Wiley

We report here the results of a study to develop natural zircon geochemical standards for calibrating the U‐(Th)‐Pb geochronometer and Hf isotopic analyses. Additional data were also collected for the major, minor and trace element contents of the three selected sample sets. A total of five large zircon grains (masses between 0.5 and 238 g) were selected for this study, representing three different suites of zircons with ages of 1065 Ma, 2.5 Ma and 0.9 Ma. Geochemical laboratories can obtain these materials by contacting Geostandards Newsletter.

Microanalytical trace element techniques (such as ion probe or laser ablation ICP‐MS) are hampered by a lack of well characterized, homogeneous standards. Two silicate glass reference materials produced by National Institute of Standards and Technology (NIST), NIST SRM 610 and NIST SRM 612, have been shown to be homogeneous and are spiked with up to sixty one trace elements at nominal concentrations of 500 μg g‐1 and 50 μg g‐1 respectively. These samples (supplied as 3 mm wafers) are equivalent to NIST SRM 611 and NIST SRM 613 respectively (which are supplied as 1 mm wafers) and are becoming more widely used as potential microanalytical reference materials. NIST however, only certifies up to eight elements in these glasses. Here we have compiled concentration data from approximately sixty published works for both glasses, and have produced new analyses from our laboratories. Compilations are presented for the matrix composition of these glasses and for fifty eight trace elements. The trace element data includes all available new and published data, and summaries present the overall average and standard deviation, the range, median, geometric mean and a preferred average (which excludes all data outside ± one standard deviation of the overall average). For the elements which have been certified, there is a good agreement between the compiled averages and the NIST data. This compilation is designed to provide useful new working values for these reference materials.

Within a short period of one year (November 1992‐ October 1993), ninety‐two IWG‐Member laboratories have been able to characterize the chemical composition of a candidate reference sample, Zinnwaldite ZW‐C, a Li‐mica, reputed difficult to analyse because of its high contents of F and rare alkali elements and of the presence of refractory minerals. Thanks to the help of 163 analysts from the 92 laboratories, it has been possible to assign working values for 20 major and minor elements including the rare alkali elements and for 43 trace elements; all the working values receive the status of recommended values, except H20, C02, LOI, CI and S. It is, indeed, a rare success for such a difficult sample!

In this special issue, working values are reported for 272 international geostandards along with sample description. For many geostandards, the number of compiled data were not adequate enough for assigning working values. Users of geostandards are solicited to contribute more and more data particularly on trace elements. Think Geostan is a slogan that we wish to launch to set this problem in the limelight.

Chúng tôi mô tả các quy trình phân tích cho việc xác định các nguyên tố vi lượng được phát triển tại CNRS Service d'Analyse des Roches et des Minéraux (SARM) và báo cáo kết quả thu được cho năm vật liệu tham chiếu địa hóa: bazan BR, điôrit DR‐N, serpentinit UB‐N, anorthosit AN‐G và granit GH. Kết quả cho các nguyên tố đất hiếm, U và Th cũng được báo cáo cho các vật liệu tham chiếu khác bao gồm dunit DTS‐1, peridotit PCC‐1 và bazan BIR‐1. Tất cả các mẫu đá đã được phân hủy bằng cách nóng chảy kiềm. Các phân tích được thực hiện bằng cách tiêm dòng ICP‐MS và bằng sắc ký lỏng áp suất thấp online (LC)‐ICP‐MS cho các mẫu có nồng độ REE, U và Th rất thấp. Phương pháp sau mang lại giới hạn phát hiện thấp hơn nhiều so với dữ liệu bằng cách giới thiệu trực tiếp và loại bỏ khả năng can thiệp đồng vị trên các nguyên tố này. Mặc dù các kết quả đồng ý với hầu hết các giá trị làm việc, khi có sẵn, nhưng kết quả cho một số nguyên tố khác nhau nhẹ so với nồng độ khuyến nghị. Trong những trường hợp này, chúng tôi đề xuất các giá trị mới cho Co, Y và Zn trong bazan BR, Zr trong điôrit DR‐N, Sr và U trong granit GH, và Ga và Y trong anorthosit AN‐G. Hơn nữa, mặc dù nồng độ Sb đo được trong AN‐G rất gần với giới hạn phát hiện của chúng tôi, giá trị của chúng tôi (0.3 ± 0.1 μg g⁻¹) thấp hơn nhiều so với giá trị làm việc được báo cáo là 1.4 ± 0.2 μg g⁻¹. Các giá trị mới này cần được xác nhận bởi một chương trình liên phòng thí nghiệm mới để phân loại thêm các vật liệu tham chiếu này.

Kết quả thu được cho nồng độ REE, Th và U sử dụng LC‐ICP‐MS áp suất thấp online cung cấp giới hạn phát hiện tốt (ng g⁻¹ đến sub‐ng g⁻¹ cho đá và ng l⁻¹ đến sub‐ng l⁻¹ cho nước tự nhiên) và kết quả chính xác. Hiệu quả tách nền cho phép đo chính xác Eu mà không cần chỉnh sửa can thiệp đồng vị BaO cho các mẫu có tỷ lệ Ba/Eu cao tới 27700. Đối với nồng độ REE trong PCC‐1 và DTS‐1, sự khác biệt với các giá trị được báo cáo trong tài liệu được giải thích là do khả năng không đồng nhất của các vật liệu tham chiếu. Các giá trị Thorium và U được đề xuất cho hai mẫu này, cũng như cho AN‐G và UB‐N.

Forty two major (Na, Mg, Ti and Mn) and trace elements covering the mass range from Li to U in three USGS basalt glass reference materials BCR‐2G, BHVO‐2G and BIR‐1G were determined using laser ablation‐inductively coupled plasma‐mass spectrometry. Calibration was performed using NIST SRM 610 in conjunction with internal standardisation using Ca. Determinations were also made on NIST SRM 612 and 614 as well as NIST SRM 610 as unknown samples, and included forty five major (Al and Na) and trace elements. Relative standard deviation (RSD) of determinations was below 10% for most elements in all the glasses under investigation. Consistent exceptions were Sn and Sb in BCR‐2G, BHVO‐2G and BIR‐1G. For BCR‐2G, BHVO‐2G and BIR‐1G, clear negative correlations on a logarithmic scale exist between RSD and concentration for elements lower than 1500 μg g^‐1 with logarithmic correlation coefficients between ‐0.75 and ‐0.86. There is also a clear trend of increasing RSD with decreasing concentration from NIST SRM 610 through SRM 612 to SRM 614. These suggest that the difference in the scatter of apparent element concentrations is not due to chemical heterogeneity but reflects analytical uncertainty. It is concluded that all these glasses are, overall, homogeneous on a scale of 60 μm.

Our first results on BHVO‐2G and BIR‐1G showed that they generally agreed with BHVO‐2/BHVO‐1 and BIR‐1 within 10% relative. Exceptions were Nb, Ta and Pb in BHVO‐2G, which were 14‐45% lower than reference values for BHVO‐2 and BHVO‐1. Be, Ni, Zn, Y, Zr, Nb, Sn, Sb, Gd, Tb, Er, Pb and U in BIR‐1G were also exceptions. However, of these elements, Be, Nb, Sn, Sb, Gd, Tb, Pb and U gave results that were consistent within an uncertainty of 2s between our data and BIR‐1 reference values. Results on NIST SRM 612 agreed well with published data, except for Mg and Sn. This was also true for elements with m/z 85 (Rb) in the case of NIST SRM 614.

The good agreement between measured and reference values for Na and Mg in BCR‐2G, BHVO‐2G and BIR‐1G, and for Al and Na in NIST SRM 610, 612 and 614 up to concentrations of at least several weight percent (which were possible to analyse due to the dynamic range of 10⁸) indicates the suitability of this technique for major, minor and trace element determinations.

Thirty‐seven trace elements, including rare‐earth elements, have been determined by ICP‐MS in twenty‐eight international rock standards using routine sample preparation techniques. Samples were decomposed by either pressurized HF‐HCIO₄‐aqua regia attack, or by lithium borate fusion. Generally, the ICP‐MS data for geological rock standards presented here agree well with certified values. However, the results for light rare earth elements appear to be systematically low in comparison with the published working values.

Elemental composition data on eight older (AGV‐1, BCR‐1, DTS‐1, G‐1, G‐2, GSP‐1, PCC‐1 and W‐1) and three newer (BIR‐1, DNC‐1 and W‐2) USGS rock standards have been collected from institutional reports and journal articles from 1972–1981. This collection was combined with data from previous compilations and “consensus values” for up to 79 elements determined by comparing overall means, medians, and individual means based on analytical techniques.

Concentration data obtained by instrumental neutron activation analysis (INAA) are presented for up to 36 chemical elements in 93 geochemical reference samples, including some for which there are little previous data. Because all data are based on at least three independent analyses, and for many of the data the uncertainty associated with counting is an insignificant source of error, the values presented here are considered of higher precision than generally reported by INAA. Information on subsampling error (sample heterogeneity) is also presented.