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: We investigated the controls of hydrography and of scavenging on the distribution of the particle reactive radionuclides 231Pa and 230Th in the water column and in surface sediments off Southwest Africa (Angola and Cape basins). Based on a vertical section of total 230Thex concentrations in the water column we show that small differences in the salinity between the North Atlantic Deep Water (NADW) in the Angola Basin and the NADW in the Cape Basin as well as the advection of NADW associated with the Namib Col Current are reflected in total 230Thex concentrations. These variable total concentrations are believed to reflect the flow path and mixing history of NADW with the NADW in the Angola Basin being relatively older and 230Th enriched compared to the NADW in the Cape Basin. In the area investigated we found high 231Paex/230Thex ratios (231Paex/230Thex 〉 0.093) in surface sediments at the continental margin and lower ones (231Paex/230Thex 〈 0.093) in the open ocean. Such a distribution is normally interpreted to result from high particle flux at ocean margins (boundary scavenging). However, the lack of any significant depletion of dissolved 230Th and 231Pa in the water column does not indicate extensive scavenging at the continental margin. High 231Paex/230Thex ratios are constrained to shallow waters depths (〈 2000 m) only and coincide with low fractionation between 231Pa and 230Th indicating that preferential scavenging of 231Pa on opal may have caused high 231Paex/230Thex ratios in the sediments. The observed close negative correlation (r2 = 0.82) between 231Paex/230Thex ratios in sediments and water depths is believed to reflect changes in the particle composition, i.e. a decrease in opal content with water depth. In the Angola and Cape basins the total 231Paex concentrations in NADW were the highest observed so far in the Atlantic Ocean, and they are attributed to the meridional export of 231Pa from the North Atlantic. This caused the average dissolved 231Pa/230Th in the Southeast Atlantic to be about a factor 2 higher when compared to the North Atlantic (Labrador Sea). These differences in the dissolved 231Pa/230Th were not reflected in 231Pa/230Th ratios of surface sediments because the fractionation is lower in the Labrador Sea compared to the Southeast Atlantic, i.e. fractionation counteracts changes in the dissolved 231Pa/230Th. This suggests that fractionation is more important for the determination of 231Paex/230Thex ratios in sediments than the meridional export of 231Pa from the North Atlantic.

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: While recent changes in subarctic North Pacific climate had dramatic effects on ecosystems and fishery yields, past climate dynamics and teleconnection patterns are poorly understood due to the absence of century-long high-resolution marine records. We present the first 117-year long annually resolved marine climate history from the western Bering Sea/Aleutian Island region using information contained in the calcitic skeleton of the long-lived crustose coralline red alga Clathromorphum nereostratum, a previously unused climate archive. The skeletal δ18O-time series indicates significant warming and/or freshening of surface waters after the middle of the 20th century. Furthermore, the time series is spatiotemporally correlated with Pacific Decadal Oscillation (PDO) and tropical El Niño-Southern Oscillation (ENSO) indices. Even though the western Bering Sea/Aleutian Island region is believed to be outside the area of significant marine response to ENSO, we propose that an ENSO signal is transmitted via the Alaskan Stream from the Eastern North Pacific, a region of known ENSO teleconnections.

Description: Here, we present a new technique for the direct measurement of 44Ca/40Ca isotope ratios on a Multicollector Inductively Coupled Plasma Mass Spectrometer (MC–ICP–MS, AXIOM) using the “cool plasma” technique. By reducing the plasma energy to about 400 W, the isobaric effect resulting from 40Ar+ can be significantly reduced, enabling the simultaneous and precise measurement of 44Ca and 40Ca beam intensities in different Faraday cups. In contrast to the TIMS technique requiring a 43Ca/48Ca double spike, the isotope measurements on MC–ICP–MS can be performed by bracketing standards. We express the calcium isotope variation relative to NIST SRM 915a (δ44/40Ca [‰]=[((44Ca/40Ca)sample/(44Ca/40Ca)NIST SRM 915a)−1]*1000). Isobaric effects of 24Mg16O+ and 23Na16OH+ interfering with 40Ca and 26Mg16OH2+ with 44Ca can be neglected by measuring calcium isotopes near the low-mass edge of the peaks. No influence of 87Sr2+ monitored on 43.5 atomic mass units (amu) was found. Repeated measurements of two Johnson Matthey CaCO3 standards (lot No. 4064 and lot No. 9912) revealed values of about −11.29 (‰ SRM 915a) and 0.57 (‰ SRM 915a). These values are in accordance with previous values published by Russell et al. [Geochim. Cosmochim. Acta 42 (1978) 1075], Heuser et al. [Int. J. Mass Spectrom. 220 (2002) 385], Hippler et al. [Geostand. Newsl. 27 (2003) 267] and Schmitt et al. [Geochim. Cosmochim. Acta 67 (2003) 2607]. Repeated measurement of the NIST SRM 915a CaCO3 standard showed that the variance of a single δ44/40Ca measurement is about 0.14‰ RSD being comparable with TIMS. MC–ICP–MS-based δ44/40Ca values measured on inorganically precipitated aragonite samples are indistinguishable from earlier measurements based on TIMS, confirming the positive correlation of δ44/40Ca and temperature. MC–ICP–MS-based δ44/40Ca measurements on cultured Orbulina universa showed a slope of about 0.026‰/°C being similar to the TIMS-based δ44/40Ca measurements showing a slope of about 0.019‰/°C. The large offset of about 5‰ between the two techniques is shown to be caused by a “matrix” effect, indicating that any δ44/40Ca measurements on MC–ICP–MS are sensitively controlled by the Ca concentration and the acidity of the solution. Our study demonstrates the possibility to measure the whole dispersion of calcium isotopes with MC–ICP–MS, showing that 40Ca can be used for normalization of 44Ca.

Description: Hydrothermal vent deposits form on the seafloor as a result of cooling and mixing of hot hydrothermal fluids with cold seawater. Amongst the major sulfide and sulfate minerals that are preserved at vent sites, barite (BaSO4) is unique because it requires the direct mixing of Ba-rich hydrothermal fluid with sulfate-rich seawater in order for precipitation to occur. Because of its extremely low solubility, barite crystals preserve geochemical fingerprints associated with conditions of formation. Here, we present data from petrographic and geochemical analyses of hydrothermal barite from the Endeavour Segment of the Juan de Fuca Ridge, northeast Pacific Ocean, in order to determine the physical and chemical conditions under which barite precipitates within seafloor hydrothermal vent systems. Petrographic analyses of 22 barite-rich samples show a range of barite crystal morphologies: dendritic and acicular barite forms near the exterior vent walls, whereas larger bladed and tabular crystals occur within the interior of chimneys. A two component mixing model based on Sr concentrations and 87Sr/86Sr of both seawater and hydrothermal fluid, combined with 87Sr/86Sr data from whole rock and laser-ablation ICP-MS analyses of barite crystals indicate that barite precipitates from mixtures containing as low as 17% and as high as 88% hydrothermal fluid component, relative to seawater. Geochemical modelling of the relationship between aqueous species concentrations and degree of fluid mixing indicates that Ba2+ availability is the dominant control on mineral saturation. Observations combined with model results support that dendritic barite forms from fluids of less than 40% hydrothermal component and with a saturation index greater than ∼0.6, whereas more euhedral crystals form at lower levels of supersaturation associated with greater contributions of hydrothermal fluid. Fluid inclusions within barite indicate formation temperatures of between ∼120 °C and 240 °C during barite crystallization. The comparison of fluid inclusion formation temperatures to modelled mixing temperatures indicates that conductive cooling of the vent fluid accounts for 60–120 °C reduction in fluid temperature. Strontium zonation within individual barite crystals records fluctuations in the amount of conductive cooling within chimney walls that may result from cyclical oscillations in hydrothermal fluid flux. Barite chemistry and morphology can be used as a reliable indicator for past conditions of mineralization within both extinct seafloor hydrothermal deposits and ancient land-based volcanogenic massive sulfide deposits.