Trace element geochemistry of altered volcanic ash layers (tonsteins) in Late Permian coal-bearing formations of eastern Yunnan and western Guizhou Provinces, China

Trace element compositions were determined (by instrumental neutron activation analysis; INAA) in 30 samples of synsedimentary volcanic ash-derived tonsteins and detrital claystones from coal seams within the late Permian coal-bearing formation of eastern Yunnan and western Guizhou Provinces, China. The characteristics of trace-element geochemistry in the tonsteins can be distinguished from those of detrital claystones because of the former's unique volcanic-ash origin. The detrital claystones are characterized by their relatively high content of V, Ti, Sc, Cr, Co and Ni, relatively low content of Th and U, Th/U ratio, and small negative Eu anomaly (Eu/Eu* 0.63–0.93). Overall, these trace element characteristics are consistent with a mafic source similar to the composition of basalt rocks in the erosional region on the western edge of the study area. In contrast, the tonsteins are low in V, Ti, Sc, Cr, Co and Ni contents and have a high Th/U ratio with a distinct negative Eu anomaly (Eu/Eu* normally in the range of 0.2–0.4), consistent with a silicic magmatic source.Within the group of tonsteins, those from the lower section (P_2.1) of the coal-bearing formation are relatively high in Ti, Zr, Hf, Nb, Ta and rare earth elements (REE), as compared to those from the middle and upper sections (P_2.2+3). In trace-element discrimination diagrams (scatter plots) of Hf–Ta, Ti–Ta, Ti–V, Hf–Sc, Lu–Hf and Lu–Th, tonsteins from the P_2.1 horizon always fall in isolated distribution areas, separate from the tonsteins of the P_2.2+3 horizon. These results suggest that the source materials of tonsteins from the two separate horizons were probably derived from volcanic ash falls of two distinctly different natures. Based on a comparison of the concentrations and assemblages of trace elements between various magmatic rocks, the source materials of tonsteins from P_2.1 horizon were mostly composed of calc-alkalic, silica-poor volcanic ash (similar to rhyodacitic magma), whereas those from P_2.2+3 were apparently more siliceous and K-rich (rhyolitic magma). Thus, tonsteins from the two different horizons are characterized by unique geochemical properties, which remain constant over a wide lateral extent. Integration of trace-elemental compositions with mineralogical and textural observations makes possible the establishment of tonstein stratigraphy, thus, facilitating more precise and reliable coal-seam correlations.     

次火山热变质煤中Ge、Ga、As、S的分布特征

五牧场区是内蒙东部伊敏褐煤盆地中一个因次火山侵入作用形成的局部的烟煤区。在煤变质过程中,锗、硫从高变质煤中逸出,并在上部低变质煤中富集。锗、硫、砷与煤中有机质呈正相关,镓与煤中灰分呈正相关,随变质程度增加相关性下降。      

U-Th-Pb dating of garnet based on LAICP-MS mapping technology: A case study of the Tonglvshan large-scale Cu -Fe-Au skarn depositSCIEI北大核心CSCD

矽卡岩矿床的年代学信息对研究矽卡岩矿床的矿床成因、演变过程、成矿规律和找矿勘查具有重要的指示意义。石榴子石是矽卡岩矿床中的常见矿物,它具有一定的U含量,但是由于其普通铅高以及铀分布不均一的原因,导致激光剥蚀电感耦合等离子体质谱仪(LA-ICP-MS)点分析获得年龄成功率不高。针对点分析定年遇到的深度分馏和剥蚀点选取、普通铅校正等问题,本文提出一种利用LA-ICP-MS面扫描分析数据的虚拟点构建技术,在Tera-Wasserburg(TW)图中实现普通铅校正来确定含普通铅石榴子石年龄。通过理论推导、数值模拟和实验分析研究发现,利用相关联的^(208)Pb、^(232)Th、^(238)U测量数据校正生成^(208)Pb_(c)/^(238)U指标并据此对TW图中的数据进行数据分组抽样构造虚拟测量点,可以有效地把面扫描测量数据转换为与点分析测量类似但放射母子比例展布更优的数据。利用此方法对长江中下游成矿带鄂东矿区铜绿山大型Cu-Fe-Au矽卡岩矿床石榴子石进行面扫描分析。仅使用15min的样品面扫描数据,在获得了微量元素含量分布的同时,也获得了同位素比值虚拟点,交点年龄为139.2±2.9Ma(MSWD=0.7,n=126),与前人矿床研究结果相一致,验证了此方法的可行性。利用LA-ICP-MS面扫描定年技术不仅可以获得样品元素含量的二维分布图,有利于对样品期次的筛选,剔除包裹体等异常数据;还可以避免点分析中深度分馏和繁复的选点流程及二次分析等步骤,在获得样品元素含量分布的同时获得矿物年龄,为当前矽卡岩型矿床相关的关键金属研究提供了更为便捷的方法。     

西秦岭温泉混浆花岗岩的微量与稀土元素地球化学特征

西秦岭温泉岩体是壳、幔岩浆混浆的产物。寄主岩石高Mo、Sn、Bi、W等高温热液成矿元素及Co、Ni、Cr等亲铁元素,而基性端元的暗色微细粒镁铁质包体及基性岩墙则异常富集轻稀土和Ba、Rb、Sr、Zr、Th、Hf、Nb等大离子亲石元素,贫Co、Ni、Cr等亲铁元素。微量元素的反常分布,指示了两个端元元素演化的显著依从性和交换性。LREE/HREE值在寄主岩石中为10～15,受岩浆混合作用影响在基性端元为9.98～13.5,异常富轻稀土。δEu值及(La/Sm)N、(Gd/Yb)N、(La/Yb)N等比值,显示该岩体为混浆花岗岩。岩浆混合作用强烈的混浆暗色花岗岩具有显著的壳幔过渡性质。     

辽东湾北部浅海沉积物铅地球化学评价

依据对辽东湾北部表层沉积物样品化验结果,分析了工作区浅海铅元素分布特征,并探讨其环境生态效应.结果表明：辽东湾北部浅海沉积物中铅含量13.9×10-6~344×10-6,平均含量28.4×10-6.存在形态主要为残渣态、铁锰氧化态和碳酸盐结合态.分布特点为西高东低,异常突出并且集中分布于锦州湾西南部.异常源主要为锌厂排污,及其他工业生产的污水、烟尘排放所致.该异常区的环境质量属三类及超三类沉积物,面积约12 km2,占研究区总面积的0.36%.通过与生物效应数据库法导出的沉积物质量基准值（ERL/ERM和TEL/PEL）的比较,锦州湾有3件样品铅的潜在生物毒性较大,不利生物效应可能频繁发生.     

脆硫锑铅矿单矿物分析方法

采用加入与试样相当的锑量进行EDTA标准溶液的标定，并以此计算EDTA对铅滴定度的方法，消除了试样中大量锑的干扰，解决了铅结果系统偏低的问题，并拟定了脆硫锑铅矿单矿物分析流程。     

淮北花沟西井田煤中微量元素及其环境意义分析

通过对30件煤样微量元素含量的测定,分煤层、分类型(稀土元素、环境意义微量元素)讨论了煤中微量元素的分布特征。研究发现各样品的稀土元素主要赋存于矿物质中,稀土元素含量均呈正常质量分数水平分布,各煤层的稀土元素分布表现为轻稀土富集、重稀土亏损。受陆源影响的煤,ΣREE含量高,稀土元素主要由陆源物质继承而来。受海水影响的煤,ΣREE含量低,分布模式具有海水性质。形成后受河流冲刷的煤,灰分增加,煤中稀土元素含量增加。该研究成果为煤炭资源的合理开发和利用提供基础资料。     

An Evaluation of Methods for the Chemical Decomposition of Geological Materials for Trace Element Determination using ICP-MS

Complete dissolution is essential to obtain accurate analytical results using ICP-MS. In this study, decomposition techniques (i.e. acid digestions using Savillex Teflon vials, a high pressure digestion system and microwave oven, a combined lithium tetraborate fusion - HF/HNO3 acid decomposition and sodium peroxide sinter) for the total dissolution of different types of geological reference materials have been investigated. Savillex Teflon vial HF/HNO3 digestion is effective for basaltic samples. The high pressure HF/HClO4 digestion (PicoTrace TC-805 digestion system, Bovenden, Germany) allows dissolution of basalts and ironstones. Granites and magnetite-rich samples can be dissolved using a high pressure HF/H₂SO₄ method. Geological samples cannot be effectively attacked by microwave acid digestion. A combined lithium tetraborate fusion - HF/HNO3 acid digestion method allows complete dissolution of many different types of geological materials; however, this method precludes the determination of volatile elements due to the high fusion temperature (1000 °C). A sodium peroxide sinter method at 480 °C has the potential for the rapid determination of Y, Sc and REE in different types of geological materials. However, the lack of ultra-pure reagents precludes the use of lithium tetraborate fusion and sodium peroxide sinter methods for the measurement of geological samples with low trace element abundances.     

草酸铵为基体改进剂石墨炉原子吸收光谱法测定碳酸盐岩中的痕量银

目前采用酸溶分解试样,以硫脲或磷酸氢二铵为基体改进剂,应用石墨炉原子吸收光谱法(GFAAS)可以直接测定各类地质样品中的痕量银;但应用于测定碳酸盐岩中的痕量银时,基体元素钙镁会产生干扰,同时影响石墨管的使用寿命。本文采用盐酸-硝酸-氢氟酸-高氯酸四酸溶样,硝酸提取,以草酸铵(45.5 g/L)作基体改进剂,试液中的钙镁与草酸铵快速反应生成白色沉淀物而分离,并形成了具有挥发性的铵盐介质环境,可显著提高石墨炉的灰化温度进一步除去铵盐介质,从而消除了基体元素的各种影响。本方法操作简单,经国家标准物质验证,其测定值与标准值的相对偏差均小于10%,检出限为0.010μg/g,精密度(RSD,n=12)小于1.0%。本方法不仅分离了干扰基体,而且比前人采用的一米光栅发射光谱法的检出限(0.04μg/g)更低。