Sr Isotopic Signatures Research Articles

Strontium Isotope Composition of Triassic Coastal and Shallow Marine Carbonates in the Western Balkanides, NW Bulgaria

Whole-rock samples of Triassic coastal and shallow marine carbonates were analyzed for their Sr isotope signatures and trace element concentrations were measured in order to assess the possible impact of diagenetic alteration. The 87Sr/86Sr ratios of Anisian to lower Carnian calcite micrites reproduce the global Triassic seawater variations fairly well. The recorded higher values can be explained by an influence from detrital aluminosilicate phases and a minor postdepositional alteration. The samples of tidal-flat dolomicrites from the base of the Anisian show no significant diagenetic overprint but have considerably more radiogenic 87Sr/86Sr signatures compared to the global Sr isotope curve that corresponds to the Triassic (Mesozoic) maximum. These anomalously high values may have resulted from some interaction between the dolomitizing brines and the underlying fluvial siliciclastics (Buntsandstein facies), but more likely from the high 87Sr/86Sr river waters discharged from a silicate-dominated drainage basin to the coastal area at the beginning of the Middle Triassic. This study demonstrates that bulk micrite can be used as a proxy for seawater 87Sr/86Sr after proper sample selection and diagenetic screening. It also suggests that the 87Sr/86Sr ratios of ancient carbonates precipitated in coastal settings should be interpreted with caution, considering the possible influence of continentally-derived fluids.

Provenance of mineral dust deposited on Antarctica over the last sixty years by strontium isotopic analysis of snow from Dome C

The strontium (Sr) concentration and 87Sr/86Sr isotope ratio have been determined in 132 snow pit samples collected at Dome C, on the East Antarctic Plateau, corresponding to the period 1958–2019, and in 12 surface snow samples collected at the same site in 2016–2017. The average Sr concentration was 8.1 ± 5.7 pg g−1 (mean ± SD) in snow pit samples and 10.1 ± 8.0 pg g−1 (mean ± SD) in surface snow, without any significant temporal trend. The 87Sr/86Sr isotope ratio showed small variations (<0.15%), with an average 87Sr/86Sr value of 0.7094 ± 0.0010 (mean ± SD) in snow pit and 0.7103 ± 0.0004 (mean ± SD) in surface snow samples. These results seem to suggest that no change in the source(s) of mineral dust has occurred throughout the period investigated.Comparison of the 87Sr/86Sr isotope ratio of the snow samples with those of potential source areas suggests that the mineral dust reaching the East Antarctic plateau over the last decades is of a mixed origin, with a contribution from Patagonia and one or more other source(s) having a more radiogenic Sr isotopic signature, with a major fraction coming from South Australia.

Geochemical fingerprinting of Norway spruce from the Eastern Carpathians: Sr isotopic and multi-elemental signatures

Ensuring efficient wood traceability within procurement chains is essential for establishing sustainable forest management and minimizing environmental damage in countries that produce and export timber. While some progress has been made with key legislative reforms to tackle this issue, the effectiveness of law enforcement still relies on the availability of appropriate analytical tools to determine the provenance of wood. This study documents the Sr isotopic and multi-elemental signatures of Norway spruce trees in the Eastern Carpathians, Romania – an area known for intensive forest logging. The research focused on trees from Rodna, Rarău, and Călimani, analyzing tree rings from 1970 to 2020 to assess temporal variability and develop site-specific geochemical fingerprints. In conjunction with tree samples, corresponding soil, groundwater, and river samples were analyzed, providing a comprehensive view of the bioavailable 87Sr/86Sr ratios in these ecosystems. The study found a strong correlation between the Sr isotope ratios in the wood and those in corresponding water and soil samples, confirming that the wood accurately mirrors local geochemical signatures. The Sr isotope ratios were consistent across most of the cores from trees within the same site but varied among sites within the same region. Principal Component Analysis of the Sr isotopic and multi-elemental data highlighted closer clustering of samples from the Călimani area, though distinguishing the samples from the Rodna and Rarău regions proved more difficult due to overlapping data points. This study broadens our understanding of geochemical variability and its implications. The insights gained provide a valuable foundation for future research aimed at enhancing wood traceability methods.

Evaluating Source Complexity in Blended Milk Cheese: Integrated Strontium Isotope and Multi-Elemental Approach to PDO Graviera Naxos.

Graviera Naxos, a renowned cheese with Protected Designation of Origin status, is crafted from a blend of cow, goat, and sheep milk. This study focused on assessing the Sr isotopic and multi-elemental composition of both the processed cheese and its ingredients, as well as the environmental context of Naxos Island, including samples of milk, water, soil, and feed. The objective was to delineate the geochemical signature of Graviera Naxos cheese and to explore the utility of Sr isotopes as indicators of geographic origin. The 87Sr/86Sr values for Graviera Naxos samples ranged from 0.70891 to 0.70952, indicating a relatively narrow range. However, the Sr isotopic signature of milk, heavily influenced by the feed, which originates from geologically distinct areas, does not always accurately reflect the local breeding environment. Multi-elemental analysis revealed variations in milk composition based on type and season; yet, no notable differences were found between raw and pasteurized milk. A mixing model evaluating the contributions of milk, sea salt, and rennet to the cheese's Sr isotopic signature suggested a significant average contribution of 73.1% from sea salt. This study highlights the complexities of linking dairy products with their geographical origins and emphasizes the need for sophisticated geochemical authentication methods.

Provenance of clay-sized detrital sediments in the North Sea and the Skagerrak region based on radiogenic Nd-Sr-Hf isotopes and clay mineral compositions: assessing the impact of coastal and seabed erosion

The Skagerrak basin represents the main sink area for fine-grained sediment in the North Sea region and constitutes a natural deposition center for sediments that are supplied from the Atlantic, the Baltic Sea and the surrounding continental margins and coasts. However, the exact sources and their proportional contributions to the North Sea sediments and to the Skagerrak deposits are not well understood. To trace the predominant sources of the sediment and to gain a better understanding of the sedimentary processes in the North Sea and the Skagerrak basin, radiogenic Sr, Nd, and Hf isotope signatures and clay mineral compositions of the detrital clay fraction of surface sediment samples from the North Sea, the Scandinavian margins and the Baltic Sea were measured. The results indicate that the major source for Skagerrak clay-size sediments is the northern North Sea but Scandinavia as well as the southern North Sea including the southern England coast also contribute material. Seabed and coastal erosion in the northern North Sea are enhanced by the inflowing Atlantic Currents, which provide the Skagerrak with high amounts of clay size sediments. In contrast, the southern North Sea, the Baltic Sea and mid-European rivers such as Weser, Elbe and Ems are only minor contributors. As Skagerrak deposits are dominated by clay sized material (up to 60%), the reconstructed sediment processes in this study deviate from findings in previous sediment budget studies, which were based on both clay and silt fraction and indicated predominant influences from the southern North Sea. These results highlight that coastal and seabed erosion in the North Sea is a previously underestimated source of fine-grained sediments for depocenters in the entire North Sea. With regard to climate change, the global sea-level rise will likely enhance erosional processes and can therefore significantly influence the sediment budget of the entire North Sea.

Migratory Ecology of Pseudoplatystoma fasciatum in the Amazon Basin Revealed by Otolith Microchemistry

Fish migrate for varied reasons, including to avoid predators and to access feeding, spawning, and nursery habitats, behaviors that enhance their survival and reproductive rates. However, the migratory ecology of many important fishes, especially those in river–floodplain ecosystems, remains poorly understood. One fish of the Amazon Basin whose migratory behavior is poorly understood is the catfish Pseudoplatystoma fasciatum. Here, we used otolith elemental microchemistry to characterize the migration ecology of P. fasciatum in the Amazon Basin. The main research questions of this study were: (1) does P. fasciatum move between waters with different Sr isotopic signatures (87Sr/86Sr) and chemical compositions? (2) What distance do they migrate? (3) Is the migration of P. fasciatum related to age? And (4) does P. fasciatum migrate mainly upstream, downstream, or in both directions? We assessed whether P. fasciatum migrates between waters with different 87Sr/86Sr values, comparing the Sr isotopic signature of otolith transects of each individual with the range of Sr isotopic signatures within the respective rivers. We found that 34% of the 71 fish analyzed migrated between rivers with different Sr isotopic signatures and 66% did not. The mean migration distance migrated was 126 km, with most specimens migrating between 72 and 237 km. Apparently, no fish of age one or age six or older migrated. All fish that migrated were between two and five years of age, with 20% of the specimens that migrated being two years old, 40% three years old, 30% four years old, and 20% five years old. Sixty-six percent of all individuals that migrated between rivers with different Sr signatures did so bidirectionally, while 33% moved unidirectionally. According to our definition of homing behavior in which fish migrated back to the same river where they were born, 41% of all fish that migrated displayed apparent homing behavior. Our findings provide insights into the migratory ecology of P. fasciatum, corroborating and refining knowledge reported in the literature. Our results on the migratory ecology of P. fasciatum have implications for sustainable fisheries conservation and management: conserving P. fasciatum requires habitat maintenance and suitable fishing practices in spawning and nursery habitats, and managers must consider large geographic areas for effective fishery management and conservation.

Geochemistry and sources of boron and strontium of geothermal waters from the Pearl River Delta region, South China: Implications for water-rock interactions

Pearl River Delta (PRD) region of South China is abundant of geothermal water resources. However, the development and utilization level of geothermal resources in this region is relatively low, due in part to the lack of fundamental geochemical research. To access water-rock interaction processes of the PRD geothermal system, we analyzed the geochemistry of geothermal waters by combining trace elements (B, Sr, and Br) and isotopes (δ11B and 87Sr/86Sr) with conventional tracers (major elements) that had been reported. The Cl/Br ratios (from 31 to 639) confirm the multi-source salinity of marine origin, precipitation, and a minor dissolution of halite. Major ions chemistry highlights the influence of ions exchange, the dissolution of carbonate, silicate, and sulphate minerals as well as the contribution of seawater. The Cl/B ratios (61 to 22,583) suggest interactions with carbonate rock and felsic rock, input of seawater, and groundwater mixing. Boron isotopic compositions (δ11B) range between −9.22 and +39.78 ‰. Sr contents and 87Sr/86Sr ratios are more homogeneous, falling between 0.06 and 32.26 mg/L and between 0.71239 and 0.72121, respectively. The B and Sr isotopic signatures show that three processes contribute to geochemistry of geothermal waters: 1) water/rock interaction involving marine carbonate rock, evaporite, and granitoid or/and gneiss, 2) seawater intrusion, and 3) shallow groundwater mixing. Major-trace element chemistry and these isotope systematics on their own indicates essential information on the aspects of fluid origin or water-rock interaction processes, and however provide a more comprehensive understanding of the geothermal system in the PRD region, South China.

Origin of rare earth elements in acid mine drainage traced by strontium and neodymium isotopes

Acid mine drainage (AMD) generated from coal and sulfide mining has attracted much interest due to the high concentrations of rare earth elements (REE) observed. However, the origin of REE in AMD and particularly the mechanism of enrichment in medium REE remain uncertain. The combined study of Sr and Nd isotopes can be used to trace the processes that control the mobility and fractionation of REE in aquatic systems such as AMD. This work reports for the first time worldwide isotopic data of Sr and Nd in AMDs from sulfide mining (Iberian Pyrite Belt, SW Spain) and compare with those in host rocks. Additionally, leaching experiments have been carried out to simulate the water–rock interactions found in these acidic systems. The results obtained strongly suggest that the origin of REE in AMDs from metal mining may be related to the preferential dissolution of shales and felsic rocks. The suitability of Sr and Nd isotopic signatures to trace the REE source in AMD-affected systems has been proven, it provides a new environmental and geochemical prospecting tool which could be useful in different geological water–rock interaction systems.

Trace Element Partitioning Between Saline Aqueous Fluids and Subducted Metasediments, and the Origin of the “Sediment Fingerprint” in Arc Magmas

AbstractIsotopic and elemental signatures in arc magmas bear similarities to marine sediments from the forearc. Partial melts of subducted sediments were previously invoked as the predominant carrier of material between the slab and mantle wedge, whereas aqueous fluids were deemed too inefficient at mobilizing trace elements to account for arc magma compositions. However, trace element solubility in aqueous fluids may be significantly affected by the formation of chloride complexes. We introduced NaCl into the sediment‐H2O system, and re‐investigated trace element partitioning between aqueous fluids and metasediments in a series of piston cylinder experiments at 2.5–4.5 GPa and 600–700°C. The diamond trap method was employed to separate the fluids, which were analyzed in the frozen state. Trace element compositions of fluids and all solid phases were obtained by LA‐ICP‐MS. We combined our data with published literature to demonstrate that saline fluids and sediment melts have a comparable efficiency in extracting incompatible elements from subducted sediments, producing similar element fractionation during mobile phase expulsion. Accessory phases such as allanite may only be stable in particularly Rare Earth Elements‐enriched lithologies. The Sr, Pb and Nd isotopic signatures of arc magma suggest that the mantle wedge is infiltrated by mobile phases derived from both the sediment and basalt sections of the subducted oceanic crust. Up to several percent of either sediment‐derived saline fluid or melt can account for the isotopic and elemental compositions of most arc magma. Geochemical similarities between arc magma and forearc sediments are not necessarily evidence of slab melting.

Diagenetic effects on strontium isotopes in shallow-water carbonate sediments from Middle Miocene to Recent

Seawater 87Sr/86Sr ratios have been used as a proxy for continental weathering flux and the partial pressure of atmospheric CO2 (pCO2) in Earth's past, but the fidelity of 87Sr/86Sr records in marine carbonates under diagenesis remains controversial. To investigate this issue, we undertook an integrated chemostratigraphic study of 87Sr/86Sr, δ13C, and δ18O in bulk carbonate from three cores of the South China Sea region: lithified bulk carbonate of Late Miocene to Holocene age in the 607-m-long Xike-1 core (0–11,942 kyr B.P.) from the Paracel (Chinese: Xisha) Islands, and unlithified carbonate sediment in two shallow (<5-m deep) pushcores from the Spratly (Chinese: Nansha) Islands, Jiuzhang A (0–680 yr B.P.) and Jiuzhang B (0–350 yr B.P.). The carbonate sediment of the Jiuzhang cores yielded 87Sr/86Sr signatures matching those of modern seawater, confirming that carbonate sediments can be faithful archives of contemporaneous oceanic Sr-isotopic compositions. Four diagenetic zones were identified in the Xike-1 core based on δ13C and δ18O patterns: meteoric (Unit I, 0–161 m), mixed-diagenetic (Unit II, 161–215 m), and marine diagenetic zones (Unit III, 215–577 m), along with a second meteoric zone (Unit IV, 577–607 m). The bulk‑carbonate 87Sr/86Sr profile was not strongly altered by dolomitization or other processes in any of the diagenetic zones (although minor effects were observed in the marine zone). This study concludes that marine carbonates are likely to retain primary seawater Sr isotopic signatures even after undergoing multiple stages of diagenesis. This study provides detailed 87Sr/86Sr secular variations and continental weathering history since 12 Ma.

The role of post-mortem alteration in tooth enamel revisited: A combined strontium isotope and geochemical evaluation

Assessing post-mortem alteration of tooth enamel in archaeological burial sites of interest is critical and required in order to accurately interpret the isotope composition of bioavailable Sr for use in determining migration patterns of populations in ancient civilizations. Several statistical approaches have been established to evaluate the degree of post-mortem alteration within tooth enamel, and these are based on the incorporation of trace elements (Mn, V, Fe, REEs, Th, U) typically present within the burial environment. In this study, both new and previously reported chemical data and radiogenic Sr isotope ratios for both modern-day and archaeological tooth enamel samples are presented, which range from pristine to altered in nature. Significant correlations between elevated abundances of mobile elements (V, Fe, Nd, U) and their corresponding Sr isotope signatures are limited and are most prevalent when the latter are compared to their Fe contents. Tooth enamel samples affected by diagenesis based on their outlier chemical composition do not necessarily record perturbed Sr isotope signatures, and therefore should not be precluded precipitously from provenance studies.

Reference Sections, Fossil Ichthyofauna and Sr Isotope Signature of the Lower Frasnian Sediments of the Latvian Saddle and Orsha Depression, Belarus

Reference Sections, Fossil Ichthyofauna and Sr Isotope Signature of the Lower Frasnian Sediments of the Latvian Saddle and Orsha Depression, Belarus

Reference Sections, Fossil Ichthyofauna and Sr Isotope Signature of the Lower Frasnian Sediments of the Latvian Saddle and Orsha Depression, Belarus

The article provides a lithological description of the sections of the Lower Frasnian Stage of the Upper Devonian: the Zhelon Regional Stage and the Saria Beds of the Sargaevo Regional Stage, exposing in the basin of the Saryanka river, the Latvian Saddle. The complete lithological description of the Sargaevo and Semiluki sediments of the Frasnian Stage in the Gralevo quarry of the Vitebsk region, Orsha Depression has been presented. Macro- and micro-dimensional remains of heterostracans, placoderms, acanthodians, sarcopterygians, actinopterygians, as well as scolecodonts and conodonts have been found in the Lower Frasnian sediments; their photographic images are presented. For the first time, the Sr isotope composition was measured in the remains of ichthyofauna from the Zhelon and Sargaevo sediments of Belarus. On the basis of palaeoichthyological and taphonomic data, lithology and Sr isotope composition of ichthyofauna fragments, depositional environments in the Zhelon and Saria times were clarified, and the distant sections were correlated. The 87Sr/86Sr values in ichthyofauna samples from the Saria Beds in sections of the Latvian Saddle (sections of Kalyuty 5a and 6, Virenka 1) and the Orsha Depression (Gralevo quarry) lie within similar ranges: 0.70825–0.70842 and 0.70837–0.70856, respectively. The 87Sr/86Sr values in the ichthyofauna from the Zhelon sediments in the Kalyuty 2 and Obukhovo 1 sections (Latvian Saddle) vary within 0.70898–0.70932 and 0.71065–0.71102, respectively. High 87Sr/86Sr values in the fossil ichthyofauna of both regional stages suggest that the Early Frasnian palaeobassin was significantly desalinated, and the salinity in the Saria palaeobassin was comparable to the salinity of the modern Baltic Sea.

Contrasting appinites, vaugnerites and related granitoids from the NW Iberian Massif: insight into mantle and crustal sources

Abstract. Post-collisional Mg–K-rich mafic rocks with associated granitoids appear regularly in most orogens. They are relevant to evaluate the mantle role in the genesis of granitoids and thereby of the continental crust itself. The most characteristic Mg–K mafic rocks in the Variscan Iberian Massif are appinites and vaugnerites. Two examples with associated granitoids from NW Iberia have been compared to assess their mantle and crustal sources and the magmatic processes involved in their formation. Related granitoids are tonalites, granodiorites and monzonitic granites. Available whole-rock major and trace element compositions, as well as Sr and Nd isotopes, were used for this comparison, along with new Sr–Nd isotopic data. The appinite–granitoid association is calc–alkalic, whereas the vaugneritic one is calc–alkalic transitional to alkali–calcic. Vaugnerites are more enriched in Mg and K, compatible and incompatible trace elements and display more fractionated rare-earth element (REE) patterns than appinites. Associated granitoids provide similar differences. Appinites and vaugnerites have Sr and Nd crustal isotopic signatures resulting from partial melting of a different subduction-type metasomatised mantle: amphibole spinel lherzolites for appinites and more refractory and deeper amphibole phlogopite ± garnet peridotites for vaugnerites. Further interaction of these basic melts with coeval granitoids occurred during their ascent and emplacement. The monzonitic granites derived from partial melting of metaigneous acid granulites, without discarding contribution of metasediments and/or an increasing role of biotite incongruent melting in those related to vaugnerites. An assimilation with fractional crystallisation process between appinite magmas and granulites could explain tonalites and granodiorites. This process was not confirmed for granodiorites related to vaugnerites.

Mineral chemistry and apatite Sr isotope signatures record overprinting mineralization in the Duobaoshan porphyry Cu deposit, Heilongjiang Province, NE China

Porphyry copper deposits can be deformed by subsequent magmatic-tectonic-metamorphic evolution, resulting in the remobilization of pre-existing ores and the consequent overprinting mineralization. This process might potentially increase the ore grade and/or resource. We focus on the Duobaoshan porphyry Cu (Mo) deposit, two periods were identified in this study, i.e., porphyry period (including Stage 1: potassic alteration; 2: propylitic alteration, and 3: chlorite-sericite alteration and porphyry mineralization) and overprinting period (including Stage 4–1: ductile–brittle deformation; Stage 4–2 and Stage 4–3: overprinting mineralization). Metal sulfide veins occur along the schist in Stage 4–2 and Stage 4–3, features that differ from the typical porphyry mineralization of Stage 3 (veinlets, stockworks, and dissemination). Here, we present in situ Sr isotope data for apatite and compositions of chlorite, epidote, and apatite to reveal the source and nature of fluids and mechanism of precipitation during overprinting mineralization. The in situ 87Sr/86Sr ratios of apatite from Stages 3, which range from 0.7030 to 0.7046, are slightly higher than those observed in the Ordovician granodiorite. Meanwhile, the Sr isotope ratios for apatite from Stages 4–2 and 4–3 are 07033–0.7040 and 0.7013–0.7045 respectively. These ratios broadly consistent with those of the surrounding Ordovician granodiorite and basaltic andesite, suggesting that the ore-forming fluids for all these stages originated from magmatic sources. Chlorite in Stage 4–2 has a higher Mn, Co, Ni, Zn content compared to chlorite in Stage 3, 4–3, whereas epidote and apatite in Stage 4–2 have higher Ca, Sr, Pb content compared to those in Stage 3, 4–3, implying that the fluids in Stage 4–2 underwent strongly water–rock reactions and extracted metal elements from surrounding rocks. Copper was only detected in Stage 4–3 chlorite (15.13–500.20 ppm) and epidote (7.91–19.29 ppm), indicating a high concentration of copper in the fluid, and due to the pre-existing magnetite dissolution, chlorite, epidote, and apatite in Stage 4–3 exhibit high V and Fe relative to other stages. Fluid mixing likely occurred during Stage 3, leading to the precipitation of copper. Strong water-reaction in Stage 4–2 produce changes in fluid natures that facilitate sulfide deposition during this stage. While in Stage 4–3, copper precipitation is controlled by a combination of rising pH and changing sulfur content and valence. Our study highlights that in the Duobaoshan deposit, late magmatic-hydrothermal fluids remobilized pre-existing ore bodies, and the copper precipitation mechanisms differed during the main copper mineralization events.

Characterisation of Conventional 87Sr/86Sr Isotope Ratios in Cement, Limestone and Slate Reference Materials Based on an Interlaboratory Comparison Study

An interlaboratory comparison (ILC) was organised to characterise 87Sr/86Sr isotope ratios in geological and industrial reference materials by applying the so‐called conventional method for determining 87Sr/86Sr isotope ratios. Four cements (VDZ 100a, VDZ 200a, VDZ 300a, IAG OPC‐1), one limestone (IAG CGL ML‐3) and one slate (IAG OU‐6) reference materials were selected, covering a wide range of naturally occurring Sr isotopic signatures. Thirteen laboratories received aliquots of these six reference materials together with a detailed technical protocol. The consensus values for the six reference materials and their associated measurement uncertainties were obtained by applying a Gaussian, linear mixed effects model fitted to all the measurement results. By combining the consensus values and their uncertainties with an uncertainty contribution for potential heterogeneity, reference values ranging from 0.708134 mol mol‐1 to 0.729778 mol mol‐1 were obtained with relative expanded uncertainties of ≤ 0.007 %. This study represents an ILC on conventional 87Sr/86Sr isotope ratios, within which metrological principles were considered and the compatibility of measurement results obtained by MC‐ICP‐MS and by MC‐TIMS is demonstrated. The materials characterised in this study can be used as reference materials for validation and quality control purposes and to estimate measurement uncertainties in conventional 87Sr/86Sr isotope ratio measurement.

The alkaline intraplate Pliocene-Quaternary lavas from the Middle Atlas Volcanic Field (Morocco): Petrology, mineralogy and geochemistry

The Middle Atlas Volcanic Field (MAVF) covers an area of 1500 km2, with a total erupted volume of solid products (DRE) estimated at more than 80 km3. In this study we present and discuss new petrological, mineralogical, and geochemical data of mafic rocks from the Timahdite and Lechmine N'kettane maars and of the Hebri, Habri (H1) and Boutagarouine scoria cones. For these volcanic areas we report the exclusive presence of alkaline and sodic undersaturated basaltic rocks (nephelinites, alkaline basalts and basanites). The studied lavas exhibit compositions typical of mantle-derived melts that underwent weak magmatic evolution processes (high Mg# = 56–68; Ni = 140–420 ppm; Cr = 150–500 ppm). Olivine and diopside are the main fractionation phases. Elemental data and Sr and Nd isotopes indicate a relatively homogeneous source region for the three lithotypes, which were generated in the presence of garnet as residual phase ([Tb/Yb]N = 2.4 to 3.0) through variable degrees of partial melting, decreasing from alkaline basalts to basanites and nephelinites. Magma genesis in equilibrium with garnet suggest that the sources were placed at depths in excess of 82 km, i.e., at asthenospheric depths in a region where the lithosphere has an estimated depth of about 77 km. The present-day Sr and Nd isotope signatures (87Sr/86Sr = 0.7031–0.7036; εNd = +2.5 to +5.5) of the lavas indicate a similarity with the Canary Islands lavas and, identically, the contribution of the HIMU and EM1 to the mantle sources. The sub-chondritic Ti/Eu ratios (down to 4471) and their negative correlation with Ca/Sr, Sr/Sm, Ga/Nb suggest carbonatitic metasomatism fingerprints, which is here considered the responsible for the introduction of amphibole in the lithosphere base. We propose that this carbonatite metasomatism was originated from the earliest low-degree melts, issued from the adiabatic decompression of the ascending mantle upwelling. This created low-solidus lithospheric domains which later interacted with the ascending silicate magmas. The fact that this mantle upwelling is rooted, like the Canary plume, in the same mantle anomaly at the top of the lower mantle explains the similar elemental and isotope characteristics between the studied MAFV lavas and those observed in Canary Islands.

Discrete magma injections drive the 2021 La Palma eruption

Understanding the drivers of the onset, evolution, and end of eruptions and their impact on eruption style is critical in eruption forecasting and emergency management. The composition of erupted liquids is a key piece of the volcano puzzle, but untangling subtle melt variations remains an analytical challenge. Here, we apply rapid, high-resolution matrix geochemical analysis on samples of known eruption date spanning the entire 2021 La Palma eruption. Sr isotope signatures reveal distinct pulses of basanite melt driving the onset, restart, and evolution of the eruption. Elemental variations in matrix and microcrysts track progressive invasion, and draining, of a subcrustal crystal mush. Associated variations in lava flow rate, vent development, seismicity, and SO 2 emission demonstrate that volcanic matrix resolves eruption patterns that could be expected in future basaltic eruptions globally.

Formation of molar tooth structures in low sulfate Precambrian oceans

Molar tooth structures (MTS) comprise calcite microspar-filled voids in fine-grained shallow-water carbonate, and were commonly formed in the Mesoproterozoic and early Neoproterozoic. However, the origin of MTS and links between the temporal distribution of MTS and contemporaneous seawater chemistry remains poorly understood. Here we report elemental and isotopic data for MTS and host rocks from the Mesoproterozoic Gaoyuzhuang Formation (∼1,600–1,550 Ma), North China Craton. The results reveal similar C, S and Sr isotope signatures between MTS and host rocks, which are close to the isotopic compositions of contemporaneous global seawater, suggesting an early diagenetic, seawater-buffered origin for MTS. A small sulfur isotopic fractionation between seawater sulfate and pyrite (Δ34SCAS-Py) of 4.1 ± 1.5‰ in host rocks is consistent with previously reported data, providing support for sub-millimolar sulfate concentrations in Mesoproterozoic seawater. Our observations suggest that the widespread occurrence of MTS through the Mesoproterozoic to early Neoproterozoic was broadly linked to sulfate scarcity in the ocean. We further propose that in Proterozoic oceans with sub-millimolar seawater sulfate concentrations, where aerobic and anaerobic methane oxidation was likely inhibited, methane produced via methanogenesis may have been more prone to accumulate in sediments, creating voids during escape. The absence of MTS across periods of higher sulfate concentrations during the Palaeoproterozoic and after the mid-Neoproterozoic, suggests that elevated sulfate concentrations promoted consumption of methane via anaerobic methane oxidation, thus preventing methane accumulation and the formation of sediment voids. Rapid lithification of the substrate as a result of elevated carbonate saturation may have also hindered the formation of MTS during these intervals. The link between MTS and changes in both oceanic sulfate levels and benthic methane fluxes gives a new perspective on temporal fluctuations in Earth’s redox state through time.

An integrated geochemical spatial and temporal survey of thermal springs to characterize the geothermal resource of a volcano (Piton des Neiges, Réunion Island)

Geothermal exploration can be challenging in the absence of obvious surface indicators of a high enthalpy geothermal resource such as geysers, fumaroles or thermal springs with temperatures near 100 °C. This is the case at the Piton des Neiges volcano (Réunion Island), which displays evidence of hydrothermal activity mostly as thermal springs with temperatures not exceeding 50 °C, affected by mixing and reequilibration, and emerging in a complex geological framework, resulting from the polygenic history of this dormant volcano. Yet, these thermal springs keep a partial record of the reservoir geochemistry. Here, we propose an exploration method to set this thermal signature apart from the contribution of other processes and trace back the equilibrium conditions, enabling us to locate thermal fluid circulations, and evaluate their temperature and availability. We report its application at Piton des Neiges volcano. We led an extensive geochemical survey which nearly doubled the number of thermal springs reported on the volcano and dramatically extended the existing geochemical database in space and time. In tandem, we also monitored δ18O and δD values in rainwaters and thermal springs over two years to compare their temporal variations.Our surveys show that the repartition of thermal springs is controlled by only one of the volcanic rift zones (the N30°E axis), which is thus identified as the heat source of hydrothermal circulations. This N30°E rift zone is also a preferential pathway for the degassing of mantellic CO2. In addition, the composition of thermal waters is influenced by syenite intrusions along the rim of the caldera, acting as drains for the uprise of hydrothermal waters. O, H and Sr isotopic signatures of springs show that the geothermal resource of Piton des Neiges is in fact made of two independent and unconnected hydrothermal systems on the northern and southern circular depressions of the volcano (the cirques of Salazie and Cilaos, respectively). Their recharge is meteoric, multi-year, and mostly achieved by cyclonic events. Thermal waters experience reequilibration during their ascent and various degrees of CO2 input or degassing. Last equilibrium temperatures of water/rock interaction, estimated by multicomponent geothermometry, reach up to 125 ± 6 °C in the cirque of Salazie, and up to 141 ± 15 °C in the cirque of Cilaos, with possibility for hotter waters before reequilibration. Taken together, our results suggest that the most promising target for future exploration is located in the cirque of Cilaos, along the caldera rim, and in proximity of syenite intrusions.With a thorough prospecting of thermal springs, a comprehensive geochemical study and a geochemical monitoring of the different water reservoirs, we improved our understanding of the geothermal resource and identified future exploration targets at Piton des Neiges volcano.A separation scheme for strontium and light rare earth elements and its application to the isotopic analysis of strontium and neodymium in silicate rocks are presented. This method benefits from the selectivity and high capacity of two newly introduced extraction Chromatographic materials, referred to as Sr.Spec and TRU.Spec, respectively. These afford a straightforward separation of Sr and Sm + Nd with high yield, good purity and satisfactory blank levels, on very small (0.25 ml) columns using small volumes of solutions of a single mineral acid, HNO3. The validity of the method is illustrated by the measurement of 87Sr/ 86Sr and 143Nd/144Nd ratios in twelve international standard reference materials.