A cryptochrome-based photosensory system in the siliceous sponge Suberites domuncula (Demospongiae)

Based on the light-reactive behavior of siliceous sponges, their intriguing quartz glass-based spicular system and the existence of a light-generating luciferase [Muller WEG et al. (2009) Cell Mol Life Sci 66, 537–552], a protein potentially involved in light reception has been identified, cloned and recombinantly expressed from the demosponge Suberites domuncula. Its sequence displays two domains characteristic of cryptochrome, the N-terminal photolyase-related region and the C-terminal FAD-binding domain. The expression level of S. domuncula cryptochrome depends on animal’s exposure to light and is highest in tissue regions rich in siliceous spicules; in the dark, no cryptochrome transcri…

230Th/U dating of Last Interglacial brain corals from Bonaire (southern Caribbean) using bulk and theca wall material

Abstract We compared the suitability of two skeletal materials of the Atlantic brain coral Diploria strigosa for 230Th/U-dating: the commonly used bulk material comprising all skeletal elements and the denser theca wall material. Eight fossil corals of presumably Last Interglacial age from Bonaire, southern Caribbean Sea, were investigated, and several sub-samples were dated from each coral. For four corals, both the ages and the activity ratios of the bulk material and theca wall agree within uncertainty. Three corals show significantly older ages for their bulk material than for their theca wall material as well as substantially elevated 232Th content and (230Th/238U) ratios. The bulk mat…

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…

Bio-Sintering/Bio-Fusion of Silica in Sponge Spicules

The synthesis of siliceous spicules in both demosponges and hexactinellids is enzymatically driven via silicatein. This enzyme exists both intra-spicularly and in the extra-spicular space. It catalyzes the formation of bio-silica constituting the silica lamellae that are formed during the appositional (layer-by-layer) growth of the spicules. The extent of (bio-silica forming) activity of silicatein from the demosponge Suberites domuncula measured in vitro reflects the amount of bio-silica required for the formation of spicules in vivo. It is shown that during growth and maturation of the spicules in demosponges a bio-fusion process occurs that results in an intra-spicular sintering of the s…

Persistent link between Caribbean precipitation and Atlantic Ocean circulation during the Last Glacial revealed by a speleothem record from Puerto Rico

The sensitivity of tropical Atlantic precipitation patterns to the mean position of the Intertropical Convergence Zone (ITCZ) at different time scales is well‐known. However, recent research suggests a more complex behavior of the northern hemispheric tropical rain belt related to the ITCZ in the western tropical Atlantic. Here we present a precisely dated speleothem multi‐proxy record from a well‐monitored cave in Puerto Rico, covering the period between 46.2 and 15.3 ka. The stable isotope and trace element records document a pronounced response of regional rainfall to abrupt climatic excursions in the North Atlantic across the Last Glacial such as Heinrich stadials and Dansgaard/Oeschger…

Hardening of bio-silica in sponge spicules involves an aging process after its enzymatic polycondensation: evidence for an aquaporin-mediated water absorption.

Abstract Background Spicules, the siliceous skeletal elements of the siliceous sponges, are synthesized enzymatically via silicatein. The product formed, bio-silica, constitutes their inorganic matrix. It remained unexplored which reactions are involved in molding of the amorphous bio-silica and formation of a solid and rigid biomaterial. Methods Cell and molecular biological techniques have been applied to analyze processes resulting in the hardening of the enzymatically synthesized bio-silica. The demosponge Suberites domuncula has been used for the studies. Results Cell aggregates (primmorphs) from the sponge S . domuncula , grown in the presence of Mn-sulfate, form spicules that compris…

Mn/Ca in shells of Arctica islandica (Baltic Sea) – A potential proxy for ocean hypoxia?

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 varia…

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…

Silintaphin-1 - interaction with silicatein during structure-guiding bio-silica formation

Silicateins are unique enzymes of sponges (phylum Porifera) that template and catalyze the polymerization of nanoscale silicate to siliceous skeletal elements. These multifunctional spicules are often elaborately shaped, with complex symmetries. They carry an axial proteinaceous filament, consisting of silicatein and the scaffold protein silintaphin-1, which guides silica deposition and subsequent spicular morphogenesis. In vivo, the synthesis of the axial filament very likely proceeds in three steps: (a) assembly of silicatein monomers to form one pentamer; (b) assembly of pentamers to form fractal-like structures; and finally (c) assembly of fractal-like structures to form filaments. The …

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 …

Caribbean hydroclimate and vegetation history across the last glacial period

Abstract We present a new speleothem trace element and stable isotope record, which extends previous paleoclimate evidence from Cuban speleothems to the last 96 ka. Multiple proxies were used to reconstruct Caribbean hydroclimate and vegetation variability on orbital to millennial timescales. In particular, our proxies indicate a shift to more abundant C4 (compared to C3) vegetation and/or reduced soil activity during the Last Glacial Maximum. Our results confirm the close link of Caribbean precipitation to North Atlantic climate variability, insolation and the strength of the AMOC. The associated variations in Caribbean SSTs and the shift of the ITCZ led to substantial changes of the hydro…

Climate variations of Central Asia on orbital to millennial timescales

AbstractThe extent to which climate variability in Central Asia is causally linked to large-scale changes in the Asian monsoon on varying timescales remains a longstanding question. Here we present precisely dated high-resolution speleothem oxygen-carbon isotope and trace element records of Central Asia’s hydroclimate variability from Tonnel’naya cave, Uzbekistan and Kesang cave, western China. On orbital timescales, the supra-regional climate variance, inferred from our oxygen isotope records, exhibits a precessional rhythm, punctuated by millennial-scale abrupt climate events, suggesting a close coupling with the Asian monsoon. However, the local hydroclimatic variability at both cave sit…

Front Cover Advanced Materials 3/2012

Opposite Trends in Holocene Speleothem Proxy Records From Two Neighboring Caves in Germany: A Multi-Proxy Evaluation

Holocene climate in Central Europe was characterized by variations on millennial to decadal time scales. Speleothems provide the opportunity to study such palaeoclimate variability using high temporal resolution proxy records, and offer precise age models by U-series dating. However, the significance of proxy records from an individual speleothem is still a matter of debate, and limited sample availability often hampers the possibility to reproduce proxy records or to resolve spatial climate patterns. Here we present a palaeoclimate record based on four stalagmites from the Hüttenbläserschachthöhle (HBSH), western Germany. Two specimens cover almost the entire Holocene, with a short hiatus …

Evagination of Cells Controls Bio-Silica Formation and Maturation during Spicule Formation in Sponges

The enzymatic-silicatein mediated formation of the skeletal elements, the spicules of siliceous sponges starts intracellularly and is completed extracellularly. With Suberites domuncula we show that the axial growth of the spicules proceeds in three phases: (I) formation of an axial canal; (II) evagination of a cell process into the axial canal, and (III) assembly of the axial filament composed of silicatein. During these phases the core part of the spicule is synthesized. Silicatein and its substrate silicate are stored in silicasomes, found both inside and outside of the cellular extension within the axial canal, as well as all around the spicule. The membranes of the silicasomes are inte…

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…

230Th/U-dating of carbonate deposits from ancient aqueducts

Abstract Carbonate deposits in aqueducts, known as calcareous sinter, can reach a considerable thickness and are commonly annually laminated. Environmental and palaeoclimate proxies measured in calcareous sinter samples, such as stable oxygen and carbon isotopes and trace elements, can provide important high-resolution information on hydrological conditions, temperature, and local precipitation in the catchment area of an aqueduct. In order to utilize the proxy data for palaeoclimate reconstruction, the sinter deposits must be dated by annual laminae counting and more precisely by 230 Th/U-dating. The major problem of 230 Th/U-dating of calcareous sinter in aqueducts is the relatively large…

Fast offline data reduction of laser ablation MC-ICP-MS Sr isotope measurements: Via an interactive Excel-based spreadsheet 'SrDR'

Strontium isotopes are applied to a wide range of scientific fields and to different types of sample 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 field 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 of multiple offline steps to correct and assess the da…

Cover Picture: NanoSIMS: Insights into the Organization of the Proteinaceous Scaffold within Hexactinellid Sponge Spicules (ChemBioChem 8/2010)

Strontium and Oxygen Isotope Analyses Reveal Late Cretaceous Shark Teeth in Iron Age Strata in the Southern Levant

Skeletal remains in archaeological strata are often assumed to be of similar ages. Here we show that combined Sr and O isotope analyses can serve as a powerful tool for assessing fish provenance and even for identifying fossil fish teeth in archaeological contexts. For this purpose, we established a reference Sr and O isotope dataset of extant fish teeth from major water bodies in the Southern Levant. Fossil shark teeth were identified within Iron Age cultural layers dating to 8–9th century BCE in the City of David, Jerusalem, although the reason for their presence remains unclear. Their enameloid 87Sr/86Sr and δ18OPO4 values [0.7075 ± 0.0001 (1 SD, n = 7) and 19.6 ± 0.9‰ (1 SD, n = 6), res…

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…

Zinc isotopes in Late Pleistocene fossil teeth from a Southeast Asian cave setting preserve paleodietary information

Significance Dietary habits, especially meat consumption, represent a key aspect in the behavior and evolution of fossil hominin species. Here, we explore zinc (Zn) isotope ratios in tooth enamel of fossil mammals. We show discrimination between different trophic levels and demonstrate that Zn isotopes could prove useful in paleodietary studies of fossil hominin, or other mammalian species, to assess their consumption of animal versus plant resources. We also demonstrate the high preservation potential of pristine diet-related Zn isotope ratios, even under tropical conditions with poor collagen preservation, such as the studied depositional context in Southeast Asia. However, assessing the …

The Gabal Gerf complex: A precambrian N-MORB ophiolite in the Nubian Shield, NE Africa

We report geochemical and isotopic data for tectonically dismembered units of the Cabal Gerf mafic-ultramafic complex, the largest Neoproterozoic (Pan-African) ophiolite in the Arabian-Nubian Shield and located near the Red Sea in the border region between Egypt and the Sudan. The complex consists of basaltic pillow lavas, sheeted dykes, isotropic and layered gabbros and an ultramafic melange, all in tectonic contact along thrust sheets. Major- and trace-element data, including REE, for the pillow lavas and sheeted dykes are indistinguishable from modem high-Ti N-MORB. Chemical variations in the various rock types can be ascribed to fractionation and accumulation involving olivine, clinopyr…

Improved constraints on open-system processes in fossil reef corals by combined Th/U, Pa/U and Ra/Th dating: A case study from Aqaba, Jordan

Abstract Here we present 230Th/U, 231Pa/U as well as 226Ra/230Th isotope ratios from five fossil reef corals of Last Interglacial origin from the Gulf of Aqaba, Northern Red Sea. The results show clear evidence for open-system behaviour with strongly elevated δ234U values and U concentrations indicating post-depositional U addition. The combined application of all isotope systems enables us to better constrain the nature and timing of the open-system processes than only based on the 230Th/U data. Quantitative modelling of the diagenetic processes allowed us to reproduce the trends in the isotope ratios. Two of the five corals were probably affected by two separate phases of U addition with …

Sr and O isotope analyses reveal Late Cretaceous shark teeth in Iron Age strata of Jerusalem

Diagenesis of speleothems and its effect on the accuracy of 230 Th/U-ages

Abstract Speleothems can be precisely dated by U-series disequilibrium methods. One basic assumption of the 230Th/U-dating method is that the system remains closed and U and Th isotopes are neither lost nor added after deposition. For stalagmites, this requirement is usually fulfilled due to their protected environment in caves. However, undersaturated drip water may lead to diagenesis of speleothem CaCO3 and altered 230Th/U-ages. Here we present a detailed petrographic investigation using thin sections and 230Th/U-ages of a stalagmite from the Riesenberghohle, northern Germany, which grew during Marine Isotope Stages 5e, c and a. The occurrence of a mosaic fabric in large parts of the stal…

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…

NanoSr - A New Carbonate Microanalytical Reference Material for In Situ Strontium Isotope Analysis

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),…

Speleothem δ13C record suggests enhanced spring/summer drought in south-eastern Spain between 9.7 and 7.8 ka – A circum-Western Mediterranean anomaly?

South-eastern Spain is one of the driest regions in Europe and thus, prone to drought. Terrestrial climate records covering the late Glacial and Holocene from this area are sparse. Here, we present a flowstone record from Cueva Victoria, south-eastern Spain, which covers the late Glacial (15 ka) to the mid-Holocene (7 ka) including the Younger Dryas (YD). Between the onset of the Bølling/Allerød (B/A) and the early Holocene, flowstone δ18O values progressively decrease in accordance with sea-surface temperatures in the Alboran Sea, indicating an increase in precipitation in south-eastern Spain and a supra-regional signal of North Atlantic temperature change. At the same time, decreasing δ13…

Geochemistry of ultramafic and mafic rocks from the northern Central Asian Orogenic Belt (Tuva, Central Asia) - constraints on lower and middle arc crust formation linked to late Proterozoic intra-oceanic subduction

Abstract The Agardagh Tes-Chem complex (ATCC) in Tuva, Central Asia (50.5°N, 95°E) exposes a rare mafic to ultramafic crust-mantle fragment that developed within a late Neoproterozoic (~570 Ma) intra-oceanic island arc system that was accreted to the Tuva-Mongolian microcontinent during the formation of the Central Asian Orogenic Belt. Residual mantle rocks (harzburgites and dunites) are highly refractory with high Cr# (0.59–0.83) and intermediate Mg# (0.46–0.52) in spinel and experienced high degrees of total melt extraction (up to 25%). In ultramafic cumulate rocks (wehrlites and pyroxenites), Cr# and Mg# in spinel are distinctly lower (0.22–0.45 and 0.34–0.37), and rare earth element (RE…

High‐Resolution Proxy Records From Two Simultaneously Grown Stalagmites From Zoolithencave (Southeastern Germany) and their Potential for Palaeoclimate Reconstruction

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 an…

A Pearl Identification Challenge

Speleothem records decadal to multidecadal hydroclimate variations in southwestern Morocco during the last millennium

Abstract This study presents the first well-dated high resolution stable isotope ( δ 18 O and δ 13 C ) and trace element (Mg and Sr) speleothem records from southwestern Morocco covering the last 1000 yrs. Our records reveal substantial decadal to multidecadal swings between dry and humid periods, consistent with regional paleorecords with prevailing dry conditions during the Medieval Climate Anomaly (MCA), wetter conditions during the second part of the Little Ice Age (LIA), and a trend towards dry conditions during the current warm period. These coherent regional climate signals suggest common climate controls. Statistical analyses indicate that the climate of southwestern Morocco remaine…

Western Mediterranean Climate Response to Dansgaard/Oeschger Events: New Insights From Speleothem Records

The climate of the western Mediterranean was characterized by a strong precipitation gradient during the Holocene driven by atmospheric circulation patterns. The scarcity of terrestrial paleoclimate archives has precluded exploring this hydroclimate pattern during Marine Isotope Stages 5 to 3. Here we present stable carbon and oxygen isotope records from three flowstones from southeast Iberia, which show that Dansgaard/Oeschger events were associated with more humid conditions. This is in agreement with other records from the Iberian Peninsula, the Mediterranean, and western Europe, which all responded in a similar way to millennial‐scale climate variability in Greenland. This general incre…

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…

TERMITE: AnRscript for fast reduction of laser ablation inductively coupled plasma mass spectrometry data and its application to trace element measurements

RATIONALE High spatial resolution Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICPMS) determination of trace element concentrations is of great interest for geological and environmental studies. Data reduction is a very important aspect of LA-ICP-MS, and several commercial programs for handling LA-ICPMS trace element data are available. Each of these software packages has its specific advantages and disadvantages. METHODS Here we present TERMITE, an R script for the reduction of LA-ICPMS data, which can reduce both spot and line scan measurements. Several parameters can be adjusted by the user, who does not necessarily need prior knowledge in R. Currently, ten reference m…

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…

Climate and structure of the 8.2 ka event reconstructed from three speleothems from Germany

Abstract The most pronounced climate anomaly of the Holocene was the 8.2 ka cooling event. We present new 230Th/U-ages as well as high-resolution stable isotope and trace element data from three stalagmites from two different cave systems in Germany, which provide important information about the structure and climate variability of the 8.2 ka event in central Europe. In all three speleothems, the 8.2 ka event is clearly recorded as a pronounced negative excursion of the δ18O values and can be divided into a ‘whole event’ and a ‘central event’. All stalagmites show a similar structure of the event with a short negative excursion prior to the ‘central event’, which marks the beginning of the …

NanoSIMS: insights into the organization of the proteinaceous scaffold within Hexactinellid sponge spicules.

The giant basal spicules (GBS) from Monorhaphis chuni (Porifera [sponges], Hexactinellida) represent the largest biosilica structures on Earth and can reach lengths of 300 cm (diameter of 1.1 cm). The amorphous silica of the inorganic matrix is formed enzymatically by silicatein. During this process, the enzyme remains trapped inside the lamellar-organized spicules. In order to localize the organic silicatein scaffold, the inside of a lamella has been analyzed by nano-secondary ion mass spectrometry (NanoSIMS). It is shown that the GBSs are composed of around 245 concentrically arranged individual siliceous lamellae. These surround an internal siliceous axial cylinder. The lamellae adjacent…

Detection and origin of different types of annual laminae in recent stalagmites from Zoolithencave, southern Germany: Evaluation of the potential for quantitative reconstruction of past precipitation variability

Abstract. An arrangement of three stalagmites from Zoolithencave (southern Germany) was analysed for different types of annual laminae using both microscopic and geochemical methods. The speleothems show visible laminae (consisting of a clear and a brownish, pigmented layer pair) as well as fluorescent and elemental laminae. The age of the speleothems was constrained to 1800 to 1970 AD by 14C-dating of a charcoal piece below the speleothems, detection of the 14C bomb peak, as well as counting of annual laminae. Dating by the 230Th/U-method was impossible due to detrital contamination. On the annual time-scale, the variability of Mg, Ba, and Sr is controlled by Prior Calcite Precipitation (P…

Reorganization of the North Atlantic Oscillation during early Holocene deglaciation

Laurentide ice-sheet retreat continued into the mid-Holocene. Speleothem-based precipitation records suggest the cessation of melt led to the establishment of the present precipitation patterns associated with the North Atlantic Oscillation. The North Atlantic Oscillation is the dominant atmospheric pressure mode in the North Atlantic region and affects winter temperature and precipitation in the Mediterranean, northwest Europe, Greenland, and Asia1. The index1 that describes the sea-level pressure difference between Iceland and the Azores is correlated with a dipole precipitation pattern over northwest Europe and northwest Africa. How the North Atlantic Oscillation will develop as the Gree…

Opposite trends in Holocene speleothem proxy records from two neighboring caves in Germany : a multi-proxy evaluation

Holocene climate variability in Central Germany and a potential link to the polar North Atlantic: A replicated record from three coeval speleothems

Here, we present high-resolution trace element and stable isotope records from three coeval Holocene stalagmites from the Herbstlabyrinth cave system, Central Germany. All stalagmites were precisely dated using MC-ICPMS 230Th/U-dating. One stalagmite started to grow at 13.62 ± 0.13 ka BP, covering the late Glacial; the other two speleothems started to grow at 11.13 ± 0.08 and 10.26 ± 0.08 ka BP, respectively. The combined record covers the entire Holocene. The interpretation of the different climate proxies is supported by data from a detailed cave monitoring programme. Cold conditions during the Younger Dryas are reflected by intermittent stalagmite growth at the Herbstlabyrinth. The δ18O…

Reproducibility of trace element time-series (Na/Ca, Mg/Ca, Mn/Ca, Sr/Ca, and Ba/Ca) within and between specimens of the bivalve Arctica islandica – A LA-ICP-MS line scan study

Abstract Trace element time-series in bivalve mollusk shells and other (biogenic) materials can potentially serve as environmental proxies. Yet, the applicability of element-to-calcium ratios is often challenging, because non-environmental factors such as vital effects distort or mask environmental signals. If a trace element time-series is driven by an environmental factor, it should be reproducible within and between coeval specimens of the same species. In the present study, we tested whether time-series of trace element-to-calcium ratios can be reproduced within and between coeval specimens of the bivalve Arctica islandica and thus whether an external signal is encoded in the temporal v…

History of bioavailable lead and iron in the Greater North Sea and Iceland during the last millennium – A bivalve sclerochronological reconstruction

We present the first annually resolved record of biologically available Pb and Fe in the Greater North Sea and Iceland during 1040-2004 AD based on shells of the long-lived marine bivalve Arctica islandica. The iron content in pre-industrial shells from the North Sea largely remained below the detection limit. Only since 1830, shell Fe levels rose gradually reflecting the combined effect of increased terrestrial runoff of iron-bearing sediments and eutrophication. Although the lead gasoline peak of the 20th century was well recorded by the shells, bivalves that lived during the medieval heyday of metallurgy showed four-fold higher shell Pb levels than modern specimens. Presumably, pre-indus…

Flashing light signaling circuit in sponges: Endogenous light generation after tissue ablation in Suberites domuncula

The skeleton of siliceous sponges (phylum Porifera: classes Demospongiae and Hexactinellida), composed of tightly interacting spicules that assemble to a genetically fixed scaffold, is formed of bio-silica. This inorganic framework with the quality of quartz glass has been shown to operate as light waveguide in vitro and very likely has a similar function in vivo. Furthermore, the molecular toolkit for endogenous light generation (luciferase) and light/photon harvesting (cryptochrome) has been identified in the demosponge Suberites domuncula. These three components of a light signaling system, spicules—luciferase—cryptochrome, are concentrated in the surface layers (cortex) of the poriferan…

Self-healing, an intrinsic property of biomineralization processes

The sponge siliceous spicules are formed enzymatically via silicatein, in contrast to other siliceous biominerals. Originally, silicatein had been described as a major structural protein of the spicules that has the property to allow a specific deposition of silica onto their surface. More recently, it had been unequivocally demonstrated that silicatein displays a genuine enzyme activity, initiating and maintaining silica biopolycondensation at low precursor concentrations (<2 mM). Even more, as silicatein becomes embedded into the biosilica polymer, formed by the enzyme, it retains its functionality to enable a controlled biosilica deposition. The protection of silicatein through the biosi…

Circumferential spicule growth by pericellular silica deposition in the hexactinellid sponge Monorhaphis chuni.

SUMMARY The giant basal spicule of the hexactinellid sponge Monorhaphis chuni represents the longest natural siliceous structure on Earth. This spicule is composed of concentrically arranged lamellae that are approximately 10 μm thick. In the present study, we investigated the formation of outer lamellae on a cellular level using microscopic and spectroscopic techniques. It is shown that the formation of an outermost lamella begins with the association of cell clusters with the surface of the thickening and/or growing spicule. The cells release silica for controlled formation of a lamella. The pericellular (silica) material fuses to a delimited and textured layer of silica with depressions …

Evidence of warm and humid interstadials in central Europe during early MIS 3 revealed by a multi-proxy speleothem record

Marine Isotope Stage 3 (MIS 3, 57-27 ka) was characterised by numerous rapid climate oscillations (i.e., Dansgaard-Oeschger (D/O-) events), which are reflected in various climate archives. So far, MIS 3 speleothem records from central Europe have mainly been restricted to caves located beneath temperate Alpine glaciers or close to the Atlantic Ocean. Thus, MIS 3 seemed to be too cold and dry to enable speleothem growth north of the Alps in central Europe. Here we present a new speleothem record from Bunker Cave, Germany, which shows two distinct growth phases from 52.0 (+0.8, -0.5) to 50.9 (+0.6, -1.3) ka and 473 (+1.0, -0.6) to 42.8 (+/- 0.9) ka, rejecting this hypothesis. These two growth…

A New Find of Danburite in the Luc Yen Mining Area, Vietnam

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…

Supplement_Budsky – Supplemental material for Speleothem δ13C record suggests enhanced spring/summer drought in south-eastern Spain between 9.7 and 7.8 ka – A circum-Western Mediterranean anomaly?

Supplemental material, Supplement_Budsky for Speleothem δ13C record suggests enhanced spring/summer drought in south-eastern Spain between 9.7 and 7.8 ka – A circum-Western Mediterranean anomaly? by Alexander Budsky, Denis Scholz, Jasper A Wassenburg, Regina Mertz-Kraus, Christoph Spötl, Dana FC Riechelmann, Luis Gibert, Klaus Peter Jochum and Meinrat O Andreae in The Holocene

Determination of aragonite trace element distribution coefficients from speleothem calcite–aragonite transitions.

The processes that govern the incorporation of (trace) elements into speleothems can often be linked to environmental changes. Although element incorporation into speleothem calcite is now reasonably well understood, current knowledge regarding trace element variability in speleothem aragonite is very limited. Of particular interest is whether trace element distribution coefficients are above or below one in order to assess the extent to which prior aragonite precipitation has affected speleothem aragonite trace element records. This study uses nine calcite-to-aragonite transitions in seven speleothems from diverse environmental settings to derive the first quantitative estimates of the dis…

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

Sr-isotope analysis of speleothems by LA-MC-ICP-MS: High temporal resolution and fast data acquisition

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 (87Sr/86Sr) 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 appropriate…

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…

Calcium Carbonate and Phosphate Reference Materials for Monitoring Bulk and Microanalytical Determination of Sr Isotopes

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 Sr-87/Sr-86 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 s…

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 …

Coupled evolution of back-arc and island arc-like mafic crust in the late-Neoproterozoic Agardagh Tes-Chem ophiolite, Central Asia: evidence from trace element and Sr-Nd-Pb isotope data

We report major-element, trace-element and isotopic data of volcanic rocks from the late-Neoproterozoic (570 Ma) Agardagh Tes-Chem ophiolite in Central Asia, south-west of Lake Baikal (50.5°N, 95°E). The majority of samples are high-alumina basalts and basaltic andesites having island-arc affinities. They were derived from an evolved parental magma (Mg#≥0.60, Cr~180 ppm, Ni~95 ppm) by predominantly clinopyroxene fractionation. The parental magma developed from a primary mantle melt by fractionation of about 12% of an olivine+spinel assemblage. The island-arc rocks have high abundances of incompatible trace elements (light rare-earth element abundances up to 100 times chondritic, chondrite-n…

Speleothems in a north Cuban cave register sea-level changes and Pleistocene uplift rates

Influence of Compensating Defect Formation on the Doping Efficiency and Thermoelectric Properties of Cu2-ySe1–xBrx

The superionic conductor Cu_(2−δ)Se has been shown to be a promising thermoelectric at higher temperatures because of very low lattice thermal conductivities, attributed to the liquid-like mobility of copper ions in the superionic phase. In this work, we present the potential of copper selenide to achieve a high figure of merit at room temperature, if the intrinsically high hole carrier concentration can be reduced. Using bromine as a dopant, we show that reducing the charge carrier concentration in Cu_(2−δ)Se is in fact possible. Furthermore, we provide profound insight into the complex defect chemistry of bromine doped Cu_(2−δ)Se via various analytical methods and investigate the conseque…

Chemical separation and MC-ICPMS analysis of U, Th, Pa and Ra isotope ratios of carbonates

Diagenetic alteration of fossil reef corals may have severe effects on the reliability of 230Th/U-ages. The widely applied criteria introduced to test for the reliability of coral 230Th/U-ages are often not sufficient to identify all altered ages. The combination of 230Th/U- with 231Pa/U-dating has been suggested as a promising method to identify altered ages. Furthermore, 226Ra/230Th ratios can provide information about the diagenetic history during the last 10 000 years. Here we present a method to chemically separate U, Th, Pa and Ra from the same aliquot of a carbonate sample. The isotope ratios of our mixed U–Th–Pa–Ra spike are calibrated using a secular equilibrium material treated in…

Evaluating the potential of tree-ring methodology for cross-dating of three annually laminated stalagmites from Zoolithencave (SE Germany)

Abstract Three small stalagmites from Zoolithencave (southern Germany) show visible laminae, which consist of a clear and a brownish, pigmented layer pair. This potentially provides the opportunity to construct precise chronologies by counting annual laminae. The growth period of the three stalagmites was constrained by the 14C bomb peak in the youngest part of all three stalagmites and 14C-dating of a piece of charcoal in the consolidated base part of stalagmite Zoo-rez-2. These data suggest an age of AD 1970 for the top laminae and a lower age limit of AD 1973–1682 or AD 1735–1778. Laminae were counted and their thickness determined on scanned thin sections of all stalagmites. On stalagmi…

Holocene interaction of maritime and continental climate in Central Europe: New speleothem evidence from Central Germany

Central European climate is strongly influenced by North Atlantic (Westerlies) and Siberian High circulation patterns, which govern precipitation and temperature dynamics and induce heterogeneous climatic conditions, with distinct boundaries between climate zones. These climate boundaries are not stationary and shift geographically, depending on long-term atmospheric conditions. So far, little is known about past shifts of these climate boundaries and the local to regional environmental response prior to the instrumental era.\ud \ud High resolution multi-proxy data (stable oxygen and carbon isotope ratios, S/Ca and Sr/Ca) from two Holocene stalagmites from Bleßberg Cave (Thuringia) are used…

Evidence for a biogenic, microorganismal origin of rock varnish from the Gangdese Belt of Tibet

In the present study we examined material from the Ashikule Basin of Tibet. Chemical analyses were performed by use of energy dispersive X-ray spectroscopy and electron probe microanalysis to clarify whether the varnish layers that had developed on the surface of the rhyolite are indeed composed of varnish bodies and silica glaze. Electron microscopic analyses revealed that the surface of the varnish is covered both by filamentous hyphae bacterial and cocci-shaped forms. Within the varnish mineral layer in those samples two forms of bacteria-like microorganisms exist; cocci as tightly packed bacterial aggregates [within varnish bodies], and bacillus-like microorganisms [within the varnish m…

Moroccan speleothem and tree ring records suggest a variable positive state of the North Atlantic Oscillation during the Medieval Warm Period

We present a magnesium (Mg) and strontium (Sr) record from an aragonitic speleothem (Grotte de Piste, Morocco, 34‬°N; 04°W) providing a reconstruction of effective rainfall from 619 to 1962 AD. The corresponding drip site was monitored over 2 yr for drip water Mg/Ca and Sr/Ca ratios. Results show evidence for prior aragonite precipitation, which can explain negative correlations between speleothem Mg and Sr concentrations. The data shown here have important climate implications concerning the evolution of the North Atlantic Oscillation (NAO). A comparison of the stalagmite data from Grotte de Piste with an updated tree ring based drought reconstruction from Morocco and other NAO related pro…

(Supplement Table S2) Results of 230Th/U-dating

We compared the suitability of two skeletal materials of the Atlantic brain coral Diploria strigosa for 230Th/U-dating: the commonly used bulk material comprising all skeletal elements and the denser theca wall material. Eight fossil corals of presumably Last Interglacial age from Bonaire, southern Caribbean Sea, were investigated, and several sub-samples were dated from each coral. For four corals, both the ages and the activity ratios of the bulk material and theca wall agree within uncertainty. Three corals show significantly older ages for their bulk material than for their theca wall material as well as substantially elevated 232Th content and (230Th/238U) ratios. The bulk material sam…

Stable isotopes covering 96-7 ka BP from stalagmite CM (Santo Tomas Cave, Cuba)

We present a new speleothem trace element and stable isotope record, which extends previous paleoclimate evidence from Cuban speleothems to the last 96 ka. Stable isotope samples were micromilled at a resolution of 0.10-0.33mm, and measured using an IRMS equipped with a Gasbench. Line scans of Element/Calcium ratios of the speleothem were measured by laser ablation ICPMS and were reduced to the resolution of the stable isotope records.

Trace element data covering 96-7 ka BP from stalagmite CM (Santo Tomas Cave, Cuba)

We present a new speleothem trace element and stable isotope record, which extends previous paleoclimate evidence from Cuban speleothems to the last 96 ka. Stable isotope samples were micromilled at a resolution of 0.10-0.33mm, and measured using an IRMS equipped with a Gasbench. Line scans of Element/Calcium ratios of the speleothem were measured by laser ablation ICPMS and were reduced to the resolution of the stable isotope records.