湘中奥陶纪锰矿带成矿特征及资源前景

湘中奥陶纪沉积锰矿带位于湖南省安化县、桃江县、宁乡县境内,呈近EW向展布,矿带内锰矿以质量好而著称。该成矿带的成锰沉积盆地受控于加里东期张性断裂系统,为一断陷盆地。盆地内发育一组NW向同沉积断裂,形成了一系列断陷槽,控制了沉积岩相的分布。锰矿主要产于盆地中心亚相的黑色页岩夹碳酸锰矿微相内。据矿带中锰矿的地质和地球化学特征以及微量元素和碳、氧、锶同位素组成,笔者认为,该锰矿属于热水沉积成因。综合对比表明,该成矿带具有良好的成矿条件和值得注意的资源潜力,有可能发展为大型锰成矿带。     

Composition and Useful Properties of Tailings of Marine Manganese Nodules and Crusts

Marine manganese nodules and crusts, when processed, yield tailings which may be utilized for environmental and economic benefit. The key to the reasonable and effective utilization of these tailings lies in making a systematic appraisal of their composition and properties. This article gives an introduction to the investigation of manganese tailings properties. The tailings have a high iron and/or manganese content, high surface area, high porosity, and fine grain size. Some tailings have a high rare earth element content which is valuable. They may also have high SO₃, arsenic, and uranium contents which are harmful. Depending on the process used to produce the tailings, there will likely be some differences in chemical composition, mineral assemblages, surface area and adsorption capability, pore diameter and volume, density and pH. In assigning potentially beneficial applications for these tailings, these differences should be taken into account to optimize utilization.     

氧化锰矿物的生物成因及其性质的研究进展

土壤中的氧化锰矿物是原生矿物风化和成土过程的产物,是最具反应活性的一类矿物,决定着环境中许多物质的形态、迁移和转化,在元素生物地球化学循环中起着重要的作用,其形成机制和环境效应备受关注。已有的研究表明,环境中氧化锰的形成与微生物作用紧密相关,微生物作用可使自然环境中的Mn(Ⅱ)氧化速率提高105倍。参与Mn(Ⅱ)氧化的微生物在环境中广泛存在,已知的典型锰氧化细菌分布在变形菌门、放线菌门或厚壁菌门,它们均通过胞外聚合物中的多铜氧化酶来催化氧化Mn(Ⅱ)。细菌氧化Mn(II)成Mn(Ⅳ)是酶催化的两个连续的快速单电子传递过程,Mn(Ⅲ)在溶液中以与酶结合的瞬时中间态出现。生物形成氧化锰的最初形态为层状锰矿物,与δ-MnO2或酸性水钠锰矿很类似,且结晶弱,粒径小,锰氧化度高,结构中的八面体空穴多,因而比化学形成的氧化锰具有更强的吸附、氧化等表面活性。环境中Mn(Ⅱ)微生物氧化及形成的Mn(Ⅲ)中间体与碳、氮、硫等生命元素的地球化学循环的关系令人关注。     

Changes in manganese and lead in the environment and young children associated with the introduction of MMT in gasoline

This is a 4-year longitudinal study to evaluate changes to the environment and exposure of young children associated with the introduction of methylcyclopentadienyl manganese tricarbonyl （MMT） into Australia in 2000. The cohort includes 57 females and 56 males; age range of 0.29 to 3.9 years. Samples are collected every 6 months from children in residences located at varying distances from major traffic thoroughfares in Sydney. Environmental samples： air, house and day care dustfall, soil, dust sweepings and gasoline. Samples from children： blood, urine, handwipes prior to and after playing outdoors, and a 6-day duplicate diet. All samples are analyzed for a suite of 20 elements using ICP-MS. Results are presented for the first three 6-month sampling periods for Pb and Mn. For dustfall accumulation, there was no significant change over the 3 sampling periods （time） for Pb or Mn, and a positive relationship between ‘traffic exposure＇ （traffic volume and proximity to the road） and Pb but not Mn. For handwipes, Pb and Mn in wipes taken from children after playing outdoors were usually significantly greater than for wipes taken prior to playing. There was no significant association between Pb or Mn in handwipes with traffic exposure. Dustfall accumulation was a significant predictor for Pb in the handwipes, and dust sweepings were a significant predictor of Mn in handwipes.     

XANES analysis of the mechanisms of arsenic removal in biological iron and manganese treatment unit

Biological iron and manganese removal utilizing indigenous iron and manganese oxidizing bacteria （IRB hereafter） in groundwater can also be applied to arsenic removal according to our pilot-scale test. The arsenic removal probably occurred through sorption and complexation of arsenic to iron and manganese oxides formed by enzymic action of IRB. We investigated the chemical properties of iron and manganese oxides in IRB floc and the valence state of arsenic sorbed to the floc to clarify the mechanisms of the arsenic [especially As （Ⅲ）] removal. The floc samples were collected from two drinking water plants using IRB （Jyoyo and Yamatokoriyama, Japan）, and our pilot - scale test site where arsenic and iron removal using IRB is under way （Mukoh, Japan）. The Jyoyo and Yamatokoriyama IRB floc samples were subjected to As （Ⅲ） and As（Ⅴ） sorption experiments. The elemental composition of the floc samples was measured. XANES spectra were collected on As, Fe and Mn K-edges at synchrotron radiation facility Spring 8 （Hyogo, Japan）. FT-IR and the X-ray diffraction spectra of the samples were also obtained. The IRB floc contained ca. 35 % Fe, 0.3%-3.5% Mn and 2%-6% P. The samples were highly amorphous and contained ferrihidrites and hydrated iron phosphate. According to XANES analyses of IRB, As associated with IRB was in ＋5 valence state when As （Ⅲ） （or As （Ⅴ）） was added in laboratory sorption test, Fe in ＋3 valence state, and Mn a mixture of＋3 and ＋4 valence states. Small shift was observed in the XANES spectra of IRB on As K-edge as the equilibration time of the sorption experiment was increased. Gradual oxidation of a small amount of As （Ⅲ） associated with IRB or change in arsenic binding with sorption site were the probable mechanism.     

Geochemistry and Origin of Ananai Stratiform Manganese Deposit in the Northern Chichibu Belt, Central Shikoku, Japan

Abstract. Major and trace element contents are reported for Permian manganese ore and associated greenstone from the Ananai manganese deposit in the Northern Chichibu Belt, central Shikoku, Japan. The manganese deposit occurs between greenstone and red chert, or among red chert beds. Chemical compositions of manganese ore are characterized by enrichments in Mn, Ca, P, Co, Ni, Zn, Sr and Ba, and negative Ce and positive Eu anomalies relative to post-Archean average Australian Shale (PAAS). Geochemical features of the manganese ore are similar to those of modern submarine hydrother-mal manganese deposits from volcanic arc or hotspot setting. In addition, geochemical characteristics of the greenstone closely associated with the Ananai manganese deposit are analogous to those of with-in plate alkaline basalt (WPA). Consequently, the Ananai manganese deposit was most likely formed by hydrothermal activity related to hotspot volcanism in the Panthalassa Ocean during the Middle Permian. This is the first report documenting the terrestrially-exposed manganese deposit that was a submarine precipitate at hotspot.     

过硫酸铵氧化容量法测定矿石中锰方法的改进

采用过硫酸铵氧化容量法测定锰时,可在低酸度(0.18mol/LH2SO4、0.29mol/LH3PO4)和大体积(300mL)溶液中氧化Mn2 至Mn7 。所测得的结果十分稳定,回收率为100%。采用管理样分析验证方法,其结果与铋酸钠容量法结果一致。对于w(Mn)=11.36%的试样进行10次分析测定,RSD=0.33%。方法可测定w(Mn)≥0.01%的常见矿种样品。     

多金属结核中二氧化锰的测定

用过量的含有Ｈ２ＳＯ４的（ＮＨ４）２Ｆｅ（ＳＯ４）２溶液分解多金属结核的同时，还原了试样中的ＭｎＯ２，然后以Ｋ２Ｃｒ２Ｏ７标准溶液滴定测定了多金属结核中的ＭｎＯ２。就样品分解过程中的加热温度和时间对测定结果的影响及标准溶液的标定等问题进行了讨论，经多次测定，方法重现性好。应用此方法为新研制的多金属结核标准物质提供了ＭｎＯ２的定值数据，其结果与初定值相符，无剔除值，精密度（ＲＳＤ，ｎ＝８）小于０６％。     

痕量铁和锰的化学发光检测

评述了国内外有关铁、锰的化学发光分析进展。从发光体系、操作方式、最佳条件、干扰离子、检测限等各个方面对化学发光法测定铁、锰及其它们与其它组分同时测定中的应用进行分类评述。