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.     

基于无机成因的油气勘查概念模型(BRCF)

基于超基性岩蛇纹石化成油理论,根据构造条件和沉积条件,提出了石油勘查概念模型——"BRCF"模型:B代表侵入地壳超基性岩;R代表储油层;C代表盖层;F代表深大断裂。运用该模型分析了波斯湾地区油气田和中国典型油气田油气成藏规律,并预测了中国大陆油气勘查靶区。     

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。     

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。     

长江口滨岸湿地无机氮界面交换通量量算

基于3年长江口滨岸湿地沉积物－水界面无机氮季节性交换通量连续实测数据,建立无机氮界面交换通量空间插值模型与量算模型,对无机氮界面交换通量季节性空间分布特征、滨岸湿地不同岸段无机氮季节性界面交换总通量量算等研究。结果表明：修正GIDS插值模型在无机氮界面交换通量空间插值预测过程中精度明显优于IDS方法,而略优于普通Kriging方法;长江口滨岸湿地沉积物－水界面无机氮交换通量空间分布在不同季节表现出复杂的空间分异特征;利用修正GIDS插值模型对长江口滨岸湿地无机氮交换通量进行空间插值过程中,为提高通量量算模型精度,应采用1.2'×1.2'的空间尺度为最佳;长江口滨岸湿地无机氮界面交换总通量量算表明,长江口滨岸湿地在春季向水体释放无机氮,是水体无机氮的释放源,释放量为1.33×10⁴ t,夏季、秋季和冬季表现为净化水体中无机氮,是水体无机氮的吸收汇,分别净化无机氮量为4.36×10⁴ t、6.81×10⁴ t和2.24×10⁴ t,全年总体表现为净化水体中无机氮,净化量为12.1×10⁴ t;长江口多年水体中无机氮通量多项式拟合分析得出,2002~2004年3年长江口水体中无机氮通量平均值为52.6×10⁴ t,滨岸湿地对长江口水体中无机氮的年均净化率达23.0%。     

地磁台站建设中磁测异常现象分析

地磁台建设磁性跟踪测试工作很重要,通过对跟踪磁测中发现的一个异常现象的分析,计算了不同重量、距离的铁磁性物质对磁房建筑场地磁场的影响,讨论了排除施工现场磁性干扰的一些办法,并得出各种重量铁磁性物质与磁房建筑物的安全距离,还讨论了地磁台部分建筑材料的选择问题。