西藏多不杂铜矿床稀土元素地球化学特征研究

探讨稀土元素地球化学对多不杂铜矿床成矿物质及流体来源的指示意义。选择相关岩矿石及金属矿物样品,测试其稀土元素组成。研究表明,岩矿石及金属矿物均具有轻稀土富集的特征,这是地幔流体作用成矿的标志。由磁铁矿→浸染状黄铁矿→脉状黄铁矿→黄铜矿演化,δEu值逐步从大于1过渡为小于1,即由正铕异常→负铕异常演化,这是含矿地幔流体作用导致熔浆→热液演化,引发交代蚀变,促使壳幔物质混染叠加成矿的依据。从花岗闪长斑岩→变质砂岩→玄武安山岩,总稀土元素呈现出逐步上升的趋势;花岗闪长斑岩和变质砂岩均为含矿地质体,构成了接触带成矿体系,它们的δEu值分别表现为大于1和小于1,即分别呈现出正铕异常和负铕异常;玄武安山岩不含矿,无明显的铕异常。     

贵州省六枝、遵义矿区煤中汞和硫的赋存相关特性研究

选取贵州省六枝（LZ)、遵义（ZY）两不同矿区的高汞高硫煤为研究对象,对煤样进行煤浮沉、逐级化学萃取等实验,利用低温灰化（LTA）和X射线衍射（XRD）等手段,分析研究煤中汞和硫存在形式和两种元素之间的相关性。结果表明,在LZ煤中,硫主要以黄铁矿硫的形式存在,汞主要赋存于黄铁矿中,煤中硫和汞有很好的相关性;在ZY煤中,硫主要以有机硫的形式存在,汞主要赋存于黏土矿中,汞与硫不存在相关性。     

Texture and Structure Characteristics of Ore from Typical Deposits of Lead-Zinc Ore Belt in the Southwestern Margin of Tarim

通过对位于西昆仑北带奥依塔格-库尔良晚古生代（弧后）裂陷盆地塔西南缘铅锌矿带典型矿床矿石结构构造特征进行研究,总结出该矿带各个矿床（点）之间具有相同或相似的矿物共生组合（黄铁矿-方铅矿-闪锌矿-黄铜矿）以及相似的组构特征。主要结构包括草莓状结构、骸晶结构、自形晶结构、固溶体分离结构、交代结构及揉皱结构等;构造包括浸染状构造、流动构造、条带状构造、脉状构造及角砾状构造等,这些组构特征的共性表明成矿作用均具有多期多阶段的特征,并指示出热水沉积成矿兼有后期热液改造的结构构造特征。结合野外地质特征,该区铅锌矿床形成经历了同生沉积与后期改造过程。     

循环伏安法定性分析矿物中某元素硫氧化物占比

根据硫化矿和氧化矿在电解液为硫酸钠的三电极体系中循环伏安曲线的差异，建立了循环伏安法定性分析矿物中某元素硫氧化物占比的方法，以铜的硫化物(黄铜矿)和氧化物(孔雀石)纯矿物进行循环伏安法测试。结果表明，在扫描速率0.1 V/s,扫描电压范围-0.8 V～0.8 V时，黄铜矿循环伏安曲线出现氧化还原峰，孔雀石循环伏安曲线未见明显氧化还原峰；黄铜矿和孔雀石混合物循环伏安曲线上的氧化还原峰电位与单一黄铜矿的氧化还原峰电位几乎一致，但峰电位对应的电流大小与矿物占比存在一定的关系。由此，可以通过循环伏安法定性判断混合矿中黄铜矿与孔雀石的占比，实现循环伏安法定性分析矿物中某元素硫氧化物占比。     

硫化铜精矿物相分析及氧化机理研究

在海轮运输及样品的制备过程中,进口硫化铜精矿氧化的现象普遍存在,使得货物的重量和铜品位发生变化,但该种现象的机理研究不多。针对硫化铜精矿的物相进行分析,并对硫化铜精矿的氧化机理进行研究。首先,利用显微镜、扫描电子显微镜、X射线荧光光谱(XRF)、X射线衍射(XRD)等方法对两个硫化铜精矿进行物相分析,并对其中的主要元素和含铜主要物相进行定量化学分析。再次,利用热重分析(TGA)研究这两个硫化铜精矿发生氧化反应的温度,结果表明在400℃时铜精矿样品重量开始增加,在约650℃重量达到顶峰,随后重量开始下降。最后,分别在400、650和900℃对两个铜精矿样品进行灼烧,并利用XRF和XRD方法进行测定,从而研究铜精矿的氧化机理,结果表明在400℃时,出现了铁的氧化物和铜的硫氧化物,说明黄铜矿和黄铁矿开始氧化,但还没有完全氧化,在650℃时,化合物中的氧含量继续增加,硫含量逐步减少,在900℃时,铜和铁的化合物只剩氧化物,硫已全部被氧化。结果表明,硫化铜精矿中的铜、铁等元素在温度和时间的作用下逐步氧化,硫氧化物的产生为中间态,氧化物的产生为最终态。实验解释了进口硫化铜精矿氧化的原理,有助于贸易双方减少分歧,有助于海关技术中心更规范地制备样品,降低数据误差。     

燃烧碘量法-光电滴定测定地质样品中的硫

正硫元素在自然界中分布较广,通常以硫化物、硫酸盐或单质形式存在。硫是亲和力非常强的非金属元素,通常与铁、铜、铅、锌等有色金属元素形成硫化物组合,并常伴有金、银、钴、铂族元素等多种有益元素,形成黄铁矿型块状硫化物矿床,分布于世界各主要造山带的不同时代的海相火山岩系中。地质调查样品的化学分析数据是地质填图的基础,地质调查样品除了分析各类造岩元素外,根据不同的需求,还包括硫、稀散元素、稀土元素及贵金属     

四川拉拉铜矿中辉铜矿、黄铁矿和黄铜矿的分离

本文研究了四川拉拉铜矿中辉铜矿、黄铁矿和黄铜矿的分离。采用硫酸(5+95)加氟化物溶解总氧化铜,及用硫脲-盐酸溶解次生硫化铜(辉铜矿等)后,提出用硝酸(1+1)溶浸黄铁矿而与黄铜矿分离。     

高硫煤中各种成因硫的光电子能谱研究

对煤中不同成因的黄铁矿和高有机硫煤进行ESCA测试分析。结果表明不同成因黄铁矿的氧谱峰形差异较大。后生黄铁矿氧谱峰形向高电子伏特方向呈不对称峰,主峰为533.0eV;而原生黄铁矿氧谱则以531.5eV峰为主;成岩期黄铁矿氧谱峰形宽,强度也不如前两种。半定量分析表明黄铁矿氧化比值与铁氧化率、氧含量呈正比,由原生→成岩→后生黄铁矿方向,氧化比值依次增加。高有机硫的四川南桐6号煤和贵州贵定煤的ESCA所测硫与湿式化学分析所测硫是相一致的,其中有机硫有脂类硫化物、噻吩和砜等,且主要为噻吩硫。运用光电子能谱法能较好地判断不同成因的黄铁矿。     

DTPM光度法测定含铜较高矿石中的铋

二硫代二安替吡啉甲烷(DTPM)光度法测定铋,铜的允许量低,对于含铜较高的试样,一般采用氨水分离的方法,操作冗长。本文探讨了铜的干扰及消除方法,选用适宜的酸度和掩蔽体系,扩大了铜的允许量。对于含铜较高的试样,提出了一个简易萃取分离的方法,即在比色管中将铋的氯阴离子与二安替吡啉甲烷形成的络合物萃入二氯甲烷中,弃去上层水相后直接在原比色管中用EDTA反萃取并显色。     

硫化物矿物LA-ICP-MS激光剥蚀元素信号响应

采用193 nm ArF准分子激光剥蚀电感耦合等离子体质谱(LA-ICP-MS)对5种天然硫化物矿物进行激光剥蚀分析, 基于不同硫化物矿物的剥蚀形貌特征和元素瞬时信号响应, 考察了硫化物矿物的元素分馏效应及激光频率、能量和激光斑径对硫化物矿物激光剥蚀行为的影响. 结果表明, 不同硫化物矿物的激光剥蚀形貌和元素分馏效应存在明显差异, 其中黄铁矿、辉钼矿和闪锌矿的剥蚀晕约为剥蚀斑径的10倍, 而黄铜矿和磁黄铁矿的剥蚀晕约为剥蚀斑径的14倍; 黄铜矿、磁黄铁矿和闪锌矿元素分馏因子(EFI)约为1.0, 其元素分馏效应可以忽略, 而黄铁矿和辉钼矿存在明显的元素分馏效应. 在对硫化物矿物的LA-ICP-MS分析中, 选择较大的激光剥蚀斑径、较小的激光剥蚀频率与激光能量可获得理想的信号强度和准确的分析结果.     

Chalcopyrite and pyrite floatabilities in the presence of sodium sulfide and sodium metabisulfite in a high pyritic copper complex ore

One of the principal problems in flotation of copper complex ores is the presence of pyrite and copper-activated pyrite in moderately alkaline pHs. Misreported pyrite into copper concentrates dramatically declines copper grade and its recovery. In this study, the effect of sodium sulfide, sodium metabisulfite (SMBS), and their dosages (100, 200, 300, and 400 g/t) were investigated on chalcopyrite and pyrite floatabilities in a high pyritic copper sulfide ore. Furthermore, the role of particle size distribution (PSD) in three different levels (i.e., d₇₀, d₇₅, and d₈₀ of passing 75 µm) was evaluated by a series of batch flotation experiments. It was revealed that using 200 g/t SMBS provides not only the highest and the lowest chalcopyrite and pyrite recoveries, but also the maximum and minimum copper and iron grades. Pyrite recovery was sharply increased by the addition of sodium sulfide in light of sodium sulfide-induced collectorless flotation; however, it showed a very weak effect on chalcopyrite floatability. In addition, the highest and lowest chalcopyrite and pyrite recoveries were, respectively, identified when d₇₅ equaled to 70% 75 µm. In other words, for the high pyritic copper ore type, it is feasible to achieve the highest chalcopyrite recovery consuming the lowest grinding energy.     

碳质金矿中金的化学物相分析方法改进

为了解决碳质金矿金化学物相分析结果与选矿试验结果不符的问题,基于岩矿鉴定和测试结果对分析流程进行改进。方法改进后测试项目包括裸露金和半裸露金、有机碳石墨包裹金、碳酸盐包裹金、褐铁矿包裹金、黄铁矿包裹金、石英和硅酸盐包裹金6项。有机碳石墨包裹金选用Na_2S_2O_3–CuCl_2–NH_4OH–NH_4Cl体系为浸金剂,取代I_2–NH_4I体系,该体系中金的测定采用铜置换原子吸收法。裸露金半裸露金、有机碳石墨包裹金和黄铁矿包裹金的相和为82.34%,与选矿试验金精矿实际回收率(75.83%)基本吻合。改进后的方法适合碳质金矿金化学物相分析。     

Selective separation of pyrite and chalcopyrite by biomodulation

Selective separation of pyrite from other associated ferrous sulphides at acidic and neutral pH has been a challenging problem. This paper discusses the utility of Acidithiobacillus ferrooxidans for the selective flotation of chalcopyrite from pyrite. Consequent to interaction with bacterial cells, pyrite remained depressed even in the presence of potassium isopropyl xanthate collector while chalcopyrite exhibited significant flotability. However, when the minerals were conditioned together, the selectivity achieved was poor due to the activation of pyrite surface by the copper ions in solution. The selectivity was improved when the sequence of conditioning with bacterial cells and collector was reversed, since the bacterial cells were able to depress collector interacted pyrite effectively, while having negligible effect on chalcopyrite. The observed behaviour is analysed and discussed in detail. The separation obtained was significant both at acidic and alkaline pH. This selectivity achieved was retained when the minerals were interacted with both bacterial cells and collector simultaneously.     

Adsorption of <Emphasis Type="Italic">N</Emphasis>-hydrocinnamoyl-<Emphasis Type="Italic">N</Emphasis>-phenylhydroxylamine on pure minerals

Equilibrium adsorption studies of N-hydrocinnamoyl-N-phenylhydroxylamine (HCNPHA) on galena, sphalerite, pyrite, chalcopyrite and quartz at pH 9 and 10 are reported. All adsorption isotherms followed Langmuir model, however, Freundlich type was observed for quartz. As HCNPHA is a strong chelating agent, formation of monolayers by chemisorption appeared to be the most probable mechanism of adsorption on the base-metal sulphide minerals. Specific adsorption of HCNPHA on iron containing minerals, namely, chalcopyrite and pyrite, was about three times that on galena and sphalerite, and specific adsorption on quartz was the lowest amongst the minerals studied. Specific adsorptions (in μmol/g) of HCNPHA on the minerals at pH 9 are: sphalerite: 30.5; galena: 26.9; chalcopyrite: 112.3; pyrite: 145.4; quartz: 2.9. Compared to pH 9, specific adsorption of HCNPHA on the minerals decreased at pH 10, indicating hydroxylation of mineral sites due to higher hydroxide ion concentration at pH 10. A spectral-colorimetric procedure was developed for the quantitative estimation of HCNPHA. Due to deprotonation of hydroxamic acids direct estimation using UV absorption was not possible. Hence, complexation of HCNPHA with Fe³⁺ was used to develop a purple coloured complex that absorbs in the visible region with λ _max=500 nm. Change in concentration of HCNPHA was measured from absorbance of the HCNPHA- Fe³⁺ complex at 500 nm.     

XPS and ToF‐SIMS study of a chalcopyrite–pyrite–sphalerite mixture treated with xanthate and sodium bisulphite

We present data from the surface analysis of a mineral mixture of chalcopyrite, pyrite, and sphalerite, elucidating surface reactions occurring during grinding and flotation. Flotation tests are also performed on the mixture, carried out in the presence of collector (SIBX) and also in the absence and presence of sodium bisulphite (NaHSO₃), a gangue sulphide mineral depressant. X‐ray photoelectron spectroscopy (XPS) studies on the ground mineral sample prior to flotation indicate that the mineral feed is heavily oxidised, especially the sphalerite in the mixture. Flotation recovery data clearly shows the effect of this oxidation, with the mineral recoveries of all three phases being lower than those observed in single mineral studies. In addition, the flotation recoveries show the effect of the inadvertent copper activation of pyrite and sphalerite, and the effect of bisulphite in reducing the flotation of sphalerite and pyrite in the mixture. Time of flight secondary ion mass spectrometry(ToF‐SIMS) data indicates that the depressing effect of bisulphite is due to the removal of copper and sulphur‐like species from the surface of pyrite and sphalerite and a consequent increase in the oxidation of these minerals. ToF‐SIMS data also indicates that the low recovery of pyrite and chalcopyrite in the absence of collector is most likely due to precipitation of zinc hydroxide on the surfaces of these minerals, formed in solution due to copper activation of sphalerite. Copyright © 2005 John Wiley & Sons, Ltd.     

Combined remote LIBS and Raman spectroscopy at 8.6m of sulfur-containing minerals, and minerals coated with hematite or covered with basaltic dust

Combined remote laser-induced breakdown spectroscopy (LIBS) and Raman spectroscopy investigations at a distance of 8.6m have been carried out in air and under a simulated Martian atmosphere of 933Pa (7Torr) CO(2) on calcite (CaCO(3)), gypsum (CaSO(4).2H(2)O), and elemental sulfur (S), and LIBS investigations on chalcopyrite (CuFeS(2)) and pyrite (FeS(2)). Both Raman and LIBS techniques have also been used sequentially in air on hematite-coated calcite crystals and on a sample of anhydrite covered with basaltic dust. These experiments demonstrate that by using a frequency-doubled Nd:YAG pulsed laser co-radiating 1064 nm and 532 nm laser beams with a 5x beam expander, it is possible to measure simultaneously both the Raman and LIBS spectra of calcite, gypsum and elemental sulfur by adjusting the laser power electronically. The spectra of calcite, gypsum, and elemental sulfur contain fingerprint Raman lines; however, it was not possible to measure the remote Raman spectra of pyrite and chalcopyrite because of low intensities of Raman lines. In the cases of CuFeS(2), FeS(2), and elemental sulfur, S atomic emission lines in the LIBS spectra were detected only in 7Torr of CO(2) pressure and not in air. No S atomic emission lines were detected for gypsum in air or in CO(2). In the case of coated/dusted minerals, it was possible to remove the coating or dust with the focused LIBS laser and measure the Raman spectra of subsurface minerals with a 532 nm laser excitation. The complementary nature of these two techniques is highlighted and discussed.     

Electroreduction of oxygen on copper-containing sulfide minerals

The state of the surface of and the oxygen electroreduction on the naturally occurring minerals bornite, chalcopyrite, and chalcosine are studied in borate buffer solutions using X-ray photoelectron spectroscopy, cyclic voltammetry, and the rotating disk electrode technique. The surface of the minerals in an oxygen-containing atmosphere is covered with compounds of copper and iron in the highest oxidation states, and the oxygen electroreduction occurs on these compounds. Electrocatalytic activity of sulfide minerals during cathodic polarization is presumably due to the participation in the oxygen electroreduction reaction of redox centers, i.e. ions of Fe(II) in bornite and chalcopyrite, and ions of Cu(I) bonded with the sulfide sulfur in each of the minerals.     

电感耦合等离子体质谱测试硫化物中的微量元素

采用多种酸组合消解方法消解硫化物样品,最终选取A:HNO3密闭消解法;B:HCI+HF与HNO3两步消解法对硫化物标准物质GBW07267(黄铁矿)、GBW07268(黄铜矿),GBW07270(闪锌矿)及硫化物标准物质WMS-1a(块状硫化物)样品进行消解,采用ICP-MS测试了39种微量元素.结果表明,HNO3密闭...     

油页岩热解过程矿物质行为分析

采用XRD、SEM、灰成分测定等方法对桦甸两个矿区的油页岩样品以及制备的半焦样品矿物质组成进行了分析,确认其主要成分均为,石英、方解石和黏土矿物。而半焦中矿物组成反映了油页岩中矿物质在热解中的变化。研究表明,在热解过程中油页岩中矿物质变化细微,其中,石英、长石没有变化;方解石有微量分解,生成的固体产物CaO与黄铁矿分解的硫反应生成CaS矿物;黏土矿物质受热脱除羟基,放出大量水分,同时分解产生的无定形玻璃体氧化硅与其他金属形成低熔点的共融物,导致部分半焦样品颗粒表面出现熔融态囊状结构。