High Precision Sr‐Nd‐Hf‐Pb Isotopic Compositions of USGS Reference Material BCR‐2

The Lamont‐Doherty Earth Observatory radiogenic isotope group has been systematically measuring Sr‐Nd‐Pb‐Hf isotopes of USGS reference material BCR‐2 (Columbia River Basalt 2), as a chemical processing and instrumental quality control monitor for isotopic measurements. BCR‐2 is now a widely used geochemical inter‐laboratory reference material (RM), with its predecessor BCR‐1 no longer available. Recognising that precise and accurate data on RMs is important for ensuring analytical quality and for comparing data between different laboratories, we present a compilation of multiple digestions and analyses made on BCR‐2 during the first author's dissertation research. The best estimates of Sr, Nd and Hf isotope ratios and measurement reproducibilities, after filtering at the 2s level for outliers, were ⁸⁷Sr/⁸⁶Sr = 0.705000 ± 11 (2s, 16 ppm, n = 21, sixteen digestions, one outlier), ¹⁴³Nd/¹⁴⁴Nd = 0.512637 ± 13 (2s, 25 ppm, n = 27, thirteen digestions, one outlier) and ¹⁷⁶Hf/¹⁷⁷Hf = 0.282866 ± 11 (2s, 39 ppm, n = 25, thirteen digestions, no outliers). Mean Nd and Hf values were within error of those reported by Weis et al. (2006, 2007) in their studies of RMs; mean Sr values were just outside the 2s uncertainty range of both laboratories. Moreover, a survey of published Sr‐Nd‐Hf data shows that our results fall within the range of reported values, but with a smaller variability. Our Pb isotope results on acid leached BCR‐2 aliquots (n = 26, twelve digestions, two outliers) were ²⁰⁶Pb/²⁰⁴Pb = 18.8029 ± 10 (2s, 55 ppm), ²⁰⁷Pb/²⁰⁴Pb = 15.6239 ± 8 (2s, 52 ppm), ²⁰⁸Pb/²⁰⁴Pb = 38.8287 ± 25 (2s, 63 ppm). We confirm that unleached BCR‐2 powder is contaminated with Pb, and that sufficient leaching prior to digestion is required to achieve accurate values for the uncontaminated Pb isotopic compositions.     

An Investigation of Digestion Methods for Trace Elements in Bauxite and Their Determination in Ten Bauxite Reference Materials Using Inductively Coupled Plasma‐Mass Spectrometry

Trace elements from samples of bauxite deposits can provide useful information relevant to the exploration of the ore‐forming process. Sample digestion is a fundamental and critical stage in the process of geochemical analysis, which enables the acquisition of accurate trace element data by ICP‐MS. However, the conventional bomb digestion method with HF/HNO₃ results in a significant loss of rare earth elements (REEs) due to the formation of insoluble AlF₃ precipitates during the digestion of bauxite samples. In this study, the digestion capability of the following methods was investigated: (a) ‘Mg‐addition’ bomb digestion, (b) NH₄HF₂ open vessel digestion and (c) NH₄F open vessel digestion. ‘Mg‐addition’ bomb digestion can effectively suppress the formation of AlF₃ and simultaneously ensure the complete decomposition of resistant minerals in bauxite samples. The addition of MgO to the bauxite samples resulted in (Mg + Ca)/Al ratios ≥ 1. However, adding a large amount of MgO leads to significant blank contamination for some transition elements (V, Cr, Ni and Zn). The NH₄HF₂ or NH₄F open vessel digestion methods can also completely digest resistant minerals in bauxite samples in a short period of time (5 hr). Unlike conventional bomb digestion with HF/HNO₃, the white precipitates and the semi‐transparent gels present in the NH₄HF₂ and NH₄F digestion methods could be efficiently dissolved by evaporation with HClO₄. Based on these three optimised digestion methods, thirty‐seven trace elements including REEs in ten bauxite reference materials (RMs) were determined by ICP‐MS. The data obtained showed excellent inter‐method reproducibility (agreement within 5% for REEs). The relative standard deviation (% RSD) for most elements was < 6%. The concentrations of trace elements in the ten bauxite RMs showed agreement with the limited certified (Li, V, Cr, Cu, Zn, Ga, Sr, Zr and Pb) and information values (Co, Ba, Ce and Hf) available. New trace element data for the ten RMs are provided, some of which for the first time.     

Production and Certification of Synthetic Selenium Isotopic Reference Materials

Due to intensive research into selenium isotopes in recent years, the increasing requirement for reliable and comparable measurement results has created a strong demand for selenium isotopic certified reference materials (iCRM) that were previously not available. To address this, eleven selenium iCRMs were developed, including ten synthetic iCRMs (GBW 04447–GBW 04456) and one natural iCRM (GBW 04457). The synthetic iCRMs were prepared with ⁷⁶Se, ⁷⁸Se, ⁸⁰Se and ⁸²Se solutions and a natural selenium solution; the natural iCRM was prepared with highly pure selenium material. The property values of isotope ratios in these iCRMs were certified by calibrated mass spectrometry with a collision cell multi‐collector ICP‐MS. The mass discrimination effect of the instrument was corrected with corresponding ⁷⁸Se/⁷⁶Se isotope mixtures and ⁸²Se/⁷⁶Se isotope mixtures, which were gravimetrically prepared with purified, isotopically enriched selenium materials. Homogeneity and stability tests were performed, and no significant influences were found. The uncertainty of the property values of the iCRMs was evaluated according to the Guide to the Expression of Uncertainty in Measurement (GUM) of ISO/BIPM and ISO Guide 35. The δ^82/76Se value of GBW 04457 relative to NIST SRM 3149 was also calculated. These iCRMs are intended for use in calibration of instruments and evaluation of methods for the determination of selenium isotope ratios.     

冻融循环对不同孔隙率页岩相似材料影响的试验研究

基于地质力学模型试验的相似理论,针对寒区岩体工程,分别制作了5种不同孔隙率的页岩相似材料,进行冻融循环试验,探究不同孔隙率的页岩相似材料在冻融前后,其主要物理力学参数的变化规律。试验研究表明：在冻融循环后,页岩相似材料的单轴抗压强度、三轴抗压强度、弹性模量、粘聚力、内摩擦角有不同程度的减小,孔隙率、泊松比有不同程度的增大。页岩相似材料的物理力学参数受冻融循环的影响随孔隙率的增大先增大后减小,孔隙率处于9.4%~13.6%时,受冻融循环影响最大;孔隙率处于5.8%~9.4%时,受冻融循环的影响随孔隙率的增大有增大的趋势;孔隙率处于13.9%~19.1%时,受冻融循环的影响随孔隙率的增大有减小的趋势。研究结果可以为西部寒区的岩土工程建设和减灾提供相关的科学依据。     

滇西芦子园远程矽卡岩Pb-Zn-Fe(Cu)多金属矿床流体包裹体初探及矿床成因探讨

滇西镇康芦子园是"三江"成矿带保山地块内迄今发现的唯一超大型Pb-Zn-Fe(Cu)多金属矿床,是区内系列同类层控热液铅锌矿床的典型代表。矿体呈似层状、脉状及透镜状产于寒武系碳酸盐岩建造的矽卡岩和大理岩层间破碎带,矿石构造以条带状、浸染状和脉状-网脉状为主要特征;围岩蚀变复杂、分带明显,由下至上依次为石榴子石-透辉石-透闪石-阳起石化带→绿泥石-绿帘石-阳起石-蔷薇辉石化带→碳酸盐-大理岩化带。矿床成矿流体从早期到晚期经历了多个矿化阶段。本文选取了该矿床早矽卡岩阶段、晚矽卡岩阶段、石英硫化物阶段和石英碳酸盐阶段的多种脉石矿物及闪锌矿进行了系统的流体包裹体研究。结果显示,早矽卡岩阶段发育微溶CO_2富液相和纯液相水溶液包裹体,并含大量K~+、Na~+、Ca~(2+)、F~-和Cl~-和少量SO_4~(2-),气相成分主要为H_2O、CO_2及少量CH_4和N_2,包裹体均一温度为233.6~315.6℃,盐度为10.6%~17.6%NaCleqv;晚矽卡岩阶段发育含CO_2和子矿物三相包裹体,均一温度214.9~388.0℃,盐度5.9%~16.4%NaCleqv;石英硫化物阶段发育含CO_2的水溶液包裹体,气相成分为CH_4、H_2O和少量CO_2,均一温度150.0~285.0℃,盐度为2.5%~13.8%NaCleqv;石英碳酸盐阶段为单一成分的水溶液包裹体,均一温度为105.0~187.5℃,盐度为0.5%~12.3%NaCleqv。结合H-O同位素研究表明,成矿流体最初来源于具中高温、中高盐度、高K、Na,富CO_2、Cl、F等特征的深部岩浆热液,在石英硫化物阶段开始有大气降水混入,演化为中阶段中低温、低盐度、贫CO_2的热液流体,至成矿晚阶段转化为以大气降水占主导。该矿床成矿环境的改变、流体混合以及流体的沸腾作用可能是导致成矿物质富集沉淀的重要机制。综合矿床地质特征、成矿流体包裹体和HO同位素研究认为,该矿床为与陆陆碰撞造山和深部隐伏岩体有关的远程矽卡岩成矿系统。     

四川盆地下古生界硅质页岩层系中硅质来源及其对有机质保存的影响初探

四川盆地下古生界两套硅质页岩层系是其重要的页岩气产层,五峰组—龙马溪组硅质含量与TOC及含气量呈正相关性,暗示硅质矿物对该地区页岩气的生成具有重要意义。但硅质来源复杂,且存在后期硅质流体的注入。因此,本文在总结前人的研究成果基础上,对四川盆地寒武系底部硅质岩系与五峰组—龙马溪组硅质岩系的硅质特征进行了详细的岩石学分析,揭示了3种硅质来源特征：①同沉积无机硅质流体;②生物硅;③后期无机硅质流体。其中寒武系底部以同沉积无机硅质流体与生物硅来源为主,同沉积硅质流体导致有机质快速石化埋藏,有机质内部结构及形态保存较好;五峰组—龙马溪组硅质来源以后期无机硅质流体与生物硅来源为主,有机质在保存过程中受硅质流体的影响很小,有机质腐泥化作用充分,内部结构和形态多数保存较差。该研究初步揭示了两套页岩层系的硅质发育岩石学特征,及其对有机质保存的影响,期望能为四川盆地两套页岩气储层差异性提供新的思路与基础地质数据。     

水基钻井液防塌封堵材料封堵特性实验研究

提高钻井液封堵能力是有效解决硬脆性页岩、煤层等复杂地层井壁失稳的主要技术手段。本文以在一定温度、压力条件下30 min的滤失量为评价标准,对几种封堵材料的封堵特性进行了实验研究。结果表明：除超细碳酸钙外,其他材料随着加量的增加,封堵效果越来越好;乳化沥青、乳化石蜡和油溶性酚醛树脂随着温度的升高,封堵效果变差,而聚乙二醇和聚酯先变差然后又有一定程度的恢复;聚酯和超细碳酸钙能够快速封堵微裂缝;几种封堵剂均对钻井液的流变性能有较明显的影响。对各封堵材料的封堵机理分析表明：不同的封堵材料具有不同的封堵特性,分别适应不同的温度、压力条件。只有根据井下实际情况,有针对性地选择与之相适应的封堵材料,才能有效提高水基钻井液的封堵能力。     

深孔纳米复合水泥基护壁堵漏材料研究

本文围绕深部钻探技术中护壁堵漏材料性能的实际需要,研制了一种深孔纳米复合水泥基护壁堵漏新材料。首先,通过分析100 ℃条件下2种水泥材料的基本性能,确定了G级油井水泥为胶凝材料;然后,基于深孔钻探护壁堵漏材料的性能缺陷,采用特种纤维、纳米材料针对性改善水泥基浆液的力学性能,并优选早强剂（ZQ）、减水剂（GB）作为外加剂进行正交实验,进而研制出纳米复合水泥基护壁堵漏材料优化配方;最后,对其主要性能进行分析评价。结果表明该材料在深孔钻探中浆液流动性好,力学性能优异,综合性能满足深孔钻探护壁堵漏需求。     

含部分晶须的钛酸锂的制备及其性能表征

L i4T i5O12是一种循环性能好、有很好的充放电平台、理论比容量较大、不与电解液反应的新型负极材料,研究探索以偏钛酸和碳酸锂为主要原料制备含部分晶须的尖晶石型晶型L i4T i5O12的一种方法。通过此工艺在1 000℃煅烧8 h后在样品中约20%的晶须出现,晶须的直径≤0.5μm,晶须的长度约为7μm。     

四川甘洛铅锌矿集区闪锌矿Rb-Sr等时线年龄及其地质意义

四川甘洛铅锌矿集区位于扬子地块西南缘的川滇黔铅锌成矿带北段,是四川主要的铅锌产地,具有重要经济价值。为研究该矿集区铅锌成矿时代、成矿大地构造背景和成矿机制,以支撑区域找矿勘查,在区内选择赤普和尔呷地吉两个典型铅锌矿床开展闪锌矿Rb-Sr同位素体系研究,获得Rb-Sr等时线年龄246 ± 17 Ma（MSWD= 2.3）,表明区内铅锌矿化作用发生于早三叠世,与古特提斯洋闭合时限吻合;闪锌矿(87Sr/86Sr)i值变化于0.71061~0.71393,高于幔源87Sr/86Sr值0.70355及峨眉山玄武岩87Sr /86Sr值0.704979~0.706938,低于基底岩石87Sr /86Sr值0.7243~0.7288,暗示成矿物质主要来源于地壳。综合前人研究,认为在古特提斯洋闭合背景下,强烈造山运动诱发盆地卤水深循环并萃取基底地层中的成矿物质,在峨眉山玄武岩岩浆活动的热动力条件下,含矿流体沿马拉哈断裂进一步迁移沉淀形成了赤普和尔呷地吉铅锌矿床。马拉哈深大断裂及造山作用派生的层间或断层破碎带、碳酸盐岩地层是甘洛地区主要的控矿要素。