A Story of Two Rocks

An attempt is made to assess the impact that the investigation on reference (standard) rocks G-1 and W-1 has had on the geological fraternity. It is pointed out that prior to 1950, most geologists, petrologists, geochemists and the analysts themselves had a false impression of the quality of the data as obtained by classical methods of chemical analysis.
As a result of the G-1 W-1 investigation, numerous other rock standards have been prepared, yet, despite the G-1, W-1 experience and the availability of several other reference rocks, progress on the improvement on data quality is often disappointingly slow.
The G-1, W-1 investigation has had significant consequences for the development of geochemistry and the extra-terrestrial chemistry; one example is given.     

1988 Compilation of Elemental Concentration Data for USGS DTS-1, G-1, PCC-1 and W-1

Concentration data on up to 91 individual constituents in USGS DTS-1, G-1, PCC-1, and W-1 have been collected from 1647 journal articles and technical reports. These data are summarized in consensus (mean) values with uncertainties expressed as one standard deviation. Mean values are also calculated as a function of analytical procedure and all raw data are given in the tables. Recommended values are proposed based upon data criteria used by NIST (National Institute of Standards and Technology, formerly the National Bureau of Standrds or NBS).     

Chemische und spektrochemische Analyse internationaler Referenzgesteinsproben

Zusammenfassung Siebzehn internationale Referenzgesteinsproben (USGS: G-1, G-2, W-1, GSP-1, AGV-1, PCC-1, DTS-1, BCR-1; ZGI: GM, BM, TB; CRPG: GR, GA, GH, BR; MRT: T-1; CSS: SY-1) wurden zum Teil naßchemisch auf Haupt- und Nebenbestandteile und emissionsspektrographisch mittels der Kohlenbogen- und Doppelbogenmethode auf 25 Spurenelemente unter Verwendung eines Spektrographen großer Dispersion quantitativ analysiert. Unter Einsatz eines thermochemischen Mischreagens (BaSO₄+LaF₃) wurden mit der Doppelbogenmethode Nachweisgrenzen von0,1 bis 5 ppm erreicht. Bei Mehrfachanalysen wurde mit dem Kohlebogen ein relativer Fehler von±4 bis±16% erhalten, bei der Doppelbogenmethode von±5 bis±30%. Es wird die Konzentrationsabhängigkeit des relativen Fehlers dargestellt.

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Chemical and spectrochemical analysis of international reference samples rocks

Summary Seventeen international reference samples of rocks (USGS: G-1, G-2, W-1, GSP-1, AGV-1, PCC-1, DTS-1, BCR-1; ZGI: GM, TB; CRPG: GR, GA, GH, BR; MRT: T-1; SSC: SY-1) were analysed partly for the main and minor constituents using methods of wet analysis. Twenty-five trace elements were determined with a large optical spectrograph using the carbon and double are methods. The double are methode gives detection limites of 0.1 up to 5 ppm, if thermochemical reagents (BaSO₄+LaF₃) are applicated. The carbon arc method shows a relative error of±4 up to±16% depending mostly on the concentration of the trace element, during the double arc methode results a relative error of±5 up to±30%.

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Mit 5 Abbildungen     

Precise determination of uranium in rocks and minerals by neutron activation analysis using 133I fission product

A radiochemical neutron activation technique for uranium determination in rock and mineral samples is presented. The method is based on an alkaline fusion, a selective oxidation of iodine by a sodium-nitrite solution, followed by an iodine distillation technique for the isolation of the ¹³³I produced in fission. The outlined scheme is rapid, sensitive and reliable. Determination of uranium in U.S. Geological Survey standard rocks (G-1, W-1, G-2, BCR-1, AGV-1, GSP-1), C.R.P.G. Nancy geochemical standards (GA, GH, BR, Mica-Fe, Mica-Mg), C.A.A.S. reference syenite rocks (SY-1, SY-2, SY-3) and other analysed rock samples are reported. These results are compared with those obtained by other methods.     

Foraminiferal evidence of basin submergence in part of Sundarban mangrove delta,India

Sundarban is a largest mangrove forest delta developed along the NE-SW direction covering parts of India and Bangladesh. Little work has been done on Indian part of Sundarban in respect of heterogeneity in channel morphology which could be mostly due to the effect of tilting and basin subsidence. These changes might have played a major role on development of high marshes, which offers a congenial environment for survival of Haplophragmoides wilberti, Jadammina macrescens, Trochammina inflata, and Miliammina fusca. These marsh benthonic foraminiferal assemblages provide a direct evidence of recent past sea level changes. To establish the depositional pattern and their effects rendered by merciless changing environment, 11 pit sections have been excavated along three E-W transects from Indian Sundarban. Depth of these pit sections varies from 2 to 3 m. Generally, top 20 cm sediment (in pit section W-1 to W-11) deposited under the intertidal environment, as indicated by the presence of Ammonia tepida. However, sediment below 20 cm in some of the pit sections (W-3 and W-5) exhibits fresh water signatures as indicated by the presence of Charophytes algae. In other pit sections (W-1, W-2, W-6, W-7, W-8, W-9 and W-11), the intertidal assemblage is noticed just above the upper marshes assemblage and vice versa, signifying that depositional environment is in proximity to the mangrove dominated area as indicated by the presence of marsh benthonic foraminiferal assemblage containing T. inflata, H. wilberti, Haplophragmoides sp., J. macrescens and M. fusca. Bottom sediment in most of the pit sections from south to north have different depositional environment with alternate presence of intertidal to subtidal faunal assemblages. The peculiar presence of intertidal assemblage above the upper marshes assemblages in recent sediment points towards the theory of submergence due to relative rise in the sea level. But the effect of relative sea level rise is not uniform throughout the area because of differential subsidence due to varied rate of sediment supply (0.5 to 3.3 cm/year) and eastward tilting of the basin. Based on the upper marshes benthonic foraminiferal assemblage and radiocarbon age (in W-1 at 100 cm ~?150 years age), the average subsidence rate as recorded is approximately 0.3 to 0.5 cm/year. Hence, such depositional sequence conjectures that the Indian part of Sundarban is undergoing a phase of submergence concomitant to basin subsidence.     

Neutron-Capture Prompt Gamma-Ray Multielement Analysis of Twenty-Two Geochemical Reference Standards

Twenty-two geochemical reference standards obtained from the U.S. Geological Survey (AGV-1, PCC-1, G-2, GSP-1, BHVO-1, MAG-1, QLO-1, RGM-1, SCo-1, SDC-1, SGR-1, STM-1, BIR-1, DNC-1, W-2, Nod A-1, Nod P-1), the National Bureau of Standards (SRM 278 Obsidian, SRM 688 Basalt), the International Atomic Energy Agency (Soil-5, SL-1 Lake Sediment), and Batelle Pacific Northwest Laboratories (COS-1 Oil Shale) have been analyzed for up to twenty-one major, minor, and trace elements from the group of H, B, C, N, Na, Mg, Al, Si, P, S, Cl, K, Ca, Ti, V, Mn, Fe, Co, Ni, Cu, Cd, Nd, Sm and Gd. The technique used, in-beam neutron-capture prompt γ-ray activation analysis (PGAA), is described and the data are compared to those from other studies.     

Molybdenum Concentrations Measured in Eleven USGS Geochemical Reference Materials by Isotope Dilution Thermal Ionisation Mass Spectrometry

Molybdenum concentrations in eleven USGS geochemical reference materials AGV-1, BCR-1, BHVO-1, BIR-1, DNC-1, DTS-1, G-2, GSP-1, MAG-1, PCC-1 and W-2 were measured by isotope dilution thermal ionisation mass spectrometry (ID-TIMS). In every case but one, the concentrations determined in this study were significantly lower than the current consensus values. Molybdenum concentrations determined by ID-TIMS are inherently more accurate and precisions may be up to an order of magnitude higher than those measured by other analytical techniques.     

An Inter-Laboratory Assessment of the Thorium Isotopic Composition of Synthetic and Rock Reference Materials

We present a concerted international effort to cross-calibrate five synthetic Th isotope reference materials (UCSC Th "A", OU Th "U", WUN, IRMM-35 and IRMM-36), and six rock reference materials (UCSC TML, Icelandic ATHO, USGS BCR-2, USGS W-2, USGS BHVO-2, LV18) using multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS). We then compare our new values with a compilation of literature mass spectrometric data for these reference materials and derive recommended "consensus"²³⁰Th/²³²Th values for each. We also present isotope dilution U and Th concentration data for four rock reference materials (UCSC TML, Icelandic ATHO, USGS BCR-2, USGS W-2).     

Well log data analysis for lithology and fluid identification in Krishna-Godavari Basin,India

Well log analysis provides the information on petrophysical properties of reservoir rock and its fluid content. The present study depicts interpretation of well log responses such as gamma ray, resistivity, density and neutron logs from six wells, namely W-1, W-2, W-9, W-12, W-13 and W-14 under the study area of Krishna-Godavari (K-G) basin. The logs have been used primarily for identification of lithology and hydrocarbon-bearing zones. The gamma ray log trend indicates deposition of cleaning upward sediment. Coarsening upward, clayey-silty-sandy bodies have been evidenced from the gamma ray log. Gas-bearing zones are characterised by low gamma ray, high deep resistivity and crossover between neutron and density logs. Total 14 numbers of hydrocarbon-bearing zones are identified from wells W-9, W-12, W-13 and W-14 using conventional log analysis. Crossplotting techniques are adopted for identification of lithology and fluid type using log responses. Crossplots, namely P-impedance vs. S-impedance, P-impedance vs. ratio of P-wave and S-wave velocities (Vp/Vs) and lambda-mu-rho (LMR), have been analysed to discriminate between lithology and fluid types. Vp/Vs vs. P-impedance crossplot is able to detect gas sand, brine sand and shale whereas P-impedance vs. S-impedance crossplot detects shale and sand trends only. LMR technique, i.e. λρ vs. μρ crossplot is able to discriminate gas sand, brine sand, carbonate and shale. The LMR crossplot improves the detectability and sensitivity of fluid types and carbonate lithology over other crossplotting techniques. Petrophysical parameters like volume of shale, effective porosity and water saturation in the hydrocarbon-bearing zones in these wells range from 5 to 37%, from 11 to 36 and from 10 to 50% respectively. The estimated petrophysical parameters and lithology are validated with limited core samples and cutting samples from five wells under the study area.     

Spectrochemical determination of trace elements in the U.S.G.S. silicate rock standards

Spectrographic determinations for twenty trace elements in the six new U.S.G.S. silicate rock standards along with the rock standards G-1, W-1, SR-1, GR and BR are given. Most of the results represent the average of triplicate determinations on each of five splits of the portions of the standards available to the authors. Thus, the preferred values represent, in most cases, the average of fifteen replicate determinations.     

1987 Compilation of Elemental Concentration Data for USGS BIR-1, DNC-1 and W-2

Elemental concentration data on up to 73 individual constituents in BIR-1, DNC-1, and W-2 have been collected from 94 journal articles and technical reports. These data are summarized in consensus (mean) values with uncertainties expressed as one standard deviation. Mean values are also calculated as a function of analytical procedure and all raw data are given in the tables.
Ce rapport rassemble des données analytiques sur 73 éléments dans trois échantillons, BIR-1, DNC-1 et W-2, publiées dans 94 articles scientifiques ou rapports techniques. Quand cela a été possible, les valeurs de consensus (moyenne) sont présentées pour chaque élément avec l'incertitude exprimée un écart-type. Des valeurs moyennes en fonction des procédures analytiques sont également présentées.     

Trace Determination of Strontium and Barium in River Waters by Inductively Coupled Plasma-Atomic Emission Spectrometry Using an Ultrasonic Nebulizer

Inductively coupled plasma-atomic emission spectrometry in conjunction with an ultrasonic nebulizer was employed for the determination of Sr and Ba in river waters at parts per billion (μg l⁻¹) levels without pre-concentration. The ultrasonic nebulizer, equipped with a desolvation system, enhanced the analytical sensitivity by ten to twenty fold compared to conventional pneumatic nebulizers. The detection limits for Sr and Ba, ascertained from blanks and reference samples made in 0.05% NaCl solution, were 0.045 μg l⁻¹ and 0.16 μg l⁻¹ respectively. The accuracy of measurements, based on analyses of solutions of reference materials (G-2 and W-1) and multielement commercial standards (Merck®), was ± 10%. Replicate analyses of samples and reference samples showed measurement precision to be to be better than ± 5%, which is adequate considering that the concentration of Sr and Ba in river waters varies by one to two orders of magnitude.     

TERMINOLOGY FOR GEOLOGICAL REFERENCE MATERIAL VALUES: A PROPOSAL TO THE INTERNATIONAL ORGANISATION FOR STANDARDISATION (ISO), PRODUCERS AND USERS

A new terminology is proposed for categorising values in geological reference materials based on the confidence that may be placed in an individual datum. This classification scheme is designed to be applicable to data derived from both cooperative analysis programmes and compilations of data published in the literature. Use of the following terminology is proposed: "certified value equivalent", "recommended value" and "provisional value", depending on the associated one sigma confidence limits and other analytical criteria listed in Table 1. To demonstrate the application to data that was originally assessed using different criteria and terminology, the proposed scheme has been used to reclassify data derived from the cooperative analysis program for USGS SDO-1 (Devonian Shale) and a compilation of published data for USGS G-1 (granite).     

Statistical model of silicate analysis and results of investigation of G-1 and W-1 samples

An analysis of the results of investigation of the G- 1 and W- 1 samples are given and differ from F. Chayes’ point of view. Results of the samples can be evaluated by comparison of frequency-distribution properties of determinations for chemical elements from different laboratories with some standard distribution, which gives the idea of a statistical model. The comparative results indicate that oxides from minerals of the same density have positive correlations and that oxides from minerals of different density have negative correlations. The different results therefore are not from the precision of analysis, but rather from differentiation of sample powder particles by density and shape in the course of preparation.     

Multi-collector ICP-MS Analysis of Pb Isotope Ratios in Rocks: Data, Procedure and Caution

The authors measured Pb isotope compositions of seven USGS rock reference standards, i.e. AGV-1, AGV-2, BHVO-1, BHVO-2, BCR-2, BER-1/1 and W-2, together with NBS 981 using a micromass isoprobe multi-collector inductively-coupled plasma mass spectrometer (MC-ICP-MS) at the University of Queensland. 203Tl-205Tl isotopes were used as an internal standard to correct for mass-dependant isotopic fractionation. The results for both NBS 981 and USGS rock standards AGV-1 and BHVO-1 are comparable to or better than double- and triple-spike TIMS (thermal ionization mass spectrometry) data in precision. The data for BHVO-2 and, to a lesser extent, AGV-2 and BCR-2 are reproducibly higher for 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb than double-spike TIMS data in the literature. The authors also obtained the Pb isotope data for BIR-1/1 and W-2, which may be used as reference values in future studies. It is found that linear correction for Pb isotopic fractionation is adequate with the results identical to those corre     

Neutron Activation Analysis of Two USGS Rock Reference Samples (Granite G-2, Andesite AGV-I) and Discussion in The Light of Compiled Data

New data for 21 trace elements including eight rare-earths, determined by neutron activation analysis (NAA) in two rook reference samples (Granite G-2, Andesite AGV-1), are compared with the preferred values previously proposed. Using compiled data published in 1969 and in 1972, further comparisons are made with the preferred means calculated for different methods of trace analysis. NAA data compiled in 1969 and in 1972 and new results published since then are assembled in two tables for the 21 elements. These 1976 NAA data lead us to suggest slight revisions of the preferred values for five to ton elements in each sample.     

The Precision of Classical Rock Analysis

Three rock reference samples. W-2, DNC-1, and BIR-1, were analysed five times over several months by classical chemical methods using a Youden Square as the experimental design. A significant variation for the data classified by months was found for SiO₂, CaO, H₂O^-, and TiO₂ among the 15 constituents determined. Nevertheless, most standard deviations for the five data for each oxide in any sample, as well as the error standard deviations from the analyses of variance, are less than or approximately equal to the allowable difference between duplicate determinations traditionally used as limits of error. We also determined nine constituents in three portions each of two samples, W-2 and DNC-1, the six portions being analysed concurrently. F ratios for 16 comparisons of the variances of the five data for an oxide obtained over several months and of the three data determined as a group were significant for only one oxide, total iron as Fe₂O₃ in W-2. We conclude that, if a chemist analyses rock samples carefully, the variation of the determinations will be the same for portions analysed as a group, or analysed over a time interval.     

准噶尔盆地北部顶山地区乌伦古河组W-1旋回岩石-地球化学特征

顶山地区是1992—1994年在准噶尔盆地开展的小比例(1：100万-1：50万)砂岩型铀矿区域预测工作中，划分出的一级远景区，并于1998—2002年进行的1：25万～1：20万带钻铀矿区域预测评价工作进一步落实的砂岩型铀成矿远景区，在主要目的层乌伦古河组的W-1旋回中已发现3个工业铀矿化孔．通过对研究区的地质构造特征W-1旋回岩石-地球化学特征等分析研究，认为该旋回为一套厚大的砾质辫状平原相砾岩、砂砾岩、(含砾)粗砂岩组合，夹薄层泥岩、粉砂岩，根据岩石结构、构造等特征，划分出3种岩石类型．同时乌伦古河组W-1旋回原生灰色岩石分布较为局限，大致呈EW向带状展布，并向东部延伸至杜热一带．东部杜热地区是值得进一步工作的远景区．     

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.