Sr Isotopic Variations Research Articles

The Merensky-Bastard interval at Hackney, eastern Bushveld Complex: results of a combined Sr–Nd-isotopic investigation

The Merensky and Bastard reefs of the Bushveld Complex occur within what has been called a transitional macro-unit along the boundary of the Critical and Main zones. The transitional unit is characterised by a geochemical hiatus recording distinct inflections in mineral chemistry and isotopic compositions. Previously these inflections in mineral chemistry and changes in isotopic compositions were attributed mostly to the influx of a magma that was compositionally distinct from the resident magma and that was parental to the Main Zone of the complex. Sr-isotopic variations across this interval have been particularly well-studied, but despite this, little consensus exists regarding the petrogenesis and metallogenesis of this economically important interval. Here we report whole-rock Sr–Nd-isotopic, major- and trace element geochemical and mineral chemical data across the Merensky-Bastard interval as intersected by borehole BH8172 on the farm Hackney in the eastern Bushveld Complex. Variations in whole-rock Cr/MgO values and initial Sr isotopic ratios across the interval are consistent with the results of previous studies that argued for the co-accumulation of minerals from compositionally and isotopically distinct magmas, of Critical and Main Zone lineages, respectively. In our model, a magma of Critical Zone affinity enters the chamber causing erosion along the chamber floor. Orthopyroxene and plagioclase crystallise from the Critical Zone magma to form the Merensky Reef, as suggested by high whole-rock Cr/MgO ratios (> 80) and unradiogenic Sr-isotopic compositions (87Sr/86Sri < 0.7068). A plagioclase-laden magma of Main Zone affinity subsequently intruded the chamber as a basal flow, elevating the resident Critical Zone magma. Plagioclase within the former floated, forming a solid raft onto which the Bastard Reef was deposited, a model that is entirely consistent with density considerations and an upward increase in the An-content of plagioclase as observed in the anorthositic package between the Merensky and Bastard reefs. From a metallogenetic viewpoint, this would imply that the Main Zone could not have been the source of the PGEs within the Merensky Reef.

Reconstructing the depositional environment and diagenetic modification of global phosphate deposits through integration of uranium and strontium isotopes

The geochemistry of phosphate rocks can provide valuable information on their depositional environment and the redox condition of global oceans through time. Here we examine trace metal concentrations and uranium (δ238U, δ234U) and strontium (87Sr/86Sr) isotope variations of marine sedimentary phosphate rocks and the phosphate-bearing carbonate fluorapatite (CFA) mineral phase, originating from Precambrian to mid-Miocene aged major global phosphate deposits. We find elevated concentrations of several trace elements (Al, V, Cr, Cd, U, Mn, Co, Cu, As, and Rb) in the CFA mineral phase of young phosphate rocks (Miocene to Late Cretaceous) relative to those of older (Devonian to Precambrian) rocks. The δ238U of phosphate rocks of Mid-Miocene to Permian age range from −0.311‰ to 0.070‰, exhibiting a positive fractionation relative to modern seawater (−0.38‰). This is similar to the isotope fractionation reported for carbonate and shale sediments, likely resulting from the reduction of uranium in porewaters during CFA precipitation. Cambrian to Precambrian phosphate rocks have lower δ238U of −0.583‰ to −0.363‰, indicating different depositional redox conditions likely resulting from seafloor anoxia and/or diagenetic modification. The 87Sr/86Sr ratios of phosphate rocks of Cretaceous to Mid-Miocene age generally follow the secular 87Sr/86Sr seawater curve. Phosphate rocks with 87Sr/86Sr that deviate from this curve have characteristic trace metal trends, such as lower Sr/Ca and Sr concentrations, suggesting later diagenetic modification. Older phosphate rocks of Precambrian age are systematically more radiogenic than the expected secular Sr seawater composition at the time of deposition, possibly due to the greater influence of terrestrial input in peritidal zones and/or more pervasive diagenetic modification. Overall, our study reveals connections between U and Sr isotope variations for reconstructing the depositional and diagenetic conditions of global phosphate rock formation through Earth history and the transition to an oxic ocean following the Paleozoic Oxygenation Event.

Petrology and source characteristics of the Arbarastakh alkaline ultramafic carbonatite-phoscorite complex, the Aldan-Stanovoy Shield

Late Neoproterozoic Arbarastakh alkaline ultramafic carbonatite-phoscorite complex in the southern margin of the Siberian craton (Aldan-Stanovoy shield), includes carbonatites and phoscorites closely associated with pyroxenites-ijolites and ultramafic lamprophyres. Major and trace elements data, Sr, Nd and Pb isotope compositions for the Arbarastakh rocks have been obtained to characterize the sources involved in their formation, primary melt composition and to build the petrogenetic model.All rock varieties, excluding nepheline syenites, are characterized by incompatible elements enrichments, including light rare earth elements, and strong fractionation of REEs. The initial isotope ratios of the analyzed samples, calculated at 645 Ma, display limited variations: εNd from +5.9 to +6.9 and 87Sr/86Sr from 0.70225 to 0.70272, excluding nepheline syenite with εNd +5.4. The initial Pb isotope ratios for the most studied samples overlap with each other within uncertainties. They yield an age of 642 ± 5 Ma. The Nd and Sr isotope data of the Arbarastakh rocks generally fit the patterns of the other Neoproterozoic alkaline ultramafic carbonatite complexes of the southwestern and southern margins of the Siberian craton. Observed Sr, Nd and Pb isotope variations indicate mixing of the asthenosphere and the depleted mantle components.It is supposed that the primary melts for the Arbarastakh rocks were generated directly by low-degree melting of metasomatic phlogopite‑carbonate veins with apatite and Ti-oxides in garnet peridotite, which formed shortly before the onset of melting. Ultramafic lamprophyre (aillikite) is closest to the primary melt composition in terms of high #MgO, Cr and Ni. The aillikite and latter pyroxenite crystallized from primitive melt by fractionating the olivine, phlogopite and clinopyroxene dominated mineral assemblage that was free of feldspar. This fractionation forced Na-enrichment in the magmas resulted in liquid silicate‑carbonate immiscibility. Major and trace element and isotope data indicate that the nepheline syenites are unlikely to be related with other alkaline silicate rocks through fractional crystallization and could have been formed through pre-emplacement interaction with the ambient crustal materials. Emplacement of calcite carbonatites resulted in metasomatism of surrounding pyroxenites with formation of clinopyroxene-phlogopite-calcite carbonatites. Subsequent portions of Fe-P-enriched carbonatite magmas crystallized phoscorites and apatite-dolomitic carbonatites.

Use of strontium isotope ratios in potential geolocation of Ajnala skeletal remains: a forensic archeological study.

Stable isotope methods for provenance of unidentified human remains are relatively a newer field of enquiry in forensic archeology. It is of great interest for forensic experts these days. The application of strontium isotope analyses for estimating geolocation of archeological remains is of great interest in bioarcheology and modern forensics. The strontium (Sr) isotope composition of human bones and teeth has been widely used to reconstruct an individual's geo-affiliation, residential mobility, and migration history. Thousands of unknown human remains, reportedly belonging to 282 Indian soldiers of 26th Native Bengal regiment and killed in 1857, were exhumed non-scientifically from an abandoned well situated underneath a religious structure at Ajnala (Amritsar, India). Whether these remains belonged to the individuals, local or non-local to the site, was the important forensic archeological question to be answered by doing their thorough forensic anthropological examinations. In the present study, 27 mandibular teeth (18s molars, 6 first molars, and 3 premolars) collected from the Ajnala skeletal assemblage were processed for strontium isotope analysis, and the measured ratios were compared with published isotope baseline data to estimate the locality status of these remains. The Sr isotopic values were concentrated in the range of 0.7175 to 0.7270. The comparative analysis of isotopic ratios revealed that most individuals buried in the Ajnala well have 87Sr/86Sr values close to the river as well as groundwater of the Gangetic plain (less radiogenic 87Sr/86Sr ~ 0.716); most likely originated near Varanasi (Uttar Pradesh, India) region, whereas the individuals with higher 87Sr/86Sr ratios (~ 0.7200) probably resided in the West Bengal and Bihar areas where the river as well as groundwater of the Gangetic plain is relatively more radiogenic. Thus, the strontium isotope results reveal that the Ajnala individuals did not grow up or live in the Amritsar region during their childhood, and this observation complemented the previous forensic anthropological and molecular findings. There is very little Indian data on the bioavailable strontium, so the inferences from the present study estimating Sr isotope abundances are expected to provide baseline data for future forensic provenance studies that will contribute to the global efforts of mapping Sr isotope variations by the isotope community.

Resetting of soil compositions by irrigation in urban watersheds: Evidence from Sr isotope variations in Austin, TX

Human activities in urban areas disturb the natural landscape upon which they develop, disrupting pedogenic processes and ultimately limiting the ecosystem services urban soils provide. To better understand the impacts on and resiliency of soils in response to urban development, it is essential to understand the processes by which and degree to which soil physical and chemical properties are altered in urban systems. Here, we apply the source-tracing capabilities of Sr isotopes (87Sr/86Sr) to understand the impacts of urban processes on the composition of soils in eight watersheds in Austin, Texas. We evaluate natural and anthropogenic Sr sources in watersheds spanning a wide range of urbanization, comparing soils by variations in their natural (including mineralogy, thickness, soil type, and watershed) and anthropogenic (including irrigation, soil amendments, and fertilization) characteristics. A strong positive correlation between soil thickness and 87Sr/86Sr is observed among unirrigated soils (R2 = 0.83). In contrast, this relationship is not observed among irrigated soils (R2 = 0.004). 95 % of 42 irrigated soil samples have 87Sr/86Sr values approaching or within the range for municipal supply water. These results indicate soil interaction with municipal water through irrigation and/or water infrastructure leakage. Soils irrigated with municipal water have elevated 87Sr/86Sr values relative to unirrigated soils in seven of eight watersheds. We propose that original soil 87Sr/86Sr values are partially to completely reset by irrigation with municipal water via ion exchange processes. Our results demonstrate that in urban systems, Sr isotopes can serve as an environmental tracer to assess the overprint of urbanization on natural soil characteristics. In the Austin region, resetting of natural soil compositions via urban development is extensive, and the continued expansion of urban areas and irrigation systems may affect the ability of soils to retain nutrients, filter contaminants, and provide other ecosystem services that support environmental resilience.

Seawater carbon and strontium isotope variations in the eastern Tarim Basin during the Cambrian: Implications for connection with the open ocean

Cambrian was a critical period in Earth's history, marked by rapid diversification of early animals and significant changes in oceanic conditions. Marine sediments, particularly carbonates, have been used to study variations in the global carbon cycle, seawater redox, weathering input, etc. In search of new archives of Cambrian paleo-seawater chemistry, we conducted an integrated study of Cambrian C and Sr isotope stratigraphy using the carbonates of the Xingdi section in the Kruqtagh region of the eastern Tarim Basin. Based on reported paleontological data, the C isotope record is comparable to the Cambrian global seawater C isotope variation, providing a feasible stratigraphic framework for the Cambrian strata in the eastern Tarim Basin. A sharp δ13C increase at the top of the Xidasan Formation probably corresponds to the recovery of the Redlichiid–Olenellid Extinction C isotope Excursion. Additionally, a negative C isotope excursion in the lower part of the Mohuosan Formation and a positive C isotope excursion at the bottom of the Tuersaketagh Formation likely correspond to DrumIan Carbon isotope Excursion and Steptoean Positive Carbon Isotope Excursion, respectively. However, the Sr isotope curve in the eastern Tarim Basin decoupled from global seawater Sr isotope variations during Cambrian Series 2–3 until Furongian, indicating that the eastern Tarim Basin was not well connected with the open ocean until Furongian. It also highlights a significant impact of paleogeographical connections of basins with the open ocean on their seawater Sr isotopic signal.

Barium and strontium isotope fractionation by cyanobacteria forming intracellular carbonates

While barium (Ba) and strontium (Sr) stable isotopes are increasingly used as tracers of biogeochemical processes and paleo-proxies, the role of biotic processes on Ba and Sr isotope fractionation is poorly understood. Here, Ba and Sr stable isotope fractionations were studied in the laboratory using Gloeomargarita lithophora, a cyanobacterium that selectively hyperaccumulates Ba and Sr within intracellular amorphous carbonate biominerals. Our results show that lighter Ba and Sr isotopes are enriched in G. lithophora cells compared to the initial solution by –0.24‰ to –0.03‰ (δ137Ba) and –0.33‰ to –0.01‰ (δ88Sr) depending on the stage of the experiment. The fractionation of Ba and Sr isotopes is distinct in magnitude from that occurring during abiogenic and other known biogenic carbonate formation cases. Additionally, using a Rayleigh fractionation model, the fractionation factors of Ba and Sr isotopes between G. lithophora cells and the fluid (the growth medium), i.e., Δ137Ba(bac-sol) and Δ88Sr(bac-sol), were equal to –0.25‰ and between –0.46‰ and –0.38‰, respectively. Interestingly, δ137Basol and δ88Srsol decreased at the end of Ba and Sr uptake stages back towards their initial values, which caused departures from the Rayleigh fractionation model. This suggests the existence of a back reaction resulting in a Ba and Sr outflux from cells to the solution. Possible hypotheses for this back-reaction include dissolution of amorphous carbonate inclusions in response to cellular stress, or a first-order rate dependence of amorphous carbonate dissolution on the amount of Ba and Sr inside the cell. Our findings suggest that bacteria forming intracellular amorphous carbonates could introduce Ba and Sr isotope variability in environmental records, especially in environments where they thrive. Moreover, the enrichment of lighter isotopes of Ba and Sr during amorphous carbonate formation is consistent with that occurring during the formation of other biogenic carbonates but slightly differs in magnitude, opening a discussion about the possibility to use Δ137Ba(bac-sol) and Δ88Sr(bac-sol) as an indicator of intracellular amorphous carbonate biomineralization in the fossil rock record. Overall, this work highlights the complexity of the biological uptake of alkali-earth metals and stresses the overlooked role of bacteria forming intracellular amorphous carbonates in Ba and Sr biogeochemical cycles.

Machine learning-based Sr isoscape of southern Sardinia: A tool for bio-geographic studies at the Phoenician-Punic site of Nora.

Since prehistoric times, the island of Sardinia-in the western Mediterranean-has played a leading role in the dynamics of human population and mobility, in the circulation of raw materials and artefacts, idioms and customs, of technologies and ideas that have enriched the biological, linguistic and cultural heritage of local groups. For the Phoenician and Punic periods (from the 9th to the 3rd centuries BCE), the ancient site of Nora-in southern Sardinia-represents an emblematic case in the study of migratory phenomena that occurred on the Island from the Iron Age until the Roman conquest. Despite the importance of exploring (and characterising) such movements from a wider bio-cultural perspective, the application of bio-geochemical tools for geographical provenance to the ancient skeletal populations of Sardinia is yet scarce. The present work is the first step towards filling this gap with the development of the first isoscape of southern Sardinia using new bioavailable Sr isotope data and a machine-learning approach. From a geolithological point of view, Sardinia is rather heterogeneous and requires detailed studies to correctly assess the distribution of the isotopic signature of bioavailable Sr. The random forest model employed here to construct the Sr isoscape uses several external environmental and geological variables. The most important predictors are related to age and bedrock type, with additional input from local soil properties. A 10-fold cross-validation gives a mean square error of 0.0008 and an R-squared of 0.81, so the model correctly predicts the 87Sr/86Sr ratio of unknown areas. By using a Bayesian provenance assignment workflow, we tested the isoscape here produced to determine the geographic origin and the mobility of archaeological and modern fauna collected from the Phoenician-Punic site of Nora and the surrounding Pula Plain. Our results indicate that archaeological sheep and goats (87Sr/86Sr < 0.7090) are compatible with areas close to Nora and Pula Plain, in agreement with archaeological evidence of pastoralism in those areas. Modern wild and domesticated fauna (87Sr/86Sr > 0.7090) show compatibility with several natural and anthropogenic locations in southern Sardinia, as expected based on modern species distribution data. Finally, we discuss the large Sr isotopic variability of the Nora baseline, where human mobility studies of human cremated and inhumed individuals are currently underway.

First insights into human mobility in Neolithic Belgium using strontium isotopic analysis and proteomics: A case study of Grotte de La Faucille (Sclayn, province of Namur).

So far, no 87 Sr/86 Sr mobility studies have been done for Neolithic remains from Belgium and information on the Sr isotopic variability in the region is scarce. This study aims to explore mobility in a Final Neolithic population from the funerary cave 'Grotte de La Faucille', contribute to the understanding of the isotopic composition of bioavailable Sr in Belgium, assess evidence for male mobility using proteomic analysis, and explore possible places of origin for nonlocal individuals. The 87 Sr/86 Sr isotope ratio of dental enamel from six adults and six juveniles was determined. Liquid chromatography mass spectrometry-based protein analysis was employed to identify individuals of male biological sex. 87 Sr/86 Sr of micromammal teeth, snail shells, and modern plants from three geological areas in Belgium were measured to establish isotopic signatures for bioavailable strontium. Nonlocality was assessed by comparing human 87 Sr/86 Sr isotope ratios to the 87 Sr/86 Sr range for bioavailable Sr. Four individuals yielded 87 Sr/86 Sr isotope ratios consistent with a nonlocal origin. No statistical differences were found between adults and juveniles. Three males were detected in the sample set, of which two show nonlocal 87 Sr/86 Sr values. This study provides evidence for mobility in Final Neolithic Belgium. The four nonlocal 87 Sr/86 Sr signatures correspond with the 87 Sr/86 Sr of bio-available Sr in Dutch South Limburg, the Black Forest in Southwest Germany, and regions of France, such as parts of the Paris Basin and the Vosges. The results support the ruling hypothesis of connections with Northern France, brought to light by archeological research.

Hydrogeochemical modeling of the spatiotemporal variations in 87Sr/86Sr isotope ratios and Sr concentrations of spring waters in a headwater catchment (Strengbach CZO–France)

The variations in strontium (Sr) isotope ratios in river waters at a regional scale are usually discussed in terms of lithological diversity constituting the watershed bedrock. To discuss the origin of the spatiotemporal variations in Sr concentrations and isotopic compositions of spring waters at the headwater watershed scale, we analyzed the 87Sr/86Sr and 143Nd/144Nd isotopic ratios of the main constitutive minerals of the granitic bedrock of the Strengbach Critical Zone Observatory (CZO) and developed coupled hydrogeochemical modeling integrating the Sr concentration and isotopic composition. The simulation results show that the long-term (1990–2010) decrease in Sr concentrations in the CS springs of the Strengbach catchment can be explained by the response of mineral weathering along the water pathway to the pH increase that affected the incoming solutions to the weathering system during the same period. This pH increase reduces the water path proportion marked by a high flux of apatite and biotite dissolution. Thus, it reduces the Sr concentration of the outgoing spring waters. The different responses of the various CS springs to the incoming solutions' pH increase can be explained by the more or less long residence time of the water in the bedrock for the different springs. The analytical data also confirm that the 87Sr/86Sr isotope ratios of the CS springs varied little or not at all on average from 1990 to 2010. In contrast, they varied significantly during a hydrological cycle and from one spring to another. The constancy of the average 87Sr/86Sr isotope ratios over several years is explained by a granitic bedrock water path sufficiently long for soil solution pH variations to no longer influence the emergence of the spring. The simulation results also show that the isotopic variations observed in the CS springs during a hydrological cycle can be explained by differences in the transit time of the water in the substratum between high and low waters and the modifications that they entail on the degree of saturation of the water with respect to biotite and apatite. These differences do not need to be explained by differences in the mineralogy of the rocks drained by waters between high and low discharge periods. Similarly, the different average isotope ratios from one spring to another can be explained by the more or less long transit times in the bedrock of the waters feeding these different springs. Again, it is not necessary to explain them by local lithological differences from one spring to another. These different results highlight that at the scale of an upstream basin such as the Strengbach, the Sr isotopic variations observed in the CS springs should not systematically indicate lithological differences in the rock. The development of coupled isotope modeling approaches should help to disentangle the part of this process relating to hydrological processes in the isotopic variability of the spring waters.

Rapid characterisation of Mars' mantle reservoirs by in situ laser ablation 87Sr/86Sr analysis of shocked feldspar (maskelynite)

The 87Sr/86Sr isotopic properties of martian meteorites, measured by isolation and purification of Rb and Sr fractions, have long been used to partially characterise Mars' mantle. However, this method is time-consuming, destructive, and subject to incorporation of terrestrial contamination due to precipitation of phases in fractures and/or grain boundaries prior to meteorite collection. In this study, we test the effectiveness of in situ acquisition of 87Sr/86Sr by laser ablation in maskelynite - a typically low Rb/Sr (<0.1) feldspar-composition glass formed during high-P shock metamorphism – as a method of rapid characterisation of Mars' mantle Sr isotope ratios. Element concentration maps and the results of unwashed and gently surface-leached bulk rock analyses indicate that terrestrial Sr has infiltrated the studied meteorites and affected bulk rock trace element budgets. However, maskelynite trace element concentrations are largely unaffected and their martian igneous Rb/Sr is preserved. In situ87Sr/86Sr analyses of maskelynite, checked against a newly developed Sr feldspar reference material (KAN, presented here and available on demand), accurately and precisely distinguish different shergottite mantle reservoirs. The measurements reproduce published data, have uncertainties on the 4th to 5th decimal place, and yield statistically indistinguishable results in analytical sessions separated by long periods of time. The data from 11 enriched shergottites reveal there to be subtle Sr isotope variation within the enriched shergottite mantle reservoir, or that there was crustal assimilation of radiogenic components into the shergottites, or that the shergottite liquids were extracted over a time period during which the mantle reservoir 87Sr/86Sr evolved. The limited published age range of the enriched shergottites, coupled with the absence of a correlation between in situ87Sr/86Sr and REE, Sr or Pb concentration in maskelynite, suggests that the isotope range is best explained by small variations in the enriched mantle reservoir. Given the presence of maskelynite (or plagioclase) in many meteorites, the in situ method will be useful when there are only very small volumes of material available and/or where terrestrial contamination is suspected.

Spatiotemporal evolution of late Neoproterozoic marine environments on the Yangtze Platform (South China): inking continental weathering and marine C-P cycles

Abstract The geodynamic reorganization of major cratonic blocks during the assembly of Gondwana in the late Neoproterozoic caused a (bio)geochemical evolution of marine habitats that witnessed fluctuating seawater oxygenation and nutrient fluxes. Previous studies of carbonates deposited on the Yangtze Platform (South China) have shown their use as reliable archives of paleo-redox and bio-productivity changes intrinsically linked to continental weathering fluxes and water mass cycling. Despite its complex submarine morphology, only a few carbonate-bearing sections comprising deeper depositional environments of the Yangtze Platform have been evaluated. Here we report temporal, lateral, and vertical variations of stable C and radiogenic Sr, Nd, and Os isotopic compositions together with trace element and rare earth and yttrium (REY) systematics in carbonates from the Doushantuo Formation representing different paleo-marine environments of the Yangtze Platform, including I) inner shelf, II) restricted intra-shelf basin, III) slope and IV) deep-water basin sections to trace the extent and evolution of paleo water masses. Variations in shale-normalized (subscript SN) Ce anomalies argue for variably oxidizing atmosphere/ocean conditions. The combination of REY SN systematics with carbonate associated P enrichments defines three distinct local water masses from which the carbonates precipitated: i) fully oxidized shallow-water, ii) nutrient-poor intra-shelf basin waters, and iii) organic carbon-rich slope and deep-waters with temporal evolution to higher dissolved p O 2 . Negative carbon isotope excursions in the carbonates such as during the putative Shuram equivalent Doushantuo Negative Carbon Excursion (DOUNCE) correlate with less negative Ce SN anomalies and ambient seawater shifts to more radiogenic initial 87 Sr/ 86 Sr and 187 Os/ 188 Os, but unradiogenic 143 Nd/ 144 Nd compositions, arguing for coupling of redox and weathering trends. Our comprehensive geochemical study highlights the vertical and temporal variations of physicochemical water mass properties recorded in late Neoproterozoic Yangtze Platform carbonates until the emergence of the first metazoans. Highlights • Intensive geochemical study spanning four paleo-depths on the Yangtze Platform • First carbonate Osmium isotopic compositions from the Late Neoproterozoic • Os, Nd and Sr isotope variations in concert with influx of terrigenous solutions towards the end of the Doushantuo Fm • REY systematics and P enrichments reveal significantly different water masses along the passive margin of the Yangtze craton • Changes in C-P cycles during Shuram anomaly linked to intensified terrigenous solution flux

Sr isotope variations in Oligocene–Miocene and modern biogenic carbonate formations of Koko Guyot (Emperor Seamount Chain, Pacific Ocean)

The Hawaiian–Emperor Seamount Chain, a major topographic feature of the Pacific Ocean floor, is composed of seamounts capped with fossil coral reef deposits that originally formed close to sea level but are now covered by hundreds of meters of water owing to prolonged subsidence. These fossil reef deposits are important archives of paleoenvironmental change and yield information on the subsidence history of the seamounts. We studied the Sr isotope compositions of Oligocene–Miocene coral reef limestone from Koko Guyot in the southern Emperor Seamount Chain to assess the dynamics of the subsidence. The ages of the studied samples containing coral fragments established by Sr isotope stratigraphy vary from 26.3 to 20.1 Ma. In contrast, the youngest samples (15.3 Ma), which were deposited in water depths of >120 m, are barren of corals and are composed exclusively of bryozoans and coralline algae. The subsidence rate of the Koko Guyot volcanic structure was not constant over time. Integration of our new data with the results of previous studies reveals that the subsidence rate was 0.046 ± 0.005 mm/yr during the first 25–30 Myr (from 49–44 to 20 Ma). During this period, Koko Guyot was in a bathymetric interval favorable for coral reef development, and its subsidence was compensated by rapid vertical growth of the reef. Subsequently, the subsidence rate decreased to an average value of 0.019 ± 0.003 mm/yr from 20 to 15 Ma. The decrease in the rate of bottom subsidence coincided with unfavorable environmental conditions for coral reef development, leading to the disappearance of corals. The average subsidence rate has been 0.015 ± 0.002 mm/yr since 15 Ma, comparable to the present-day subsidence rate. We also analyzed the stable Sr isotope ratios (δ88/86Sr) of warm-water coral samples formed at 25–20 Ma (0.32‰ ± 0.1‰), as well as carbonate of large benthic foraminifera, coralline algae, and other non-coral species for the period 20–15 Ma (0.10‰ ± 0.09‰). We suggest that the large difference in carbonate δ88/86Sr between 25–20 and 20–15 Ma corresponds to a difference in the fractionation factor caused by environmental and benthic community change.

Magma evolution of the South China Sea basin from continental-margin rifting to oceanic crustal spreading: Constraints from In-situ trace elements and Sr isotope of minerals

The South China Sea (SCS) has undergone a complete Wilson cycle. We studied the volcanic rocks from IODP Sites U1502, U1500, U1431, U1433, and U1434 that record the exact mantle dynamics of the SCS basin from continental rifting to oceanic crustal spreading. We present in-situ major and trace element data for minerals (olivine, clinopyroxene, and plagioclase) and melt inclusions; and in-situ Sr isotopic ratios for plagioclases from the volcanic samples. All SCS volcanic rocks belong to the tholeiite series. Most Site U1431 basalts are slightly depleted in light rare earth elements (LREEs) and large-ion lithophile elements (LILEs) and similar to that of normal mid-oceanic ridge basalts (N-MORB). All clinopyroxenes and olivines, and the calculated equilibrium melts of clinopyroxene cores display depletion of LREEs and enrichment of heavy rare earth elements (HREEs) similar to N-MORB-type primary magma. Thus, these volcanic rocks are likely formed by the extension decompression partial melting of shallow depleted magma. The Sites U1502, U1500, U1433, and U1434 bulk-rocks and melt inclusions show flat LREE and HREE patterns similar to that of enriched MORB (E-MORB), likely attributed to the partial melting of a depleted mantle source with different degrees of lower continental crustal contamination. The increase in 87Sr/86Sr ratios from core to rim in Site U1500 plagioclases further prove the crustal contamination during magmatism. Site U1431 clinopyroxene and Site U1500 plagioclase show normal zoning textures and slight enrichment of incompatible elements in their rims but depletion in their cores, likely indicating significant crystallization of late-stage differentiated melts. Although some clinopyroxene and plagioclase were likely crystallized in a relatively closed environment, the existence of melt inclusions and the large Sr isotopic variations between the plagioclase rim and groundmass suggest a dynamic and open magmatic system that likely experienced melt–rock interactions and magma mixing processes. Melt supply rate changes from low to high during the SCS evolution process from initial rifting (Site U1500) to later spreading (Sites U1431 and U1433) indicating that: (1) the number of high-An plagioclase-hosted melt inclusions has gradually decreased; and (2) the zoning textures of clinopyroxene and plagioclase have gradually changed from simple to complex. The influence of mantle plumes and the upwelling of fertile subduction-related asthenospheric magma were negligible during the continental-margin breakup and initial SCS spreading, but played an important role during the late SCS spreading period, as revealed by the variation in Sr isotopic compositions of high-An plagioclase cores, the different mantle potential temperatures and source lithologies.

A strontium isoscape of Italy for provenance studies

We present a novel database of biological and geological 87Sr/86Sr values (n = 1920) from Italy, using literature data and newly analysed samples, for provenance purposes. We collected both bioavailable and non-bioavailable (i.e. rocks and bulk soils) data to attain a broader view of the Sr isotope variability of the Italian territory. These data were used to build isotope variability maps, namely isoscapes, through Kriging interpolations. We employed two different Kriging models, namely Ordinary Kriging and Universal Kriging, with a geolithological map of Italy categorized in isotope classes as external predictor. Model performances were evaluated through a 10-fold cross validation, yielding accurate 87Sr/86Sr predictions with root mean squared errors (RMSE) ranging between 0.0020 and 0.0024, dependent on the Kriging model and the sample class. Overall, the produced maps highlight a heterogeneous distribution of the 87Sr/86Sr across Italy, with the highest radiogenic values (>0.71) mainly localized in three areas, namely the Alps (Northern Italy), the Tuscany/Latium (Central Italy) and Calabria/Sicily (Southern Italy) magmatic/metamorphic terrains. The rest of the peninsula is characterized by values ranging between 0.707 and 0.710, mostly linked to sedimentary geological units of mixed nature. Finally, we took advantage of the case study of Fratta Polesine, to underscore the importance of choosing appropriate samples when building the local isoscape and of exploring different end-members when interpreting the local Sr isotope variability in mobility and provenance studies. Our user-friendly maps and database are freely accessible through the Geonode platform and will be updated over time to offer a state-of-the-art reference in mobility and provenance studies across the Italian landscape.

Magma recharge processes of the Yandangshan volcanic-plutonic caldera complex in the coastal SE China: Constraint from inter-grain variation of Sr isotope of plagioclase

Abstract In situ Sr-isotope of plagioclase can be used to elucidate the details of magmatic processes. Here we report in situ Sr isotopic compositions of plagioclase from the intra-caldera porphyritic quartz syenite and mafic microgranular enclave of the Yandangshan caldera, SE China. Plagioclase phenocrysts from porphyritic quartz syenite show consistent initial 87Sr/86Sr ratios (0.7088–0.7091). Plagioclases in groundmass of mafic microgranular enclave have low initial 87Sr/86Sr ratios (0.7080–0.7081). In contrast, the plagioclase phenocrysts of mafic microgranular enclave show relatively variable initial 87Sr/86Sr ratios of 0.7081–0.7088, which exhibit distinct inter-grain variation with high values similar to the plagioclase phenocrysts in porphyritic quartz syenite, and low values similar to the plagioclase in groundmass. However, the initial 87Sr/86Sr ratios of individual plagioclases from phenocrysts and groundmass show insignificant intra-grain variation. Furthermore, initial 87Sr/86Sr ratios (0.7080–0.7088) of plagioclase from phenocrysts and groundmass of mafic microgranular enclave are within and lower than the whole-rock initial 87Sr/86Sr ratios (0.7082–0.7088), while the values of plagioclase phenocrysts from the porphyritic quartz syenite are within and higher than the whole-rock initial 87Sr/86Sr ratios (0.7086–0.7089). Therefore, we propose that the inter-grain Sr isotope variation of plagioclase is related to magma recharge events, which induce chemical and physical exchanges between the recharge magma and the host magma and the remobilization of crystal mush in magma reservoir. Furthermore, our study shows that whole-rock Sr isotopic compositions could not represent the end-members and they may be a result of the assemblage of rock-forming minerals such as plagioclase with different initial Sr isotopic ratios.

In Situ Elemental and Sr Isotope Characteristics of Magmatic to Hydrothermal Minerals from the Black Mountain Porphyry Deposit, Baguio District, Philippines

AbstractAt the Black Mountain porphyry Cu-Au deposit in the Baguio district, Northern Luzon (Philippines), pre- and synmineralized rocks preserve magmatic and hydrothermal minerals (e.g., plagioclase, amphibole, titanite, and epidote) spanning the complete paragenesis of the deposit. Strontium isotope values in early crystallized plagioclase phenocrysts from all felsic porphyries can be divided into two types. The type-I plagioclase crystals show relatively homogeneous Sr isotope values (0.7035–0.7038, 1σ &amp;lt;0.0001), indicating crystallization from a relatively stable and long-lived felsic magma chamber. The type-II plagioclase grains have a wider range of Sr isotope compositions (0.7032–0.7039, 1σ &amp;lt;0.0001), indicating mafic and/or felsic magma recharge. In magmatic titanite, Nb/Ta values are higher than those in the whole rock, while Zr/Hf and Y/Ho values are lower. In hydrothermal titanite and epidote, the ratios are similar to those in the whole rock. These patterns reflect crystallization effects imposed during the magmatic stage but an absence of differentiation during the hydrothermal stage. The consistent gradual decrease in total rare earth element, Y, Zr, and U contents in both hydrothermal titanite and epidote from early to late stages indicates the effect of hydrothermal fluid evolution with decreasing temperature. The variation of 87Sr/86Sr values in magmatic amphibole, plagioclase, and hydrothermal epidote in felsic and mafic rocks indicates the addition of mafic magma-derived fluid into the felsic magma-derived fluid. One extra source of fluid (probably derived from wall-rock limestone) was required to generate the highly radiogenic 87Sr/86Sr values of some epidote (0.7038–0.7053). Thus, in situ elemental and Sr isotope variation in minerals from different paragenetic stages can be used to interpret formation process and source for both magmas and hydrothermal fluids.

In situ Sr isotope analysis of mantle carbonates: Constraints on the evolution and sources of metasomatic carbon-bearing fluids in a paleo-collisional setting

Carbonate-bearing wedge peridotites attest the mobilization of carbon (C) by slab fluids/melts circulating in a subduction setting. In general, COH fluids are thought to derive from the dehydration/partial melting of the crustal portions of slabs, especially during the exhumation of crust-mantle mélanges along continental subduction channels. In this study we combined textural observations with in-situ Sr isotope analyses of mantle carbonates occurring in different microstructural sites to test whether the fluids responsible for the carbonation of a mantle wedge are derived from the subducted continental crust or not. We focus on the Ulten Zone peridotites (Eastern Italian Alps) associated with high-grade felsic rocks, where carbonates occur mainly as dolomite and minor magnesite and calcite. In situ laser MC-ICP-MS analysis of peridotites representing different episodes of a complex metasomatic history, indicates that Sr isotopic variations can be linked to the different microstructural positions of carbonates. The C-metasomatism of the UZ peridotites is proposed to have occurred in two stages. The first stage is the HP‑carbonation at peak (eclogite-facies) conditions, with formation of interstitial matrix dolomite in textural equilibrium with hornblende to pargasite amphibole and Cl-apatite. This dolomite exhibits relatively unradiogenic 87Sr/86Sr present day values of 0.70487±0.00010, requiring different sources with respect to the associated migmatites and the overhanging mantle wedge. Carbonation continued during exhumation, with local injection of C-rich fluids forming a dolomite vein in association with tremolite and chlorite. The dolomite vein shows a wide range of 87Sr/86Sr (0.7036–0.7083), reflecting both the primary composition of carbonates and the consequent interaction with crustal fluids as expected in a crust-mantle mélange. The second stage is C-remobilization by dolomite dissolution and precipitation of brucite intergrowths with calcite during the final exhumation. This remobilization event has resulted in a similar Sr composition to the precursor dolomite.The mantle wedge is therefore capable of storing carbonates which have been shown to represent a complex metasomatic evolution from eclogite-facies conditions to very shallow structural levels. Therefore, fluids released from subducting slabs of continental lithosphere might be responsible for the crystallization of metasomatic minerals such as amphibole, phlogopite and zircon in the overlying ultramafic rocks. Conversely, the role of these metasomatic fluids on the carbonation of mantle wedge is likely overestimated. The combination of geochemical, isotopic and textural evidence suggests that dolomite inclusions and interstitial dolomite are derived in large part from a distinct source of C-bearing fluids that could be related to depleted mantle wedge sources and/or trondhjemitic igneous activity. In contrast, at the end of exhumation, residual COH-fluids released by the associated stromatic gneisses and orthogneisses resulted in late-stage dolomite veins having the highest Sr isotope values in the Ulten Zone peridotites.

Time-dependent Sr and Nd isotope variations during the evolution of the ultrapotassic Sabatini Volcanic District (Roman province, Central Italy)

The Sabatini Volcanic District (SVD), active between 0.8 and 0.07 Ma, is a volcanic field in the Roman province (Central Italy) located along the Tyrrhenian margin of the Italian peninsula. In this volcanic region, high-K magmas originated from a metasomatised phlogopite-bearing peridotite mantle recording subduction-related fluids and/or melting processes. Here, we investigate magma evolution during the six main eruptive phases of the SVD by means of chemical and isotopic (Sr and Nd) analyses. Specifically, we analyzed clinopyroxene crystals from juvenile pumice and scoria clasts and lavas, from 40 major SVD eruptive units chronologically well constrained by 40Ar/39Ar dating. 87Sr/86Sr and 144Nd/143Nd ratios in SVD clinopyroxene range 0.7095–0.7115 and 0.51210-0.51214, respectively. The mean Sr and Nd isotope compositions of each eruptive phases show a gradual, long-term decrease over the entire SVD eruptive history. However, when considering the distinct temporal windows of the individual eruptive phases, a significant variability of the Sr-Nd isotope ratios emerges, thus highlighting a more complex, time-dependent geochemical trend for the erupted magmas, with respect to a previously described trend at the nearby Colli Albani Volcanic District (0.6–0.04 Ma). Geochemical features of clinopyroxene in lavas and juvenile pyroclasts suggest that magma differentiation occurred in an open system due to assimilation of siliciclastic sedimentary rocks. Moreover, a critical review of the available geochemical data, in light of 40Ar/39Ar ages, allows the recognition of the SVD as the source of widespread tephra markers recorded in the central Mediterranean area by previous works.

Neogene volcanism in Elazig-Tunceli area (eastern Anatolia): geochronological and petrological constraints

The Elazig and Tunceli provinces in eastern Anatolia host a complex succession of Miocene-Pleistocene effusive and explosive volcanic rocks, divided into four distinct volcanic phases. The most abundant and widespread products are the calcalkaline Mazgirt volcanic rocks, characterized by wide Sr isotope variations (87Sr/86Sr ~0.7054-0.7077) and narrower 143Nd/144Nd (~0.51246-0.51260) and Pb isotopes (e.g., 206Pb/204Pb ~18.89-19.13). New 40Ar-39Ar ages indicate that Mazgirt volcanic activity occurred between ~16.3 and 15.1 Ma. The other three volcanic phases are represented by the Tunceli mildly alkaline basaltic lavas (~11.4-11.0 Ma), the Pliocene Karakocan (~4.1 Ma) and Pleistocene Elazig (~1.9-1.6 Ma) Na-alkali basaltic lavas with clear OIB-like geochemical signature.Mazgirt volcanics can be subdivided on the base of mode of emplacement into lava flows and lava domes units characterized by petrographic, chemical and isotopic differences: lava flows are calcalkaline, whereas lava domes mostly belong to a high-K calcalkaline series and are, on average, more LREE- and 87Sr-enriched. Lava domes are more porphyritic, with a phenocryst assemblage dominated by amphibole, whereas plagioclase and clinopyroxene are the most abundant phenocryst phases in lava flows, pointing out that evolution of dome magmas occurred in conditions of slightly higher pressure, favouring the crystallization of hydrous phases.The Karabakir Formation, previously reported as late Miocene- Pliocene, encloses Mazgirt volcanics and is capped by Tunceli basalts. These new age data constrain the Karabakir Formation emplacement from early to late Miocene.The evolution of this igneous activity mirrors the geodynamic framework of the region: the early-middle Miocene Mazgirt volcanics represent arc volcanism related to Eurasia-Arabia convergence. The late Miocene Tunceli basalts postdate the onset of post-collisional tectonics in Eastern Anatolia, whereas the Karakocan and Elazig volcanic rocks were emplaced after the initiation of strike-slip motion on the North Anatolian and East Anatolian Fault systems.