International Association of Geoanalysts' Protocol for the Certification of Geological and Environmental Reference Materials: A Supplement

The International Association of Geoanalysts (IAG) published a protocol for the certification of reference materials in close accord with the International Organisation for Standardisation (ISO) guidelines (Kane et al. 2003). This article supplements that protocol, providing additional discussion of best approaches for pre-selecting laboratories for participation in certification projects. This discussion also makes a distinction between inter-laboratory certifications, where n = 15 is the general standard, and expert laboratory certifications, where a much smaller number of laboratories will be deemed qualified to provide data of the quality needed for certification.     

Experience of the International Association of Geoanalysts as a Certifying Body

Reference materials (RMs) to support geoanalysis have a long history, dating back to the issuance of G-1 and W-1 in 1951. This paper addresses only one aspect of the most recent part of that history, the experience of the International Association of Geoanalysts (IAG) as a certifying body. In 2002, the Certification Committee of the IAG met in Potsdam to discuss becoming a certifying body able to produce RMs for the geoanalytical community. Following that meeting, the IAG developed and published a protocol to assure that IAG RMs would meet International Organization for Standardization (ISO) guidelines to the fullest extent possible. Many practical problems arise in the application of the recommendations of the ISO Guides to any one specific certification project. The recommendations describe the ideal; achievable reality is always somewhat less than that ideal, presenting a significant challenge to the IAG as a certifying body. This paper will summarise experience to date, while focusing on the most challenging issues, deriving uncertainties compliant with the Guide to Uncertainty in Measurement (GUM) and establishing traceability of certified values (CVs).     

河流沉积物多环芳烃标准样品的制备与定值

多环芳烃环境标准样品是保证多环芳烃环境监测和污染调查数据可靠性以及不同实验室间分析数据可比性必不可少的计量工具。美国NIST、欧盟IRMM、英国LGC等研究机构已有沉积物多环芳烃环境标准样品,但浓度水平大部分集中在mg/kg浓度水平,与我国当前的污染水平存在一定差距,难以满足痕量分析(μg/kg)质量保证与质量控制的要求。而我国受天然基体标准样品制备技术和定值分析技术的制约,尚没有研制沉积物多环芳烃环境标准样品。本文研制了适合我国多环芳烃环境监测和科学研究需要的河流沉积物标准样品。沉积物样品采集自松花江哈尔滨段流域,经过自然阴干、研磨、筛分、混匀和灭菌等加工处理,分层随机抽取15瓶样品对16种多环芳烃进行均匀性研究,结果表明样品均匀性良好。在30℃避光保存条件下,采用线性模型进行稳定性研究,标准样品在16个月稳定性检验期间未发现不稳定变化趋势。11家实验室对该河流沉积物标准样品采用气相色谱-质谱法和液相色谱法进行联合定值,经统计分析处理评定出14种多环芳烃的标准值和不确定度,并给出2种多环芳烃的参考值,特性量值在6.9~158 μg/kg之间,不确定度在1.5~25 μg/kg之间,可以满足多环芳烃痕量分析质量保证与质量控制的要求。该标准样品被批准为国家标准样品,填补了国内此类标准样品和标准物质空白,已成功应用于土壤和沉积物样品中多环芳烃的监测,可为进一步开展有机污染物环境基体标准样品研制提供参考和借鉴。     

Production and Certification of the Reference Material GSB 04‐3258‐2015 as a 143Nd/144Nd Isotope Ratio Reference

A new certified reference material, labelled GSB 04‐3258‐2015, for use as a ¹⁴³Nd/¹⁴⁴Nd isotope ratio reference has been prepared by the Institute of Geology, Chinese Academy of Geological Sciences, Beijing. Standardization Administration of the People's Republic of China provided the certification for this reference material. This report presents the reference ¹⁴³Nd/¹⁴⁴Nd isotope ratio and supporting production and certification procedures. The reference value was determined by an interlaboratory comparison of results from eleven participating laboratories using MC‐TIMS or MC‐ICP‐MS. The calibration of mass fractionation was conducted by using the exponential law, and the ¹⁴³Nd/¹⁴⁴Nd isotope ratios were normalised to the ¹⁴⁶Nd/¹⁴⁴Nd isotope ratio value of 0.7219. Isobaric interference of ¹⁴⁴Sm on ¹⁴⁴Nd was corrected using an interference‐free ¹⁴⁷Sm/¹⁴⁹Sm isotope ratio value for mass fractionation. GSB 04‐3258‐2015 shows sufficient homogeneity and stability for use as an international isotopic reference material. The certified value was calculated from the unweighted means of the results submitted by the participating laboratories. The ¹⁴³Nd/¹⁴⁴Nd isotope ratio value for GSB 04‐3258‐2015 is 0.512438, with a combined expanded uncertainty (k = 2) of 5 × 10^?6. Reference material GSB 04‐3258‐2015 is available upon request from the Institute of Geology, Chinese Academy of Geological Sciences, and may be used for accurate interlaboratory calibration of Nd isotope analysis.     

International Association of Geoanalysts'Protocol for the Certification of Geological and Environmental Reference Materials

This protocol has been developed by the International Association of Geoanalysts to demonstrate procedures for the certification of geological and environmental reference materials to comply to the fullest extent possible with recommendations of the International Organisation for Standardisation (ISO Guide 35). A practical approach is described on the assumption that certifications will be normally be based on collaborative analysis programmes in which participating laboratories are preselected on the basis of performance in a proficiency testing programme or on the basis of other criteria of merit.     

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.     

Certification of ERM‐EB400, the First Matrix Reference Material for Lead Isotope Amount Ratios,and ERM‐AE142, a Lead Solution Providing a Lead Isotopic Composition at the Edge of Natural Variation

Lead isotope amount ratios are commonly used in diverse fields such as archaeometry, geochemistry and forensic science. Currently, five reference materials with certified lead isotope amount ratios are available, namely NIST SRM 981, 982 and 983, GBW‐04442 and NMIJ 3681‐a. Only NIST SRM 981 and NMIJ 3681‐a have approximately natural isotopic compositions, and NIST SRM 981 is predominantly used for correcting mass discrimination/mass fractionation in the applied mass spectrometric procedures. Consequently, there is no other certified reference material available to be used for validation and/or quality control of the analytical procedures applied to lead isotope amount ratio measurements. To fill this gap, two new reference materials have been produced and certified for their lead isotope amount ratios. For both certified reference materials, complete uncertainty budgets have been calculated and SI traceability has been established. This provides the users with independent means for validating and verifying their analytical procedures and for conducting quality control measures. ERM‐EB400 is a bronze material with a nominal lead mass fraction of 45 mg kg^?1 and certified lead isotope amount ratios of n(²⁰⁶Pb)/n(²⁰⁴Pb) = 18.072(17) mol mol^?1, n(²⁰⁷Pb)/n(²⁰⁴Pb) = 15.578(18) mol mol^?1 and n(²⁰⁸Pb)/n(²⁰⁴Pb) = 38.075(46) mol mol^?1 with the associated expanded uncertainties (k = 2) given in brackets. ERM‐AE142 is a high‐purity solution of lead in 2% nitric acid with a nominal mass fraction of 100 mg kg^?1 and certified Pb isotope amount ratios of n(²⁰⁶Pb)/n(²⁰⁴Pb) = 21.114(17) mol mol^?1, n(²⁰⁷Pb)/n(²⁰⁴Pb) = 15.944(17) mol mol^?1 and n(²⁰⁸Pb)/n(²⁰⁴Pb) = 39.850(44) mol mol^?1 with the associated expanded uncertainties (k = 2) given in brackets. Both materials are specifically designed to fall within the natural lead isotopic variation and to assist users with the validation and verification of their analytical procedures. Note that while one of these reference materials requires the chemical separation of Pb from its matrix (ERM‐EB400), the other does not (ERM‐AE142). As additional information, δ^208/206Pb_{NIST SRM981} values are provided for both materials. For ERM‐AE142, a delta value of δ^208/206Pb_{NIST SRM981} = ?28.21(30)‰ was obtained, and for ERM‐EB400, a delta value of δ^208/206Pb_NIST SRM981= ?129.47(38)‰ was obtained, with the associated expanded uncertainties (k = 2) given in brackets.     

Production of Bauxite Certified Reference Material (BARC-B1201) for Nine Property Values (Al2O3, Fe2O3, SiO2, TiO2, V2O5, MnO,Cr2O3, MgO and LOI) Traceable to SI Units

The National Centre for Compositional Characterisation of Materials (NCCCM) / Bhabha Atomic Research Centre (BARC) and National Aluminium Company Limited (NALCO), India have produced an Indian origin bauxite certified reference material (CRM), referred to as BARC-B1201, certified for major (Al₂O₃, Fe₂O₃, SiO₂, TiO₂, loss on ignition - LOI) and trace contents (V₂O₅, MnO, Cr₂O₃, MgO). Characterisation was undertaken by strict adherence to ISO Guides. A method previously developed and validated in our laboratory, using single step bauxite dissolution and subsequent quantitation (of Al₂O₃, Fe₂O₃, SiO₂, TiO₂, V₂O_5, MnO, Cr₂O₃ and MgO) by ICP-AES (SSBD ICP-AES) was used for homogeneity studies and an inter-laboratory comparison exercise (ILCE) of the candidate CRM. LOI was determined by thermo-gravimetric analysis. Property values were assigned after an ILCE with participation from seventeen reputed government and private sector laboratories in India. The CRM was certified for nine property values: Al₂O₃, Fe₂O₃, SiO₂, TiO₂, V₂O_5, MnO, Cr₂O₃, MgO and LOI, which are traceable to SI units.     

A Single Step Acid Assisted Microwave Digestion Method for the Complete Dissolution of Bauxite and Quantitation of its Composition (Al2O3, Fe2O3, SiO2, TiO2, Cr2O3, MgO,MnO and V2O5) by ICP-AES

An acid assisted microwave-based method for the complete dissolution of bauxite using mixture of H₂SO₄, H₃PO₄ and HF acids in a single step was developed for the determination of various analytes (Al₂O₃, Fe₂O₃, SiO₂, TiO₂, Cr₂O₃, MgO, MnO and V₂O₅) using ICP-AES. The method was validated with respect to ruggedness, linearity, trueness, precision, limit of detection (LOD), limit of quantification (LOQ), working range and measurement uncertainties by analysing a bauxite reference material (Alcan BXT-12) and four certified reference materials (IPT-131, BXBA-4, NIST SRM 600, NIST SRM 697). The expanded uncertainties obtained for Al₂O₃ (40.0%), Fe₂O₃ (17.0%), SiO₂ (20.3%), TiO₂ (1.31%), Cr₂O₃ (0.024%), MgO (0.05), MnO (0.013), and V₂O₅ (0.60%), were 0.80, 0.40, 0.50, 0.033, 0.0008, 0.002, 0.0007 and 0.002 respectively, which are fit for the intended use to characterise bauxite. The developed method was also evaluated through participation in an interlaboratory comparison exercise organised by the Jawaharlal Nehru Aluminium Research Development and Design Centre (JNARDDC), Nagpur, India, using bauxite sample (BXT-JNA), with satisfactory z-scores achieved.     

地质标准物质中痕量元素量值溯源性探讨

标准物质的特性量值应该具备溯源性。然而地质标准物质溯源性的建立往往是很困难的。对痕量元素量值溯源的若干难点进行了讨论;提出了建立标准物质研制的质量体系的建议并就相关问题进行了阐述;应重视量值的信息反馈,提高定值的质量。     

Producing Certified Reference Materials at the Central Geological Laboratory of Mongolia

This paper briefly outlines the production and certification of reference materials at the Central Geological Laboratory (CGL) of Mongolia. The marketing of CRMs produced in Mongolia, as well as problems encountered in internationally recognised certification attempts and some proposed solutions, are discussed. The basic elements of the CGL’s strategy for the development of the CRM sector are to produce high quality CRMs according to the requirements of internationally recognised norms, to consider the market needs, to certify the RMs at the international level and to widely advertise them to the geochemical community. The CGL has already established the basis for the further development of this sector by, for instance, accreditation under ISO/IEC 17025, by modernising its preparation technology, by cooperation with international organisations in the field of CRMs and by permanent participation in the International Association of Geoanalysts’ GeoPT™ proficiency testing programme.     

关于铂族元素分析精度要求的讨论

列举了1972年、1978年、1988年、1994年、2002年和2006年6次制订、修订的质量管理制度、规定、规范(地质矿产行业标准)中关于铂族元素分析精度的规定和要求,评介了6个质量管理文件中对铂族元素分析精度要求的变化,计算、统计了中国与世界铂族元素标准物质标准值定值数据的精度。最后在上述资料的基础上讨论了当今铂族元素分析和标准物质标准值定值的精度要求问题,并据此提出了相关的建议。     

A Review of the IAG GeoPT™ and Certification Programmes,their Protocols,and the Differences between the Original and Potential Modifications to the Certification Protocol

The IAG conducts two programmes, the GeoPT ^? proficiency test and a certification programme that are closely interconnected. Both support the quality control/quality assurance activities of geochemical laboratories. Each derives an estimate of ‘true value’ for a number of samples, but arrives at that estimate, and its uncertainty, differently. This review discusses the history of the two programmes and compares the ‘true values’ and their uncertainties obtained through each. It then considers ‘fitness‐for‐purpose’ issues related to both GeoPT ^? and certification uncertainties. Issues related to potential modification of the IAG protocol for certification are also considered.     

An Evaluation of Methods for Assessing the Competence of Laboratories Based on Performance in the GeoPT Proficiency Testing Scheme

The original certification protocol, published by the International Association of Geoanalysts in 2003, specified that the competence of laboratories selected as competent to contribute certification measurements should be evaluated from their performance in the GeoPT proficiency testing programme. Round 39 of the IAG GeoPT proficiency testing programme provided an opportunity to examine four methods of evaluating laboratory competence based largely on the use of proficiency testing z‐scores as performance indicators. This opportunity arose because two test materials were co‐analysed by participating laboratories in this round: a syenite, SyMP‐1, supplied by the USGS, and an established CRM, the nepheline syenite, CGL 006. The performance of laboratories was assessed in four ways; in each case, consensus values and their uncertainties as derived from selective data sets of competent laboratories were compared with results derived from the routine GeoPT data assessment, involving all submitted measurements. An overall comparison of results showed no significant statistical differences in either consensus values or uncertainties between these data sets. This conclusion was unexpected and calls into question the widely held assumption that ‘better’ consensus data would be obtained from a subset of laboratories judged to be competent on the basis of proficiency testing performance indicators.     

Report on the 2007 Recertification of the Certified Reference Materials GAS (Serpentinite) and OShBO (Alkaline Granite)

A report is presented on the recertification of two certified reference materials (CRMs) initially prepared and certified by the Central Geological Laboratory of Mongolia (CGL), namely serpentinite GAS and alkaline granite OShBO. Subsequent work done in collaboration with the International Association of Geoanalysts (IAG) followed the International Organisation for Standardisation (ISO) guidelines for certification (ISO Guide 35, 2006) more closely than had been possible originally. The certification protocol followed was that of the International Association of Geoanalysts (IAG). The recertification added to the number of elements that were certified for OShBO (from 21 to 30), but not for GAS (decreased from 15 to 12) because of the greater analytical difficulties posed by that sample matrix in meeting the more stringent metrological requirements for recertification. Further, the uncertainties for these values were established in accordance with the Guide to Measurement Uncertainty ; individual contributions of heterogeneity and bias are reported as appropriate for each of the certified constituents. Traceability of the certified values was demonstrated to the greatest possible extent, based on concurrent analyses of the matrix-matched existing CRMs, SW and GM, by all participating laboratories. The materials are now available from the CGL for use by laboratories in controlling data quality when analysing materials of similar matrices.     

江阴南部地区建筑荷载和地下水开采与 地面沉降耦合研究

针对江阴南部地面沉降问题,结合地下水开发利用现状和城市建设规划,根据比奥固结理论,引入黏性土流变理论,将土体本构关系拓展至黏弹塑性,并考虑土体的土力学参数和水力学参数随应力场的动态变化,建立江阴南部地区建筑荷载、地下水开采与地面沉降三维全耦合数值模型,分别模拟预测了江阴南部地区2015年12月31日至2030年12月31日建筑荷载、地下水开采单独作用及二者叠加作用三种情况下地面沉降发展趋势。模拟结果显示,建筑荷载为引起江阴南部地区地面沉降的主因,其次是地下水开采,二者的主压缩层分别为第Ⅰ黏性土弱含水层和第Ⅱ黏性土弱含水层,分别占总压缩量的42.94%和62.60%;建筑荷载和地下水开采叠加作用下引发的地面沉降具有耦合效应,二者叠加量小于单独作用引发量的线性叠加。     

Preliminary study on the occurrence of geothermal systems in the tectonic compressional regions: an example from the Derman geothermal field in the Biga Peninsula, Turkey

There are numerous hot springs with temperatures ranging from 30 to 100 °C in Biga peninsula and they occur throughout the peninsula. The result of this study shows that the region is under a tectonic compressional regime. The investigation of the faults and fractures in the region indicates that the region has been affected first by N–S and then E–W compression since the Middle Miocene. Opening fractures and antithetic and synthetic faults due to the compressional movements provide paths for the deep circulation of water. In addition, the tectonic movements, granitic intrusion and volcanic activity have also played important roles as heat sources for the geothermal systems.     

A Proposal for the Publication of Geochemical Data in the Scientific Literature

A proposal is set out for the information and details that should accompany the publication of geochemical data in the research literature. This proposal is based on the principle that sufficient detail must be included both to allow independent replication of the results and for reviewers to confirm that data are fit‐for‐purpose in supporting the way in which they have been interpreted. In particular, it is recommended that all analytical measurements should be accompanied by an estimate of uncertainty that includes both field sampling and laboratory contributions together with a statement that summarises the way published data conform to the principles of traceability.