Stable Hydrogen Isotope Composition Research Articles

Exploring hydrogen isotope fractionation in lipid biomolecules of freshwater algae: implications for ecological and paleoenvironmental studies

ABSTRACT Understanding the stable hydrogen isotope (δ 2H) composition and fractionation in lipid biomolecules of primary producers, such as terrestrial and aquatic plants, is crucial for deciphering past environmental conditions, as well as applying compound-specific stable isotope analysis for the study of metabolic and ecological processes. We conducted a new tracer experiment to explore the δ 2H composition of algal fatty acid biomarkers, focusing on freshwater algae, which form the base of aquatic food webs. We selected a range of algal species widely found in freshwater ecosystems and cultivated them under controlled conditions. First, we added 2H2O to ambient water as a tracer to investigate the net hydrogen isotope fractionation during algal lipid synthesis at isotopic equilibrium, which is particularly informative for paleo-geochemical studies. Then, we conducted kinetic experiments to quantify the time needed for algal fatty acids to achieve isotopic steady-state conditions in response to the change in ambient water δ 2H values. Our findings revealed substantial variability in hydrogen isotope fractionation among different algal taxa and various fatty acids. Based on taxa, different fatty acids exhibited faster integration of water hydrogen than others, but they were not necessarily in the order of the biosynthetic pathway. This experiment underscores the complexity of hydrogen isotope fractionation and the requirement for controlled laboratory studies to properly apply compound-specific stable H isotope analysis techniques in ecological and paleo-environmental studies.

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.

Radiocarbon dating of the natural groundwater in the Ob-Zaisan folded region (Russia)

Groundwater in the Ob-Zaisan folded region (Russia) has significant differences in the stable isotope composition of oxygen and hydrogen, which cannot be explained by the geographical and relief features of the region. A probable reason for these differences could be climatic changes in the study area over the past tens of thousands of years. The method of the radiocarbon dating can be perfectly suited in order to determine such small geological ages. The dating of waters using 14C data gives an understanding of their residence time. It will make it possible to differentiate periods of recharge and accumulation of water in aquifers and track the changes of the water stable isotope composition over time. The estimated water age ranges from 650 to 19,000 years. The enrichment of δD and δ18O values with the decreasing of the water age indicates a gradual warming of the Novosibirsk region climate. These results logically complement the meteorological observations over the last century and may be useful for paleoclimate reconstructions of the region.

Landscape and paleoenvironmental change in stream valleys of the Central Great Plains, North America, during Marine Isotope Stage 3 (ca. 59–27 ka)

Recent studies of late Quaternary landscape evolution in stream valleys throughout the central Great Plains of North America have identified thick packages of MIS 3-age alluvium and colluvium beneath terraces, alluvial fans, and footslopes. Here, we review and build on these studies to highlight the geomorphic history of river systems in the Central Plains during MIS 3 and reconstruct the paleoclimatic conditions and vegetation communities that existed in the region at that time.A suite of 50 radiocarbon and optically stimulated luminescence ages indicate that late MIS 3 was a period of widespread landscape stability and soil development in the Central Plains. In general, river systems were actively aggrading during early MIS 3, but aggradation slowed after ca. 40 ka, allowing soils to develop until ca. 30–27 ka. In some river valleys, a second pulse of aggradation occurred shortly after that time followed by a period of landscape stability and pedogenesis during early MIS 2 (ca. 24–19 ka). Evidence for widespread landscape stability in stream valleys implies that high magnitude flooding was minimal. Atmospheric circulation patterns that favor these conditions include zonal airflow that inhibits incursions of moist, maritime air from the Gulf of Mexico.Paleoenvironmental conditions during late MIS 3 were reconstructed using the stable carbon, oxygen, and hydrogen isotopic composition of pedogenic phyllosilicates, carbonates, and organic matter. Estimated paleotemperatures ranged from 6 to 9 °C ± 3 °C and are approximately 4–7 °C lower than modern mean annual temperature. The estimated δ18O values of soil water from phyllosilicates range from −10.6‰ to −9.6‰. These estimates are lower (18O-depleted) by about 1.5–3‰ relative to modern meteoric δ18O values and we estimate that the δ18O of paleoprecipitation was likely 18O-depleted by up to 8.5‰ relative to modern values. Our estimated δ18O values for soil waters in the Central Plains during late MIS 3 can be explained by climatic conditions characterized by 1) cooler temperatures, 2) precipitation being sourced primarily from Pacific/Arctic air masses, 3) seasonal changes in precipitation patterns (i.e., predominantly winter precipitation), or 4) a combination of the above. δ13C values indicate the presence of a notable proportion of C4 vegetation in the Central Plains during late MIS 3. We suggest that C4 productivity was likely favored at that time by a low atmospheric CO2 environment that had sufficiently warm temperatures and effective precipitation during the growing season.

Leaf wax n-alkane distribution and hydrogen isotopic fractionation in fen plant communities of two Mediterranean wetlands (Tenaghi Philippon, Nisí fen—Greece)

Many continental paleoclimate archives originate from wetland sedimentary sequences. While several studies have investigated biomarkers derived from peat-generating vegetation typical of temperate/boreal bogs (e.g., Sphagnum), only scant information is available on emergent plants predominant in temperate/subtropical coastal marshlands, peri-lacustrine and fen environments. Here, we address this gap, focusing on two wetlands in the Mediterranean (Nisí fen and Tenaghi Philippon, Greece). We examined the concentration, homologue distribution, and hydrogen stable isotopic composition (δ2H) of leaf wax n-alkanes in 13 fen plant species, their surrounding soil, and surface water during the wet growing season (spring) and the declining water table period (summer). Our findings indicate that local graminoid species primarily contribute to the soil n-alkane signal, with a lesser influence from forbs, likely owing to differences in morphology and vegetation structure. The δ2H values of surface and soil water align with local average annual precipitation δ2H, reflecting winter-spring precipitation. Consistently, the average δ2H of local surface, soil, and lower stem water showed negligible evaporative enrichment, confirming minimal 2H-fractionation during water uptake. We find that δ2H values of source water for wax compound synthesis in local fen plants accurately mirror local annual precipitation. Furthermore, despite differences between leaves and lower stems in n-alkane production rates, their δ2H values exhibit remarkable similarity, indicating a shared metabolic substrate, likely originating in leaves. Our net 2H-fractionation values (i.e., precipitation to leaf n-alkanes) align with those in Chinese highlands and other similar environments, suggesting consistency across diverse climatic zones. Notably, our data reveal a seasonal decrease in the carbon preference index (CPI) in plant samples, indicating wax lipid synthesis changes associated with increased aridity. Additionally, we introduce a new parity isotopic difference index (PID) based on the consistent δ2H difference between odd and even n-alkane homologues. The PID demonstrates a strong anticorrelation with plant CPI, suggesting a potential avenue to trace long-term aridity shifts through δ2H analysis of odd and even n-alkane homologues in sedimentary archives. While further development of the PID is necessary for broad application, these findings highlight the intricate interplay between plant physiology, environmental parameters, and sedimentary n-alkanes in unravelling past climatic conditions.

Large enrichments in fatty acid 2H/1H ratios distinguish respiration from aerobic fermentation in yeast Saccharomyces cerevisiae

Shifts in the hydrogen stable isotopic composition (2H/1H ratio) of lipids relative to water (lipid/water 2H-fractionation) at natural abundances reflect different sources of the central cellular reductant, NADPH, in bacteria. Here, we demonstrate that lipid/water 2H-fractionation (2εfattyacid/water) can also constrain the relative importance of key NADPH pathways in eukaryotes. We used the metabolically flexible yeast Saccharomyces cerevisiae, a microbial model for respiratory and fermentative metabolism in industry and medicine, to investigate 2εfattyacid/water. In chemostats, fatty acids from glycerol-respiring cells were >550‰ 2H-enriched compared to those from cells aerobically fermenting sugars via overflow metabolism, a hallmark feature in cancer. Faster growth decreased 2H/1H ratios, particularly in glycerol-respiring cells by 200‰. Variations in the activities and kinetic isotope effects among NADP+-reducing enzymes indicate cytosolic NADPH supply as the primary control on 2εfattyacid/water. Contributions of cytosolic isocitrate dehydrogenase (cIDH) to NAPDH production drive large 2H-enrichments with substrate metabolism (cIDH is absent during fermentation but contributes up to 20 percent NAPDH during respiration) and slower growth on glycerol (11 percent more NADPH from cIDH). Shifts in NADPH demand associated with cellular lipid abundance explain smaller 2εfattyacid/water variations (<30‰) with growth rate during fermentation. Consistent with these results, tests of murine liver cells had 2H-enriched lipids from slower-growing, healthy respiring cells relative to fast-growing, fermenting hepatocellular carcinoma. Our findings point to the broad potential of lipid 2H/1H ratios as a passive natural tracker of eukaryotic metabolism with applications to distinguish health and disease, complementing studies that rely on complex isotope-tracer addition methods.

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.

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 hydrogen isotope compositions of tourmalines from the Sopron metamorphic complex: Metamorphic closure temperature and fluid composition

AbstractStable hydrogen isotope compositions of metamorphic rocks and minerals can provide information on the origin of metamorphic fluids, which is especially important in systems that had experienced multiple metamorphic events. The Sopron orthogneiss-micaschist complex is a good target as it records signs of Variscan and Alpine metamorphic events as well as Variscan granitic magmatism. In this study tourmaline-bearing rocks (pegmatitic orthogneisses and kyanite-chlorite-muscovite schists) of the Sopron metamorphic complex were sampled and their tourmaline grains were analyzed for stable hydrogen isotope compositions (δ2H). The δ2H values (−23 ± 1‰, relative to V-SMOW) are in accordance with a fluid flux from devolatilization of subducted, seawater-containing rocks. Tourmaline-chlorite hydrogen isotope fractionations correspond to about 550 °C, indicating that δ2H values formed close to peak metamorphic temperatures are preserved without retrograde isotope exchange during cooling.

Surface occurrence of dawsonite and natural CO2 emanation in Covasna, in the Eastern Carpathians: A stable isotope study

Dawsonite (NaAlCO3(OH)2) is widely known as a CO2 trapping mineral during the geological storage of CO2 (Carbon Capture and Storage). Dawsonite can occur naturally in various geological environments, however only few surface occurrences are known. The Covasna area (Eastern Carpathians) gives an excellent opportunity to study dawsonite in surface outcrop in the Hankó Valley and extend our knowledge about the possible precipitation environments of dawsonite. Based on the detailed petrographic and geochemical investigations of the rock and water samples from this area, formation environment of dawsonite and the concomitant mineral assemblage (e.g. alumohydrocalcite) were constrained. Based on our results, dawsonite and alumohydrocalcite formed at low temperature (7.6–20 °C). Utilizing the stable carbon, oxygen and hydrogen isotope composition of dawsonite separates (δ13CDaw: +8.0 − +10.1 ‰, δ18ODaw: +40.7 − +46.7 ‰, δ2HDaw: −55 - -42 ‰), the isotopic composition of the parental fluid was determined. Our results indicate that the dawsonite formed from a CO2 source, which has mantle origin. In addition, H2O which was present during the formation of dawsonite, had similar hydrogen isotope composition to recent spring waters, whereas the oxygen isotope composition is characterized by more positive values. This oxygen shifts relative to Global Meteoric Waterline might be related to water-rock interaction or contribution of metamorphic/magmatic water and oxygen isotope exchange between H2O and CO2.

The stable carbon and hydrogen isotopic composition of microbial fatty acids traces microbial metabolism in soils and peats

The compound-specific stable carbon (δ13C) and hydrogen (δ2H) isotopic compositions of microbial fatty acids have been widely used to trace microbial metabolism across a range of mesophilic environments. However, few studies have combined the δ13C and δ2H values of microbial fatty acids. So far none have determined the δ2H of microbial phospholipid fatty acids (PLFAs) in soils or peats, even though these stable isotope combinations could provide new insights into soil microbial metabolism. Here, we measured the δ13C and δ2H values of microbial PLFAs in top soils from peatlands, meadows, and woodlands in the Dajiuhu basin, central China. We observed a significant (p < 0.05) positive correlation between the δ13C and δ2H of microbial PLFAs across the three habitats studied here, indicating that central metabolic pathways affect both carbon and hydrogen isotopic compositions of microbial PLFAs. Moreover, our stable isotope data consistently indicate a relatively conservative metabolic state, which is dominated by expected heterotrophic metabolism. The exception to these observations is PLFAs associated with methanotrophs, as these appear to have decoupled carbon and hydrogen isotopes, providing an additional tool for tracing methanotrophic signals. Our results suggest that the carbon and hydrogen dual isotopic composition of microbial PLFAs can not only provide cross-validation for microbial metabolism in natural environments, but as a combined tool can also provide new insights into the perturbation of soil microbial community metabolism.

Determination of Stable Hydrogen Isotopic Composition and Isotope Enrichment Factor at Low Hydrogen Concentration.

Determination of stable hydrogen isotopic compositions (δ2H) is currently challenged to achieve a high detection limit for reaching the linear range where δ2H values are independent of concentration. Therefore, it is difficult to assess precise δ2H values for calculating the hydrogen isotope enrichment factor (εH) and for field application where the concentrations of contaminants are relatively low. In this study, a data treatment approach was developed to obtain accurate δ2H values below the linear range. The core concept was to use a logarithmic function to fit the δ2H values below the linear range and then adjust the δ2H values below the linear range into the linear range by using the fitted logarithmic equation. Moreover, the adjusted δ2H values were calibrated by using laboratory reference materials, e.g., n-alkanes. Tris(2-chloroethyl) phosphate (TCEP) and hexachlorocyclohexane (HCH) isomers were selected as examples of complex heteroatom-bearing compounds to develop the data treatment approach. This data treatment approach was then tested using δ2H values from a TCEP transformation experiment with OH radicals. Comparable δ2H values and εH between the low-concentration experiment and the reference experiment were obtained using the developed approach. Therefore, the developed data treatment approach enables a possibility of determining the hydrogen isotopic compositions of organic components in low concentrations. It is especially valuable for determining organic contaminants in environmental samples, which are usually present in low concentrations.

Studying the isotopic composition of microbial methane with a genetically-tractable methanogen

Nearly all biogenic methane is produced by a group of microorganisms called methanogenic archaea (or methanogens). Methanogens can use a variety of substrates, such as H2 + CO2, acetate, and methylated compounds, for methanogenesis. Previous studies have shown that the stable carbon and hydrogen isotopic compositions of methane produced by methanogens can vary drastically depending on the substrate composition and concentration in the environment. For instance, the concentration of H2 in the environment has a substantial impact on the isotopic composition of methane derived from hydrogenotrophic methanogenesis (reduction of CO2 to methane using H2 as the electron donor) (Valentine et al. 2004, Penning et al. 2005). While there is substantial empirical data on isotopic signatures of methane from different substrates and under different conditions, the physiological and molecular features that control these values are not as well understood. To address this, we are using the metabolically diverse and genetically tractable methanogen, Methanosarcina acetivorans as a model system to uncover key cellular processes that control the stable bulk isotopic composition of methane (i.e., 13C/12C and D/H ratios), and the distributions of the “clumped” 13CH3D and 12CH2D2 isotopologues. The methanogen M. acetivorans grows on a wide variety of compounds such as acetate, methanol, methylamines, and methylsulfides. We found that the methylotrophic pathways (for methanol and trimethylamine) and the aceticlastic pathway have large and similar primary hydrogen isotopic effects (α of ~0.45). These data are in contrast to previous findings and imply a minor isotopic exchange between CH4 and H2O (Valentine et al. 2004, Gruen et al. 2018). Focusing first on the methylotrophic pathway, we generated mutants of two key enzymes in the methylotrophic pathway: a) methyl coenzyme M reductase (Mcr) that catalyzes the last step in methanogenesis and b) methyltransferases that catalyze the first step in methylotrophic methanogenesis from methanol (Mta). A mutant with reduced Mcr expression had no observable change in the hydrogen isotopic effect relative to the wild-type, validating the initial observation of minimal H2O-CH4 hydrogen isotopic exchange. One of the Mta mutants, which only expressed a specific methyltransferase isoform, had a smaller carbon isotopic effect relative to the other isoforms (α of ~1.074 vs. ~1.080). Since the isoforms are thought to be identical in structure, the different isotopic effects could result from differential expression of each isoform, or from different kinetic properties. By combining our genetic approaches with traditional and high-resolution isotopic analytical methods, we aim to develop a quantitative understanding of the mechanisms that control the isotopic compositions of biological methane. Our preliminary results show that M. acetivorans would be an ideal candidate for such research, which could help in understanding methanogens’ physiology in natural environments in past, present, and future Earth.

Glacial–interglacial seawater isotope change near the Chilean Margin as reflected by δ2H values of C37 alkenones

Abstract. Stable hydrogen isotopic compositions of long-chain alkenones with 37 carbon atoms (δ2HC37) have been shown to reflect seawater salinity in culture and environmental studies, and this potential sea surface salinity proxy has been applied to several downcore records from different regions. However, previous studies were based solely on a single sediment core and often suggested unlikely large changes in salinity based on existing proxy calibrations. Here we present a new δ2HC37 record, in combination with oxygen isotopes of benthic foraminifera from the same samples, from a sediment core from the Chilean Margin (ODP Site 1235). The observed negative shift in δ2HC37 of 20 ‰ during the last deglaciation was identical to that of a previously published δ2HC37 record from the nearby, but deeper, ODP Site 1234, suggesting a regionally consistent shift in δ2HC37. This change translates into a negative hydrogen isotope shift in the surface seawater of ca. 14 ‰, similar to glacial–interglacial reconstructions based on other δ2HC37 records. The reconstructed bottom seawater oxygen isotope change based on benthic foraminifera during the last deglaciation is approximately −0.8 ‰, in line with previous studies. When translated into hydrogen isotopes of bottom seawater using the modern open-ocean water line, this would suggest a negative change of ca. 5 ‰, smaller than the reconstructed surface seawater shift based on alkenones. The larger change in surface water isotopes suggests that it experienced more freshening during the Holocene than bottom waters, either due to increased freshwater input, reduced evaporation, or a combination of the two.

Satellite-Based Distribution of Inverse Altitude Effect of Global Water Vapor Isotopes: Potential Influences on Isotopes in Climate Proxies

The widely-distributed altitude effect of stable isotopes in meteoric water, i.e., the negative correlation between stable hydrogen (or oxygen) isotope compositions and altitude, is the theoretical basis of isotope paleoaltimetry in climate proxies. However, as many recent local observations have indicated, the inverse altitude effect (IAE) in meteoric water does exist, and the regime controlling IAE is still unclear on a global scale. Based on a remote sensing product of the Infrared Atmospheric Sounding Interferometer (IASI), we examined the global frequency of IAE in water vapor isotopes, and the possible influences on isotopes in precipitation and climate proxies. According to the satellite-based δD values in water vapor at 2950 m and 4220 m above sea level, frequent IAEs are observed on a daily scale in North Africa, West and Central Asia, and North America, and IAEs are more likely to occur during the daytime than during the nighttime. We also converted water vapor δD to precipitation δD via equilibrium fractionation and then analyzed the potential presence of IAE in precipitation, which is more associated with climate proxies, and found that the spatial and temporal patterns of water vapor can be transferred to the precipitation. In addition, different thresholds of δD difference were also tested to understand the impact of random errors. The potential uncertainty of the changing isotope and altitude gradient should be considered in paleo-altitude reconstructions.

Moisture sources and climatic effects controlling precipitation stable isotope composition in a western Mediterranean island (Pianosa, Italy)

The Mediterranean basin is indicated as a hot spot of climate change, which is an area whose climate is especially responsive to variations. The insular environment is one of the most threatened by the current climate change, especially in terms of drought events, with serious consequences for water scarcity and water stress. This issue is even enhanced in small islands, whose ecosystems are among more sensitive to climatic changes and water availability. The stable isotope composition of hydrogen (δ2H) and oxygen (δ18O) in precipitation is globally recognized as a powerful natural tracer in the water cycle and represents the starting point to investigate hydrological processes. The understanding of the prevailing factors that drive the isotopic variability of precipitation in the Mediterranean is therefore essential to unravel the hydrological processes and to ensure proper and sustainable management of potentially vulnerable resources to climate change. Here, we discuss the results of multi-year isotopic monitoring in the period 2014–2021 of monthly precipitation collected on Pianosa Island (Italy), a small island located in the northern Tyrrhenian (western Mediterranean). The lower slope and intercept of the Local Meteoric Water Line of the island compared to the Global Meteoric Water Line indicated warmer and drier climatic conditions, suggesting the existence of sub-cloud evaporation processes of raindrops during precipitation, especially in summer. The mean δ18O of precipitation was lower with respect to other sites placed at higher elevation in this Mediterranean region, due to the lack of summer precipitation which were generally enriched in heavy isotopes. Temperature and amount effects may explain part of the δ18O variability observed at the monthly and seasonal scale. An HYSPLIT-based moisture uptake analysis indicated the area between the western Mediterranean basin, Italy, and the Adriatic Sea as the region that supplied most of the humidity associated with monthly precipitation samples on Pianosa Island. Less moisture was picked from the northwestern areas of Europe, the North Atlantic Ocean, the proximal Atlantic Ocean, the Iberian Peninsula and North Africa. Consistently with the rainout effect, the higher the moisture fraction picked from the more proximal regions, the more positive the δ18O of precipitation occurring on Pianosa Island; conversely, the higher the percentage of moisture sourced from more distal regions, the more negative the δ18O. A multiple linear model was proposed to predict the δ18O of monthly precipitation from temperature, precipitation amount and moisture origin data, which explained 45% of the δ18O variability. The deuterium excess variability on the island was partly controlled by the local climatic variables, whose effect potentially modifies the original d-excess signature imprinted at the moisture source. No relationship was found between the precipitation deuterium excess and moisture sources, suggesting that more attention should be paid when using the deuterium excess as a tracer of moisture origin, especially in the Mediterranean.

Origin and evolution of Li-rich geothermal waters from the Kawu geothermal system, Himalayas: based on hydrochemistry and H-O, Li isotopes

ABSTRACT There are 25 Li-rich geothermal fields (>15 mg/L) are displayed throughout nine geothermal zones in Tibet. The Kawu geothermal system is one of the representative high-enthalpy and Li-rich geothermal systems and is located in the Skaya dome, the Himalayas. Their boiling and hot and cold waters are Cl-HCO3-Na and HCO3-Ca types, respectively. The parent geothermal fluids are characterized by high Na, Cl, B, Si, As, Li, Rb+, Cs+ and F, and the Cl− concentration and enthalpy of the parent geothermal liquid are 515 mg/L and 1,485 J/g, respectively (corresponding to a temperature of 323.5°C). The stable oxygen and hydrogen isotopic compositions of geothermal fluids range from −19.7 to −23.4‰ and −155 to −181.2‰, indicating that the ratio of magmatic water mixed into geothermal fluid is between 11.7% and 19.5%. The lithium content in the geothermal system is high (13.04 to 20.8 ppm), but the δ7Li is relatively low (1.06 to 1.72‰). The high Cl, Li and B contents, constant Cl/Li and Cl/B ratios and low δ7Li indicate that they mainly originate from magmatic fluid, rather than from water rock reaction with the leucogranite and gneiss. While ascending from the reservoirs to the surface, the parent geothermal fluids gradually mixed with the meteoric waters infiltrated via brittle tensional small-scale faults, in turn forming four cooling processes upwelling patterns, i.e. conductive cooling, adiabatic cooling, mixing with cold water, and the combination of these processes.

A speleothem record of seasonality and moisture transport around the 8.2 ka event in Central Europe (Vacska Cave, Hungary)

AbstractA stalagmite was collected in northern Hungary from the Vacska Cave, where monitoring and ventilation-based site selection had been conducted. The stalagmite covers the 10–8 ka (relative to AD 1950) period, including the so-called 8.2 ka event, and showed preceding signs of climate change that were evaluated by petrographic observations, 14C activities, Sr concentrations, and stable isotope compositions of calcite and inclusion-hosted water. Comparisons of speleothem records show that isotope peaks at ca. 8.5 ka are related to a regional climate anomaly, rather than to a continental-scale event. In accordance with regional proxy records, the 8.2 ka event was associated with a series of temperature and precipitation amount changes, starting with cooling and a reduction in the winter-to-summer precipitation ratio, and then becoming a humid and warm phase at 8.15 ka. X-ray diffraction-based crystallinity parameter (FWHM) values provided evidence for diagenetic alteration of the stable oxygen isotope compositions of inclusion waters. Nevertheless, the stable hydrogen isotope compositions of inclusion waters and the oxygen isotope values of the host calcite revealed elevated d-excess values, and therefore increased Mediterranean moisture contribution during the 8.2 ka event, which indirectly indicate the southward displacement of moisture transport from the Atlantic Ocean.