Isotopic Variations Research Articles

Substantial in situ Ti isotope variations in rutile record source and fluid evolution of porphyry copper mineralization systems

Titanium (Ti) and its stable isotopes have been widely used as tracers for magmatic processes. However, our understanding of Ti isotope behavior in magmatic-hydrothermal systems remains limited. Hence, the in situ Ti isotope composition (δ49Ti) of magmatic titanite and hydrothermal rutile associated with magnetite and chalcopyrite mineralization was determined for the first time in four well-characterized porphyry copper deposits in southern Tibet. The rutile formed through the alteration of primary Ti-rich minerals during fluid-rock interaction in the early high-temperature magnetite and later moderate-temperature chalcopyrite stages of mineralization. Hydrothermal rutile, altered from magmatic titanite, exhibits δ49Ti values similar to those of residual magmatic titanite. This suggests that hydrothermal rutile inherited the Ti isotope composition of magmatic titanite. The average δ49Ti values of rutile are negatively correlated with whole-rock εNd(t) and zircon εHf(t) data, and positively correlated with whole-rock (87Sr/86Sr)i values, which suggests that the initial Ti isotope compositions of hydrothermal rutile in porphyry copper deposits primarily reflect their source. Rutile from the Qulong deposit sometimes exhibits fractionation of δ49Ti at levels exceeding 0.5‰, displaying a negative correlation with Zr and FeO, which may be attributed to the formation of magnetite and rutile at an early potassic alteration stage. Isotopically light Ti is preferentially incorporated into magnetite and rutile. Thus, the rutile associated with sulfide mineralization that formed from the remaining fluids during a later stage of phyllic alteration is enriched in heavy δ49Ti. These findings contribute to the understanding of how rutile fractionates Ti isotopes in hydrothermal systems related to porphyry copper deposits. In local contexts, the substantial crystallization of magnetite, along with the preferential incorporation of isotopically light Ti during the early stages, leads to a decrease in oxygen fugacity within the ore-bearing fluid. This, in turn, facilitates the formation of sulfides during later stages. The results of this study demonstrate the efficacy of in situ Ti isotope analysis as a powerful tool for tracking fluid and metal sources, and can be used to help interpret ore precipitation throughout different stages of magmatic-to-hydrothermal ore-forming processes.

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.

Carbon isotopic record of a platform-to-basin transect through the Permian Reef Complex (Guadalupian) in the Delaware Basin of Texas and New Mexico

The Guadalupian Permian Reef Complex of the Delaware Basin is one of the most studied carbonate reef systems of the Paleozoic. Despite extensive work on the carbonate sedimentology, sequence stratigraphy, and diagenetic history of the Delaware Basin, a high-resolution carbonate carbon isotope record along a platform to basin transect for the Capitanian (264.3–259.5 Ma, the youngest age of the Guadalupian Epoch) does not yet exist. The carbon isotopic record of the Delaware Basin is important because 1) it allows us to test hypotheses about controls on the carbon isotope proxy, 2) it provides constraints on how well modern carbonate platforms like the Great Bahama Banks serve as analogues for ancient carbonate settings, and 3) these types of restricted basins likely played an important role in Permian carbon cycling and the Capitanian extinctions.In this study we present 493 new Capitanian carbonate carbon isotopic values paired with a detailed sedimentological and sequence stratigraphic framework from the platform, slope, toe of slope, and deep basin of the Delaware Basin. The bulk of the new δ13C values fall within the range of previously reported unaltered carbonates from the basin, suggesting that these results record primary environmental processes and were not significantly altered by diagenetic overprinting. With this dataset, we test hypotheses about sources of carbon isotopic variability in shallow carbonate platforms. Our results indicate that in the Delaware Basin there are no systematic and resolvable depth or lateral gradients in carbon isotopic values, that δ13C values do not vary as a function of grain type, and that there is no resolvable relationship between carbon isotopic composition and sea level change. However, we do document statistically significant differences in δ13C distributions among facies associations which we attribute to the isotopic evolution of an upwelling water mass due to direct precipitation of mud along the slope. Our results support the idea that increasing carbon isotopic values through the Capitanian were driven by increased organic carbon burial in restricted basins.

Isotopic variability of short-tailed Albatrosses bone collagen (<i>Phoebastria albatrus</i>) in the Bering Sea area during the holocene

The short-tailed Albatross (Phoebastria albatrus) is a rare bird species today, whose numbers declined significantly in the Holocene due to human fishing activities. Bone remains of albatrosses from archaeological sites of Chukotka, Kamchatka and Aleutian Islands, and from coastal sediments of the Commander Islands were used to analyze the content of stable carbon and nitrogen isotopes in bone collagen. Analysis showed that the isotopic niches of Aleutian and Commander albatrosses diverged during the Holocene. Short-tailed albatrosses of the Aleutian Islands are closer to Holocene albatrosses of Vancouver Island (Canada) by isotopic characteristics.

Chemical and isotopic investigation of the I-type Bega Batholith, southeastern Australia: Implications for batholith compositional zoning and crustal evolution in accretionary orogens

Cordilleran granitic batholiths represent significant episodes of crustal growth and differentiation, and commonly display lateral isotopic and chemical variations. Establishing the tectono-magmatic processes responsible for generating this compositional asymmetry is important for understanding crustal evolutionary processes throughout the Phanerozoic. The Bega Batholith, an example of a ‘Cordilleran style’ granite batholith, is the largest I-type Siluro-Devonian granite complex in the Lachlan Fold Belt (LFB) of southeastern Australia and comprises seven granite supersuites that display systematic lateral isotopic and chemical asymmetry. From west to east towards the present-day continental margin, an increase in the content of Na2O, Sr, Al2O3, and P2O5, with concomitant decreases in CaO, Sc, Rb, and V are observed. In the same direction, whole-rock initial 87Sr/86Sr decreases from 0.7098 to 0.7039, εNd values increase from −8.3 to +4.4, and δ18O decreases from 10.2 ‰ to 7.9 ‰. Depleted-mantle model ages also decrease from ca. 1800 Ma in the west to 600 Ma in the east. Here, we address whether these chemical and isotopic variations were generated by interaction between two distinct components (mantle-derived magmas and supracrustal sources) or were alternatively produced by partial melting of infracrustal source rocks formed sequentially by much earlier episodes of crustal underplating. Combined whole-rock Nd-Sr-O isotopic and geochemical analyses indicate that several I-type supersuites exhibit chemical and isotopic correlations consistent with two-component magma mixing. This new evidence challenges the long-held view that I-type granites derive exclusively from the melting of infracrustal sources, and that granite terranes represent wholesale crustal reworking rather than new crustal growth. Our results show that the compositional zoning within the Bega Batholith is multifaceted. Firstly, the presence of two discrete mantle sources endows chemically and isotopically distinct eastern and western segments in the batholith. Secondly, within these compositionally distinct regions the lateral compositional changes across supersuites derives from mixing between mantle-derived and supracrustal sources. Finally, progressive extension within a developing back-arc environment regulates the ratio of crust-mantle contributions and compositional architecture of each I-type supersuite.

Triple oxygen isotope variability of precipitation in a tropical mountainous region

We present one year of δD, δ18O, d-excess, and Δʹ17O data from monthly precipitation at a Caribbean coastal site in Panama and from tap waters across the country to constrain geographic, climate, and moisture source controls on isotopic variability and better understand the sources and mechanisms of precipitation in Central America, a region facing significant modifications to the annual rainfall cycle due to climate change. Monthly precipitation δD ranged from –52.2 to +14.3 ‰, δ18O from –7.6 to +0.4 ‰, d-excess from +7.1 to +11.6 ‰, and Δ′17O from +11 to +29 per meg. Rainy season precipitation samples were found to have lower δD, δ18O, and d-excess due to Rayleigh distillation during the condensation and rainout of Pacific moisture over the central cordilleras, which results in decoupling between d-excess and Δ′17O. Outlier Δ′17O values during peak dry and rainy months may reflect seasonal changes in water vapor sourcing, from Caribbean to Pacific and/or locally recycled moisture, or may be a result of organic contamination. Tap water δD ranged from –82.3 to –14.3 ‰, δ18O from –11.6 to –2.4 ‰, d-excess from +4.3 to +12.2 ‰ and Δ′17O from –2 to +84 per meg. Tap water δD and δ18O values increase eastward due to lower orographic effects and Pacific and locally recycled moisture contributions to rainfall and greater secondary evaporation. Tap water d-excess and Δ′17O values are also de-coupled but lack clear spatial trends and controls. The results of this study indicate the promise of adding Δ′17O to the isotopic toolkit in tropical mountainous regions with complicated water cycling dynamics and provide a baseline for future triple oxygen isotope investigations.

Disentangling and interpreting nonlinear molecular and isotopic variations in petroleum using machine learning

Nonlinear variations in the molecular and isotopic compositions of phases in complex geosystems greatly hinder the application of geochemical proxies. This study aims to disentangle the implicit nonlinear mathematical structures embedded in geochemical datasets, effectively disaggregating overlapping geological influences that drive the intricate variations in the geochemical signatures of phases. Employing a typical hybrid petroleum system as a case study, we utilize an unsupervised machine learning algorithm to visualize the effects of source disparities and distinct evolutionary processes, such as mixing, thermal maturation, biodegradation, and evaporative fractionation, on the molecular compositions among crude oils. We further investigate the regression relationship between molecular composition and bulk δ13C signal in petroleum. Our findings reveal that by decomposing the regression model to solely reflect a specific dominant influence, the model could provide a precise geological interpretation. Accordingly, we unravel the subtle variations and underlying mechanisms of carbon isotopic fractionation in petroleum substances from different origins under the impact of maturation. Our results underscore the substantial potential of strategically applied machine learning techniques in reconstructing the geochemical evolution of complex geosystems, advocating for their broader application.

Effects of different surface water flow frequencies on water use characteristics of Tamarix ramosissima in the hinterland of the Taklimakan Desert

Tamarix ramosissima is a dominant species in desert ecosystems and an ecological barrier species in arid areas, playing a crucial role in stabilizing dunes and preventing desertification. In this study, river water, groundwater, soil water, and T. ramosissima individual samples were collected from three sites in July and October 2023 at the Daliyaboyi Oasis located at the tail of the Kriya River in the hinterland of the Taklimakan Desert. The three sites are referred to as the center (SE), west (SW), and north (SN) sites within the Daliyaboyi Oasis, and each experienced different flood frequencies. The SE site experienced flooding in July and October, the SW site experienced flooding only in July, and the SN site experienced no flooding in July or October. The spatial and temporal variation in hydrogen and oxygen stable isotopes and line-conditional excess (lc-excess) in water and plant samples were analyzed, and the potential changes in water use of T. ramosissima were analyzed by the hydrogen and oxygen stable isotope and MixSIAR model. The findings indicated that the slope of SWL at the SE, SW, and SN sites was higher in July (6.77, 6.42, and 3.05, respectively) than in October (7.37, 3.30, and 2.14, respectively). The lc-excess value of the SE site did not exhibit seasonal changes; only the lc-excess values of soil water in SW and SN sites showed seasonal changes. MixSIAR results indicated frequent flood events at the SE site, with relatively constant proportions of water source utilization by T. ramosissima in July and October. In addition, shallow soil water (0–60 cm) and deeper soil water (60–80 cm) were the main water sources of T. ramosissima at SE. The SN site was slightly influenced by surface water, resulting in statistically non-significant changes in the water source utilization by T. ramosissima. Indeed, deep soil water (60–200 cm) and groundwater were the sources of water for T. ramosissima at this site. In contrast with October, the SW site experienced flood events in July, resulting in the utilization of water by T. ramosissima from the shallow soil (0–60 cm) and deep soil (60–280 cm) in July and October, respectively. Different surface water flow patterns led to different water use characteristics of T. ramosissima, which further demonstrated that T. ramosissima has high resilience and ecological plasticity. This work provides a useful reference for the implementation of effective ecological water transport measures in the Daliyaboyi Oasis and similar arid habitats.

The Pivotal Role of Evaporation in Lake Water Isotopic Variability Across Space and Time in a High Arctic Periglacial Landscape

AbstractRapidly changing climate is disrupting the High Arctic's water systems. As tracers of hydrological processes, stable water isotopes can be used for high quality monitoring of Arctic waters to better reconstruct past changes and assess future environmental threats. However, logistical challenges typically limit the length and scope of isotopic monitoring in High Arctic landscapes. Here, we present a comprehensive isotopic survey of 535 water samples taken in 2018 and 2019 of the lakes and other surface waters of the periglacial Pituffik Peninsula in far northwest Greenland. The δ18O, δ2H, and deuterium‐excess values of these samples, representing 196 unique sites, grant unprecedented insight into the environmental drivers of the regional hydrology and water isotopic variability. We find that the spatial variability of lake water isotopes can best be explained through evaporation and the hydrological ability of a lake to replace evaporative water losses with precipitation and snowmelt. Temporally, summer‐long evaporation can drive lake water isotopes beyond the isotopic range observed in precipitation, and wide interannual changes in lake water isotopes reflect annual weather differences that influenced evaporation. Following this, water isotope samples taken at individual times or sites in similar periglacial landscapes may have limited regional representativeness, and increasing the spatiotemporal extent of isotopic sampling is critical to producing accurate and informative High Arctic paleoclimate reconstructions. Overall, our survey highlights the diversity of isotopic compositions in Pituffik surface waters, and our complete isotopic and geospatial database provides a strong foundation for future researchers to study hydrological changes at Pituffik and across the Arctic.

Diet and isotopic niche variation of mammals associated with road zones in Uruguay

AbstractThe understanding of the resource use and partitioning of medium and large terrestrial mammals in anthropogenic environments such as road areas is crucial for comprehending ecosystem dynamics and reveals how species coexist and adapt to environmental changes. The aim of this work was to characterize trophic aspects of medium and large terrestrial mammals, including the quantification of resource use, variation in isotopic trophic niche breadth and overlap among sympatric species within a road zone influence in Uruguay. To this end, stable isotope ratios (δ13C and δ15N) were examined in hair samples collected from 57 individuals from road‐killed animals including 9 medium and large mammals species, as well as potential resources. The isotopic results reflected a community that contains four trophic levels, with Galictis cuja as a predator while the species Dasypus hybridus and Subulo gouazoubira were in the primary consumer levels. Furthermore, the results showed varying degrees of isotopic trophic niche breadth, suggesting different feeding strategies and degrees of dietary specialization. Additionally, a high degree of overlap in resource use was observed among these sympatric species with the exception of Galictis cuja, suggesting that spatial and temporal differentiation in resource use could help to explain the coexistence patterns. Diet composition estimated using Bayesian stable isotope mixing models revealed that in most species, the basal food source was represented by a combination of natural grasslands of types C3 and C4. This trophic behaviour with the incorporation of diverse and variable food items helps to explain the occurrence of these species within this complex environment.

LOMU Type Alkali Basalts in East Asia Sourced from Subduction Recycling of Multiple Ancient Crustal Components

Abstract The origin of alkali basalts with distinctive time-integrated low U/Pb (low μ, LOMU) from East Asia is controversial due to the complex geochemical and tectonic signatures reported from this region. We report new data on the petrology and geochemistry of the Higashi-Matsuura and Kita-Matsuura alkali basalts from Southwest Japan, which confirm the presence of a LOMU-type mantle component below the Japanese Islands, similar to East Asian intraplate volcanoes. We use whole rock geochemistry and mineral chemistry to determine mantle melting, magma evolution conditions and isotopic evolution of the LOMU mantle source. Petrological studies show that the Higashi-Matsuura alkali basalts (~3 Ma) were derived from a hydrous mantle source with ~880 μg/g H2O, at a pressure of 1.8 to 2.3 GPa at a mantle potential temperature of ~1300°C. Trace element modelling concludes that these basalts may have been generated through the hydrous upwelling and partial melting of the asthenospheric mantle containing ~15% dehydrated eclogitic component. Higashi-Matsuura alkali basalts show 206Pb/204Pb values of 17.72 to 18.04 which are among the lowest values from Southwest Japan. Relatively older (6–8 Ma) alkali basalts from the Kita-Matsuura area showing similar physicochemical characteristics, do not show LOMU-type isotopic trends. Trace element and Pb–Sr–Nd isotopic data indicate that the Higashi-Matsuura mantle component is similar to the extreme LOMU components reported from the Northeast China alkali basalts, as well as the recently discovered Petit Spot volcanoes on the Pacific Plate. We model the origin of the LOMU signature from the lowest reported Pb isotope ratios in East Asia, from intraplate alkali basalts in Northeast China. Our model suggests that at least two separate subduction events of marine sediments, at 1.8 and 2.2 Ga, are required to explain the observed Pb isotopic variation in the East Asian region. Other LOMU type basalts from East Asia, including Southwest Japan and Petit Spot, define a linear trend between the Xiaogulihe basalts and lithospheric mantle xenoliths, with 40% to 60% Pb in Higashi-Matsuura basalts being derived from the lithospheric mantle during upwelling. This suggests that the LOMU array in East Asia may have been formed by mixing between multiple ancient, subducted sediment components accumulated at the mantle transition zone for about 2 billion years, and its recent upwelling due to dehydration of the stagnant Pacific slab and related melting of the metasomatised asthenospheric mantle.

The Ni isotopic composition of Ryugu reveals a common accretion region for carbonaceous chondrites.

The isotopic compositions of samples returned from Cb-type asteroid Ryugu and Ivuna-type (CI) chondrites are distinct from other carbonaceous chondrites, which has led to the suggestion that Ryugu/CI chondrites formed in a different region of the accretion disk, possibly around the orbits of Uranus and Neptune. We show that, like for Fe, Ryugu and CI chondrites also have indistinguishable Ni isotope anomalies, which differ from those of other carbonaceous chondrites. We propose that this unique Fe and Ni isotopic composition reflects different accretion efficiencies of small FeNi metal grains among the carbonaceous chondrite parent bodies. The CI chondrites incorporated these grains more efficiently, possibly because they formed at the end of the disk's lifetime, when planetesimal formation was also triggered by photoevaporation of the disk. Isotopic variations among carbonaceous chondrites may thus reflect fractionation of distinct dust components from a common reservoir, implying CI chondrites/Ryugu may have formed in the same region of the accretion disk as other carbonaceous chondrites.

Origin and Affinities of the Malmberget Iron Oxide-Apatite Deposit, Northern Sweden: Insights From Magnetite Chemistry and Fe-O Isotopes

European iron ore production is primarily sourced from magnetite dominated iron oxide-apatite ore deposits in the northern Norrbotten ore province of northernmost Sweden. The Malmberget iron oxide-apatite deposit is at present the largest iron ore resource in Europe and is an amphibolite facies grade analogue of the world-famous Kiirunavaara iron oxide-apatite deposit. The Malmberget rock association is characterised by multiple phases of deformation, metamorphism, and alteration that resulted in a geometrically and petrologically complex deposit that is genetically ambiguous. Primary ore textures and emplacement structures of the Malmberget iron oxide-apatite deposit have largely been recrystallised during metamorphic overprinting and now comprise dominantly medium- to coarse-grained granoblastic magnetite. However, isotopic characteristics are preserved and when combined with trace element chemistry, these can be used to understand magmatic vs. hydrothermal origin of the deposit. To unravel the primary origin of the Malmberget magnetite ore, we combined magnetite trace element chemistry and Fe-O stable isotopes to investigate the massive magnetite in the Fabian-Kapten and ViRi ore bodies of the Malmberget iron oxide-apatite deposit. Trace element correlations indicate a high-temperature magmatic to a transitional high-temperature magmatic-hydrothermal origin of the Malmberget iron oxide-apatite ore deposit, with data plotting into fields of clear magmatic affinity in trace element discrimination diagrams. Fe-O data fall into established magmatic fields regardless of subsequent metamorphic modifications, underlining a dominantly (ortho-)magmatic origin of the investigated deposits. Despite an overall magmatic to magmatic-hydrothermal origin for the two ore bodies studied, Fe-O isotope equilibrium calculations of the magnetite suggest a possible temperature discrepancy between the Fabian-Kapten ore body and the ViRi ore body, the latter showing a more pronounced magmatic character. These variations in trace element contents and Fe-O isotopes can be explained by the proximity of the more magmatic signatures to the centre of the ore forming magmatic system.

New insights into the mechanisms of plant isotope fractionation from combined analysis of intramolecular 13C and deuterium abundances in Pinus nigra tree-ring glucose.

Understanding isotope fractionation mechanisms is fundamental for analyses of plant ecophysiology and paleoclimate based on tree-ring isotope data. To gain new insights into isotope fractionation, we analysed intramolecular 13C discrimination in tree-ring glucose (Δi', i = C-1 to C-6) and metabolic deuterium fractionation at H1 and H2 (εmet) combinedly. This dual-isotope approach was used for isotope-signal deconvolution. We found evidence for metabolic processes affecting Δ1' and Δ3', which respond to air vapour pressure deficit (VPD), and processes affecting Δ1', Δ2', and εmet, which respond to precipitation but not VPD. These relationships exhibit change points dividing a period of homeostasis (1961-1980) from a period of metabolic adjustment (1983-1995). Homeostasis may result from sufficient groundwater availability. Additionally, we found Δ5' and Δ6' relationships with radiation and temperature, which are temporally stable and consistent with previously proposed isotope fractionation mechanisms. Based on the multitude of climate covariables, intramolecular carbon isotope analysis has a remarkable potential for climate reconstruction. While isotope fractionation beyond leaves is currently considered to be constant, we propose significant parts of the carbon and hydrogen isotope variation in tree-ring glucose originate in stems (precipitation-dependent signals). Asbasis for follow-up studies, we propose mechanisms introducing Δ1', Δ2', Δ3', and εmet variability.

An Evaluation of the Brine Flow in the Upper Part of the Halite Nucleus of the Salar de Atacama (Chile) through an Isotopic Study of δ18O and δ2H

A hydrogeological study of the shallowest part of the halite nucleus of the Salar de Atacama is presented, focusing on the isotopic variability in δ18O and δ2H (SMOW) in the brine. It is observed that intensive brine extraction has induced upward vertical flows from the lower aquifer, which presents with a lighter isotopic composition (δ18O: −0.87‰ to −2.49‰; δ2H: −26.04‰ to −33.25‰), toward the upper aquifer, which has more variable and enriched isotopic values. Among the possible explanations for the lighter isotopic composition of the lower aquifer waters is the influence of paleolakes formed during the wetter periods of the Late Pleistocene and Holocene that recharged the underlying aquifers. The geological structure of the Salar, including faults and the distribution of low-permeability layers, has played a determining role in the system’s hydrodynamics. This study emphasizes the need for continuous and detailed monitoring of the isotopic composition to assess the sustainability of the water resource in response to brine extraction and future climate changes. Additionally, it suggests applying this methodology to other salt flats in the region for a better understanding of hydrogeological processes in arid zones. The research provides an integrative view of the relationship between resource extraction, water management, and ecosystem conservation in one of the most important salars in the world.

Spatiotemporal variation of modern lake, stream, and soil water isotopes in Iceland

Abstract. As global warming progresses, changes in high-latitude precipitation are expected to impart long-lasting impacts on Earth systems, including glacier mass balance and ecosystem structures. Reconstructing past changes in high-latitude precipitation and hydroclimate from networks of continuous lake records offers one way to improve forecasts of precipitation and precipitation–evaporation balances, but these reconstructions are currently hindered by the incomplete understanding of controls on lake and soil water isotopes. Here, we study the distribution of modern water isotopes in Icelandic lakes, streams, and surface soils collected in 2002, 2003, 2004, 2014, 2019, and 2020 to understand the geographic, geomorphic, and environmental controls on their regional and interannual variability. We find that lake water isotopes in open-basin (through-flowing) lakes reflect local precipitation, with biases toward the cold season, particularly in lakes with sub-annual residence times. Closed-basin lakes have water isotope and deuterium excess values consistent with evaporative enrichment. Interannual and seasonal variabilities of lake water isotopes at repeatedly sampled sites are consistent with instrumental records of winter snowfall; summer relative humidity; and atmospheric circulation patterns, such as the North Atlantic Oscillation. Summer surface soil water isotopes span the entire range of seasonal precipitation values in Iceland and appear to be consistently overprinted by evaporative enrichment, which can occur throughout the year, although the sampling depths were shallower than rooting depths for many plant types. This dataset provides new insight into the functionality of water isotopes in Icelandic environments and offers renewed possibilities for optimized site selection and proxy interpretation in future paleohydrological studies on this North Atlantic outpost.

Individual isotopic niche variation of herbivores and palaeoenvironmental reconstruction of the Mid-Pleistocene Site of Kathu Pan 1 (South Africa)

Individual niche variation occurs when individuals within a population adopt unique behavioural or ecological traits, giving the population a distinct niche structure. Although widespread amongst natural populations, most of niche theory and its applications in ecological and palaeoenvironmental contexts remains focused on species level patterns, treating variation within the population as noise. Using serial stable isotope profiles sampled along teeth of herbivore fossils recovered from the Mid-Pleistocene site of Kathu Pan 1, Northern Cape (South Africa), enabling partitioning of isotopic niche variation into between- and within-individual components. Stable carbon isotope data revealed significant dietary differences between-individuals within most of the taxa sampled, but no dietary differences between taxa. By contrast, stable oxygen isotope compositions were more consistent amongst individuals, but varied across taxa. In both isotope systems, as well as in bivariate space, most taxa comprised individuals with both narrow and broad isotope niches, indicating flexibility in dietary strategies. These results indicate sufficient opportunity for individual level specialization within the Kathu palaeocommunity, afforded by a palaeoenvironment that provided a consistent supply of resources year-round. Given the herbivore sample is strongly associated with fossil hominin activities, our results imply that hominins in these landscapes would have profited from year-round accessibility to resources, accounting for the record of occupancy of Kathu Pan I during the Mid-Pleistocene.

Carbon–sulfur–calcium isotopic variability of lower Cambrian shale-hosted carbonate concretions: Insights into growth mechanisms and calcium cycling

Marine calcium cycling is closely linked with carbon cycling in the ocean, in which authigenic carbonates precipitated in sediments play a non-negligible role. However, calcium cycling during authigenic carbonate precipitation in organic-rich, shaly sediments in geological history remains underexplored. This study focuses on carbonate concretions (aggregates of authigenic carbonates) in the lower Cambrian Niutitang Formation, South China, to provide insights into calcium cycling during their growth. Sedimentological and mineralogical observations suggest that these concretions were formed through concentric growth by authigenic calcite and pyrite precipitation during the early diagenetic stage. Geochemical analyses reveal internal variations in “M-shaped” δ13Ccarb trends (from −11.9 ‰ to −4.4 ‰) and diverse δ34Spyr trends (from 4.7 ‰ to 14.0 ‰) along core-to-rim transects. These findings suggest formation through microbial sulfate reduction by organic matter in a shallow depth beneath the sediment–water interface. In contrast to the dynamic δ13Ccarb and δ34Spyr variations and multi-stage concentric growth, these carbonate concretions display nearly uniform δ44/40Cacarb values (from 0.80 ‰ to 1.03 ‰, average 0.96 ± 0.06 ‰, 1SD) and consistent internal trends, which are further attributed to strongly seawater-buffered porewater calcium geochemistry and small calcium isotope fractionation due to calcite precipitation at slow rates. This study confirms that early diagenetic carbonate concretions in the lower Cambrian Niutitang Formation are characterized by much heavier δ44/40Ca values compared to coeval shallow platform carbonates. In light of abundant authigenic carbonates observed in the lower Cambrian successions, their roles in calcium isotope mass balance in the early Cambrian ocean warrant further investigation in the future. Therefore, early diagenetic carbonate concretions in black shales could provide valuable insights into porewater and seawater calcium isotope signals, as well as early diagenetic and marine calcium cycling in geological history.

Bottom-up processes drive isotopic variation in the South American sea lion Otaria flavescens across a 2300 km latitudinal gradient

Spatial differences in the isotope values of widely distributed marine apex consumers may reflect geographical differences in the isotopic composition of basal resources (e.g., phytoplankton) fueling food webs (bottom-up effects) or spatial differences in the trophic ecology of the taxon of interest (top-down effects). We examined spatial variation in δ13C and δ15N values from 264 South American sea lions (SASL, Otaria flavescens) of different age classes (adults, subadults and juveniles), their putative prey consisting of pelagic and benthic coastal fishes, and particulate organic matter (POM) measured from locations situated across >2300 km of the Chilean coast (between 18°42′ and 39°17′ S). We used generalized least squares (GLS) models to compare the form of the relationship between δ13C and δ15N and latitude between the three functional groups. Our results show that SASL from northern, central, and southern areas were isotopically distinct, with individuals from the north having lower δ13C and higher δ15N values in comparison to individuals from the south. When the relationship for each functional group was modelled individually using GLS, results indicated that for each degree of increasing latitude δ15N decreased on average by 0.12‰ (POM), 0.15‰ (prey), and 0.14‰ (SASL), while δ13C increased by 0.06‰ (POM) and 0.05‰ in both prey and SASL. We suggest that the latitudinal differences observed in SASL δ13C and δ15N values reflect baseline isotopic variation rather than marked differences in trophic ecology of these widely distributed consumers.