Copper Speciation in a Collection of Geochemical Reference Materials Using Sequential Extraction and Evaluation of the Validity Using XANES Spectroscopy

Copper speciation in a collection of Japanese geochemical reference materials (JSO‐1, JLk‐1, JSd‐1, ‐2, ‐3 and ‐4, JMs‐1 and JMs‐2) was achieved by sequential extraction and characterised using X‐ray absorption near‐edge structure spectroscopy. In the first step of the extraction, referred to as the acid fraction, between 1% and 20% total Cu within the reference materials was extracted. Such a result is typically accounted for by absorption of Cu onto clay minerals. However, the presence of Cu sulfate (an oxidation product of chalcopyrite) was observed in some of the stream sediments affected by mining activity (JSd‐2 and JSd‐3) instead. Copper was extracted in the reducible fraction (targeting Fe hydroxide and Mn oxide) (2–49% total Cu). Between 2% and 51% Cu was extracted in the oxidised fraction (targeting sulfides and organic matter). X‐ray absorption near‐edge structure spectroscopy clarified that the reducible fraction consisted of Cu bound to Fe hydroxide, whereas the oxidised fraction was a mixture of Cu bound to humic acid (HA) and Cu sulfide. In the oxidisable fraction, chalcopyrite was the predominant species identified in JSd‐2, and Cu bound to HA was the major species identified in JSO‐1 (a soil sample).     

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.     

新疆乌苏市巴音沟煤层气勘探井护壁堵漏技术

在煤层气勘探井固体岩心钻探施工过程中,遇岩层构造发育、地下水系发达的施工条件,钻进中往往发生钻井多层漏失、护壁困难的情况。因煤层气勘探井对录井工作的特殊要求,护壁堵漏工作的成功与否成为钻探施工的关键。在进行钻井护壁堵漏处理时,因技术方法不得当或未采取正确的计算经常导致护壁堵漏失败,甚至引发重大的钻探事故。通过对工区施工的经验总结,提出了切实可行的护壁堵漏技术措施,为类似地层钻井勘探施工提供借鉴。     

A New Reference Material for Tritium Organic Molecules in Sediment: Results of an International Intercomparison Exercise

Solid matrix ³H reference materials are challenging to prepare given the volatile nature of ³H and are often unrepresentative of the range of ³H forms that may be encountered during routine analysis. As a result, few ³H reference materials are currently available, undermining verification of analytical techniques for environmental ³H measurement. To address this, an International Working Group on Organically‐Bound Tritium Analysis determined to produce a tritium natural matrix reference material (NMRM). The reference material comprises marine sediment blended with sewage sludge contaminated with ³H‐organic species arising from authorised discharges from a radiopharmaceutical manufacturing site. Previous studies have demonstrated that the ³H species have persisted in the environment over three decades providing valuable supporting data to underpin the characterisation of the NMRM. The preparation and characterisation of the NMRM are described along with the subsequent application of the reference material in an international intercomparison exercise involving nineteen laboratories from nine countries. A reference value of 168 ± 22 Bq kg^?1 was derived from the data arising from the proficiency test.     

熔融制样-X射线荧光光谱法测定电气石中12种主次量元素

电气石是一类含硼的铝硅酸盐矿物,化学成分复杂、化学稳定性强,不易湿法分解,B_2O_3含量较高,导致其主次量元素的同时测定存在一定困难。本文采用熔融法制样,建立了X射线荧光光谱法测定电气石Na_2O、MgO、Al_2O_3、SiO_2、P_2O_5、K_2O、CaO、TiO_2、V_2O_5、Cr_2O_3、MnO、TFe_2O_3等主次量元素的分析方法。样品与四硼酸锂-偏硼酸锂-氟化锂(质量比为4.5∶1∶0.4)混合熔剂的稀释比例为1∶10,消除了粒度效应和矿物效应;在缺少电气石标准物质的情况下,选择土壤、水系沉积物及多种类型的地质标准物质绘制校准曲线,利用含量与电气石类似的标准物质验证准确度,测定结果的相对标准偏差小于4.2%。采用所建方法测定四种不同类型电气石实际样品,测定值与经典化学法基本吻合。本方法解决了电气石不易湿法分解和硼的干扰问题,测定结果准确可靠,与其他方法相比操作简便,分析周期短。     

滑坡碎屑化运动物理模型相似材料特性研究

高速远程滑坡物理模型试验中,岩石相似材料的选择是模型试验成功的关键,然而目前滑坡相似材料强度高、难以在缩尺试验中模拟滑坡破碎过程。以重晶石、石英砂为骨料,石膏为胶结剂,羧甲基纤维素钠、甘油、水作为辅助材料,进行可破碎岩石相似材料的配比试验。采用控制变量法研究重晶石与石英砂比例（重石比）、骨料与胶结物比例（骨胶比）、羧甲基纤维素钠含量、拌合水量、甘油含量对相似材料物理力学性质的影响。试验结果表明:所有配比情况下各相似材料物理力学参数的范围分别为单轴抗压强度为0.12～1.47 MPa,弹性模量为25.51～148.12 MPa,黏聚力为1.63～87.39 kPa,内摩擦角为22.70°～35.89°,脆性指标主要分布在0.033～0.145之间;重石比主要控制岩石相似材料的内摩擦角;骨胶比减小,对应的黏聚力和内摩擦角先增大后减小;羧甲基纤维素钠对材料的单轴抗压强度、弹性模量、黏聚力等材料的力学特性以及材料的脆性指标影响均比较大,其中对单轴抗压强度的影响最大。因此,控制羧甲基纤维素钠和拌合水量的含量,并合理调节重石比与骨胶比,在相似比约为1∶600的试验尺度下,最终确定了适用于高速远程滑坡碎屑化过程模拟的低强度高脆性岩石相似材料的配比区间。     

Brittleness index predictions from Lower Barnett Shale well-log data applying an optimized data matching algorithm at various sampling densities

The capability of accurately predicting mineralogical brittleness index(BI)from basic suites of well logs is desir-able as it provides a useful indicator of the fracability of tight formations.Measuring mineralogical components in rocks is expensive and time consuming.However,the basic well log curves are not well correlated with BI so correlation-based,machine-learning methods are not able to derive highly accurate BI predictions using such data.A correlation-free,optimized data-matching algorithm is configured to predict BI on a supervised basis from well log and core data available from two published wells in the Lower Barnett Shale Formation(Texas).This transparent open box(TOB)algorithm matches data records by calculating the sum of squared errors be-tween their variables and selecting the best matches as those with the minimum squared errors.It then applies optimizers to adjust weights applied to individual variable errors to minimize the root mean square error(RMSE)between calculated and predicted(BI).The prediction accuracy achieved by TOB using just five well logs(Gr,pb,Ns,Rs,Dt)to predict BI is dependent on the density of data records sampled.At a sampling density of about one sample per 0.5 ft BI is predicted with RMSE～0.056 and R2～0.790.At a sampling density of about one sample per 0.1 ft BI is predicted with RMSE～0.008 and R2～0.995.Adding a stratigraphic height index as an additional(sixth)input variable method improves BI prediction accuracy to RMSE～0.003 and R2～0.999 for the two wells with only 1 record in 10,000 yielding a BI prediction error of＞±0.1.The model has the potential to be applied in an unsupervised basis to predict BI from basic well log data in surrounding wells lacking mineralogical measure-ments but with similar lithofacies and burial histories.The method could also be extended to predict elastic rock properties in and seismic attributes from wells and seismic data to improve the precision of brittleness index and fracability mapping spatially.     

基于地质建造的西南山区成土母质分类方案——以大凉山区为例

为适应生态地质调查和评价工作对成土母质研究的要求,以四川大凉山区为例,提出基于地质建造的成土母质分类方案,即以地质构造演化和地质建造环境为依据,结合残坡积物的成因类型对成土母质进行分类。大凉山区的成土母质可划分为第四纪冲洪积物、新近纪—第四纪砂泥岩类残坡积物、侏罗纪—白垩纪泥质岩类残坡积物、三叠纪砂泥岩类残坡积物、中生代中酸性岩类残坡积物、二叠纪基性—超基性岩类残坡积物、震旦纪—三叠纪砂泥岩类残坡积物、震旦纪—三叠纪碳酸盐岩类残坡积物、元古宙中酸性岩类残坡积物、元古宙火山碎屑岩类残坡积物、元古宙基性—超基性岩类残坡积物、元古宙变质岩类残坡积物等12类。研究表明,大凉山区成土母质和土壤存在差异性,但同一成土母质上的不同土壤类型具有一定相似的地球化学特征,不同成土母质形成的同一种土壤类型存在较大的地球化学差异。因此,基于地质建造的成土母质分类方案既能有效反映不同构造背景和成岩环境下的成土母质差异,又能有效表征成土母质与其上土壤的内在联系。     

Bed material texture in low order streams on the Queen Charlotte Islands,British Columbia

Low order channels comprise a large proportion of the links of every drainage basin, and are often at the centre of land management concerns. They exhibit hydrological and geomorphological characteristics atypical of higher order links. This paper examines the nature and causes of variations in the bed material texture of two streams on the Queen Charlotte Islands, British Columbia. The extant, functional exponential model is found to be inadequate for explaining observed changes in grain size parameters with distance downstream. Recurrent disruption of sediment transport by large organic debris jams, and the sporadic contamination of the fluvial sediment population by colluvial inputs, preclude the development of longitudinal structure. Rather, grain size varies erratically over short distances. A stochastic model best describes the observed variations, and should be adopted as an alternative to the exponential model in low order links. Characteristic variances are controlled by the degree of hillslope-channel coupling, and the extent and characteristics of non-alluvial storage mechanisms.     

A FINITE ELEMENT DOUBLE POROSITY MODEL FOR HETEROGENEOUS DEFORMABLE POROUS MEDIA

The mathematical base of the double porosity concept, consisting of the continuity and equilibrium equation respectively, is briefly reviewed. A quasi-steady-state transfer function, the so-called leakage term, is used. Important aspects of the developed code, based on the double porosity theory, are presented together with two hypothetical example problems. The resulting trend of the settlements are compared to those from previous work and was found to be significantly different. However, the implications are that the present study exhibits a more realistic prediction for the settlement.