽卡岩的石榴子石与成矿的关系具有现实找矿意义。通过现场观察、光学显微镜、扫描电镜、X射线衍射分析、微区能谱分析及成矿元素含量分析等,对宁镇中段矽卡岩石榴子石的形貌、结构、成分、种类及其与成矿的关系进行研究,结果表明：本区石榴子石属钙铝-钙铁榴石系列,但铜矿化区的石榴子石均属其中的钙铁榴石亚种,并且铜矿化区石榴子石的铜含量远远低于无矿化区石榴子石。研究认为,成矿元素在矽卡岩期的富集或分散趋势是石榴子石成矿元素含量高低的关键原因,若岩浆分异出来的成矿元素总量相同,则在矽卡岩期即富集到石榴子石等矿物使其成矿元素较高不利于成矿,反之则石榴子石成矿元素较低而矽卡岩期后热液具有利物质条件利于成矿。     

铜精矿样品的氧化条件及其机理探讨

考察了不同贮存和制备条件对铜精矿样品铜含量的影响,得出在包装密封不良时铜含量因氧化而产生的变化结果及其趋势;根据X射线衍射所作的矿相分析结果,利用X射线荧光光谱仪观察样品中铜、铁、硫化学态的变化,探讨了铜精矿氧化反应的机理。样品变质主要是低价硫、铜、铁离子与空气中的水和氧发生氧化反应所致,酸度增高会促使氧化反应加速进行。     

Electronic environments in carrollite, CuCo2S4, determined by soft X-ray photoelectron and absorption spectroscopy

Fracture surfaces of a natural carrollite specimen have been characterised by synchrotron and conventional X-ray photoelectron spectroscopy and near-edge X-ray absorption spectroscopy. For the synchrotron X-ray measurements, the mineral surfaces were prepared under clean ultra high vacuum and were unoxidised. The characterisation was undertaken primarily to establish unequivocally the oxidation state of the Cu in the mineral, but also to obtain information on the electronic environments of the Co and S, and on the surface species. Experimental and simulated Cu L_2,3-edge absorption spectra confirmed an oxidation state of Cu^I, while Co 2p photoelectron and Co L_2,3 absorption spectra were largely consistent with the Co^III established previously by nuclear magnetic resonance spectroscopy. S 2p photoelectron spectra provided no evidence for S to be present in the bulk in more than one state, and were consistent with an oxidation state slightly less negative than S^-II. Therefore it was concluded that carrollite can be best represented by Cu^ICo^III₂(S₄)^-VII. The Cu^I oxidation state is in agreement with that expected for Cu tetrahedrally coordinated by S, but is in disagreement with the Cu^II deduced previously from some magnetic, magnetic resonance and Cu L-edge X-ray absorption spectroscopic measurements. A significant concentration of S species with core electron binding energies both lower and higher than the bulk value were formed at fracture surfaces, and these entities were assigned to monomeric and oligomeric surface S species. The density of Cu d states calculated for carrollite differed from that previously reported but was consistent with the observed Cu L₃ X-ray absorption spectrum. The initial oxidation of carrollite in air under ambient conditions was confirmed to be congruent, unlike the incongruent reaction undergone by a number of non-thiospinel sulfide minerals.     

Ship-borne geochemical investigations of deep-sea manganese-nodule deposits in the Pacific using a radioisotope energy-dispersive X-ray system

A radioisotope energy-dispersive X-ray (EDX) system has been used on board the German research vessel “Valdivia” during an exploration expedition in the northern equatorial Pacific in 1973. The instrumentation used consisted of an X-ray detection system incorporating a 30 mm² effective-area Si (Li) detector with a measured energy resolution of 195 eV for Mn Kα X-rays, standard nuclear electronics, a 1024-channel analyser and a data read-out unit. The X-ray spectra in the manganese-nodule samples were excited by a 30-mCi ²³⁸Pu source.The six elements Mn, Fe, Co, Ni, Cu and Zn were analysed on board. Precision values for the analyses were less than 3% for Mn, Fe, Ni, Cu and Zn and about 5% for Co. A total amount of 350 analyses was carried out during a one-month cruise.Average contents of 190 analysed whole manganese-nodule samples from all the sampling sites of the covered area were 23.3% Mn, 6.7% Fe, 0.23% Co, 1.16% Ni, 0.94% Cu and 0.10% Zn. The average content of the base metals expressed as the sum of the Co, Ni, Cu and Zn contents was 2.48%. A linear relationship between Mn and Ni in all analysed samples, including whole manganese-nodule samples, zones of manganese nodules and manganese crusts, was observed. The Mn/Ni ratio calculated by regression analysis was 23.0. Zonal variations of the chemical contents of the six elements in the manganese nodules were found. A size classification of the manganese nodules has been suggested. Geochemical correlations of Cu and Ni versus Mn/Fe in the investigated samples are given.     

Polarized XANES and EXAFS spectroscopic investigation into copper(II) complexes on vermiculite

Interaction of heavy metals with clay minerals can dominate solid-solution reactions in soil, controlling the fate of the metals in the environment. In this study we used powdered and polarized extended X-ray absorption fine structure (EXAFS) spectroscopy and X-ray absorption near edge spectroscopy (XANES) to investigate Cu sorbed on Llano vermiculite and compare the results to reported Cu sorption mechanism on Wyoming (WY) smectite and reduced South African (SA) vermiculite. Analysis of the Cu K-edge spectra revealed that Cu sorbed on Llano vermiculite at high ionic strength (I) has the greatest degree of covalent bond character, followed by Cu sorbed on montmorillonite at high I, and Cu sorbed on reduced SA vermiculite at high I. Cu sorbed on clay minerals at low I has the least covalent character. EXAFS data from Cu sorbed Ca- and K-equilibrated Llano vermiculites showed the presence of a second-shell Al, Si, or Mg backscatterer at 3.02 Å. This distance is consistent with Cu sorbing via a corner-sharing monodentate or bidentate bond. Polarized XANES and EXAFS results revealed that the angle between the Cu atom and the mineral sorption sites is 68° with respect to the [001] direction. From the bond angle and the persistence of the second-shell backscatterer when the interlayer is collapsed (K-equilibration), we conclude that Cu adsorption on the Llano vermiculite is not occurring in the interlayer but rather Cu is adsorbing onto the edges of the vermiculite. Results from this research provide evidence that Cu forms inner-sphere and outer-sphere complexes on clay minerals, and does not form the vast multinuclear surface precipitates that have been observed for Co, Zn, and Ni.     

Spectroscopic investigation on the chemical forms of Cu during the synthesis of zeolite X at low temperature

The direct synthesis of zeolites in polluted soils has proved to be a promising process for the stabilization of metals inside these minerals. Nevertheless, more detailed information about this process is still needed in order to better foresee the fate of metals in treated soils. In this work, zeolite X has been synthesized under alkaline conditions in an aqueous solution containing 2500 mg kg⁻¹ of Cu, starting from Na silicate and Al hydroxide at 60 °C. Aluminium, Si and Cu concentrations in the aqueous phase, during zeolite synthesis, were measured over a period of 160 h. The solid products have been characterized over time by XRD, SEM-EDX, ESR, FT-IR, and synchrotron radiation X-ray microbeam absorption near edge structure (μ-XANES) and extended X-ray absorption fine structure (μ-EXAFS) spectroscopy. It appears that the marked reduction of Cu concentration in solution is not only due to a simple precipitation effect, but also to processes connected with the formation of zeolite X which could entrap, inside its porous structure, nano- or micro-occlusions of precipitated Cu hydroxides and/or oxides. In addition, EXAFS observations strengthen the hypothesis of the presence of different Cu phases even at a short-range molecular level and suggest that some of these occlusions could be even bound to the zeolite framework. The results suggest that zeolite formation could be used to reduce the availability of metals in polluted soils.     

紫金山金铜矿二元铜硫化物成分特点的初步研究

文章在电子显微成分分析的基础上,结合XRD、振动光谱等研究手段,对高硫型浅成热液形成的紫金山金铜矿床中铜硫化物的成分、物相特点进行了研究.首次在该区找到了久辉铜矿(Cu1.97S)、雅硫铜矿(Cu1.25S)等铜硫二元组分系列矿物,并发现了铜蓝被蓝辉铜矿明显交代的现象,进而推断它们基本上是同期形成的,但其所处的氧化-还...     

The oxidation states of copper and iron in mineral sulfides, and the oxides formed on initial exposure of chalcopyrite and bornite to air

Metal L_2,3, sulfur K and oxygen K near-edge X-ray absorption fine structure (NEXAFS) spectra for chalcopyrite, bornite, chalcocite, covellite, pyrrhotite and pyrite have been determined from single-piece natural mineral specimens in order to assess claims that chalcopyrite should be regarded as Cu^IIFe^IIS₂ rather than Cu^IFe^IIIS₂, and that copper oxide species are the principal initial oxidation products on chalcopyrite and bornite exposed to air. Spectra were obtained using both fluorescence and electron yields to obtain information representative of the bulk as well as the surface. Where appropriate, NEXAFS spectra have been interpreted by comparison with the densities of unfilled states and simulated spectra derived from ab initio calculations using primarily the FEFF8 code and to a lesser extent WIEN2k. Metal 2p and S 2p photoelectron spectra excited by monochromatised Al K_α X-rays were determined for each of the surfaces characterised by NEXAFS spectroscopy. The X-ray excited Cu LMM Auger spectrum was also determined for each copper-containing sulfide. FEFF8 calculations were able to simulate the experimental NEXAFS spectra quite well in most cases. For covellite and chalcocite, it was found that FEFF8 did not provide a good simulation of the Cu L₃-edge spectra, but WIEN2k simulations were in close agreement with the experimental spectra. Largely on the basis of these simulations, it was concluded that there was no convincing evidence for chalcopyrite to be represented as Cu^IIFe^IIS₂, and no strong argument for some of the Cu in either bornite or covellite to be regarded as Cu(II). The ab initio calculations for chalcopyrite and bornite indicated that the density of Cu d-states immediately above the Fermi level was sufficient to account for the Cu L₃-edge absorption spectrum, however these incompletely filled Cu d-states should not be interpreted as indicating some Cu(II) in the sulfide structure. It was also concluded that the X-ray absorption spectra were quite consistent with the initial oxidation products on chalcopyrite and bornite surfaces being iron oxide species, and inconsistent with the concomitant formation of copper-oxygen species.     

古琉璃着色元素的同步辐射X荧光分析

用同步辐射X射线荧光对陕西不同年代和地层出土的各色古琉璃釉中的主量和微量元素进行了分析，用SPSS统计软件对实验数据进行多元统计分析。结果表明，各色琉璃釉中主要着色元素是Fe、Cu和Co，琉璃中的多样釉色是由三种主要着色元素的含量决定。元素相关性分析表明，Fe和Co可能来自一种原料，而Cu可能来自另一种原料。