极谱法测定钼矿石中的总钼氧化钼硫化钼

钼的物相分析要求测定硫化矿物相和氧化矿物相,常用比色法和电感耦合等离子体发射光谱法等对辉钼矿、钼华矿、钼钨钙矿、钼酸铅矿等钼矿石进行物相分析,但分离物相的品种较多,方法繁琐耗时.本文用王水-硫酸消解钼矿石样品,碱溶液复溶浸提得到钼总量,使其他大多数元素形成沉淀而分离,用碳酸钠-氢氧化铵混合溶液浸取钼的氧化矿物,将残渣进一步溶解得到硫化矿物含量,在硫酸-氯酸钾-二苯羟乙酸体系中用极谱法简单快速测定钼总量、氧化钼和硫化钼含量.方法的线性范围为0.04～0.4 mg/L,检出限为0.028 mg/L.对三种钼矿样品进行物相分析,氧化矿物与硫化矿物含量的加和与钼总量相当;总钼、氧化钼、硫化钼测定结果的相对标准偏差在1.69％ ～3.56％之间,与比色法测定结果相符.方法实用快速,易于推广,适于实际批量样品的测试.     

黑龙江翠宏山铁钼多金属矿田两期钼成矿事件厘定

黑龙江省翠宏山铁钼多金属矿田属于小兴安岭-张广才岭铁多金属成矿带,发育铁、铅、锌、钼、钨等多金属大规模成矿作用.尤以钼矿化最具特色,出现矽卡岩-斑岩型钼钨矿化、斑岩型钼矿化和隐爆角砾岩型钼矿化等多种类型的钼矿化在单一矿田中并存的现象.但三种钼矿化类型的矿化特征和时空关系等缺乏系统梳理,钼成矿事件尚未清晰厘定.选取该矿田...     

某古岩溶铀矿床中铀,钼,铼的赋存状态

本文采用电子探针、透射电镜和化学物相法,查明某古岩溶铀矿床中铀主要呈显微和超显微状沥青铀矿、铀石,其次呈分散吸附状和铀酰（次生）矿物形态存在;钼主要呈蓝钼矿、钼钙矿、钼华、钼铅矿等氧化物,其次呈胶硫钼矿等形态存在;铼主要呈吸附状,其次可能在黄铁矿中呈二硫化物包裹体形态产出。最后讨论了该三个元素赋存状态与该铀矿床形成地球化学环境之间的关系。     

敞开酸溶-电感耦合等离子体光谱法测定钨矿石和钼矿石中微量元素

钨矿石和钼矿石具有丰富的共生或伴生元素,检测共生或伴生元素的含量有利于矿产资源的综合利用.在国家标准方法中钨矿石和钼矿石的共生或伴生元素含量是按元素分别检测,效率很低.本文在敞开体系中用盐酸+硝酸+氢氟酸+高氯酸消解样品,以7％盐酸溶解盐类,电感耦合等离子体发射光谱同时测定钨矿石和钼矿石中铋、钴、铜、锂、镍、磷、铅、锶、钒、锌等10种微量元素.选定了各元素的分析谱线和光谱级次,采用离峰背景校正法消除背景干扰,干扰元素校正系数法消除元素间的谱线重叠干扰.方法检出限为1.43 ～ 18.8 μg/g,加标回收率为90％ ～ 110％.经钨矿石和钼矿石标准物质分析验证,测定结果与标准值基本吻合,方法精密度(RSD,n=10)小于8％.该方法克服了碱熔引入大量碱金属元素以及可能引入杂质的缺陷,又不用处理钨酸和钼酸沉淀,能快速测定钨矿石和钼矿石中微量共生或伴生元素.     

粉末压片制样波长色散X射线荧光光谱法测定钼矿石中9种元素

X射线荧光光谱(XRF)分析方法中,采用粉末压片制样存在粒度效应和矿物效应等问题,但当样品在一定的粒度、压制压力及压制时间条件下,矿物效应和粒度效应仅仅对钠、钙等轻元素的测试有影响,而对钼、铜、铅等元素的测试并无影响。基于此本文建立了粉末压片制样波长色散XRF直接测定钼矿石中Mo、W、Cu、Pb、Zn、F、S、As、Bi等9种元素的方法。采用价格低廉的低压聚乙烯粉作衬垫镶边材料,样品在35 t的压力下压制30 s,制备的样片坚固光滑、吸潮性小,长期保存不发生形变,消除了粒度效应。选用自制的钼含量呈梯度变化的钼矿石样品及钼矿石、钨矿石、铜矿石、铅矿石、铋矿石、锌矿石等国家标准物质作为校准样品建立标准曲线,降低了矿物效应,采用经验系数法消除谱线重叠和基体干扰。本方相对标准偏差小于2.1%,各元素的测定结果与电感耦合等离子发射光谱法等其他方法测量值吻合。与已报道的玻璃熔融和粉末压片制样方法相比较,检出限较低,如钼的检出限为3.67 μg/g,比玻璃熔融法的检出限(450 μg/g或24 μg/g)要低得多;砷的检出限为1.13 μg/g,低于其他粉末压片法的检出限(7.8 μg/g)。本方法提出了克服粒度效应及光谱诸干扰因素影响的详细解决方案,有利于XRF法应用于定量分析基体组成复杂的钼矿石。     

陕西金堆城钼矿床中铁钼华的矿物学特征及其意义

铁钼华产于陕西金堆城斑岩钼矿床的氧化带内,该矿物以往被认为是钼华。笔者对该矿物进行了物理光学性质、化学成分、X射线衍射、穆斯堡尔谱、红外光谱以及失重和差热分析的研究,定名为铁钼华,其分子式为Fe_2(MoO_4)_3·6.8H_2O。同时,将其与国外天然和人工合成的铁钼华作了对比,确定其是在酸性氧化环境中形成的次生矿物。它是原生钼矿床的直接找矿标志。     

偏硼酸锂熔融-电感耦合等离子体发射光谱法测定钨钼矿石中钨钼及11种伴生元素

钨钼矿石是重要的战略性矿产资源,中国是钨钼矿的产出和消费大国,准确、高效地分析钨钼及其共伴生的有益有害元素含量对钨钼矿的矿床评价和综合利用有重要意义。钨钼矿石中钨钼及伴生元素的分析目前主要采用酸溶和碱熔方式消解样品,酸溶方式在处理高钨钼样品时无法克服水解问题,过氧化钠、氢氧化钠等碱熔方式通常会引入大量碱金属,不能完成钾钠的测定。本文建立了一种偏硼酸锂熔融,盐酸-酒石酸超声浸取,电感耦合等离子体发射光谱(ICP-OES)同时测定钨钼矿石中钨钼铜铅锌铝铁钙镁钛锰钾钠的方法。利用偏硼酸锂熔融的强解离作用使样品完全分解,溶液除硼锂外不引入其他金属元素,在盐酸提取液中加入酒石酸络合能够有效抑制钨钼水解,经超声浸取加快了熔块溶解。实验优化了各元素的分析谱线和观测方式,对熔剂用量以及仪器条件进行对比实验以获得最佳条件,采用基体匹配法绘制标准曲线消除了基体效应的影响。标准曲线线性相关系数均大于0.9990,方法检出限为1.34～46.2μg/g,标准物质测定结果的相对误差为0.14%～8.7%,相对标准偏差(RSD,n=10)为1.4%～7.6%。该方法能够准确、高效地完成钨钼矿石样品中多元素的同时测定。     

四酸溶矿——电感偶合等离子体发射光谱法测定钼矿中的钼

为了适应地质找矿和地质大普查工作对矿样测定速度和正确度的要求,对钼矿样品中的钼的测定方法进行试验,探讨在敞开体系中用盐酸+硝酸+氢氟酸+高氯酸的四酸溶矿体系消解钼矿样品,使用电感耦合等离子发射光谱仪(ICP-AES)测定钼的方法。     

钼在花岗质熔体相和流体相间的分配实验

在750—850℃、(1.5—2.5)×10~8Pa条件下,以玻璃或凝胶作为初始样品,研究了钼在流体相和花岗质熔体相间的分配系数,同时还测定了铁、钙、钾的分配系数。解释了斑岩型钼矿床的可能成矿作用。     

含钼白钨矿的矿物学特征、晶体结构与可浮性

针对白钨矿-钼钙矿系列矿物在选矿实践中浮选行为的差异,本文在对某钨钼矿床中的典型钨矿物——含钼白钨矿进行工艺矿物学研究的基础上,从矿物晶体化学角度出发,探讨矿物晶体结构和浮选行为之间的关系,为该类型矿物的浮选行为以及浮选药剂的选择提供理论指导。结果表明,该矿石中的含钼白钨矿为钨的主要回收矿物,WO₃占有率达99%,矿物晶格中约25%的W被Mo呈类质同象替代,导致Ca-O的键合能力降低,造成矿物表面与捕收剂作用的活性质点减少,晶格中阴离子基团[MoO₄]^2-的存在,不利于矿物表面与捕收剂的有效吸附,从而使含钼白钨矿的可浮性降低。     

Sardignaite, a new mineral, the second known bismuth molybdate: description and crystal structure

The new mineral sardignaite, a bismuth molybdate with formula BiMo₂O₇(OH)·2H₂O, occurs in quartz veins within a granitic rock at Su Senargiu, near Sarroch, Sardegna, Italy. The name is after the locality. Sardignaite occurs a thin prismatic crystals up to 1 mm in length, with pale yellow color and a white streak. It is transparent with adamantine lustre, non fluorescent, and brittle with a conchoidal fracture. It is associated with bismuthinite, bismoclite, molybdenite, ferrimolybdite, koechlinite, wulfenite, and the new mineral IMA 2009–022. Mohs hardness is ca. 3. D _calc is 4.82 g/cm³. The mineral is monoclinic, space group P2₁/m, with a 5.7797(7), b 11.567(1), c 6.3344(8) Å, β 113.360(9)°, V 388.8(1) ų. The strongest lines in the powder X-ray diffraction pattern are d(I)(hkl): 3.206(100)(031), 5.03(80)(?101), 1.992(45)(221), 3.120(32)(130). The crystal structure of sardignaite was solved to R(F) 0.056 using single-crystal X-ray diffraction data, and is characterized by edge-sharing dimers of [MoO₅(H₂O)] octahedra, linked to each other through corner-sharing to give rise to corrugated columns running along b. Such columns are held together by Bi³⁺ cations, eight-fold coordinated by 7 O + 1 (OH). Both the mineral and its name were approved by the IMA-CNMNC.     

Geochemical modeling for predicting potential solid phases controlling the dissolved molybdenum in coal overburden,Powder River Basin,WY, U.S.A.

Surface coal mining processes may increase the dissolved Mo concentrations in overburden (mine spoils) and in nearby soils. Spoil and soil samples were subjected to solubility studies for determining potential solid phases controlling the dissolved Mo. Additionally, native soil samples were included in the study for comparison. Ion activity products (IAPs) were calculated from the total elemental concentrations of aqueous extracts and compared with solubility products (K_sps) of Mo solid phases. Effects of dissolved organic carbon (DOC) on metal ion complexation were also evaluated. The pH of aqueous extracts ranged from 7.14 to 8.31. DOC in aqueous extracts varied from 17.3 to 58.7 mg/l. Molybdenum concentrations in aqueous extracts ranged between 11.5 and 35.6 μg/l for spoils, 13.5 and 20.0 μg/l for soils near mine site and 14.5 and 29.6 μg/l for native soils. Initially, IAPs suggested varying degrees of supersaturation with respect to wulfenite (PbMoO₄). However, when DOC-Pb²⁺ complexes were considered, the IAPs indicated a close approach to saturation with respect to PbMoO₄. Furthermore, the IAPs suggested a high degree of undersaturation with respect to powellite (CaMoO₄) and ferrimolybdite (FeMoO₄). Results in this study suggest the dissolved Mo concentrations in mine spoils and soils that are near coal mine may be controlled by PbMoO₄ solid phase.     

钼矿石与钼精矿成分分析标准物质研制

钼矿勘查开发与综合利用评价等工作需对其化学成分进行准确测试,标准物质可为分析测试提供基础标准和技术支撑。我国已有的钼矿石和钼精矿标准物质系列性不足,且余量不多,多数样品已耗尽。本文为满足钼矿资源勘查、开发与贸易的总体需求,研制了3个钼矿石和1个钼精矿成分分析标准物质。根据设计的钼含量的梯度范围和钼矿的矿床成因,在钼矿资源储量最多的河南省采集了1个钼尾矿(Mo含量0.02%)、1个钼矿石(Mo含量0.09%)和1个钼精矿(Mo含量50.0%)。3个钼矿石采用重量法组合制备的方式加工,1个钼精矿为原样粉碎加工,钼精矿在加工制备过程向球磨机内充氩气保护,防止硫化物氧化。按照一级标准物质研制规范,采用13家实验室使用多种准确可靠的方法共同定值,定值元素包括成矿元素(Mo),可综合利用元素(W、S、Cu、Pb、Zn、Fe、Bi),具找矿和矿产评价意义的微量元素(Ag、As、Cd、Mn、P、Pb、Sb)及构成脉石的主成分(SiO₂、Al₂O₃、Fe₂O₃、CaO、MgO、Na₂O、K₂O)共计26种。3个钼矿石标准物质Mo的含量分别为0.066%、0.15%、0.54%,1个钼精矿标准物质Mo的含量为50.08%,是已有标准物质的良好补充和完善。标准物质经均匀性和稳定性统计检验具有良好的均匀性和稳定性;标准值计算方法正确,不确定度评定合理,经国家质量监督检验检疫总局批准为国家一级标准物质(编号为GBW 07141~GBW 07144),可用于钼矿的勘查、开发、选冶及贸易中化学成分测试的量值标准与分析质量监控。     

On the presence of hydrous defects in differently coloured wulfenites (PbMoO4): an infrared and optical spectroscopic study

Several samples of wulfenite, PbMoO₄, varying in colour from colourless to yellow, orange and red, have been characterised by means of IR and optical absorption spectroscopy and by microprobe analyses. A distinct pleochroic band group with absorption maxima centred at 3,380 and 3,150 cm^?1 can be seen in the IR spectra of wulfenite single-crystals, indicating the presence of hydroxyl groups. The pleochroic and thermal behaviour of the OH stretching bands along with deuteration experiments, as well as results obtained from synthetic flux-grown samples, exclude the presence of submicroscopic hydrous mineral inclusions as their primary origin. The pleochroic scheme and the band positions were used to postulate a model for the OH incorporation mode, based on the assumption of vacancies on Mo and Pb sites in the structure of this ‘nominally anhydrous mineral’. Optical absorption spectra of coloured natural samples show a broad and polarised band around 23,000–24,000 cm^?1, preceding the fundamental UV absorption edge, which has been identified as the reason for the colour of the mineral. The comparison with synthetic PbMoO₄ single-crystals, doped with variable amounts of Cr⁶⁺, yielded conclusive evidence that trace amounts of the CrO₄ ^2? anion group, substituting for MoO₄ ^2?, determine the variable colour. Besides, in one sample, trace amounts of Nd³⁺ have been spectroscopically identified.     

电感耦合等离子体发射光谱法测定稀土矿石中15种稀土元素——四种前处理方法的比较

稀土元素在矿石中有多种不同的赋存形式,主要有离子吸附型和矿物晶格型,稀土不同赋存形态对其本身准确分析测定有很大的影响。本文从稀土元素在矿石中不同赋存形态的角度出发,探讨了不同前处理方法对稀土准确测试结果的影响,采用盐酸-硝酸-氢氟酸-高氯酸(四酸)敞开酸溶、盐酸-硝酸-氢氟酸-高氯酸-硫酸(五酸)敞开酸溶、氢氟酸-硝酸封闭压力酸溶、氢氧化钠-过氧化钠碱熔四种方法对离子吸附型和矿物晶格型两类赋存类型的稀土矿石样品进行前处理,电感耦合等离子体发射光谱法测定其中的15种稀土元素。结果表明:对于离子吸附型的稀土矿石标准物质(GBW 07161、GBW 07188),四酸敞开酸溶法测定的结果明显偏低,15种稀土元素大都偏低10%~20%,五酸敞开酸溶法、封闭压力酸溶法和碱熔法的测定值与标准值吻合;而对于稀土以离子化合物及类质同象置换的形式赋存于矿物晶格中的白云鄂博轻稀土矿石样品,三种酸溶法结果较碱熔法均偏低,其中四酸敞开酸溶法偏低最多,约偏低20%左右,五酸敞开酸溶法和封闭压力酸溶法偏低5%~15%。本文提出,对于离子吸附型稀土矿,五酸敞开酸溶法和封闭压力酸溶法可以代替传统操作复杂的碱熔法,但对于稀土以离子形式赋存于矿物晶格型的稀土矿,目前最合适的前处理法是传统的碱熔法。     

Mineralogical and geochemical zoning of sediments at the Semenov cluster of hydrothermal fields, 13°31′-13°30′ N, Mid-Atlantic Ridge

New material from eight columns recovered during Cruise 32 of the R/V Professor Logachev in 2009 was used to explore the lithological facies, biostratigraphy, mineralogy, and geochemistry of sediments from the northwestern (active) and eastern (inactive) hydrothermal vent fields of the Semenov cluster. Mineral types of sediments were distinguished, and a general scheme was proposed for the vertical structure of the hydrothermal-sedimentary sequence overlying massive sulfide ores. It was found that the ore-bearing sediments exhibit a vertical zoning in the distribution of mineral assemblages, which are controlled by oxygen activity. The mechanisms of the formation of atacamite, CuCl₂ · 3Cu(OH)₂, which is a widespread mineral in red iron-oxide bodies replacing sulfides (gossans), were evaluated.     

Uranium deposits with a new phosphate type of blacks

Data on ningyoite [CaU(PO₄)₂ · 2H₂O] occurrences in uranium ores and on deposits with ores composed entirely or largely of this mineral are considered. Most of the recent findings of ningyoite mineralization are confined to infiltration deposits, and only sporadic ones, to pegmatites and hydrothermal deposits. The geological settings and mineral assemblages indicate that ningyoite ores are formed from neutral or slightly alkaline solutions at higher Eh values relative to other types of uranium blacks (uraninite, coffinite) and are localized in the reducing zone at the boundary of redox zoning. The factors that testify to the decisive role of microbiological processes in the formation of monomineral ningyoite ore are considered. All hydrogenic deposits (occurrences) of ningyoite ore known to date in Japan, Bulgaria, Canada, Kazakhstan, and Siberia belong to the same ground-infiltration genetic type.     

Mineral phases on the fracture of a glass particle and in the fines of a Luna 24 regolith sample

This paper reports new findings of native molybdenum and iron from Mare Crisium. Native tin, copper, and nickel were detected for the first time in this area of the lunar surface. Native tantalum and indium, intermetallic compound Ta₂Mo, and barium titanate Ba₂TiO₄ were found for the first time on the Moon. The latter two phases were observed for the first time in nature. It was shown that the investigated mineral phases correspond to different genetic groups (preimpact, impact, and postimpact mineral assemblages), which is in general typical of lunar regolith. Based on the morphological features of the identified mineral phases, the history of the formation of impact glass particles was reconstructed in part. They were probably affected by at least three impact events. It was concluded that the peculiar molybdenum geochemical anomaly observed in a group of orange impact glass fragments was not related to the impactor material but rather to the intrinsic enrichment in molybdenum of lunar rocks (target) in the area of the impact events. It was supposed that this enrichment could be of exhalative (fumarole) nature.