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Mn/Ca of foraminiferal calcite has been proposed as a tool to reconstruct past oxygen conditions, but the impact of the concentration of Mn ([Mn]) in seawater on partitioning of Mn in foraminiferal calcite remains unclear. Here, we explore Mn incorporation of different species of foraminifera across a gradient of seawater [Mn] by culturing small and large benthic foraminifera in hypoxic conditions using a controlled laboratory set‐up. Our observations confirm previous results that Mn incorporation varies greatly between species and underline the need for species‐specific calibrations and mono‐species application of Mn‐based proxies. We explore whether the observed species‐specific incorporation of Mn could be due to an interaction between Mn incorporation and Mg content, or other processes related to the co‐uptake, ‐transport and ‐precipitation of Mn and Mg to the calcification site and ultimately foraminiferal calcite. Furthermore, results show that for several species (Ammonia confertitesta, Bulimina marginata, Cassidulina laevigata and Amphistegina lessonii) partitioning of Mn increases below a species‐specific threshold of seawater [Mn]. For application of the Mn‐proxy, this slightly higher Mn partitioning can lead to a slight overestimation (up to 5‐fold) of reconstructed seawater Mn/Ca at very low concentrations close to 0 (e.g., well oxygenated conditions), when assuming a constant distribution coefficient for this proxy. However, this only occurs at extremely low seawater Mn/Ca, below 1.06 mmol/mol. This trend is less clear for the larger benthic foraminifera (Amphistegina lessonii and Operculina ammonoides), where it is potentially masked by the larger range of Mn/Ca data and additional impacts on Mn incorporation, such as ontogeny.

The abundances of 60 elements in 616 Ocean Floor Basaltic (OFB) glasses from the Abyssal Volcanic Glass Data File (AVGDF) of the Smithsonian Institution have been determined by laser‐ablation (LA)‐ICP‐MS and electron microprobe analysis (EMPA). The elements analyzed include all 28 of the refractory lithophile elements, which provide the framework for establishing the geochemical behavior and source abundances of volatile, chalcophile and siderophile elements. In addition to the traditionally analyzed elements (rare earth elements (REE), high field strength elements (HFSE), large ion lithophile elements (LILE) and first row transition elements (FRTE)), we report analyses for lesser‐analyzed elements (Li, Be, Ga, Ge, As, Se, Mo, Ag, Cd, In, Sn, Sb, W, Tl and Bi). The precision of the method for most elements is between 2 and 4%, one standard deviation, although ratios of elements determined simultaneously are more precise (e.g., REE, Zr/Hf). Subsets of 329 glasses were analyzed by electron microprobe for S and 154 glasses for Cl. The results define a representative trace element geochemistry of OFB, against which local variations resulting from differences in basalt petrogenesis in a range of tectonic settings or different styles of magmatic differentiation may be compared. Key Points New data file of analyses of 60 elements in 616 volcanic glass samples The results define a representative trace element array for OFB Improvement in the precision of data available for ocean floor basalts

Understanding post‐depositional processes altering the layer sequence in ice cores is especially needed to avoid misinterpretation of the oldest and most highly thinned layers. The record of soluble and insoluble impurities represents an important part of the paleoclimate proxies in ice cores but is known to be affected through interaction with the ice matrix, diffusion, and chemical reactions. Laser ablation inductively coupled plasma mass spectrometry (LA‐ICP‐MS) has been recognized for its micron‐scale resolution and micro‐destructiveness in ice core impurity analysis. Employing LA‐ICP‐MS for 2D chemical imaging has already revealed a close relationship between the ice grain boundary network and impurity signals with a significant soluble component, such as Na and Mg. Here we show the latest improvements in chemical imaging with LA‐ICP‐MS, by increasing the spatial resolution to 20 μm and extending the simultaneous analysis to also mostly insoluble impurities, such as Al and Fe. All analytes reveal signals of dispersed spots in a sample of an East Greenland ice core. Based on their average size around 50–60 times larger than an average particle and their heterogeneous elemental ratios these spots are interpreted as particle clusters. To distinguish their origin, a simple colocalization classification reveals elemental ratios consistent with marine and mineral dust aerosol. Based on already existing data from cryo‐Raman spectroscopy, we discuss potential ways to integrate the two methods in a future comparison. Such a combined approach may help constraining post‐depositional changes to the dust‐related insoluble impurity components, such as cluster formation and chemical reactions at grain boundaries. Plain Language Summary Aerosols of marine and terrestrial origin delivered to the polar ice sheets are archived in the ice and can be studied via the analysis of ice cores. The chemical composition and size of mineral dust can deliver important information about past climatic changes and atmospheric transport. However, it has already been shown that this insoluble material is not always passively archived in the ice but can undergo changes in its chemical composition and size, for example, by forming particle aggregates. To investigate these processes, it is preferable to study the chemical composition of insoluble particles and their localization within the ice matrix. Here we show how this can be done by a new chemical imaging method for ice using laser ablation inductively coupled plasma mass spectrometry. In a sample of a Greenland ice core we find clear signals of particle clusters, 50–60 times larger than a single particle. Based on their chemical composition, it is possible to differentiate between marine and terrestrial material. We discuss the results against findings previously obtained for the same sample from a different method, cryo‐Raman spectroscopy. Bringing together several methods may provide important added value for a more comprehensive understanding of these important indicators of past climate. Key Points Laser ablation inductively coupled plasma mass spectrometry imaging investigates the geochemical composition and localization of particles in samples of the East Greenland Ice Core Project ice core, East Greenland The maps reveal clusters of insoluble particles 50–60 times larger than an average particle, at intra‐grain locations and grain boundaries Geochemical signals of the particles are consistent with cryo‐Raman spectroscopy and with known dust sources and sea salt aerosol

Understanding the microscopic variability of impurities in glacier ice on a quantitative level has importance for assessing the preservation of paleoclimatic signals and enables the study of macroscopic deformational as well as dielectric ice properties. Two‐dimensional imaging via laser‐ablation‐inductively‐coupled‐plasma‐mass‐spectrometry (LA‐ICP‐MS) can provide key insight into the localization of impurities in the ice. So far, these findings are mostly qualitative and gaining quantitative insights remains challenging. Recent advances in LA‐ICP‐MS high‐resolution imaging now allow ice grains and grain boundaries to be resolved individually. These resolutions require new adequate quantification strategies and, consequently, accurate calibration with matrix‐matched standards. Here, we present three different quantification methods, which provide a high level of homogeneity at the scale of a few tens of microns and are dedicated to imaging applications of ice cores. One of the proposed methods has a second application, offering laboratory experiments to investigate the displacement of impurities by grain growth, with important future potential to study ice‐impurity interactions. Standards were analyzed to enable absolute quantification of impurities in selected ice core samples. Calibrated LA‐ICP‐MS maps indicate similar spatial distributions of impurities in all samples, while impurity levels vary distinctly: Higher concentrations were detected in glacial periods and Greenland, and lower levels in interglacial periods and samples from central Antarctica. These results are consistent with ranges from complementary meltwater analysis. Further comparison with cm‐scale melting techniques calls for a more sophisticated understanding of the ice chemistry across spatial scales, to which calibrated LA‐ICP‐MS maps now contribute quantitatively. Plain Language Summary Compared to the large amount of information relating to paleoclimate signals reconstructed from cm‐scale impurity measurements on ice cores, knowledge about the spatial variability of impurities at the micro‐scale is extremely sparse—and becomes even more rare once quantitative datasets are concerned. However, there is an increasing demand for quantitative data for assessing the preservation of paleoclimatic signals and for the study of macroscopic deformational as well as dielectric ice properties in ice flow modeling and remote sensing. Two‐dimensional imaging via laser‐ablation‐inductively‐coupled‐plasma‐mass‐spectrometry (LA‐ICP‐MS) has shown great potential in this context, but so far, gaining reliable quantitative results for micro‐scale imaging has not been possible. Here, we present new quantification strategies that finally allow accurate calibration using ice standards. We carefully discuss the pros and cons of each method, apply the calibration to different samples from Greenland and Antarctica, and deliver the first calibrated LA‐ICP‐MS impurity maps at 40 μm resolution. Our results are consistent with bulk measurements performed on melted samples. The calibrated LA‐ICP‐MS maps will be essential for further comparison with bulk meltwater analysis, which may ultimately deliver an improved understanding of paleoclimate signals stored in deep ice. Key Points This study presents new quantification strategies for two‐dimensional micro‐scale impurity imaging on ice cores with laser‐ablation‐inductively‐coupled‐plasma‐mass‐spectrometry (LA‐ICP‐MS) Calibrated LA‐ICP‐MS maps reveal similar spatial distributions of impurities in all ice core samples, while concentrations vary distinctly We developed a method to investigate the displacement of impurities by grain growth and to study ice‐impurity interactions in the laboratory

This study investigates the potential of laser ablation inductively coupled plasma mass spectrometry (LA‐ICP‐MS) U‐Pb dating for carbonate nodules in the Late Triassic Ischigualasto Formation of northwestern Argentina. We establish a fully characterized paragenetic sequence to guide the analysis of three pedogenic carbonates and compare the U‐Pb ages with published geochronology from volcanic ashes within the sedimentary succession. Our findings demonstrate the importance of interpreting U‐Pb data within a well‐defined paragenetic framework for accurate age interpretation of pedogenic carbonates. We observe variations in U‐Pb isotopic signatures across different generations of carbonate precipitates and identify syn‐pedogenic and early burial calcite cements as most suitable for precise dating. Respectively, these two calcite cements are interpreted as microcodium and crack‐lining calcite cements formed early in the paragenetic sequence during pedogenesis to early burial of the paleosols as they transitioned from the unsaturated vadose to saturated phreatic zone below the water table. The U‐Pb ages obtained from the carbonate nodules agree with the radioisotopic ages of volcanic ashes, supporting the validity of our dating strategy. These results contribute to advancing U‐Pb carbonate geochronology and highlight its increased potential for dating sedimentary records in the terrestrial realm. Future research should focus on replicating similar work on different carbonate nodules within the Ischigualasto Fm and expanding the application of LA‐ICP‐MS U‐Pb dating to other carbonate‐bearing formations, especially in successions with limited absolute ages or where volcanic ashes are sparse or absent. Plain Language Summary Carbonate minerals that formed in fossil soils can provide valuable insights into past physical, biological, and chemical processes on Earth's surface. Despite their significance in reconstructing ancient climates and environments, determining the age of these fossil soils via uranium‐to‐lead dating has proven challenging. This difficulty arises from factors associated with soil carbonate minerals, including low uranium content, high lead content, complex formation chemistry, multiple formation episodes (generations), and potential for post‐formation chemical alteration. To address these issues, we first identified the order in which carbonate minerals formed within three samples from the Late Triassic Ischigualasto Formation of Argentina. Then, we dated each generation within each sample and compared the results to identify and understand the most optimal sample locations for dating. Analysis of our data shows that carbonate minerals formed due to biological processes near the surface as well as during the burial and submersion of the fossil soils below the water table are the most suitable for dating and approximate the timing of soil formation. Importantly, the ages from these soil carbonate samples align with ages from volcanic ashes found within the Ischigualasto Formation, thus validating our results and the potential to apply our strategy in other locations. Key Points A well‐defined paragenetic framework is necessary to interpret laser ablation inductively coupled plasma mass spectrometry U‐Pb data for accurate age interpretation of pedogenic carbonates U‐Pb isotopic signatures vary across generations of carbonate precipitates, with syn‐pedogenic and early burial cements being the most suitable for precise dating Syn‐pedogenic and early burial cements approximate the timing of pedogenesis and transition from the unsaturated vadose to the saturated phreatic zone, respectively

The metaturbidite‐hosted, ∼380 Ma Dufferin gold deposit, Meguma terrane, northeastern Appalachian Orogen (Nova Scotia, Canada) is an orogenic gold deposit with mineralized saddle reef‐type quartz veins hosted by metasandstones and black slates in a tightly folded anticline. Together with native gold inclusions, genetically related hydrothermal carbonaceous material (CM) in veins occurs as pyrobitumen in cavities and along fractures/grain boundaries proximal to vein contacts and wallrock fragments. Integrating several microanalytical methods we document the precipitation of gold via coupled fluid‐fO2 reduction (via interaction with CM) and pH increase. These changes in fluid chemistry destabilized gold bisulfide complexes, leading to efficient Au precipitation from a gold‐undersaturated (0.045 ± 0.024 ppm Au; 1σ; n = 58 fluid inclusions) aqueous‐carbonic fluid (H2O‐NaCl‐CO2 ± N2 ± CH4). The proposed mineralization mechanism is supported by: (a) a complementary decrease in Au and redox‐sensitive semimetals (As, Sb), and increase in wall rock‐derived elements (i.e., Mg, K, Ca, Sr, Fe) concentrations in fluid inclusions with time; (b) a corresponding decrease in the XCO2, consistent with CO2 removal via reduction/respeciation and late carbonate precipitation; and (c) gold embedding in, or on, the surface of CM inside mineralized cavities and fractures. Despite mineralizing fluids transporting low concentrations of Au far from saturation, precipitation of gold was locally evidently high where such fluids interacted with CM, contributing to the overall gold endowment of Meguma deposits. This work re‐emphasizes CM as a potential prerequisite for efficient gold precipitation within the overall genetic model for similar orogenic metasedimentary settings globally where the presence and/or role of CM has been documented. Plain Language Summary The Dufferin gold deposit in Nova Scotia, Canada, formed ∼380 million years ago within metamorphosed sedimentary rocks called the Meguma Group. The deposit contains gold‐bearing quartz veins sandwiched between layers of tightly folded rocks. This study focused on unraveling the mechanisms behind some of the gold deposition within this deposit, specifically where associated with carbonaceous matter (CM). We found a close association between gold and CM, which represents organic matter preserved in the rocks. CM is abundant within small cavities throughout the quartz veins that also contain appreciable gold occurring as microscopic particles in the CM. By using a variety of analytical techniques, we determined that efficient gold mineralization occurred in response to specific chemical changes to the gold‐carrying fluid, including a decrease in the oxidation potential and a decrease in the acidity of the fluid through interaction with the CM‐rich rocks. Such changes to the fluid caused gold to become insoluble and form particles that were deposited in the rocks and vein material. Importantly, despite the fluid having a low concentration of dissolved gold, it exhibited a remarkable ability to deposit significant quantities of the precious metal, underscoring the important role of CM in facilitating efficient gold precipitation from fluids. Key Points First fluid gold concentrations (0.045 ± 0.024 μg/g) measured from an economic, Meguma‐type metasediment‐hosted gold deposit Fluid Au, S, As, W, and B concentrations comparable to Alpine and Variscan metamorphic fluids hosted in uneconomic, Au‐poor vein systems Gold and carbonaceous matter are coeval and co‐distributed in flysch wallrocks and vein laminae

Submarine caldera volcanoes may host several hydrothermal systems along the caldera wall and related to volcanic cones. Fluid boiling and magmatic volatile influx are common processes in shallow (<2,000 mbsl) subduction zone‐related environments causing variations in the mineralogical and chemical composition of seafloor hydrothermal mineralizations that remain poorly constrained. The submarine caldera of Niuatahi volcano, Tonga rear‐arc, hosts four active vent sites discharging high temperature fluids (<334°C) with variable salinities (369–583 mM Cl) that are indicative of fluid boiling, recorded by distinct Te/As and Te/Au in pyrite, sphalerite, and chalcopyrite. High sulfidation mineral assemblages (e.g., enargite), stable S isotope data and similar trace element signatures in sulfides and native S condensates suggest a minor and/or infrequent contribution of magmatic SO2 to the hydrothermal systems located proximal to the caldera center causing a volatile element (e.g., Se, Bi, Te) enrichment. The hydrothermal system at the northern caldera wall is decoupled from the magmatic SO2 source, as revealed by radiogenic Pb isotopes. Instead, S isotope and trace element constraints propose a host rock‐dominated hydrothermal system, lacking a magmatic volatile influx. The observed hydrothermal fractionation processes (fluid boiling) and the distinct metal (loid) sources (magmatic volatiles vs. host rock) represent a continuum from magmatic volatile‐ to host rock‐dominated hydrothermal systems within the Niuatahi caldera. This leads to seafloor mineralizations with spatially selective trace element enrichments, like Te, Se, and Bi (±Au, Ag) in the caldera center compared to Au, Ag, Zn, Cd, and Pb at the northern caldera wall. Plain Language Summary Seafloor mineralization (e.g., black smokers) with different compositions can occur at hot springs at submarine caldera volcanoes associated with volcanic cones or the caldera wall. The effect of boiling fluids and the addition of magmatic gases results in local differences in the metal budget in the related hydrothermal sulfide minerals, which are poorly constrained. The Niuatahi volcano in the western Pacific is such an example, where four different hot springs are discharging up to 334°C hot fluids with variable salt and metal contents. The trace element and isotope composition of hydrothermal sulfide minerals agree with the hot fluid composition and indicate that fluid boiling at the caldera center is a common process, alongside the influx of magmatic gases, which drastically enhances the metal budget of the mineralization. By contrast, metal transfer due to magmatic gas is not evident in the hot springs at the northern caldera wall, which is rather controlled by evolved seawater and fluid interaction with the surrounding rocks. The observed chemical variations show that Niuatahi caldera is host to a continuum from magmatic gas‐rich to host rock‐controlled hydrothermal systems, which ultimately results in seafloor mineralization that exhibit spatially selective trace element enrichments. Key Points Niuatahi rear‐arc caldera is host to a metallogenic continuum of magmatic volatile‐ to host rock‐dominated mineralization Variable proportions of magmatic volatile influx and fluid boiling result in spatially selective trace element enrichment (Te, Se, Bi) Fluid boiling and magmatic volatile input is recorded by distinct Te/As, Te/Au, and low δ34S values in hydrothermal sulfides and native S

A detailed Raman spectroscopic, electron microprobe, and laser ablation-induced coupled plasma-mass spectrometric study of 46 natural tourmalines [XY3Z6(T6O18)(BO3)3V3W] from 10 subgroups was performed to evaluate the potential of the Raman scattering, in particular of the OH bond stretching vibrations, for the identification of tourmaline species and site-occupancy analysis. The widespread chemical variety of the studied samples is reflected in the different spectral shapes. The positions and intensities of the observed vibrational modes can be used for tourmaline species identification. Taking into account the charge of the Y- and Z-site cations as well as the X-site occupancy, the Raman peaks generated by the bond stretching mode of the VOH groups were attributed to different YZZ-YZZ-YZZ cationic configurations, while the peaks originating from WOH stretching is due to chemically different YYY triplets next to an X-site vacancy, XNa, or XCa. It is shown that the integrated intensities of the VOH-stretching peaks can be used to calculate the contents of the major Y-site elements Mg, (Fe2++Mn2+), Li, and Al. The analysis of the VOH-peak positions yields information on the X-site occupancy. The fitted linear equations can be used to determine the content of X(Na+Ca) and X-site vacancy per formula unit. Guidelines for how to gain crystallochemical information from the Raman spectra of tourmaline are suggested. This study, along with Part 1 dedicated to amphiboles (Leissner et al. 2015), reveals that Raman spectroscopy is well suited as a non-destructive, preparation-free, and easy-to-handle method for species identification and site-occupancy analysis in complex hydrous silicate. Our results demonstrate that the chemistry on the non-tetrahedral positions substantially influences the Raman-active H-O bond stretching phonon modes, which allows for quantitative compositional analysis, including the content of lithium.

Glauconite is an authigenic clay mineral that is common in marine sedimentary successions. Dating of glauconite to determine the depositional age of sedimentary sequences has a long history but has fallen into disfavor due to the difficulty of obtaining “pure” glauconite separates. Recent advances in sedimentary petrography and reaction cell mass spectrometry permit rapid in situ Rb‐Sr dating of carefully screened glauconite grains. However, glauconite remains susceptible to burial alteration so that successful application of in situ Rb‐Sr glauconite geochronology requires improved, microscale constraints on the impact of postdepositional alteration on glauconite Rb‐Sr systematics and articulation of robust criteria for identifying grains suitable for geochronology. Here, we address these questions by combining SEM‐EDS mineral mapping, geochemical characterization, and in situ Rb‐Sr dating of glauconite grains in partially altered lower Cambrian sedimentary sequences from the Arrowie and Amadeus basins in Australia. Our approach provides information at high spatial resolution, representing new insights into the interplay between source material, burial fluids, and diagenetic processes. Among the different glauconite classes, which we classify based on alteration and inclusion type, only the primary apatite‐bearing “pristine” glauconite returns an age within the error of the expected stratigraphic age. We attribute the preservation of a depositional Rb‐Sr age to the influence of Sr‐rich, alteration‐resistant apatite and the limited permeability of the clay‐rich strata hosting these grains. We conclude that our combined petrographic–geochemical screening approach holds considerable potential for identifying the best preserved glauconite grains for in situ Rb‐Sr geochronology. Key Points New technology permits in situ Rb‐Sr dating of carefully screened glauconite grains Apatite resists Sr exchange, and apatite‐bearing glauconite preserves primary Rb‐Sr age Young and old ages are due to Sr exchange with burial fluids and uptake of radiogenic Sr in secondary carbonate inclusions, respectively

We characterized the chemical composition and microstructure of six ultramafic cumulates from the Kaupulehu lava flow, Hualālai (Hawai'i Island), to decipher their origin. The samples are mostly wehrlites with poikilitic textures. The chemical compositions obtained from electron probe microanalyses and laser ablation inductively coupled plasma mass spectrometry confirm the magmatic origin of pyroxenes. Olivines display homogeneous compositions in major, minor and trace elements. Their Fo# (81–88) are typical of magmatic compositions, but first row transition element concentrations are intermediate between mantle and magmatic olivine compositions. Rare Earth element (REE) patterns are similar to those of mantle olivine, but Kaupulehu olivines are more enriched in heavy REE than mantle specimens. Results from Fourier transform infrared spectroscopy showed that nominally anhydrous minerals are very poor in hydrogen: 1.3–2.2 ppm H2O by weight in olivine, 6.4 in orthopyroxene, and 12.6–48.2 in clinopyroxene. Nevertheless, fluid inclusions and bubbles evidenced by scanning electron microscopy demonstrate the presence of volatiles, which are expected to exsolve during degassing. Despite the undeniable magmatic imprint in these ultra‐mafic cumulates, electron backscatter diffraction maps evidence subgrain boundaries in olivine, important internal misorientation (>10°), and Crystallographic preferred orientation (CPO) (axial [010], orthorhombic and transitional toward axial‐[001]), not associated with shape preferred orientation or euhedral olivine shape. All these features are evidence of high temperature dislocation creep within the asthenospheric mantle, prior to melt percolation and chemical resetting, well before their mobilization by the volcanic eruption. We conclude that olivines are mantle‐inherited, whereas clinopyroxenes result from crystallization of percolating melt.