Boron isotope composition of geothermal fluids and borate minerals from salar deposits (central Andes/NW Argentina)

We have measured the boron concentration and isotope composition of regionally expansive borate deposits and geothermal fluids from the Cenozoic geothermal system of the Argentine Puna Plateau in the central Andes. The borate minerals borax, colemanite, hydroboracite, inderite, inyoite, kernite, teruggite, tincalconite, and ulexite span a wide range of d 11B values from 229.5 to 20.3‰, whereas fluids cover a range from 218.3 to 0.7‰. The data from recent coexisting borate minerals and fluids allow for the calculation of the isotope composition of the ancient mineralizing fluids and thus for the constraint of the isotope composition of the source rocks sampled by the fluids. The boron isotope composition of ancient mineralizing fluids appears uniform throughout the section of precipitates at a given locality and similar to values obtained from recent thermal fluids. These findings support models that suggest uniform and stable climatic, magmatic, and tectonicconditions during the past 8 million years in this part of the central Andes. Boron in fluids is derived from different sources, depending on the drainage system and local country rocks. One significant boron source is the Paleozoic basement, which has a whole-rock isotopic composition of d 11B ¼ 28.9 ^ 2.2‰ (1 SD); another important boron contribution comes from Neogene-Pleistocene ignimbrites (d 11B ¼ 23.8 ^ 2.8‰, 1 SD). Cenozoic andesites and Mesozoic limestones (d 11B # þ 8‰) provide a potential third boron source.Fil: Kasemann, Simone A.. German Research Centre for Geosciences; AlemaniaFil: Meixner, Anette. German Research Centre for Geosciences; AlemaniaFil: Erzinger, Jörg. German Research Centre for Geosciences; AlemaniaFil: Viramonte, Jose German. Universidad Nacional de Salta; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Alonso, Ricardo Narciso. Universidad Nacional de Salta; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Franz, Gerhard. Technishe Universitat Berlin; Alemani

Geochemistry and paleogeographic implications of Permo-Triassic metasedimentary cover from the Tauern Window (Eastern Alps)

The chemical composition of metasediments is a valuable source of paleogeographic information about the protolith's sedimentary environment. Here, we compile major- and trace-element whole-rock data, including B contents, and 10/11 B-isotope ratios from the Permo-Triassic metasedimentary cover of the Pfitsch–Mörchner basin, overlying the Variscan basement in the western Tauern Window, Eastern Alps (Austria and Italy). The basement consists of orthogneiss (“Zentralgneis”, metamorphosed Variscan granitoids with intrusion ages between 305 and 280 Ma), and the roof pendant consists of granites (amphibolites, paragneiss, and minor serpentinites). The Zentralgneis is partly hydrothermally altered into pyrite quartzite with high Al–S contents, low Na–Sr–Ca–Mg contents, and very strong depletion of the light rare earth elements. Comparison with published detailed mapping of this and other time-equivalent basins in the western Tauern Window, with radiometric age data in the literature, and with unmetamorphosed basins in the South Alpine realm yields a late Permian to Early Triassic age of sedimentation. Although during Alpine metamorphism all rocks were strongly deformed, the whole-rock chemical compositions of the metasediments were not pervasively changed during deformation. We show that the sediments were deposited in a small, probably lacustrine–fluviatile, intramontane basin, under arid to semi-arid climatic conditions. The sequence starts with metaconglomerates, which can be interpreted as a mixture of the different basement rocks, based on a combination of major-element ratios Na2O /  (Na2O + K2O) and MgO / (MgO + Fe2O3) with concentrations of trace elements Cr, V, and Ni. The sequence is overlain by a fining-upwards sequence of clastic sediments, in which the behavior of K, Rb, and Sr allows the reconstruction of intense diagenetic K–B metasomatism, which raised the K2O contents up to ∼ 10 wt %. The average B content of 218 µg g−1 is well above the B content of common sediments, and the B-isotope composition reaches extremely low values of down to −33 ‰ δ11B. The top of the sequence is a lazulite quartzite, interpreted as a former conglomeratic phosphatic sandstone, which marks the transition from a closed Permian basin to an open Triassic basin. Within the clastic sequence, the presence of hydrothermal tourmalinite veins documents a hydrothermal event after deposition but before the onset of Alpine metamorphism. A metamorphosed mafic dike swarm in the orthogneiss indicates a post-Variscan event of basaltic magmatism, and this event is tentatively correlated with increased heat flow in the Triassic basin and hydrothermal activity. A consistent conceptual model of this basin and its diagenetic modifications, based on a combination of geochemical data with petrographical and field information, provides the geodynamic context of the European margin at the onset of the Alpine orogeny.DFG, 414044773, Open Access Publizieren 2021 - 2022 / Technische Universität Berli

Iron isotope signals: Use and limitations in natural marine sediments

Oral presentatio

Tourmaline Reference Materials for the In Situ Analysis of Oxygen and Lithium Isotope Ratio Compositions

Three tourmaline reference materials sourced from the Harvard Mineralogical and Geological Museum (schorl 112566, dravite 108796 and elbaite 98144), which are already widely used for the calibration of in situ boron isotope measurements, are characterised here for their oxygen and lithium isotope compositions. Homogeneity tests by secondary ion mass spectrometry (SIMS) showed that at sub‐nanogram test portion masses their 18O/16O and 7Li/6Li isotope ratios are constant within ± 0.27‰ and ± 2.2‰ (1s), respectively. The lithium mass fractions of the three materials vary over three orders of magnitude. SIMS homogeneity tests showed variations in 7Li/28Si between 8% and 14% (1s), which provides a measure of the heterogeneity of the Li contents in these three materials. Here we provide recommended values for δ18O, Δ’17O and δ7Li for the three Harvard tourmaline reference materials based on results from bulk mineral analyses from multiple, independent laboratories using laser‐ and stepwise fluorination gas mass spectrometry (for O), and solution multi‐collector inductively coupled plasma‐mass spectroscopy (for Li). These bulk data also allow us to assess the degree of inter‐laboratory data that might be present in such datasets. This work also re‐evaluates the major element chemical composition of the materials by electron probe microanalysis and investigates the presence of a chemical matrix effect on SIMS instrumental mass fractionation with regards to δ18O determinations, which was found to be < 1.6‰ between these three materials. The final table presented here provides a summary of the isotope ratio values that we have determined for these three materials. Depending on their starting mass either 128 or 256 splits have been produced of each material, assuring their availability for many years into the future

Isotopic evidence (⁸⁷Sr/⁸⁶Sr, δ⁷Li) for alteration of the oceanic crust at deep-rooted mud volcanoes in the Gulf of Cadiz, NE Atlantic Ocean [(Sr-87/Sr-86, delta Li-7) ]

The chemical and isotopic composition of pore fluids is presented for five deep-rooted mud volcanoes aligned on a transect across the Gulf of Cadiz continental margin at water depths between 350 and 3860 m. Generally decreasing interstitial Li concentrations and Sr-87/Sr-86 ratios with increasing distance from shore are attributed to systematically changing fluid sources across the continental margin. Although highest Li concentrations at the near-shore mud volcanoes coincide with high salinities derived from dissolution of halite and late-stage evaporites, clayey, terrigenous sediments are identified as the ultimate Li source to all pore fluids investigated. Light delta Li-7 values, partly close to those of hydrothermal vent fluids (delta Li-7: +11.9 parts per thousand), indicate that Li has been mobilized during high-temperature fluid/sediment or fluid/rock interactions in the deep sub-surface. Intense leaching of terrigenous clay has led to radiogenic Sr-87/Sr-86 ratios (similar to 0.7106) in pore fluids of the near-shore mud volcanoes. In contrast, non-radiogenic Sr-87/Sr-86 ratios (similar to 0.7075) at the distal locations are attributed to admixing of a basement-derived fluid component, carrying an isotopic signature from interaction with the basaltic crust. This inference is substantiated by temperature constraints from Li isotope equilibrium calculations suggesting exchange processes at particularly high temperatures (&gt;200 degrees C) for the least radiogenic pore fluids of the most distal location.Advective pore fluids in the off-shore reaches of the Gulf of Cadiz are influenced by successive exchange processes with both oceanic crust and terrigenous, fine-grained sediments, resulting in a chemical and isotopic signature similar to that of fluids in near-shore ridge flank hydrothermal systems. This suggests that deep-rooted mud volcanoes in the Gulf of Cadiz represent a fluid pathway intermediate between mid-ocean ridge hydrothermal vent and shallow, marginal cold seep. Due to the thicker sediment coverage and slower fluid advection rates, the overall geochemical signature is shifted towards the sediment-diagenetic signal compared to ridge flank hydrothermal environments. (C) 2009 Elsevier Ltd. All rights reserved

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 Association of Geoanalysts (IAG). The reference values were derived from the results of 16 independent techniques, including definitive (isotope dilution) and comparative bulk (e.g., INAA, ICPMS, SSMS) and microanalytical (e.g., LA-ICPMS, SIMS, EPMA) methods. Agreement between two or more independent methods and the use of definitive methods provided traceability to the fullest extent possible. We also present new and recently published data for the isotopic compositions of H, B, Li, O, Ca, Sr, Nd, Hf, and Pb. The results were mainly obtained by high-precision bulk techniques, such as TIMS and MC-ICPMS. In addition, LA-ICPMS and SIMS isotope data of B, Li, and Pb are presented

Lithium and Sr isotopic composition of salar deposits in the Central Andes across space and time: the Salar de Pozuelos, Argentina

The Central Andes of South America host the largest known lithium resources in a confined area, but the primary lithium sources of the salar deposits and the mobilisation process of lithium are still a matter of speculation. Chemical weathering at or near the surface and leaching in hydrothermal systems of the active magmatic arc are considered the two main mechanisms of Li extraction from the source rock. The lithium and strontium isotope composition of typical salar deposits offer insights into the processes on how Li brine deposits in Andean evaporites are formed. Data from the Salar de Pozuelos indicate near-surface chemical weathering in a cold and dry climate as the dominant mobilisation process of Li, with evaporation being responsible for the enrichment. The Cenozoic ignimbrites are the favoured source rock for the Li, with subordinate additions from the Palaeozoic basement. The identification of the source rocks is supported by radiogenic Nd and Pb and stable B isotope data from salar deposits. A comparison with other Li brine and salt deposits in the Altiplano-Puna Plateau and its western foothills places the Salar de Pozuelos as an endmember of Li solubilisation by chemical weathering with only minor hydrothermal mobilisation of Li.Universität Bremen (1013

Multiple batch experiments toto investigate Li and B partitioning and isotope fractionation between rock and water during serpentinization

Multiple batch experiments (100 °C, 200 °C; 40 MPa) were conducted, using Dickson-type reactors, to investigate Li and B partitioning and isotope fractionation between rock and water during serpentinization. We reacted fresh olivine (5 g; Fo90; [B] = <0.02 µg/g; d11BOlivine -14 per mil; [Li] = 1.7 µg/g; d7LiOlivine = +5.3 per mil) with seawater-like fluids (75 ml, 3.2 wt.% NaCl) adjusted with respect to their Li (0.2, 0.5 µg/ml; and d7LiFluid +55 per mil) and B (~10 µg/ml and d11BFluid -0.3 per mil) characteristics. At 200 °C a reaction turnover of about 70% and a serpentinization mineral assemblage matching equilibrium thermodynamic computational results (EQ3/6) developed after 224 days runtime. Characterization of concomitant fluid samples indicated a distinct B incorporation into solid phases ([B]final_200 °C = 55.61 µg/g; DS/FB200 °C = 13.42) and a preferential uptake of the lighter 10B isotope (Delta11BS-F = -3.46 per mil). Despite a low reaction turnover at 100 °C (<12%), considerable amounts of B were again incorporated into solid phases ([B]final_100 °C = 25.33 µg/g; DS/FB100 °C = 24.2) with even a larger isotope fractionation factor (Delta11BS-F = -9.97? per mil. While magnitude of isotope fraction appears anti-correlated with temperature, we argue for an overall attenuation of the isotopic effect through changes in B speciation in saline solutions (NaB(OH)4(aq) and B(OH)3Cl-) as well as variable B fixation and fractionation for different serpentinization product minerals (brucite, chrysotile). Breakdown of the Li-rich olivine and limited Li incorporation into product mineral phases resulted in an overall lower Li content of the final solid phase assemblage at 200 °C ([Li]final_200 °C = 0.77 µg/g; DS/FLi200 °C = 1.58). First order changes in Li isotopic compositions were defined by mixing of two isotopically distinct sources i.e. the fresh olivine and the fluid rather than by equilibrium isotope fraction. At 200 °C primary olivine is dissolved, releasing its Li budget into the fluid which shifts towards a lower d7LiF of +38.62 per mil. Newly formed serpentine minerals (d7LiS = +30.58 per mil) incorporate fluid derived Li with a minor preference of the 6Li isotope. At 100 °C Li enrichment of secondary phases exceeded Li release by olivine breakdown ([Li]final_100 °C = 2.10 µg/g; DS/FLi100 °C = 11.3) and it was accompanied by preferential incorporation of heavier 7Li isotope that might be due to incorporation of a 7Li enriched fluid fraction into chrysotile nanotubes

Lithium and Sr isotopic composition of salar deposits in the Central Andes across space and time: the Salar de Pozuelos, Argentina

&lt;jats:title&gt;Abstract&lt;/jats:title&gt;&lt;jats:p&gt;The Central Andes of South America host the largest known lithium resources in a confined area, but the primary lithium sources of the salar deposits and the mobilisation process of lithium are still a matter of speculation. Chemical weathering at or near the surface and leaching in hydrothermal systems of the active magmatic arc are considered the two main mechanisms of Li extraction from the source rock. The lithium and strontium isotope composition of typical salar deposits offer insights into the processes on how Li brine deposits in Andean evaporites are formed. Data from the Salar de Pozuelos indicate near-surface chemical weathering in a cold and dry climate as the dominant mobilisation process of Li, with evaporation being responsible for the enrichment. The Cenozoic ignimbrites are the favoured source rock for the Li, with subordinate additions from the Palaeozoic basement. The identification of the source rocks is supported by radiogenic Nd and Pb and stable B isotope data from salar deposits. A comparison with other Li brine and salt deposits in the Altiplano-Puna Plateau and its western foothills places the Salar de Pozuelos as an endmember of Li solubilisation by chemical weathering with only minor hydrothermal mobilisation of Li.&lt;/jats:p&gt