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Amphistegina are common larger benthic foraminifer in coral reefs, with a nearly circumtropical distribution, and are major contributors to the CaCO3 budget of shallow marine environments. The family Amphisteginidae is dominant in Cenozoic carbonates. However, its potential as a proxy for paleoclimate reconstruction has not been completely explored. The intratest variability in trace elements of Amphistegina lessonii has been investigated using femtosecond‐laser ablation‐inductively coupled plasma‐mass spectrometry (fs‐LA‐ICP‐MS). We collected and analyzed adult specimens of A. lessonii in September 2003, November 2003, January 2004, and March 2004, from ∼2 m water depth in the coral reefs of Akajima, Okinawa, Japan. Tests of A. lessonii from these four collections were analyzed for Mg/Ca of the septa to observe Test Size‐Lifespan relationships. The lifespan of a specimen of A. lessonii of 1,200 µm in diameter is estimated at ∼3 and ∼2 months for specimens 900 µm in size. Over the estimated lifespans, Mg/Ca of individual specimens of A. lessonii is highly variable and displays co‐variation with temperature and tidal heights. Future projects may apply and further test this approach for the reconstruction of the tropical shallow marine paleoenvironments. Plain Language Summary: Larger Benthic Foraminifera (LBF) have slow growth rates and can be used as a proxy to reconstruct seasonal variations in temperature. Amphistegina, a common genus of LBF found within the Cenozoic era including the past 55 million years, was sampled across four seasons from a modern coral reef of Okinawa, Japan. The trace element concentrations in nine specimens of A. lessonii were measured using femtosecond LA‐ICP‐MS. The intratest variation in Mg/Ca covaried with tidal heights and seawater temperature, assuming the ages of the specimens to be 2–3 months. We provide a temperature calibration equation for A. lessonii for reconstructing paleotemperatures of shallow marine environments of the Cenozoic. Key Points: Specimens of Amphistegina lessonii sampled across 4 months from Akajima are used for calibration for Mg/Ca temperature using femtosecond‐laser ablation‐inductively coupled plasma‐mass spectrometry.The Mg/Ca along the septa of A. lessonii covaries with seawater temperature and tidal heights while Na/Ca and Sr/Ca show no correlationIntratest variations in Mg/Ca of A. lessonii are affected by light intensity attenuation by sediment re‐suspension caused by tidal currents [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]

In situ laser ablation analyses rely on the microanalytical homogeneity of reference materials (RMs) and a similar matrix and mass fraction between unknown samples and RMs to obtain reliable results. Suitable carbonate and phosphate RMs for determination of Sr isotope ratios in such materials are limited. Thus, we determined 87Sr/86Sr ratios of several carbonate (JCt‐1, JCp‐1, MACS‐1, MACS‐3) and phosphate (MAPS‐4, MAPS‐5, NIST SRM 1400, NIST SRM 1486) international RMs using dissolved samples and two different multi‐collector inductively coupled plasma‐mass spectrometers (MC‐ICP‐MS). Our Sr isotope data are in agreement with published data and have an improved measurement precision for some RMs. For MACS‐1, we present the first 87Sr/86Sr value. We tested the suitability of these materials for microanalytical analyses by LA‐MC‐ICP‐MS, with two different laser ablation systems: a conventional nanosecond laser and a state‐of‐the‐art femtosecond laser. We investigated the RMs micro‐homogeneity and compared the data with our solution data. Both laser ablation systems yielded identical 87Sr/86Sr ratios within uncertainty to the solution data for RMs with low interferences of REEs. Therefore, these carbonate and phosphate RMs can be used to achieve accurate and precise results for in situ Sr isotope investigations by LA‐MC‐ICP‐MS of similar materials. [ABSTRACT FROM AUTHOR]

This GGR biennial critical review covers developments and innovations in key analytical methods published since January 2014, relevant to the chemical, isotopic and crystallographic characterisation of geological and environmental materials. In nine selected analytical fields, publications considered to be of wide significance are summarised, background information is provided and their importance evaluated. In addition to instrumental technologies, this review also presents a summary of new developments in the preparation and characterisation of rock, microanalytical and isotopic reference materials, including a précis of recent changes and revisions to ISO guidelines for reference material characterisation and reporting. Selected reports are provided of isotope ratio determinations by both solution nebulisation MC-ICP-MS and laser ablation-ICP-MS, as well as of radioactive isotope geochronology by LA-ICP-MS. Most of the analytical techniques elaborated continue to provide new applications for geochemical analysis; however, it is noted that instrumental neutron activation analysis has become less popular in recent years, mostly due to the reduced availability of nuclear reactors to act as a neutron source. Many of the newer applications reported here provide analysis at increasingly finer resolution. Examples include atom probe tomography, a very sensitive method providing atomic scale information, nanoscale SIMS, for isotopic imaging of geological and biological samples, and micro-XRF, which has a spatial resolution many orders of magnitude smaller than conventional XRF. [ABSTRACT FROM AUTHOR]

LA- ICP- MS is one of the most promising techniques for in situ analysis of geological and environmental samples. However, there are some limitations with respect to measurement accuracy, in particular for volatile and siderophile/chalcophile elements, when using non-matrix-matched calibration. We therefore investigated matrix-related effects with a new 200 nm femtosecond (fs) laser ablation system ( NWRFemto200) using reference materials with different matrices and spot sizes from 10 to 55 μm. We also performed similar experiments with two nanosecond (ns) lasers, a 193 nm excimer ( ESI NWR 193) and a 213 nm Nd: YAG ( NWR UP-213) laser. The ion intensity of the 200 nm fs laser ablation was much lower than that of the 213 nm Nd: YAG laser, because the ablation rate was a factor of about 30 lower. Our experiments did not show significant matrix dependency with the 200 nm fs laser. Therefore, a non-matrix-matched calibration for the multi-element analysis of quite different matrices could be performed. This is demonstrated with analytical results from twenty-two international synthetic silicate glass, geological glass, mineral, phosphate and carbonate reference materials. Calibration was performed with the certified NIST SRM 610 glass, exclusively. Within overall analytical uncertainties, the 200 nm fs LA- ICP- MS data agreed with available reference values. [ABSTRACT FROM AUTHOR]

Advances in the chemical and isotopic characterisation of geological and environmental materials can often be ascribed to technological improvements in analytical hardware. Equally, the creation of novel methods of data acquisition and interpretation, including access to better reference materials, can also be crucial components enabling important breakthroughs. This biennial review highlights key advances in either instrumentation or data acquisition and treatment, which have appeared since January 2010. This review is based on the assessments by scientists prominent in each of the given analytical fields; it is not intended as an exhaustive summary, but rather provides insight from experts of the most significant advances and trends in their given field of expertise. In contrast to earlier reviews, this presentation has been formulated into a unified work, providing a single source covering a broad spectrum of geoanalytical techniques. Additionally, some themes that were not previously emphasised, in particular thermal ionisation mass spectrometry, accelerator-based methods and vibrational spectroscopy, are also presented in detail. [ABSTRACT FROM AUTHOR]

Abstract: The high spatial resolution of laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) microanalysis of speleothems and biogenic calcium carbonates makes it possible to improve our understanding of past climatic conditions. However, there are analytical problems associated with this method, such as molecular interferences, elemental fractionation, and mass-load-dependent matrix effects, when using NIST silicate reference glasses for calibration. Our study with a sector-field ICP-MS shows that many masses are affected by interferences, such as 24Mg+ by 48Ca++ or 31P+ by 15N16O+. Elemental fractionation and mass-load-dependent matrix effects have been detected for both 213 and 193nm Nd:YAG lasers. They are small for refractory lithophile elements, in particular for the 193nm laser (<5%). For chalcophile/siderophile trace elements with low boiling points, however, these effects are large (up to 40% and 20% for the 213 and 193nm lasers, respectively), and variable for the NIST glasses and carbonates. In this paper, a protocol for precise and accurate LA-ICP-MS analysis of calcium carbonates is established. Isotopes for interference-free measurements at low (M/ΔM ~300) and medium (M/ΔM ~4000) mass resolution have been identified. The NIST glasses are suitable for calibration of refractory lithophile element concentrations. However, matrix-matched calibration with carbonate reference materials, such as USGS MACS-1 or MACS-3, is necessary for accurate analysis of chalcophile/siderophile elements with low boiling points. Analytical reproducibility (RSD) is a factor of ~2 better using the 193nm laser than the 213nm laser. As shown by the analysis of MACS-1 and MACS-3, LA-ICP-MS analyses yield results that agree with the reference values within relative uncertainties of ca. 5–10% at the 95% confidence level. We have applied LA-ICP-MS for the determination of trace element concentrations in calcite and aragonite layers of a stalagmite and found large variations for Mg, Zn, Sr, and U. In ostracod shells, the concentrations of some trace elements (e.g., Sr and Ba) vary significantly, indicating the potential for paleoclimate research. [Copyright &y& Elsevier]

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In this paper we describe a flux-free fusion technique for the highly precise LA-ICP-MS bulk analysis of geological samples. For this purpose we have developed an automated iridium-strip heater with temperature and melt time control. To optimise the homogeneity of the fused glasses and to reduce possible depletion of volatile elements during melting, we undertook experiments with basaltic rock and glass powders using different melting temperatures (1300–1700 °C) and melting times (5-80 s). Major and trace element microanalysis was performed using EPMA and LA-ICP-MS. Homogeneous glasses were obtained for temperatures ≥ 1500 °C and melting times ≥ 10 s. High loss (20-90%) of highly volatile elements (e.g., Cs, Ge, Sn, Pb) was observed for high melting temperatures (≥ 1600 °C) and long melting times (80 s). Standard melting conditions (1600 °C, 10 s) represent a compromise, as the glasses were homogeneous with respect to major and trace elements and, at the same time, were not depleted in elements with condensation temperatures (at a pressure of 10−4 bar) higher than about 900 K (e.g., Zr, Hf, Ba, Sr, REE, U, Mo, Ni, Rb, Ga). Several international geological reference materials with SiO2 ranging between 47% m/m and 59% m/m were prepared using our standard melting conditions (1600 °C, 10 s) and subsequently analysed by LA-ICP-MS. These samples also include the new Brazilian basaltic reference material BRP-1. Matrix-matched calibration of the LA-ICP-MS data was performed using the basaltic reference glasses KL2-G, ML3B-G, BCR-2G and BHVO-2G. Most analytical data agreed within uncertainty at the 95% confidence level with the GeoReM preferred values published in the GeoReM database for reference materials of geological and environmental interest. To demonstrate routine bulk LA-ICP-MS analyses of geochemical and cosmochemical samples using the whole rock fusion technique, we also present trace element data for ocean island basalts from Lanai (Hawaii) and of Martian meteorites. [ABSTRACT FROM AUTHOR]

In 2005 the Geostandards and Geoanalytical Research editorial team, in the true spirit of scientific endeavour, embarked on an experiment of our own. We decided to trial a new kind of review, somewhat different from those more typically observed in journals, and one that would provide readers with a summary of analytical developments across a broad range of topics appropriate to the Earth sciences. The first contribution of this kind appeared in 2005, and reported on developments in 2003 (Hergt et al. 2005). The second, this time a biennial review, was published in 2006 and reported on highlights of the 2004 and 2005 literature (Hergt et al. 2006). Based on reprint requests, positive remarks at conferences and strong citations we consider the experiment a resounding success and proudly present here the third in this series. This comprises six individual review sections that cover the main analytical technologies and topical application fields in geoanalysis and geochemistry, including geological and environmental reference materials, ICP-thermal and secondary ionisation-mass spectrometry, as well as neutron activation analysis, X-ray fluorescence and atomic absorption spectrometry. [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]

Abstract: Intra-bone rare earth element (REE) fractionation trends were studied by LA-ICPMS analysis to put constraints on (1) the mechanisms controlling REE fractionation within fossil bones; (2) the relative timing of REE uptake in various parts of fossil bone and (3) the origin of REE in fossil bones. We have evaluated REE bone profiles across 54 fossil bones from a broad range of well-characterised taphonomic settings ranging in age from Triassic to early Medieval. REE patterns and concentration gradients are highly variable and intra-bone fractionation trends in (La/Yb)N vs. (La/Sm)N space of few specimens cover almost the entire range previously observed for bulk samples. Intra-bone variability of Ce anomalies, as well as variable Y/Ho and (La/La∗)N is also observed. Sometimes, diagenetic fluids with fractionated, HREE enriched compositions have entered the bone from the marrow cavity, producing secondary REE uptake profiles. Theoretical intra-bone fractionation trends, modelled using lattice strain theory, concur with most REE data but some trends cannot be modelled using realistic boundary conditions. This fact, as well as the occurence of positive and negative Ce anomalies within the same fossil sample, hint towards changing REE compositions of diagenetic fluids over the timescales of REE uptake. Because apparent Ce anomalies frequently evolve over bone profiles and Ce anomalies can be inherited from previous fractionation events, Ce anomalies are a highly ambiguous tracer for constraining ambient redox conditions. In general, bioapatite REE signatures may not always reliably reflect ambient taphonomic or redox conditions and diagenetic fluid compositions. Therefore REE patterns and Ce anomalies of fossil bones must be interpreted cautiously as they vary spatially within skeletal remains and are affected by intra-bone fractionation processes as well as changing compositions of the diagenetic fluid. [Copyright &y& Elsevier]

Oxygen depletion threatens an increasing number of shallow water environments, specifically habitats below the seasonal halocline in coastal settings of the Baltic Sea. To understand the natural variations of dissolved oxygen levels on seasonal and inter-annual time-scales prior to the instrumental era, high-resolution archives are urgently required. The present study evaluates the potential use of Mn/Ca values in shells of the bivalve, Arctica islandica to infer concentrations of past dissolved oxygen concentrations. This study is based on laser ablation – inductively coupled plasma – mass spectrometry (LA-ICP-MS) data of six contemporaneous specimens and demonstrates that background variations of shell Mn/Ca are inversely linked to dissolved oxygen concentrations in the water column (r = −0.68; R2 = 0.46, p < 0.0001), which in turn are coupled to the amount of dissolved Mn. The regular seasonal changes were superimposed by sharp Mn/Ca peaks, most likely resulting from the ingestion of a large amount of Mn-rich organic particles. The availability of such particles can increase due to the resuspension of food particles by strong bottom currents or alternatively, result from increased particle flux from surface waters after major river discharges and subsequent phytoplankton blooms. Besides sharp Mn/Ca peaks, often accompanied by sharp Ba/Ca peaks and increased shell growth rate. In addition, after exceptional major barotropic inflows from the North Sea, the biogeochemical steady-state conditions remained disturbed for up to ca. two years, because the redox-sensitive elements were removed from the water column by oxygenated waters, and it took time for them to build up again in the water column. Therefore, subsequent to such Major Baltic Inflows (MBIs), dissolved Mn levels and shell Mn/Ca values were strongly reduced despite summertime low-oxygen conditions. As demonstrated here, Mn/Ca data of A. islandica shells can potentially serve as a proxy for dissolved oxygen levels in the water column. To further develop this proxy, a set of additional environmental and physiological proxies such as shell Ba/Ca values and growth rate should be critically assessed and used in combination with shell Mn/Ca. • Shell Mn/Ca of Arctica islandica records changes of dissolved and particulate Mn. • Shell Mn/Ca can potentially serve as a proxy for dissolved oxygen levels. • Major Baltic Inflows and river discharge events affect shell Mn, Ba and growth rate. [ABSTRACT FROM AUTHOR]