Range Of Isotopic Compositions Research Articles

Decoding paleomire conditions of paleogene superhigh-organic-sulfur coals

Superhigh-organic‑sulfur (SHOS) coals (coals with organic sulfur content >4 wt%) are unique coal deposits found at a few notable locations in the world. Specific peat accumulation and preservation conditions must be met to form SHOS coals. Organic sulfur is a major constituent of such coals, and it may have various sources depending on the prevailing paleomire conditions. Understanding such paleomire conditions sheds light on the formation mechanisms of SHOS coals. This investigation decodes the paleomire conditions of the Paleogene SHOS coals from Meghalaya, India, using sulfur isotopic compositions (δ34S) of organic sulfur (δ34SOS) and pyritic sulfur (δ34SPy) along with organic petrography, pyrite morphology and trace element ratios. Thirty coal samples were collected from the Jaintia Hills in the east, Khasi Hills in the middle, and Garo Hills in the west of Meghalaya. The organic sulfur content in the Garo, Khasi, and Jaintia coals varies from 1.0 to 3.3 wt%, 1.4 to 13.8 wt%, and 1.0 to 7.2 wt%, respectively. Further, after separation from pyritic sulfur and sulfate sulfur phases, the organic sulfur content ranges from 54.4 to 69.2%, 63.8 to 79.9%, and 59.3 to 73.8%, in the Garo, Khasi, and Jaintia Hills, respectively, suggesting the SHOS nature of these coal samples. The δ34SPy varies from −29.3 ‰ to +5.7 ‰, −21.3 ‰ to +27.3 ‰, and −12.1 ‰ to −4.3 ‰, in the Jaintia, Khasi, and Garo Hills, respectively, while the δ34SOS fluctuates from −4.6 ‰ to +3.7 ‰, −9.3 ‰ to +7.8 ‰, and − 9.0 ‰ to −5.0 ‰, respectively. The δ34S values of pyrite and organic sulfur (OS) in Jaintia coals are 34S depleted compared to seawater sulfate (+22 ‰), leading to fractionations in the range of −51.3 ‰ to −16.3 ‰ (mean − 31.6 ‰) and − 26.6 ‰ to −18.3 ‰ (mean − 23.1 ‰) for pyritic and organic sulfur (OS), respectively. Pyrite in Khasi coals show a relatively heavier δ34S composition averaging at −20.5 ‰, whereas organic sulfur (OS) isotope compositions range from −31.3 ‰ to −14.2 ‰ with a mean of −22.6 ‰. Pyrite and OS in the Garo coals are depleted compared to seawater sulfate. Isotope variations in the Jaintia, Khasi, and Garo coals indicate microbial sulfate reduction (MSR) of seawater sulfate. Large isotopic fractionations between Eocene seawater sulfate and pyritic sulfur (Δ34SSO4Eocene – pyrite = up to −51.3 ‰; mean − 31.6 ‰) in Jaintia coals indicate their possible formation in the water column/near the sediment-seawater interface (open system) and also hint toward dissimilatory sulfate reduction pathways that prevailed under anoxic redox conditions. However, mean values of Δ34SSO4Eocene – pyrite (−20.5 ‰) in the Khasi coals imply pyrite formation deeper in the sediments (more closed system) under dysoxic conditions. The dominance of OS over pyritic sulfur, framboidal pyrite, and its microcrystal size distributions in Jaintia coals may suggest syngenetic pyrite formation in open water reducing/anoxic conditions under paralic environments. Elevated Sr/Ba and U/Th values in these coals further confirm the anoxic conditions. Nevertheless, the presence of euhedral pyrite with the alleviated pyrite framboids in the Khasi coals and their complete absence in the Garo coals may suggest dysoxic-suboxic and suboxic-oxic depositional conditions, respectively. The isotopic signatures of the Garo coals suggest sulfur contribution from the parent paleobiota and MSR under a freshwater-oxic environment. Insignificant fractionations between δ34SPy and δ34SOS indicate limited iron and sulfate availability for additional sulfur cycling and disproportionation reactions, typical of oxic conditions. The absence of framboidal pyrite, elevated sulfate concentration, and mean Sr/Ba and U/Th values of 0.5 and 0.3, respectively, further suggest the freshwater peat deposition in the Garo Hills under limnotelmatic to telmatic freshwater conditions. Moreover, high inertinite content (Immf = 9.77–33.16 vol%), possibly induced by atmospheric peat exposure, supports the interpretation of suboxic-oxic paleomire conditions in Garo Hills. Gradually decreasing mineral matter content from Jaintia (mean 13.6 vol%) to Garo coals (mean 7.4 vol%) additionally projects a transition from mesotrophic brackish to freshwater limnotelmatic environment, complementing the shift in the paleomire condition from eastern (Jaintia) to western (Garo) Meghalayan Hills.

Magnesium isotope fractionation during magmatic differentiation in the lower continental crust

The Mg isotopic compositions display a significant disparity between the lower continental crust and the mantle. However, due to the limited availability of representative samples from the lower crust, our understanding remains incomplete regarding whether Mg isotope fractionation occurred during its formation and its potential influence on the observed isotopic differences. This study addresses this gap by presenting Mg isotopic data for juvenile lower crustal mafic xenoliths from Daoxian, Southeast China, providing new insights into this poorly understood process. The xenoliths, classified as websterites and two-pyroxene granulites, equilibrated at 818–912 °C and 10.6–15.4 kbar. They exhibit high Mg# (77–85), Cr (154–1451 ppm), and Ni (143–312 ppm), as well as trace element patterns resembling those of island arcs and evolved Sr–Nd–Pb isotopic compositions (87Sr/86Sri = 0.7046–0.7071; εNd(t) = −2.44 to +4.62; 206Pb/204Pbi = 18.379–19.017), indicating their derivation primarily from an enriched mantle source. Despite this, these xenoliths display a diverse range of Mg isotopic compositions. Websterite xenoliths exhibit mantle-like δ26Mg values (−0.27‰ to −0.29‰), indicating no influence from hybridized mantle source or pyroxene fractional crystallization/accumulation on their Mg isotopes. In contrast, granulite xenoliths show lower and variable δ26Mg values (−0.26‰ to −0.49‰), which positively correlate with Mg#, Cr, and V, but negatively correlate with Na2O + K2O, indicating that magmatic processes likely influenced Mg isotope fractionation in these samples. Petrological features, coupled with correlations between MgO and CaO/Al2O3, Cr, Co, and Ni, indicate that fractional crystallization and/or accumulation of olivine, spinel, clinopyroxene, orthopyroxene, and plagioclase played crucial roles in the formation of the granulite protoliths. Furthermore, the segregation of spinel during magmatic differentiation could have enriched residual melts in light Mg isotopes inherited by the cumulate Cpx + Opx + Pl (i.e., the granulite protoliths). Overall, the weighted average δ26Mg value of the lower crust in South China is estimated to be −0.36 ± 0.06‰. This finding, together with previous studies on granulite xenoliths in North China and Australia, strongly indicates heterogeneous Mg isotopic compositions in the lower continental crust relative to the mantle.

Li-mineralized pegmatite of anatectic origin: Constraints from Li[sbnd]Hf isotopes and geochemical modeling

Pegmatites are important reservoirs of lithium resources. There is an ongoing debate as to whether Li-mineralized pegmatites were generated from evolved granitic systems via extreme differentiation or by direct melting of metasedimentary rocks. The Chinese Altay is one of the largest pegmatite provinces in the world, and includes many rare-metal pegmatites (e.g., Koktokay, Kelumute, Kaluan and Azubai). However, they display significant differences in formation ages and isotopic compositions compared with the neighbouring or potential parental granites. In this contribution, we present a case study of the Kaluan Li ore deposit in the Chinese Altay, elucidating the origins of pegmatites and related Li mineralization. The Kaluan Li-mineralized pegmatites are characterized by high SiO2, K2O, Na2O, Li, Cs, Ta, and Rb contents; low Fe2O3T, MgO, Ba, and Sr contents; and peraluminous signatures. They have homogeneous HfLi isotopic compositions (εHf (t) = −0.6 to +2.5; δ7Li = +1.6 to +5.8‰) that are within the range of HfLi isotopic compositions of the Kulumuti Group schists (εHf (t) = −2.8 to +7.5; δ7Li = −8.6 to +10.8‰). In addition, the chemical compositions of the melt derived from the partial melting of the Kulumuti Group by phase equilibrium modeling are compatible with our analyses of the Kaluan Li-mineralized pegmatites. These similarities suggest that the Kaluan Li-mineralized pegmatites were derived from the partial melting of the Kulumuti Group schists at depths during the Triassic, in a post-orogenic and extensional setting. The generation of these pegmatites was mostly controlled by biotite dehydration melting at relatively high temperatures, rather than by the low-temperature melting of muscovite. Trace elements modeling results show that approximately 33–36% partial melting of the average Kulumuti Group schist may produce melts with maximum Li concentrations ranging from 664 to 751 ppm. Subsequently, a high degree of fractionation exceeding 85%, was required for the Li concentration of the residual melt to reach concentrations suitable for crystallization into albite-spodumene pegmatites. Based on our research, an anatectic origin model may have general applicability in explaining the genesis and mineralization of rare-metal pegmatites in the Chinese Altay.

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.

Oxygen isotopic compositions of fresh rooftop micrometeorites from the Budel collection—Insights into the contemporary cosmic dust flux

AbstractCosmic dust particles originate from a wide variety of solar system and interstellar objects, including sources not identified among meteorite collections. Particles that survive atmospheric entry are retrieved on the Earth's surface as micrometeorites. The recovery of these micrometeorites has recently advanced to rooftop sites. Here, we present the results of an extensive isotopic study on this type of rooftop micrometeorite from the Budel collection, the Netherlands, accreted to the Earth between October 31, 2018 and June 16, 2021. The triple oxygen isotopic compositions of 80 silica‐dominated cosmic spherules (CSs) with diameters ranging between 105 and 515 μm are obtained relying on 213 in situ spot analyses determined using ion microprobe. Our analyzed population spans a large range of isotopic compositions and is dominated by carbonaceous chondritic sources. In situ measurements on several CSs support a possible continuum between 16O‐rich and 16O‐poor compositions following the CM mixing line, showing that 16O‐poor CSs may be genetically related to aqueously altered carbonaceous chondrites. We demonstrate that weathering in the terrestrial environment has negligible effects on the isotopic compositions of the studied CSs and attempt to quantify the effects of kinetic mass‐dependent fractionation and admixture of terrestrial oxygen during atmospheric entry. The results further corroborate previously suggested relations between CS texture and the duration and intensity of the heating pulse experienced during atmospheric deceleration. Finally, the young and well‐constrained terrestrial age of the collection provides insights into the most recent flux of cosmic dust. Our results indicate no major recent changes in the global flux compared with collections sampled over thousand‐ to million‐year time scales and demonstrate that 16O‐poor material is still represented in the modern‐day cosmic dust flux at a relative abundance of ~13%–15%. As such, rooftop micrometeorites represent a valuable reservoir to study the characteristics of the contemporary cosmic dust flux.

Two common pitfalls in the analysis of water-stable isotopologues with cryogenic vacuum extraction and cavity ring-down spectroscopy.

Water stable isotopologue analysis is widely used to disentangle ecohydrological processes. Yet, there are increasing reports of measurement uncertainties for established and emerging methods, such as cryogenic vacuum extraction (CVE) or cavity ring-down spectroscopy (CRDS). With this study, we investigate two pitfalls, that potentially contribute to uncertainties in water-stable isotopologue research. To investigate fractionation sources in CVE, we extracted pure water of known isotopic composition with cotton, glass wool or without cover and compared the isotopologue results with non-extracted reference samples. To characterise the dependency of δ2H and δ18O on the water mixing ratio in CRDS, which is of high importance for in-situ applications with large natural variations in mixing ratios, we chose samples with a large range of isotopic compositions and determined δ2H and δ18O for different water mixing ratios with two CRDS analysers (Picarro, Inc.). Cotton wool had a strong fractionation effect on δ2H values, which increased with more 2H-enriched samples. δ2H and δ18O values showed a strong dependency on the water mixing ratio analysed with CRDS with differences of up to 34.5‰ (δ2H) and 3.9‰ (δ18O) for the same sample at different mixing ratios. CVE and CRDS, now routinely applied in water stable isotopologue research, come with pitfalls, namely fractionation effects of cover materials and water mixing ratio dependencies of δ2H and δ18O, which can lead to erroneous isotopologue results and thus, invalid conclusions about (ecohydrological) processes. These practical issues identified here should be reported and addressed adequately in water-stable isotopologue research.

A laser–laser method for carbonate C and O isotope measurement, metrology assessment, and stratigraphic applications

The stable isotopic compositions of carbon and oxygen (δ13Ccarb and δ18Ocarb) measured from carbonates are widely used in geology, notably to reconstruct paleotemperatures and the secular evolution of the biogeochemical carbon cycle, to characterize limestone sediment diagenesis, and to provide chemostratigraphy records. The standard technique used since the mid-20th century to measure C and O isotopic ratios is based on a wet chemical acid digestion protocol in order to evolve CO2 from carbonates—the latter being analyzed by mass spectrometry and, more recently, infrared spectroscopy. A newly developed laser-based method aims to circumvent this chemical preparation step by producing CO2 via an instant and spatially resolved calcination reaction. We describe an evolution of the laser calcination benchtop system previously described and used as a proof of concept toward a portable system, and we present the efficiency of this tool for performing carbon and oxygen isotope measurements from carbonate matrixes following standard evaluation metrology protocol. This metrological study explores the following: i) the use of internal standards; ii) inter-calibration with the traditional acid chemical preparation method; iii) analysis of the uncertainties of using GUM and ANOVA. Using 15 different types of carbonate minerals encompassing a range of isotopic VPDB compositions between −18.6‰ and +16.06‰ and between −14.80‰ and −1.72‰ for δ13Ccarb and δ18Ocarb, we show that isotopic cross-calibration is verified for both carbon and oxygen, respectively, and we demonstrate that the uncertainties (1σ) of the δ13Ccarb and δ18Ocarb measurements of laser–laser isotopic analysis are within 0.41‰ and 0.68‰, respectively. The advantages of this method in saving time and spatially resolved and automated analysis in situ are demonstrated by high-resolution chemostratigraphic analysis of a laminated lacustrine travertine sample.

Silver isotope analysis and systematics of native gold from the Rajapalot Co-enriched gold deposit, Finnish Lapland

Silver is probably the closest isotopic proxy to track monoisotopic gold and has been shown to have great potential to yield new information on the origin and enrichment processes of gold. This study describes the development of a tailored analytical protocol for accurate analysis of Ag isotopes and provides the first Ag isotope data for the Paleoproterozoic Rajapalot Au-Co deposit, Finnish Lapland. Six native Au samples yield ε109Ag values (relative to NIST SRM 978a) from −6.8 to +2.1 and are within the range of Ag isotopic compositions reported for native Au samples. The mean of the analyzed Au samples is ε109Ag = −3.8 ± 1.7 (2SD) with most of the samples with negative ε109Ag values (−6.7 to −2.0); one sample has a positive ε109Ag value of +2.1 ± 0.5. Silver isotope fractionation in the Rajapalot Au deposit was likely associated with physicochemical processes related to deposition and/or re-mobilization of the ore rather than with source region inheritance. It is suggested that redox reactions involving Ag+ ↔ Ag0 phase change primarily account for the isotopic differences within the deposit. Our results also suggest that the Rajapalot Au-Co deposit was formed via multistage ore-forming processes and/or that the primary ore was re-mobilized, which caused isotope fractionation along fluid pathways. Silver isotope variation within a deposit may mark a fractional crystallization trend with the lightest isotopic composition representing the earliest precipitate. Hence, Ag isotopes show potential as an isotopic vectoring tool in search of Au-enriched domains.

Early Eocene Arctic volcanism from carbonate-metasomatized mantle

Melilitite, nephelinite, basanite, and alkali basalt, along with phonolite differentiates, form the Freemans Cove Complex (FCC) in the south-eastern extremity of Bathurst Island (Nunavut, Canada). New 40Ar/39Ar chronology indicates their emplacement between ~ 56 and ~ 54 million years ago within a localized extensional structure. Melilitites and nephelinites, along with phonolite differentiates, likely relate to the beginning and end phases of extension, whereas alkali basalts were emplaced during a main extensional episode at ~ 55 Ma. The melilitites, nephelinites, and alkali basalts show no strong evidence for significant assimilation of crust, in contrast to some phonolites. Partial melting occurred within both the garnet- and spinel-facies mantle and sampled sources with He, O, Nd, Hf, and Os isotope characteristics indicative of peridotite with two distinct components. The first, expressed in higher degree partial melts, represents a relatively depleted component (“A”; 3He/4He ~ 8 RA, εNdi ~ + 3 εHfi ~ + 7, γOsi ~ 0). The second was an enriched component (“B” 3He/4He < 3 RA, εNdi < – 1 εHfi < + 3, γOsi > + 70) sampled by the lowest degree partial melts and represents carbonate-metasomatized peridotite. Magmatism in the FCC shows that rifting extended from the Labrador Sea to Bathurst Island and reached a zenith at ~ 55 Ma, during the Eurekan orogeny. The incompatible trace-element abundances and isotopic signatures of FCC rocks indicate melt generation occurred at the base of relatively thin lithosphere at the margin of a thick craton, with no mantle plume influence. FCC melt compositions are distinct from other continental rift magmatic provinces worldwide, and their metasomatized mantle source was plausibly formed synchronously with emplacement of Cretaceous kimberlites. The FCC illustrates that the range of isotopic compositions preserved in continental rift magmas are likely to be dominated by temporal changes in the extent of partial melting, as well as by the timing and degree of metasomatism recorded in the underlying continental lithosphere.

Assessing earlywood-latewood proportion influence on tree-ring stable isotopes

Tree-ring stable isotopes are typically measured in latewood cellulose to mitigate potential carry-over effects from previous year storage pools. The isotopic composition of individual tree-ring segments is thought to include considerable intra-annual variability. This sampling strategy may be complicated by steep intra-annual isotope gradients that can rival the inter-annual variability, however. Consistent sampling of latewood material may not always be possible due to low sample availability or high prevalence of narrow rings or low amounts of latewood because of species-specific changes in ring width. Therefore, years that contain samples with higher portions of non-latewood (earlywood) material may influence the final chronology of isotopic variability. Here, we analyze the potential influence that changing earlywood and latewood components of individual tree rings can have on stable carbon and oxygen records from Quercus spp. and Pinus heldreichii chronologies. Analysis of stable isotopes in oak tree rings with varying amounts of latewood show no statistically significant differences in the range of isotopic composition, nor any major differences when considering the same calendric year. Similar results were found for the pine data, when comparing stable isotope measurements with earlywood-to-latewood ratio and maximum density. We argue that this simple approach should be applied to any long-term tree-ring stable isotope record in order to provide a better understanding of the potential biases that could arise from previously recorded intra-annual variability in the wood.

Subcretion of altered oceanic crust beneath the SW São Francisco Craton, Brazil – A stable isotope study on diamonds and their inclusions

The presence of diamonds of lherzolitic, eclogitic and websteritic paragenesis in proximal alluvial deposits on the southwestern edge of the São Francisco Craton documents the incorporation of subducted oceanic crust and associated metasomatism through slab dehydration fluids affecting the local SCLM. To better constrain the subduction-association of diamond substrates and metasomatic events, we conducted a combined study of the δ13C-δ15N-[N] characteristics of 81 diamonds and the δ18O values of four of their eclogitic garnet inclusions. Diamond carbon isotope compositions range from −25.5 to +0.5‰, with 13C-depleted diamonds (≤ −7‰) being exclusively of eclogitic/websteritic paragenesis while the 13C-enriched (≥ −2‰) tail of the distribution is related to diamonds with lherzolitic inclusions. Nitrogen isotope values range from −14.2 to +25.5‰, with about half of the values being positive. A general absence of coherent trends in δ13C-δ15N-[N] across growth zones implies that diamond formation did not occur under fluid-limited conditions. Instead, the observed heterogeneity in carbon and nitrogen isotope compositions reflects contributions of distinct source reservoirs hosted in both altered oceanic crust and Earth's mantle. Nitrogen contents peak around a δ15N value of −3.5‰, indicating that more N-rich fluids, presumably representing a primitive endmember composition, have a mantle-like δ15N signature. While positive and negative δ15N values occur equally near the δ13C mantle value (−5 ± 2‰), 13C-depleted diamonds have nitrogen isotope compositions skewed towards positive values.13C depletion and 15N enrichment is a signature of biogenic carbonates/organic matter and low-T clays in uppermost, basaltic sections of oceanic crust that experienced low-temperature seawater alteration prior to subduction. Correspondingly, the oxygen isotope compositions of eclogitic garnet inclusions fall in a restricted range between +5.5‰ to +7.0‰. For three of the four samples, the stable isotope signatures of inclusions and host diamonds display perfect agreement, with the intensity of seawater alteration signatures, in the form of garnet inclusion 18O enrichment and host diamond 13C depletion and 15N enrichment, increasing together. For the fourth sample, the δ18O signature of the garnet inclusion (+5.5‰) and δ13C-δ15N signatures of the diamond host (−25 and + 19‰, respectively) are decoupled. While the mantle-like δ18O signature indicates a diamond substrate derived from deeper levels in oceanic crust (e.g., deep sheeted dikes), the diamond-forming fluids must have originated from sources that originally resided near the sea water interface. A viable mode of mixing such disparate isotopic signatures is the interaction of diamond-forming fluids derived from shallow oceanic crust altered at low-temperatures with eclogitized substrates originally formed in deeper levels of oceanic crust. This process likely occurred during diamond formation in a tectonic subduction mélange, which juxtaposes deeper and shallower levels of oceanic crust. In the lithospheric mantle above the subcreted oceanic slab, the elevated carbon isotope and highly variable nitrogen isotope compositions of diamonds formed in lherzolitic substrates likely relate to devolatilization and/or melting of principally oceanic sediments containing marine carbonates and clays and subsequent mixing with mantle-derived volatile components. In combination, our diamond and inclusion stable isotope data provide insight into multiple processes that promote diamond formation both inside subducted slabs accreted to the São Francisco cratonic keel and in adjacent subcontinental lithospheric mantle.

Origin of carbonatites and associated silicate rocks revealed by Mg triple-isotope approach

Carbonatites are rare carbonate-rich igneous rocks derived from carbon and carbonate-rich regions of Earth's mantle. Although a number of igneous processes are recognized to have controlled their compositions, the origin of the carbonate-rich nature of these magmas remains debated and has been linked to various mantle-related processes, including subduction and plume–lithosphere interaction. High-precision isotope measurements can provide insights into carbonatite petrogenesis, including the identification of subducted crustal material in their source region. In particular, combining mass-dependent and kinetically corrected Mg isotope data, also known as the triple-isotope approach, provides insights into mass fractionation processes driving mass dependent fractionation, which in turn allows to distinguish between equilibrium and kinetic processes. In this work, we report high-precision Mg stable isotope data for 59 carbonatites and associated silicate rocks from different localities and ages ranging from 3000 Ma to present-day, as well as C and O isotopic analysis for 38 carbonatites and Sr isotopic analysis for 41 carbonatites and silicate rocks. In addition, we also report Mg isotope data for 17 Phanerozoic carbonate rocks, with the aim of identifying the isotopic signature of carbonate-rich material potentially recycled to the carbonatite mantle source regions. Collectively, the data reveal a range of stable Mg isotope compositions from δ25/24MgDTS-2 = −1.20 ± 0.01‰ to +0.08 ± 0.01‰. We observe positive residual deviations after kinetic mass fractionation correction of the Mg isotope data for our carbonatites; an isotope signal that is also present in Phanerozoic carbonates. This observation establishes that a component of the Mg present in these samples experienced mass-dependent equilibrium isotopic fractionation processes, which are significantly larger at low temperatures. Given that the Mg results do not covary with C and O isotopic signals, the magnitude of the fractionation following the equilibrium law observed in carbonatites provides strong evidence for recycled material from the Earth's surface in the mantle source of Ca- and Mg-rich carbonatites. Furthermore, associated silicate rocks present mantle-like Mg isotopic compositions in contrast with the genetically linked carbonatites - based on the Sr isotopes - for some complexes, which is best explained if the carbonatites and associated silicate rocks represent distinct generation of partial melts of a mantle source containing recycled carbonate.

Formation and Evolution of Chromitites in the Hongshishan Complex, Beishan Orogenic Collage, NW China: Constraints from Mineralogical Compositions, Re‐Os Isotopes and Platinum‐Group Element Geochemistry

AbstractThe Hongshishan chromitite deposits are situated to the north of the Beishan orogenic collage, in the southern part of the Central Asian Orogenic Belt. This study describes the mineral chemistry, Re‐Os isotopes and platinum‐group elements geochemistry of the Hongshishan chromitites for the purpose of constraining the origin, evolution and composition of their parental melts. The restricted ranges of Al2O3, Cr2O3 and Cr#‐Mg# variation of chromite‐cores and chromites fall within the field of the mid‐ocean ridge and ophiolitic podiform chromite settings. The (187Os/188Os)i ratios of the chromitites are in the range of 0.12449–0.12745 (average 0.12637) and the γOs are from –1.92 to –0.06 (average –0.83). In the Re‐Os isotope diagrams, all the samples fall in the field of chromitites and show a residual peridotitic trend. The range of Os isotopic compositions and γOs values indicate that they overlap the depleted MORB mantle (DMM) as well as being close to global Os isotopic data and γOs of ophiolite chromitites. The characteristics of the PGE contents can be roughly subdivided into two groups: podiform chromitites and Ural‐Alaskan type complexes. For the ferritchromite cores, the calculated Al2O3 concentrations of the parental melt are higher (average 16.65 wt%) in high‐Cr than high‐Al chromitite (average 16.17 wt%) and for the chromite, the calculated Al2O3 concentrations are even higher (average 16.48 wt%) in the high‐Cr than the high‐Al examples (average 15.38 wt%). In the (TiO2)melt vs. TiO2 diagrams, most high‐Al melts fall in the MORB, while the high‐Cr melts fall in the ARC field. The calculated FeO/MgO ratios for the parental melt show the closest resemblance to a MORB magma composition. The inferred parental melt composition for studied chromitites falls in the field of mid‐ocean ridge basalt (MORB) magmas and far away from boninite. The calculated degrees of partial melting producing the chromitites are 16%–22% (average 19%), which is around the range of those of the MORB magmas. The chromitites are suggested to have been formed in a MORB setting. The chromites and ferritchromite cores are mostly scattered along the MORB and SSZ harzburgite–dunite fields. Ferritchromite rims and ferritchromites with high YFes formed as a result of alteration during serpentinization. .

Petrogenesis and Geodynamic Evolution in the Northern Westfjords, Iceland, Elucidated by Iceland's Oldest Silicic Rocks

AbstractIceland's oldest silicic rocks provide unique insight into the island's early crustal evolution. We present new zircon U‐Pb ages bolstered with zircon trace element and isotopic compositions, and whole rock Nd, Hf, and Pb isotope compositions, from three silicic magmatic centers—Hrafnsfjörður, Árnes, and Kaldalón—to understand the petrogenesis of large silicic volcanic centers in the northern Westfjords, Iceland. Our data confirm Hrafnsfjörður as the oldest known central volcano in Iceland (∼14 Ma) and establish an older age for Árnes (∼13 Ma) than previously estimated. We also report the first U‐Pb zircon dates from Kaldalón (∼13.5 Ma). Zircon oxygen isotope compositions range from δ18O∼+2 to +4‰ and indicate involvement of a low‐18O component in their source magmas. Hrafnsfjörður zircon Hf (mean sample εHf ∼ +15.3–16.0) and whole rock Hf and Nd (εHf = +14.5 to +15; εNd = +7.9 to +8.1) isotopic compositions are more radiogenic than those from Árnes (zircon sample εHf ∼ +11.8–13; whole rock εHf = +12.8 to +15.1; εNd = +7.3 to +7.7), but Hrafnsfjörður whole rock Pb isotope compositions (208/204Pb = 37.95–37.96; 206/204Pb = 18.33–18.35) are less radiogenic than those from Árnes (208/204Pb = 38.34–38.48; 206/204Pb = 18.64–18.78). Kaldalón has zircon Hf isotope compositions of εHf∼+14.8 and 15.5 (sample means). These age and isotopic differences suggest that interaction of rift and plume, and thus the geodynamic evolution of the Westfjords, is complex. Isotopic compositions of Hrafnsfjörður and Árnes support involvement of an enriched mantle (EM)‐like mantle component associated with a pulsing plume that resulted in variable spreading rates and magma fluxes and highlight the heterogeneity of the Icelandic mantle.

Isotopic fractionation of chlorine and potassium during chloride sublimation under lunar conditions

The Moon is depleted in volatile elements and compounds, and lunar samples exhibit a wide range of Cl isotopic compositions, which is believed to result from the volatilization of metal chlorides (e.g., NaCl, KCl, and FeCl2). However, the Cl isotopic fractionation behavior during volatilization is not well constrained, particularly for metal chlorides. Furthermore, the effect of metal chloride evaporation on metal isotopes is poorly known. In the present study, we performed NaCl and KCl sublimation experiments to study Cl and K isotopic fractionations at temperatures ranging from 923 K to 1061 K and at pressures of 7×10–5 bar to 1 bar in an N2 atmosphere. The isotope fractionation factors of 37/35Cl(αgas–solid) from NaCl sublimation experiments are 0.9985±0.0002, 0.9958±0.0004, and 0.99807±0.00004 at 1, 10–2, and 7×10–5 bar, respectively. Those of 41/39K(αgas–solid) and 37/35Cl(αgas–solid) from KCl sublimation experiments are 0.99884±0.00004 and 0.9988±0.0003 at 1 bar, 0.9977±0.0002 and 0.9972±0.0003 at 10–2 bar, and 0.9989±0.0002 and 0.9989±0.0001 at 7×10–5 bar, respectively. Chlorine and K isotopes fractionate more at 10–2 bar than at 7×10–5 bar and 1 bar. The saturation index in all the sublimation experiments was >95%, which resulted in near-equilibrium isotopic fractionation at the sublimation interface. Therefore, the isotopic fractionation was controlled by mass transfer processes in the gas and solid phases. The isotopic fractionation at 10–2 bar was controlled by the chemical diffusion of sublimated gas in an N2 atmosphere with almost no convection effect, (i.e., Pe number close to zero), whereas the isotopic fractionation at 1 bar was suppressed by atmospheric convection with a turbulence factor of 0.4±0.1 (i.e., Pe number >1). The extremely high sublimation rate and the very slow diffusion in the sublimating solid at 7×10–5 bar suppressed isotopic fractionations. Based on our experimental results, calculations using Cl/K and Na/K in lunar materials reveal that degassing of KCl contributed very little (<0.2‰) to the K isotopic fractionation (>0.58‰) during lunar magma ocean degassing. The Cl isotopic fractionation factor from lunar samples is similar to our results at 10–2 bar. This similarity of Cl isotope fractionation indicates that there may have been a transient atmosphere above the lunar magma ocean.

Assessing the Impact of Holocene Climate Change on Bioavailable Strontium Within the Nile River Valley

The impact of the climate drying during the Holocene within the Nile River Valley System (NRVS) has been the focus of recent debate in the archaeological community. It is argued that the increased contribution of aeolian material from the neighboring Sahara Desert during the last ~7,000 years has changed the isotope compositions of bioavailable Sr relative to the geological background and thus hinders provenance investigations of human remains within the NRVS. This study reports new trace element and strontium (Sr), neodymium (Nd), and lead (Pb) isotope compositions for a combined total of 125 samples consisting of human tooth enamel and various faunal samples from different time periods, and present-day botanical samples from 11 archaeological sites along the NRVS. The new isotope data combined with published data do not support a time-dependent increase in a Saharan aeolian bioavailable Sr component during the Holocene within the NRVS; in general, Sr isotope compositions for human enamel samples match those of their corresponding faunal matrices, and these define a similar range of isotope compositions over the various time periods. The Nd and Pb isotope compositions for human tooth enamel reported here also support the limited contribution of Saharan aeolian dust within the NVRS.

A fluid inclusion and stable-isotope study of hydrothermal vein mineralization, Schwarzwald district, Germany

A combined fluid inclusion and stable isotope study has been carried out on over 180 individual samples from 89 post-Variscan hydrothermal veins (Pb-Zn-Cu-bearing fluorite-barite-quartz veins, Co-Ni-Ag-Bi-U-bearing barite-fluorite-quartz veins and barren barite-fluorite-quartz veins) from the Schwarzwald district, Germany. The salinities of fluid inclusions in post-Variscan primary fluorite, calcite, barite and quartz are in the range of 22–25 wt.% equivalent (eqv.) NaCl, and the eutectic temperatures range between –57 and –45°C, indicating the presence of H2O-NaCl-CaCl2 fluids. Homogenization temperatures vary from 130 to 180°C. A low-salinity fluid (0 to 15 wt.% eqv. NaCl) was observed in some late stage fluorite, calcite and quartz samples, which were trapped similar temperature, range of high salinity fluids.&#x0D; Raman microprobe analyses show that the only detectable volatile in the vapour is CO2. Almost all δ18O (n=86) measurements of quartz from the fluorite-bearing post-Variscan veins range between +11.1 and +20.9 ‰. The calculated δ18OH2O values are between –11.0 and +4.4 ‰, using known quartz-water fractionation and fluid inclusion homogenization temperatures. The δ18OH2O values of directly extracted fluid inclusion water of fluorites range from –11.6 to +1.1 ‰, very consistent with the calculated values. The δD values of fluid inclusion water in calcites (extracted from primary and late calcite samples) lie in a narrower range between –26 and –15 ‰. The extracted fluid inclusion water from quartz samples has significantly more variable δD values between –63 and +9 ‰. The δ13C and δ18O values of fluid inclusion gas (CO2) range between –21.4 and –6.7 ‰ and between –16.3 to –7.1 ‰, respectively.&#x0D; Calculations for fluorite-barite-quartz veins combining oxygen isotope equilibria with microthermometric data result in quartz precipitation temperatures of 120–170°C at pressures between 0.3 to 0.5 kbar. The δ18OH2O and δD data, particularly the observed wide range in hydrogen isotopic compositions, indicate that the hydrothermal mineralization formed through large-scale mixing of a basement-derived saline NaCl-CaCl2 brine with meteoric water.

High-precision Pb isotopes of drinking water lead pipes: Implications for human exposure to industrial Pb in the United States

Millions of lead (Pb) pipes are still used in the drinking water distribution systems in many regions in the world. Human exposure to Pb from contaminated drinking water continues to be of concern in the United States (U.S.), as illustrated by the widely publicized “Flint Water Crisis” in 2015. The Pb isotopic composition of Pb-pipes potentially can be useful to identify human exposure to Pb from lead service lines (LSLs). In addition, as the LSLs were likely manufactured from similar industrial Pb sources as other Pb objects and materials in the USA, the Pb-pipes isotope data can provide information about the overall isotopic composition of the U.S. industrial Pb.In this work we present high-precision Pb isotope data from Pb-pipes excavated from different U.S. municipalities. The Pb-pipes show an extremely wide range of Pb isotopic compositions, with 206Pb/204Pb ranging from 17.004 to 22.010, 207Pb/204Pb from 15.460 to 15.921, and 208Pb/204Pb from 36.687 to 41.120. The wide isotope range is observed even in a single town, suggesting that no regional Pb isotope patterns can be expected within the continental USA. However, the high-precision MC-ICP-MS Pb data form a clear linear trend that, depending on the context, can be used to identify human Pb exposure. Furthermore, as the linear trend is a result of utilization of Pb ores from different domestic and international sources and secondary recycling of metallic Pb, it is likely representative of the overall isotopic composition of the U.S. industrial Pb pool. Therefore, the identified trend is the most accurate isotope representation of the U.S. anthropogenic Pb at present and can be used as first-order evaluation to determine if a person with elevated blood Pb levels was exposed to U.S. industrial Pb sources.

Diverse assemblage of presolar and solar system materials in anhydrous interplanetary dust particles: Coordinated NanoSIMS and TEM analyses

A coordinated TEM and NanoSIMS isotopic imaging study of microtome sections of three anhydrous interplanetary dust particles (IDPs) revealed a diverse collection of primitive materials having disparate origins and histories. Presolar silicate grains that likely originated in asymptotic giant branch (AGB) stars were present in each IDP at abundances ranging from 140 (+320/-120) ppm to 2000 (+4600/-1700) ppm. A unique compound presolar grain was identified that consisted of a crystalline spinel core and amorphous silicate mantle having heterogeneous Fe content. This compound grain traces the changing conditions in the circumstellar region during condensation and is the first identified presolar spinel in an IDP. A presolar SiC grain, also rare in IDPs, was found to be enriched in 13C, 14N, and 28Si, consistent with mainstream SiC that originated in ∼ solar metallicity AGB stars. We determine presolar spinel and presolar SiC abundances of 760 (+1700/-630) ppm and 190 (+440/-160) ppm, respectively, in the individual IDPs.Two elongate whisker-like enstatite grains and one platy enstatite were found to have near-terrestrial O isotopic compositions (δ18O = -17 – 18 ‰) and show chemical evidence of equilibrium condensation from a high temperature gas. Two highly 16O-rich silicates with near-solar O isotopic compositions (δ18O = -79 ‰ and -83 ‰) were also identified and may represent the primordial dust reservoir. These silicates were crystalline equilibrated aggregates. The wide range of isotopic compositions observed in these silicate grains suggests they condensed from isotopically diverse reservoirs in the protoplanetary disk in different locations and/or times. The 16O-rich grains likely condensed in the inner solar system and were subsequently transported to the outer solar system, while grains having terrestrial O isotopic compositions likely condensed from the gas phase in the terrestrial planet forming region or beyond.The IDPs showed bulk 15N enrichments (δ15N = 15 – 129 ‰) and contained 15N-rich hotspots up to 1150 ‰, consistent with the presence of molecular cloud material. IDPs U2015D21 and W7013E17 had bulk O isotopic compositions that were offset from the carbonaceous chondrite anhydrous minerals line by ∼ 10 ‰ to more 17O-rich compositions. This 17O enrichment cannot be explained by the observed abundance of 17O-rich presolar grains in these particles and the source remains unknown. IDP W7027E6 had an unusual isotopically heavy bulk O isotopic composition (δ17,18O = 40 ‰, Δ17O = 19 ‰). W7027E6 lacked hydrous phases and was therefore not likely altered by isotopically heavy primordial water. We propose that the high temperature mineral assemblage in W7027E6 condensed in the inner solar system from an 16O-poor reservoir that existed prior to O isotope homogenization in the early nebula and was subsequently transported to the outer solar system.

Geochemical and Sr-Isotopic Study of Clinopyroxenes from Somma-Vesuvius Lavas: Inferences for Magmatic Processes and Eruptive Behavior

Somma-Vesuvius is one of the most dangerous active Italian volcanoes, due to the explosive character of its activity and because it is surrounded by an intensely urbanized area. For mitigating the volcanic risks, it is important to define how the Somma-Vesuvius magmatic system worked during the past activity and what processes took place. A continuous coring borehole drilled at Camaldoli della Torre, along the southern slopes of Somma-Vesuvius, allowed reconstructing its volcanic and magmatic history in a previous study. In this work, the wide range of chemical (Mg# = 92–69) and isotopic (87Sr/86Sr = 0.70781–0.70681) compositions, collected on single clinopyroxene crystals separated from selected lava flow units of the Camaldoli della Torre sequence, have been integrated with the already available bulk geochemical and Sr-isotopic data. The detected chemical and isotopic signatures and their variation through time allow us to better constrain the behavior of the volcano magmatic feeding system, highlighting that mixing and/or assimilation processes occurred before a significant change in the eruptive dynamics at Somma-Vesuvius during a period of polycyclic caldera formation, starting with the Pomici di Base Plinian eruption (ca. 22 ka).