Hydrogen Isotopic Composition Research Articles

Asteroid (101955) Bennu in the laboratory: Properties of the sample collected by OSIRIS‐REx

AbstractOn September 24, 2023, NASA's OSIRIS‐REx mission dropped a capsule to Earth containing ~120 g of pristine carbonaceous regolith from Bennu. We describe the delivery and initial allocation of this asteroid sample and introduce its bulk physical, chemical, and mineralogical properties from early analyses. The regolith is very dark overall, with higher‐reflectance inclusions and particles interspersed. Particle sizes range from submicron dust to a stone ~3.5 cm long. Millimeter‐scale and larger stones typically have hummocky or angular morphologies. Some stones appear mottled by brighter material that occurs as veins and crusts. Hummocky stones have the lowest densities and mottled stones have the highest. Remote sensing of Bennu's surface detected hydrated phyllosilicates, magnetite, organic compounds, carbonates, and scarce anhydrous silicates, all of which the sample confirms. We also find sulfides, presolar grains, and, less expectedly, Mg,Na‐rich phosphates, as well as other trace phases. The sample's composition and mineralogy indicate substantial aqueous alteration and resemble those of Ryugu and the most chemically primitive, low‐petrologic‐type carbonaceous chondrites. Nevertheless, we find distinct hydrogen, nitrogen, and oxygen isotopic compositions, and some of the material we analyzed is enriched in fluid‐mobile elements. Our findings underscore the value of sample return—especially for low‐density material that may not readily survive atmospheric entry—and lay the groundwork for more comprehensive analyses.

Origin of the Red‐veined Darter dragonflies migrating into the European part of Russia revealed by stable isotopes of hydrogen

Abstract Dragonflies are well‐known migratory insects, and stable isotopes have been used successfully to study their migrations in America and Asia but less so in Europe. Here we used the isotopic composition of hydrogen (δ2H value) in metabolically inert wing tissues of the dragonfly Sympetrum fonscolombii (Selys, 1840) to investigate migration patterns and likely origin of immigrants into the European part of Russia. During spring–summer, sexually mature dragonflies arrive to Russia for reproduction and individuals of the summer generation (descendants of immigrants) presumably migrate in the opposite direction in the fall. Analyses included 39 specimens of immigrant S. fonscolombii dragonflies, 11 specimens from 3 species of resident dragonflies (including S. fonscolombii) from the European part of Russia and 16 specimens representing 9 resident dragonfly species from Iran. The average δ2H values of the wings of immigrant S. fonscolombii (−71.9 ± 23.4‰) were significantly higher than those of resident dragonflies in European Russia (−121.7 ± 9.5‰) and similar to those of resident dragonfly species from Iran (−72.3 ± 18.4‰). Based on a geostatistical model of the global δ2H values in precipitation, and considering the distribution of S. fonscolombii, the most probable natal area of immigrants arriving in European Russia is located in Southwest Asia. The suggested migration zone covers regions located between approximately 26°–28° N in the south and 56°–58° N in the north, while the migration distance can reach 2000–4000 km.

Hydrochemical Characteristics and Evolution of Underground Brine in Lop Nur, Northwestern China

AbstractLop Nur is located at the eastmost end of the Tarim Basin in Xinjiang, Northwestern China. This study reviews the hydrochemical characteristics and evolution of underground brine in Lop Nur, based on analytical data from 429 water samples (mainly brine). It is found that in the NE–SW direction, from the periphery to the Luobei sub‐depression, while the hydrochemical type varies from the sodium sulfate subtype (S) to the magnesium sulfate subtype (M), the corresponding brine in the phase diagram transfers from the thenardite phase (Then) area, through the bloedite phase (Blo), epsomite phase (Eps), picromerite phase (Picro), finally reaching the sylvite phase (Syl) area. As for the degree of evolution, the sequence is the periphery < Luobei horizontally and the overlying glauberite brine < the underlying clastic brine vertically. It is concluded that the oxygen and hydrogen isotopic compositions of the brine have evidently been affected through the effects of evaporation and altitude, as well as the changes in local water circulation in recent years. Boron and chloride isotopic compositions show that the glauberite brine is formed under more arid conditions than the clastic one. The strontium isotopic composition indicates that the Lop Nur brine primarily originates from surface water; however, deep recharge may also be involved in the evolution of the brine, according to previous noble gas studies. It is confirmed that the brine in Lop Nur has become enriched with potassium prior to halite precipitation over the full course of the salt lake's evolution. Based on chemical compositions of brine from drillhole LDK01 and previous lithological studies, the evolution of the salt lake can be divided into three stages and it is inferred that the brine in Lop Nur may have undergone at least two significant concentration‐dilution periods.

Direct Phototransformation of Sulfamethoxazole Characterized by Four-Dimensional Element Compound Specific Isotope Analysis.

The antibiotic sulfamethoxazole (SMX) undergoes direct phototransformation by sunlight, constituting a notable dissipation process in the environment. SMX exists in both neutral and anionic forms, depending on the pH conditions. To discern the direct photodegradation of SMX at various pH levels and differentiate it from other transformation processes, we conducted phototransformation of SMX under simulated sunlight at pH 7 and 3, employing both transformation product (TP) and compound-specific stable isotope analyses. At pH 7, the primary TPs were sulfanilic acid and 3A5MI, followed by sulfanilamide and (5-methylisoxazol-3-yl)-sulfamate, whereas at pH 3, a photoisomer was the dominant product, followed by sulfanilic acid and 3A5MI. Isotope fractionation patterns revealed normal 13C, 34S, and inverse 15N isotope fractionation, which exhibited significant differences between pH 7 and 3. This indicates a pH-dependent transformation process in SMX direct phototransformation. The hydrogen isotopic composition of SMX remained stable during direct phototransformation at both pH levels. Moreover, there was no variation observed in 33S between the two pH levels, indicating that the 33S mass-independent process remains unaffected by changes in pH. The analysis of main TPs and single-element isotopic fractionation suggests varying combinations of bond cleavages at different pH values, resulting in distinct patterns of isotopic fractionation. Conversely, dual-element isotope values at different pH levels did not significantly differ, indicating cleavage of several bonds in parallel. Hence, prudent interpretation of dual-element isotope analysis in these systems is warranted. These findings highlight the potential of multielement compound-specific isotope analysis in characterizing pH-dependent direct phototransformation of SMX, thereby facilitating the evaluation of its natural attenuation through sunlight photolysis in the environment.

Lower crustal control in the iron isotope systematics of plutonic xenoliths from Adak Island, Central Aleutians, with implications for arc magma geochemistry

We present bulk-rock and mineral Fe isotope data of ultramafic to mafic xenoliths and basaltic to andesitic lavas from Adagdak Volcano (Adak Island, Central Aleutians) to study the effects of early differentiation on the Fe isotopic evolution of island arc basalts and their crystallization products. The Fe isotope composition of ultramafic cumulate xenoliths increases from dunite (δ56Fe = –0.09 to –0.02 ‰) to clinopyroxenite (δ56Fe = +0.06 to +0.09 ‰), consistent with higher modal proportions of clinopyroxene (δ56Fe = –0.05 to +0.11 ‰) relative to olivine (δ56Fe = –0.10 to +0.06 ‰) in the latter. Mid-crustal cumulate amphibole gabbro and hornblendite cumulates also record heavier Fe isotope compositions (δ56Fe = +0.04 to +0.08 ‰) due to the abundance of isotopically heavy amphibole (δ56Fe = +0.07 to +0.09 ‰) and magnetite (δ56Fe = +0.11 to +0.13 ‰) in these rocks. High inter-mineral fractionations observed in spinel-olivine and spinel-clinopyroxene pairs (Δ56Fespl-ol = +0.12 to +0.28 and Δ56Fespl-cpx = +0.06 to +0.19) suggest that spinel is not recording equilibrium crystallization conditions for the ultramafic assemblages, likely due to subsolidus Fe-Mg exchange. Our data also include Fe isotope measurements of one mantle dunite (δ56Fe = +0.03 ± 0.05 ‰). Five Adagdak lavas, spanning from basalts to andesites, yield a narrow range of δ56Fe between +0.03 and +0.06 ‰. Our results highlight the potential of amphibole in driving the Fe isotope depletion trends observed in many erupted arc lavas, as amphibole hosts 28–99 % of the FeOT budget in the amphibole gabbro and hornblendite cumulates. This is also supported by single-crystal synchrotron Mössbauer spectroscopy of two amphibole grains, the first from an amphibole gabbro and the second from a hornblendite, which yield Fe3+/ΣFe ratios of 0.55 ± 0.06 and 0.58 ± 0.02, respectively. Water content and hydrogen isotope compositions determined by secondary-ion mass spectrometry from the same amphibole grains indicate partial dehydrogenation. Using Rayleigh fractionation modeling to account for oxidation during post-crystallization dehydrogenation, we calculate magmatic Fe3+/ΣFe ratios of 0.41 ± 0.04 for the amphibole gabbro and 0.30 ± 0.05 for the hornblendite. These data are then used to estimate an appropriate Fe force constant for Adagdak amphibole and quantitatively evaluate the effects of amphibole fractionation. Through a fractional crystallization model, we show how arc melts may experience periods of increasing δ56Fe during olivine-dominated fractionation, followed by decreasing δ56Fe once magnetite and amphibole saturate as cumulate phases. Notably, this dichotomy between fractionation of isotopically light versus heavy cumulate assemblages and its effects on the Fe isotope evolution of arc magmas is not captured by the Adagdak lava record, highlighting the utility of cumulates in chronicling the early isotopic evolution of magmatic systems.

Hydrogen and oxygen isotopic compositions of serpentinite and their influencing factors

Hydrogen and oxygen isotopic compositions of serpentinite and their influencing factors

Hydroclimate of the Messinian Salinity Crisis constrained from paleo-water triple oxygen, hydrogen, and strontium isotopes

Giant evaporite deposits formed during the Messinian Salinity Crisis (MSC) in the Mediterranean Sea during the upper Miocene. The primary cause is a restricted Atlantic-Mediterranean connection, but the detailed hydroclimate evolution of this event is still a matter of debate. Here we reconstruct the triple oxygen and hydrogen isotopic composition of paleo brines from structurally bonded water in Messinian gypsum from Cyprus. A two-stage evaporation model is constructed to best approximate the hydrological conditions at which Messinian gypsum formed in marginal basins of the Mediterranean Sea. Subsequently, hydroclimatic parameters like paleo relative humidity (RH) are modelled using an iterative curve fitting isotope model approach. The results of our limited dataset reveal a slightly lower RH during the third compared to the second stage of the MSC. This apparent drop in RH is consistent with previous observations from the literature.Besides absolute values of RH, our model allows reconstructing the triple oxygen and hydrogen isotopic composition of the open Mediterranean Sea. This provides an estimate for the proportions of continental water vs. Atlantic seawater flowing into the basin, serving as a proxy for the size of the strait of Gibraltar. The model implies a continental water fraction of around 75–81 % both for the second and third stage of the MSC. In addition, we determined the 87Sr/86Sr of our samples to: i) confirm their stratigraphy; and ii) estimate the relative proportion of continental water vs. Atlantic seawater entering the Mediterranean using Sr mass balance calculations. The combined oxygen and Sr isotope records indicate a persistent connection to the Atlantic supporting the hypothesis that the striking drop in 87Sr/86Sr at the beginning of MSC stage 3 is mainly related to an increased contribution of continental water with low 87Sr/86Sr and high Sr concentrations from the Paratethys. Our results show that the combination of triple oxygen, hydrogen, and Sr isotope data provides a powerful tool to disentangle paleo-hydroclimate even in such complicated hydrological settings as the Mediterranean Sea during the MSC.

Carbon and hydrogen isotopic compositions of C7 hydrocarbons and their geochemical significance in light oils/condensates from the Kuqa Depression, Tarim Basin, NW China

In this study, the geochemical significance of the δ13C and δ2H values of selected C7 light hydrocarbons (nC7 = n-heptane; MCH = methylcyclohexane; Tol = toluene) is investigated in 58 light oil/condensate (LOC) samples from the Kuqa Depression of the Tarim Basin, NW China. For most of the LOCs in the western region, the nC7, MCH, and Tol exhibit systematic differences where δ13CnC7 < δ13CMCH < δ13CTol and δ2HTol < δ2HnC7 < δ2HMCH. LOCs from the eastern area have higher δ13Coil, δ13CTol, and δ13CMCH values than those from the western area and their δ13C values for C7 hydrocarbons are similar and δ2HnC7 < δ2HMCH < δ2HTol. These organic geochemical differences indicate that the LOCs from the western and eastern areas of the Kuqa Depression were mainly derived from lacustrine and coaly parent materials, respectively. The LOC reservoirs generally received a late hydrocarbon charge of the high-maturity natural gas, and the LOCs from the western Kela–Keshen areas subsequently experienced gas leakage. Hierarchical cluster analysis indicates that the most important influencing factor on the LOCs of the Kuqa Depression is the sedimentary facies (coaly and lacustrine), followed by gas leakage and then parent organic type (lacustrine sapropel and humic organic matter). A cross-plot of the Δδ2HTol–MCH versus Tol/MCH can distinguish the origins of continental facies parent materials and gas leakage of the LOCs.

Water use characteristics and the mechanism of water uptake in two typical sand-fixing species in Mu Us sandy land

Understanding water absorption mechanisms of sand-fixing plants is important for the rational establishment of plant community structures, thereby providing a scientific basis for desertification control and the efficient utilization of water resources in sandy areas. Based on the hydrogen and oxygen isotopic compositions of precipi-tation, soil water, xylem water, and groundwater, coupled with soil water-heat dynamics, annual water consumption characteristics of vegetation, using the multi-source linear mixing model (IsoSource), we analyzed the differences in water sources between Salix psammophila and Artemisia ordosica, during winter and the growing season. We further examined the effects of groundwater depth (2 m and 10 m), soil freezing-thawing, and drought on their water utilization to elucidate water absorption mechanisms of those species. The results showed that: 1) During soil freezing-thawing period (January to March), S. psammophila mainly utilized soil water in 60-120 cm depths below the frozen layer (69.1%). In the green-up season (April and May), soil water from the 0-60 cm layers could satisfy the water demand of S. psammophila (30.9%-87.6%). During the dry period of the growing season (June), it predominantly utilized soil water at the depth of 120-160 cm (27.4%-40.8%). Over the rainy season (July and September), soil water in 0-60 cm depths provided 59.8%-67.9% of the total water required. A. ordosica, with shallow roots, could not utilize soil water after complete freezing of root zone but could overwinter by storing water in rhizomes during autumn. During the growing season, it primarily relied on 0-40 cm soil layer (23.4%-86.8%). During the dry period, it mainly utilized soil water from 40-80 cm and 80-160 cm soil layers, with utilization rates of 14.6%-74.4% and 21.8%-78.2%, respectively. 2) With decreasing groundwater depth, vegetation shifted its water absorption depth upward, with water source of S. psammophila transitioning from 120-160 cm to 60-160 cm layers, while A. ordosica shifted water absorption depth from 80-160 cm to 0-40 cm. S. psammophila's utilization of soil water is influenced by transpiration, adopting an "on-demand" approach to achieve a balance between water supply and energy conservation, whereas A. ordosica tends to utilize shallow soil water, exhibiting a higher depen-dence on water sources from a single soil layer.

Different responses of oxygen and hydrogen isotopes in leaf and tree-ring organic matter to lethal soil drought.

The oxygen and hydrogen isotopic composition (δ18O, δ2H) of plant tissues are key tools for the reconstruction of hydrological and plant physiological processes and may therefore be used to disentangle the reasons for tree mortality. However, how both elements respond to soil drought conditions before death has rarely been investigated. To test this, we performed a greenhouse study and determined predisposing fertilization and lethal soil drought effects on δ18O and δ2H values of organic matter in leaves and tree rings of living and dead saplings of five European tree species. For mechanistic insights, we additionally measured isotopic (i.e. δ18O and δ2H values of leaf and twig water), physiological (i.e. leaf water potential and gas-exchange) and metabolic traits (i.e. leaf and stem non-structural carbohydrate concentration, carbon-to-nitrogen ratios). Across all species, lethal soil drought generally caused a homogenous 2H-enrichment in leaf and tree-ring organic matter, but a low and heterogenous δ18O response in the same tissues. Unlike δ18O values, δ2H values of tree-ring organic matter were correlated with those of leaf and twig water and with plant physiological traits across treatments and species. The 2H-enrichment in plant organic matter also went along with a decrease in stem starch concentrations under soil drought compared with well-watered conditions. In contrast, the predisposing fertilization had generally no significant effect on any tested isotopic, physiological and metabolic traits. We propose that the 2H-enrichment in the dead trees is related to (i) the plant water isotopic composition, (ii) metabolic processes shaping leaf non-structural carbohydrates, (iii) the use of carbon reserves for growth and (iv) species-specific physiological adjustments. The homogenous stress imprint on δ2H but not on δ18O suggests that the former could be used as a proxy to reconstruct soil droughts and underlying processes of tree mortality.

Impact of Noodle Formulation, Boiling Methodology and Their Interactions on Stable Hydrogen and Oxygen Isotope Ratios.

Stable isotopes are commonly utilized for the geographical origin verification of foods, including wheat. However, assessing processed products poses a greater challenge due to the alterations that take place during processing and which have not been fully elucidated yet. In the current study, the effects of the formulation (the mass ratios of gluten to starch), boiling process and their interaction on the stable hydrogen (δ2H) and oxygen (δ18O) isotopic ratios of wheat noodles were evaluated. The δ2H and δ18O of noodles with different formulations (the mass ratios of gluten to starch) as raw materials, in uncooked and cooked (boiled in water) noodles, were examined. The results indicated that the δ2H of the boiled noodles ranged from -80.1‱ to -46.8‱ and were significantly lower than those of the raw materials, which ranged from -73.0‱ to -39.2‱, and the uncooked noodles, which ranged from -73.3‱ to -39.6‱. Oppositely, 18O was enriched in the boiled noodles, ranging from 27.7‱ to 31.3‱, compared with the uncooked noodles, ranging from 28.4‱ to 29.6‱. In addition, a significant interaction effect between the formulation and the boiling process was recorded for δ18O. This study shows that the hydrogen and oxygen stable isotopic compositions of noodles were significantly changed during the boiling process, and the isotopic fractionation varies with the different formulations.

Evolution of winter precipitation in the Nile river watershed since the last glacial

Abstract. Between 14.5 and 5 ka, the Sahara was vegetated owing to a wet climate during the African humid period. However, the climatic factors sustaining the “green Sahara” are still a matter of debate. Particularly the role of winter precipitation is poorly understood. Using the stable hydrogen isotopic composition (δD, where D stands for deuterium) of high molecular weight (HMW) n-alkanoic acids in a marine sediment core from the eastern Mediterranean, we provide a continuous record for winter precipitation in the Nile river delta spanning the past 18 kyr. Pairing the data with δD records from HMW n-alkanes from the same core, we show that HMW n-alkanoic acids constantly derived from the delta, while the HMW n-alkanes also received significant contributions from the headwaters between ∼ 15–1 ka when fluvial runoff enhanced. This enables us to reconstruct the evolution of Mediterranean (winter) and monsoonal (summer) rainfall in the Nile river watershed in parallel. In the delta, the Heinrich stadial 1 (HS1) evolved in two phases, with a dry episode between ∼ 17.5–16.0 ka, followed by wet conditions between ∼ 16–14.5 ka. Winter rainfall enhanced substantially between 11–6 ka, lagging behind the intensification of the summer monsoon by ca. 3 kyr. Heavy winter rainfall resulted from a southern position of the Atlantic storm track combined with elevated sea surface temperatures in the eastern Mediterranean, reinforcing local cyclogenesis. We show that during the green Sahara, monsoon precipitation and Mediterranean winter rainfall were both enhanced and infer that the winter rainfall zone extended southwards, delivering moisture to the Sahara. Our findings corroborate recent hypotheses suggesting that winter rains that extended southward were a crucial addition to the northward displacement of the summer monsoon in helping to sustain a green Sahara.

Spatiotemporal Absorption Features of Yellow Willow Water Usage on the Southern Edge of the Semi-Arid Hunshandak Sandland in China

The improvement of water usage efficiency and productivity, as well as the development of effective water management plans, necessitates a comprehensive understanding of how water utilization patterns in different soil layers within arid and semi-arid climates impact the capacity of plant roots to absorb water. However, there is currently no knowledge regarding the water use strategies employed by artificial yellow willow. So, we conducted a study on the hydrogen and oxygen isotopic composition of rainfall in yellow willow (Salix gordejevii) from the semi-arid region located at the southern edge of the Hunshandak Sandland in China. This study utilized measured data on xylem water, groundwater, soil moisture, and rainfall. By employing a combination of the direct comparison method and the MixSIAR model, we investigated the water uptake strategies employed by yellow willow throughout its growing season. The findings revealed that the mean δ D was highest in precipitation and lowest in groundwater, whereas the mean δ18O was highest in stem water and lowest in groundwater. The δ D and δ18O fluctuated significantly in precipitation but were steady in groundwater. Because precipitation was significantly less than evaporation, the slope and intercept were lower for the local than global atmospheric precipitation line. Water availability steadily declined with increasing depth. Lower δ18O values were caused by precipitation diluting the soil water. The MixSIAR results indicated that the primary source in May, September, and October was utilized at 19%, 18%, and 18%, respectively. In contrast, the utilization rate of each source varied considerably in June, July, and August (the primary source was utilized at 19%, 18%, and 18%, respectively). Comparatively high rates of water absorption and utilization were observed in June (19% of the total water source), July (18%), and August (23%). Therefore, the vertical distribution of the root system and variations in the soil water content regulate water usage for the yellow willow. To prevent excessive water usage and promote ecosystem restoration with artificial yellow willow plantations in water-limited desert settings, policy makers should consider the patterns of plant water use and soil water availability. By selecting drought-adapted plant species and optimizing irrigation management, it is possible to reduce water wastage and ensure that water is used efficiently for revegetation and ecosystem restoration, avoiding overuse of water and maintaining the sustainability of revegetation in water-stressed desert areas.

Hydrogen isotope records of long-chain alkanes from the monsoon boundary zone over the last 2400 years in North China

The East Asian Summer Monsoon (EASM) plays a key role in the climate dynamics of East Asia, affecting the livelihood of millions of people by contributing to agriculture and water resources. The monsoon boundary zone (MBZ) is particularly sensitive to shifts in climate patterns. However, the complexity of water vapor sources in the region makes it difficult to understand precipitation processes. To address this issue, the records of lipid biomarker abundances and leaf wax stable hydrogen isotope composition of C31–alkanes (δDwax-C31) from a 238 cm sediment core extracted in Lake Dali, located at the northern edge of the EASM, were sampled and examined by 2 cm per sample. Based on analyses of the biogenic molecular indicators(biomarkers), precipitation isotopes, and other indicators of the evolution of the climate environment, we have reconstructed precipitation change history over the past 2400 years. The results show the decrease in alkanes concentrations, along with high A.I. values in Lake Dali sediments indicate an arid trend over the past 2400 years, which have led to a decrease in basin productivity and the development of grasslands. The low temperatures greatly limit the growth of C4 vegetation in this cold region, so the long-chain alkanes in the lake sediments is mainly derived from the leaf wax lipids of C3 vegetation in the grassland. The increase of Paq and the reduction of ACL indicate that the decrease of grass vegetation inputs in the basin and the outbreak of aquatic vegetation. Notably, aquatic vegetation outbreaks may be due to reduced precipitation leading to shrinking lakes and increased nutrients in the lakes. By comparing with the biogenic indicators of Lake Dali and other regional records, the δDwax-C31 value can be used as a proxy for the regional precipitation, with a gradual decrease from about −240 ‰ to about −190 ‰, which indicates a general decreasing trend in the precipitation in the last 2400 years. Specifically, in exception of some significant fluctuations on the centennial to millennial scale, δDwax-C31 value decrease by about 40 ‰ between 1800 and 1600 cal.a BP over a period of only 200 years. As we know, the diminishing solar radiation might lead to a weaker EASM and a reduction in precipitation. Thus, the decrease in regional temperature became the main reason for the anomalous negative precipitation isotope phenomenon due to the lower precipitation from 1800 to 1600 cal.a BP in the monsoon boundary zone (MBZ, this represents only the northern boundary). This study contributes to our understanding of δDwax-C31 within the MBZ and its significance as an indicator of rainfall processes. By analyzing this molecular proxy, the researchers gain insights into the past precipitation patterns and their implications for regional climate. Importantly, the study demonstrates the value of combining biogenic molecular indicators with geochemical indicators, as it leads to improved accuracy in reconstructing regional climate conditions. The findings shed light on long-term climate trends and provide a more comprehensive understanding of the historical impacts of climate change on the EASM region. Moreover, the study's contribution to interpreting the paleoclimate record is crucial for validating climate models used to project future climate scenarios. Overall, this research enhances our knowledge of regional climate dynamics and their implications, offering valuable insights for both historical analysis and future climate projections.

Stable hydrogen and oxygen isotope geochemistry of Fe3+-rich, interstratified clay minerals from seafloor hydrothermal sites

Chemical and structural complexities in interstratified clay minerals arising from mineral transformations and evolving formation conditions should be recorded in their stable isotope signatures. This paper examines the controls on the stable hydrogen and oxygen isotope compositions of Fe3+-rich, glauconite-nontronite, talc-nontronite and talc-saponite from submarine hydrothermal sites, with a focus on the Red Sea Atlantis II Deep. Values of δ18O became less positive in the order nontronite > glauconite-nontronite > talc-nontronite > talc-saponite, yielding oxygen isotope temperatures ranging from ∼40 °C for nontronite to ∼135–300 °C for talc-saponite. These clay minerals have low δ2H, ranging from −145 to −127‰ for talc-nontronite, −135‰ for nontronite, −129 to −85‰ for glauconite-nontronite, and −95 to −59‰ for talc-saponite. The clay mineral-water hydrogen isotope fractionation is strongly affected by Fe3+ content, with increasing structural Fe3+ causing progressive weakening of O-H bonds. The large ionic radius and high charge of Fe3+ cause it to be more poorly shielded by surrounding oxygen from hydroxyl hydrogen relative to other octahedral or tetrahedral cations. The resulting lengthening of O-H bonds favours 1H over 2H. Our results confirm that Fe-rich phases, such as nontronite-glauconite, are produced at the lowest temperatures and Mg-rich phases, such as talc-saponite, are formed at the highest temperatures in seafloor hydrothermal environments. Evolving fluid chemistry and fluid pathways during clay mineral formation are also important. Glauconite layer formation from precursor nontronite likely occurred during diagenesis; redox changes causing Fe-reduction and an increase in layer charge facilitated interlayer K-fixation. Talc-saponite compositions vary with temperature and fluid chemistry, forming at variable sediment depths depending on access to the hottest hydrothermal fluids.

Application of geochemical tracers for the investigations of groundwater resources in semi‐arid region (Central‐East Tunisia)

AbstractGroundwater resources in Mahdia‐Ksour Essef region, located in the central‐eastern part of Tunisia, suffer from intensive exploitation and degradation of water quality. The assessment of groundwater vulnerability, the well‐understanding of geochemical processes and the investigation of groundwater quality variations are of particular importance for water resources management in this semi‐arid region. The results of this multi‐disciplinary investigation show that groundwaters of Mahdia‐Ksour Essef region are flowing from El Jem and Boumerdes regions in the South, towards the Mediterranean Sea and the sebkha of Moknine in the North. The groundwaters are classified as either Na‐Cl or Ca‐SO4. Stable oxygen and hydrogen isotope compositions (δ18O and δ2H) confirm a recharge by rapid water infiltration, evaporate surface water and water‐rock interaction processes in the salinity increase. The rock‐water interaction processes of the mineralization of groundwaters include the cation‐exchange reactions and the dissolution of carbonates and evaporate. The high values of the water quality index (WQI) and of the total dissolved solids (TDS) (3.7–11 g/L) of these groundwaters indicate their unsuitability for drinking purpose. Moreover, the combination of the WQI, TDS and nitrate results prove the vulnerability of the studied groundwater to the anthropogenic pollution linked to agriculture and domestic activities and to the salt water contamination.

Stable isotopes in the shell organic matrix for (paleo)environmental reconstructions

Stable isotope ratios of mollusc shell carbonates have long been used to reconstruct past environmental conditions. Although shells also contain organics, they are seldom used in (paleo)climatic studies. Here, we extract the acid-soluble and insoluble fractions of the organic matrix of modern Mytilus galloprovincialis shells from three sites along a coast–to-upper-estuary environmental gradient to measure their hydrogen (δ2H) and oxygen (δ18O) isotope compositions. Both organic fractions showed isotopic signatures significantly different from those of carbonate and water at each site, indicating the involvement of different fractionation mechanisms. The soluble fraction showed gradual differences in isotope values along the gradient, while the insoluble fraction showed δ2H-δ18O correlation regressions subparallel to the Global and Local Meteoric Water Lines. These results showed the great potential of the shell organic matrix stable isotopes as possible (paleo)environmental proxies, stimulating further research to better define the fractionation mechanisms involved.

Detection of apatite in ferroan anorthosite indicative of a volatile-rich early lunar crust

Determination of the systematics of volatile elements (for example, H, Cl, S) of the early Moon is one of the main objectives of lunar science. This has been hindered by the lack of the main volatile-bearing mineral, apatite, in ferroan anorthosites (FANs), which are thought to represent the primary products of the lunar magma ocean and the earliest lunar crust. Due to the absence of apatite, plagioclase and bulk samples of the FAN suite have been previously utilized for the studies of volatiles in samples representing the earliest-formed lunar crust. Here we provide evidence of apatite in a FAN clast in the lunar meteorite Arabian Peninsula 007. We report that Arabian Peninsula 007 has an ancient age, comparable to those of Apollo FAN samples, with lighter hydrogen (δD = −45‰) and heavier chlorine (δ37Cl = +44‰) isotopic compositions than FAN bulk and plagioclase data. These results suggest that the early lunar crust was significantly more volatile rich than previously thought.

Geochemical characteristics of shale gas hydraulic fracturing flowback/produced water in Zheng’an block, northern Guizhou Province, China

Guizhou Province of China is rich in shale gas resources. In recent years, important progress has been made in the exploration and development of shale gas in the Upper Ordovician Wufeng Formation-Lower Silurian Longmaxi Formation in Zheng'an block in northern Guizhou, adjacent to Sichuan Basin. Due to the complex geological conditions and fragile ecological environment in the shale gas distribution area, serious environmental pollution risks may exist in shale gas exploitation. Therefore, this paper conducted element, hydrogen and oxygen isotope analyses for shale gas fracturing flowback/produced water of Well AY7-4 in Zheng'an block. The results showed that the contents of K, Na, Ca, Mg and NH4+ in the flowback/produced water of Well AY7-4 were very high, with an average of 118 mg/L, 7616 mg/L, 266 mg/L, 47 mg/L and 76 mg/L, respectively. The content of Na, Ca and Mg is similar to that of shale gas flowback/produced water in Weiyuan, but lower than that in Changning and Fuling. NH4+ content was similar to that in Changning, but much higher than that in Weiyuan. The average Cl content was 11605 mg/L, which was similar to that in Weiyuan, but lower than that in Changning and Fuling. The average Br content is 48 mg/L, slightly lower than that of Weiyuan, and about half of that of Changning and Fuling. Correspondingly, the Br/Cl value of Well AY7-4 is the lowest, reflecting its relatively low Br content. The average content of Li, B and Sr is 17 mg/L, 10 mg/L and 45 mg/L, respectively, which is similar to that of the Weiyuan, Changning and Fuling shale gas fields. The distribution model of Li and Sr is similar to that of Cl, Br and Na, but the B content and B/Cl value of Well AY7-4 are the lowest. The linear relationship between Br and Cl contents and between δD and δ18O of flowback/produced water of Well AY7-4, freshwater used for hydraulic fracturing and hydraulic fracturing injected fluid indicates that flowback/produced water of Well AY7-4 is mainly the mixed product between low salinity injected fracturing fluid and high salinity brine retained in shale formation. The hydrogen and oxygen isotopic compositions gradually become heavier over time, indicating that the proportion of high salt end formation brine in flowback/produced water is increasing. The contents of Cl, Br, Na and NH4+ in the flowback/produced water of Well AY7-4 are far higher than the allowable discharge value, which is a potential environmental pollution risk and cannot be discharged directly.

Late Quaternary human-environment relationship in the Ganga Plain, India

Here, we present the first-ever attempt to combine palaeoenvironmental records (n = 17) from dated stratigraphic sequences with Geographic Information System (GIS) spatial modelling of archaeological sites (3 phases; n = 306 sites) in the Ganga Plain. The spatial modelling assesses the distribution of archaeological sites and phases on maps showing changing elevation, geology, geomorphology, biome, and rainfall variability within the Ganga Plain, aiming to evaluate the human-environment relationship during the Late Quaternary Period.The compilation of oxygen and hydrogen isotopic composition (δ18O and δD values) and pollen-based environment reconstructions for the last ∼100 ka indicates high rainfall conditions during ∼100–75 ka, ∼10–5 ka, and ∼3.6–1.3 ka. Fluctuating rainfall conditions were observed during ∼75–25 ka and ∼18–15 ka, while the period from ∼25 to 18 ka was the weakest monsoon phase, marking the Last Glacial Maximum. Arid conditions were also observed during ∼15–10 ka and ∼5–3.6 ka. The archaeological review suggests the presence of the Acheulian culture, diverse Mesolithic cultures, and the Neolithic phase marked by advanced agriculture and pottery production in the Ganga Plain. The past environmental analyses show changes in settlement areas correlating with rainfall variations. Frequent climate changes and increasing population density during the Late Pleistocene-Early Holocene boundary probably forced prehistoric humans to adopt agricultural practices. The distribution of archaeological sites representing different cultural phases on the modern spatial maps of landscape variability (e.g., elevation, rainfall, geomorphology, and geology) reflects an intricate relationship between prehistoric human settlements, monsoonal rainfall, and climate-driven landform processes.Our assessment suggests that the integration of archaeological sites, geological mapping, vegetation analysis, and palaeoclimate records has the potential to provide valuable insights into ancient human-environment interactions. Therefore, we recommend continued interdisciplinary research in these fields to further enhance our knowledge of prehistoric societies and their responses to changing landscapes and climates in the Ganga Plain.