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Mg/Ca is an independent proxy in paleoceanography to reconstruct past seawater temperature. Femtosecond Laser Ablation Inductively Coupled Plasma Mass Spectrometry (fs-LA-ICP-MS) was employed to determine the Mg/Ca composition of tests (shells) of the planktic foraminifer species Globigerinoides ruber albus (white chromotype) and G. ruber ruber (red/pink chromotype) sampled alive from the temperate to subtropical eastern North Atlantic with the research sailing yacht Eugen Seibold. Mg/Ca data are compared to (i) the measured in-situ temperature of ambient seawater, (ii) average mixed layer temperature, and (iii) sea surface temperature (SST). The pooled mean chamber Mg/Ca from each plankton tow site exhibits a positive relationship with SST. Two chamber-specific calibrations are derived, which are consistent with previous calibration equations for comparable paleo-archives. The results confirm fs-LA-ICP-MS as reliable method for determining Mg/Ca in G. ruber, and both the penultimate and antepenultimate chambers of adult specimens may provide comprehensible Mg/Ca temperatures of the surface ocean. [ABSTRACT FROM AUTHOR]

Two stalagmites from B7-Cave in northwest Germany, which is part of the same cave system as the intensively studied Bunker Cave, were re-dated by multi collector inductively coupled plasma mass spectrometry (MC-ICPMS) 230Th/U-dating. Furthermore, the concentration of Mg, Sr, Ba, P, Y, Zn, and Al were determined at high-resolution by laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS). Stalagmite B7-1 grew from 10.8 to 5.8 ka BP. Stalagmite B7-7 grew during three growth phases from 11.0 to 6.2, 3.13 to 2.86 (late Bronze Age), and 1.27 to 1.15 ka BP (early Medieval Period). Aluminium is a proxy for detrital material and corresponds very well with the visible detrital layers in stalagmite B7-1 and the oldest growth phase of stalagmite B7-7. The two younger growth phases of stalagmite B7-7 are very clean and show very low Al concentrations. Phosphorus, Y, and Zn show positive correlations in both stalagmites and all growth phases, but do not show a relationship to temperature or precipitation. This may be related to the elevated detrital content in both stalagmites. Barium and Sr also show a positive correlation in both stalagmites and all growth phases, which is related to their dependency on growth rate. Magnesium is most probably influenced by prior calcite precipitation and therefore a proxy for past precipitation/infiltration. The Mg records of stalagmite B7-1 and of the oldest growth phase of stalagmite B7-7 show decreasing Mg concentration with time reflecting decreasing prior calcite precipitation and therefore increasing precipitation during the Early to Mid-Holocene. This is consistent with other climate reconstructions from Central Europe. [ABSTRACT FROM AUTHOR]

Three natural geological glasses (andesitic glass OJY‐1, and rhyolitic obsidians OH‐1 and OA‐1) of specimen sizes 50–150 g were characterised as reference materials for in situ microanalysis of major and trace elements, and Pb isotope ratios. Utilised techniques include isotope‐dilution analyses by TIMS and MC‐ICP‐MS, bulk analyses by XRF, ICP‐OES, ICP‐MS, and microanalysis (10–120 μm spot size) by electron probe microanalyser, LA‐ICP‐MS and LA‐MC‐ICP‐MS. Microanalyses (10–120 μm) indicate that all three glasses are homogeneous with respect to fifty‐four out of fifty‐eight determined elements and Pb isotope ratios, except for Ni in OJY‐1, and Cu, Zr and Ce in OH‐1. The determination of reference values as well as their uncertainties at the 95% confidence level closely followed International Organization for Standardization (ISO) guidelines and the certification protocol of the International Association of Geoanalysts (IAG). These three glasses are fully natural without any subsequent heat treatment, and they represent useful additions to the widely distributed MPI‐DING, USGS and CGSG reference glasses for microanalytical techniques such as electron probe microanalysis, μ‐XRF, LA‐ICP‐MS and SIMS. [ABSTRACT FROM AUTHOR]

We investigated rock varnish, a thin, manganese- and iron-rich, dark surface crust, on basaltic lava flows and petroglyphs in the Owens and Rose Valleys (California) by portable X-ray fluorescence (pXRF) and femtosecond laser-ablation inductively-coupled-plasma mass spectrometry (fs-LA-ICPMS). The major element composition of the varnish was consistent with a mixture of Mn-Fe oxyhydroxides and clay minerals. As expected, it contained elevated concentrations of elements that are typically enriched in rock varnish, e.g., Mn, Pb, Ba, Ce, and Co, but also showed unusually high enrichments in U, Cu, and Th. The rare earth and yttrium (REY) enrichment pattern revealed a very strong positive cerium (Ce) anomaly and distinct negative europium (Eu) and Y anomalies. The light rare earth elements (REE) were much more strongly enriched than the heavy REY. These enrichment patterns are consistent with a formation mechanism by leaching of Mn and trace elements from aeolian dust, reprecipitation of Mn and Fe as oxyhydroxides, and scavenging of trace elements by these oxyhydroxides. We inferred accumulation rates of Mn and Fe in the varnish from their areal densities measured by pXRF and the known ages of some of the lava flow surfaces. The areal densities of Mn and Fe, as well as their accumulation rates, were comparable to our previous results from the desert of Saudi Arabia. There was a moderate dependence of the Mn areal density on the inclination of the rock surfaces, but no relationship to its cardinal orientation. We attempted to use the degree of varnish regrowth on the rock art surfaces as an estimate of their age. While an absolute dating of the petroglyphs was not possible because of the lack of suitable calibration surfaces and a considerable amount of variability, the measured degree of varnish regrowth on the various petroglyphs was consistent with chronologies based on archeological and other archaeometric techniques. In particular, our results suggest that rock art creation in the study area continued over an extended period of time, possibly starting around the Pleistocene/Holocene transition and extending into the last few centuries. [ABSTRACT FROM AUTHOR]

Two small annually laminated stalagmites from Zoolithencave (southeastern Germany) grew between CE 1821 and 1970 (Zoo‐rez‐1) and CE 1835 and 1970 (Zoo‐rez‐2), respectively. Trace element concentrations were determined by Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA‐ICP‐MS). Samples for δ13C and δ18O analyses were micromilled on annual and subannual resolution. Soil and host rock samples were analyzed by X‐Ray Diffraction (XRD) and their elemental concentrations determined via inductively coupled plasma optical emission spectrometer (ICP‐OES). Trace element concentrations in the stalagmites show two groups in the principal component analyses: one with Mg, Ba, and Sr and another with Y, P, and Al, respectively. The second group reflects the content of detrital material. Increased weathering of soil minerals seems to have a strong influence on the silicate/carbonate weathering ratio controlling the variability of Mg, Ba, and Sr. Meteorological and Global Network of Isotopes in Precipitation (GNIP) station data were used to calculate the δ18O values of the drip water (infiltration‐weighted, mean annual, and the mean of the winter precipitation δ18O values) as well as the corresponding speleothem calcite. The δ18O values calculated by the infiltration‐weighted model show similar patterns and amplitudes as the measured δ18O values of the two stalagmites. This suggests that the δ18O values of speleothem calcite reflect the δ18O values of infiltration‐weighted annual precipitation, which zis related to mean annual temperature, resulting in a significant correlation between mean annual temperature and the measured δ18O values of stalagmite Zoo‐rez‐2. This relationship could potentially be used for quantitative climate reconstruction in the future by extending the time series back in time with further stalagmites from Zoolithencave. Key Points: Silicate versus carbonate weathering has an influence on speleothem trace elementsYttrium, phosphorus, and aluminum reflect detrital content of the speleothemsδ18O values of the stalagmites are a proxy for mean annual temperature [ABSTRACT FROM AUTHOR]

Strontium isotopes are applied to a wide range of scientific fields and to different types of materials, providing valuable information foremost about provenance and age, but also on diagenetic processes and mixing relationships between different Sr reservoirs. The development of in situ analytical techniques, such as laser ablation ICP-MS, has improved our understanding of Sr isotope variability in several fields of application, because of the possibility to discriminate small-scale changes and their spatial distribution. However, large outputs of Sr isotope data are produced by laser ablation MC-ICP-MS systems, which necessitate multiple offline steps to correct and assess the data. This requires the availability of simple and user-friendly tools, easily manageable by non-specialists too. With this in mind, we developed SrDR, an Excel-based interactive data reduction spreadsheet ('SrDR', Sr-Data-Reduction) for the processing of Sr isotopes measured by LA-MC-ICP-MS. The SrDR spreadsheet is easily customizable (a) to meet user-specific analytical protocols, (b) for different instruments (i.e. Nu plasma vs. Neptune), and (c) for diverse target materials (e.g. rare earth element enriched or depleted samples). We also include several examples relevant to low and high temperature geochemistry fields – a fossil tooth, a modern seashell, a speleothem sample and plagioclase crystals – to show how different sample materials are corrected for different interfering masses. [ABSTRACT FROM AUTHOR]

The in situ measurement of Sr isotopes in carbonates by MC‐ICP‐MS is limited by the availability of suitable microanalytical reference materials (RMs), which match the samples of interest. Whereas several well‐characterised carbonate reference materials for Sr mass fractions > 1000 µg g−1 are available, there is a lack of well‐characterised carbonate microanalytical RMs with lower Sr mass fractions. Here, we present a new synthetic carbonate nanopowder RM with a Sr mass fraction of ca. 500 µg g−1 suitable for microanalytical Sr isotope research ('NanoSr'). NanoSr was analysed by both solution‐based and in situ techniques. Element mass fractions were determined using EPMA (Ca mass fraction), as well as laser ablation and solution ICP‐MS in different laboratories. The 87Sr/86Sr ratio was determined by well‐established bulk methods for Sr isotope measurements and is 0.70756 ± 0.00003 (2s). The Sr isotope microhomogeneity of the material was determined by LA‐MC‐ICP‐MS, which resulted in 87Sr/86Sr ratios of 0.70753 ± 0.00007 (2s) and 0.70757 ± 0.00006 (2s), respectively, in agreement with the solution data within uncertainties. Thus, this new reference material is well suited to monitor and correct microanalytical Sr isotope measurements of low‐Sr, low‐REE carbonate samples. NanoSr is available from the corresponding author. [ABSTRACT FROM AUTHOR]

Homogeneity, mass fractions of about forty trace elements and Sr isotope composition of Ca carbonate reference materials (RMs) between original and nano‐powdered pellets are compared. Our results using nanosecond and femtosecond LA‐(MC)‐ICP‐MS show that the nano‐pellets of the RMs MACS‐3NP, JCp‐1NP and JCt‐1NP are about a factor of 2–3 more homogeneous than the original samples MACS‐3, JCp‐1 and JCt‐1, and are therefore much more suitable for microanalytical purposes. With the exception of Si, the mass fractions of the synthetic RM MACS‐3 agree with its fine‐grained analogue MACS‐3NP. Very small, but significant, differences between original and nano‐pellets are observed in the RMs JCp‐1 and JCt‐1 for some trace elements with very low contents, indicating the need for re‐certification. Strontium mass fractions in the analysed RMs are high (1500–7000 mg kg−1), and their isotope compositions determined by LA‐MC‐ICP‐MS in the original and the nano‐pellets agree within uncertainty limits. [ABSTRACT FROM AUTHOR]

Atmospheric dust has a substantial impact on climate, and climate in turn affects the dust flux and origin. Knowing its composition helps to determine dust sources and climate processes. We have therefore determined 46 major and trace elements in dust samples, using in-situ 200 nm-femtosecond laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). Very small test portions of 4–7 μg were enough to enable analyses down to detection limits of femtograms and ng g − 1 , respectively. The data agree within 40 to 15% with the reference values for test portions of 1 to 100 μg, respectively. The femtosecond laser results are compared to those obtained using a 213 nm nanosecond laser, which show the advantages of the femtosecond laser, such as the ability to use non-matrix-matched calibration, reliable measurements of volatile elements, and smaller quantities of material ablation with similar results for the repeatability. The technique is especially useful for measurements of small amounts of dust on filters, and for 2D-distribution maps of selected elements to identify minerals or contamination. To demonstrate the applicability, five dust samples from Niger and Chad, in the Sahara zone, were analyzed. The samples are characterized by enrichment in light REEs and a distinct Eu anomaly, with surface soils as their source. [ABSTRACT FROM AUTHOR]

More than 100 volcanoes have been discovered in Antarctica, however, the sources of many Antarctic tephras are not yet constrained. In this study, four tephra samples recovered from the environment of Site 27 on an area of blue ice at Allan Hills, South Victoria Land, provide information on magma and crustal sources for the tephra erupted in Antarctica. We report data on the chemistry of Antarctic tephra glasses and minerals analysed by electron microscopy, electron probe microanalysis and laser ablation inductively coupled plasma mass spectrometry. The tephra amphibole chemistry indicates magma residence at ~1 GPa and ~1100 °C. Abundant Ca–Al–Si-rich minerals imply that the magma ascended from a reservoir at 29.4 ± 2.7 km depth was affected by the assimilation of calc-silicate crust. The high Fe and Ti contents in the magmatic minerals and the trace element patterns of the glasses typical of a hydrothermally altered oceanic crust suggest that the Allan Hills tephra originated from a mantle plume-derived magma. The fragmented morphology of the glasses implies that the magmatic activity was associated with explosive eruptions during the mid-Pleistocene. The chemistry of the glasses and the presence of rhönite and Al-rich spinel minerals suggest that the magma might be genetically related to the currently active McMurdo volcanic group. [ABSTRACT FROM AUTHOR]

Speleothems are well established climate archives. A wide array of geochemical proxies, including stable isotopes and trace elements are present within speleothems to reconstruct past climate variability. However, each proxy is influenced by multiple factors, often hampering robust interpretation. Sr isotope ratios ( 87 Sr/ 86 Sr) can provide useful information about water residence time and water mixing in the host rock, as they are not fractionated during calcite precipitation. Laser ablation multi-collector-inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) has rarely been used for determination of Sr isotope signatures in speleothems, as speleothems often do not possess appropriately high concentrations of Sr to facilitate this analysis. Yet the advantages of this approach include rapid data acquisition, higher spatial resolution, larger sample throughput and the absence of chemical treatment prior to analysis. We present LA-MC-ICP-MS Sr isotope data from two speleothems from Morocco (Grotte de Piste) and India (Mawmluh Cave), and we compare linescan and spot analysis ablation techniques along speleothem growth axes. The analytical uncertainty of our LA-MC-ICP-MS Sr data is comparable to studies conducted on other carbonate materials. The results of both ablation techniques are reproducible within analytical error, implying that this technique yields robust results when applied to speleothems. In addition, several comparative measurements of different carbonate reference materials (i.e. MACS-3, JCt-1, JCp-1), including tests with standard bracketing and comparison of the 87 Sr/ 86 Sr ratios with a nanosecond laser ablation system and a state-of-the-art femtosecond laser ablation system, highlight the robustness of the method. [ABSTRACT FROM AUTHOR]

The article presents a study conducted by the Gemological Institute of America (GIA) and the Max Planck Institute for Chemistry (MPIC) on the trace-element characteristics of two nacreous pearl samples. The results revealed that the pearls comprised layer-like zones having distinct trace-element signatures related to both freshwater and saltwater environments, as confirmed by spot analysis conducted by laser ablation inductively coupled plasma mass spectrometry.