Mass Spectrometric Isotope Dilution Determination Of Palladium in Geochemical Reference Samples

Fifteen geochemical reference samples have been analysed for palladium using the stable isotope dilution technique. These include seven USGS, five CRPG and three CCRMP samples. Our results ape in reasonable agreement with the presently accepted values for the USGS samples, but are significantly lower than the present CCRMP values. Our data for the CRPG samples are the first to be published. This is the first reported study of the determination of palladium in silicate samples using the isctope dilution technique.     

Reproducibility Tests for INAA Determinations With AGV-I, BCR-I and GSP-I and New Data For 17 Geochemical Reference Materials

During 1975–1977, the USGS reference rocks GSP-1, BCR-1 and from 1977 onwards AGV-1 have been systematically analysed in routine INAA as test samples. The results are given for up to 26 elements per sample and the reliability of our setup is demonstrated. For further 17 geochemical reference samples, new results are presented and compared with available data.     

Chlorine in 27 Geochemical Reference Samples

27 reference samples have been analysed for Cl by automated photometric analysis following alkali fusion. The results are in general agreement with the compilation values listed. However, it is apparent that in the case of the six USGS samples included, values are generally lower than those previously quoted for photometric determinations, particularly for G-2 and AGV-1.     

Determination of Fluorine and Chlorine in Eight USGS Reference Samples Using Automated Photometric Analysis

Eight USGS reference samples have been analysed for F and Cl by automated photometric analysis following alkali fusion. The results obtained are, generally, in fairly good agreement with those quoted in the literature.     

Chemical Characterisation of the USGS Reference Glasses GSA-1G, GSC-1G, GSD-1G, GSE-1G, BCR-2G, BHVO-2G and BIR-1G Using EPMA, ID-TIMS, ID-ICP-MS and LA-ICP-MS

The USGS reference glasses GSA-1G, GSC-1G, GSD-1G, GSE-1G, BCR-2G, BHVO-2G and BIR-1G were investigated by different analytical techniques. All these materials have a geological (basaltic) matrix and are therefore useful in igneous geochemistry as matrix-matched reference materials for microanalytical techniques. The new GS glasses have trace elements in groups at concentration levels of about < 0.01, 5, 50 and 500 μg g^-1. Their major element compositions have been determined by EPMA, and trace elements have been analysed by LA-ICP-MS and two isotope dilution techniques using TIMS and ICP-MS. EPMA and LA-ICP-MS analyses indicated that the USGS reference glasses are homogeneous at the μm to mm scale with respect to major (variations < 1-2%) and most trace elements (variations 1-4%). Trace element data obtained from the different analytical techniques agreed within an uncertainty of 1-5%, indicating that between method results are comparable. Therefore, the preliminary working values for the four USGS GS glasses calculated from these data have a low level of uncertainty.     

Radiochemical Determination of Gold in Rocks

A method developed for radiochemical determination of gold in rock samples has been applied to six Bulgarian, four ZGI (GDR) and one USGS geostandards. The method is based on acid dissolution of the sample, followed by extraction of gold with copper diethyldithiocarbamate solution in CHCl₃. The chemical yield was determined by using ¹⁹⁹Au tracer. The present data are compared with published values for the ZGI and USGS samples.     

Determination of Selenium in Twenty-Eight Geological Reference Materials by Atomic Absorption Spectrometry

Twenty-eight geological reference samples have been analysed for selenium using atomic absorption spectrometry with hydride generation and quartz cell atomizer and/or with solvent extraction and carbon tube atomizer. Data are presented for 5 CCRMP, 6 USGS, 3 NBS, 6 NIM and 8 GSJ reference materials.     

Neutron Activation Determination of The Fourteen Rare-Earth Elements In Five Rock Standards

Five geochemical reference samples. Granite GA and Basalt BK from CRPG, Diorite DR-N and Serpentine UB-N from ANRT and Andesite AGV-1 from USGS were analysed for their rare-earth element (REE) contents. All the fourteen REE were determined using neutron activation analysis. The results are presented and compared with published data.     

Preliminary REsults of Mercury in CRPG And ANRT Rock and Mineral Standards

Nine CRPG and ANRT reference samples have been analyzed for Hg by flameless atomic absorption spectrophotometry. Preliminary data are given but mercury homogeneity has not been tested. Results of determinations on USGS samples are reported and compared with available literature values.     

DETERMINATION OF B, SM AND GD IN TWENTY-THREE GEOLOGICAL REFERENCE MATERIALS BY NEUTRON-CAPTURE PROMPT GAMMA-RAY ACTIVATION ANALYSIS (PGAA)

Eleven USGS geological reference materials and twelve French geological reference materials have been measured for B, Sm and Gd concentrations by prompt-gamma activation analysis. For those materials that have already been analysed, our data is in agreement with published recommended values. These values constitute the first measured data for several French geological reference materials     

RARE EARTH ELEMENT CONCENTRATIONS IN USGS AND CCRMP IGNEOUS ROCK STANDARDS DETERMINED BY HIGH PERFORMANCE ION CHROMATOGRAPHY

Eleven rare earth elements (REE) have been determined in ten USGS and two CCRMP igneous rock standards using high performance ion chromatography. Duplicate analyses of two or more separately prepared aliquots of each sample were undertaken; reproducibility was better than 5% for each of the REE. In most cases, the results compare closely with published REE values for those samples for which the REE are well characterised. Where the results for individual elements are in disagreement with published data, the more erratic patterns yielded by the earlier data when plotted on chondrite-normalised REE diagrams suggest that values determined in this study are of greater accuracy.     

Neutron Activation Analysis of Seven B.C.S. Certified Reference Materials of Geological Interest

The concentrations of 26 elements have been investigated in seven BCS certified reference samples using three varieties of neutron activation analysis. The ANRT granite GS-N was used as the comparator reference material while the USGS basalt BHVO-1 and the GIT-IWG basalt BE-N were analysed concurrently to assess the analytical accuracy.     

Determination of Selenium in Fifty Two Geochemical Reference Materials by Hydride Generation Atomic Absorption Spectrometry

The selenium content of fifty two geochemical reference samples, issued by several reference material producers (ANRT, GIT-IWG, USGS, NIST and GSJ) has been determined by continuous hydride generation and atomic absorption spectrometry. Selenium(VI) in the digested solutions was pre-reduced to selenium(IV) by heating in 6 mol l⁻¹ HCl solution. The limit of detection was 3 ng g⁻¹ selenium in common geological samples. Some samples which contain a large amount of heavy metals were analysed by the standard addition technique. The agreement between the reported results and published data is satisfactory.     

Determination of Bromine and Iodine in Twenty-three Geochemical Reference Materials by ICP-MS

Trace amounts (from nanogram to microgram levels) of bromine and iodine were determined by inductively coupled plasma-mass spectrometry (ICP-MS) in twenty-three geochemical reference materials issued by the GSJ, USGS, IAEA etc. The pyrohydrolysis technique was used to separate bromine and iodine from samples analysed in the form of powder. The accuracy and precision of the experimental values were assessed by the comparative analysis of well established reference materials such as USGS AGV-1, BCR-1 and IGGE GBW07312. The measured values agreed well with reported values within a 10% error range. We also report reliable new data for these elements in these geochemical reference materials.     

DETERMINATION OF NINE RARE EARTH ELEMENTS IN EIGHT USGS REFERENCE SAMPLES AND IN THE ANRT GLAUCONITE, GL-O, BY SEQUENTIAL INDUCTIVELY COUPLED ARGON PLASMA SPECTROMETRY

Nine rare earth elements have been determined by inductively coupled plasma spectrometry (ICP) in eight USGS reference samples, MAG-1, SCo-1, SDC-1, BIR-1, DNC-1, W-2, BCR-1 and BHVO-1 and in the ANRT Glauconite, GL-O. Along with these new data, updated compilations are presented for these samples. Good agreement is observed between the present work and the compiled values.     

Isotope Dilution MC-ICP-MS Rare Earth Element Analysis of Geochemical Reference Materials NIST SRM 610, NIST SRM 612, NIST SRM 614, BHVO-2G, BHVO-2, BCR-2G, JB-2, WS-E, W-2, AGV-1 and AGV-2

We present data for the concentrations of eleven rare earth elements (La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Er, Yb, Lu) in eleven international geochemical reference materials obtained by isotope dilution multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS). We have analysed both rock powders and synthetic silicate glasses, and the latter provide precise data to support the use of these as reference materials for in situ trace element determination techniques. Our data also provide precise measurements of the abundance of mono-isotopic Pr in both glasses and powders, which allows more accurate constraints on the anomalous redox-related behaviour of Ce during geochemical processes. All materials were analysed in replicate providing data that typically reproduce to better than one percent. Sm/Nd ratios in all these materials also reproduce to better than 0.2% and are accurate to < 0.2% and can thus be used as calibrants for Sm-Nd geochronology. Our analyses agree well with existing data on these reference materials. In particular, for NIST SRM 610, USGS BHVO-2, AGV-1 and AGV-2, our measured REE abundances are typically within < 2% (and mostly 1%) of REE concentrations previously determined by isotope dilution analysis and thermal ionisation mass spectrometry, consistent with the higher degree of precision and accuracy obtained from isotope dilution techniques. Close agreement of results between basaltic glass reference materials USGS BHVO-2G and BCR-2G and the BHVO-2 and BCR-2 powders from which they were created suggests that little fractionation, concentration or dilution of REE contents occurred during glass manufacture.     

Sr and Pb isotopic composition of five USGS glasses (BHVO-2G, BIR-1G, BCR-2G, TB-1G, NKT-1G)

Sr isotopic compositions and Rb / Sr ratios of three USGS glasses (BHVO-2G, BIR-1G, BCR-2G) are identical to those of the original USGS reference materials. NKT-1G and TB-1G give values of 0.70351 and 0.70558, respectively. Pb isotopic ratios were measured by the standard-sample bracketing technique on an MC-ICP-MS, which give results that are comparable in accuracy and reproducibility to double spike analyses. However, assessment of the reproducibility of the technique is hampered by inhomogeneous contamination of all USGS reference materials analysed. This contamination is likely to be the reason why the USGS glasses do not all have the same Pb isotopic composition as their unfused originals. Powdered glasses, distributed for characterisation of the glasses by bulk analytical techniques, do not all have the same Pb isotopic compositions as the solid glass material, and can therefore not be used for this purpose.     

High-Precision Trace Element Data for the USGS Reference Materials BCR-1, BCR-2, BHVO-1, BHVO-2, AGV-1, AGV-2, DTS-1, DTS-2, GSP-1 and GSP-2 by ID-TIMS and MIC-SSMS

Different batches of the new US Geological Survey (USGS) reference materials (RMs) BCR-2, BHVO-2, AGV-2, DTS-2 and GSP-2 and the original USGS RMs BCR-1, BHVO-1, AGV-1, DTS-1 and GSP-1 have been analysed by isotope dilution using thermal ionisation mass spectrometry (ID-TIMS) and by multi-ion counting spark source mass spectrometry (MIC-SSMS). The concentrations of K, Rb, Sr, Ba and the rare earth elements were determined with overall analytical uncertainties of better than 1% (ID-TIMS) and 3% (MIC-SSMS). The analyses of different aliquots and batches of BCR-2, BHVO-2, AGV-2 and GSP-2, respectively, agree within 1%, i.e. approximately the analytical uncertainties of the data. This indicates an homogeneous distribution of the trace elements in these RMs. Differences in element concentrations of up to 17% in different aliquots of the depleted RM DTS-2 are outside the analytical uncertainty of our data. They may be attributed to a slightly heterogeneous distribution of trace elements in this dunite sample. Our trace element data for BCR-2, BHVO-2, AGV-2 and GSP-2 agree within about 3% with preliminary reference values published by the USGS. They also agree within 1-6% with those of the original RMs BCR-1, BHVO-1, AGV-1 and GSP-1. Large compositional differences are found between DTS-2 and DTS-1, where the concentrations of K, Rb, Sr and the light REE differ by factors of 2 to 24.     

Determination of Selenium in Twenty Geological Reference Materials by Neutron Activation And Inorganic Ion Exchange

Twenty geological reference samples have been analyzed for selenium using thermal neutron activation followed by radiochemical separation of ⁷⁵Se. Data are presented for 3 NBS, 11 USGS, and 6 CCRMP materials.     

First Co-Operative Study on Four Tropical Soil Samples and One Lateritic Bauxite (Suriname) Proposed as Geochemical Reference Samples

Five samples from Suriname have been analysed for their chemical composition by 18 laboratories. The proposed reference samples are four soil samples and one lateritic bauxite. The samples were analyzed for major and minor elements as well as for 36 trace elements. More data are needed for better characterization of these samples, particularly for trace elements.