Geochemistry of environmentally sensitive trace elements in Permian coals from the Huainan coalfield, Anhui, China

To study the geochemical characteristics of 11 environmentally sensitive trace elements in the coals of the Permian Period from the Huainan coalfield, Anhui province, China, borehole samples of 336 coals, two partings, and four roof and floor mudstones were collected from mineable coal seams. Major elements and selected trace elements were determined by inductively coupled plasma optical emission spectrometry (ICP-OES), inductively coupled plasma mass spectrometry (ICP-MS), and hydride generation atomic absorption spectrometry (HAAS). The depositional environment, abundances, distribution, and modes of occurrence of trace elements were investigated. Results show that clay and carbonate minerals are the principal inorganic constituents in the coals. A lower deltaic plain, where fluvial channel systems developed successively, was the likely depositional environment of the Permian coals in the Huainan coalfield. All major elements have wider variation ranges than those of Chinese coals except for Mg and Fe. The contents of Cr, Co, Ni, and Se are higher than their averages for Chinese coals and world coals. Vertical variations of trace elements in different formations are not significant except for B and Ba. Certain roof and partings are distinctly higher in trace elements than underlying coal bench samples. The modes of occurrence of trace elements vary in different coal seams as a result of different coal-forming environments. Vanadium, Cr, and Th are associated with aluminosilicate minerals, Ba with carbonate minerals, and Cu, Zn, As, Se, and Pb mainly with sulfide minerals.     

Mineralogy and geochemistry of a Late Permian coal in the Dafang Coalfield, Guizhou, China: influence from siliceous and iron-rich calcic hydrothermal fluids

This paper describes the influence of siliceous and iron-rich calcic low-temperature hydrothermal fluids (LTHF) on the mineralogy and geochemistry of the Late Permian No. 11 Coal (anthracitic, R_r=2.85%) in the Dafang Coalfield in northwestern Guizhou Province, China. The No. 11 Coal has high contents of vein ankerite (10.2 vol.%) and vein quartz (11.4 vol.%), with formation temperatures of 85 and 180 °C, respectively, indicating that vein ankerite and vein quartz were derived from low-temperature calcic and siliceous hydrothermal fluids in two epigenetic episodes. The vein quartz appears to have formed earlier than vein ankerite did, and at least three distinct stages of ankerite formation with different Ca/Sr and Fe/Mn ratios were observed.The two types of mineral veins are sources of different suites of major and trace metals. Scanning electron microscope and sequential extraction studies show that, in addition to Fe, Mg, and Ca, vein ankerite is the dominant source of Mn, Cu, Ni, Pb, and Zn in the coal, and the contents of these five elements are as high as 0.09% and 74.0, 33.6, 185, and 289 μg/g, respectively. In contrast, vein quartz is the main carrier mineral for platinum-group elements (PGEs) Pd, Pt, and Ir in the coal, and the contents of Pd, Pt, and Ir are 1.57, 0.15, and 0.007 μg/g, respectively. Sequential extraction showed a high PGE content in the silicate fraction, up to 10.4 μg/g Pd, 1.23 μg/g Pt, and 0.05 μg/g Ir, respectively. It is concluded that the formation of ankerite and quartz and the anomalous enrichment of trace elements in the No. 11 Coal in the Dafang Coalfield, Guizhou, result from the influx of calcic and siliceous low-temperature hydrothermal fluids.     

Micrometeorological Observations of a Microburst in Southern Finland

On the afternoon of 3 July 2004 in Hyytiälä (Juupajoki, Finland), convective cells produced a strong downburst causing forest damage. The SMEAR II field station, situated near the damage site, enabled a unique micrometeorological analysis of a microburst with differences above and inside the canopy. At the time of the event, a squall line associated with a cold front was crossing Hyytiälä with a reflectivity maximum in the middle of the squall line. A bow echo, rear-inflow notch, and probable mesovortex were observed in radar data. The bow echo moved west-north-west, and its apex travelled just north of Hyytiälä. The turbulence data were analysed at two locations above the forest canopy and at one location at sub-canopy. At 1412 EET (Eastern European Time, UTC+2), the horizontal and vertical wind speed increased and the wind veered, reflecting the arrival of a gust front. At the same time, the carbon dioxide concentration increased due to turbulent mixing, the temperature decreased due to cold air flow from aloft and aerosol particle concentration decreased due to rain scavenging. An increase in the number concentration of ultra-fine particles (< 10 nm) was detected, supporting the new particle formation either from cloud outflow or due to rain. Five minutes after the gust front (1417 EET), strong horizontal and downward vertical wind speed gusts occurred with maxima of 22 and 15 m s^?1, respectively, reflecting the microburst. The turbulence spectra before, during and after the event were consistent with traditional turbulence spectral theory.     

Timing of UHP metamorphism in the Hong’an area,western Dabie Mountains,China: evidence from zircon U–Pb age,trace element and Hf isotope composition

The Hong’an area (western Dabie Mountains) is the westernmost terrane in the Qinling-Dabie-Sulu orogen that preserves UHP eclogites. The ages of the UHP metamorphism have not been well constrained, and thus hinder our understanding of the tectonic evolution of this area. LA-ICPMS U–Pb age, trace element and Hf isotope compositions of zircons of a granitic gneiss and an eclogite from the Xinxian UHP unit in the Hong’an area were analyzed to constrain the age of the UHP metamorphism. Most zircons are unzoned or show sector zoning. They have low trace element concentrations, without significant negative Eu anomalies. These metamorphic zircons can be further subdivided into two groups according to their U–Pb ages, and trace element and Lu–Hf isotope compositions. One group with an average age of 239 ± 2 Ma show relatively high and variable HREE contents (527 ≥ Lu_N ≥ 14) and ¹⁷⁶Lu/¹⁷⁷Hf ratios (0.00008–0.000931), indicating their growth prior to a great deal of garnet growth in the late stage of continental subduction. The other group yields an average age of 227 ± 2 Ma, and shows consistent low HREE contents and ¹⁷⁶Lu/¹⁷⁷Hf ratios, suggesting their growth with concurrent garnet crystallization and/or recrystallization. These two groups of age are taken as recording the time of prograde HP to UHP and retrograde UHP–HP stages, respectively. A few cores have high Th/U ratios, high trace element contents, and a clear negative Eu anomaly. These features support a magmatic origin of these zircon cores. The upper intercept ages of 771 ± 86 and 752 ± 70 Ma for the granitic gneiss and eclogite, respectively, indicate that their protoliths probably formed as a bimodal suite in rifting zones in the northern margin of the Yangtze Block. Young Hf model ages (T _DM1) of magmatic cores indicate juvenile (mantle-derived) materials were involved in their protolith formation. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

贵州半边街锗锌矿床锗的富集特征及其地质意义

锗(Ge)属于战略性关键矿产资源, 是众多高新技术领域的重要原材料。Ge主要以共/伴生形式产出于Zn、Pb和Cu等热液贱金属矿床和煤矿床中, 目前全球Ge资源主要来源于铅锌矿的副产品。近期取得较大找矿突破的半边街锌矿床(7.70Mt矿石, Zn平均品位5.1%)伴生有超大型规模的金属Ge(>900t @110×10-6), 然而Ge超常富集的机制不清。本次研究利用LA-ICPMS对闪锌矿进行了微区原位微量元素组成和Mapping分析, 以揭示Ge等元素的富集特征、赋存状态和替代方式, 探讨Ge的富集机制。分析结果表明, 半边街矿床闪锌矿中高含量(平均值>100×10-6)微量元素有Fe、Pb、Ge和Cd等, 较高含量(平均值100×10-6~10×10-6)的有Mn、Ga、Sn和Tl, 以及较低含量(平均值< 10×10-6)的有Ag、Cu、In和Sb。相比于各类型铅锌矿床, 半边街闪锌矿Ge超常富集(274×10-6~1938×10-6, 平均为1055×10-6, 达到1000倍富集)。该矿床中Ge以类质同象或纳米颗粒形式赋存于闪锌矿中。微量元素摩尔量相关性图揭示Ge替代Zn的方式以Ge4++Pb2+↔3Zn2+为主, 其次为nGe4++Mn2+↔(2n+1)Zn2+和nGe4++2Tl3+↔(2n+3)Zn2+。综合分析认为, 半边街矿床Ge可能来源于相对富Ge的前寒纪基底; 富有机质的盆地流体在Ge的搬运中发挥重要作用; Ge、Cd等稀散元素的共生分异制约了Ge的最终超常富集。因此, 半边街矿床中Ge的超常富集是"源、运、聚"复杂过程多要素耦合作用的结果。     

地幔流体的前缘研究

地幔流体是与地幔环境处于平衡的气体和挥发分。其主要化学组分为碳、氢、氧、氮、硫（ＣＨＯＮＳ）。它以富于地球内部原始组分为特征，但也包含部分再循环组分。地幔挥发分在弱还原条件下主要为ＣＯ２－Ｈ２Ｏ，强还原环境则以ＣＨ４－Ｈ２Ｏ－Ｈ２为主。地幔流体地球化学的重要性质为：（１）易溶于硅酸盐熔体；（２）净化作用；（３）再沉淀作用。近年来，有关地幔流体中稀有气体和挥发分的起源、分布及同位素组成等前缘领域的研究已取得重要进展。当前拟优先探索的问题包括气体裂化与金刚石成因，非生物成因地幔烃，地幔流体与成矿作用，以及地幔挥发分注入与地壳重熔等。     

Quartz resources in the Serra de Santa Helena formation,Brazil: A geochemical and technological study

This study presents an evaluation of Brazilian quartz deposits of Corinto and Olhos D'água, in Minas Gerais State, as potential high purity raw material for the production of silica glass. Both deposits are part of the Serra de Santa Helena formation, which holds other quartz deposits. Several quartz samples from these mines were analyzed to evaluate their chemical purity, by determination of the content of trace elements by ICP-MS after acid digestion. The technological characteristics of the ores after flame-fusion into silica glass were evaluated according to their bubble generation and UV transparency. The results indicate that silica glass with chemistry suitable for crucible applications can be obtained from materials of both mines, and even optical grade silica glass can be manufactured using transparent ore from one of the mines. In addition, this work explores the trace elements composition of each mine, as well as their fluid inclusions, and characterizes the mines as being of hydrothermal origin. Small differences in the physical and chemical characteristics of quartz that could affect the technological behavior of the ores are related to the geological history of the mines and provide interesting insights regarding the exploration of other quartz resources within the same geological formation.     

苏鲁榴辉岩中磷灰石的矿物学和微量元素地球化学

磷灰石是榴辉岩中最常见的副矿物之一,见证了高压-超高压变质岩从原岩形成、俯冲和折返所伴随的物理化学过程。为进一步揭示苏鲁超高压榴辉岩经历的物理和化学过程,我们对取自中国大陆科学钻探工程（CCSD）主孔岩心和苏北地表露头榴辉岩中的磷灰石进行了详细的岩相学分析和LA-ICP-MS原位微量元素分析。分析结果表明,在苏鲁榴辉岩中,磷灰石绝大多数是在超高压变质作用阶段重结晶生长的。未受退变质影响的磷灰石富含LREE和Sr元素,退变质作用促使磷灰石中活动性较强的LREE和Sr明显降低而HREE含量略微升高,并产生负Eu异常。磷灰石边部HREE的升高可能与折返过程中的升温作用和石榴子石分解有关,Eu负异常的产生可能还与退变质过程中发生了氧逸度f^O2的降低有关;结合前人对磷灰石中“出溶”现象的研究,提出榴辉岩磷灰石中的独居石“出溶体”很可能是磷灰石与富含NaCl和硅酸盐的退变质流体发生交代反应所致,磷灰石中硫化物“出溶体”的形成除了氧逸度降低的原因外,可能也与折返过程中发生的短期升温作用有关。超高压变质岩从进变质-峰期→早期退变质→角闪岩相退变质阶段,变质流体可能经历了氧化→还原→氧化状态的复杂变化。     

华南前寒武系基底变质杂岩和中-新生代地幔岩的稀有气体同位素组成及其大地构造意义

对华南前寒武系变质岩浆杂岩稀有气体He、Ne、Ar和Xe的系统研究表明:扬子克拉通基底为含高3He的下地壳"原始岩石层",(3He/4He)×10-6比值为2.8～4.6;而华夏板块基底变质岩浆杂岩则是在缺乏3He、低(3He/4He)×10-8比值(3.15～17.7)的构造环境下形成的大陆中-上地壳变质岩浆杂岩层,反映出两者基底性质迥然不同。华南中-新生代爆破岩筒He同位素组成相反,相对稳定的扬子克拉通(3He/4He)×10-8比值仅0.18～4.22,而郯庐—四会—吴川断裂以东,中-新生代活动地块(太平洋构造域)(3He/4He)×10-8比值高达3.7～20.5。He同位素表明郯庐—四会—吴川断裂带为切割深至地幔的边界深大断裂,是扬子克拉通与华夏板块间的边界且控制了燕山期火山—侵入岩浆向西扩展。Ar同位素组成表明华南大陆中-新生代地幔形成接近"均一"的地幔组份。136Xe/130Xe—129Xe/130Xe相关组份表明它们具有地幔柱岩石同位素组成特征。     

南极普里兹湾表层沉积物微量元素分布特征及其物源指示意义

利用电感耦合等离子体质谱仪测定了中国南极科考21~27航次期间获取的普里兹湾表层沉积物中Cu、Pb、Zn、Cd、Cr、Co、Al、Fe、Mn的含量,分析了普里兹湾微量元素的分布特征,结合沉积物粒度分布、生物硅含量,并利用富集系数和主成分分析的方法,探讨了微量元素的物源指示意义。研究结果表明:普里兹湾沉积物中的微量元素含量与南大洋其他海域具有很好的可比性。Cu、Zn、Cr、Co、Fe、Mn含量在陆坡深海区明显高于冰架边缘区和陆架区;Al、Pb含量在冰架边缘区较高;而Cd含量在陆架区相对较高。人类活动对普里兹湾沉积物中的微量元素没有明显的影响,南极大陆岩石风化产物和海洋生物源性沉降是其主要来源。冰架边缘区及陆架破折处P2-9站位的微量元素主要为岩源性输入。陆架区、陆坡深海区的微量元素Cu、Zn、Cr、Co、Fe、Mn明显受到生源性物质输入的影响。而普里兹湾沉积物中Cd则主要来源于硅藻的吸收利用及硅质软泥的富集。