三斜水钠锰矿层间阳离子交换作用的拉曼谱学

水钠锰矿为自然界中常见的锰氧化物矿物,其离子交换作用及结构转变理解尚不深刻,矿物表征手段较为局限.为探究水钠锰矿的离子交换特性以及结构转变在拉曼光谱上的反映,利用MnSO₄和NaOH合成了三斜晶系的Na型水钠锰矿,进行了NH₄+、K+、Mg2+、Ca2+、Ba2+、Co2+、Zn2+的离子交换实验,使用ICP-OES、XRD、拉曼光谱等手段对离子交换水钠锰矿进行表征.拉曼光谱分析表明,570~585 cm-1与640~655 cm-1两个锰氧八面体伸缩振动模式的相对强度及570~585 cm-1附近拉曼峰峰位指示水钠锰矿的结构对称型;570~585 cm-1拉曼峰强度大、振动频率高指示三斜对称型.280 cm-1与500 cm-1附近的拉曼峰是层间离子种类的识别标志.水钠锰矿层间若为Na+、K+、Mg2+、Ca2+、Ba2+等碱金属、碱土金属离子,则在280 cm-1附近存在1个峰值,500 cm-1存在2个分立的峰值;其他种类的层间离子仅500 cm-1处有1个孤峰,指示层间离子排列无序.      

1 nm锰矿相的人工合成及其金属阳离子交换特性

人工合成了纯净的1 nm锰矿相,并进行1 nm锰矿相的离子交换实验,发现1 nm锰矿相具有很强的离子交换能力,这可能是多金属结核为何能够大量富集铜、钴、镍等有价金属元素的重要原因之一;不同的金属离子和1 nm锰矿相发生交换反应的能力也不相同,结核中几种主要的金属离子和 1nm锰矿相的交换能力的优先顺序排列为Cu2+＞ Co2+＞ Zn2+≥Ni2+＞ Ca2+＞ Mg2+,其原因可能是由于1 nm锰矿相具有特殊的类似隧道结构以及各金属离子的特性不同所造成的.     

贵州从江高增新元古代大塘坡组锰矿沉积地球化学特征

贵州新元古代大塘坡期是重要的成锰时期,在贵州东部、湖南西部形成了一系列锰矿床。近年来在贵州东南部从江发现的大塘坡期锰矿,表明大塘坡期成锰范围更广,成锰环境更为复杂。通过对从江高增新元古代大塘坡组锰矿的沉积特征、矿物学和沉积地球化学特征的研究,含锰岩系具有热液(水)沉积、富集Cu、Zn、Ni、Nb、Co、Mo、As、Sb、Sr、Ba、V、Ga、Ag、Th、U等特征,特别是Pb、Co、W均显著富集,显示热液沉积特征。含锰岩系中黑色块状锰矿、深灰色纹层状锰矿和灰白色纹层状含锰凝灰岩在U-Th相关图、Cr-Zr相关图、Co/Zn-(Co+Ni+Cu)相关图上均显示具有热液(水)沉积特征,稀土配分曲线类似碧口群海底火山喷流沉积。含锰岩系为由凝灰岩、硅质岩、碳酸锰互层和黑色碳质泥岩沉积组合,其岩石组合与海底火山喷流沉积类似。因此,认为从江高增锰矿属于海底热液(水)喷流沉积产物,该地区锰矿找矿应该沿同生深大断裂进行。     

大洋多金属结核中1nm锰矿相的相变及其主要控制因素研究

多金属结核样品在室温中放置或加热干燥后 ,其中的 1nm锰矿相会部分或全部地相变为 0 7nm锰矿相 ,这说明 0 7nm锰矿相可能不是多金属结核的原生锰矿相 ,而仅仅是 1nm锰矿相的相变产物。研究结果表明 :1nm锰矿相结构中的Cu2 + 、Co2 + 、Ni2 + 等金属阳离子的含量与其结构稳定性有正相关关系 ,即金属离子含量越高 ,其结构越稳定 ,1nm锰矿相越不易相变为 0 7nm锰矿相 ,反之亦然 ;另外 ,不同金属阳离子稳定 1nm锰矿相结构的能力也不同 ,结核中几种主要金属阳离子对 1nm锰矿相结构的稳定能力从大到小为 :Ni2 + >Cu2 + >Co2 + >Zn2 + >Ca2 + =Mg2 + 。     

贵州遵义二叠纪锰矿地球化学特征与沉积环境分析：以遵义谢家坝富锰矿床为例

为分析贵州遵义二叠纪锰矿的沉积环境,对谢家坝锰矿床进行常量元素、微量和稀土元素地球化学研究。研究认为：谢家坝锰矿赋存于茅口组顶部含锰岩系中,可分为下矿层豆状、角砾状菱锰矿、似层状菱锰矿,以及上矿层碎屑状、块状菱锰矿的二元结构矿石类型组合,可广泛代表遵义锰矿的矿石特征。谢家坝锰矿上下矿层之间主量元素和稀土元素含量差异较大,常量元素SiO2、TiO2、S、Fe2O3含量上矿层均大于下矿层,MnO、MgO与 Al2O3之间均呈负相关关系;上矿层Fe/Mn值较高,属高Fe低P型锰矿,而下矿层Fe/Mn值较低,属中低Fe低P型锰矿。上矿层稀土元素PAAS标准化配分后呈现较明显的重稀土亏损、弱的轻稀土富集、右倾配分的特征,具有弱的Ce正异常,类似海底铁锰结核稀土元素特征;下矿层呈现弱的中稀土富集,轻、重稀土亏损,弱的帽式分配特征,具明显的Ce负异常,类似典型深部海水沉积稀土元素特征。微量元素Th/U、Ni/Co、V/Cr、V/（V+Ni）、AU等沉积环境古氧相分析指标和稀土元素PAAS标准化配分模式指示,谢家坝锰矿下矿层是在贫氧-厌氧条件下Mn2+与CO32-直接形成菱锰矿,上矿层在常氧-贫氧环境下Mn3+、Mn4+以氧化物或氢氧化物形式沉淀。     

铁锰结核的矿物相变和其它次生变化

本文通过对太平洋中部61个铁锰结核的研究,发现在结核形成后,发生了渐近相变、退化相变和Mn、Ni、Cu的次生富集作用。渐近相变是,随着结核成岩作用的增强(伴随着氧化还原电位由高到低的变化),锰矿物发生了由原生δ-MnO_2→环带状、薄层状钠水锰矿和钡镁锰矿→块状磷片状钡镁锰矿集合体的相变。在这一相变系统中钠水锰矿是相变的过渡阶段,钡镁锰矿是相变的高级阶段。退化相变:具层纹构造的原生δ-MnO_2在底层水(可能贫Mn、Ni、Cu而富Fe)的作用下,其中一部分Mn、Ni、Cu等被水带走而沉淀下Fe,形成新的富Fe、δ-MnO_2或非晶质水合铁锰氧化物。Mn、Ni、Cu的次生富集作用。结核在重结晶作用或由结核成岩作用到成岩后生作用过程中均发生了Mn、Ni、Cu的次生富集作用。它不仅表现在由原生δ-MnO_2→环带状钠水锰矿和钡镁锰矿→块状钡镁锰矿过程中,而且还表现在由早期到后期形成的δ-MnO_2成分上。     

大洋多金属结核中几种常见锰矿相的特征及其相关性

大洋多金属结核中的1 nm锰矿相常以陆上钡镁锰矿命名,但两者在晶体结构等方面有很大的差别,并不属同一种矿物,1 nm锰矿相与人工合成的布塞尔矿却有更多的相似性。1 nm锰矿相会因干燥失水而相变成0.7 nm锰矿相,因此结核中的大多数0.7 nm锰矿相很可能不是原生矿物,而仅仅是1 nm锰矿相的相变产物。水羟锰矿和1 nm锰矿相是多金属结核中最主要的两种锰矿物,它们两者均有0.24 nm和0.14 nm这两条特征X射线衍射峰,因此在对结核进行锰矿物相的鉴定中要注意把它们区分开。     

贵州二叠系茅口组顶部锰矿沉积特征及矿床成因研究

通过对遵义、纳雍营盘等地含锰岩系沉积特征及沉积地球化学特征研究,结果表明,锰矿体形态主要以层状、似层状、透镜状、脉状产出,具有角砾状构造、递变层理等,常夹硅质岩和凝灰岩,具有热水喷流沉积构造特征。锰矿层位于玄武岩之下,夹于茅口组灰岩顶部,说明锰矿成矿在玄武岩喷发之前。含锰岩系中的矿物组合有浸染状黄铜矿,黄铁矿,重晶石,天青石,菱锰矿、钙菱锰矿、锰方解石、黄铜矿、蓝铜矿、褐铁矿、绿泥石、石英及其他碳酸盐岩矿物等,这些矿物组合与热水沉积矿物组合类似。对含锰岩系进行微量元素、稀土元素、碳同位素分析测试表明,含锰岩系富集As、Co、Cu、Cr、Mo、Ni、Pb、U和V等元素,Fe/Ti、(Fe+Mn)/Ti及Al/(Al+Fe+Mn)比值,Fe-Mn-(Cu+Co+Ni)×10三角图解等均显示锰矿属于热水沉积成因。锰矿石碳同位素值δ~(13) C介于+4.17‰~-18.53‰,氧同位素δ~(18) O介于-6.98‰~-10.05‰显示,碳同位素组成具有热水沉积特征。含锰岩系稀土配分曲线与峨眉山玄武岩稀土配分曲线类似,表明锰矿成矿物质来源与峨眉地幔热柱密切相关。     

四川省青川县马公锰矿地质特征及找矿预测

马公锰矿是川西北地区近年来新发现的具有找矿潜力的石坎式锰矿床,矿区共发现2个锰矿层,共圈出锰矿体5个,矿体倾向NW,呈层状、似层状分布,厚度大、延深稳定,地表以氧化锰矿为主,深部为碳酸锰.在阐述马公锰矿矿床地质特征的基础上,总结了矿区的找矿标志,认为马公锰矿属于海相沉积型锰矿,严格受地层层位的控制,多形成于沉积环境转变...     

新疆西天山莫托萨拉热水沉积型铁锰矿床矿物学与地球化学特征

莫托萨拉铁锰矿床位于西天山阿吾拉勒成矿带东端,研究程度相对薄弱,在矿床成因方面存在热水沉积、沉积-热液改造、胶体化学沉积等争论。本文详细研究了莫托萨拉最上层锰矿及其围岩的矿物组成、结构构造和地球化学特征,并综合前人资料对整个铁锰矿床的成因做了进一步探讨。本研究首次在矿区发现了热液长石岩,其主要由钠长石、钾长石以及少量重晶石、霓石、锌铁黄长石等矿物组成,类似于"白烟型"热水沉积岩。莫托萨拉最上层锰矿主要由锰橄榄石、褐锰矿、红硅锰矿、磁锰铁矿以及少量重晶石、方铁锰矿等矿物组成,发育有典型的热水内碎屑结构,指示其沉积于海底热液喷流口附近。该层锰矿的Al/(Al+Fe+Mn)值很低(0～0.02)、Si/Al值较高(7.9～10.9)、Fe/Ti值很高(428～1353),通过UCC标准化后发现明显富集Zn、Ba、Pb等元素,而Co、Ni、Cu等元素未见富集,以上地球化学特征与现代海底热液成因铁锰沉积物一致。在Fe/Ti-Al/(Al+Fe+Mn)、Si O2-Al2O3、10×(Co+Ni+Cu)-Fe-Mn、100×(Zr+Ce+Y)-15×(Cu+Ni)-(Fe+Mn)/4等判别图中,莫托萨拉的锰矿层和铁矿层样品均落在海底热液沉积区。锰矿层和铁矿层的稀土元素经PAAS标准化后具有明显的Ce负异常、Eu正异常和Y正异常,与现代海底热液成因铁锰沉积物的稀土配分模式非常相似。综合分析本次研究的矿物学、岩石学、地球化学特征以及前人资料,本文认为莫托萨拉铁锰矿床为海相热水沉积成因,成矿与同期海底火山的间歇性活动密切相关,海底热液的化学组分、温度高低和活动强弱都具有明显的脉动性。莫托萨拉矿区铁锰共存但各自独立成矿,且铁锰分离程度较高,这在显生宙沉积型锰矿中独具特色。鉴于前人曾报道莫托萨拉铁矿石中存在菌藻类微生物化石,我们推测,该矿床的铁锰分离过程除了受控于沉积环境的氧化还原条件变化外,微生物的选择性氧化沉淀可能也发挥了重要作用,值得开展深入研究。     

Wavelength-dispersive X-ray fluorescence spectrometric determination of Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb, Ba, Pb, and Th in komatiites

Komatiites are mantle-derived ultramafic volcanic rocks. Komatiites have been discovered in several States of India, notably in Karnataka. Studies on the distribution of trace-elements in the komatiites of India are very few. This paper proposes a simple, accurate, precise, rapid, and non-destructive wavelength-dispersive x-ray fluorescence (WDXRF) spectrometric technique for determining Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb, Ba, Pb, and Th in komatiites, and discusses the accuracy, precision, limits of detection, x-ray spectral-line interferences, inter-element effects, speed, advantages, and limitations of the technique. The accuracy of the technique is excellent (within 3%) for Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Zr, Nb, Ba, Pb, and Th and very good (within 4%) for Y. The precision is also excellent (within 3%) for Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb, Ba, Pb, and Th. The limits of detection are: 1 ppm for Sc and V; 2 ppm for Cr, Co, and Ni; 3 ppm for Cu, Zn, Rb, and Sr; 4 ppm for Y and Zr; 6 ppm for Nb; 10 ppm for Ba; 13 ppm for Pb; and 14 ppm for Th. The time taken for determining Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb, Ba, Pb, and Th in a batch of 24 samples of komatiites, for a replication of four analyses per sample, by one operator, using a manual WDXRF spectrometer, is only 60 hours.     

高压微波消解法测定醋酸纤维过滤器采集的微尘粒子中的砷镉钴铬铜铁锰镍铅钒锌

最新的流行病学研究表明,空气中较高浓度的悬浮细颗粒可能对人类的健康有不利的影响。根据该项研究显示,由于心脏病、慢性呼吸问题和肺功能指标恶化而导致死亡率的升高与细尘粒子有关。这些研究结果已经促使欧盟于1999年4月出台了限制空气中二氧化硫、二氧化氮、氧化氮、铅和颗粒物含量的法案(1999/30/EC),对各项指标包括对可吸入PM10颗粒的浓度提出了新的限制性指标。PM10颗粒是指可以通过预分级器分离采集的气体动力学直径小于10μm的细颗粒。目前研究的兴趣重点逐步偏向PM2.5这些更细微颗粒物,PM2.5这种颗粒物对健康有明显的不利影响。在欧盟指令2008/50/EC中,对PM10和PM2.5都提     

Isotopic systematics of He,Ar, S,Cu, Ni,Re, Os,Pb, U,Sm, Nd,Rb, Sr,Lu, and Hf in the rocks and ores of the Norilsk deposits

This paper reports the first results of a study of 11 isotope systems (³He/⁴He, ⁴⁰Ar/³⁶Ar, ³⁴S/³²S, ⁶⁵Cu/⁶³Cu, ⁶²Ni/⁶⁰Ni, ⁸⁷Sr/⁸⁶Sr, ¹⁴³Nd/¹⁴⁴Nd, ^206–208Pb/²⁰⁴Pb, Hf–Nd, U–Pb, and Re–Os) in the rocks and ores of the Cu–Ni–PGE deposits of the Norilsk ore district. Almost all the results were obtained at the Center of Isotopic Research of the Karpinskii All-Russia Research Institute of Geology. The use of a number of independent genetic isotopic signatures and comprehensive isotopic knowledge provided a methodic basis for the interpretation of approximately 5000 isotopic analyses of various elements. The presence of materials from two sources, crust and mantle, was detected in the composition of the rocks and ores. The contribution of the crustal source is especially significant in the paleofluids (gas–liquid microinclusions) of the ore-forming medium. Crustal solutions were probably a transport medium during ore formation. Air argon is dominant in the ores, which indicates a connection between the paleofluids and the atmosphere. This suggests intense groundwater circulation during the crystallization of ore minerals. The age of the rocks and ores of the Norilsk deposits was determined. The stage of orebody formation is restricted to a narrow age interval of 250 ± 10 Ma. An isotopic criterion was proposed for the ore-bearing potential of mafic intrusions in the Norilsk–Taimyr region. It includes several interrelated isotopic ratios of various elements: He, Ar, S, and others.     

硅酸盐中铁、锰、钛、钙、钾、磷、硅、铝、镁、钠、锶、铷、钡的X-射线荧光光谱定量测定

本文介绍样品经四硼酸锂熔融制成玻璃小饼。采用Lachance模式和理论a系数来校正元素间的效应,由3080E型X-射线荧光谱仪和DF-350B数据处理系统完成硅酸盐中十三个项目的测定。     

硅酸盐类样品中硅、铁、铝、钛、锰、钙、镁、钾、钠和磷的x射线荧光光谱测定

本文拟定了一种以熔融法制备样片,用X射线荧光光谱测定硅酸盐类样品中Si、Fe、Al、Tj、Mn、Ca、Mg、K、Na、P等元素的分析方法。在对不同靶材X光管和分光晶体实验对比的基础上,选择了最佳的测量条件。该法具有快速、准确,测量范围广,检测限低,价格便宜等优点。经过近百个各种类型标样或管理样品的分析对比表明,本法不仅适用于硅酸盐类岩石样品的分析,还适用于铁矿、铝土矿、碳酸盐类岩矿样品以及水泥、耐火材料等样品的分析。     

Viscous, cohesive, non-Newtonian, depositing, radial slurry flow

Mining induced subsidence can significantly affect mining costs where major surface facilities and natural environment need to be protected. Overburden grout injection is a technology used to control coal mine subsidence by injecting the mine waste material extracted from the coal back into the inter-burden rock during longwall mining. The flowing slurry is here categorised as a nonlinear viscous cohesive (Bingham plastic) fluid. During longwall mining the grout slurry is pumped into the separated beds of the rock mass through a central vertical borehole, which is drilled deep into the inter-burden rock strata above the coal seam. However, a blockage can occur in the injection system when the slurry velocity falls below a certain critical threshold velocity, indicating a material phase change from cohesive-viscous to cohesive-frictional. In situ field injection tests through boreholes have been simulated at a smaller scale at the CSIRO laboratory in Brisbane by pumping the slurry through a radial disk (gap = 4 mm) from its centre. Laboratory experiments indicate a general, nonlinear, cohesive, viscous, frictional model for shear behaviour of the slurry, in which the material shear parameters are functions of the disk radial distance. Complete dimensional and dimensionless analytical solutions have been developed based on an approach related to Bingham–Herschel–Bulkley fluid mechanics. The derived formulae include relations for minimum pump pressure, local pressure and pressure gradient, wall shear stress, volume rate, velocity and velocity gradient. The theoretical results match the experimental measurements. The experiments covered slurries with maximum particle sizes of 0.5 to 2 mm with about 50% being larger than 100 µm. The viscosities at the various solids concentrations were measured with a standard torsion viscometer. This study differs from the previous research in several distinct aspects, namely, consideration of the variable shear parameters rather than fixed values, inclusion of total nonlinear behaviour, and implementation of a friction function to mimic behaviour of the deposited and consolidating stiff slurry, which can cause a significant pressure rise as a result of the increased shear resistance.     

Mountains,nations, parks,and conservation

Between 1985 and 1991, two new mountain protected areas (MTNPA) covering more than 35,000 km² and based on participatory management models — the Makalu-Barun National Park and Conservation Area, Nepal, and Qomolangma Nature Preserve, Tibet Autonomous Region — were successfully established through the collaborative efforts of Woodlands Mountain Institute and conservationists in China and Nepal. Characteristics common to both projects include the importance of establishing (1) effective rationales, (2) local support constituencies, (3) a senior advisory group, (4) a task force, (5) linkages between conservation and development, and (6) fund raising mechanisms. The lessons derived from the experiences of Woodlands Mountain Institute are of significant value to others in preserving MTNPA. Increased collaboration and communication between all interested in conservation, however, will remain a critical component for expanding mountain protected area coverage to throughout the world.     

Regional distribution of Al,B, Ba,Ca, K,La, Mg,Mn, Na,P, Rb,Si, Sr,Th, U and Y in terrestrial moss within a 188,000 km2 area of the central Barents region: influence of geology,seaspray and human activity

Five hundred and ninety-eight samples of terrestrial moss (Hylocomium splendens and Pleurozium schreberi) collected from a 188,000 km² area of the central Barents region (NE Norway, N Finland, NW Russia) were analysed by ICP-AES and ICP-MS. Analytical results for Al, B, Ba, Ca, K, La, Mg, Mn, Na, P, Rb, Si, Sr, Th, U and Y concentrations are reported here. Graphical methods of data analysis, such as geochemical maps, cumulative frequency diagrams, boxplots and scatterplots, are used to interpret the origin of the patterns for these elements. None of the elements reported here are emitted in significant amounts from the smelting industry on the Kola Peninsula. Despite the conventional view that moss chemistry reflects atmospheric element input, the nature of the underlying mineral substrate (regolith or bedrock) is found to have a considerable influence on moss composition for several elements. This influence of the chemistry of the mineral substrate can take place in a variety of ways. (1) It can be completely natural, reflecting the ability of higher plants to take up elements from deep soil horizons and shed them with litterfall onto the surface. (2) It can result from naturally increased soil dust input where vegetation is scarce due to harsh climatic conditions for instance. Alternatively, substrate influence can be enhanced by human activity, such as open-cast mining, creation of ‘technogenic deserts’, or handling, transport and storage of ore and ore products, all of which magnify the natural elemental flux from bedrock to ground vegetation. Seaspray is another natural process affecting moss composition in the area (Mg, Na), and this is most visible in the Norwegian part of the study area. Presence or absence of some plant species, e.g., lichens, seems to influence moss chemistry. This is shown by the low concentrations of B or K in moss on the Finnish and Norwegian side of the (fenced) border with Russia, contrasting with high concentrations on the other side (intensive reindeer husbandry west of the border has selectively depleted the lichen population).     

NEW SET OF LOW CONCENTRATION STANDARDS FOR LA, CE, SM, YB, LU, Y, SC, V, NB AND TA IN SILICATES

We have developed a set of four synthetic standards for the rare earth and high field strength elements designed for use in the determination of those elements in silicates. The base material is a glass nominally at the eutectic of the MgO-Al₂O₃-SiO₂ ternary system. The nominal doping level was 2 wt% of the elements as oxides. To avoid problems associated with peak interference, the elements were doped in four separate glasses.