Abstract: Sensitive methods for quantitative elemental analysis of micro-sized samples are limited. In this study, total-reflection X-ray fluorescence (TXRF) method was applied as fast and cost-efficient method to apatite microcrystals. In situ acid digestion based on direct treatment of single crystal onto the carrier was used as sample preparation strategy. Since the internal standard addition is complicated in the case of micro-sized samples, new quantification approaches based on external calibration for TXRF analysis of apatite were offered. An experimental design was created for apatite samples with a differentiation of specimen masses from 1.0 to 100 μg to find patterns in the spectral information. A workflow has been proposed for analyzing apatite crystals of various sizes (100, 500, 1000 µm) with TXRF based on an external calibration using an apatite powder sample as a standard and normalizing the spectra to the P-Kα and Mo-Kα peaks. The conditions of the workflow should be the following: Ca/P ratio is in a range between 19 and 23, and a dead time value does not exceed 4.0 %. The dead time value was used as a main factor of quantification, when calibration sample should match the unknown sample. Limit of detection values of the proposed method are from 1.0 to 100 μg/g depending on the crystal size and element of interest. Validation of the TXRF method was performed by analysis of Durango and McClure apatite samples. Comparison of TXRF results with laser ablation inductively coupled plasma mass spectrometry data showed the good agreement between two methods.

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Abstract: The new generation of laser ablation inductively coupled plasma mass spectrometry (LAICP-MS/MS) and Cameca IMS-1280-HR2 SIMS with high resolving power (ca. 40,000) theoretically allows to rapidly analyze on a scale of a few tens of micrometers of isotopic ratios whose in-situ measurement has so far suffered from isobaric interference problems that cannot be resolved with conventional instrumentation applicable to this scale. This opens major perspectives, particularly for the Rubidium (Rb)-Strontium (Sr) isotopic system, which has been used in geosciences to date and trace geological processes. This isotopic system is particularly suited to Rb-rich minerals (e.g., micas and feldspars) which are complementary to minerals traditionally dated using Uranium-Lead isotopic systems (e.g., zircon or monazite), which may be absent from certain geological contexts (e.g., hydrothermalism) and/or affected by post-crystallization alteration which affects this geochronometer. These new prospects for in-situ application of isotopic systems such as Rb-Sr are made possible, respectively, by the introduction of a reaction gas via a reaction cell and by a high resolution power favored by a new instrumental configuration.

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Abstract: The chemical composition of foraminiferal shells is a well-known tool in paleoceanography to reconstruct past environments and climate. Their application is based on the relation between environmental variables and the concentration of elements incorporated or stable isotope fractionation during calcification. The vast majority of these so-called proxy relationships are based on the foraminiferal order of the Rotaliida, which, for example, encompasses all living planktonic species. However, there are more orders of foraminifera with calcifying members, some of which have fundamentally different biomineralization pathways, such as the Nodosariida, the Polymorphinida and the Vaginulinida. All these belong to the class of the Nodosariata and produce calcite shells, which may serve as carriers of paleoenvironmental and climate signals. The microstructures of these shells and overall morphology of these foraminifera strongly deviate from the Rotaliida, suggesting that their elemental and stable isotopic composition do not necessarily respond similarly to environmental parameters. A potential advantage of the Nodosariata is that they appear considerably earlier in the fossil record (Carboniferous) than the Rotaliida (Jurassic), thereby possibly extending the range of foraminifer-based paleoceanographic reconstructions considerably. To test the potential application of Nodosariata foraminifera as paleoproxies, we investigated incorporation of 5 elements in 11 species as a function of environmental parameters from a transect sampled in the Gulf of Mexico. Their element composition (B / Ca, Na / Ca, Mg / Ca, Sr / Ca and Ba / Ca) shows a distinct geochemical signature for these foraminifera, different to that of members of other foraminiferal orders. Results also show an increase in Mg / Ca values with increasing temperature, similar to that known for the Rotaliida, which suggest that Nodosariata shells might be useful for paleotemperature reconstructions. The difference in Mg / Ca temperature calibration in Nodosariata compared to Rotaliida, with the large differences in their morphology, shell microstructures and overall geochemical composition, suggests that the Mg / Ca to temperature relationship is partly independent of the exact calcification mechanism. We compare Mg / Ca temperature sensitivities across foraminiferal orders and describe a relationship between the average Mg / Ca and the sensitivity of the Mg / Ca temperature calibration. For other elements, the variability across orders is smaller compared to that in Mg / Ca, which results in more similar El / Ca environmental calibrations.

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Abstract: Biotite–melt Nb and Ta partition coefficients (D_Nb and D_Ta) are crucial for understanding Nb−Ta enrichment and fractionation in rare metal granites (RMGs). However, the key factor(s) affecting biotite–melt D_Nb, D_Ta, and D_Nb/D_Ta values remain unclear. To elucidate the physicochemical factors that control the partition coefficients, we performed piston−cylinder experiments at 0.5−1.0 GPa and 850−1000°C with H₂O-added (4−10 wt.%) mixtures of granitic and biotitic glasses as starting materials. Two series of experiments (graphite-buffered and unbuffered fO₂ conditions) were conducted with calculated fO₂ values ranging from ∼FMQ–1.5 to ∼FMQ+4. Under these experimental conditions, biotite–melt D_Nb, D_Ta, and D_Nb/D_Ta values are 0.30–2.63, 0.24−1.02, and 1.01−2.15, respectively. Biotite–melt D_Nb, D_Ta, and D_Nb/D_Ta values increase with decreasing melt NBO/T value (non-bridging oxygens per tetrahedron), melt H₂O content, and biotite Mg#^T value [molar 100 × MgO/(MgO + FeO^T)]. In addition, D_Nb and D_Ta exhibit good correlations with D_Ti, suggesting that D_Nb and D_Ta are predictable via D_Ti values. With our and literature data, we used multiple linear regressions to obtain empirical expressions of D_Nb and D_Ta as functions of the three parameters. By applying the empirical models to granite differentiation process, we found that ∼99% crystallization of biotite ± muscovite-bearing assemblages results in an enrichment in magma Ta contents by >10 times with a decrease in Nb/Ta values from 10−13 to ∼1, which reproduces the Ta–Nb/Ta features of most RMGs. However, additional processes, such as columbite-group mineral precipitation, may be required to account for the extremely low Nb/Ta values (<1) of some RMGs.

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Abstract: Draining into the northern Baltic Sea, River Simojoki is an important spawning river for Atlantic salmon. The present study aimed to preliminary explore the potential of analysing the elemental composition of otoliths to distinguish the within-river nursery area of origin for salmon. Parr were sampled at three nursery areas in the river and smolts of unknown origin were sampled near the river mouth during the migration to the sea. The concentrations of multiple elements and the strontium 87Sr/86Sr isotopic ratio in the otoliths were analysed using single- and multi-collector laser ablation inductively coupled plasma mass spectrometry, respectively. Based on the otolith elemental variables, parr could be reclassified to the sampled nursery areas using discriminant function analysis and random forest with a success rate of 53.3% and 63.3%, respectively. However, for parr sampled at the uppermost nursery area in the river, the success rates were 90% and 100%, respectively. Applying the classification models trained on the parr samples to determine which nursery area sampled smolt originated from was constrained by the limited sampling of parr, both in sample sizes and the coverage of the nursery areas found in the river. 

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Abstract: Insights into past marine carbon cycling and water mass properties can be obtained by means of geochemical proxies calibrated through controlled laboratory experiments with accurate seawater carbonate system (C-system) manipulations. Here, we explored the use of strontium/calcium ratio (Sr/Ca) of the calcite shells of benthic foraminifera as a potential seawater C-system proxy through a controlled growth experiment with two deep-sea species (Bulimina marginata and Cassidulina laevigata) and one intertidal species (Ammonia T6). To this aim, we used two experimental set-ups to decouple as much as possible the individual components of the carbonate system, i.e., changing pH at constant dissolved inorganic carbon (DIC) and changing DIC at constant pH. Four climatic chambers were used with different controlled concentrations of atmospheric pCO₂ (180ppm, 410ppm, 1000ppm, 1500ppm). Our results demonstrated that pH did not influence the survival and growth of the three species. However, low DIC conditions (879μmolkg⁻¹) negatively affected B. marginata and C. laevigata through reduced growth, whereas no effect was observed for Ammonia T6. Our results also showed that Sr/Ca was positively correlated with total Alkalinity (TA), DIC and bicarbonate ion concentration ([HCO3⁻]) for Ammonia T6 and B. marginata; i.e., DIC and/or [HCO3⁻] were the main controlling factors. For these two species, the regression models were coherent with published data (existing so far only for Ammonia T6) and showed overall similar slopes but different intercepts, implying species-specific effects. Furthermore, the Sr/Ca - C-system relationship was not impacted by ontogenetic trends between chamber stages, which is a considerable advantage for paleo-applications. This applied particularly to Ammonia T6 that calcified many chambers compared to the two other species. However, no correlation with any of the C-system parameters was observed for Sr/Ca in C. laevigata. This might imply either a strong species-specific effect and/or a low tolerance to laboratory conditions leading to a physiological stress, thereby impacting the Sr incorporation into the calcite lattice of C. laevigata.

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Abstract:

Introduction: Growth experiments present a powerful tool for determining the effect of environmental parameters on growth and carbonate composition in biogenic calcifiers. For successful proxy calibration and biomineralization studies, it is vital to identify volumes of carbonate precipitated by these organisms at precise intervals during the experiment. Here, we investigate the use of strontium labelling in mollusc growth experiments.

Methods: Three bivalve species (Cerastoderma edule, Mytilus edulis and Ostrea edulis) were grown under monitored field conditions. The bivalves were regularly exposed to seawater with elevated concentrations of dissolved strontium chloride (SrCl₂). In addition, the size of their shells was determined at various stages during the experiment using calliper measurements and digital photography. Trace element profiles were measured in cross sections through the shells of these molluscs using laser ablation ICPMS and XRF techniques.

Results: Our results show that doses of dissolved strontium equivalent to 7-8 times the background marine value (~0.6 mmol/L) are sufficient to cause reproducible peaks in shell-incorporated strontium in C. edule and M. edulis shells. No negative effects were observed on shell calcification rates. Lower doses (3-5 times background values) resulted in less clearly identifiable peaks, especially in M. edulis. Strontium spiking labels in shells of O. edulis are more difficult to detect, likely due to their irregular growth. 

Discussion: Strontium spiking is a useful technique for creating time marks in cultured shells and a reproducible way to monitor shell size during the growing season while limiting physical disturbance of the animals. However, accurate reconstructions of growth rates at high temporal resolution require frequent spiking with high doses of strontium.

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Abstract: In an era of rapid environmental change and increasing human presence, researchers need efficient tools for tracking contaminants to monitor the health of Antarctic flora and fauna. Here, we examined the utility of leopard seal whiskers as a biomonitoring tool that reconstructs time-series of significant ecological and physiological biomarkers. Leopard seals (Hydrurga leptonyx) are a sentinel species in the Western Antarctic Peninsula due to their apex predator status and top-down effects on several Antarctic species. However, there are few data on their contaminant loads. We analyzed leopard seal whiskers (n = 18 individuals, n = 981 segments) collected during 2018–2019 field seasons to acquire longitudinal profiles of non-essential (Hg, Pb, and Cd) and essential (Se, Cu, and Zn) trace elements, stable isotope (ẟ15N and ẟ13C) values and to assess Hg risk with Se:Hg molar ratios. Whiskers provided between 46 and 286 cumulative days of growth with a mean ~ 125 days per whisker (n = 18). Adult whiskers showed variability in non-essential trace elements over time that could partly be explained by changes in diet. Whisker Hg levels were insufficient (<20 ppm) to consider most seals being at “high” risk for Hg toxicity. Nevertheless, maximum Hg concentrations observed in this study were greater than that of leopard seal hair measured two decades ago. However, variation in the Se:Hg molar ratios over time suggest that Se may detoxify Hg burden in leopard seals. Overall, we provide evidence that the analysis of leopard seal whiskers allows for the reconstruction of time-series ecological and physiological data and can be valuable for opportunistically monitoring the health of the leopard seal population and their Antarctic ecosystem during climate change.

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Abstract: The Oman upwelling zone (OUZ) creates an unfavorable environment and a major biogeographic barrier for many coral reef species, such as giant clams, thus promoting and maintaining faunal differences among reefs on the east and west side of the Arabian Peninsula. We record the former existence of Tridacna in the Gulf of Oman and review its stratigraphic distribution in the Persian Gulf to provide new insights on the connectivity of coral reef habitats around southern Arabia under changing climate and ocean conditions. Fossil shells were carbon-14 dated and employed as sclerochronological proxy archives. This reveals that the Omani population represents a last glacial colonization event during the Marine Isotope Stage 3 interstadial under colder-than-present temperatures and variable upwelling intensity linked to Dansgaard-Oeschger climate oscillations. It was favored by temperatures just above the lower threshold for the habitat-forming reef coral communities and instability of the upwelling barrier. We conclude that the distribution of Tridacna in the northern Arabian Sea is generally limited by either strong upwelling or cool sea surface temperature under gradually changing climate conditions at the interglacial-glacial scale. Opportunities for dispersal and temporary colonization existed only when there was a simultaneous attenuation of both limiting factors due to high-frequency climate variability. The OUZ will unlikely become a future climate change refuge for giant clams because they will be exposed either to thermal stress by rapid anthropogenic Indian Ocean warming or to unfavorable upwelling conditions.

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Abstract: Studying the lacustrine microbialites in the Qaidam Basin may provide clues to the occurrence and mineralization processes of microbial communities in extremely harsh terrestrial environments. In the Eocene lacustrine systems of the Qaidam Basin, thick thrombolites (~0.4 to 1 m thick) generally formed in near-shore settings with rare to plentiful terrigenous admixtures and are characterized by four different clotted structures (i.e., maze-like, cortoid-like, tightly bound, and aggregated). In contrast, the small-scale stromatolitic, thrombolitic, and composite clotted-laminated microbialites (cm level) exhibit domical, columnar, and stratiform shapes, likely indicating that they developed in very shallow settings (e.g., a lagoon). The early lithification of the outer crusts and the internally laminated and clotted textures facilitated the preservation of the microbialites. The laminated and clotted textures of the Eocene microbialites analyzed in this study were composed of crypto- to micro-crystalline (mimetic) dolomite, which likely formed during the early mineralization process. This was likely caused by the strong evaporative lacustrine conditions on the Qinghai-Tibetan Plateau during the Eocene-Oligocene climate transition. The microbial mineralization process in dolomite-supersaturated pore fluids may also have contributed to early dolomitization. In contrast, the medium to coarsely crystalline components of the microbialites are composed of calcite minerals, implying that these components experienced cementation/recrystallization during diagenesis. In addition, large quantities of authigenic sulfate (celestite-barite) and sulfide (framboidal pyrite) minerals are exclusively distributed within the mimetically-dolomitized, laminated and clotted microbial structures. It is inferred that the saline lake conditions and the mineral dissolution (both carbonate and terrigenous particles) contributed to the SrSO4- and BaSO4-supersaturated fluid conditions and enabled the crystallization of celestite-barite. The development of Eocene lacustrine microbialites on the northeastern Qinghai-Tibetan Plateau provides a case for comparison with widely-distributed records of lake microbial carbonates, and the microstructural characteristics and analytical tools used in this study may offer a new perspective to explore the complex mineralization processes of microbialites.

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Abstract: Studying the lacustrine microbialites in the Qaidam Basin may provide clues to the occurrence and mineralization processes of microbial communities in extremely harsh terrestrial environments. In the Eocene lacustrine systems of the Qaidam Basin, thick thrombolites (~0.4 to 1 m thick) generally formed in near-shore settings with rare to plentiful terrigenous admixtures and are characterized by four different clotted structures (i.e., maze-like, cortoid-like, tightly bound, and aggregated). In contrast, the small-scale stromatolitic, thrombolitic, and composite clotted-laminated microbialites (cm level) exhibit domical, columnar, and stratiform shapes, likely indicating that they developed in very shallow settings (e.g., a lagoon). The early lithification of the outer crusts and the internally laminated and clotted textures facilitated the preservation of the microbialites. The laminated and clotted textures of the Eocene microbialites analyzed in this study were composed of crypto- to micro-crystalline (mimetic) dolomite, which likely formed during the early mineralization process. This was likely caused by the strong evaporative lacustrine conditions on the Qinghai-Tibetan Plateau during the Eocene-Oligocene climate transition. The microbial mineralization process in dolomite-supersaturated pore fluids may also have contributed to early dolomitization. In contrast, the medium to coarsely crystalline components of the microbialites are composed of calcite minerals, implying that these components experienced cementation/recrystallization during diagenesis. In addition, large quantities of authigenic sulfate (celestite-barite) and sulfide (framboidal pyrite) minerals are exclusively distributed within the mimetically-dolomitized, laminated and clotted microbial structures. It is inferred that the saline lake conditions and the mineral dissolution (both carbonate and terrigenous particles) contributed to the SrSO4- and BaSO4-supersaturated fluid conditions and enabled the crystallization of celestite-barite. The development of Eocene lacustrine microbialites on the northeastern Qinghai-Tibetan Plateau provides a case for comparison with widely-distributed records of lake microbial carbonates, and the microstructural characteristics and analytical tools used in this study may offer a new perspective to explore the complex mineralization processes of microbialites.

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