ALBERT

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: delta Sr-88/86 values of standards and a variety of natural samples were measured by MC-ICP-MS using the double-spike (DS) method and compared to results obtained by the standard-sample-bracketing (SSB) method and to DS-TIMS measurements. The external reproducibility of the SRM987 measurements carried out by DS-MC-ICP-MS was 0.021 parts per thousand (1SD), slightly better than previously published DS-TIMS and SSB-MC-ICP-MS results. The value of the IAPSO seawater standard (0.388 +/- 0.018; 2SEM) agrees with the results of the current SSB and DS-TIMS measurements and with previously published values. Using these values a variance-weighted mean for seawater was calculated (0.387 +/- 0.002, 2SEM). Compared to measurements carried out by the SSB method, natural sample measurements by the DS method are more accurate and more precise. An excellent agreement between DS-MC-ICP-MS and DS-TIMS methods was demonstrated for delta Sr-88/86 determination in natural samples over a range of similar to 0.5 parts per thousand. The DS-TIMS delta Sr-88/86 results had a smaller standard error than the DS-MC-ICP-MS measurements but required a much longer acquisition time

Description: A new in situ method using LA-MC-ICP-MS (193 nm excimer laser) for the determination of stable boron isotope ratios (δ11B) in carbonates was developed. Data were acquired via a standard sample standard bracketing procedure typically providing a reproducibility of 0.5‰ (SD) for samples containing 35 ppm of boron. A single ablation interval consumed about 5 µg of sample corresponding to about 0.2 ng of boron. The major finding was the similar instrumental fractionation behaviour of carbonates, soda-lime glass and sea salt with respect to boron isotopes. As no matrix induced offset was detectable between these distinct materials we propose the use of NIST glasses as internal standards for boron isotope ratio measurements via LA-MC-ICP-MS. This finding overcomes the problem of a missing matrix matched carbonate standard for in situ boron isotope studies. As a first application a set of coral samples from a culturing experiment was analysed. δ11B values range from 19.5 to 25‰ depending on the pH of the water used in the particular treatment. This is in good agreement with the results of earlier studies.

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: 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.

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: 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.