Stable Isotope Composition Research Articles

Geographic variability of carbon and nitrogen isotope ratios of nonvolant terrestrial small mammals (Rodentia) across 3 Brazilian biomes

Abstract In this study, we investigated landscape variability of the carbon and nitrogen isotopic composition of nonvolant small mammals in the 3 main Brazilian biomes (Amazon, Atlantic Forest, and Cerrado) while also considering the differential spatial distribution of C4 plants in these biomes. We compiled a subset of data on stable carbon and nitrogen isotope ratios from nonvolant small mammals of the order Rodentia and compared the aggregated isotopic variability at the biome level using classical δ13C–δ15N biplot. The concept of isotopic niche width was used to test whether different foraging attributes drive their isotopic composition, while a Bayesian isotopic mixing model was used to estimate the proportion of 3 main food categories available to these small mammals. We also developed isoscapes in the Brazilian biomes, interpolating animals δ13C and δ15N based on the geographic coordinates of each sample and “sourcescapes” considering geographic variation of the dietary sources. The findings of this study advance our understanding of the foraging ecology of small mammals in biodiversity-rich regions of the Neotropics. Classical methodologies such as stomach content confirmed dietary choices revealed by the stable isotopic composition and also highlighted the importance of C3 and C4 plants in the diet of this group of animals, especially in biomes such as the Atlantic Forest and Cerrado, where there is a predominance of highly altered landscapes. These results confirm that replacing the original vegetation with C4 crops has altered the feeding patterns of small mammals, which could lead to critical ecological changes in the trophic structure of these areas. Vertical stratification of the dietary niche and the interaction between biome and foraging lifestyle were also observed. However, in each biome, there was significant intraspecific and interspecific variation caused by preferences for ingestion of plant and animal material, leading to different degrees of omnivory. Finally, the high local variability between individuals and species requires a larger sampling design that may also contribute to improved spatial resolution of the isoscapes.

Improved Standard Addition Method for Measuring Stable Isotopic Compositions and Its Application to Sulfur Isotope Composition.

The standard addition method (SAM) is widely used to measure the isotopic compositions of natural samples, particularly those with a complex matrix. However, traditional SAM has limitations for isotope systems with significant variations in isotope composition due to its reliance on approximation in calculation and the requirement for a priori estimates of analyte isotopic compositions and accurate concentrations. To overcome the issues, our work proposes an improved SAM that explicitly calculates isotope ratio R (i.e., XE/YE, 34S/32S for example) instead of approximating R* (mass number of isotope X divided by total mass number of all isotopes of an element) with R in SAM. Additionally, the sample fraction within standard-sample mixture in improved SAM is determined using the isotope compositions of standards, sample-standard mixtures, and the mixtures of both standards, rather than relying on sample concentrations and volumes. Both improvements not only overcome the shortcomings of traditional SAM but also empowered the approach's ability to accurately determine sample concentrations. To validate its effectiveness, we applied the improved SAM to natural samples with substantial sulfur (S) isotope variation (1.94 to 27.19‰) and low S concentration (0.81 to 3.47 μg g-1). The calculated δ34S values and concentrations of these samples are consistent with direct measurements within the error ranges while reducing sample sizes to 20% of those required for direct measurement. Moreover, our method achieves higher accuracy in δ34S values compared with traditional SAM. Both comparisons affirm the reliability and superiority of improved SAM.

A cross-regional examination of camelid herding practices in Peru from 900 BCE to 1450 CE: Insights from stable isotopes in camelid bone collagen and fiber.

The economic, socio-political, and cultural significance of camelids in the Andean region is well-recognized, yet an understanding of their management evolution over pre-historical periods remains limited. This study aims to fill this gap by conducting the first cross-regional assessment of camelid pastoralism in Peru from 900 BCE to 1470 CE, using stable carbon and nitrogen isotopic compositions from the bone collagen and fibers of 577archaeological camelids across 21 sites. This research investigates the spatio-temporal shifts in camelid dietary habits, focusing on how the rise of intensive agriculture may have influenced change and led to the evolution of distinct roles for camelids in coastal versus non-coastal Andean economies. Our analysis indicates an increase in δ13C values over time on the coast, suggesting a shift towards maize-based camelid diets. Conversely, δ13C values decrease over time in highland environments, suggesting camelids consumed relatively more wild C3 forage and/or cultivated crops such as tubers. The study also reveals a significant positive relationship between latitude and δ15N values, suggesting increasing environmental aridity enriches δ15N in bone collagen. After controlling for this latitudinal effect, we observe a rise in δ15N values in both coastal and non-coastal camelids, suggesting that in later periods camelids may have been foddered in agricultural fields that were enriched with guano or dung fertilizer used to intensify production. Importantly, this research uncovers a distinct dietary divergence between coastal and inland camelids. The observed divergence in diets suggests contrasting socio-economic uses of camelids, where coastal camelids were predominantly involved in ceremonial and political activities, while those in non-coastal areas were crucial to the subsistence economy.

Trace element contamination biomonitoring: A comparative study between the polychaetes Alitta virens and Hediste diversicolor

Trace elements (TEs) remain of significant toxicological concern as many are critical for global decarbonisation. TEs accumulate in sediments so benthic polychaetes (e.g. Hediste diversicolor and Alitta virens) are highly relevant for ecotoxicology. However, ecological/biological differences could influence TE accumulation and biomonitoring suitability. Exploiting multiple sympatric populations (Solent, UK), we measure sediment and tissue concentrations generating EFs (enrichment factors), AEIs (Adverse Effects Indexes) and tissue bioaccumulation factors. We also assess stable isotope compositions to elucidate diet influences. Despite diverse anthropogenic activity in the Solent, the majority of TEs present low levels of sediment contamination at the sites. For Ni, Pb and As, a combination of mean AEIs >1 and some sediment concentrations exceeding SQVs (Sediment Quality Values) indicate a slight toxicological risk. For Cu and Hg, high EFs and AEI scores confirm they are the greatest risk, thus requiring source identification/control. However, only mean As tissue concentrations reflect contaminated sites, therefore, identifying the As-source(s) is also a priority. Sediment and tissue concentration relationships were generally negative and not significant for both species. Although a significant negative relationship for Cd for A. virens requires further investigation, the lack of evidence for TE bioaccumulation from sediment may limit both species' biomonitoring suitability for low-contamination sites. Species differences in tissue concentration were also TE specific: H. diversicolor had significantly higher concentrations for Ag, Cu, Hg, Ni and Zn, whilst the reverse was true for Cd, Fe, Cr and As. Whilst ecological differences and that feeding sources are site and species-specific (as evidenced by C, N and S stable isotopes analysis) cannot be ignored, the diverse tissue concentrations strongly suggest different TE regulation strategies per species. Together these data will be important for ecotoxicologists and regulators to select the ‘best’ polychaete biomonitor and assess TE toxicity under future global decarbonisation trajectories for TE inputs.

Intra-tooth isotopic analysis shows seasonal variability in the high-elevation context of Melka Kunture (Upper Awash Valley, Ethiopia) during the Early Pleistocene

In order to investigate seasonal changes in diet, environment and climate, we analyzed the stable carbon and oxygen isotopic composition of intra-tooth sequential profiles (14 teeth, 282 enamel samples) of Hippopotamidae, Equidae, Bovidae and Suidae from Melka Kunture, Upper Awash Valley, central Ethiopian Highlands (2000–2200 m a.s.l.).We found that during the Early Pleistocene, between 1.95 and 1 Ma, most of the analyzed hippos display a seasonally stable C4 diet, even if the δ13C values within hippos show a degree of variability that we interpret as the outcome of feeding on plants that use different C4 photosynthetic pathways. Several hippo specimens display a seasonal shift from C4 to mixed C3-C4 diets. The sampled equid, bovid and suid specimens recorded both stable C4 diets and mixed C3-C4 feeding with a seasonal progressive increase of δ13C values. When affected by seasonal changes, the serially analyzed taxa show different niche partitioning: hippos increase the consumption of C3 vegetation, whereas equids and suids include more C4 vegetation in their diets. The intra-individual δ18O variability in the analyzed taxa is interpreted as the outcome of different water sources, depending on animal habitat, behavior and mobility patterns.Our data are placed in controlled stratigraphic and chronological sequences and combined with the outcome of other proxies, allowing us to evaluate the site paleoecology comprehensively. We suggest that the central Ethiopian Highlands, where MK is located, possibly acted as a refugium-like area during the Early and Middle Pleistocene, characterized by a specific type of montane vegetation (DAF) and diverse faunal and hominin species that demonstrated their resilience and adaptability to changing environments and climates.

Mercury Stable Isotopes Reveal the Vertical Distribution and Trophic Ecology of Deep-Pelagic Organisms over the North-East Atlantic Ocean Continental Slope.

Deep-pelagic species are central to marine ecosystems and increasingly vulnerable to global change and human exploitation. To date, our understanding of these communities remains limited mainly due to the difficulty of observations, calling for complementary innovative tools to better characterize their ecology. We used mercury (Δ199Hg, δ202Hg, Δ201Hg, and Δ200Hg), carbon (δ13C), and nitrogen (δ15N) stable isotope compositions to segregate deep-pelagic species caught on the continental slope of the Bay of Biscay (NE Atlantic) according to their foraging depth and trophic ecology. Decreasing fish Δ199Hg values with corresponding depth estimates from the surface to down to 1,800 m confirmed that mercury isotopes are able to segregate deep species over a large vertical gradient according to their foraging depth. Results from isotopic compositions also identified different mercury sources, likely reflecting different trophic assemblages over the continental slope, in particular, the demersal influence for some species, compared to purely oceanic species. Overall, our results demonstrate how mercury stable isotopes can inform the vertical foraging habitat of little-known species and communities feeding in the deep.

Climate-driven peatlands development and vegetation dynamics in Northeastern China since the mid-Holocene: New evidence from Huanan peatlands

Studying peatland evolution and vegetation patterns in response to climate change provides valuable insights into future ecosystem trends. This study focuses on the Huanan peatland located in Changbai Mountain regions in Northeast China, utilizing phytolith analysis and stable carbon isotope composition (δ13C) to reconstruct late Holocene vegetation dynamics. Additionally, grain size, total organic carbon (TOC), and total nitrogen (TN) analyses were conducted to understand peatland development and paleoclimate since the late Holocene. The research identifies three distinct climate periods since 5500 cal yr BP: an initial warm, humid phase (5500–4000 cal yr BP) characterized by high river levels that formed lacustrine sediments; a subsequent transition to cold, dry conditions (4000–1500 cal yr BP) that initiated peat formation; and continued dry, cold conditions (1500 cal yr BP to the present) with sustained peat growth. Phytolith data reveal a dominant forest vegetation type since 2000 cal yr BP, further divided into three periods: 2000–1300 cal yr BP, marked by diverse and dense vegetation; 1300–750 cal yr BP, with declining plant cover; and 750 cal yr BP to the present, characterized by an increase in woody plants but a reduction in local grass cover.

The Cumulative Effect of Wintertime Weather Systems on the Ocean Mixed‐Layer Stable Isotope Composition in the Iceland and Greenland Seas

AbstractThe Iceland and Greenland Seas are characterized by strong heat fluxes from the ocean to the atmosphere during wintertime. Here we characterize the atmospheric signal of this strong evaporation in terms of water vapor isotopes and investigate if such a signal can have a cumulative imprint on the ocean mixed‐layer. Observations include continuous water vapor isotope measurements, event‐based precipitation samples, and sea‐water samples taken at various depths from the research vessel Alliance during the Iceland‐Greenland Seas Project cruise in February and March 2018. In conjunction with a simulation from a regional, isotope‐enabled atmospheric model, we find that the predominant atmospheric isotope signature during predominant marine cold‐air outbreak conditions is −129.8 ± 16.6‰ for δ2H and −18.10 ± 2.87‰ for δ18O, with a d‐excess of 15.1 ± 7.9‰, indicating enhanced non‐equilibrium fractionation compared to the global average. During events of warm‐air intrusion from mid‐latitudes, near‐surface vapor becomes saturated and the vapor d‐excess approaches equilibrium or becomes negative. Similarly, precipitation d‐excess is lower and thus closer to equilibrium conditions during warm‐air intrusions. There are indications that an evaporation signal of waters exiting the Nordic Seas through Denmark Strait could be locally enhanced over seasons to years, as supported by simple model calculations. Our findings thus suggest that evaporation signals could be transferred into the ocean isotope composition in this region, potentially enabling mass‐balance constraints in isotope‐enabled coupled ocean‐atmosphere models.

Microscale δ34S and δ18O variations of barite as an archive for fluid mixing and microbial sulphur metabolisms in igneous rock aquifers

ABSTRACT The stable isotope compositions of sulphur (δ34S) and oxygen (δ18O) in barite are frequently used as proxies for microbial sulphate reduction (MSR) in diverse environments, such as in relation to anaerobic oxidation of methane in marine cold seeps. There, isotopically heavy barite is used as a marker for MSR from a sulphate pool that has undergone semi-closed system conditions. Closed-system MSR is also a commonly observed feature in igneous rock hosted fracture aquifers, as shown by extremely 34S-enriched pyrite. What is less well-constrained is whether δ34S in barite can be used as a proxy for MSR in such systems. Here we explore the microscale heterogeneity of δ34S and δ18O via secondary ion mass spectrometry and the trace element Sr via LA-ICP-MS maps in barite precipitated in granite-hosted boreholes during a 17-year experiment, at Äspö, Sweden. We compare it with δ18Osulfate, δ34Ssulfate, and δ34Ssulfide of the fracture fluids and with paragenetic pyrite with δ34S values reflecting closed system MSR. The δ18O values in barite (+9.4 to +16.9 ‰) represent two generations of barite, one with low values and one with high values. The latter are likely impacted by sulphur disproportionating or -oxidizing bacteria. The barite reflects a much smaller span in δ34S (+14.5 to +28.6 ‰) than the pyrite (−47.2 to +53.3 ‰). This lack of extremely high δ34Sbarite values is proposed to be due to that barite saturation only occurred in the early parts of the Rayleigh cycle. Additionally, fluid migration has affected the δ34S values to lower values, accompanied by higher Sr concentrations. Taken together, barite δ34S values cannot be regarded as a reliable independent proxy for MSR in deep sulphate-poor igneous rock hosted aquifers. However, the relation between the δ34S values of coeval barite and pyrite is regarded as a useful proxy for MSR-related fractionation during early stages of MSR.

Tracking subduction-related metasomatism of the subcontinental lithospheric mantle using Ca-, O-, and H-isotopes

Mantle xenoliths provide effective records of the metasomatic processes that affect continental lithosphere evolution, such as interaction with subducted components or modification via small-degree melts. Correlations between major/trace element geochemistry with stable and radiogenic isotope compositions can help constrain the source and timing of this metasomatism. We report new δ18O, δ44/40Ca, and δD values for twelve kimberlite-hosted mantle xenoliths from the Slave Craton (NWT, Canada), which show varying degrees of metasomatism. The δ18O values of olivine (δ18Ool = +5.33 ± 0.13‰; 1σ; n = 12) overlap average mantle values. Clinopyroxene and garnet δ18O values (δ18Ocpx = +5.31 ± 0.10‰; δ18Ogrt = +5.37 ± 0.23‰; 1σ) extend below those reported in most mantle peridotites and are strongly correlated with clinopyroxene δ44/40Ca (avg. = +1.00 ± 0.10‰; 1σ) and garnet δ44/40Ca (avg. = +1.18 ± 0.19‰; 1σ) respectively, extending from typical mantle values to low δ18O and high δ44/40Ca values. In general, Δ18Ocpx-ol and Δ18Ogrt-ol (ranging from −0.19‰ to +0.19‰ and from −0.56‰ to +0.35‰, respectively) are lower than expected equilibrium values at mantle temperatures. Strong negative correlations are found between δ18Ogrt and Δ18Ogrt-ol and garnet major and trace element composition (Na2O, H2O, La/YbN). Furthermore, phlogopite-bearing kelyphitic rims have δD values (avg. = −126 ± 13‰; 1σ) lower than typical mantle values. Whole rock Sm-Nd model ages and oxygen isotope diffusion modeling suggest that metasomatism occurred during the Mesozoic, shortly before kimberlite entrainment, consistent with indications from diamond-forming fluids from the Slave craton. The combined low δ18O, δD, and high δ44/40Ca signature of the mantle peridotite xenoliths, along with the age constraints, suggest the metasomatic fluid/melt is sourced from a recycled oceanic crust component related to Mesozoic subduction in western North America.

Produced water geochemistry from hydraulically stimulated Niobrara Formation petroleum wells: Origin of salinity and temporal perspectives on treatment and reuse

Produced water (i.e., a mixture of returned injection fluids and geologic formation brines) represents the largest volumetric waste stream associated with petroleum production in the United States. As such, produced water has been the focus of intense study with emphasis on understanding the geologic origin of the fluids, environmental impacts of unintended or intentional release, disposal concerns, and their commodity (e.g., lithium) potential. However, produced water geochemistry from many active petroleum plays remain poorly constrained leading to knowledge gaps associated with the origin of brine salinity and parameters (e.g., radium levels) that can impact treatment, disposal, and possible reuse. Here we evaluate the major ion geochemistry, radium concentrations, and stable water isotope composition of ~120 produced water samples collected from 17 producing unconventional petroleum wells in Weld County, Colorado from the Late Cretaceous Niobrara Formation. This sample set encompasses eight produced water time series from four new wells across production days 0 to ~365 and from four established wells across production days ~1000 to ~1700. Additionally, produced water from nine other established Niobrara Formation wells were sampled at discrete time points ranging from day 458 to day 2256, as well as hydraulic fracturing input fluids. These results expand the available Niobrara Formation produced water geochemical data, previously limited to few wells sampled within the first year of production, allowing for the heterogeneity of major ions and radium to be evaluated. Furthermore, we explore the geochemical relationships between major ion ratios and stable water isotope composition to understand the origin of salinity in Niobrara Formation brines from the Denver-Julesburg Basin. These findings are discussed with perspective toward potential treatment and reuse of Niobrara produced water prior to disposal.

Long-term dynamics of dissolved oxygen and isotopic composition in Lake Erie and Lake Ontario: Implications for eutrophication and ecosystem health

This study, focusing on Great Lakes Erie and Ontario, Canada, explores dissolved oxygen (DO) dynamics and its stable isotopic composition (δ18ODO) in the Great Lakes. Using historical dissolved oxygen data from 1965 to 2021, combined with synoptic isotopic data collected in the early 2000s, the research examined the spatiotemporal trends in DO and δ18O-DO to assess the effects of biotic and abiotic processes such as photosynthesis, respiration, and atmospheric gas exchange. The study revealed significant seasonal and depth-related variations in DO levels, with hypolimnetic hypoxia and metalimnetic oxygen minima (MOM) observed in both lakes. With its comparatively shallow depth and higher nutrient loads, Lake Erie exhibited more pronounced dissolved oxygen fluctuations, with DO levels reaching as low as 3.65 mg L−1 and δ18ODO values falling below +24.6 ‰. These findings indicated Lake Erie’s more dynamic metabolic environment, particularly during the thermally stratified season. In contrast, Lake Ontario showed more stable oxygen concentration levels, with occasional dissolved oxygen depletions down to 6.80 mg L−1 and δ18ODO values up to +32.1 ‰, suggesting more localised influences of external inputs and biological processes. This study provides a long-term perspective on dissolved oxygen status in these lakes and offers essential insights into their ecological health. This work contributes valuable data for managing and protecting the Great Lakes ecosystem.

Late-stage evolution of hypogene caves at Tyuya-Muyun (Kyrgyzstan): Quantitative insights from mineral deposits

The Tyuya-Muyun massif in SW Kyrgyzstan hosts a number of caves some of which contain Ra- and U-bearing minerals that were extensively mined in the early 20th century. Previous studies have suggested that the caves of the Tyuya-Muyun have experienced a complex speleogenetic history, including epigene and hypogene processes. Here, we reconstruct the late stages of hypogene processes by studying subaqueous (calcite and barite spars, cave clouds), near-water table (rafts, folia) and vadose (flowstone) mineral deposits in Great Barite and Surprise caves. We determined the chronology (230Th dating), stable isotope composition (δ18O, δ13C and Δ47), and formation temperature (fluid inclusion microthermometry and Δ47) of these minerals and reconstructed the oxygen isotopic composition of the paleo-water (δ18Ow). In contrast to previous hypotheses about cave evolution, we found no evidence of an initial epigenic karst phase. The earliest mineral deposits suggest already hydrothermal conditions, with calcite and barite forming at ~40–50 °C prior to 600 ka. Cave clouds in Great Barite Cave mark the beginning of the lowering of the groundwater table and also record a decrease in water temperature from 29.7 ± 8.3 °C to 12.7 ± 5.6 °C, as shown by Δ47 thermometry. The latter temperature remained stable, within analytical uncertainties, during the past 600 ka, as indicated by Δ47 results of near-water table and vadose speleothems in Surprise Cave. At the same time, the decrease in δ18Ow suggests a reduced contribution of thermal water and an increased input of colder meteoric water. By around 540–450 ka Surprise Cave emerged from the phreatic zone, as indicated by 230Th ages of the highest folia and flowstone. This lowering of the water table continued until 84 ka and may have been related to the final uplift phase of the Tyuya-Muyun massif and the concomitant incision of the Aravan River forming the Dangi Gorge.

Freshwater Mussel (Unio pictorum) Shells Reveal Hydrological and Environmental Change From 1300 BC to the Present Day.

Preserved biological communities can provide baseline data about the historical ecosystems and environmental conditions that preceded recent anthropogenic alteration. Freshwater mussel shells show particularly good preservation, and the shell assemblages commonly found during archaeological excavations can offer insights into past ecosystems. We studied assemblages of Unio pictorum mussel shells from palaeochannel silts associated with the Late Bronze Age site of Must Farm in eastern England (c. 850 BC), on an ancient tributary of the modern-day River Nene. We compared archaeological shells from two sediment horizons (broadly 1300-700 BC) to live individuals collected from two analogous sites on the present-day Nene. Size and growth rate, interannual growth variability and stable isotope (δ18O and δ13C) composition were compared between the populations. Size and the von Bertalanffy growth parameter L∞ differed among all four populations. Mean lengths and L∞ were higher in the two modern populations (mean lengths 77.3 ± SE 0.8 and 73.8 ± SE 1.1 mm, L∞ 91.8 ± 5.4 and 79.0 ± 8.1 mm) than the ancient populations (mean lengths 58.1 ± SE 1.6 mm and 68.4 ± SE 0.9 mm; L∞ 71.5 ± 16.9 and 76.8 ± 6.2 mm). Modern individuals also showed greater variation in age-corrected year-to-year growth. δ13C was lower in modern shells (-11.8‰ for modern shells, -9.03‰ and -9.02‰ for ancient shell populations), potentially reflecting altered hydrological and nutrient regimes. δ18O and δ13C were positively correlated for all but one sampled ancient shell, but not modern shells. These results reflect changes in local environmental conditions, particularly the transition from a shallow, slow-flowing tributary to a deeper, canalised river with faster flow, as well as effects of anthropogenic nutrient enrichment. The findings demonstrate the importance of long-term data in studying anthropogenic ecosystem alteration and avoiding shifting baseline syndrome in conservation planning.

The use of combined C[sbnd]Mg isotope compositions of carbonates from orogenic Sb[sbnd]Au deposits as a tracer of fluid interaction with sea-floor altered crust

The Mesoarchaean Murchison Greenstone Belt is composed of a strongly deformed volcano-sedimentary succession metamorphosed up to amphibolite facies and surrounded by metaluminous and peraluminous granitoids in the north of the Kaapvaal Craton of southern Africa. A circa 40 km-long shear-zone of strongly carbonatised rocks (the Antimony Line, or Sb-Line) oriented along the main trend of the greenstone belt (WSW–ENE) hosts important Sb deposits with accessory Au. These commodities mostly occur as stibnite and native gold hosted by quartz‑carbonate rocks at the centre of the Sb-Line, underlining the importance of CO2-rich fluid flow for mineralisation during deformation and metamorphism.In this study, we compare the elemental and stable isotope (C-O-Mg) composition of carbonates from the Sb-Line with regionally distributed carbonates hosted by the volcano-sedimentary succession distal to mineralisation. The carbonates of the Sb-Line and regional rocks have overlapping major element compositions. Both magnesite and dolomite in most Sb-Line samples have marked light-REE-depleted patterns with variable positive Eu anomalies. Carbon isotope ratios define two clusters, with marked δ13C peaks at ca. -5 ‰ for Sb-Line rocks and ca. -2 ‰ for regional rocks, implying separate C-sources. The peak at ca. -2 ‰ likely represents early carbonatisation through sea-floor alteration, whereas the first peak at ca. -5 ‰ is indicative of deep CO2 (mantle, or magma-derived) introduced during tectonic activity of the Sb-Line. Magnesium isotope ratios of regional rocks reveal limited fractionation (bulk δ26Mg = −0.27 ± 0.10 ‰) that overlap with mantle values, but some carbonate-bearing veins present 26Mg-depleted compositions (bulk δ26Mg = −1.91 to −0.40 ‰). Sb-Line carbonated rocks have more fractionated Mg isotope compositions (bulk δ26Mg = −0.8 to 0.0 ‰) and carbonates display marked negative 26Mg values (δ26Mg from −1.46 to −0.31 ‰). We interpret these results in terms of preferential remobilisation of isotopically light Mg during fluid-rock interaction and dissolution of carbonate in the host-rocks. The lack of correlation between δ13C and δ26Mg indicates decoupling of these isotopic systems, implying contribution from isotopically distinct sources of C and Mg to the mineralised zone.Similar to other structurally controlled AuSb mineralisation in Archaean greenstone belts, metal transport and ore deposition in the Murchison Greenstone Belt was closely related to the deep cycle of carbon, linking C-draw-down during sea-floor alteration, carbonate re-mobilisation during metamorphism and CO2 degassing from deep sources along major crustal discontinuities. In contrast to models for orogenic AuSb deposits invoking a purely intra-crustal, metamorphic origin of mineralising fluids, our results underline the importance of deep-sourced fluids originating from an external source from the volcano-sedimentary succession.

Basin inversion, drifting and hyper-extension in the Central Atlantic Ocean and Maghrebian Tethys as fluid driving mechanisms for the superimposed base metal mineralization events in the Jbel Bou Dahar carbonate-hosted Pb-Zn-Ba deposits (High Atlas, Morocco)

The Early Jurassic Jbel Bou Dahar reef-bearing carbonate platform in the eastern High Atlas, Morocco, contains numerous carbonate-hosted and fault-controlled Pb-Zn-Ba deposits, prospects, and showings. Combined field, petrographic and geochemical data, including REE + Y analyses, stable (C-O-S), radiogenic (SrPb) and noble gas (He, Ne, Ar) isotopic compositions, record two temporally distinct metallogenic events. Both events are related to post-rifting and inversion of the inherited Mesozoic Atlas paleorift. The ore deposits are thought to have been formed during large-scale episodes of transtensional basin evolution, which developed as a far-field effect of the drifting of the Central Atlantic Ocean and Maghrebian Tethys while the basin continued to invert in response to the ongoing convergence between the African and the Eurasian plates. The paragenetically earliest Zn-rich ore was generated in a transtensional setting coincident with the hyper-extension of Maghrebian Tethys and the initial stages of drifting and formation of the Central Atlantic passive margin. Crustal extension and high heat fluxes provided by the hot upwelling mantle would have triggered buoyancy-driven convection of deeply sourced fluids and maturation of organic matter dispersed within the host carbonates to produce hydrocarbons within an extensional basin setting. These relatively reduced Zn-rich ore-forming fluids acquired metals mainly through protracted interaction with the country rocks including the underlying Triassic siliciclastic series and the granitic basement rocks. Regional ENE- to E-W-trending major faults would have acted as conduits for upward fluid flow and traps for Zn-Pb-Ba mineralization. Conversely, the late Pb-rich mineralization stage II is broadly constrained to have occurred between ca. 70 Ma and 10 Ma and is thought to be related to the transition from orogenic shortening (late Eocene) to post-orogenic crustal extension and exhumation (early Miocene) following Alpine orogenic collapse. Mixing of down-ward percolating meteoric fluids and ascending rock-buffered hydrothermal brines that had previously equilibrated with the radiogenic basement rocks along with thermochemical sulfate reduction of transported sulfate and/or thermal cracking, would have been the main ore-forming processes that controlled ore deposition. Given these fluid characteristics and geodynamic settings, the Jbel Bou Dahar ore field is classified as a hybrid carbonate-hosted Pb-Zn-Ba district formed by the juxtaposition of two deposit types rather than one progressively evolving mineralizing system. From an exploration standpoint, new delineation here of the two metallogenic events provides valuable exploration tools for further targeting PbZn and barite resources in the Atlas system of North Africa and other areas where similar orogenic belts experienced post-rift subsidence and basin inversion.

Triple oxygen and hydrogen isotopes of glacial diamictites record crustal maturation and changing surface conditions through geologic time

The triple oxygen and hydrogen stable isotopic compositions of 24 glacial diamictite composites with depositional ages from 2.9 to 0.3 Ga are used to reconstruct the evolution of the continental crust and surface environments. The δ18O of the diamictite composites increases from the Archean to the Phanerozoic by ~4 ‰ (3–5 ‰ in Mesoarchean to 13.5 ‰ in Neoproterozoic), a trend that is comparable to those seen in shales and granites, although the diamictites plot on the lower δ18O end of the range seen in shales. The Δ’17O0.528 decreases from −0.04 to −0.15 ‰, overlapping with shales and granites. Nine zircon separates extracted from individual diamictites also show a ~3 ‰ increase in δ18O from 3.75 to 4.5 ‰ to 7 ‰ between 2.9 and 0.6 Ga. The δ18O of diamictites and zircon separates negatively correlates with ɛNd(i) of the diamictites, suggesting that the longer the rocks reside in the upper continental crust (the lower the ɛNd), the more they are subjected to repeated weathering cycles, thus acquiring a higher δ18O and lower Δ’17O0.528 during each cycle. On a triple O isotope plot (δ17O vs δ18O), diamictites define an array with a slope of 0.523, analogous to granites and shales.The δD values of nearly all diamictites overlap with the typical mantle and crustal ranges of −58 ± 12 ‰ and − 69 ± 24 ‰, respectively, but are on the lower end of coeval shale values. Water, contained primarily in sheet silicates, ranges from 2.85 wt% (pre-2.4 Ga) and 2.35 wt% (post-2.4 Ga), showing no temporal change. The youngest diamictites (0.3 Ga Dwyka Group) exhibit low δD values of −105 to −111 ‰, lower than the typical crustal values, potentially reflecting the near-polar position of South Africa at the time of their deposition, which is corroborated by the reconstructed δ18O value of −26 ‰ based on triple oxygen isotopic systematics.The chemical index of alteration (CIA) allows inverting measured δ18O and Δ’17O values of diamictite composites into a pure weathering product (wp) end member by subtracting values of coeval unweathered crust based on tzircon δ18O. This reveals that the δ18Owp also increases with time, suggesting that the increase in δ18O (decrease in Δ’17O) of the maturing crust is insufficient to fully explain the trends. Therefore, at least part of the increasing δ18Owp likely reflects increasing δ18O of the hydrosphere. Reconstructed surface temperatures around the time of diamictite deposition using δ18Owp and Δ’17Owp display a general decrease since the Archean. Given the diagenetic and post-diagenetic history experienced by the diamictites, the temporal and global trends should be interpreted with caution. Nonetheless, reconstructed δ18Owater shows an increase from −21 ‰ at 2.9 Ga to −11 ‰ at 0.6 Ga. Thus, diamictites, like shales, broadly monitor the evolution of surface conditions on Earth from warmer to colder and from lower to higher δ18Owater values of the hydrosphere.

Stable isotopic, bulk, and molecular compositions of post-monsoon biomass-burning aerosols in Delhi suggest photochemical ageing during regional transport is more pronounced than local processing

Stable isotopic, bulk, and molecular compositions of post-monsoon biomass-burning aerosols in Delhi suggest photochemical ageing during regional transport is more pronounced than local processing

Monitoring of stable isotope composition of precipitation reveals thunderstorm dynamics

ABSTRACT The summer of 2019 is particularly well known for the famous heatwaves that swept across the European continent, with its associated drought and record-breaking air temperatures. This was followed by powerful thunderstorms, characterised by hail and heavy rain that damaged the crops on a regional scale. Here, we investigated one of the largest storm cells, lasting more than 6 h, which struck southwestern Romania. High-temporal resolution sampling of storm precipitation was performed for stable isotope measurements, rainfall and air temperature, to follow the storm dynamics. Hydrogen and oxygen isotope measurements show an abrupt decreasing temporal trend followed by superimposed V-shaped patterns interpreted as reflecting moisture replenishment by successive rain bands. To model the stable isotope values of precipitation in relation to the general trend of decreasing air temperatures, we applied a numerical Rayleigh condensation model for a non-constant α isotopic fractionation factor between liquid water and water vapour. The storm is powered by four consecutive moisture fronts, each following a Rayleigh distribution. About 40 % of the water vapour condenses during the sampled storm due to adiabatic expansion and cooling, which lowers saturation. Condensation ceases when cooling and absolute humidity can no longer sustain the dew point, stopping the rain. The timing of the event, occurring late at night and early in the morning, its duration of over 6 h as well as its synoptic scale may indicate a mesoscale convective complex.

Carbon Isotopic Composition Reflects Intrinsic Water Use Efficiency But Not its Component Traits in Sugarcane

Water is the most important resource in plant growth and is a major limiting factor in sugarcane productivity worldwide. Improving water use efficiency (WUE) can increase sugarcane productivity relative to available water resources by increasing photosynthetic capacity relative to transpiration and stomatal conductance instead of decreasing stomatal conductance. Leaf carbon stable isotopic composition (δ13Cleaf) can serve as a proxy for intrinsic WUE (WUEi) because WUEi and δ13Cleaf are theoretically related through the link between intracellular and ambient CO2 concentrations (Ci/Ca) and leaf CO2 discrimination (Δ13Cleaf). In this study we surveyed 55 sugarcane genotypes for WUEi, leaf WUE (WUEleaf), Ci/Ca, and δ13Cleaf by gas exchange measurements and stable isotope analysis. We hypothesized that significant genotypic variation was found in WUEi, WUEleaf, and δ13Cleaf within the sugarcane population in Louisiana. We also hypothesized that both WUEi and δ13Cleaf and Δ13Cleaf and Ci/Ca were correlated and that δ13Cleaf could be used as a proxy for WUEi in sugarcane. Here WUEi and WUEleaf had a genetic effect and were controlled mostly by water loss (stomatal conductance or transpiration). WUEi, WUEleaf, Ci/Ca, and δ13Cleaf were correlated, but δ13Cleaf was not correlated with the component traits of WUEi (photosynthetic rate and stomatal conductance). δ13Cleaf shows promise as a proxy for WUEi to at least be able to select the tails of the distribution, but the relationship between WUEi and δ13Cleaf may not be sufficiently strong to select WUE at a finer scale.