Reference Values Following ISO Guidelines for Frequently Requested Rock Reference Materials

We present new reference values for nineteen USGS, GSJ and GIT‐IWG rock reference materials that belong to the most accessed samples of the GeoReM database. The determination of the reference values and their uncertainties at the 95% confidence level follows as closely as possible ISO guidelines and the Certification Protocol of the International Association of Geoanalysts. We used analytical data obtained by the state‐of‐the‐art techniques published mainly in the last 20 years and available in GeoReM. The data are grouped into four categories of different levels of metrological confidence, starting with isotope dilution mass spectrometry as a primary method. Data quality was checked by careful investigation of analytical procedures and by the application of the Horwitz function. As a result, we assign a new and more reliable set of reference values and respective uncertainties for major, minor and a large group of trace elements of the nineteen investigated rock reference materials.     

On the Evaluation of Rock Reference Materials -A “Five-Mode’ Approach*

The concentrations of numerous constituents must be evaluated in rock samples if they are to be used as reference materials. Because of varying degrees of specialized skills in earth-science laboratories, the collaboration of many institutions is required in order to establish reliable values. Analytical data reported in such operations are highly variable. The number of constituents reported per sample varies from one laboratory to another. The number of values reported varies from one constituent to another. The reported values for each constituent are generally incoherent, often displaying skewed distributions. The problem is then how to deduce the most probably “true’ concentration for each constituent. Various computation schemes, based on medians, means and related measures, are discussed. A new scheme, involving a combination of modes, is proposed.     

Preparation and Characterisation of Two Geochemical Reference Materials: DG‐H (Granite) and AM‐H (Amphibolite) from the Himalayan Orogenic Belt

Two geochemical reference materials of Himalayan origin named DG‐H (a granite) and AM‐H (an amphibolite) prepared by the Wadia Institute of Himalayan Geology Dehradun are described. Both samples were collected from the NW Himachal Himalaya in India. With the participation of analysts from more than forty international laboratories, element determination data collected during the past 10 years for characterisation of the samples was processed to assign working values using statistical procedures in use for this purpose. Earlier work published on these samples is incorporated in the present communication making it an updated document. The typical chemical and petrological characteristics of these two samples may prove useful for method validation and calibration of analytical instruments used for analysing similar rock types, and for widening the analytical range of several analytical methods used for geochemical analysis.     

便携式X射线荧光光谱仪在岩石样品分析中的应用研究

便携式X射线荧光光谱仪(PXRF)因具有快速、无损检测元素含量的能力,通常被用于野外或实验室地质样品的元素含量检测工作中,对于大多数地质样品,在2 min内就能够获得几十种元素的半定量-定量分析结果。但在实际应用中,被测样品的表面平整度、样品中物质的均一性和施测时间等因素都会影响元素分析结果。为了进一步了解样品类型和分析测试方法等因素对元素分析的具体影响,本文对比了PXRF与实验室分析结果、岩石和粉末样品PXRF分析结果、不同检测时间所得PXRF分析结果的关系,在不损失过多分析精度的前提下提出了通过PXRF降低勘查成本、提高工作效率的方案。结果表明:用PXRF直接分析岩石样品时,大多数元素的分析结果可靠性较差,尤其是成矿预测工作中常用的Cu、Pb、Zn、As和Ni等元素;粉末样品的PXRF分析结果与实验室分析结果具有较好的相关性,表明对岩石样品进行粉碎处理能够明显改善PXRF分析质量;元素种类不同,岩石和粉末样品PXRF测量结果的相关性也不同。因此,在实际工作中可以根据感兴趣的目标元素确定是否需要对岩石样品进行粉碎制样处理;检测时间对元素含量分析结果没有明显影响,对于特定元素,如果能够在较短时间内获得其含量信息,则无需增加检测时间。     

全岩热模拟新方法及其在气源岩评价中的应用

由中国石油勘探开发研究院廊坊分院建立的全岩热模拟仪器分析方法是采用岩心样品(岩石颗粒0.5～2 mm)来模拟烃类生成的一项实验新技术.该方法模拟结果表明:(1)不同类型样品单位质量岩石的产气率与传统的加水温压模拟法结果具有可比性;(2)能够反映源岩在不同演化阶段的产气量;(3)比常规的有机碳评价方法能更准确地反映源岩在不同演化阶段的产气潜力.(4)全岩热模拟新方法经济、简便、分析周期短,可以用于大量常规样品分析,是判识有效气源岩及定量评价的一种快速、可靠的方法,在油气勘探过程中,将对烃源岩的评价发挥重要作用。     

Microspectrofluorescence measurements of coals and petroleum source rocks

Good, reproducible microspectrofluorescence data, similar to published fluorescence trends, are obtainable from samples of coals and petroleum source rocks (shales). These data are reproducible when measured by different operators, different instruments, or at different times (for example, the remeasurement of samples several months apart). These fluorescence data are used to predict maturity or rank to within about 0.10% R₀ (mean vitrinite reflectance, oil immersion). Commercially available computerized fluorescence equipment, with customized software and specific hardware mod modifications, makes the acquisition of fluorescence data feasible. Fluorescence can be used for measuring low-maturity samples, in which the measurement of vitrinite reflectance is difficult. Source rocks from oil-rich basins frequently do not contain enough particles of vitrinite for a reflectance determination, but they may contain fluorescing particles which can be measured. Although the results from only two different kinds of fluorescence equipment (Zeiss Zonax and Vickers Gamma-Scientific) are discussed, any instrument with equivalent stability and sensitivity can be used to attain reproducible and accurate fluorescence data.We propose the use of the term “R_F” to report fluorescence data in equivalent vitrinite reflectance values. Although the principles and techniques of measuring fluorescence were introduced several years ago, much work remains to establish standardized methods of maesuring as well as data evaluation. The current method of reporting fluorescence data in terms of spectral characteristics (such as the wavelength of maximum intensity or wavelength ratios) is awkward to use and difficult to compare results from various laboratories. R_F values convey rank or maturation meaning and can be easily compared among laboratories.Data from fluorescing grains in both coal and petroleum source rock samples are given in this study. Polished samples of coal, this sections, and kerogen strewn slides of source rocks are measured. Spectral data are evaluated by four parameters: the wavelength of maximum intensity (Peak), the red/green ratio (Q), the coordinates of a metric color system (CIE), and the relative intensity at 490 nm. The measurement of intensity, reported in units of radiance, is possible with the Vickers Gamma-Scientific instrument. Measuring both fluorescent colors (R_F) and intensities may help explain some of the relationships among organic particles, maturation, and hydrocarbon generation.     

Software Dedicated for the Curation of Geochemical Data Sets in Analytical Laboratories

Software designed for analytical laboratories to guarantee traceability and accessibility of rocks with their geochemical properties has been developed. The software documents the sample origin, current sample location and the location of any sample subsets (e.g., thin sections, solutions, etc.), and archives all associated geochemical data sets. The software can be installed on a personal computer so is available for use in any laboratory and allows curation before and after publication. The software will be of use in integrating and sharing geological reference materials within and among institutes. In this article, the system design and implementation are detailed. All source codes for the software are available at http://dream.misasa.okayama-u.ac.jp/ .     

Certificate of Analysis of the Reference Material BRP-1 (Basalt Ribeirão Preto)

Reference materials (RM) are essential to achieve traceability of measurements. Specific uses of RM in analytical laboratories are the validation of methods, the calibration of instruments, the quality control and the demonstration of proficiency. This paper describes the certification of a new geochemical reference material, named BRP-1 (Basalt Ribeirão Preto), and acts as the certificate of analysis for this RM. The rock sample was crushed and pulverised at the USGS (Denver, USA), homogenised and split into 1920 bottles, with 55 g each. BRP-1 was transported back to Brazil and the homogeneity between and within bottles was assessed to demonstrate sufficient homogeneity for certification. The chemical characterisation was performed by twenty-five laboratories. Each laboratory received two bottles of BRP-1 and one of BCR-2 (Basalt Columbia River) used for quality control (QC). Reference values and uncertainties were calculated for forty-four constituents of BRP-1, following ISO Guide 35 recommendations and the IAG Protocol. The calculation of each reference value included data of proven traceability from at least ten laboratories using two or more analytical techniques and the uncertainties combines the characterisation and between bottle homogeneity contributions.     

地质调查通用标准物质及标准方法信息系统

根据各地质实验室的特点和质量管理规范需求，结合实验室认可及检测实验室能力的需要，建立了地质调查通用标准物质和标准方法信息系统。该系统不仅能提供地质调查通用标准物质、标准方法的基本信息，还增加了与能力分析相关的检测参数信息，并实现了标准信息网上查询和维护管理。该系统适用于地质调查实验室的质量管理系统。     

NEW REFERENCE SAMPLES OF MAGMATIC ROCKS: QUARTZ DIORITE SKD-1 AND SVIATONOSSITE SSV-1

The preparation and study of the two rock reference samples, Quartz Diorite SKD-1 and Sviatonossite SSv-1, are described, along with mineralogical and petrographic features. After its homogeneity studies, the two samples were analysed by seventy-five former USSR laboratories in the framework of an interlaboratory analytical program. The two samples have been certified respectively for 41 and 39 major, minor and trace elements; additionally, values are proposed for about 20 trace elements. The compiled data on the two samples are presented as an Appendix. Both the samples, processed in about 280 kg, form now part of the set of eight magmatic rock reference samples prepared by the Institute of Geochemistry in Irkutsk.     

Inter-comparison exercises on dissolved gases for groundwater dating – (1) Goals of the exercise and site choice,validation of the sampling strategy

Two international inter-comparison exercises devoted to dissolved gases and isotope analyses in groundwater, used as tools for groundwater dating were organized in 2012 in France (IDES – Université Paris Sud – CNRS and OSUR – Université Rennes 1 – CNRS). The goal was to compare sampling and analytical protocols through results obtained by the community of groundwater dating laboratories. The two exercises were: GDAT1 on three supply boreholes in a homogeneous sand-aquifer of Fontainebleau (Paris Basin, France) and GDAT2 on two supply boreholes (shallow and deep) in a fractured rock aquifer in French Brittany. This two-step exercise is the first exercise which included a large number of gases and isotopes usually used in groundwater as dating tools and also permit to discuss the uncertainties related to sampling protocols issuing from each laboratory methods. The two tests allowed 31 laboratories from 14 countries to compare their protocols for both sampling and analyses. This paper presents the participants and parameters measured, and focuses on the validation of the sampling strategy. Two laboratories analyzed CFC and SF₆ samples collected at regular intervals during the sampling operations in order to verify water homogeneity. The results obtained by the two “reference” laboratories along with monitoring of field parameters showed no clear trend of gas concentration or physic-chemical properties. It can be concluded that the pumped groundwater composition remained constant during sampling. This study also shows the potential for relatively constant pumped groundwater composition from a specific well despite the complexity and/or mixing processes that may occur at a larger scale in the aquifer.     

http://www.sciencedirect.com/science/article/pii/S1674987111000168

Actual granitoid analytical data of 767 composited samples are presented here.The data source is 6080 samples collected mainly from 750 large- to middle-sized granitoid bodies across China. Data from the composited samples,which includes that of 70 elements,is analyzed according to geological age—Archeozoic(Ar),Proterozoic(Pt),Eopaleozoic(Pz_1),Neopaleozoic(Pz_2),Mesozoic(Mz), and Cenozoic(Cz)—and three major compositional varieties,e.g.alkali-feldspar granite,syenogranite and adamellite.Petrochemical pa...     

U‐Pb Detrital Zircon Analysis – Results of an Inter‐laboratory Comparison

Inter‐laboratory comparison of laser ablation ICP‐MS and SIMS U‐Pb dating of synthetic detrital zircon samples provides an insight into the state‐of‐the art of sedimentary provenance studies. Here, we report results obtained from ten laboratories that routinely perform this type of work. The achieved level of bias was mostly within ± 2% relative to the ID‐TIMS U‐Pb ages of zircons in the detrital sample, and the variation is likely to be attributed to variable Pb/U elemental fractionation due to zircon matrix differences between the samples and the reference materials used for standardisation. It has been determined that ~ 5% age difference between adjacent age peaks is currently at the limit of what can be routinely resolved by the in situ dating of detrital zircon samples. Precision of individual zircon age determination mostly reflects the data reduction and procedures of measurement uncertainty propagation, and it is largely independent of the instrumentation, analytical technique and reference samples used for standardisation. All laboratories showed a bias towards selection of larger zircon grains for analysis. The experiment confirms the previously published estimates of the minimum number of grains that have to be analysed in order to detect minor zircon age populations in detrital samples.     

U.S.G.5. II Revisited*

Based on the most recent compilation of analytical data, a new set of “usable values” is calculated for six of the best known silicate rock reference samples produced by the U.S. Geological Survey. The latest version of the “best laboratories” method is described and results are compared with other recently published values.     

Direct major- and trace-element analyses of rock varnish by high resolution laser ablation inductively-coupled plasma mass spectrometry (LA-ICPMS)

Laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) was used to determine major and trace element concentrations in rock varnish samples from the Lahontan Range, near Fallon, NV and from a remote wilderness area near the San Juan River, in southeastern Utah. The data indicate that rapid LA-ICPMS analyses provide ample analytical resolution for semi-quantitative compositional determinations of both trace and major elements in the varnish despite the presence of a rock substrate component in most analyses. The overall major element contents of rock varnish from the two localities are grossly similar to rock varnish from other locations analyzed by solution ICPMS, electron microprobe, and energy dispersive scanning electron microscopy (SEM). Differences between microprobe and LA-ICPMS analyses may stem from different sampling scales and different degrees of substrate involvement. It was possible to detect significant variations in trace element contents in the rock varnish samples. The Lahontan Range is situated within a belt of W mineralization, and varnish from that locality contained significantly higher W and Mo contents than varnish from localities outside the W belt. Lead, Tl, Bi, Cd and As contents of varnish-coated pebbles from near the San Juan River in southeastern Utah, varied by an order of magnitude as a function of the position of the sampling site on the pebble. Elevated heavy element contents on the skyward-facing varnish surfaces indicate that heavy elements may be preferentially scavenged at the locations most likely to receive direct inputs of atmospherically-deposited airborne particulates. The source of metal-rich airborne particulates, in this case, is probably any one of several large coal-fired power plants in the Four Corners region, proximal to the San Juan study area. These patterns indicate that rock varnish chemistry is influenced by atmospherically-derived fluxes of both dissolved and particulate constituents, and that rock varnish can be used as a passive environmental indicator for a wide variety of elements, in much the same manner as moss and lichens.     

Report (1980) on Three GIT-IWG Rock Reference Samples: Anorthosite from Greenland, AN-G; Basalte d'Essey-la-Côte, BE-N; Granite de Beauvoir, MA-N

Three rock reference samples, Anorthosite AN-G, Basalt BE-N and Granite MA-N were analysed for their chemical composition by 122 laboratories belonging to the International Working Group "Analytical Standards of Minerals, Ores and Rocks" (IWG). 243 analysts took part in this first collaborative study which lasted only nine months, from June 1979 to March 1980. Despite this very short period, it has been possible to harvest over 6000 units of analytical data on major, minor and 53 trace elements. This excellent performance of the IWG members has rendered possible the chemical characterization of the three samples for not only the usual major and minor elements but also for 30 trace elements. This first study by the IWG Members demonstrates well their immense analytical potential and is exemplary in many respects.     

Application of light hydrocarbons (C4–C13) to oil/source rock correlations:: a study of the light hydrocarbon compositions of source rocks and test fluids from offshore Mid-Norway

Relatively little work has been published on the correlation between the light hydrocarbon distributions in reservoir fluids and their proposed source rocks [Philippi, G. T. (1981)]. The aim of our work was to study this relationship in detail for samples from Mid-Norway. The main source rocks offshore Mid-Norway are the marine shales of the Late Jurassic Spekk Formation and the coals and paralic shales of the Early Jurassic Åre Formation. Reliable light hydrocarbon (C₄–C₁₃) data for source rock samples were acquired by thermal extraction-GC of the source rocks. Of these, notably the hydrocarbons in the C₆–C₈ range (routinely measured in test fluids) were used to discriminate between the Spekk and Åre Formation samples. A total of twenty-six samples from the Spekk Formation and twenty-four samples from the Åre Formation at different maturity levels and facies were analyzed. In general, the two source rock types differ in their light hydrocarbon composition by the presence of relatively more aromatics and cyclohexanes in the Åre samples, while the Spekk samples are richer in cyclopentanes and acyclic hydrocarbons. We show that source rock facies is a more important indicator of light hydrocarbon composition than maturity variation. Differences in the chemical composition, which can be used to discriminate between the two source rocks, were supported by differences in the carbon isotope composition of individual components of the same fraction, as determined by GHM-IR-MS analysis of eleven samples. Further, the light hydrocarbon compositions of reservoir fluids (oils and condensates) were compared with those for the source rock(s). Sixty-six gas chromatograms of oils and condensates, representing most of the known petroleum accumulations in Mid-Norway, were collected. Of these, five oil samples were selected for detailed isotopic analysis of individual components (GC-IR-MS). When using a classification scheme based on data from sediment samples, data for the light hydrocarbon fraction of oils and condensates indicate that the Spekk Formation is the dominant source for most of the fields from Mid-Norway, with a significant contribution from the Åre Formation being detected principally in one field. Differences in the chemical composition of the C₆–C₈ fractions were supported by differences in the carbon isotope composition of individual components, which also discriminate between the oils. Although the classification diagrams used in this study are based on source rock data from Mid-Norway, the method can be applied to other areas, providing that the diagrams are calibrated with source rock data from the area of interest.     

Report (1968–1978) on Two Mica Reference Samples: Biotite Mica-Fe and Phlogopite Mica-Mg

Since 1967–68, two mica reference samples, Biotite Mica-Fe and Phlogopite Mica-Mg, were made available to several geochemical laboratories. The analytical data reported during the past ten years by 142 geoanalysts belonging to 74 international laboratories are presented and assessed for deriving preferred values. Reaomrmended or proposed values are assigned for major, minor and several trace elements. The biotite Mica-Fe is better characterized for its chemical composition than the Phlogopite Mica-Mg. Both the samples are also proposed as geochronological standards. Because very few mica reference samples have been processed in large quantities, the international geochemiaal community is invited to contribute further useful data.     

The Abbey Evaluation of Reference Sample IF-G. The Significance of Abbey's Method For Laboratory Quality

Abbey's select laboratories method has been applied to the reported data for major and minor elements in the proposed GIT-IWG reference sample IF-G. The final values obtained by this method have been compared with the recommended values published by Govindaraju in 1984. Slightly different percentages are suggested for MgO, K₂O and Fe₂O₃T. The importance of applying the Abbey method by participants in co-operative studies is emphasized. Such an application gives a better understanding of data treatment and of the degree of reliability of published final values; furthermore the objective score obtained for laboratory quality will stimulate participating laboratories to improve their analytical methods and procedures. As an illustration some improvements in the laboratory of the authors are mentioned.     

Empirical and numerical analyses of support requirements for a diversion tunnel at the Boztepe dam site, eastern Turkey

This paper presents the engineering geological properties and support design of a planned diversion tunnel at the Boztepe dam site that contains units of basalt and tuffites. Empirical, theoretical and numerical approaches were used and compared in this study focusing on tunnel design safety. Rock masses at the site were characterized using three empirical methods, namely rock mass rating (RMR), rock mass quality (Q) and geological strength index (GSI). The RMR, Q and GSI ratings were determined by using field data and the mechanical properties of intact rock samples were evaluated in the laboratory. Support requirements were proposed accordingly in terms of different rock mass classification systems. The convergence–confinement method was used as the theoretical approach. Support systems were also analyzed using a commercial software based on the finite element method (FEM). The parameters calculated by empirical methods were used as input parameters for the FEM analysis. The results from the two methods were compared with each other. This comparison suggests that a more reliable and safe design could be achieved by using a combination of empirical, analytical and numerical approaches.