Hydrogen Isotope Fractionation Research Articles

Position-specific distribution of hydrogen isotopes in natural propane: Effects of thermal cracking, equilibration and biodegradation

Intramolecular isotope distributions, including isotope clumping and position specific fractionation, can provide proxies for the formation temperature and formation and destruction pathways of molecules. In this study, we explore the position-specific hydrogen isotope distribution in propane. We analyzed propane samples from 10 different petroleum systems with high-resolution molecular mass spectrometry. Our results show that the hydrogen isotope fractionation between central and terminal positions of natural propanes ranges from −102‰ to +205‰, a much larger range than that expected for thermodynamic equilibrium at their source and reservoir temperatures (36–63‰). Based on these findings, we propose that the hydrogen isotope structure of catagenic propane is largely controlled by irreversible processes, expressing kinetic isotope effects (KIEs). Kinetic control on hydrogen isotope composition of the products of thermal cracking is supported by a hydrous pyrolysis experiment using the Woodford Shale as substrate, in which we observed isotopic disequilibrium in the early stage of pyrolysis. We make a more general prediction of KIE signatures associated with kerogen cracking by simulating this chemistry in a kinetic Monte Carlo model for different types of kerogens. In contrast, unconventional shale fluids or hot conventional reservoirs contain propane with an isotopic structure close to equilibrium, presumably reflecting internal and/or heterogeneous exchange during high temperature storage (ca. 100–150 °C). In relatively cold (<100 °C) conventional gas accumulations, propane can discharge from its source to a colder reservoir, rapidly enough to preserve disequilibrium signatures even if the source rock thermal maturity is high. These findings imply that long times at elevated temperatures are required to equilibrate the hydrogen isotopic structure of propane in natural gas host rocks and reservoirs. We further defined the kinetics of propane equilibration through hydrogen isotope exchange experiments under hydrous conditions; these experiments show that hydrogen in propane is exchangeable over laboratory timescales when exposed to clay minerals such as kaolinite. This implies rather rapid transfer of propane from sources to cold reservoirs in some of the conventional petroleum systems. Propane is also susceptible to microbial degradation in both oxic and anoxic environments. Biodegradation of propane in the Hadrian and Diana Hoover oil fields (Gulf of Mexico) results in strong increases in central-terminal hydrogen isotope fractionation. This reflects preferential attack on the central position, consistent with previous studies.

Fractionation of carbon and hydrogen isotopes of TSR-altered gas products under closed system pyrolysis

Thermochemical sulfate reduction (TSR) is common in marine carbonate gas reservoirs, leading to complicated isotope characteristics of TSR-altered gas. This study aims to better understand how TSR affects the geochemical and isotopic compositions of alkanes in pyrolysis products. Pyrolysis of TSR were conducted with crude oil, nonane (C9) and methylnaphthalene (MN) in the presence of MgSO4 solution at temperatures of 350 °C, 360 °C, and 370 °C for different durations of 4–219 h in a closed system. Results show that carbon and hydrogen isotope compositions of alkane gas resulting from TSR (pyrolysis with crude oil and MgSO4) became heavier with increasing carbon number, i.e., δ13C1 < δ13C2 < δ13C3 and δ2H–C1 < δ2H–C2 < δ2H–C3. Compared with the δ13C1, δ13C2 and δ13C3 increased in a much wider range as heating continued. Carbon and hydrogen isotopes of alkane gas produced by TSR became heavier with increasing gas souring index. Values for δ13C1–δ13C2 and δ2H–C1– δ2H–C2 typically decreased as oil and C9 underwent thermal cracking. Comparative experiments using C9 in the presence of MgSO4 produced partially reversed carbon isotope series (δ13C1 > δ13C2), which, for the first time, confirmed the ability of TSR to cause isotopic reversal from pyrolysis. The residual heavy alkanes gradually became 13C-enriched during TSR, which increased δ13C2 values and changed the partially reversed isotope sequence to a positive sequence (δ13C1 < δ13C2). The discovery of a partial reversal of the carbon isotope series of alkane gases through pyrolysis will further deepen the understanding of TSR-altered natural gas.

Hydrogen isotope fractionation in modern plants along a boreal-tundra transect in Alaska

An increasing number of studies from high latitude settings use the stable hydrogen isotope ratio (δ2H) of plant leaf waxes to quantify changes in past precipitation. Calibration of modern vegetation and source water use from these landscapes is important to more accurately reconstruct past hydroclimate variability using sedimentary leaf wax δ2H values. Here, we determine plant-water fractionations from 12 sites along a south-north transect in central Alaska, from Fairbanks to Deadhorse (64-70°N). We characterize the δ2H values of n-alkanes and n-alkanoic acids from modern plants and their xylem and leaf water δ2H values, as well as plant source water using surface soils, a soil core, and previously collected meteoric water data from the region. We find both transpiration (εLW/XW) and biosynthetic (εwax/LW) fractionation are sensitive to environmental controls with latitude, with increased leaf transpiration and biosynthetic fractionation to the north, potentially due to increased summer sunlight hours. Soil water δ2H values show near linear 2H enrichment toward the surface associated with evaporation, with the δ2H value ∼40 cm matching mean annual precipitation (MAP). Average net fractionation was calculated using xylem water and chain length weighted wax δ2H values (εwax/XW) and we find nearly the same mean values for both n-alkanes, −112 ± 27‰, and n-alkanoic acids, −110 ± 23‰, from 12 common high latitude vascular plants. To provide the range of likely net fractionations along this transect, we also calculate the average net fractionation using MAP, finding values are less negative than using xylem waters (εwax/MAP, −89 ± 28‰ for n-alkanes, and −86 ± 24‰ for n-alkanoic acids). To compare across studies, we determined the average εwax/MAP of n-alkanes from all available high latitude calibration studies and found more 2H enriched (smaller fractionations) for C27 (-87 ± 29‰), C29 (-87 ± 32‰), and C31 (-91 ± 31‰) than those of global εwax/MAP homolog averages. This new work in Alaska contributes to our growing understanding of plant water-wax fractionation in the high latitudes and is potentially important for the use of sedimentary δ2H values for paleoprecipitation estimates.

Carbon and hydrogen isotope fractionation in lipid biosynthesis by Sporosarcina sp. DSK25

Carbon and hydrogen isotope fractionation in lipid biosynthesis by Sporosarcina sp. DSK25

VolcDeGas: A program for modelling hydrogen isotope fractionation during degassing of rhyolitic melts

Magma degassing mechanisms are key determinants of explosive and effusive eruption styles. Paired measurements of H2O content and hydrogen isotopic ratios (e.g., δD) in pyroclastic and effusive products can elucidate end-member degassing mechanisms (e.g. closed and open system) during eruption. Here we present VolcDeGas, a MatLab program that models δD-H2O degassing trajectories of rhyolitic magma. Operating within an intuitive GUI, VolcDeGas calculates degassing paths based on: initial δD (in ‰), the H2O content of the melt (wt.%), degassing step size, and temperature. VolcDeGas also calculates hydrous speciation based on either empirical models or analytical data, and incorporates this effect in simulations. VolcDeGas solves open-, closed-, and batched-system fractionation equations, and also combines these into multi-stage (e.g. closed-to-open) degassing paths. Tests show that degassing is highly sensitive to step size, and multi-stage scenarios involving progressively declining steps (e.g. batched-system) provide the best statistical fit to pyroclastic and effusive obsidian geochemical datasets.

Membrane Properties of Montmorillonite, Saponite and Clinoptilolite During Electroosmotic Fractionation of Hydrogen Isotopes

Based on experimental studies, the possibility and efficiency of usage of montmorillonite, saponite, and clinoptilolite as separation membranes during electroosmotic fractionation of hydrogen isotopes in an aqueous electrolyte solution was evaluated. For the experiments, the following samples were used: bentonite (Cherkasy deposit) with a content of montmorillonite of 75% (hereinafter referred to as montmorillonite), saponite (Varvariv deposit) and clinoptilolite (Sokyrnytsya deposit). It was found that under the influence of an electric field, electroosmotic filtration of the tritiated electrolyte occurs through weakly permeable membranes. Depending on the structural features of the mineral substance, various proton conductivity of the membranes was recorded, which determines the different intensity of the redistribution of ions of dissociated HTO molecules between the anode and cathode chambers. The largest difference between the specific activity of tritium in the anolyte and catholyte was obtained in the system where the mineral membrane was made of saponite (11% and 26% of the specific activity of tritium in the initial HTO, respectively). The least was the stability of the montmorillonite membrane. Its destruction upon interaction with a Na2CO3 solution led to electrolyte leakage and a decrease in the extraction of tritium from the filtrate (catholyte). The use of clinoptilolite when creating a composite with montmorillonite made it possible to increase the stability of the membrane and additional possibilities for fractionating hydrogen isotopes in an electrolyte. Electroosmotic filtration of the electrolyte was accompanied by fractionation of hydrogen isotopes in the mineral membranes of the experimental systems. The largest isotope effect was obtained in montmorillonite and composite montmorillonite-zeolite membranes, where the fractionation coefficient α in the fraction extracted from the interlayer space was 1.16 and 1.12, respectively. In a composite membrane, where the amount of clinoptilolite was 67.5%, isotopic hydrogen fractionation was also observed in the surface-adsorbed fraction (α = 1.5) and in a structurally bound form (α = 1.1). The use of saponite as an electroosmotic membrane leads to a smaller isotope effect than in a montmorillonite membrane, and is manifested in surface-adsorbed water (α = 1.08) and in the interlayer space (α = 1.02). The addition of quartz sand to montmorillonite reduces the efficiency of fractionation of hydrogen isotopes detected only in the surface-adsorbed fraction (α = 1.02).

Hydrogen isotopic fractionation of methane at the formation of synthetic mixed-gas hydrate composed of methane and propane

Hydrogen isotope fractionation for methane occurs between gas and hydrate phases at the formation of methane hydrate; D of hydrate-bound methane is about 5 lower than that of residual methane. We suppose that the relation between the sizes of guest molecules and cage size of crystallographic structure affects the isotopic fractionation. Methane is enclathrated in both large and small cages of the structure I gas hydrate, therefore the isotopic difference is D in mainly determined by molecules enclathrated in the large cages. On the other hand, in the case of methane and propane mixed-gas hydrate, methane prefers to be enclathrated in small cages, because propane is enclathrated only in the large cages of the structure II gas hydrate. In this study, we checked the effect of cage size on the hydrogen isotopic fractionation for methane by comparing pure methane hydrate and the mixed-gas hydrate composed of methane and propane. Synthetic gas hydrates were formed from fine ice powder and guest gases in a pressure cell. We retrieved residual and hydrate-bound gases and measured D of methane by a CF-IRMS. The hydrogen isotopic differences between hydrate-bound and residual methane in the case of mixed-gas hydrate was smaller than those of pure methane hydrate reported by previous works, indicating that isotopic difference in methane D for small cages is smaller than those for large cages.

The hydrogen isotopic compositions of sedimentary mid-chain n-alkanes record ecological change at a Portuguese paleowetland

The origin of mid-chain (C23 and C25) and C27n-alkanes in sedimentary archives can be ambiguous. In coastal Portugal, a peat deposit representing a mid-Holocene paleowetland (PRC-South) that was initially dominated by Sphagnum presents an ideal setting for assessing methods of mid-chain n-alkane source elucidation. In particular, we examine a comprehensive record of the difference in δD between mid-chain (δDmid) and C29n-alkanes (ΔDmid-C29) in relation to n-alkane molecular distributions and compound-specific δ13C values in order to improve interpretations of paleoenvironmental change and evaluate the reliability of δDmid values for hydrologic reconstructions. Mid-chain n-alkane production remains significant at PRC-South after a substantial Sphagnum decline, yet an increase in ΔDmid-C29 values indicates a primarily terrestrial origin of mid-chain n-alkanes in the upper 50 cm of the deposit. This progression towards more positive ΔDmid-C29 values coincides with a relative increase in n-C27 abundance and potentially represents the replacement of Sphagnum moss by tree species that produce abundant mid-chain n-alkanes, such as Betula, Quercus, or Fagus spp. According to our analysis, ΔDmid-C29 displays promise as a tool for mid-chain n-alkane source attribution in Sphagnum paleoenvironments, but interspecies variability of hydrogen isotope fractionation in Sphagnum mosses and terrestrial vegetation could critically hinder its application. Our use of ΔDmid-C29 at PRC-South ultimately exemplifies the importance of accounting for vegetation composition when qualitatively or quantitatively interpreting sedimentary δDn-alkane values, particularly in Sphagnum wetlands.

Hydrogen isotope fractionation variations of n-alkanes and fatty acids in algae and submerged plants from Tibetan Plateau lakes: Implications for palaeoclimatic reconstruction

The hydrogen isotope compositions (δD) of n-alkanes and fatty acids (FAs) are widely applied in palaeoclimatic reconstructions, and the determinations of their hydrogen isotope fractionation factor values (ε) are vital for quantitatively reconstructing past precipitation variations. Currently, studies on n-alkane and FA ε values focus on terrestrial plants, which, however, show large uncertainties because of the influence of evapotranspiration. Therefore, in this study, we analysed the ε values of algae and submerged plants immersed in lakes, which are not affected by evapotranspiration, to understand the hydrogen isotope fractionation of plant lipid synthesis. By investigating the δD values of lipids (n-alkanes and FAs) in algae and submerged plants and the δD values of co-existing water (including lake bottom water, surface sediment water, and leaf water of algae and submerged plants) from five Tibetan Plateau lakes, we find that the n-alkane ε values of algae and submerged plants show narrow changes, ranging from −176 to −159‰ and −167 to −142‰, respectively. The FA ε values of algae and submerged plants also show small variations, ranging from −160 to −121‰ (except Chara) and −161 to −138‰, respectively. Therefore, the average biosynthetic hydrogen isotope fractionation of these plants is −162‰ for n-alkanes and −145‰ for FAs, and the small ε differences between FAs and n-alkanes can be related to the different magnitudes of FA utilization in n-alkane synthesis. Finally, we find that the biosynthetic hydrogen isotope fractionation factors of aquatic plants are close to those of terrestrial grasses but slightly more negative than those of terrestrial woody plants. Thus, our results are helpful for understanding the hydrogen isotope fractionation variations in terrestrial plant lipids, which is beneficial for palaeohydrological reconstructions.

Hydrogen isotopic compositions along a precipitation gradient of Chinese Loess Plateau: Critical roles of precipitation/evaporation and vegetation change as controls for leaf wax δD

The hydrogen isotopic compositions (δD) of long-chain plant leaf waxes can reflect changes of continental hydrology and thus have been increasingly utilized for paleoclimate reconstruction. One of the unresolved major issues is whether variations of leaf wax δD (δDwax) signals along a precipitation gradient reflect changes of precipitation δD, precipitation amount, and/or evapo-transpiration. This ambiguity limits our interpretation of δDwax in geological records as well as the quantitative reconstruction of paleohydrological variability. Here we systematically investigated δD of soil water and waxes extracted from soil and plant leaves in the Chinese Loess Plateau (CLP) and its surrounding areas along a precipitation gradient with mean annual precipitation (MAP) varying from 140 mm to 676 mm. The results showed that while the variation of modeled precipitation δD has no significant correlation with MAP, soil water δD, soil δDwax, and individual plant δDwax exhibit negative correlations with MAP. In relatively arid areas, the δD values of soil water and plant leaf waxes are significantly more positive due to much lower precipitation relative to evapo-transpiration, suggesting that effective precipitation (P:E ratio) has played a crucial role in the D-enrichment of soil and plant leaf waxes in this region. While parallel decreasing trends in δDwax are found along the increase of precipitation gradient among dominant plants (including Artemisia spp., Aster hispidus, Stipa bungeana, and Cleistogenes squarrosa) in the region with similar slopes, the large δD offsets between plant groups suggest that plant type is an important factor in controlling plant hydrogen isotope fractionations. Our results indicate that δDwax preserved in paleosols can be used to infer past conditions of water availability in arid and semi-arid inland regions, but with a mechanism that is different from the influence of “amount effect” in humid areas. Moreover, vegetation changes should be constrained by independent paleobotanical data before monsoon related paleohydrology in the CLP and its surrounding areas can be quantitatively reconstructed using the plant wax δD proxy.

The subseafloor thermal gradient at Iheya North Knoll, Okinawa Trough, based on oxygen and hydrogen isotope ratios of clay minerals

We measured the oxygen and hydrogen isotope ratios of smectite, chlorite, and illite in hydrothermally active sediments at the Iheya North Knoll, Okinawa Trough, obtained by seafloor drilling of active hydrothermal fields during the Integrated Ocean Drilling Program (IODP) Expedition 331. Formation temperatures calculated from oxygen isotope data were compared to the downhole temperatures that were measured during the same expedition. The δ18O values ranged from +9.9‰ to +13.3‰ for smectite, +1.3 to +3.0‰ for chlorite or chlorite/smectite mixed-layer mineral, and +2.1‰ to +5.1‰ for illite or illite/smectite mixed-layer mineral with minor chlorite. For samples of illite that contained minor chlorite, δ18O values for illite or illite/smectite mixed-layer mineral of +4.4‰ to +6.1‰ were calculated, based on the proportion of the two clay minerals calculated from chemical composition of the individual mineral and the mixture determined by TEM-EDS and EPMA. We estimated the formation temperatures of the minerals using oxygen isotope fractionation data and assumed values of 0 to +1.2‰ for the fluid that was equilibrated with the minerals, based on the reported values of the seawater and vent fluid measured in previous studies. The temperature range calculated was 111–175 °C for a shallow layer less than about 25 m below seafloor (mbsf) that contained smectite and a minor kaolinite component, 177–297 °C for a deeper layer between about 25 and 40 mbsf that was dominated by chlorite or chlorite/smectite mixed-layer mineral, and 220–314 °C for the deepest layer between about 40 and 120 mbsf that contained illite or illite/smectite mixed-layer mineral with less chlorite. The temperatures of mineral formation calculated from the oxygen stable isotope data were slightly higher at some depths, but both calculated and measured temperatures demonstrated a steep, step-wise thermal gradient below the active hydrothermal field, where temperatures of >200 °C were determined at as little as 50 mbsf. Hydrogen isotope values mostly ranged between −40 and −55‰ and did not vary significantly or systematically between the layers, except in the clay fractions containing smectite above 25 mbsf that had relatively low values between −65 and −72‰. Hydrogen isotope results of the clay minerals were problematic to interpret and not consistent with interpretation of the oxygen data. Calculated temperatures from illite and smectite were mostly negative, whereas temperatures calculated from chlorite were more positive (average 145 °C), but lower than those from the oxygen isotope data. Additional work is still required to determine the hydrogen isotope fractionation between clay minerals and water with respect to temperature.

2H and 13C isotope fractionation analysis of organophosphorus compounds for characterizing transformation reactions in biogas slurry: Potential for anaerobic treatment of contaminated biomass

The ability of anaerobic digestion (AD) to eliminate organophosphorus model compounds (OPs) with structural elements of phosphate, phosphorothioate and phosphorodithioate esters was studied. The enzymatic mechanism of the first irreversible degradation reaction was characterized using metabolite pattern and kinetic 2H/13C-isotope effect in original, cell-free and heat sterilized biogas slurry. The isotope fractionation study suggests different modes of degradation reactions. Representatives for phosphate ester, tris(2-chloroethyl) phosphate and tris(1,3-dichloro-2-propyl) phosphate, were hydrolyzed in biogas slurry without carbon or hydrogen isotope fractionation. Representatives for phosphorodithioate, Dimethoate and Malathion, were degraded in original slurry yielding carbon enrichment factor (εC) of −0.6 ± 0.1‰ and −5.5 ± 0.1‰ (−0.9 ± 0.1‰ and −7.2 ± 0.5‰ in cell-free slurry), without hydrogen isotope fractionation. Phosphorothioate degradation represented by Parathion and Parathion-methyl yielded surprisingly different εC (−0.7 ± 0.2 and −3.6 ± 0.4‰) and εH (−33 ± 5 and −5 ± 1‰) in original slurry compared to cell-free slurry (εC = −2.5 ± 0.5 and −8.6 ± 1.4‰; εH = -61 ± 10 and −10 ± 3‰) suggesting H-C bond cleavage. Degradation of Parathion and Parathion-methyl in sterilized slurry gave carbon but not hydrogen fractionation implying relative thermostable enzymatic activity with different mechanism. The correlation of 2H and 13C stable isotope fractionation of Parathion in biogas slurry showed distinct pattern (Λoriginal = 31 ± 11, Λcell-free = 20 ± 2), indicating different mechanism from chemical hydrolysis. Overall, AD can be a potential treatment for OPs contaminated biomass or contaminated organic waste material.

Hydrogen isotopic anomalies in extraterrestrial organic matter: role of cosmic ray irradiation and implications for UCAMMs

Context. Micrometeorites represent, at timescales shorter than a few million years, the dominant source of extraterrestrial matter at the surface of the Earth. Analyses of ultracarbonaceous micrometeorites recovered from Antarctica, known as UCAMMs reveal an exceptionally N-rich organic matter associated with spatially extended high D enrichments. Experiments show that this specific organic matter might have been formed in the outer solar system by energetic irradiation of N-rich icy surfaces. Aims. We experimentally investigate the hydrogen isotopic fractionation resulting from irradiation of normal and D-rich N2-CH4 ices by high energy ions, simulating the exposition to Galactic cosmic rays of icy bodies surfaces orbiting at large heliocentric distances. Methods. Films of N2-CH4 ices and a N2-CH4/CD4/N2-CH4 “sandwich” ice were exposed to 129Xe13+ ion beams at 92 and 88 MeV. The chemical evolution of the samples was monitored using in situ Fourier transform infrared spectroscopy. After irradiation, targets were annealed to room temperature. The solid residues of the whole process left after ice sublimation were characterized in situ by infrared spectroscopy, and the hydrogen isotopic composition measured ex situ by imaging secondary ion mass spectrometry at the sub-micron scale (NanoSIMS). Results. Irradiation leads to the formation of new molecules and radicals. After annealing, the resulting poly-HCN-like macro-molecular residue exhibits an infrared spectrum close to that of UCAMMs. The residue resulting from irradiation of N2-CH4 ices does not exhibit a significant deuterium enrichment comparable to that found in extraterrestrial organic matter. The residue formed by irradiation of D-rich ices shows the formation of isotopic heterogeneities with localised hotspots and an extended contribution likely due to the diffusion of the radiolytic products from the D-rich layer. Conclusions. These results show that high-energy cosmic ray irradiation does not induce the large hydrogen isotopic fractionation observed at small spatial scale in interplanetary organics. By contrast, large D/H ratio heterogeneities at the sub-micron spatial scale in extraterrestrial organic matter can result from isotopically heterogeneous ices mixtures (i.e. condensed with different D/H ratios), which were transformed into refractory organic matter upon irradiation.

Carbon and hydrogen isotope fractionation for methane from non-isothermal pyrolysis of oil in anhydrous and hydrothermal conditions

In this study, to ascertain the carbon and hydrogen isotope fractionation of oil cracking gas (secondary gas) in hydrothermal conditions, non-isothermal pyrolysis of oil with and without water was carried out by a gold-tube system. By determination of the yields of individual gas products, it is found that the presence of water enhanced the yields of hydrocarbon gases. However, kinetic calculations indicate that Ea for the generation of methane and C2–5 in pyrolysis in hydrothermal conditions are essentially identical with those in anhydrous pyrolysis. The yields of carbon dioxide (CO2) and alkene gases in pyrolysis in hydrothermal conditions are evidently higher than those in anhydrous pyrolysis. It is reasonable that water–hydrocarbon reactions occurred and contributed to the generation of secondary gas in hydrothermal conditions. Meanwhile, the presence of water resulted in a slight depletion of 13C for methane and an evident depletion of 13C for CO2. Thermodynamic calculations suggest that water–hydrocarbon reactions in non-isothermal pyrolysis are dominated by free radical mechanism rather than ionic mechanism. Moreover, δ2H values of methane are apparently different in pyrolysis involving water with different δ2H. This result demonstrates that water provided hydrogen for hydrocarbon gas generation. Finally, we established mathematical models based on isotope fractionation to quantitatively determine the contribution of water–hydrocarbon reactions for gas generation in both experimental and geological conditions.

Hydrogen isotope fractionation response to salinity and alkalinity in a calcifying strain of Emiliania huxleyi

Hydrogen isotope ratios of long-chain alkenones (δ2HC37) correlate with water isotope ratios and salinity, albeit with varying degrees of biological fractionation between alkenones and water. These differences in fractionation are the result of environmental and species related effects, which in some cases have consequences for the magnitude of the δ2HC37 response per unit increase in salinity. Earlier culture experiments have focused on constraining hydrogen isotope fractionation factor α in non-calcifying strains of Emiliania huxleyi. Here we studied isotopic fractionation in a calcifying strain of E. huxleyi and show that although absolute fractionation is different, the response to changes in salinity and alkalinity is similar to those of non-calcifying species. This suggests that calcification does not alter the δ2HC37 response to salinity significantly.

Aridity-controlled hydrogen isotope fractionation between soil n-alkanes and precipitation in China

Leaf-wax n-alkane hydrogen isotope composition (δDalk) is widely applied as a proxy for paleohydroclimatic changes, but the factors controlling δDalk remain to be clarified. In this study, in order to determine the dominant controls, we measured δDalk in 54 surface soils along a southeast–northwest transect across a steep climatic gradient in China. δDalk is positively correlated with annual precipitation δD (δDpann) and better correlated with growing season (April–October) precipitation δD (δDpgs). However, the variability of δDpann (38‰) and δDpgs (35‰) does not explain all of the variance in δDalk (84‰). The apparent fractionation of hydrogen isotopes between n-alkanes and precipitation (εalk/p) is significantly correlated with variables related to aridity: relative humidity, rainfall amount, and aridity index (defined as the ratio of average precipitation to average potential evapotranspiration). This result demonstrates the important control of aridity on δDalk, which may result from the increasing soil evaporation and plant transpiration, as well as decreasing biosynthetic fractionation, in arid climates. We compiled published δDalk data from surface lake/soil sediments in China, and found that aridity effects are pronounced in regions with mean annual precipitation (MAP) < 800 mm. Therefore, we suggest that soil δDalk reflects precipitation δD modified by aridity, with a greater degree of modification in arid environments (e.g., MAP < 800 mm). Future work to quantitatively determine the effects of aridity on δDalk is needed to improve the reliability of the application of δDalk in paleoenvironmental studies.

Effect of Hydrous Pyrolysis on the Distribution of Carbon and Hydrogen Isotopes between Fractions of Organic Matter. The Nature of Oil Seeps in the Uzon Caldera, Kamchatka, Russia

The paper presents data on the transformations of oil from seeps in the caldera of Uzon volcano under the effect of hydrous pyrolysis at a temperature of 350°C in an argon and oxygen atmosphere. The carbon and hydrogen isotopic-fractionation characteristics (IFC) are proved to reflect processes occurring in the organic matter at its hydrous pyrolysis in oxidizing and neutral environments. Similarities in configuration are detected between the carbon IFC of Uzon oil seeps, Bogachevskoe field, and the biota of hydrothermal springs. The hydrogen IFC are of more complicated form, perhaps, because of exchange processes in the hydrothermal water. It is hypothesized that oil seeps in the interiors of the Uzon caldera can provide material for the origin of oil at the Bogachevskoe field. At the same time, it cannot be ruled out that hydrothermal water circulating in the caldera of Uzon volcano brings the material of the Bogachevskoe oil to the surface.

Aerobic microbial oxidation of hydrocarbon gases: Implications for oil and gas exploration

Abstract The molecular and carbon and hydrogen isotope compositions associated with the aerobic consumption of methane (Cl), ethane (C2) and propane (C3) were determined from incubations of marine sediments collected from the seafloor surface of the gas- and oil-bearing Bohai Bay in eastern China. The fresh sediment samples were incubated aerobically at 28 °C and treated with three types of hydrocarbon gas mixtures as follows: mixture I (C1:C2:C3 = 100:0:0), II (C1:C2:C3 = 99.00:0.70:0.30) and III (C1:C2:C3 = 79.96:10.04:10.00), corresponding to incubations i, ii and iii, respectively. All the hydrocarbons are of thermogenic origin, except C1 (microbial) in incubation ii. The oxidation of C1-C3 was observed in all three treatments, with variations in carbon isotope fractionation factors (eC) of C1 and average values of −10.5 ± 0.1, −5.7 ± 1.6, and −10.9 ± 2.9, respectively. The hydrogen isotope fractionation factors (eH) of C1 in the three incubations also display variation, with average values of −118.4 ± 3.0, −68.3 ± 15.0 and −56.3 ± 8.4, respectively. Experiments with thermogenic C1 display greater carbon fractionation than those with microbial C1. The eC and eH values for C2 and C3 were obtained only in incubation iii. Compared to C1, C2 and C3 exhibit weaker carbon isotope fractionation but stronger hydrogen isotope fractionation. The fractionation factors presented in this study can be applied to estimate the extent of C1-C3 oxidation in natural environments, especially at seafloor and terrestrial seeps where aerobic microbes are commonly present. Our study has important implications in oil and gas exploration, with an alert for exercising caution when using the molecular and isotopic characteristics of hydrocarbon gases to evaluate the gas sources because these are susceptible to aerobic microbial oxidation.

2H-enrichment of cellulose and n-alkanes in heterotrophic plants.

Hydrogen (H) isotopes of plant organic compounds are rarely employed in ecological studies. If so, these values are interpreted as being indicative of the plant source and/or leaf water. Recent observations suggest, however, that variations in hydrogen isotope fractionation that occur during the biosynthesis of plant compounds (2H-εbio) imprint valuable metabolic information into the hydrogen isotope composition (δ2H values) of plant organic compounds. Here we show a consistent 2H-enrichment of compounds in heterotrophically growing plants across a series of autotrophic/heterotrophic plant pairs. We suggest that this is due to a higher recycling of compounds in the Calvin and tricarboxylic acid cycles in heterotrophic plants that is associated with a more complete exchange of C-bound H with the surrounding 2H-enriched foliar water. Interestingly, we found that 2H-enrichment in heterotrophic plants was larger for carbohydrates than for lipids, with an average 2H-enrichment of 76 ± 9‰ in α-cellulose and 23 ± 23‰ in n-alkanes. We propose that this systematically larger 2H-enrichment for carbohydrates than for lipids is either due to different level of 2H-fractionation associated with heterotrophically produced NADPH, or to the potential uptake of lipids by heterotrophic plants. With the work we present here, we contribute to a better mechanistic understanding of what the biochemical principles are that couple the carbohydrate dynamics of plants to their δ2H values and hope to foster as such the application of H isotopes in plant sciences.

Carbon and hydrogen isotopic fractionation during abiotic hydrolysis and aerobic biodegradation of phthalate esters

We systematically investigated the changes of carbon and hydrogen isotope signatures of three phthalate esters (PAEs) during (i) abiotic hydrolysis over the pH range of 2, 7 and 10, and (ii) aerobic biodegradation initiated by hydrolysis by Rhodococcus opacus strain DSM 43250. Significant carbon isotopic fractionation was exhibited under all investigated conditions. Hydrogen isotopic fractionation was observed in some experiments and is hypothesized to be a secondary isotope effect due to the absence of a hydrogen bond cleavage during hydrolysis. Dual stable isotope analysis (Λ = Δδ2H/Δδ13C) resulting from abiotic hydrolysis and aerobic biodegradation showed similar magnitudes for dimethyl phthalate (DMP) and diethyl phthalate (DEP). The calculated carbon apparent kinetic isotope effects (AKIEC) for the hydrolytic pathway (CO bond cleavage) of PAEs fall within an expected range of 1.03–1.09, with the exception of lower AKIEC values for dibutyl phthalate (DBP) during hydrolysis at pH 2 and aerobic biodegradation. The lower AKIEC of DBP at pH 2 and aerobic biodegradation is likely related to a transition state from reactant-like to tetrahedral intermediate-like structure. Abiotic and biotic hydrolysis of PAEs resulted in similar AKIEC and Λ values due to the CO bond cleavage pathway, indicating the potential of dual isotope analysis to detect and quantify hydrolytic processes of PAEs in the environment. The pronounced primary carbon and typically low secondary or absent hydrogen isotopic fractionation might form a typical pattern to identify the hydrolytic reaction of PAEs in the environment. The characteristic Λ values of the hydrolytic reaction were different from Λ values of chemical oxidation of PAEs and showed diagnostic potential of dual HC isotope analysis to analyze reactions.