Carius Tube Digestion Research Articles

Application of addition HClO4 to improve the dissolution process and sensitivity of Os for low-concentration of Os in pyrite

The rhenium (Re) and osmium (Os) isotope systems have long been recognized as effective tools to directly date mineralization and trace the source of metals. In general, 0.4 g of pyrite was dissolved by 11 mL of inverse aqua regia in a 30-mL Carius tube. Larger volumes of acids and a larger Carius tube were required if the sample weight was over 0.4 g. Herein we present an improved dissolution process of the Carius tube digestion method by adding HClO4 to dissolve larger sample weights in smaller volumes of acid. This approach is more suitable for determining low concentrations of Os in metal sulfides. In detail, 0.4 g of pyrite was completely dissolved in a mixture of 1 mL of HClO4 and 3 mL of inverse aqua regia. Notably, addition of 1 mL of HClO4 to 8 mL of inverse aqua regia significantly increases the amount of sample from 0.4 to 0.8 g. Based on our data, while the sample weight was no >0.8 g, addition of 1 mL of HClO4 to inverse aqua regia can not only improve the dissolving capacity significantly, but also avoid Carius tube explosion. Furthermore, the dissolving capacity of HClO4-inverse aqua regia method is much higher than that of H2O2-inverse aqua regia method, which is a typical digestion method for Re-Os dating. This method was certified by reference materials (HLP and JDC). In brief, this new method allows dissolution of larger amounts of sample while consuming less acid. Therefore, this method has more potential for determining low concentrations of Re and Os in metal sulfides.

High‐precision Determination of Gold Mass Fractions in Geological Reference Materials by Internal Standardisation

Determination of gold abundances in natural rock is critical for applications, but very challenging. Here, we report a method for determining gold with a very low mass fraction (> 0.01 ng g−1) in rocks. The method involves Carius tube digestion with reverse aqua regia, chromatographic separation to remove most of the sample matrix and measurement by high‐sensitivity ICP‐MS. The mono‐isotopic element gold was quantified by external calibration using an internal standardisation of gold to platinum that was precisely determined by isotope dilution. The method is robust and the obtained results are indistinguishable (< 5–10%, 2s) from those independently obtained by a standard addition technique on the same solution. The results from reference materials TDB‐1 and GPt‐2 are consistent with the certified values and those determined by HF‐aqua regia digestion, confirming the validity of the method. TDB‐1 (n = 20), GPt‐2 (n = 6), BHVO‐2 (n = 9) and other mafic RMs are homogenous for gold (10–20%, 2s) at the 2 g test portion level; however, sample heterogeneity affects some RMs. Gold and platinum‐group elements also display different extents of sample heterogeneity for different RMs. Given the homogeneity observed for TDB‐1, GPt‐2 and BHOV‐2, they are recommended as well‐suited RMs for inter‐laboratory comparison studies of gold.

Determination of Rhenium in Geological Samples by Isotope Dilution–Multicollector–Inductively Coupled Plasma-Mass Spectrometry with Novel Chromatographic Separation

ABSTRACTA method was developed to determine rhenium contents in geological samples using multicollector–inductively coupled plasma-mass spectrometry (MC–ICP-MS) and extraction with an ion-exchange resin. Samples were digested in Carius tubes and osmium was converted into volatile OsO4, which was purified by distillation and microdistillation. The purified Os contents and isotopic ratios were determined using negative thermal ionization mass spectrometry. After the distillation of Os, the samples were treated with HF, then 1.2 M HCl, and loaded on ion-exchange resin columns. Re was eluted using 0.75 M HNO3 and directly determined by MC–ICP-MS. This method was validated using a series of reference materials and the analytical Re data are consistent with the literature values. This method precision (relative standard deviation) ranged from 0.8 to 6%. The procedural blank and detection limit (3σ) of Re were 1.1 pg and 0.5 pg/g (for a sample size of 2g), respectively. These results indicate that the proposed method can be applied to determine trace Re in geological samples. Using Carius tube digestion combined with HF desilicification and redissolution, the Re and Os contents found in the soluble and insoluble phases of several reference materials indicated that the distributions of Re and Os were homogeneous and heterogeneous, respectively.

Reassessment of Hydrofluoric Acid Desilicification in the Carius Tube Digestion Technique for Re–Os Isotopic Determination in Geological Samples

In this study, Re and Os isotopes were systematically determined in six geological reference materials (RMs; covering a wide range of lithologies) using the Carius tube (CT) digestion technique with and without hydrofluoric acid desilicification. Our results show that the HF desilicification increased the Re extraction efficiency (by 9–15%) evidenced from basaltic and andesitic rocks (e.g., BHVO‐2, TDB‐1 and AGV‐2). This implies that a small proportion of Re resides in silicate phases. For mafic–ultramafic rocks (e.g., BCR‐2, WGB‐1 and WPR‐1), Re extraction efficiencies obtained by the CT digestion with and without HF desilicification were similar. This may indicate that Re in these rocks may dominantly reside in some phases (e.g., magnetite and sulfides) that could be completely dissolved in aqua regia solutions without the aid of HF desilicification. Our results also show that the HF desilicification increased Os extraction efficiency (by 13–99%) in some RMs (e.g., BHVO‐2, WGB‐1 and AGV‐2). This observation suggests that a portion of Os‐rich trace phases may occur as inclusions in the silicate phases that act as isolators at ~ 200 mesh sizes. This study demonstrates that the HF desilicification step prior to CT digestion is important for complete extraction of Re and Os in geological samples.

Determination of Osmium Concentrations and 187Os/188Os of Crude Oils and Source Rocks by Coupling High-Pressure, High-Temperature Digestion with Sparging OsO4 into a Multicollector Inductively Coupled Plasma Mass Spectrometer

The (187)Os/(188)Os ratio that is based on the β(-)-decay of (187)Re to (187)Os (t1/2 = 41.6 billion years) is widely used to investigate petroleum system processes. Despite its broad applicability to studies of hydrocarbon deposits worldwide, a suitable matrix-matched reference material for Os analysis does not exist. In this study, a method that enables Os isotope measurement of crude oil with in-line Os separation and purification from the sample matrix is proposed. The method to analyze Os concentration and (187)Os/(187)Os involves sample digestion under high pressure and high temperature using a high pressure asher (HPA-S, Anton Paar), sparging of volatile osmium tetroxide from the sample solution, and measurements using multicollector inductively coupled plasma mass spectrometry (MC-ICPMS). This methods significantly reduced the total procedural time compared to conventional Carius tube digestion followed by Os separation and purification using solvent extraction, microdistillation and N-TIMS analysis. The method yields Os concentration (28 ± 4 pg g(-1)) and (187)Os/(188)Os (1.62 ± 0.15) of commercially available crude oil reference material NIST 8505 (1 S.D., n = 6). The reference material NIST 8505 is homogeneous with respect to Os concentration at a test portion size of 0.2 g. Therefore, (187)Os/(188)Os composition and Os concentration of NIST 8505 can serve as a matrix-matched reference material for Os analysis. Data quality was assessed by repeated measurements of the USGS shale reference material SCo-1 (sample matrix similar to petroleum source rock) and the widely used Liquid Os Standard solution (LOsSt). The within-laboratory reproducibility of (187)Os/(188)Os for a 5 pg of LOsSt solution, analyzed with this method over a period of 12 months was ∼1.4% (1 S.D., n = 26), respectively.

Re–Os geochronology of the El Salvador porphyry Cu–Mo deposit, Chile: Tracking analytical improvements in accuracy and precision over the past decade

Sulfide minerals from the El Salvador porphyry Cu–Mo deposit, Chile, were dated by Re–Os geochronology to clarify the timing and duration of mineralization. As these data are collected over the past 10years, they chronicle the evolution of Re–Os analytical procedures and improvements in spike-sample equilibration, mass spectrometry and data reduction. Included in the data is the first tennantite–pyrite Re–Os isochron along with tennantite–enargite–pyrite Os tracing of ore metals based on initial osmium systematics (187Os/188Osi). Porphyry-associated mineralization follows the traditional early (A), transitional (B), and late (D) stage classification of relative timing of vein formation. Most Cu- and Mo-bearing sulfides were deposited during stages A and B. Field relationships clearly show the B-stage veins are older than the D-stage veins. Samples analyzed with Carius tube digestion and mixed-double spike indicate B-stage molybdenite mineralization between 41.8 and 41.2Ma. These ages best represent the timing of main-stage mineralization at El Salvador. A five-point 187Re–187Os isochron for pyrite–tennantite from the latest D-stage veins yields an age of 42.37±0.45Ma. The isochron age, while older, is within error of early analyses of molybdenite by alkaline fusion digestion using single Re and Os spikes (42.4–42.0Ma). A separate pyrite and tennantite–enargite pair containing significant common Os yields an initial 187Os/188Os ratio of 0.134±0.042, compatible with a predominantly mantle origin. We appreciate the early analyses for their historical significance while emphasize the geological implications of the 41.8–41.2Ma molybdenite ages. Temperature estimates by sulfur thermometry and fluid inclusions are 390–510°C for the B-stage molybdenites and 230–240°C for the latest D-stage pyrite and tennantite.Analyses based on Carius tube digestion and updated spike calibrations suggest a ∼0.6m.y. duration (∼41.8 to 41.2Ma) in-line with published deposit geochronology. The timing and duration of mineralization from Re–Os dating of ore minerals is more precise than estimates from previously reported 40Ar/39Ar and K–Ar ages on alteration minerals. The Re–Os results suggest that the mineralization is temporally distinct from pre-mineral rhyolite porphyry (42.63±0.28Ma) and is immediately prior to or overlapping with post-mineral latite dike emplacement (41.16±0.48Ma).Based on the Re–Os and other geochronologic data, the Middle Eocene intrusive activity in the El Salvador district is divided into three pulses: (1) 44–42.5Ma for weakly mineralized porphyry intrusions, (2) 41.8–41.2Ma for intensely mineralized porphyry intrusions, and (3) ∼41Ma for small latite dike intrusions without major porphyry stocks. The orientation of igneous dikes and porphyry stocks changed from NNE-SSW during the first pulse to WNW-ESE for the second and third pulses. This implies that the WNW-ESE striking stress changed from σ3 (minimum principal compressive stress) during the first pulse to σHmax (maximum principal compressional stress in a horizontal plane) during the second and third pulses. Therefore, the focus of intense porphyry Cu–Mo mineralization occurred during a transient geodynamic reconfiguration just before extinction of major intrusive activity in the region.

A Method for Rapid Determination of Re and Os Isotope Compositions Using ID‐MC‐ICP‐MS Combined with the Sparging Method

A simple, rapid method for the determination of Re and Os concentrations and isotope compositions using isotope dilution multi‐collector inductively coupled plasma‐mass spectrometry (ID‐MC‐ICP‐MS) combined with Carius tube digestion and sparging introduction of Os was developed. For Os measurement, four channeltron ion counters to detect different Os isotopes were used simultaneously, which led to a drastic reduction in the measurement time. Rhenium isotopes were measured by means of eight Faraday cups with solution nebulisation and an ultrasonic membrane desolvator. The representative 188Os count rate of an Os standard solution containing 50 pg of total Os was approximately 110000–120000 cps at the onset of measurement; the Re intensity of our in‐house 10 pg g−1 standard solution reached 1820 V/μg g−1 with a sample uptake rate of 95–99 μl min−1. These values indicate that the sensitivity of the method was sufficient even for samples with low Re and Os concentrations, such as chert. As the temporal variations of the amplification efficiency of the ion counters differed from one another, we adopted a sample‐calibrator bracketing method to correct the measured Re and Os isotope ratios. The Re and Os concentrations via the isotope dilution method and the 187Os/188Os ratios of two sedimentary rock reference materials (JMS‐2 and JCh‐1) on the basis of the isotope ratios determined by the MC‐ICP‐MS and by negative thermal ionisation mass spectrometry (N‐TIMS) were comparable within their ranges. Based on Os isotope measurement of the IAG reference material [Durham Romil Os (DROsS)], the average difference from the recommended value and precision of Os isotope measurements by the sparging method in combination with multi‐ion‐counters were 0.72% and 0.76% [1RSD (%), n = 29], respectively. The precisions in the 187Os/188Os ratios [1RSD (%)] of JMS‐2, JCh‐1 and DROsS were 0.35–0.71, 1.56–3.31 and 0.99–1.28%, respectively, which depended on their Os ion intensities. No systematic difference was observed between the Re and Os geochemical compositions of JCh‐1 and JMS‐2 obtained by means of digestion with inverse aqua regia and CrO3‐H2SO4 solutions, suggesting that either acid solution can be used for the sparging method of sedimentary rock samples. As CrO3‐H2SO4 solution is believed to liberate predominantly the hydrogenous Re and Os fraction from organic‐rich sediment, the sparging method combined with CrO3‐H2SO4 digestion and multi‐ion‐counters in the mass spectrometry is expected to be a powerful tool for reconstructing the secular change in marine Os isotope compositions with high sample throughput.

Osmium concentrations and 187Os/188Os ratios of three sediment reference materials

187Os/188Os ratios and osmium concentrations were analyzed in sedimentary reference materials JSd-3, JMS-1, and JMS-2, issued by the Geological Survey of Japan, using the isotope dilution method with negative thermal ionization mass spectrometry (ID-N-TIMS). The chemical procedures used in this study are based on Carius tube digestion combined with carbon tetrachloride extraction to separate Os. The obtained 187Os/188Os ratios of JSd-3, JMS-1, and JMS-2 were 0.941-1.149, 0.3894-0.465, and 0.747-0.848, respectively, and their Os abundances were 27.07-39.32 ppt, 80.8-106.6 ppt, and 281-317.2 ppt, respectively. Variations among the samples presumably reflect differences in sources and depositional environments. The Os isotopic ratios and abundances were variable within individual samples. The relative 95% confidence intervals of Os concentrations and isotopic ratios were respectively 13% and 6.2% for JSd-3, 15% and 9.8% for JMS-1, and 4.3% and 4.2% for JMS-2. These variations probably reflect the heterogeneity of the original rock of each reference material. Low concentration and high isotope ratio of JSd-3 probably results from the derivation of the original rocks from continental components with low Os abundance and elevated 187Os/188Os. Inputs of anthropogenic Os were inferred in JMS-1, a nearshore sediment from an urbanized locality, which had high Os contents and relatively low Os isotopic ratios. Greatly elevated Os concentrations and high 187Os/188Os in JMS-2, a pelagic clay, may reflect the scavenging of Os in seawater into Mn-Fe oxyhydroxides deposited on the seafloor.

Ruthenium in komatiitic chromite

The distinction between Ru in solid solution and Ru-bearing inclusions is essential for the predictive modeling of platinum-group element (PGE) geochemistry in applications such as the lithogeochemical exploration for magmatic sulfide deposits in komatiites. This study investigates the role of chromite in the fractionation of Ru in ultramafic melts by analyzing chromite grains from sulfide-undersaturated komatiites and a komatiitic basalt from the Yilgarn Craton in Western Australia. In situ analysis using laser ablation ICP-MS yields uniform Ru concentrations in chromites both within-grain and on a sample scale, with concentrations between 220 and 540 ppb. All other platinum-group elements are below the detection limit of the laser ablation ICP-MS analysis. Carius tube digestion isotope dilution ICP-MS analysis of chromite concentrates confirms the accuracy of the in-situ method. Time resolved laser ablation ICP-MS analyses have identified the presence of sub-micron Ir-bearing inclusions in some chromite grains from the komatiitic basalt. However, Ru-bearing inclusions have not been recognized in the analyzed chromites and this combined with the in situ data suggests that Ru exists in solid solution in the crystal lattice of chromite. These results show that chromite can control the fractionation and concentration of Ru in ultramafic systems.

Re-Os (ICP-MS) DATING OF MARINE OIL SHALE IN THE QIANGTANG BASIN, NORTHERN TIBET, CHINA

Marine oil shale from the Shenglihe oil shale section in the Qiangtang basin, northern Tibet, China, was dated by the Re-Os technique using Carius Tube digestion, Os distillation, Re extraction by acetone and ICP-MS measurement. An isochron was obtained giving an age of 101±24 Ma with an initial 187 Os/ 188 Os ratio of 1.84±0.11(n = 11, MSWD = 3.5). The Re-Os age agrees with the geological age derived from biostratigraphic data, indicating the great potential of the Re-Os method for dating the marine oil shale. Our new data (Bilong Co oil shale) also show that the samples must derive from the same layer of oil shales to determine an accurate and precise depositional age for the marine oil shale with the 187 Re- 187 Os radioisotope system.

Determination of Be in alumina by ICP-OES after Carius tube digestion

Standard Reference Material (SRM®) 699 Alumina (Reduction Grade) was digested in HCl at 240 °C inside Carius tubes. Beryllium was measured with inductively coupled plasma optical emission spectrometry at the 313.107 nm line and quantified to be 2.90 ± 0.24 μg g−1 by the method of standard addition. The uncertainty of the measurement was evaluated by taking into account the often-neglected contribution from the correlation between the intercept and the slope of the regression curve.

Evaluation of a technique for determining Re and PGEs in geological samples by ICP-MS coupled with a modified Carius tube digestion

In the determination of Re and platinum group elements in geological samples, various techniques have been employed for digesting samples, including Carius tube, high-pressure asher (HPA-S), alkali fusion and nickel sulfide fire assay. The normal Carius tube technique is able to digest relatively small amount of sample and has a possible safety problem caused by a high internal pressure. This paper reports a modified Carius tube method which utilizes a sealed stainless steel high-pressure autoclave filled with water to prevent explosion of the tube. During heating, the external and internal pressures of the Carius tube increase simultaneously, such that the possible explosion of Carius tube can be avoided. Consequently, this technique allows a higher temperature (up to 330°C), a greater volume of aqua regia (up to 2/3 of the total volume of the Carius tube) and thus larger sample mass (12 g) relative to the normal Carius tube technique. Fairly good agreement were obtained for PGE poor mafic rocks (IPGE < 0.03 ng/g). The efficiency to dissolve ultramafic rocks and chromites at different temperatures was investigated. We demonstrate that this technique is more effective than normal Carius tube technique for ultramafic rocks and chromites containing refractory minerals and the detection limits and precision can be improved for PGE poor mafic samples. The total procedural blanks are lower than 0.003 ng for Os, 0.03 ng for Re, Ir, Ru and Rh and 0.4 ng for Pd and Pt.

Re-Os (ICP-MS) dating of the massive sulfide ores from the Jinchuan Ni-Cu-PGE deposit

Massive sulfide ore from the Jinchuan Ni-Cu-PGE deposit was dated by Re-Os technique using Carius Tube digestion, Os distillation, Re extraction by acetone and ICP-MS measurement. An isochron giving an age of 833 ± 35 Ma, initial 187 Os/ 188 Os ratio of 0.279 ± 0.018 (MSWD = 1.7) and γ Os = 130 ± 15 is obtained. The Re-Os age obtained agrees, within analytical uncertainties, with previous SHRIMP zircon U-Pb age of 827 ± 8 Ma ( n =5, MSWD = 4.3). The result suggests that the deposit was formed at Neoproterozoic and that the formation of the Jinchuan Ni-Cu-PGE sulfide deposit may be closely related to the plume activity, which were attributed to the breakup of the Rodinia supercontinent. The high γ Os of the massive ores suggests that crustal material was involved in the formation of the Jinchuan deposit, however, the quantity of the added crustal material is less than 10%.

Highly siderophile element geochemistry of 187Os-enriched 2.8 Ga Kostomuksha komatiites, Baltic Shield

New analyses of highly siderophile elements (HSE; Re, Os, Ir, Ru, Pt, and Pd) obtained by Carius tube digestion isotope dilution inductively coupled plasma mass-spectrometry (ID-ICPMS) technique are reported for 187Os-enriched 2.8 Ga komatiites from the Kostomuksha greenstone belt. As a result of a significant improvement in the yield over our previous digestions by the NiS fire-assay technique, these komatiites have now been shown to contain 22 to 25% more Os, Ir, and Pt and 34% more Ru. The emplaced komatiite lavas at Kostomuksha thus had siderophile element abundances comparable to those of the Abitibi belt. The discrepancies observed between the two techniques are interpreted to be the result of incomplete digestion of HSE carriers (particularly chromite) during the NiS fire-assay procedure. Our results for UB-N peridotite reference material agree well with those obtained by the high-pressure ashing digestion ID-ICPMS technique reported in the literature. Two types of komatiite lavas have been distinguished in this study based on the IPGE (Os, Ir, and Ru) behavior during lava differentiation. The Kostomuksha type is unique and is characterized by an incompatible behavior of IPGEs, with bulk solid-liquid partition coefficients for IPGEs being close to those for olivine. Cumulate zones in this type of komatiite lava occupy <20% of the total thickness of the flows. The Munro type exhibits a compatible behavior of IPGEs during lava differentiation. The cumulate zone in this type of komatiite occupies >20% of the total thickness of the flows. The calculated bulk partition coefficients indicate that, as with the other Munro-type komatiite lavas, the bulk cumulate contained an IPGE-rich minor phase(s) in addition to olivine. The non-CI chondritic HSE pattern for the source of the Kostomuksha komatiites calculated here is similar to that of Abitibi komatiites and to average depleted spinel lherzolite (ADSL) and supports the hypothesis of a non-CI chondritic HSE composition of the Earth’s mantle. The absolute HSE abundances in the source of the Kostomuksha komatiite have been demonstrated to be comparable to those of the source of Abitibi komatiites, even though the two komatiites contrast in their Os isotopic compositions. This supports the earlier hypothesis that if core-mantle interaction produced the 187Os/ 188Os radiogenic signature in the Kostomuksha source, it must have occurred in the form of isotope exchange at the core-mantle boundary. Other explanations of the radiogenic Os signature are similarly constrained to conserve the elemental abundance pattern in the mantle source of Kostomuksha komatiites.

A comparison of high accuracy isotope dilution techniques for the measurement of low level sulfur in gas oils

A comparison of high accuracy methods for the analysis of total sulfur in gas oils by three metrology institutes is described. The work contains a comparison of three different aspects of the analysis: sample digestion, instrumental measurement and isotope dilution strategies. Thermal ionisation mass spectrometry (TIMS) in combination with high pressure asher (HPA) or Carius tube digestion has traditionally been used for such high accuracy analysis. However, this paper demonstrates that the faster, less laborious technique of ICP-MS in combination with microwave digestion is equally capable. Results from the comparison experiments show excellent agreement for fuel samples containing sulfur concentrations in the range 11–200 μg g −1. This excellent agreement across the different sample preparation, measurement and isotope dilution techniques has been exploited in the certification of two new diesel fuel reference materials.

Platinum group element geochemistry of komatiites from the Alexo and Pyke Hill areas, Ontario, Canada

Thirty-three whole-rock drill core samples and thirteen olivine, chromite, and sulfide separates from three differentiated komatiite lava flows at Alexo and Pyke Hill, Canada, were analyzed for PGEs using the Carius tube digestion ID-ICP-MS technique. The emplaced lavas are Al-undepleted komatiites with ∼27% MgO derived by ∼50% partial melting of LILE-depleted Archean mantle. Major and minor element variations during and after emplacement were controlled by 30 to 50% fractionation of olivine Fo93–94. The emplaced lavas are characterized by (Pd/Ir)N = 4.0 to 4.6, (Os/Ir)N = 1.07, and Os abundances of ∼2.3 ppb. Variations in PGE abundances within individual flows indicate that Os and Ir were compatible (bulk DOs,Ir = 2.4–7.1) and that Pt and Pd were incompatible (bulk DPt,Pd < 0.2) during lava differentiation, whereas bulk DRu was close to unity. Analyses of cumulus olivine separates indicate that PGEs were incompatible in olivine (DPGEsOl-Liq = 0.04–0.7). The bulk fractionation trends cannot be accounted for by fractionation of olivine alone, and require an unidentified Os-Ir-rich phase. The composition of the mantle source (Os = 3.9 ppb, Ir = 3.6 ppb, Ru = 5.4 ppb, Pt and Pd = 5.7 ppb) was constrained empirically for Ru, Pt, and Pd; the Os/Ir ratio was taken to be identical to that in the emplaced melt, and the Ru/Ir ratio was taken to be chondritic, so that the absolute IPGE abundances of the source were determined by Ru. This is the first estimate of the PGE composition of a mantle source derived from analyses of erupted lavas. The suprachondritic Pd/Ir and Os/Ir of the inferred Abitibi komatiite mantle source are similar to those in off-craton spinel lherzolites, orogenic massif lherzolites, and enstatite chondrites, and are considered to be an intrinsic mantle feature. Bulk partition coefficients for use in komatiite melting models derived from the source and emplaced melt compositions are: DOs,Ir = 2.3, DRu = 1.0, DPt,Pd = 0.07. Ruthenium abundances are good indicators of absolute IPGE abundances in the mantle sources of komatiite melts with 26 to 29% MgO, as Ru fractionates very little during both high degrees of partial melting and lava differentiation.

Determination of Cr in certified reference material HISS-1, marine sediment, by cold plasma isotope dilution ICP-MS and INAA: comparison of microwave versus closed (Carius) tube digestion

The recovery of Cr from National Research Council Canada (NRCC) certified reference material HISS-1 sediment was investigated by non-destructive instrumental neutron activation analysis (INAA) and isotope dilution inductively coupled plasma mass spectrometry (ID-ICP-MS) after two different chemical treatments: (1) microwave dissolution using HNO3, HF, and HClO4, followed by reflux with concentrated HClO4, and (2) a closed system method using sealed Carius tube digestion with HNO3 and HCl at high temperature (240 °C) and high pressure (1 × 107 Pa, ∼100 atm). The first chemical treatment gave recoveries of only ∼50% in agreement with observations of Yang et al. of NRCC. Samples digested in Carius tubes gave recoveries that ranged from 79 to 110% which may reflect heterogeneity in the samples rather than differing recoveries. This is supported by the excellent agreement of the mean value determined by INAA of 31.4 ± 4.5 µg g−1, and the mean value of 28.1 ± 3.9 µg g−1 by Carius tube digestion and the observation that these standard deviations are essentially equal and much larger than the measurement precisions. The results from this study are also in excellent agreement with the certified value of 30.0 ± 6.8 µg g−1. This preliminary study demonstrates that chemical treatment of this sediment with HNO3 and HCl acids in closed system Carius tubes is an efficient and capable preparation method for the determination of Cr in silicate materials which typically contain refractory Cr-bearing minerals. This study also demonstrates the unique advantage of using two independent methods for the determination of Cr in a complex matrix which has a high potential for low chemical recovery.

Rapid determination of Os isotopic composition by sparging OsO 4 into a magnetic-sector ICP-MS

We present a method for the rapid determination of Os isotopic compositions and platinum group element (PGE) concentrations using ICP-MS on the same sample split. The method makes use of transfer of volatile OsO 4 by an Ar gas stream into the torch of a magnetic sector ICP-MS for analysis. A variety of partial or complete sample dissolution methods can be used, namely (1) microwave oven digestion of samples in pressurized Teflon vessels under oxidizing acidic conditions, (2) NiS fire assay for complete sample dissolution and PGE preconcentration, (3) acid leaching techniques to extract labile PGE fractions, and (4) Carius tube digestion. Microwave oven sample digestion with HF–HNO 3–HCl in an all-Teflon system as well as Carius tube digestion also allows the determination of Os isotopic composition and Os and Re concentrations on the same sample split. Spike–sample equilibration can be monitored on-line during sparging into the ICP-MS. The elimination of a nebulizer for Os isotope ratio measurements minimizes memory problems that are often associated with the determination of Os isotope ratios in liquid samples by ICP-MS. The external reproducibility of 187 Os/ 188Os measurements of an in-house Os standard solution using a single-collector, magnetic sector ICP-MS (Finnigan ELEMENT) is 0.78% (1 S.D., n=13) for analyte amounts ranging from 81 pg to 1.22 ng total Os. The ion yield for 7-min data acquisitions is ∼5×10 −5. Compared to negative thermal ionization mass spectrometry (N-TIMS), sample throughput is about on an order of magnitude higher. If NiS fire assay is used for PGE preconcentration, complementary PGE can be determined in the liquid residue by ICP-MS using a microconcentric nebulizer after the extraction of OsO 4.

Ir, Ru, Pt, and Pd in basalts and komatiites: new constraints for the geochemical behavior of the platinum-group elements in the mantle

The concentrations of the platinum-group elements (PGE) Ir, Ru, Pt, and Pd were determined in 18 mantle-derived basalts from a variety of tectonic settings and six komatiites from three locations. All analyses were performed using isotope dilution, Carius tube digestion, and the precise technique of multiple collector inductively coupled plasma mass spectrometry. Multiple analyses of two samples indicate external reproducibilities, based upon separate dissolutions, of approximately 2–9% in the ppt to ppb concentration range. Mid-ocean ridge basalts from the Kolbeinsey Ridge, tholeiites from Iceland and alkali basalts from the Cameroon Line define three individual sample suites that are characterized by distinct major, trace, and platinum-group element systematics. All three-sample suites display correlations of the PGE with MgO, Ni, and Cr. The new analytical results are employed to constrain the geochemical behavior of the PGE during the formation and differentiation of mantle–derived melts. The PGE are inferred to be compatible in sulfides during partial melting with sulfide-silicate melt partition coefficients of ∼1 × 10 4. The fractionated PGE patterns of mantle melts are a consequence of the incompatibility of Pd in nonsulfide phases, whereas Ir and Ru must be compatible in at least one other mantle phase. Model calculations indicate that PGE alloys or spinel may be responsible for the higher compatibility of the latter elements during partial melting. It is further demonstrated that the shape of the melting regime has a profound effect on the PGE systematics of mantle magmas. The systematic trends of the three sample suites in plots of PGE against Ni and Cr are the result of magma differentiation processes that involve fractional crystallization of silicate minerals and the concurrent segregation of an immiscible sulfide liquid. The behavior of the PGE during magma fractionation indicates that the segregated sulfides probably equilibrate with >90% of the silicate magma and that PGE scavenging by sulfides is best described by a combination of batch and fractional equilibrium partitioning.

Carius Tube Digestion for Low-Blank Rhenium-Osmium Analysis

A relatively high-temperature oxidizing digestion using aqua regia has been developed for <0.1-5 g size samples of various types of rocks including silicates, sulfides, and metals prior to Re-Os isotopic analysis. Reactions are accomplished in sealed, thick-walled Pyrex tubes (Carius tubes) at 240 °C and elevated pressures for ∼12 h. This digestion technique dissolves platinum-group element minerals, metals, and sulfides and evidently sufficiently reacts with silicates to release most or all Re and Os contained in a silicate matrix. The procedure also leads to the oxidation of Re and Os to their highest valences and, therefore, promotes the complete chemical equilibration of sample Re and Os with enriched isotopes of Re and Os that are added for isotope dilution analysis. Once sample digestion and equilibration are complete, subsequent Os separation is accomplished by conventional double distillation from sulfuric acid, and Re is separated by anion exchange chromatography. Comparison of conventional Teflon vessel digestions and Carius tube digestions for a diverse suite of geological samples shows that the Carius tube digestion both liberates more Os from most matrices and also is a much more robust method for reproducibly measuring the isotopic composition of a sample.