The Precision of "Rapid" Rock Analysis And the Homogeneity of New USGS Standard Rock Samples

Additional analytical data for the thirteen oxides usually determined in a rock analysis by wet methods and estimates and, conclusions from the analysis of variance are presented for the eight new USGS rock standards STM-1, RGM-1, QLO-1, SCo-1, MAG-1, SDC-1, BHVO-1 and SGR-1. The "single-solution" method of sample dissolution, and the "rapid methods" described by Shapiro were used. Three bottles of each standard were analyzed in duplicate, providing six replicate analyses of each sample. Relative standard deviations ranged from 0. 00 to 202 %, with only 12 of the possible 104 sample-oxide combinations exceeding 10 %. Most deviations exceeding 10 % occur with oxides at very low concentrations or with the determi-nation, of H₂O⁺ and CO₂, all of which often yield poor precision. These data indicate that the rapid wet chemical methods, except possibly for H₂O⁺ and CO₂, or when very low concentrations are present, can be considered reliable. Of the 104 F-ratios calculated during the analysis of variance for sample-oxide combinations, only eight equal or exceed the tabled value of 9. 55 for F_0.95 (d. f. 2, 3). These data strongly support the conclusion that the contents of the bottles may be considered homogeneous for most oxides determined. When our data for an oxide in the several samples are plotted versus similar data in the USGS Prof. Paper 840 by several methods, the plots generally show good agreement for most sample-oxide combinations, but approximately thirty of the 104 show substantial differences, with no obvious correlation between the various methods used or the nature or magnitude of the differences.     

Atomic Absorption Determination of Ultratrace Elements in Geological Materials by Vapor. Hydride-Forming Techniques. I. Mercury

A method is described for the determination of mercury at nanogram levels in geological materials by flameless atomic absorption spectroscopy after metal vapor generation. Mercury is converted to a soluble form by H₂SO₄-HNO₃ attack in a teflon bomb at 180°C for 90 minutes. Metal Hg vapor is obtained by reaction with combined NaBH₄-NaOH using the Perkin-Elmer MHS - 10 hydride system and determined at room temperature. Mercury can be easily determined in most silicate materials. The sensitivity of the method depends essentially on the purity of the reagents and contaminations during handling rather than on instrumental capabilities. A detection limit of about 10 ng/g Hg for 0.5 g samples has been achieved with the use of normal "suprapure" reagents. Mercury contents on some USGS, CRPG and ANRT reference samples are reported.     

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.     

3D seismic study of a ductile shear zone from laboratory and petrofabric data (Saint Barthélémy Massif, Northern Pyrenees, France)

In order to constrain interpretations of seismic reflection records more effectively, the seismic properties of a middle crustal section exposed in the Saint Barthélémy Massif have been determined. The massif, transected by a 200 m thick shear zone has been systematically sampled for density measurements and modal analysis has been performed in order to define the spatial variations of physical properties. Seismic velocities ( V _p, V _S, shear wave birefringence), have been measured on five representative samples to 600 MPa and 600°C simultaneously in the three structural directions (X, Y and Z). For two samples, the experimental data have been compared with calculated values, based on petrofabric analyses. The Lattice Preferred Orientation (LPO) is determined using universal stage, electron channelling microscopy and neutron diffraction goniometry. Using the experimental and calculated velocity data, we establish a lateral homogeneous anisotropic model.     

Major Element Data (1966–1978) for The Six "Nimroc" Reference Samples

The results are given for all the determinations made by the co-operating laboratories of major elements in the six NIMROC rock samples (granite, syenite, lujavrite, norite, pyroxenite and dunite) prepared by the National Institute for Metallurgy in 1966. Relevant statistical data are given for the sets of results for each major constituent, and recommended values for all constituents except Al₂0₃, Na₂0, K₂0and CO₂ in dunite, Fe₂O₃, MgO and CO₂ in the granite, Fe₂₃ and CO₂ in the norite and CO₂ in the pyroxenite.
This report and that on the trace and minor elements issued in 1978 complete the revision of the recommended values. It is suggested that analysts should concentrate rather on those constituents for which the results have shown such a wide scatter that they can be of no usc for reference purposes, than on those for which the ualues are fairly well established.     

Geology and Mineralization at the Dajing Tin-polymetallic Ore Deposit, Inner Mongolia, China

Abstract: Dajing is a large-scale tin–polymetallic ore deposit in north China with Sn, Cu, Pb, Zn, Ag, and minor elements such as Co and In. The deposit is controlled by a passage-host structure system. Two groups of NE direction faults such as F₂ and F₁ are characterized by sinistral and multiphase activities, and the syn-ore NE faults with their derivative faults nearly in N-S direction constitute an important structure system as channelway for ore fluid. Around F₂ fault (mineralization center), metallic elements display horizontal zoning outwards from Sn, Cu to Cu, Sn, Pb, Zn, Ag and to Pb, Zn, Ag. Controlled by sinistral pull-apart vein system, the WNW direction host structure yielded the ore vein to "W" shape on horizontal plan while to staircase shape on vertical profile. Multiperiodic activities of the host structures system lead to multistage of ore mineralization. Four mineralization stages are recognized in the main mineralization, i.e. 1) cassiterite–arsenopyrite–quartz stage, 2) cassiterite-sulfide (or Cu–poly–metallic mineralization) stage, 3) massive pyrite stage, and 4) galena-sphalerite stage. Besides, fluid activities are identified here at the pre-mineral stage of the formation of quartz veins and sheared deformation, and at the post-mineral stage of quartz–calcite–fluorite deposition.
The earlier tin-rich ore solution raised from NE faults and its nearly N-S derivatives filled the NW-WNW direction fractures, and formed tin ore veins. Subsequent mineralization of Cu-polymetallic stage, pyrite stage and galena-sphalerite stage, overlapping on the same fracture system, sequentially expanded outwards from the fractures, and produced different kinds of ore types and mineralization zoning.     

Determination of Lithium Contents in Silicates by Isotope Dilution ICP-MS and its Evaluation by Isotope Dilution Thermal Ionisation Mass Spectrometry

A precise and simple method for the determination of lithium concentrations in small amounts of silicate sample was developed by applying isotope dilution-inductively coupled plasma-mass spectrometry (ID-ICP-MS). Samples plus a Li spike were digested with HF-HClO₄, dried and diluted with HNO₃, and measured by ICP-MS. No matrix effects were observed for ⁷Li/⁶Li in rock solutions with a dilution factor (DF) of 97 at an ICP power of 1.7 kW. By this method, the determination of 0.5 μg g^-1 Li in a silicate sample of 1 mg can be made with a blank correction of < 1%. Lithium contents of ultrabasic to acidic silicate reference materials (JP-1, JB-2, JB-3, JA-1, JA-2, JA-3, JR-1 and JR-2 from the Geological Survey of Japan, and PCC-1 from the US Geological Survey) and chondrites (three different Allende and one Murchison sample) of 8 to 81 mg were determined. The relative standard deviation (RSD) was typically < 1.7%. Lithium contents of these samples were further determined by isotope dilution-thermal ionisation mass spectrometry (ID-TIMS). The relative differences between ID-ICP-MS and ID-TIMS were typically < 2%, indicating the high accuracy of ID-ICP-MS developed in this study.     

Cu–Fe Bearing Zinc Sulfide from Laloki Stratabound Massive Sulfide Deposit, Papua New Guinea: Chemical Characterization

Abstract: A strange, unidentified, Cu-Fe bearing zinc sulfide occurs in the Laloki massive sulfide deposit, Papua New Guinea. The mineral is optically uniform in texture but is chemically variable and zoned even within a single grain. Copper contents vary from 0.1 up to 8.85 wt%. Iron reaches 18.31 wt% at maximum and decreases as Cu increases. It is remarkable, however, that the total Fe+Cu remains essentially unchanged between roughly 18 and 20 wt%. Zn and S are least variable, giving 45.85–47.84 wt% and 33.48–34.58 wt%, respectively. Other trace elements such as Cd and Mn are in general less than 0.2 wt%. It is strongly suggested that the mineral in question constitutes a unique Fe-Cu substitutional solid solution series belonging essentially to the Zn–Fe–Cu–S system.
The ideal chemical formula of the solid solution series can well be presented as Zn₁₀(Fe, Cu)₅S₁₅ or Zn₂(Fe, Cu)S₃, where Fe is always greater than Cu. It is intriguing that chalcopyrite blebs are recognizable restrictively only in nearby portions of the Cu-rich end member with the ideal composition close to Zn₁₀Fe₃Cu₂S_15. It has been confirmed by vacuum-sealed heating experiments that this mineral is decomposed to produce chalcopyrite and Fe-bearing normal sphalerite at temperatures below 200C. This would provide another evidence for the existence of such distinct phase as suggested here.     

Zircon U–Pb age, trace element and Hf isotope composition of Kongling terrane in the Yangtze Craton: refining the timing of Palaeoproterozoic high-grade metamorphism

U–Pb age, trace element and Hf isotope compositions of zircon were analysed for a metasedimentary rock and two amphibolites from the Kongling terrane in the northern part of the Yangtze Craton. The zircon shows distinct morphological and chemical characteristics. Most zircon in an amphibolite shows oscillatory zoning, high Th/U and ¹⁷⁶Lu/¹⁷⁷Hf ratios, high formation temperature, high trace element contents, clear negative Eu anomaly, as well as HREE-enriched patterns, suggesting that it is igneous. The zircon yields a weighted mean ²⁰⁷Pb/²⁰⁶Pb age of 2857 ± 8 Ma, representing the age of the magmatic protolith. The zircon in the other two samples is metamorphic. It has low Th/U ratios, low trace element concentrations, variable HREE contents (33.8 ≥ Lu_N≥2213; 14.7 ≤ Lu_N/Sm_N ≤ 354) and ¹⁷⁶Lu/¹⁷⁷Hf ratios (0.000030–0.001168). The data indicate that the zircon formed in the presence of garnet and under upper amphibolite facies conditions. The metamorphic zircon yields a weighted mean ²⁰⁷Pb/²⁰⁶Pb age of 2010 ± 13 Ma. These results combined with previously obtained Palaeoproterozoic metamorphic ages suggest a c. 2.0 Ga Palaeoproterozoic collisional event in the Yangtze Craton, which may result from the assembly of the supercontinent Columbia. The zircon in two samples yields weighted mean two-stage Hf model ( T _DM2) ages of 3217 ± 110 and 2943 ± 50 Ma, respectively, indicating that their protoliths were mainly derived from Archean crust.     

Determination of Carbonate Carbon in 41 International Geochemical Reference Samples by Coulometric Method

The carbonate-carbon (CO₂) content of forty-one geochemical reference samples has been determined by coulometric method following acid treatment of the sample for releasing CO₂. The method is superior to the conventional methods in speed, accuracy, sensitivity, specificity, and the coverage of CO₂ range. The results on NBS limestone samples agree well with the certified values. The precision of the method is 0.5 % r.s.d., and the practical detection limit is 10 ppm C.     

The H2O+ Contents of Some Geochemical Standards Predicted by a Calibration Line

The combined water (H₂O⁺) in 30 geochemical standards having known and unknown water contents was determined by an elemental analyzer on 1 day during each of 6 weeks over a period of several months. The analysis of variance of the data measured in the form of a Youden square shows an extremely significant variation due to some unknown cause during the weeks in which the data were obtained. The higher water contents of the first two sets were obtained in the fall season when this area (Reston, Va.) has high and variable humidity, whereas the last four sets were measured during winter months. Humidity, however, was not included as a variable in the design and was not measured. The first two of three average blanks for H₂O⁺, measured after determining H₂O⁺ contents of about 11 percent for two samples, are noticeably higher than the third average blank. Similarly, the first of two average blanks for H₂O⁺, measured after determining the H₂O⁺ content (4.70 percent) of PCC-1, is higher than the second. Data for the last 4 weeks were used to calculate the line of regression and the extremely significant correlation coefficient. The line is used to predict suggested revisions of the “best” H₂O⁺ contents of the standards. Coefficients of variation calculated from the data for the last 4 weeks indicate that there is no severe sampling problem due to the small sample size (20 mg) taken for the determinations. The coefficients follow the general trend of large coefficients for samples containing the least amount of the constituent (BHVO-1: x?= 11.76% H₂O⁺; C.V. = 7.3%) and of small coefficients for samples containing the greatest amount (BX-N: x?= 11.76% H₂O⁺; C.V. = 0.4%).     

Mass Transfer, Oxygen Isotopic Variation and Gold Precipitation in Epithermal System: A Case Study of the Hishikari Deposit, Southern Kyushu, Japan

Abstract: Transportation of various kinds of elements occurred in wall rocks (Quaternary andesites) during the hydrothermal alteration accompanied by the Hishikari epithermal gold mineralization. For example, K₂O and MgO contents of wall rocks decrease away from the gold-quartz veins, while (CaO+Na₂O) content increases, and SiO₂ content is variable near the veins. Hydrothermal alteration zoning and bulk compositional variations in wall rocks suggest that the mixing of hydrothermal solution and acidic groundwater took place an important role as the cause for the hydrothermal alteration and bulk compositional variations. The relationship between dissolved silica concentration and temperature of hydrothermal solution mixed with groundwater is obtained based on precipitation kinetics-fluid flow–mixing model, and the computed results are compared with the distribution of SiO₂ minerals (quartz and cristobalite) in the hydrothermal alteration zones. This comparison suggests that the most reasonable flow rate of fluids migrating through hydrothermal alteration zones, and A/M (A: surface area of rocks interacting with fluid, M: mass of fluid) are estimated to be ca. 10^-4.2 m/sec, and ca. 0.10 m²/kg, respectively. The mixing of two fluids (hydrothermal solution and acidic groundwater) can also explain δ¹⁸O zoning in the altered country rocks, hydrothermal alteration zoning from K-feldspar through K-mica to kaolinite from the center (veins) to margin, and deposition of gold.     

Observations on New Approaches for the Determination of Platinum-Group Elements, Gold and Silver in Different Geochemical Samples from Siberia and the Far East

Some recent experiments on the determination of Au and the platinum-group elements (PGE) in geochemical samples are reviewed. Emphasis is given to the determination of ultra-low levels of PGE concentrations in resistant matrices, including chromites, molybdenites and ultrabasic ores. The problems and features of PGE determination in samples of various chemical composition are considered. For each sample type studied, a series of sample preparation techniques are proposed. These techniques included acid digestion, fusion with sodium peroxide, cold sintering with an oxidizing mixture of Na₂O₂+ Na₂CO₃ and also oxidizing fluorination with bromine trifluoride. A new approach for preparing geochemical material prior to digestion, based on mechano-chemical activation with simultaneous hyperfine grinding, is proposed and studied. The instrumental determination of PGE contents was carried out directly by AAS from extracted organic phases. It was found that a combination of digestion processes was required to achieve geochemical background levels of Au and PGE concentrations with the following detection limits: Pd, Rh - 1 ng g⁻¹, Pt, Ru - 10 ng g⁻¹, Au - 0.2 ng g⁻¹, Ag - 0.1 ng g^−1. The uncertainty in PGE and Au determination in geochemical samples is dependent on metal concentration, and also on their distribution in samples. The total analytical uncertainty of the proposed method is between 15-30%.     

The selenium content of U.S.G.S. standard rocks

Selenium was determined in duplicate portions from three bottles of six U.S.G.S. standard rocks by a spect rofluorimetric procedure. The following averages, as p.p.m. Se, were obtained: PCC-1, 0.031; GSP-1, 0.088; BCR-1, 0.12; SCo-1, 0.91; MAG-1, 1.3; and SGR-1, 3.7. One-way analysis of variance of the several sets of data showed no significant differences in the selenium content among bottles of any specific rock; these samples may be accepted as homogeneous for their selenium contents by this analytical method.     

Carbon sources in arc volcanism, with implications for the carbon cycle

New CO₂/³ He data from the East Sunda Arc (Indonesia) confirm earlier observations that arc volcanic gases have higher CO₂/³ He ratios than MOR environments.On average, > 80% of arc volcanic CO₂ is recycled, exogene carbon. Addition of a few percent of carbonate-bearing sediments to the mantle wedge explains much of the carbon abundance andcarbon isotopic data of arc gases, but can not explain the He isotope observations. The CO₂/³He in arc volcanoes is not strongly dependent on the composition of modem trough sediments (e.g. deep sea clays vs carbonate-rich sequences), and calcite veins in the hydrothermally altered subducted slab may provide a contribution to the recycled carbon flux of, arcs. The sum of globally deep-subducted sediment and slab carbon exceeds the estimated arc CO₂ flux, and approximately 3.5 teramole of carbon may return annually to the mantle in convergent zones. The modem combined processes of MOR volcanism, slab alteration, and subduction volcanism do not produce a substantial carbon flux into the exosphere, and rate-changes in ocean floor spreading are unlikely to cause major changes in atmospheric CO₂ as a result of changes in the volcanic CO₂ fluxes. Intense pulses of flood basalt volcanism, however, may alter the CO₂ contents of the atmosphere over the course of a millenium or so, and influence global climate.     

Magmatic and hydrothermal processes in the Bouvet Triple Junction Region (South Atlantic)

Results of electron microprobe and microthermometric studies of samples collected from the Bouvet Triple Junction Region (BTJR) during a joint Russian-Italian geological expedition on the R/V Academician Nikolaj Strakhov (1994) have revealed new data on the composition of basaltic magmas and oceanic hydrothermal fluids connected with magmatic processes. Detailed analysis of basaltic glasses shows that the modem Mid-Atlantic Ridge (MAR) rift valley is composed of normal mid-ocean ridge basalts with low concentrations of K₂ O and TiO_z (N-MORB), while its flanks are more enriched with these components approaching E-MORB. A marked influence of the Bouvet hot spot volcanism on magma generation on the South-West Indian Ridge (SWIR) near Bouvet Island is observed. Basaltic melts in this area belong to alkalic and transitional series and have maximum contents of K₂O, TiO₂, H₂O.
Microthermometric analyses of fluid inclusions in the samples from the BTJR have revealed major differences in the oceanic hydrothermal fluid systems on the MAR and near SWIR, which depends on the peculiarities of magma. In the area of the MAR (with dry melts) only H₂O solution inclusions in quartz were found; thus, seawater is probably the only primary source of hydrothermal fluids (NaCl + MgCl₂+ H₂O; T = 170–200°C). In the SWIR area (with the high content of water in melts) syngenetic liquid CO₂ and H₂O solution inclusions in quartz indicate the influence of the magmatic fluid component on the ore-forming water/carbon dioxide solutions (NaCl + CaC1₂+ H₂O + CO₂; T = 200–310 °C; P = 900–1700 bar).     

Two-stage growth of porphyroblastic biotite and garnet in the Barrovian metapelites of the Imjingang belt, central Korea

Porphyroblastic biotite and garnet in the Barrovian metapelites of the Imjingang belt, Korea, were investigated to unravel the sequence and mechanism of mineral growth. Poikiloblastic biotite contains straight inclusion trails (S_i) discontinuous to the major foliation, and develops clear zones at the grain margin. These microstructures suggest an initial growth of biotite between two contractional deformations (D_n−1 and D_n) followed by an overgrowth during D_n. Although garnet poikiloblasts contain variable S_i patterns, their major growth is likely to have occurred during D_n on the basis of compositional relationships among variable garnet types. Early poikiloblasts of both minerals were formed by chemical replacement of the matrix that consisted mainly of chlorite, muscovite and quartz. Subsequent growth of biotite was governed by a crack-filling mechanism, and was accompanied by the production of extensional cracks inside or around biotite, providing fluid pathways. The overgrowth of garnet was favoured at the biotite–garnet interface, and the consequence was a partial replacement of inclusion-poor garnet after biotite subsequent to D_n. In addition, clear zones and pressure shadows as well as the matrix around biotite porphyroblasts were replaced by garnet, suggesting an inheritance of various pre-existing microstructures in the S_i pattern of garnet. Further attention is thus required for any attempt to delineate the microstructural interaction between deformation and metamorphism, particularly in a sample containing early-grown porphyroblasts. Microstructural evidence for the two-stage growth of biotite and garnet is present up to the kyanite zone, indicating that this growth mechanism is prevalent during progressive metamorphism of Barrovian metapelites.     

Multi-Element Reference Samples of Black Shale

This paper describes the creation of two new reference samples of black shale, SCHS-1 and SLg-1, collected in the Bodaibo Region of Irkutsk District (Siberia, Russia). These samples have been developed as State Standard Samples to meet the requirements of Russia's Normative Documents, so that they can be recognised by the Russian State Certification Agency and included on the State Register of certified reference materials. SCHS-1 was produced from shale of the Khomolkho suite; SLg-1 represents the average composition of the Sukhoy Log gold deposit (within Au mineralisation). The homogeneity was assessed by applying the concept of potential inhomogeneity, and the inhomogeneity uncertainties (σ_inhom) for the indicator elements that were estimated experimentally by silicate XRF analysis. It was found that a majority of the indicator elements was characterised by σ_inhom/Δ_p < 1/8 (Δ_p is the permissible certification uncertainty), and so σ_inhom was neglected for the indicator elements and all other elements that were included in their respective group. The value of σ_inhom calculated for Fe (σ_inhom,Fe/Δ_p > 1 /8) was taken into consideration for the noble metals and their associated elements (e.g., Ag, As, Au, etc.). More than fifty laboratories (thirty-seven from Russia) were involved in the interlaboratory experiment (ILE) to analyse these reference samples. The data obtained from the ILE allowed SCHS-1 and SLg-1 to be certified for, fifty-one and forty-three elements, respectively, as State Standard Samples.     

Primary carbonate/CO2 inclusions in sapphirine-bearing granulites from central Sri Lanka

High-density CO₂-rich fluid inclusions from a sapphirine-bearing granulite (Hakurutale, Sri Lanka) have been studied by microthermometry, Raman spectrometry and SEM analysis. Based on textural evidence, two groups of inclusions can be identified: primary, negative crystal shaped inclusions (group I) and pseudo-secondary inclusions, which experienced a local, limited post-trapping modification (group II). Both groups contain magnesite as a daughter mineral, occurring in a relatively constant fluid/solid inclusion volume ratio (vol_solid =0.15 total volume). CO₂ densities for group I and II differ only slightly. Both groups contain a fluid, which was initially trapped at peak metamorphic conditions as a homogeneous (CO₂+MgCO₃) mixture. Thermodynamic calculations suggest that such a fluid (CO₂+15 vol% MgCO₃) is stable under granulite facies conditions. After trapping, magnesite separated upon cooling, while the remaining CO₂ density suffered minor re-adjustments. A model isochore based on the integration of the magnesite molar volume in the CO₂ fluid passes about 1.5–2 kbar below peak metamorphic conditions. This remaining discrepancy can be explained by the possible role of a small quantity of additional water.     

Metamorphic decarbonation, silicate weathering and the long-term carbon cycle

The seawater ⁸⁷Sr/⁸⁶Sr curve implies a 50–100 Myr episodicity in weathering rate which requires a corresponding variation in CO₂ degassing from the solid earth to the atmosphere. It is proposed that this is caused by orogenesis, which both produces CO₂ as a result of metamorphic decarbonation reactions, and consumes extra CO₂ as a consequence of erosion-enhanced weathering. Global climate on the geological time-scale is therefore contTolled by the difference between the relatively large and variable orogenic-moderated degassing and weathering CO₂ fluxes.