宝坑锰矿床中的磷酸锌矿物

宝坑锰矿为一次生氧化锰矿床.在矿区的南部发现三种罕见的磷酸锌矿物——付磷锌矿、磷钙锌矿、三斜磷锌矿.这些矿物与微晶磷灰石、锰土、褐铁矿等伴生,组成块状高磷富锌的氧化矿石.这些矿石与氧化锰矿石、褐铁矿石及各种成分的砂、砾石堆积于山坡上,由于雨水冲刷而裸露地表.发现有七块直径为30～60厘米大小的这种矿石.据R.丁希尔(Min Mag1974 684—95)报导,澳大利亚的利福希尔锌矿区的铁锰帽带曾发现有这三种矿物共生的产状.     

应用能谱扫描电镜与X射线衍射等分析技术研究西藏扎西康铅锌矿中伴生元素锰的赋存状态

西藏扎西康铅锌多金属矿床是我国首次发现的喷流沉积-热泉水改造型锰铁锑铅锌银矿床,已有研究表明矿床中除了铅锌矿还伴生有银、锑、铜、硫、锰、砷等多种元素。本文在化学多元素分析和光学显微镜镜下鉴定的基础上,结合能谱扫描电子显微镜和X射线衍射分析等手段对扎西康铅锌矿中伴生组分Mn的含量、矿物种类、嵌布和包裹等特性进行了研究。分析结果表明,原生矿石的主要成矿元素Pb和Zn的含量分别为6.00%和4.00%,伴生元素Mn的含量平均达到4.36%;原生矿石中的主要矿物为方铅矿、闪锌矿,其次为黄铁矿、毒砂和菱锰矿等。原生矿石中伴生元素Mn主要以独立的菱锰矿和铁菱锰矿形式存在,与闪锌矿和方铅矿密切共生,是成矿早期重要的载矿矿物,嵌布在石英、黄铁矿、闪锌矿和毒砂的粒间、边部及空隙间,其次以类质同象形式赋存于菱铁矿和菱锌矿中。进一步对扎西康铅锌矿选冶产物中的伴生元素Mn的含量和赋存状态进行研究,研究表明Mn具有较高的综合利用价值,在原生矿石、铅精矿、锌精矿和尾矿中的质量分数分别为4.36%、0.51%、0.95%和5.36%,显示Mn很少一部分进入铅精矿和锌精矿,而绝大部分进入尾矿;Mn在尾矿中仍主要以菱锰矿形式存在,存在形式与原生矿石相比未发生改变,可通过强磁选工艺从铅锌尾矿中综合回收利用Mn。     

辽吉裂谷区铅锌金矿床S、Pb同位素组成特征及其地质意义

辽吉裂谷区发育有众多大中型铅锌、金等多金属矿床,本文选择该地区的青城子榛子沟铅锌矿、白云金矿、五龙金矿、荒沟山铅锌矿和临江金矿作为研究对象,开展其矿石S、Pb同位素分析及其地质意义研究.数据显示榛子沟脉状铅锌矿δ34SCDT值介于-10.3‰～6.8‰之间,白云金矿δ34SCDT值介于-7.7‰～1.9‰之间,五龙金矿δ34 SCDT值介于0.8‰～3.6‰之间,荒沟山铅锌矿δ34 SCDT值介于6.7‰～17.8‰之间,临江金矿δ34 SCDT值介于0.7‰～1.5‰之间.研究区铅锌金矿床的矿石硫同位素主要有两种来源,其一来自于早期火山喷流沉积而成的地层硫,如青城子榛子沟层状铅矿矿体和荒沟山层状铅锌矿;另一类为后期岩浆硫,如青城子榛子沟脉状铅锌矿、白云金矿、五龙金矿以及临江金矿,此类岩浆硫形成过程中,对早期地层硫进行了混染.辽吉裂谷区典型多金属矿床矿石铅同位素值变化较大,206 pb/204 Pb值介于15.72～24.02,207pb/204 Pb值介于15.32～16.43,208pb/204 Pb值介于34.96～39.79,不同的矿床其比值具有不同特点.研究区铅同位素μ值相对集中且较大,显示铅源具有上地壳物质特征,但均受到了不同铅源的混合.榛子沟铅锌矿脉状矿体矿石铅和岩体铅均为混合铅源,矿石铅为上地壳与地幔的混合源铅,而岩体铅则是造山带铅与上地壳的混合源铅;白云金矿床矿石铅为造山带铅,而其岩体铅为上地壳与地幔的混合源铅;五龙金矿的铅同位素主要来源于元古宙造山带铅,同时又有幔源铅的混合;荒沟山铅锌矿矿石铅一组为正常铅,微偏钍铅,来源于统一矿源层,另外一组铅为放射成因铅,即铀铅,而临江金矿矿石铅属于放射成因铅.     

新疆火烧云铅锌矿矿石特征研究

新疆火烧云铅锌矿是2011年在新疆发现的世界级超级大型铅锌矿,为新疆和田地区首次发现碳酸盐岩沉积层控型超大型铅锌矿床。本文借助偏反光显微镜和电子探针大型仪器,通过对岩矿石光薄片中岩矿石矿物分析,研究了矿床围岩和矿石特征,认为其围岩蚀变微弱、矿石类型及矿物组合简单,为原生铅锌碳酸盐(即菱锌矿和白铅矿),硫化物极少,从微观上确认其矿床成因为碳酸盐型原生喷流-沉积铅锌矿,属于SEDEX型铅锌矿的新类型。     

新疆和田县火烧云铅锌矿成因类型初探

新疆和田县火烧云铅锌矿矿体呈层状、似层状整合产出于下侏罗统碳酸盐岩中,矿石矿物是原生铅锌碳酸盐(即菱锌矿和白铅矿)。根据矿床、矿体宏-微观、同位素等方面的特征,推断火烧云铅锌矿属于"原生喷流-沉积铅锌碳酸盐型铅锌矿",属于SEDEX型铅锌矿床的新类型。     

云南大平掌铜多金属矿床硫、铅、氢、氧同位素地球化学

对云南大平掌铜多金属火山岩型块状硫化物矿床的矿石矿物和火山岩围岩的Ｓ、Ｐｂ同位素及脉石矿物、硅 化岩、硅质岩等的Ｈ、Ｏ同位素地球化学特征进行了研究,认为矿床中大多数硫来源于热液对火山岩的淋滤,或直接 来源于火山喷气作用;矿石铅与火山岩铅属同一来源,且以富放射性成因铅为特征;成矿流体可能主要来源于深循环的海水与岩浆水的混合流体,而大气降水参与的可能性很小。     

江西相山矿田硫铅同位素地球化学特征

为查明江西相山矿田内铅锌矿和铀矿床的成矿物质来源,对与铅锌矿、铀矿有关的矿石矿物进行了S、Pb同位素研究,结果显示,与铅锌矿有关的金属矿物δ34S值为1.3‰~4.7‰,同铀矿伴生的黄铁矿δ34S值为7.9‰~14.9‰;赋矿围岩、基底变质岩、铀矿床黄铁矿和铅锌矿硫化物的206Pb/204Pb、207Pb/204Pb及208Pb/204Pb比值整体上有逐渐降低的趋势,均表现出放射性成因铅的特征,不同岩石或矿石的样品铅同位素组成范围基本一致。结合前人研究,说明铅锌矿和铀矿并非来自同一次成矿事件;铅锌矿的成矿期次具有阶段性,硫源具有均一性,主要以深部硫源为主,在其向上迁移的过程中有少量基底变质岩中的硫加入,按照硫化物共生矿物对计算出铅锌矿的成矿温度:早阶段为424~382℃,晚阶段为331~290℃,属中高温热液矿床;铀矿的硫源具有地层硫特征,主要来自于基底变质沉积岩。铀矿床伴生的黄铁矿铅同位素组成比铅锌矿硫化矿的铅同位素组成更具放射性成因铅,铅锌矿的铅源主要与上地壳基底变质岩有关,铀矿的铅源主要以相山火山-侵入杂岩体为主,但是可能还具有少量幔源铅参与。     

兰坪金顶铅锌矿的氧化带特征

矿体被沟谷切割,剥蚀垂深达三百米以上,约有一半的矿石为氧化矿。大气降水为地下水的唯一补给来源。含矿带为透水、含水层,矿带顶、底板隔水性良好,渗透水、地下水具层间流动性质。大气降水在渗透过程中对硫化矿物进行氧化的同时,其自身也被改造为宙含金属离子的含矿水。随着硫化物被溶解,氢氧化物、碳酸盐、硫酸盐矿物沉淀的反应往复进行,水中自由氧被大量消耗,缓慢流动的地下水在还原条件下释放出所携带的金属离子,最后形成硫化物沉淀,至使铅、锌、铁的氢氧化物,及硅酸盐、碳酸盐、硫酸盐、次生硫化物在氧化带依次出现。按标型矿物组合,可划分为褐铁矿——氢氧化物亚带;白铅矿——异极矿亚带;白铅矿——(水)菱锌矿亚带;铁菱锌矿——次生硫化物亚带;松散硫化物亚带。由于上述表生作用,矿石中碳酸盐围岩被大量淋失,铁、铅、锌成倍富集,形成规模巨大的次生氧化富集和次生硫化富集,地表分布有壮观的锌帽。矿体形状、内部结构都大为简单化,厚度增大,产状变缓。金顶铅锌矿氧化带分带,可与其他硫化矿床的氧化带相对比,但又自具特征。特别是发育铁菱锌矿——次生硫化物亚带。     

贵州水城铅锌-矿带成矿条件及控矿因素与成因

水城铅-锌矿带是贵州重要的铅锌矿化集中区,铅锌矿主要产于上石炭统碳酸盐岩中,受断裂构造控制明显.铅锌矿产出以延深大、品位富、经济价值高为特点.文章探讨了水城铅-锌矿带的成矿地质背景和控矿地质条件.依据青山、杉树林等典型矿床成矿流体性质及Pb、S、C及O同位素特征,初步建立了成矿模式,指出本区铅锌矿属热水喷流沉积.     

内蒙古中部元古宙火山沉积铁、铜、多金属矿床的成矿区划

一、矿床成因分类形成独立的矿床成因类型的火山沉积矿床,一般分为火山碎屑冲积层、含矿熔岩和含矿水流、热液沉积矿层、热液淋滤和热液交代矿层四类.内蒙古中部元古宙火山沉积矿床是以火山喷气沉积和火山热液沉积为基础,伴随热液淋滤和热液交代的产物.苏联矿床学者B·E、波波夫,据沉积成矿的方式、矿石矿物成分和围岩(反映自己层序岩相特点的成分)特点,把火山沉积铜、铅、锌矿床分为三大组:1)含金属矿的熔岩;2)在火山活动带堆积起来的火山岩和火山沉积岩层中的热液沉积和上升热液交代的块状矿层(黄铁矿的、含铜黄铁矿的和黄铁多金属矿床);3)在离火山活动带很大距离内     

东菲律宾海新型铁锰结壳中元素的赋存状态

为了解东菲律宾海新型铁锰结壳中元素的赋存状态, 采用化学提取方法对3个结壳样品进行了物相分析.不同类型结壳中成矿和稀土元素的赋存状态总体一致, 表明它们形成于相近的地质和海洋环境中.成矿元素中的Fe和Cu绝大部分赋存在残渣态中, Mn、Co和Ni则主要赋存在锰氧化物结合态、有机结合态和残渣态中, 并且埋藏型结壳样品锰氧化物结合态中赋存了相对更高比例的成矿元素.三价稀土元素主要集中在锰氧化物结合态中.两个沉积物表层结壳样品中的Ce主要集中在残渣态中.而埋藏型结壳样品中的Ce则主要赋存在锰氧化物结合态中, 这可能与该样品此相态中赋存了相对较多的Mn有关.呈碳酸盐结合态和有机结合态的稀土元素含量仅各占稀土总量的1%左右, 表明两者对结壳中稀土元素的富集作用很小.      

Spectrographic determination of tungsten in ores and concentrates employing an intermittent a.c. arc between copper electrodes

Tungstic oxide has been determined in ores and concentrates by emission spectrography in the range 6–65%. Silica is used to dilute the sample ten-fold. Silver chloride is used as a buffer and nickel (oxide) as internal standard. To avoid formation of refractory tungsten carbide over graphite electrodes, copper electrodes are used. The effect of the presence of calcium oxide, manganese dioxide and iron oxide on tungsten determination is studied. Samples analysed by chemical and spectrographic methods show good agreement.     

Oxidation of manganese by spores of a marine bacillus: Kinetic and thermodynamic considerations

The catalytic properties of spores of a marine Bacillus known to oxidize divalent manganese were used to perform laboratory Mn(II) oxidation experiments at environmental conditions of pH and Mn(II) concentration. We found that at pH 7.8 the initial kinetics of Mn(II) oxidation facilitated by the spores was four orders of magnitude greater than that which would be expected for abiotic autocatalysis on a colloidal MnO₂ surface. The rate progressively decreased as the spores became coated with manganese oxide, eventually becoming very near that predicted for abiotic surface catalysis. Transmission electron microscopic observations and oxidation state measurements of solids precipitated at pH 7.5 and [Mn(II)] < 50 nM indicated that the initial oxidation product was hausmannite (Mn₃O₄ or MnO_x where x = 1.33) which aged to more highly oxidized MnO₂ (x = 1.9) in the time scale of weeks. By utilizing spores to catalyze the oxidation rate, we were able to maintain our experimental system within the seawater range of pH and Mn(II) where highly oxidized manganese oxide precipitates are thermodynamically stable. In doing so we obtained, for the first time, laboratory precipitates with oxidation states similar to that found in marine particulate material. These results suggest that the concentration of manganese in seawater and the oxidation state of marine manganese oxides are controlled by the rapid precipitation of Mn₃O₄, which can be microbially mediated, followed by the disproportionation to MnO₂.     

Actual Problems of Prediction of Manganese Deposits in the Urals

Based on recent publications and our long-standing investigations, the most reasonable ways were proposed to obtain the manganiferous raw material for the Uralian metallurgic industry, which lost the traditional raw base (Ukrainian and Georgian deposits) after the USSR breakdown. The Urals is region is perspective for the discovery of two types of manganese deposits. (1) Insignificantly metamorphosed siliceous–carbonate ores with silica modulus M_Si (i.e., MnO : SiO₂) ranging from 1 to 2 and manganese content of 17–20%. The most promising are the areas with different-age, mainly carbonate rocks in the Urals (Northern and Polar) and Pai-Khoi regions. (2) Oxide, mainly pyrolusite–psylomelane ores with Mn content of 30–35% in the Meso–Cenozoic manganese hats developed in the Paleozoic manganiferous (volcanogenic–siliceous and carbonate–siliceous) rocks and noneconomic (small) deposits. The most promising areas are Late Cretaceous and Paleogene peneplains of the Southern Urals (Trans-Uralian and Zilair regions). It is necessary to intensify works on the improvement of concentration technique for manganese ores and to carry out the marketing study of the expediency of replacing imported manganiferous concentrates by those obtained from the Uralian ores.     

The uptake of cobalt into ferromanganese nodules,soils, and synthetic manganese (IV) oxides

Strong enrichments of cobalt occur in marine manganese nodules, soils, wads, and natural and synthetic minerals such as hollandite, cryptomelane, psilomelane, lithiophorite, birnessite, and δ-MnO₂. Previously, it was suggested that Co³⁺ ions in these minerals replace either Mn³⁺ or substitute for Fe³⁺ in incipient goethite epitaxially intergrown with δ-MnO₂. Neither of these interpretations is now considered to be satisfactory on account of the large discrepancy of ionic radius between octahedrally coordinated low-spin Co³⁺ and high-spin Mn³⁺ or Fe³⁺ in oxide structures. The close agreement between the ionic radii of Co³⁺ and Mn⁴⁺ suggests that some cobalt substitutes for Mn⁴⁺ ions in edge-shared [MnO₆] octahedra in many manganese(IV) oxide mineral structures. It is proposed that hydrated cations, including Co²⁺ ions, are initially adsorbed on to the surfaces of certain Mn(IV) oxides in the vicinity of essential vacancies found in the chains or sheets of edge-shared [MnO₆] octahedra. Subsequently, fixation of cobalt takes place as a result of oxidation of adsorbed Co²⁺ ions by Mn⁴⁺ and replacement of the displaced manganese by low-spin Co³⁺ ions in the [MnO₆] octahedra or vacancies.     

Formation of freshwater Fe-Mn coatings on gravel and the behavior of 60Co, 90Sr,and 137Cs in a small watershed

Iron and manganese oxide coatings are actively forming on stream substrates in the White Oak Creek watershed in East Tennessee. Although oxidizing conditions are required for Fe-Mn oxide precipitation, coatings accumulate only if dissolved iron and manganese exceed 50 μg/L. Below this, coatings are lost by abrasion as fast as or faster than they form. Annual rates of formation of 3 mg/g on substrate (gravel) were observed. Manganese is dissolved from coatings between Eh values of 100 to 300 mV and below 1 mg/L dissolved O₂ at pH 6.5 to 7.5. Iron oxides can be precipitated under these conditions.Uncontaminated gravels with oxide coatings (composed of illite, quartz, and feldspar) adsorbed radionuclides rapidly from waters below MPC (Maximum Permissible Concentration) levels. Contaminated gravels placed in uncontaminated waters lost ⁶⁰Co by abrasion in oxidizing conditions and by dissolution of manganese coatings in reducing conditions. Exchangeable ⁹⁰Sr was completely lost after one month whereas nonexchangeable ⁹⁰Sr was lost more slowly; ¹³⁷Cs was totally retained by the gravels. Gravels such as these can be used to monitor the radionuclide content of waters in the environment.     

The sorption of silver by poorly crystallized manganese oxides

The sorption of silver by poorly crystallized manganese oxides was studied using synthesized samples of three members of the manganous manganite (birnessite) group, of different chemical composition and crystallinity, and a poorly organized γ-MnO₂. All four oxides sorbed significant quantities of silver. The manganous manganites showed the greatest sorption (up to 0.5 moles silver/mole MnO_x at pH 7) while the γ-MnO₂ showed the least (0.3 moles silver/ mole MnO_x at pH 7). Sorption of silver was adequately described by the Langmuir equation over a considerable concentration range. The relationship failed at low pH values and high equilibrium silver concentrations. The sorption capacity showed a direct relationship with pH. However, the rate of increase of sorption capacity decreased at the higher pH values.Silver sorption maxima. were not directly related to surface area but appeared to vary with the amount of occluded sodium and potassium present in the manganese oxide. The important processes involved in the uptake of silver by the four poorly crystallized manganese oxides ara considered to be surface exchange for manganese, potassium and sodium as well as exchange for structural manganese, potassium and sodium.     

铁锰氧化物对苯酚氧化降解的实验研究

为了考察铁锰氧化物对酚类污染物的氧化降解能力,采用天然以及合成的铁锰氧化物对苯酚的氧化降解进行对比实验研究。土壤中铁锰氧化物样品分别为天然针铁矿及氧化锰,合成铁锰氧化物样品分别为合成针铁矿及软锰矿。结果表明：苯酚与铁锰氧化物发生氧化还原作用时,还可能与土壤中杂质发生吸附等作用;铁锰氧化物还原反应强度随着反应介质pH值的升高而迅速下降;可用零级反应动力学方程拟合铁氧化物还原溶解反应,针铁矿溶解反应的强度与介质的pH值呈负相关关系;天然针铁矿对酚类污染物的氧化降解能力明显高于合成针铁矿,pH值对天然针铁矿溶解反应影响较大;可用一级指数衰减方程拟合锰氧化物还原溶解反应,锰氧化物溶解反应的强度与介质的pH值呈指数衰减关系;pH值对软锰矿还原溶解反应的影响大于对土壤中氧化锰的影响,pH值越小,影响越显著;对比pH值对铁和锰还原作用的影响发现,在pH=6.5时,锰氧化物仍有较强的氧化性能。     

Guidelines for finding concretionary Mn-Fe oxides in streams

Concretionary Mn-Fe oxides in streams form at interfaces between oxidizing and reducing environments. A reducing environment produces waters high in dissolved Mn and Fe, and an oxidizing environment causes precipitation. Mineralogical, microprobe, and optical studies of concretionary Mn-Fe oxides may further our understanding of the role of Mn-Fe oxides in determining the trace-element geochemistry of stream sediments.     

碧口古陆周边锰矿找矿分析

前震旦系碧口群,属四川古陆核西北缘,中新元古代发育的岛弧型建造,经晋宁运动碰撞拼贴,组成扬子地台的一部分,本身固结成为古陆。在其周边及东部成带分布了含锰岩系。目前各含锰矿带上的锰矿床,具体层位归属有蓟县纪、震旦纪、寒武纪等之不同认识。经分析研究认为,含锰岩系均属前震旦纪摩大岭复背斜褶皱带（即碧口古陆）之上的盖层型震旦寒武纪沉积,大致应为同一时代,即晚震旦世。由于各带所处地质构造背景、沉积环境的不同,锰矿特征明显有异,南含锰矿带临接扬子地台,为弱还原地质环境相对稳定,以优质锰矿类型为主;北含锰矿带紧邻秦岭地槽,凹陷较深为还原环境,以高磷锰矿为主。在该带含锰岩系的构造岩性有利部位,易形成风化淋积型锰矿床。故在寻找锰矿过程中,应区别对待,注意优质锰矿的辨认,并对本区锰矿找矿标志及找矿方向提出建议。