Hydrogen Isotope Fractionation Research Articles

Position-specific and clumped isotope equilibria in propane: Ab initio calculations beyond the harmonic and Born-Oppenheimer approximations

Position-specific and clumped isotope compositions that reveal intramolecular isotope distributions can offer novel insights into the physical and chemical properties of substances. In particular, the intramolecular isotope effects observed in propane have demonstrated significant potential for constraining the formation and evolution of hydrocarbons. To calibrate measurements and interpret observations, a comprehensive understanding of equilibrium isotope fractionation within propane is required. However, previous studies yielded inconsistent calculations of position-specific isotope equilibria, and lacked any prediction of clumped isotope equilibria in the methyl group of propane. Here, we employ quantum chemical calculations beyond the harmonic approximation and the Born-Oppenheimer approximation to study the intramolecular isotope equilibria in propane. Benchmark coupled cluster calculations (CCSD(T)) were used to produce reliable frequencies of propane isotopologues. By integrating the CCSD(T) outcomes with effects beyond the harmonic and Born-Oppenheimer approximations, we present high-accuracy equilibrium carbon and hydrogen isotope fractionation between the methylene and methyl sites, and report for the first time the equilibrium Δ13CH2D and Δ12CHD2 signatures of the methyl group in propane. Our results of position-specific isotope equilibria can serve as a reference frame for calibrating both theoretical calculations and experimental measurements. The equilibrium Δ13CH2D and Δ12CHD2 values provide a theoretical framework for further studies of 13CD and DD clumping in methyl groups of alkanes, and are valuable for tracing the sources and sinks of methyl groups as well as processes related to methylation.

Fractionation of Methane Isotopologues during Preparation for Analysis from Ambient Air.

Preconcentration of methane (CH4) from air is a critical sampling step in the measurement of singly and doubly substituted isotopologue ratios. We demonstrate the potential for isotope fractionation during preconcentration onto and elution from the common trapping material HayeSep-D and investigate its significance in laser spectroscopy measurements. By altering the trapping temperature for adsorption, the flow direction of CH4 through the trap and the time at which CH4 is eluted during a desorption temperature ramp, we explain the mechanisms behind fractionation affecting δ13C(CH4) and δ2H(CH4). The results highlight that carbon isotope fractionation is driven by advection and diffusion, while hydrogen isotope fractionation is driven by the interaction of CH4 with the adsorbing material (tending to smaller isotopic effects at higher temperatures). We have compared the difference between the measured isotope ratio of sample gases (compressed whole air and a synthetic mixture of CH4 at ambient amount fraction in an N2 matrix) and their known isotopic composition. An open-system Rayleigh model is used to quantify the magnitude of isotopic fractionation affecting measured δ13C(CH4) and δ2H(CH4), which can be used to calculate the possible magnitude of isotopic fractionation given the recovery percentage. These results provide a quantitative understanding of isotopic fractionation during the sample preparation of CH4 from ambient air. The results also provide valuable insights applicable to other cryogenic preconcentration systems, such as those for measurements that probe the distribution of rarer isotopologues.

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.

The determining factors of hydrogen isotope offsets between plants and their source waters.

A fundamental assumption when using hydrogen and oxygen stable isotopes to understand ecohydrological processes is that no isotope fractionation occurs during plant water uptake/transport/redistribution. A growing body of evidence has indicated that hydrogen isotope fractionation occurs in certain environments or for certain plant species. However, whether the plant water source hydrogen isotope offset (δ2 H offset) is a common phenomenon and how it varies among different climates and plant functional types remains unclear. Here, we demonstrated the presence of positive, negative, and zero offsets based on extensive observations of 12 plant species of 635 paired stable isotopic compositions along a strong climate gradient within an inland river basin. Both temperature and relative humidity affected δ2 H offsets. In cool and moist environments, temperature mainly affected δ2 H offsets negatively due to its role in physiological activity. In warm and dry environments, relative humidity mainly affected δ2 H offsets, likely by impacting plant leaf stomatal conductance. These δ2 H offsets also showed substantial linkages with leaf water 18 O enrichment, an indicator of transpiration and evaporative demand. Further studies focusing on the ecophysiological and biochemical understanding of plant δ2 H dynamics under specific environments are essential for understanding regional ecohydrological processes and for conducting paleoclimate reconstructions.

ВЗАЄМОДІЯ Н(D,Т)О З МІНЕРАЛЬНИМИ АДСОРБЕНТАМИ У СТАЦІОНАРНИХ СИСТЕМАХ

Background. The theoretical basis of the experiments is the idea that the significant adsorption properties of layered silicates of the montmorillonite and palygorskite groups and clinoptilolite with a developed specific surface due to the dynamic nature of adsorption-desorption processes due to kinetic isotope effects can ensure priority retention of mineral particles of more inert hydroxide groups ОТ– near the adsorption surfaces. Methods. Cherkasy bentonite with a montmorillonite content of 75 % (hereafter montmorillonite), Varvarivska saponite, and Sokyrnytsky clinoptilolite were used for the experiments. Experiments were performed in stationary mode in hermetically sealed containers (two-phase watermineral system). Results. During the first 7 days of interaction of the aqueous and mineral phases, the specific activity of tritium in the working solution decreased by 31.8–69.5 %. Subsequently, during the 92 days of interaction of the aqueous solution of H(D,T)O with mineral adsorbents, the change in the specific activity of tritium did not exceed 2–4 %. At the same time, the initial concentration of deuterium in the working solution of Н(D,Т)О of two-phase water-mineral systems decreased by only 0.8–14 %, ranging from 0.0066 % to 0.0408 %. During the experiment, in closed water-mineral systems, a partial interphase redistribution of the initial stock of hydrogen isotopes, which was accumulated in the initial working solution Н(D,Т)О, took place. In the process of adsorption of the solution by mineral adsorbents, the initial moisture in the mineral phase was replaced by Н(D,Т)О and the content of hydrogen isotopes increased in them. The content of tritium in the adsorbate, depending on the mineral type of the adsorbent, increased by 31.8 to 69.5 %. Concentration of deuterium increased by 10.1–48.6 %, which was due to the different adsorption capacity of mineral adsorbents. Adsorption of the H(D,T)O working solution by mineral adsorbents was accompanied by fractionation of heavy hydrogen isotopes. Сonclusions. Аs a result of the interaction of the Н(D,Т)О solution with mineral adsorbents, kinetic isotope effects determined the priority retention of more inert hydroxide ОТ-groups than OD- groups near the adsorption surface of mineral particles. Consequently, interphase fractionation of heavy hydrogen isotopes occurred in stationary water-mineral systems. The coefficients of tritium interphase fractionation range from α = 1.26 for palyhorskite to α = 2.96 for clinoptilolite. For deuterium, this indicator is equal to α = 0.89 for clinoptilolite and to α = 1.10 for saponite.

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.

Carbon and hydrogen isotope fractionation of phthalates during photocatalysis reactions in aqueous solution containing Fe(III) complexes or iron minerals

The hydrogen and carbon isotope fractionation factor (ε2H, ε13C) of dimethyl-, diethyl‑ and dibutyl phthalic acid ester during photosensitized degradation by artificial sunlight with Fe(III) ions and iron minerals (hematite, goethite and magnetite) in aqueous solution were examined by compound-specific isotope analysis (CSIA) in order to analyze the degradation mechanism. Hematite does not catalyze photosensitized degradation of phthalates. The correlation of 2H and 13C isotope fractionation (Λ = Δδ2H/Δδ13C) of phthalates with increasing chain length (dimethyl-; diethyl‑; and dibutyl-) were compared with values of the ∙OH radical model reaction with the aromatic ring as well as acidic and alkaline hydrolysis. The Λ values of die photosensitized reaction of diethyl phthalate with goethite (-5.1 ± 1.8) and magnetite (-18.9 ± 3.9) show a large difference compared to Fe(III) solutions (4.7 ± 0.9 to 4.8 ± 1.0) suggesting specific reaction mechanisms. The fractionation factors determined here have potential to characterize the degradation of phthalates catalyzed by photo-induced reaction of Fe(III), goethite and magnetite in natural system and in remediation approaches.

Carbon and hydrogen stable isotope fractionation due to monooxygenation of short-chain alkanes by butane monooxygenase of Thauera butanivorans Bu-B1211.

Multi element compound-specific stable isotope analysis (ME-CSIA) is a tool to assess (bio)chemical reactions of molecules in the environment based on their isotopic fingerprints. To that effect, ME-CSIA concepts are initially developed with laboratory model experiments to determine the isotope fractionation factors specific for distinct (bio)chemical reactions. Here, we determined for the first time the carbon and hydrogen isotope fractionation factors for the monooxygenation of the short-chain alkanes ethane, propane, and butane. As model organism we used Thauera butanivorans strain Bu-B1211 which employs a non-haem iron monooxygenase (butane monooxygenase) to activate alkanes. Monooxygenation of alkanes was associated with strong carbon and hydrogen isotope effects: εbulkC = -2.95 ± 0.5 ‰ for ethane, -2.68 ± 0.1 ‰ for propane, -1.19 ± 0.18 ‰ for butane; εbulkH = -56.3 ± 15 ‰ for ethane, -40.5 ± 2.3 ‰ for propane, -14.6 ± 3.6 ‰ for butane. This resulted in lambda (Λ ≈ εHbulk/εCbulk) values of 16.2 ± 3.7 for ethane, 13.2 ± 0.7 for propane, and 11.4 ± 2.8 for butane. The results show that ME-CSIA can be used to track the occurrence and impact of monooxygenase-dependent aerobic processes converting short-chain alkanes in natural settings like marine and terrestrial seeps, gas reservoirs, and other geological formations impacted by natural gas.

Hydrogen isotope biogeochemistry of plant waxes in paired lake catchments

Studies of plants in modern catchment systems can serve to improve the level of understanding of sedimentary plant wax hydrogen isotope (δ2H) data by directly investigating the link between local climate conditions, plant source water, leaf water, and plant lipids for individual plant species. Here we present such an application to compare two lake catchments with different basin morphologies in Estonia. We sampled leaf and xylem water, as well as leaf waxes from the seven common plant species in each catchment, and soil water. We then measured the δ2H values of all waters, and of n-alkanes (δ2Hn–alk) from the plant waxes, as well as surface lake sediments. We applied a Péclet modified Craig-Gordon leaf water model using local precipitation isotope and climate data to characterize the δ2H values of the biosynthetic source water pool throughout the entire growth season. The data and model results provide a detailed view of how the input hydro-climatic signals from the precipitation δ2H values were modified by environmental and plant physiological conditions and ultimately by the biosynthetic isotope fractionation associated with n–alkane production by each plant species. We report both average apparent (εapp = –92 ± 21 ‰) and biosynthetic (εbio = –132 ± 19 ‰) hydrogen isotope fractionation factors of all species from the studied catchments. This information serves as a foundation for sedimentary organic geochemistry and paleoclimate studies, which allows for more direct and quantitative links to be made between sedimentary plant wax δ2H values and the climate signal contained in plant source water.

Hydrogen and Oxygen Isotope Fractionation Effects in Different Organ Tissues of Grapes under Drought Conditions.

A study of different grapevine tissues and organs (root, stem, leaf, fruit) water isotope fractionation models from high-quality wine grapes produced in the Helan Mountains, a key wine-producing area in northwestern China, was undertaken. Results showed that δ2H values of local groundwater sources were more negative than rivers and precipitation. Soil water δ2H and δ18O values were significantly higher than those of other environmental water sources. Water from the soil surface layer (0-30 cm, δ2H and δ18O values) was more positive than the deeper layer (30-60 cm), indicating that soil water has undergone a positive fractionation effect. δ2H and δ18O values of tissues and organs from different grape varieties followed a similar pattern but were more negative than the local atmospheric precipitation line (slope between 4.1 to 5.2). The 2H and 18O fractionation relationship in grapevine organs was similar, and 18O has a higher fractionation effect than 2H. δ2H and δ18O values showed a strong fractionation effect during the transportation of water to different grape organs (trend of stem > fruit > leaf). This study showed that 18/16O fractionation in grapes is more likely to occur under drought conditions and provides a theoretical basis to improve traceability accuracy and origin protection of wine production areas.

Palmitic Acid Is Not a Proper Salinity Proxy in Baffin Bay and the Labrador Sea but Reflects the Variability in Organic Matter Sources Modulated by Sea Ice Coverage

AbstractPalmitic acid (PA) is ubiquitous in the biosphere and its hydrogen isotopic composition (δ2HPA) was proposed as a potential paleoenvironmental proxy for salinity, with δ2HPA values increasing with salinity. In this study, we analyzed 40 surface sediment samples from Baffin Bay and the Labrador Sea to examine the isotopic composition of PA in relation to local environmental variables, including salinity. In contrast to expectations, our results show a negative relationship between the δ2HPA and sea‐surface salinity, raising questions about its pertinence and usefulness as a salinity proxy. Instead, our results suggest that the relative abundance of distinct organisms that employ different metabolisms is the key in determining the hydrogen isotopic fractionations in PA. While we show that PA is mostly produced through photoautotrophic metabolisms by diatoms and dinoflagellates, varying contributions from heterotrophic metabolisms may obscure the stable isotope composition of PA. Surprisingly, we found no correlation between the stable carbon isotopic composition of the sedimentary organic matter (δ13Corg) and PA (δ13CPA), implying major differences in either the dominant organisms producing sedimentary PA or in carbon isotope fractionation during lipid biosynthesis. We also found that the presence of extended sea‐ice cover leads to enriched carbon and hydrogen isotopic compositions in PA. These enriched values suggest heterotrophic biodegradation in the water column and/or in the sediment as well as an increase in grazing activities. We propose that sea‐ice cover and surface water oxygenation modulate the relative impact of phototrophic and heterotrophic metabolisms, and therefore the isotopic composition of marine sedimentary PA.

Characteristics of Hydrogen and Oxygen Isotope Composition in Precipitation, Rivers, and Lakes in Wuhan and the Ecological Environmental Effects of Lakes

Wuhan has a dense network of rivers and lakes. Due to the city’s development, the water system has been fragmented, the degradation of lakes is becoming increasingly severe, and the eco-environment has been significantly damaged. By collecting samples of the central surface water bodies in Wuhan, including Yangtze River water, Han River water, lake water, and precipitation, and by utilizing hydrogen and oxygen isotopes and multivariate statistical methods, the hydraulic connectivity and ecological environmental effects between the Yangtze River, the Han River, and the lakes were revealed. The results indicated the following: (1) The local meteoric water Line (LMWL) in the Wuhan area was δD = 7.47δ18O + 1.77. The river water line equation was approximately parallel to the atmospheric precipitation line in the Wuhan area. The intercept and slope of the lake waterline equation were significantly smaller. The enrichment degree of δ18O and δD was Yangtze River < Hanjiang River < lake water. (2) The cluster analysis showed that the lakes could be divided into two types, i.e., inner-flow degraded (IFD) lakes and outer-flow ecological (OFE) lakes. Urban expansion has resulted in fragmentation of the IFD lakes, changing the connectivity between rivers and lakes and weakening the exchange of water bodies between the Yangtze River and lakes. Simultaneously, evaporation has caused hydrogen and oxygen isotope fractionation, resulting in the relative enrichment of isotopes. The IFD lakes included the Taizi Lake, Yehu Lake, and the Shenshan Lake. The OFE lakes and the Yangtze River were active, evaporation was weak, and the hydrogen and oxygen isotopes were relatively depleted, mainly including the Huangjia Lake, the East Lake, the Tangxun Lake, etc. (3) The excessive deuterium (d-excess) parameter values in the Yangtze River and the Han River water were positive. In contrast, the d values in the lakes were mainly negative. In the case of a weakened water cycle, the effect of evaporation enrichment on lake water δ18O and δD had a significant impact. It is suggested that the water system connection project of “North Taizi Lake-South Taizi Lake-Yangtze River” and the small lakes connecting to large lakes project of “Wild Lake-Shenshan Lake-Tangxun Lake” should be implemented in time to restore the water eco-environment.

Fractionation of Hydrogen Isotopes in a Hydrogel during Dehydration

Fractionation of Hydrogen Isotopes in a Hydrogel during Dehydration

Experimental evidence suggests dominance of species effect on the variability in hydrogen isotope fractionation between leaf wax compounds and source water

Quantifying the hydrogen isotope fractionation between leaf wax compounds and source water (εapp) is a prerequisite for hydrogen isotopic composition (δD) based paleo-hydrological studies. However, characterization of the εapp values, mostly done in field-based studies, are predominantly carried out in northern mid-latitude regions, as compared to that in the tropics. Further, the εapp values estimated in field-based studies are often associated with inherent uncertainties which could stem from (i) incorrect source water δD values, (ii) a species-effect, and (iii) varying climatic conditions (as in transect studies). Hence, to characterize the εapp values in tropics and to decouple the factors affecting the variability of εapp, we conducted an outdoor experiment wherein four evergreen and three deciduous angiosperm trees were grown under similar climatic conditions for 85 days with water of known δD value (−2‰). The εapp values in the studied species were −119 ± 23‰ (n = 14) for n-alkanes and −126 ± 27‰ (n = 12) for n-alkanoic acids of chain lengths C31 and C30, respectively. We observed inter-species variabilities in εapp values that are consistent with previous field and transect studies. As the plants were grown under similar climatic conditions and irrigated with water of the same δD value, the variability in εapp values observed here suggested that the species-specific hydrogen isotopic fractionation likely has a dominant control over the uncertainty in the community-averaged εapp values. Further, the εapp values of deciduous and evergreen species showed no systematic differences, suggesting that changes in the relative proportion of these taxa may not affect the community-averaged εapp and the reconstructed δD values of paleo-precipitation in angiosperm tree dominated catchments.

Experimental determinations of carbon and hydrogen isotope fractionations and methane clumped isotope compositions associated with ethane pyrolysis from 550 to 600 °C

Methane clumped isotope compositions signify the relative natural abundances of rare, doubly substituted isotopic species of methane (13CH3D and 12CH2D2) and have emerged as a new isotopic tool to trace the sources, sinks, and lifecycles of methane in the environment. Such measurements can identify equilibration (or re-equilibration) temperatures if found to be in isotopic equilibrium or non-equilibrium processes (e.g., kinetically controlled reactions or mixing) if not in isotopic equilibrium. Naturally occurring thermogenic methane—formed by the thermally activated breakdown of larger organic molecules—has been found to have clumped isotope compositions consistent with equilibrium at reasonable gas formation temperatures in some settings and non-equilibrium processes occurring during either formation, migration, storage, or extraction in others. To explore the potential controls on the isotopic composition of thermogenic methane, we conducted isothermal time-series ethane pyrolysis experiments at 550 and 600 °C to measure methane and ethane 13C/12C and D/H fractionations and methane clumped isotope compositions (resolved 13CH3D and 12CH2D2). We explore the effects of modifying the initial clumped isotope composition of ethane and the addition of water vapor to pyrolysis experiments. We observe that ethane and methane 13C/12C are controlled by kinetic isotope effects and Rayleigh distillation processes. In contrast, ethane and methane D/H and methane clumped isotope compositions appear to be controlled by a combination of these processes and hydrogen isotope exchange. The hydrogen isotope exchange processes lead to isotopic equilibrium as reaction completion is approached for both D/H (ethane/methane) and methane clumped isotope compositions. We develop a chemical model based on a mass balance approach that accounts for inheritance vs. hydrogen-abstraction formation pathways for singly and doubly substituted isotopologues of ethane and methane that is compared to the experimental data. The model allows the determination of carbon and hydrogen kinetic isotope effects associated with ethane cracking and hydrogen abstraction reactions that, where applicable, we compare to prior theoretical constraints. From the comparison of the model to the experimental data, we infer that the kinetically controlled ethane and methane bulk isotope compositions and methane clumped isotope compositions are controlled by kinetic isotope effects (both primary and secondary) associated with both CC bond and CH bond cleavage reactions. Specifically, the methane clumped isotope compositions likely result from a combination of clumped isotope effects associated with ethane breakdown and/or assembly of methane isotopologues (expressed in terms of γ-factor parameters ≠ 1) and combinatorial effects that arise probabilistically. We discuss our experimental results in the context of recent pyrolysis experiments and observations of naturally occurring thermogenic methane. We consider a proposal consistent with observations from nature that the hydrogen isotope exchange reactions that promote equilibration of methane isotopic molecules at or near formation temperature may be facilitated by free radicals generated by pyrolysis reactions. In this framework, isotope exchange effectively ceases when pyrolysis effectively ceases locking in compositions that can be consistent with peak formation temperatures.

Influence of salinity on hydrogen isotope fractionation of n-alkanes in mangrove leaves and surface sediments: A comparison across various geomorphological settings

Increasing attention has recently been paid to hydrogen isotope ratios of mangrove lipids due to their potential for reconstructing past salinity and hydrology. This proxy is based on several observations that net 2H/1H fractionation, εn-alkane/water, between mangrove leaf waxes and surface water, increases with surface water salinity. However, the extent to which hydrogeomorphic conditions, on a regional scale, affect the hydrogen isotope fractionations of n-alkanes in mangrove trees and sediments is not yet understood. This study aimed to assess the robustness of negative εn-alkane/water – salinity for six mangrove species and adjacent surface sediments from the Zhanjiang mangrove across different hydrogeomorphic settings. The results indicated that a significant inverse relationship exists between εn-C31/water and εn-C33/water and salinity for all samples from the three fringe and basin/interior mangroves, with εn-C31/water decreasing by −2.57 ± 0.87 ‰ ppt−1 and εn-C33/water decreasing by −3.64 ± 1.14 ‰ ppt−1. These trends, as well as interspecific differences among mangrove species, could be attributed to biochemical changes in response to salt stress, such as using different proportions of amino acids and soluble carbohydrates as compatible solutes. In contrast, the relationship between sedimentary εn-alkane/water and salinity differed significantly across hydrogeomorphic conditions and land-use changes, possibly due to variations in hydrology and input of allochthonous organic matter. A comparison of fitted parameters of linear regressions among riverine, fringe, and interior mangroves suggests that the slop and intercept describing the linear relationship between sedimentary εC27–33/water of basin/interior mangroves and salinity are generally consistent with that of the corresponding mangrove trees. This suggests that the basin/interior mangroves and their sedimentary deposits may be better candidates for paleoenvironmental reconstruction using hydrogen isotope ratios of long-chain n-alkanes.

Hydrogen isotope fractionation in carbohydrates of leaves and xylem tissues follows distinct phylogenetic patterns: a common garden experiment with 73 tree and shrub species.

Recent methodological advancements in determining the nonexchangeable hydrogen isotopic composition (δ2 Hne ) of plant carbohydrates make it possible to disentangle the drivers of hydrogen isotope (2 H) fractionation processes in plants. Here, we investigated the influence of phylogeny on the δ2 Hne of twig xylem cellulose and xylem water, as well as leaf sugars and leaf water, across 73 Northern Hemisphere tree and shrub species growing in a common garden. 2 H fractionation in plant carbohydrates followed distinct phylogenetic patterns, with phylogeny reflected more in the δ2 Hne of leaf sugars than in that of twig xylem cellulose. Phylogeny had no detectable influence on the δ2 Hne of twig or leaf water, showing that biochemistry, not isotopic differences in plant water, caused the observed phylogenetic pattern in carbohydrates. Angiosperms were more 2 H-enriched than gymnosperms, but substantial δ2 Hne variations also occurred at the order, family, and species levels within both clades. Differences in the strength of the phylogenetic signals in δ2 Hne of leaf sugars and twig xylem cellulose suggest that the original phylogenetic signal of autotrophic processes was altered by subsequent species-specific metabolism. Our results will help improve 2 H fractionation models for plant carbohydrates and have important consequences for dendrochronological and ecophysiological studies.

Simulation Experiment Study on Impacting the δD Value of Aromatic Compounds

Little is known about the effects of sedimentary environment and maturity on δD values of aromatic compounds deposited in geological bodies. Our simulation experiments showed that the δD value of pyrolytic polycyclic aromatic hydrocarbons (PAHs) was significantly different between the studied samples from high and low latitude regions. Comparative studies showed that the δD values of PAHs produced by pyrolysis were related to those of water in the two regions. With increasing maturity, the δD value of the PAHs becomes higher. Additionally, it was observed that some PAHs exhibited a propensity to increase the δD value upon demethylation. The thermodynamic fractionation of hydrogen isotopes between the PAHs produced by pyrolysis and both the n-alkanes and methane produced by pyrolysis indicated that the hydrogen isotopic value of the PAHs was higher than that of the n-alkanes or methane. The long-chain alkylbenzene produced by pyrolysis has a higher mean δD value compared with the n-alkanes produced by pyrolysis, but it is lower than that of the PAHs in the same sample. The lowest δD value among the aromatics was found in the ring A monoaromatic steroids produced by pyrolysis. The low δD values of these steroids should originate from isotopic fractionation during isoprenoid lipid biosynthesis.

Impact of metabolism and temperature on 2H ∕ 1H fractionation in lipids of the marine bacterium Shewanella piezotolerans WP3

Abstract. Compound-specific hydrogen isotopes have increasingly been used as a powerful proxy for investigating biogeochemical cycles and climate change over the past 2 decades. Understanding the hydrogen isotope in extant organisms is fundamental for us to interpret such isotope signals preserved in natural environmental samples. Here, we studied the controls on hydrogen isotope fractionation between fatty acids and growth water by an Fe-reducing heterotrophic marine bacterium Shewanella piezotolerans WP3 growing on different organic substrates, including N-acetyl-D-glucosamine (GlcNac), glucose, acetate, pyruvate, L-alanine, and L-glutamate. Meanwhile, we also evaluated the impact of growth temperature on the hydrogen isotope composition of fatty acids using GlcNac as the sole organic substrate. Our results show that the abundance-weighted mean fatty-acid / water fractionations (εFA/water) display considerable variations for cultures grown on different substrates. Specifically, WP3 yielded the most 2H-enriched fatty acids growing on L-glutamate and pyruvate with an εFA/water of 52 ± 14 ‰ and 44 ± 4 ‰, respectively, and exhibited 2H depletion using GlcNac (−76 ± 1 ‰) and glucose (−67 ± 35 ‰) as sole carbon sources and relatively small fractionations on acetate (23 ± 3 ‰) and L-alanine (−4 ± 9 ‰). Combined with metabolic model analysis, our results indicate that the central metabolic pathways exert a fundamental effect on the hydrogen isotope composition of fatty acids in heterotrophs. Temperature also has an obvious influence on the δ2H values of fatty acids, with strong 2H depletion at an optimal growth temperature (−23 ± 2 ‰ and −23 ‰ growing at 15 and 20 ∘C, respectively) and relatively small fractionations at non-optimal temperatures (4 ± 5 ‰, −4 ± 12 ‰, and 15 ± 41 ‰ at 4, 10, and 25 ∘C, respectively). We hypothesized that this may be associated with temperature-induced enzyme activity for nicotinamide adenine dinucleotide phosphate (NADPH) production. This study helps understand the controlling factors of hydrogen isotope fractionation by marine bacteria, laying the foundation for further interpreting the hydrogen isotope signatures of lipids as an important proxy to decode the biogeochemical cycles and ecological changes in marine sediments.

Effect of Pressure on Hydrogen Isotope Fractionation in Methane during Methane Hydrate Formation at Temperatures Below the Freezing Point of Water

Isotopic fractionation of methane between gas and solid hydrate phases provides data regarding hydrate-forming environments, but the effect of pressure on isotopic fractionation is not well understood. In this study, methane hydrates were synthesized in a pressure cell, and the hydrogen isotope compositions of the residual and hydrate-bound gases were determined. The δ2H of hydrate-bound methane formed below the freezing point of water was 5.7–10.3‰ lower than that of residual methane, indicating that methane hydrate generally encapsulates lighter molecules (CH4) instead of CH32H. The fractionation factors αH-V of the gas and hydrate phases were in the range 0.9881–0.9932 at a temperature and pressure of 223.3–268.2 K and 1.7–19.5 MPa, respectively. Furthermore, αH-V increased with increasing formation pressure, suggesting that the difference in the hydrogen isotopes of the hydrate-bound methane and surrounding methane yields data regarding the formation pressure. Although the differences in the hydrogen isotopes observed in this study are insignificant, precise analyses of the isotopes of natural hydrates in the same area enable the determination of the pressure during hydrate formation.