A comparison of black claystones,lignites and dump materials from the Maritsa Iztok Coal Basin,Bulgaria, using organic geochemical proxies

Geochemical analysis of dump materials from the opencast Maritsa Iztok mines, Bulgaria, was carried out based on biomarker assemblages of hydrocarbon fractions. Organic matter (OM) and secondary transformations in three representative samples (massive black claystones and materials from the Iztok and Staroselets dump sites) were studied using geochemical proxies.A number of differences were recognised in the respective OM compositions of the samples compared to both published data and between the individual dump samples themselves. The ОM of the studied samples was found to be polar, but also contains some apolar compounds. It consists mainly of resins and asphalthenes. Claystone OM is of the dispersed type, with intense oxidative-reductive interactions in a lacustrine environment resulting in its transformation into an inert material. Dump sample kerogen is of Type II and mixed Type II/III. In all samples, “odd” numbered n-alkanes are found in higher amounts. Diterpenoids (С₁₉, С₂₀) with pimarane, abietane and phyllocladane skeletons are preponderant. Tri- and tetracyclic terpenoids and steranes have been identified in the black claystones OM only. Hopanes are present in low amounts in extractable OM from all three samples. Biomarkers indicate that black claystone OM is formed from aqueous flora, with a minor supply of gymnosperms (mainly G. Sequoia). Iztok Dump OM is structured by higher plants with an aqueous vegetation input. The Staroselets Dump OM formation is assigned to an active microbial reworking of aqueous vegetation and bacteria with a minor coniferous supply. Different geochemical parameters admit anoxic stratified bottom waters for the black claystones with an addition of deep water stagnation for Staroselets sample in a Maritsa Iztok Basin (MIB) aqueous environment.An attempt was also made to track the effect of secondary processes (oxidation, destruction, dearomatisation), temperature, water drainage and wash-out on dump materials. Leaching and weak degradation processes in the MIB dump environment are likely for a time span of ca. 40–50 years, considering the low percentage of short-chain n-alkanes, long-chain prevalence and low Pr/nC₁₇ and Ph/nC₁₈ ratios, with the Iztok Dump sample experiencing more advanced transformations.     

Recognition features of felsic pyroclastics of Serra do Tombo formation,Minas Gerais,Brazil

In this contribution we report a study of poorly exposed, rhyodacitic welded-ignimbrite deposit from Minas Gerais. A petrographic study of textures indicate high temperature of emplacement. Key features include eutaxitic texture, flattened and agglutinated lapilli and glass menisci. Most of the feldspar minerals and glass are extensively altered to clay minerals, which pseudomorph the original volcanic textures. Glass menisci and spherules suggest a possible process of liquid immiscibility. Immobile trace element distribution indicates a possible link with other post-Palaeozoic felsic volcanic rocks in Brazil, a magmatism interpreted as due to basaltic underplating and partial melting of a hydrous continental crust. A peculiar feature is a high Light REE/Heavy REE ratio. Depletion in heavy rare earth elements is possibly due to a residual HREE-bearing phase in the source. The geologic context of these rocks suggests a Lower Cretaceous age and a tectonic relationship with a continental rifting event.     

扬子西缘乡城-丽江结合带燕山期斑岩Mo多金属矿床成矿系统

位于扬子陆块西缘与西南三江造山带结合部位的乡城-丽江地区,北起四川乡城经云南格咱南至丽江地区,在印支期斑岩铜矿带上新发现叠加了燕山期斑岩Mo多金属成矿作用,形成乡城-丽江斑岩Mo矿带。受印支期古特提斯洋盆闭合后地壳缩短与加厚的影响,燕山晚期下地壳发生拆沉作用,导致后碰撞型花岗质岩浆侵位,发育了Mo多金属成矿作用,并构成斑岩成矿系统。岩石地球化学特征表明,燕山晚期含矿斑岩具高硅(SiO_2=66.29%~79.36%)、高碱(K_2O+Na_2O=5.07%~9.24%)、富钾(K_2O/Na_2O=0.71~2.13)的特点,属于高钾钙碱性岩石系列。岩石富集轻稀土元素(LREE),具有负δEu异常;微量元素具富集大离子亲石元素K、U、Th、Rb,亏损高场强元素Nb、Ta、P、Ti的特征;大离子亲石元素的富集和Nb、Ta等高场强元素的亏损,表明形成这些岩体的岩浆主要来自地壳,具有造山带花岗岩的地球化学特征。区内代表性含矿斑岩相似的地球化学组成及分布特征表明,乡城-丽江结合带燕山晚期的成矿斑岩是由同源岩浆分异演化而来。成矿系统的分析表明,燕山晚期主要含矿斑岩成矿物质以壳源为主,但具有少量地幔物质的加入,成岩成矿物质来源具有相似或一致的源区特征。在成矿元素的组合上,由成矿斑岩体向外带表现出W、Mo→W、Mo、Cu→Pb、Zn、Ag的演化趋势。研究表明,本区燕山晚期花岗岩浆的侵入及Mo多金属成矿作用并不是独立或个别的成矿事件,而是纵跨义敦岛弧、甘孜-理塘结合带及扬子西缘的带状成矿活动,属于区内与燕山晚期岩浆侵入作用相关的统一斑岩成矿系统。     

Molybdenum Mass Fractions and Isotopic Compositions of International Geological Reference Materials

The double‐spike method with multi‐collector inductively coupled plasma‐mass spectrometry was used to measure the Mo mass fractions and isotopic compositions of a set of geological reference materials including the mineral molybdenite, seawater, coral, as well as igneous and sedimentary rocks. The long‐term reproducibility of the Mo isotopic measurements, based on two‐year analyses of NIST SRM 3134 reference solutions and seawater samples, was ≤ 0.07‰ (two standard deviations, 2s, n = 167) for δ^98/95Mo. Accuracy was evaluated by analyses of Atlantic seawater, which yielded a mean δ^98/95Mo of 2.03 ± 0.06‰ (2s, n = 30, relative to NIST SRM 3134 = 0‰) and mass fraction of 0.0104 ± 0.0006 μg g^?1 (2s, n = 30), which is indistinguishable from seawater samples taken world‐wide and measured in other laboratories. The comprehensive data set presented in this study serves as a reference for quality assurance and interlaboratory comparison of high‐precision Mo mass fractions and isotopic compositions.     

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。     

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。