Description: Strontium isotopes in various marine carbonates were determined using an “AXIOM” MC-ICP-MS in combination with a NewWave UP193 laser ablation unit. Using a modified measurement and data reduction strategy, an external reproducibility of 87Sr/86Sr ratios in carbonates of about 19 ppm (RSD) was achieved. For recent and sub-recent marine carbonates a mean radiogenic strontium isotope ratio 87Sr/86Sr of 0.709170 ± 0.000007 (2SE) was determined, which agrees well with the value of 0.7091741 ± 0.0000024 (2SE) reported for modern sea water (J. M. McArthur, D. Rio, F. Massari, D. Castrodi, T. R. Bailey, M. Thirlwall and S. Houghton, Palaeogeogr. Palaeoclimatol. Palaeoeco., 2006, 242(126), 2006). Compared to published laser-based methods, an improved accuracy and precision was achieved by applying a new data reduction protocol using the simultaneous responses of all isotopes measured. The latter is considered as a new principal approach for isotope ratio evaluation using LA-MC-ICP-MS. A major advantage of the presented method is the direct determination of the stable strontium isotope fractionation. Providing reproducible sample ablation, introduction into the plasma and stable plasma condition, this method excludes the efforts of a quantitative strontium recovery after ion chromatographic separation to avoid additional fractionation of the sample strontium due to chemical pre-treatment/separation (ion chromatography and solution preparation), and is therefore, together with the quicker sample preparation and spatially resolved analysis, advantageous when compared to published solution–nebulization bracketing-standard MC-ICP-MS methods for stable strontium isotope determination.

Description: In order to improve and extend the application of U- and Th-series isotope measurements a new technique for MIC-ICP-MS (multiple ion counting inductively coupled plasma mass spectrometry) was developed. This method uses either two (double MIC) or three (triple MIC) multipliers to measure in static mode in turn the U-isotopes 233U, 234U, 235U and 236U. For online internal standardization, mass bias correction and cross calibration of the multipliers a 233U/236U double spike was used. Applying this method the level of 1‰ 2σ internal precision is reached in less than 30 min, consuming less than 5 ng of total U. The multi-static MIC-ICP-MS method improves the precision by a factor of 5 for U isotope measurement compared with TIMS and by a factor of 2 compared with published ICP-MS methods. Repeated measurements of uranium CRM-145 (otherwise NBL 112A) were performed to test the reproducibility and accuracy of the method. An average 234U/238U value of (5.285 84 ± 0.000 87) × 10−5 or a δ234U value of −36.96 ± 0.16, respectively, was determined for CRM-145 in good agreement with reference data. Based on the precisely determined U isotope ratios we furthermore developed a combined multi-static U- and Th-measurement method. This approach extends this new MIC-ICP-MS technique to those U- and Th-series isotope systems having no constant isotope ratio for normalization (e.g., 230Th/232Th, 230Th/229Th) and is the key for new approaches to determining 226Ra/228Ra and 231Pa/233Pa. The applicability of the methods presented here is demonstrated by accurate dating of very young corals (10–350 y).

Description: Near quantitative separation of analyte elements from the sample matrix is commonly required to obtain precise and accurate stable isotope data, especially if MC-ICP-MS is used in conjunction with the standard-sample bracketing (SSB) technique for mass bias drift correction. Here, we report a robust procedure that allows for the combined chemical separation of Mg, Ca and Fe, using ion-exchange columns that contain 1 ml AG50W-X8 (200-400 mesh) cation exchange resin. Magnesium was separated for isotope ratio analyses from many geological sample types by a single pass through this column. For Mg purification, Be, Ti, Mn, Fe and Al are selectively eluted using dilute HF and an acetone-HCl mixture. The separation of Mg from Ca-dominated carbonate samples and/or a combination of Mg, Ca and Fe separation from the same sample aliquot, is achieved by the adsorption of Ca and Fe onto the ion-exchange resin from 10 M HCl. Following purification, geological reference materials, including water, bone, carbonate and sediment samples, igneous and sedimentary rocks and a chondritic meteorite were analysed by MC-ICP-MS (Mg and Fe isotopes) and double-spike TIMS (Ca isotopes). Average external repeatabilities were +/-0.16 parts per thousand for Mg-26/Mg-24, +/-0.26 parts per thousand for Ca-44/Ca-40 and +/-0.05 parts per thousand for Fe-56/Fe-54 (2sd; n >= 5). Comparison with published data documents the accuracy of the results. For Mg isotope analyses using SSB-MC-ICP-MS, matrix-induced mass bias effects were studied using element additions. The artificial matrices left a memory in subsequent standard analyses, likely due to depositions on the cones. This observation allowed for the detection of matrix effects in unknown samples. Finally, the current status of Mg and Ca zero-delta reference materials is briefly discussed.

Description: Aragonitic clathrites are methane-derived precipitates that are found at sites of massive near-seafloor gas hydrate (clathrate) accumulations at the summit of southern Hydrate Ridge, Cascadia margin. These platy carbonate precipitates form inside or in proximity to gas hydrate, which in our study site currently coexists with a fluid that is highly enriched in dissolved ions as salts are excluded during gas hydrate formation. The clathrites record the preferential incorporation of 18O into the hydrate structure and hence the enrichment of 16O in the surrounding brine. We measured δ18O values as high as 2.27‰ relative to Peedee belemnite that correspond to a fluid composition of −1.18‰ relative to standard mean ocean water. The same trend can be observed in Ca isotopes. Ongoing clathrite precipitation causes enrichment of the 44Ca in the fluid and hence in the carbonates. Carbon isotopes confirm a methane source for the carbonates. Our triple stable isotope approach that uses the three main components of carbonates (Ca, C, O) provides insight into multiple parameters influencing the isotopic composition of the pore water and hence the isotopic composition of the clathrites. This approach provides a tool to monitor the geochemical processes during clathrate and clathrite formation, thus recording the evolution of the geochemical environment of gas hydrate systems.

Description: The marine calcifying algae Emiliania huxleyi (coccolithophores) was grown in laboratory cultures under varying conditions with respect to the environmental parameters of temperature and carbonate ion concentration [CO32-] concentration. The Ca isotope composition of E. huxleyi's coccoliths reveals new insights into fractionation processes during biomineralization. The temperature-dependent Ca isotope fractionation resembles previous calibrations of inorganic and biogenic calcite and aragonite. Unlike inorganically precipitated calcite, the [CO32-] concentration of the medium has no significant effect on the Ca isotope composition of the coccoliths. These results indicate a decoupling of the chemical properties of the bulk medium and the calcifying vesicle. Cellular Ca pathways of E. huxleyi indicate that fractionation cannot occur at the crystal surface, as occurs during inorganic precipitation. The dominant processes leading to the observed Ca isotope fractionation pattern in E. huxleyi are most likely the dehydration of the Ca aquocomplex at the plasma membrane and the attachment of dissolved Ca to proteins of Ca channels. The independence of Ca isotope fractionation from [CO32-] and the small temperature dependence of E. huxleyi are also important for defining the isotopic signature of the oceanic Ca sink. Since coccolithophores contribute to about half the global CaCO3 production, a relatively uniform isotopic composition of the oceanic Ca sink is further supported.

Description: We report delta Ca-44/40((SRM 915a)) values for eight fused MPI-DING glasses and the respective original powders, six USGS igneous rock reference materials, the U-Th disequilibria reference material TML, IAEA-CO1 (Carrara marble) and several igneous rocks (komatiites and carbonatites). Sample selection was guided by three considerations: (1) to address the need for information values on reference materials that are widely available in support of interlaboratory comparison studies; (2) support the development of in situ laser ablation and ion microprobe techniques, which require isotopically homogenous reference samples for ablation; and (3) provide Ca isotope values on a wider range of igneous and metamorphic rock types than is currently available in the scientific literature. Calcium isotope ratios were measured by thermal ionisation mass spectrometry in two laboratories (IFM-GEOMAR and Saskatchewan Isotope Laboratory) using Ca-43/Ca-48- and Ca-42/Ca-43-double spike techniques and reported relative to the calcium carbonate reference material NIST SRM 915a. The measurement uncertainty in both laboratories was better than 0.2 parts per thousand at the 95% confidence level. The impact of different preparation methods on the delta Ca-44/40((SRM 915a)) values was found to be negligible. Except for ML3-B, the original powders and the respective MPI-DING glasses showed identical delta Ca-44/40((SRM 915a)) values; therefore, possible variations in the Ca isotope compositions resulting from the fusion process are excluded. Individual analyses of different glass fragments indicated that the glasses are well homogenised on the mm scale with respect to Ca. The range of delta Ca-44/40((SRM 915a)) values in the igneous rocks studied was larger than previously observed, mostly owing to the inclusion of ultramafic rocks from ophiolite sections. In particular, the dunite DTS-1 (1.49 +/- 0.06 parts per thousand) and the peridotite PCC-1 (1.14 +/- 0.07 parts per thousand) are enriched in Ca-44 relative to volcanic rocks (0.8 +/- 0.1 parts per thousand). The Carrara marble (1.32 +/- 0.06 parts per thousand) was also found to be enriched in Ca-44 relative to the values of assumed precursor carbonates (〈 0.8 parts per thousand). These findings suggest that the isotopes of Ca are susceptible to fractionation at high temperatures by, as yet, unidentified igneous and metamorphic processes.

Description: The calcium isotopic composition of NIST SRM 915b and 1486 provided by the National Institute of Standards and Technology was analysed. The δ44/40Ca values of the two reference materials relative to NIST SRM 915a were: NIST SRM 915b =+0.72 ± 0.04‰ and NIST SRM 1486 =−1.01 ± 0.02‰. NIST SRM 1486 did not require any chemical separation prior to measurement. La composition isotopique du calcium de NIST SRM 915b et 1486, fournis par l'Institut National des Standards et de la Technologie (NIST), a été analysée. Les valeurs du δ44/40Ca obtenues sur ces deux matériaux de référence, relativement au NIST SRM 915a sont: NIST SRM 915b =+0.72 ± 0.04‰ et NIST SRM 1486 =−1.01 ± 0.02‰. Le NIST SRM 1486 n'a nécessité aucune séparation chimique avant analyse.

Description: Recent findings of natural strontium isotope fractionation have opened up a new field of research in non-traditional stable isotope geochemistry. While previous studies were based on data obtained by MC-ICP-MS we here present a novel approach combining thermal ionization mass spectrometry (TIMS) with the use of an 87Sr/84Sr double spike (DS). Our results for the IAPSO sea water and JCp-1 coral standards, respectively, are in accord with previously published data. The strontium isotope composition of the IAPSO sea water standard was determined as δ88/86Sr = 0.386(5)‰ (δ values relative to the SRM987), 87Sr/86Sr* = 0.709312(9) n = 10 and a corresponding conventionally normalized 87Sr/86Sr = 0.709168(7) (all uncertainties 2SEM). For the JCp-1 coral standard we obtained δ88/86Sr = 0.197(8)‰, 87Sr/86Sr* = 0.709237(2) and 87Sr/86Sr = 0.709164(5) n = 3. We show that by applying this DS-TIMS method the precision is improved by at least a factor of 2–3 when compared to MC-ICP-MS.

Description: Stable chlorine isotopes (37Cl, 35Cl) are considered as important tracers of geochemical processes, especially in subduction zone systems. However, high-quality chlorine isotope data are scarcely available. Here we present a comparatively simple procedure for the precise and accurate determination of stable chlorine isotope ratios (δ37Cl) using LA-MC-ICP-MS. Chlorine was extracted from solid samples by pyrohydrolysis. After quantitative precipitation as AgCl the dried precipitates where analysed in a sample-standard bracketing approach using a weak laser ablation (0.3 J/cm2) for sample evaporation. Atlantic Ocean sea salt and the sea water standard IAPSO were used as SMOC (standard mean ocean chloride) for normalisation (δ37Cl = 0 ‰). The precision and accuracy of the presented method was validated analysing the reference materials JB-1a and JB-2. The chlorine isotope ratios of these standards were determined as δ37ClJB-1a = (−0.99 ± 0.06) ‰ and δ37ClJB-2 = (−0.60 ± 0.03) ‰ (errors 2SE), respectively, in accordance with published data. Applying the presented method a total amount of less than 1 μg of chlorine was consumed during a typical measurement including 10 ablation periods on the sample.