In-situ high spatial resolution LA-MC-ICPMS 230Th/U dating enables detection of small-scale age inversions in speleothems

Abstract We present an in-situ method for Th and U isotope measurements by laser ablation multi-collector inductively coupled plasma mass spectrometry (LA-MC-ICPMS) to determine possible age inversions of stalagmites, using a 213 nm Nd:YAG laser connected to an MC-ICPMS. Due to the low ion beam intensity of 230 Th (20–120 counts per second, cps), we carefully optimized the operating parameters to get highest possible ion beam intensities, i.e., laser fluence (25 J cm −2 ), spot size (110 μm), pulse repetition rate (20 Hz), scan speed (4 μm s −1 ), integration time (1000 s), and He and Ar gas flow (∼0.9 L min −1 and ∼0.6 L min −1 respectively). A precision (2 relative standard error, 2RSE) o…

Vanadium pentoxide nanoparticles mimic vanadium haloperoxidases and thwart biofilm formation

Marine biofouling—the colonization of small marine microorganisms on surfaces that are directly exposed to seawater, such as ships' hulls—is an expensive problem that is currently without an environmentally compatible solution1. Biofouling leads to increased hydrodynamic drag, which, in turn, causes increased fuel consumption and greenhouse gas emissions. Tributyltin-free antifouling coatings and paints1, 2, 3, 4 based on metal complexes or biocides have been shown to efficiently prevent marine biofouling. However, these materials can damage5 the environment through metal leaching (for example, of copper and zinc)6 and bacteria resistance7. Here, we show that vanadium pentoxide nanowires ac…

MPI-DING reference glasses for in situ microanalysis: New reference values for element concentrations and isotope ratios

We present new analytical data of major and trace elements for the geological MPI-DING glasses KL2-G, ML3B-G, StHs6/80-G, GOR128-G, GOR132-G, BM90/21-G, T1-G, and ATHO-G. Different analytical methods were used to obtain a large spectrum of major and trace element data, in particular, EPMA, SIMS, LA-ICPMS, and isotope dilution by TIMS and ICPMS. Altogether, more than 60 qualified geochemical laboratories worldwide contributed to the analyses, allowing us to present new reference and information values and their uncertainties (at 95% confidence level) for up to 74 elements. We complied with the recommendations for the certification of geological reference materials by the International Associ…

Determination of Reference Values for NIST SRM 610-617 Glasses Following ISO Guidelines

We present new reference values for the NIST SRM 610–617 glasses following ISO guidelines and the International Association of Geoanalysts’ protocol. Uncertainties at the 95% confidence level (CL) have been determined for bulk- and micro-analytical purposes. In contrast to former compilation procedures, this approach delivers data that consider present-day requirements of data quality. New analytical data and the nearly complete data set of the GeoReM database were used for this study. Data quality was checked by the application of the Horwitz function and by a careful investigation of analytical procedures. We have determined quantitatively possible element inhomogeneities using different …

Non-Matrix-Matched Calibration for the Multi-Element Analysis of Geological and Environmental Samples Using 200 nm Femtosecond LA-ICP-MS: A Comparison with Nanosecond Lasers

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 l…

Whole-Ocean Changes in Silica and Ge/Si Ratios During the Last Deglacial Deduced From Long-Lived Giant Glass Sponges

Microanalytical methods for in-situ high-resolution analysis of rock varnish at the micrometer to nanometer scale

Abstract A wide range of analytical techniques were used to investigate rock varnish from different locations (Negev, Israel; Knersvlakte, South Africa; Death Valley and Mojave Desert, California): a 200 nm-femtosecond laser ablation-inductively coupled plasma-mass spectrometer (LA-ICP-MS), an electron probe microanalyzer (EPMA), focused ion beam (FIB) slicing, and scanning transmission X-ray microscopy–near edge X-ray absorption fine structure spectroscopy (STXM–NEXAFS). This combination enables comprehensive high-spatial-resolution analysis of rock varnish. Femtosecond LA-ICP-MS and EPMA were used for quantitative determination of element concentrations. In-situ measurements were conducte…

Chemical composition of modern and fossil hippopotamid teeth and implications for paleoenvironmental reconstructions and enamel formation – Part 2: Alkaline earth elements as tracers of watershed hydrochemistry and provenance

Abstract. For reconstructing environmental change in terrestrial realms the geochemistry of fossil bioapatite in bones and teeth is among the most promising applications. This study demonstrates that alkaline earth elements in enamel of Hippopotamids, in particular Ba and Sr are tracers for water provenance and hydrochemistry. The studied specimens are molar teeth from Hippopotamids found in modern and fossil lacustrine settings of the Western Branch of the East African Rift system (Lake Kikorongo, Lake Albert, and Lake Malawi) and from modern fluvial environments of the Nile River. Concentrations in enamel vary by ca. two orders of magnitude for Ba (120–9336 μg g−1) as well as for Sr (9–21…

Investigation of matrix effects in 193nm laser ablation-inductively coupled plasma-mass spectrometry analysis using reference glasses of different transparencies

Abstract The degree of transparency of glasses, which depends on the Fe content, may influence the ablation behavior during laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) analysis. To test possible matrix effects when using a 193 nm Nd:YAG laser, we have analyzed transparent and opaque NIST, BAM and USGS reference glasses. These reference materials are ideal for such investigations, because they are well characterized, most elements are homogeneously distributed at the micrometer scale, and their Fe content varies over a very large range, from 16 to 130,000 μg g− 1. Our measurements show that the fractionation factors of refractory and volatile lithophile elements, …

Silica-protein composite layers of the giant basal spicules from Monorhaphis: Basis for their mechanical stability

The hexactinellid sponge Monorhaphis chuni possesses with its giant basal spicules the largest biosilica structure on Earth. The approximately 8.5-mm-thick spicules are composed of up to 800 lamellae. By application of high-resolution electron microscopy (HR-SEM), it is shown that within the siliceous lamellae a proteinaceous scaffold exists which is composed of one protein of a size of 27 kDa. Analyses with Fourier transform infrared (FT-IR) emission and energy-dispersive X-ray (EDX) spectroscopy support this localization of the protein. No evidence for the presence of protein on the surfaces of the lamellae could be obtained. Heating the giant basal spicule to 600 °C destroys and eliminat…

A Pearl Identification Challenge

Geochemical insights into the relationship of rock varnish and adjacent mineral dust fractions

Abstract Rock varnishes are μm-thin, dark, manganese(Mn)-rich crusts that accrete in the order of few μm/ka on weathering-resistant lithologies. Although these crusts can form in all climates, they are best known in arid to semi-arid settings. Aeolian dust is understood as a major contributor to the distinct trace metal and REE enrichments in rock varnish. However, the exact proportions of abiotic and biotic formation mechanisms that may explain the oxidation-reactions of Mn2+ to Mn4+, present as Mn oxyhydroxides in the varnish, are still a matter of ongoing debate. We present here the first systematic study of trace element enrichment processes between the uppermost layer of the varnish se…

Accurate trace element analysis of speleothems and biogenic calcium carbonates by LA-ICP-MS

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…

FeMnOx-1: A new microanalytical reference material for the investigation of Mn–Fe rich geological samples

Suitable Mn-Fe rich microanalytical reference materials (MRMs) as calibration material for laser ablation-inductively coupled plasma mass spectrometry (LA-ICPMS) have not been available. The United States Geological Survey (USGS) in collaboration with the Max Planck Institute for Chemistry has prepared a synthetic MRM, FeMnOx-1, with elevated mass fractions of MnO (25 g/100 g), Fe2O3 (8.5 g/100 g) and high mass fractions of 25 trace elements varying between 200 and 5000 mg/kg. This new MRM has been designed as calibration material for a wide range of different Mn-Fe deposits, such as desert/rock varnish, ocean crusts and nodules as well as Mn accumulations in soils and lakes. Small-scale an…

Nano‐Powdered Calcium Carbonate Reference Materials: Significant Progress for Microanalysis?

Trace element variability in single ostracod valves as a proxy for hydrochemical change in Nam Co, central Tibet, during the Holocene

Ostracod shells, belonging to three taxa (Leucocytherella sinensis Huang, 1982, ?Leucocythere dorsotuberosa Huang, 1982 and ?L. dorsotuberosa f. postilirata sensu Pang, 1985), were collected from two sediment cores from Lake Nam Co, on the central Tibetan Plateau. Two variants of LA–ICP–MS (laser ablation–inductively coupled plasma–mass spectrometry), spot and line-scan analyses, were used to investigate trace element concentrations (Mg, Sr, Ba, U and rare earth elements [REEs]) in single ostracod shells. The results suggest that the line-scan method can provide better precision than the spot analysis and is therefore preferred. No significant difference in trace element composition between…

Characterization and differentiation of rock varnish types from different environments by microanalytical techniques

© 2017 Elsevier B.V. We investigated rock varnishes collected from several locations and environments worldwide by a broad range of microanalytical techniques. These techniques were selected to address the challenges posed by the chemical and structural complexity within the micrometer- to nanometer-sized structures in these geological materials. Femtosecond laser ablation-inductively coupled plasma-mass spectrometry (fs LA-ICP-MS), scanning transmission X-ray microscopy-near edge X-ray adsorption fine structure spectroscopy (STXM-NEXAFS) in combination with scanning electron microscopy (SEM) of focused ion beam (FIB) ultra-thin (100–200 nm) sections, conventional and polarization microscop…

LA-ICP-MS analyses on coral growth increments reveal heavy winter rain in the Eastern Mediterranean at 9 Ma

Abstract Sediment particles incorporated into coral skeletons reflect variation in composition and amount of suspended material in ambient water during coral growth. They can be used to identify periods of enhanced storm frequency and associated freshwater discharge. Tortonian (Late Miocene) Porites corals from Crete (Aegean Sea, Eastern Mediterranean) show pronounced annual density bands in X-ray photographs. δ18O compositional variability reflects the annual banding equivalent with a ~ 7 °C annual sea surface temperature (SST) cycle over a seven-year period. Fine sediment particles are concentrated in layers with skeletal porosity parallel to growth increments. Variations in the chemical …