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: An alternative approach for the evaluation of isotope ratio data using LA-MC-ICP-MS will be presented. In contrast to previously applied methods it is based on the simultaneous responses of all analyte isotopes of interest and the relevant interferences without performing a conventional background correction. Significant improvements in precision and accuracy can be achieved when applying this new method and will be discussed based on the results of two first methodical applications: a) radiogenic and stable Sr isotopes in carbonates b) stable chlorine isotopes of pyrohydrolytic extracts. In carbonates an external reproducibility of the 87Sr/86Sr ratios of about 19 ppm (RSD) was achieved, an improvement of about a factor of 5. 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 [1]. Stable chlorine isotope ratios were determined ablating pyrohydrolytic extracts with a reproducibility of about 0.05‰ (RSD). For basaltic reference material JB1a and JB2 chlorine isotope ratios were determined relative to SMOC (standard mean ocean chlorinity) δ37ClJB-1a = (-0.99 ± 0.06) ‰ and δ37ClJB-2 = (-0.60 ± 0.03) ‰ (2SE), respectively, in accordance with published data [2]. The described strategies for data reduction are considered to be generally applicable for all isotope ratio measurements using LA-MC-ICP-MS. [1] McArthur, Rio, Massari, Castradori, Bailey, Thirlwall & Houghton (2006) Palaeogeo. Palaeoclim. Palaeoeco. 242, 126, doi: 10.1016/j.palaeo.2006.06.004 [2] Fietzke,. Frische, Hansteen & Eisenhauer (2008) J. Anal. At. Spectrom. 2008, doi:10.1039/B718597A.

Description: Large explosive volcanic eruptions inject gases, aerosols, and fine ashes into the stratosphere, potentially influencing climate. Emissions of chlorine (Cl) and bromine (Br) from such large eruptions play an important role for catalytic destruction of ozone in the stratosphere, but hitherto the global effects of simultaneous catastrophic release of volcanic Br and Cl into the stratosphere have not been investigated. The Br release from 14 large explosive eruptions throughout Nicaragua covering an entire subduction zone segment in the past 70 ka was determined with petrologic methods. Melt inclusions in volcanic phenocrysts were analyzed using a new optimized synchrotron–X-ray fluorescence microprobe set-up. Single eruptions produced Br outputs of 4–600 kt, giving an average Br emission of 27 kt per eruption. Using the assumption that 10% of the emitted halogens reach the stratosphere, the average Br and Cl loading to the stratosphere would be 3 ppt and 1500 ppt, respectively, which together would account for 185% of the preindustrial equivalent effective stratospheric Cl loading. We thus conclude that many large tropical volcanic eruptions had and have the potential to substantially deplete ozone on a global scale, eventually forming future ozone holes.