Re-Os Isotopic Measurements at the Femtomole Level in Natural Samples

Here we describe a new chemical separation method for Os and an improved mass spectrometric procedure for Re and Os. This technique is based on the selective extraction of OsO₄ from aqueous solution in liquid bromine. Among other advantages, this procedure avoids the cumbersome distillation procedure for Os and uses only commercial "off the shelf" PFA teflon labware. Blank levels for 0.5 g sample sizes are: 0.06 pg and 0.5 pg for Os and Re respectively. Samples containing as little as 1 pg g⁻¹ Os can be analysed reliably with this method. Adaptation to other dissolution methods is also discussed.     

Effective Correction of Mass Bias for Rhenium Measurements by MC-ICP-MS

The geochemistry of Re-Os and the recent use of Re as a non-traditional stable isotope both need accurate and precise quantification of ¹⁸⁷Re/¹⁸⁵Re ratios. This paper reports rhenium isotopic data obtained from the analysis of a standard solution and geological samples by MC-ICP-MS. We show that measured isotopic ratios are modified by matrix effects that cannot be accounted for by the standard solution bracketing technique. The bias resulting from measurements on a spiked (¹⁸⁵Re-enriched) sample is shown to alter the apparent Re concentration by several percent. When spiking samples and calibrators with tungsten, simultaneous measurement of tungsten and rhenium isotopes compensates for the matrix-induced modification of mass bias. Rhenium and tungsten are shown to have different fractionation factors. This may be due to the fact that the two elements fractionate in a different but systematic way, or that the reference isotopic ratios used for elemental Re and W are incoherent with one another. The consistency of fractionation through time can be used to obtain an empirical relationship between W and Re measured ratios from a standard solution to obtain a sample's fractionation-corrected ¹⁸⁷Re/¹⁸⁵Re spiked ratio on samples containing pg g⁻¹ levels of Re, even if some matrix capable of affecting mass bias remains in the final solution.     

Quantitative Separation of Molybdenum and Rhenium from Geological Materials for Isotopic Determination by MC-ICP-MS

We have developed a new chemical procedure for the quantitative separation of molybdenum (Mo) and rhenium (Re) from a wide variety of geological samples. A single pass anion exchange separation provided complete recovery of pure Mo and Re in a form that was ideal for subsequent isotope and abundance determination by multi-collector inductively coupled plasma-mass spectroscopy (MC-ICP-MS). An enriched ¹⁰⁰Mo-⁹⁷Mo solution, mixed with the sample before digestion, enabled natural mass-dependant isotopic fractionation of Mo to be determined with an external reproducibility of < 0.12‰ (δ⁹⁸Mo/⁹⁵Mo, 2 s ). Determination of the concentration of Mo and Re in the same sample was achieved by isotope dilution, with instrumental mass-fractionation of Re being corrected by the simultaneous measurement of the ¹⁹¹Ir/¹⁹³Ir ratio. We have applied the new procedure to a variety of samples, including seawater, basalt and organic-rich mudrock. The procedure is ideally suited to palaeoredox studies requiring the precise determination of the Mo isotope composition and the Re/Mo ratio from the same sample.     

Accurate Isotopic and Concentration Analyses of Small Amounts of Pb Using Isotope Dilution Coupled with the Double Spike Technique

A new method has been developed for the simultaneous determination of Pb abundance and Pb isotopic composition with high precision and accuracy for small test portion masses by thermal ionisation mass spectrometry. In this method, a ²⁰⁵pb-²⁰⁴pb double spike is added to samples prior to the chemical separation of Pb, and the isotopic composition of the spike-sample mixture is determined rigorously by the double spike technique using a ²⁰⁷Pb-²⁰⁴Pb spike. The isotopic composition and concentration of Pb in the sample are then obtained by utilising the principle of isotope dilution. Using this technique, replicate determinations of Pb from NIST SRM 981 and GSJ JP-1 (peridotite; 0.07 μg g⁻¹ Pb) were performed. The measured concentration and isotopic data were identical, within uncertainty, to published data or to data that were determined independently in this study. The application of this method to U-Pb dating and the determination of the "initial" Pb isotopic composition was also tested. Lead isotopic compositions and the concentrations of Pb, Th and U were determined for a single batch of samples, through the addition of ²⁰⁵pb-²⁰⁴pb, ²³⁰Th and ²³⁵U spikes to samples prior to chemical separation. Also in these experiments, we confirmed that this routine gives accurate data for Pb, Th and U concentrations and Pb isotopic compositions.     

Determination of Scandium, Yttrium and Rare Earth Elements in Rocks by High Resolution Inductively Coupled Plasma-Mass Spectrometry

The high sensitivity, minimal oxide formation and single internal standard capability of high resolution inductively coupled plasma-mass spectrometry (HR-ICP-MS) is demonstrated in the direct determination of Sc, Y and REE in the international reference materials: basalts (BCR-1, BHVO-1, BIR-1, DNC-1), andesite (AGV-1) andultramafics (UB-N, PCC-1 and DTS-1). Time consuming ion exchange separation or preconcentration were found to be unnecessary. Smooth chondrite normalized plots of the REE in PCC-1 and DTS-1 were obtained in the range 0.8-50 ng g-1 (0.01-0.1x chondrite). Method precision was found to be digestion dependent with an average external repeatability of 2-4% for the basalts, AGV-1 and UB-N, and 10% for PCC-1 and DTS-1. The mass peak due to ⁴⁵Sc was completely resolved from ²⁹Si¹⁶O and ²⁸Si¹⁶O¹H spectral interferences using medium resolution, which casts doubt on the accuracy of Sc determinations using quadrupole ICP-MS. Literature values for Y in rock reference materials were found to be approximately 9% high after HR-ICP-MS and XRF analysis.     

CO2-Laser Extraction-Static Mass Spectrometry Analysis of Ultra-Low Concentrations of Nitrogen in Silicates

A new installation for the analysis of picomole quantities of nitrogen has been designed and constructed. It permits the simultaneous analysis of N and rare gases extracted from silicates by heating. The extraction procedure involves the use of a CO₂ laser as a heater, and the analysis is made by static mass spectrometry using a high sensitivity, high resolution mass spectrometer. Procedural blanks of 2 picomoles N₂ (60 picogram N) allow us to analyse routinely N in mg-sized samples such as mantle-derived and meteoritic minerals, and Lunar soil grains.     

Petrographic Characteristics and Alteration Geochemistry of Granite-hosted Tungsten Mineralization at Degana, NW India

Abstract. Vein type tungsten mineralization at Degana is genetically and spatially associated with the Degana Granite. The deposit is characterized by pervasive wall rock alteration around the mineralized quartz veins. Laterally three different alteration zones, greisen, silicification and potassic zones, are marked based on the field features, mineral assemblages and geo-chemical characteristics. In the present paper, systematic mineralogical and chemical variation in these alteration zones is reported. Thick mono-mineralic (zinnwaldite) selvages around the veins characterize the deposit. Plagioclase and alkali feldspar are low in the greisen zones while K-feldspar shows more increase than plagioclase in the potassic zone. Quartz is uniformly high in all the alteration zones, but it shows an anomalous value in the silicification zone. Al₂O₃ concentration shows initial depletion in greisen zone with gradual increase away from the contact. MgO and FeO are higher in greisen zone than silicification and potassic zones. The potassic zone is characterized by the depletion of Na₂O and higher value of K₂O.
The common presence of topaz and fluorite as both primary and secondary minerals and fluorine-bearing micas suggest fluorine partitioning in substantial amount between granitic melt and coexisting aqueous fluid phase and higher HF activity during the evolution of hydrothermal fluid. The mutual relationship of the fluorine minerals (topaz and fluorite) in the different alteration zones suggests an increase in the Ca²⁺ activity and decrease of H+ activity during the fluid evolution from greisenization towards alkali-metasomatised granite and the fluid is assumed to change from low to high activity ratio of Ca²⁺/H+.     

The occurrence of deerite in highly oxidizing conditions within the 'schistes lustrés'of eastern Corsica

Abstract A deerite-bearing rock occurs at the boundary between quartzite and metabasites within the 'schistes lustrés'of eastern Corsica. It contains the typomorphic assemblage pyroxene, blue amphibole, hematite and magnetite. Pyroxene shows homogeneous composition close to the aegirine end-member and blue amphibole is zoned from crossite core to riebeckite rim. The bulk chemical analysis of the rock is remarkable by its very high iron content and the presence of an unusually large amount of Zn which is concentrated in both deerite and amphibole. Electron microprobe analyses of the Corsican deerite are compared with those published in the literature; as shown by deerite from the Fransciscan iron formation, the principal substitution for Fe²⁺ is Mn whereas the amount of substitution for Fe³⁺ is low. In the system SiO₂-FeO-Fe₂O₃-Al₂O₃-Na₂O-MgO-H₂O the typomorphic paragenesis can be described by an univariant reaction interpreted as the result of a pressure decrease. P-T conditions of metamorphism, previously estimated to be 8 kbar and 300°C, are in good agreement with present knowledge of the deerite stability field. The occurrence of hematite and magnetite in equilibrium permits an estimation of the oxygen fugacity (log f o₂= -29.41 bar). Oxidation conditions are higher than those previously mentioned in the literature for similar assemblages.     

Natural Cadmium Isotopic Variations in Eight Geological Reference Materials (NIST SRM 2711, BCR 176, GSS-1, GXR-1, GXR-2, GSD-12, Nod-P-1, Nod-A-1) and Anthropogenic Samples, Measured by MC-ICP-MS

In this study, the Cd isotopic composition of various geological reference materials and anthropogenic samples was investigated. The measurements were made by multicollector ICP-MS and instrumental mass fractionation was controlled using a "sample-standard bracketing" technique. Cadmium isotopic data are reported relative to an internal Cd solution (Cd Spex) and expressed as the ¹¹⁴ Cd/¹¹⁰Cd delta value. Two other Cd solutions (Prolabo and JMC) were analysed and yielded the same 0% delta value. A fractionated Cd metal sample (Münster Cd) was used as a secondary reference material for Cd isotopic measurements and we obtained a ¹¹⁴ Cd/¹¹⁰ Cd delta value of 4.48% relative to Cd Spex solution. As opposed to multi-stage Cd purification previously published in the literature, a new one step anionic exchange purification using dilute HCl for the analysis of Cd isotopes in geological samples was developed. This method enabled a high recovery (> 95%) and effective separation of the sample matrix to be achieved. The long-term external reproducibility was evaluated at 0.12% (2 standard deviations) for the ¹¹⁴ Cd/¹¹⁰Cd ratio, based on reference solutions and replicated measurements of samples over one year. The variation of Cd isotopic composition of natural terrestrial samples is restricted to a small range of 0.4%, which is similar to previously reported results. In contrast, large variations of Cd isotopic composition were found for anthropogenic samples with values as low as −0.64% for a dust sample issued from a lead smelter and values as high as +0.50% for NIST SRM 2711 (metal-rich soil). These variations are 10 times larger than the reproducibility and suggest that Cd isotopes can be useful as tracers of anthropogenic sources of Cd in the environment.     

High Precision Determination of 48Ca/42Ca Ratio by TIMS for Ca Isotope Fractionation Studies

For studies of mass-dependent fractionation of calcium isotopes in natural materials, the ⁴⁸Ca/⁴²Ca ratio is a superior choice to the conventionally measured ⁴⁴Ca/⁴⁰Ca ratio for two important reasons. These are (1) mass-dependent fractionation can be determined free from the effects of inherited or ingrown radiogenic ⁴⁰Ca and (2) this ratio increases the spread of measured isotopic masses by 50%, resulting in statistically better resolution of fractionation, assuming similar precision. A third, though strictly technical, advantage is the inherent ability of a mass spectrometer to measure ratios close to unity (⁴⁸Ca/⁴²Ca) more precisely than very small or large ratios (⁴⁴Ca/⁴⁰Ca). However, because of the very low natural abundance of both ⁴⁸Ca and ⁴²Ca, their ratio has been very difficult to measure, the only attempt so far being on a high mass resolution MC-ICP-MS with a precision of 0.33%. We report here determination of the ⁴⁸Ca/⁴²Ca ratio by the more commonly available and user-friendly multi-collector TIMS using a ⁴³Ca-⁴⁶Ca double-spike, with a significantly better precision of 0.18% (2s). The ⁴⁸Ca/⁴⁰Ca or ⁴⁴Ca/⁴⁰Ca ratio can also be measured in the same mass spectrometer run to provide complementary information on any radiogenic component.     

Nickel–bearing Djerfisherite in Gehlenite-Spurrite Skarn at Kushiro, Hiroshima Prefecture, Japan

Abstract: Djerfisherite occurs intimately intergrown with troilite and pentlandite in gehlenite-spurrite skarn at Kushiro, mainly as inclusions in gehlenite and andradite grains. The mode of occurrence indicates that the djerfisherite formed in the culminated stage of the contact metamorphic-metasomatic process. The chemical compositions of the mineral are approximately represented by a formula of K₆Na(Fe, Ni, Cu)₂₄S₂₆Cl with Ni up to 4. 85. It is likely that high temperature condition corresponding to the formation of gehlenite-spurrite skarn as well as low f_O2 and f_S2 conditions are responsible for the formation of djerfisherite in the potassium-rich chemical environments.     

Determination of High Field Strength Elements, Rb, Sr, Mo, Sb, Cs, Tl and Bi at ng g−1 Levels in Geological Reference Materials by Magnetic Sector ICP-MS after HF/HClO4 High Pressure Digestion

Six low abundance rock reference materials (basalt BIR-1, dunite DTS-1, dolerite DNC-1, peridotite PCC-1, serpentine UB-N and basalt TAFAHI) have been analysed for high field strength elements (Zr, Nb, Hf, Ta, Th and U), Rb, Sr, Mo, Sb, Cs, Tl and Bi at ng g⁻¹ levels (in rock) by magnetic sector inductively coupled plasma-mass spectrometry after HF/HClO₄ high pressure decomposition. The adopted method uses only indium as an internal standard. Detection limits were found to be in the range of 0.08 to 16.2 pg ml⁻¹ in solution (equivalent to 0.08 to 16.2 ng g⁻¹ in rock). Our data for high field strength elements, Rb, Sr, Mo, Sb, Cs, Tl and Bi for the six selected low abundance geological reference materials show general agreement with previously published data. Our Ta values in DTS-1 and PCC-1 (1.3 and 0.5 ng g⁻¹) are lower than in previously published studies, providing smooth primitive mantle distribution patterns. Lower values were also found for Tl in BIR-1, DTS-1 and PCC-1 (2, 0.4 and 0.8 ng g⁻¹). Compared with quadrupole ICP-MS studies, the proposed magnetic sector ICP-MS method can generally provide better detection limits, so that the measurement of high field strength elements, Rb, Sr, Mo, Sb, Cs, Tl and Bi at ng g⁻¹ levels can be achieved without pre-concentration, ion exchange separation or other specialised techniques.     

Talnakhite Associated with Andradite Skarn at Fuka, Okayama Prefecture, Japan

Abstract. Talnakhite occurs in an andradite skarn forming adjacent to a leucocratic quartz monzonite dike intruded into limestone at Fuka. The mineral densely contains exsolution lamellae of chalcopyrite, and the talnakhite-chalcopyrite inter-growth is intimately associated with bornite that contains chalcopyrite as a lattice-form exsolution. The chemical composition of the talnakhite acquired on an electron probe microanalyzer corresponds to Cu_9.00Fe_8.08S_15.92, very close to the ideal chemical formula Cu₉Fe₈S₁₆. Nickel is not detected. The X-ray powder diffraction lines are well indexed on a body-centered cubic cell with a = 10.589 Å. The characteristic (110) reflection of talnakhite is clearly observed at 7.49 Å. The present talnakhite retains the chalcopyrite-like colored polished surface without tarnish in air more than a month.
Talnakhite at Fuka is likely to be derived from breakdown of Cu-rich intermediate solid solution ( iss ), which was in equilibrium with Fe-rich bornite at elevated temperatures. Talnakhite thus formed has survived the subsequent cooling processes, probably because the ƒ_s2 was maintained in suitable levels preventing its decomposition into bornite and chalcopyrite.     

Ijolite versus carbonatite as sources of fenitization

Ijolite-carbonatite complexes are ubiquitously surrounded of an aureole of metasomatically altered rocks. The process of alteration is termed fenitization and is generally caused by peralkaline fluids emanating from cooling alkaline, i.e. ijolite and carbonatite magmas. Ijolites and carbonatites normally occur together and attempts to determine the source of the fenitizing fluids may therefore lead to controversial, if not erroneous, conclusions.
Mineralogical and chemical data of fenites from Oldoinyo Lengai (Tanzania), Fen (Norway), and Alnö (Sweden) are reviewed in the present paper in order to reveal the main factors controlling the fenitization around ijolite and carbonatite. Despite the overall alkaline nature of the process, variables such as XCO₂ of the fluid, activity gradients of SiO₂, Al₂O₃ and CaO, FeO/MgO ratio, f O₂ and temperature gradients may differ, producing distinctive patterns of fenitization around the two magmatic sources. The ijolitic-type fluid has low XCO₂, high activities of alkalies, SiO₂ and Al₂O₃, and low activity of CaO. The f O₂ evolves along the hm-mt buffer conditions and the temperature falls gradually with distance from the magmatic source. The carbonatitic-type fluid has high XCO₂, high activities of alkalies and CaO, and low activities of SiO₂ and Al₂O₃. Temperatures and f O₂ are initially high, but decrease sharply with distance from the source. Moreover, the CO₂-rich fluid may complex and transport the REE.     

钨的气态迁移与岩浆-热液成矿作用:实验研究及其成矿学意义

低密度的水热蒸气和超临界似气流体广泛存在于中地壳至地球表面的各种地质环境中, 是成矿金属搬运和富集的重要介质。火山喷气凝结水、火山结壳和升华物、矿床的流体包裹体气相中均存在具有地质意义的W含量或含钨矿物, 表明W同样可在含水气相中溶解和迁移。本文在350 ℃~400 ℃和压力为60~200 bar的实验条件下, 测定了WO₃-H₂O体系中W在水蒸气和似气流体中的溶解度, 考察了水蒸气压力对W溶解度的影响。结果显示, W在水蒸气中的逸度(或含量)远高于依据无水体系中固体WO₃挥发性数据计算的蒸气压力, 证明气态溶质W与溶剂水蒸气之间存在促进W溶解的水合作用。经热力学方法分析, 认为可能形成了WO₃·nH₂O(g)形式的水合气体物种, 其水合数n在350 ℃、370 ℃和400 ℃时分别为1.4、1.6和2.9。因此WO₃·3H₂O(g)或H₂WO₄·2H₂O(g)及H₆WO₆(g)在温压较高的岩浆-热液或气成-热液成矿环境中(如斑岩系统)对W的气态迁移和浓集可能具有重要作用, 而在温压较低的水热蒸气条件下, W的迁移形式可能以水合数较小的WO₃·H₂O(g)(或H₂WO₄)和WO₃·2H₂O(g)(或H₂WO₄·H₂O)物种为主, 其含量或比例随水蒸气的压力而改变。某些斑岩型和脉型钨(钼)矿床常存在富气体包裹体, 伴随酸性岩浆结晶出溶的以低盐度含水蒸气占优势的岩浆流体对斑岩系统中W、Mo在高温阶段的气态迁移和矿质在花岗岩体顶部和上覆岩层的聚集具有重要意义, 之后蒸气冷凝可产生高盐度的含矿卤水或与渗流地下水混合形成低-中等盐度的成矿流体, 流体的减压沸腾(相分离)和对围岩的交代蚀变导致W、Mo等金属在不同阶段和构造-岩性部位沉淀富集。     

Determination of Platinum and Palladium in Geological Samples by Inductively Coupled Plasma-Atomic Emission Spectrometry after Preconcentration with Immobilised Nanometric Titanium Dioxide

A new method has been developed for the determination of platinum and palladium based on separation and preconcentration with a microcolumn packed with nanometric TiO₂ immobilised on silica gel (immobilised nanometric TiO₂) prior to their determination by inductively coupled plasma-atomic emission spectrometry. The optimum experimental parameters for the preconcentration of Pt and Pd, such as the pH of the sample solution, its flow rate and volume, the type and concentration of eluent and interfering ions, have been investigated. Platinum and Pd could be quantitatively retained by immobilised nanometric TiO₂ in the pH range 6–8, then eluted completely with 2.0 ml of 3% m/v thiourea in 1.0 mol l⁻¹ HNO₃. The detection limits of this method for Pt and Pd were 12 and 7. 6 ng l⁻¹ with an enrichment factor of 100, and the relative standard deviations were 4.7% and 3.3% at the 10 ng ml⁻¹ level. The method has been applied for the determination of Pt and Pd in geological samples with satisfactory results.     

Ionic association in H2O–CO2 fluids at mid-crustal conditions

The equilibrium constant, K _a, of the association reaction to form ion pairs from charged solute species in supercritical solutions can be calculated from a model based on published equations. Log K _a at constant pressure is a linear function of the inverse in the dielectric constant of the fluid times temperature. The dielectric properties of H₂O and CO₂ at supercritical pressures and temperatures can also be evaluated using the Kirkwood equation. Using Looyenga mixing rules, the dielectric constant of H₂O–CO₂ mixtures can be obtained and the change in log K _a with addition of CO₂ in aqueous solutions evaluated. These changes in log K _a with addition of CO₂ are consistent with measured changes of log K _a with addition of Ar in supercritical H₂O–Ar solutions.
Log K _a of KCl and NaCl increase to an increasing extent as the mole fraction of CO₂ increases in H₂O–CO₂ solutions. For instance, at 2 kbar and constant temperature between 400 and 600° C, log K _a of KCl increases by about two orders of magnitude whilst that of NaCl increases by over four orders of magnitude as the CO₂ mole fraction increases from 0.0 to 0.35. Such changes in log K _a will have dramatic effects on the solubility of minerals in CO₂-rich environments.     

Preliminary Investigation into the Use of a High Resolution Inductively Coupled Plasma-Mass Spectrometer with Laser Ablation for Bulk Analysis of Geological Materials Fused with Li2B4O7

The paper presents preliminary results of the use of a high resolution double-focussing, magnetic sector inductively coupled plasma-mass spectrometer (HR-ICP-MS) with ultraviolet laser ablation (LA) for the bulk analysis of geological materials fused with Li₂B₄O₇. Detection limits are based on data from precision measurements of a fused SiO₂ sample of high purity, and sensitivity data (cps/μg g^-1) obtained on the Reference Material (RM) Syenite SY-2. For many trace elements, the detection limits are better than 0.05 μg g^-1 using a sample to flux weight ratio of 1:7.
Calibration curves, which are based entirely on RMs, are established for Hf, Ta, Tb, Tm and Lu. They indicate that, even at this early stage in the development of the technique, data accurate to ˜ 25% can be collected. It is concluded that the method may prove to be a valuable supplement to XRF for low level element concentration measurements; it is also very practical, as the same sample discs can be used for both XRF and LA-ICP-MS analyses.