Hydrogen Isotopic Composition Research Articles

Controls on the hydrogen isotope composition of tetraether lipids in an autotrophic ammonia-oxidizing marine archaeon

The stable hydrogen isotope composition of persistent biomolecules is used as a palaeohydrological proxy. While much previous work has focused on plant leaf wax-derived n-alkanes, the potential of prokaryotic lipid biomarkers as carriers of H isotope signatures remains underexplored, particularly in the Archaea. Here we investigated H isotope distributions in the membrane lipids of the ammonia-oxidizing chemoautotroph Nitrosopumilus maritimus strain SCM1. Hydrogen isotope ratios were measured on the cleaved biphytane chains of tetraether membrane lipids extracted from steady-state continuous cultures cultivated at slow, medium, and fast growth rates. In contrast to recent work on bacterial fatty acids, where the direction and magnitude of isotopic fractionation varies widely (ca. 600‰ range) as a function of central C and energy metabolism, archaeal biphytane data in the present work are relatively invariant. The weighted average 2H/1H fractionation values relative to growth water (2εL/W) ranged from –272 to –260‰, despite a three-fold difference in doubling times (30.8–92.5 hr), yielding an average growth-rate effect <0.2‰ hr−1. These 2εL/W values are more negative than most heterotrophic microbial lipid H isotope measurements in the literature, and are on par with those from other autotrophic archaea, as well as with phytol from photoautotrophic algae. N. maritimus values of 2εL/W also varied systematically with the number of internal rings (cyclopentyl + cyclohexyl), increasing for each additional ring by 6.4 ± 2.7‰. Using an isotope flux-balance model in tandem with a comprehensive analysis of the sources of H in archaeal lipid biosynthesis, we use this observation to estimate the kinetic isotope effects (KIEs) of H incorporation from water; from reducing cofactors such as flavins and NADPH, and for the transhydrogenation reaction(s) that convert the electron-donor derived NADH into these cofactors. Consistent with prior studies on bacteria and plants, our results indicate the KIEs of reducing cofactors in archaea are highly fractionating, while those involving exchange of water protons are less so. When combined with the observation of minimal growth-rate sensitivity, our results suggest biphytanes of autotrophic 3HP/4HB utilizing Nitrososphaerota (a.k.a. Thaumarchaeota) may be offset from their growth waters by a nearly constant 2εL/W value. Together with the ring effect, this implies that all biphytanes originating from a common source should have a predictable ordering of their isotope ratios with respect to biphytane ring number, allowing precise reconstruction of the original δ2H value of the environmental water. Collectively, these patterns indicate archaeal biphytanes have potential as paleo-hydrological proxies, either as a complement or an alternative to leaf wax n-alkanes.

Influence of hydrothermal asteroidal conditions on the molecular structure and isotopic compositions of polycyclic aromatic hydrocarbons

A variety of polycyclic aromatic hydrocarbons (PAHs) are reported in carbonaceous chondrites (CCs) and in the interstellar medium (ISM). Although PAHs in CCs are not as large as those detected in the ISM, their carbon isotope composition is interpreted as pinpointing an interstellar origin. In contrast, their hydrogen isotope composition can be related to the extent of secondary processes, as is the proportion of alkylated PAHs within CCs. Here, we experimentally investigate the molecular and isotopic evolution of PAHs under simulated asteroidal hydrothermal conditions at 150 °C. Results show that PAHs are chemically stable under these conditions whatever their size, i.e. no destruction, conjugation nor alkylation occurs, even in the presence of other reactive organic molecules. Plus, PAHs retain their carbon isotope compositions even in the presence of another carbon-rich reservoir, either organic or inorganic. On the other hand, their hydrogen isotope composition is modified through exchange with water. Of note, as shown by additional experiments, the presence of smectites, abundant in CCs, impacts the relative abundances of extractable PAHs, saponite trapping more efficiently the larger PAHs. Altogether, results of the present experiments show that PAHs of CCs can be used as tracers of both pre-accretion and secondary processes.

Species and biosynthetic effects cause uncorrelated variation in oxygen and hydrogen isotope compositions of plant organic compounds

Strong variation in plant organic compound δ2H and δ18O values such as leaf waxes or cellulose among species is commonly observed; however, the extent to which this isotopic variation is driven by leaf water or biochemical isotope effects is relatively unknown. Therefore, we compared variation in leaf water and organic compound δ2H and δ18O values (cellulose - δ2H and δ18O, and n-alkanes – δ2H) across 192 species grown in a botanical garden to assess covariation of isotope values (1) between elements in a given compound, (2) between different (organic) compounds of a given element, and (3) across different growing seasons. Our results suggest that variation in leaf water δ2H values are likely not a strong driver for the observed variation in organic compound δ2H values across species, and that this may also be true for δ18O values. Furthermore, even though correlation between leaf water δ2H and δ18O values appears to be transferred to organic compounds, the explanatory power of this correlation is strongly diminished (R2 < 0.04). This indicates that additional biochemical isotope fractionation leads to substantial variation in organic compound δ2H and possibly also δ18O values across species. Moreover, the low explanatory power of the correlation between cellulose and n-alkane δ2H values (R2 = 0.06) suggests that the biochemical pathways associated with the different compounds are accompanied by different isotope effects. Lastly, cellulose δ2H and δ18O values appeared sensitive to environmental differences between growing seasons, while differences in model-predicted source water δ18O and δ2H values and also climate were negligible between years. By contrast, the species pattern in n-alkane δ2H values was highly conserved between the two years. This indicates that the environmental forcing effects on isotope values were not equal between compounds. Therefore, we conclude that variation in organic compound δ2H (and possibly also δ18O) values among species and growing seasons was more strongly driven by biochemical isotope fractionation rather than by isotope values of plant water. This should be considered in the application of organic compound δ2H and δ18O values to reconstruct past climate, where invariable biochemical isotope fractionation is often assumed. Alternatively, organic compound δ2H and δ18O values could be further developed into a tool to extract plant metabolic information.

Environmental controls on the hydrogen isotopic composition of volcanic glass from the Southern Afar rift, eastern Ethiopia

Hydrogen stable isotope values of hydrated volcanic glass as a proxy for the isotopic composition of past meteoric waters provide an opportunity for reconstructing past climates. Here we present new hydrogen stable isotope values from 63 individual tuffs from the Afar region in the lower Awash Valley of eastern Ethiopia. The hydrogen isotopic results from volcanic glass spanning the last 6.4 Ma show a wide distribution with values ranging between −89 and − 32 ‰ (VSMOW). The variability is consistent with the observed paleo-depositional setting (i.e., lower values for fluvial settings while higher values are recorded in lacustrine settings). The reconstructed hydrogen isotopic values of parent waters are considerably lower than those of modern meteoric waters, suggesting a bias toward lower values during the hydration of volcanic glass.Reconstructed hydrogen stable isotope values of water derived from volcanic glass differ from other proxies of regional climate in northeast Africa, pointing to the controls of local meteoric waters on the hydrogen isotopic composition of volcanic glass. There is agreement between the reconstructed isotopic composition of parent waters and the lowest hydrogen isotopic values of modern precipitation in the Awash catchment that correspond to periods of large rainfall. This correspondence probably indicates that volcanic glass is preferentially hydrated during the wettest seasons. To test this idea, we compared the isotopic results from volcanic glass with the reconstructed isotopic composition of surface waters from soil carbonates deposited during the Pliocene and Pleistocene in the lower Awash Valley. The comparison reveals a considerable difference between proxies, with volcanic glass recording lower isotopic values than soil carbonates. Evaporative isotopic enrichment of water in shallow (<1 m) soil profiles probably accounts for the elevated values in soil carbonates. In contrast, the presence of smectite-rich vertisols above volcanic deposits appears to retard infiltration of meteoric waters deep into the subsurface. During rainfall events, vertisols swell and prevent all but the largest rainfall events from penetrating deep (>1 m) into the profiles and promoting the hydration of volcanic glass that display systematically lower isotopic values of meteoric waters than the mean annual rainfall.

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.

Effect of thermal maturation on the isotopic compositions of volatile organic sulfur compounds released from a kerogen by hydrous and anhydrous pyrolysis

Volatile organic sulfur compounds (VOSCs) may provide an alternative and improved approach in the evaluation of source and thermal maturity of natural gas. However, the role of water in the generation and decomposition of VOSCs is still ambiguous. Hydrous pyrolysis experiments were conducted on the isolated type Ⅱ-S kerogen of a source rock collected from the Ghareb Formation, Israel at 200–360 ℃ for 72 h (Easy%Ro = 0.32–1.20). The evolved gases were quantified for C1-C5 hydrocarbons, CO2, H2S and VOSCs. Compound specific isotope analysis were conducted both on the VOSCs and H2S (δ34S), and also on the C1-C5 hydrocarbons and CO2 (δ13C, δ2H). The results show that thiols concentration increased from 200 ℃ to 300 ℃ and then decreased from 300 ℃ to 360 ℃. The formed thiols isotopically co-vary with H2S from 200 ℃ to 340 ℃ and present the opposite trend with H2S from 340 ℃ to 360 ℃. The δ34S values of thiols are usually 3–7‰ lighter than the parent kerogen and 0.5–4‰ heavier than H2S. The concentrations of thiophenes generally increased with thermal stress with peak generation at 360 ℃, the δ34S values of thiophenes are mostly < 2–4‰ lighter than the parent kerogen and 2–8‰ heavier than H2S through the experiments. The δ13C and δ2H values of gaseous hydrocarbons are gradually enriched in heavy isotopes with increased thermal maturity. VOSCs dominated by thiols and thiophenes are generated by two ways: 1. the interactions between H2S and hydrocarbon molecules (synthetic pathway), 2. thermal cracking of OMs including kerogen and associated bitumen primary cracking and hydrocarbon secondary cracking (thermal cracking pathway). The synthetic pathway played the major role in the generation of thiols at the immature and early mature stages (200–300 ℃, Easy%Ro = 0.32–0.71), the cracking pathway has the dominant effect on the occurrence of thiols at higher thermal maturity levels (300–360 ℃, Easy%Ro = 0.71–1.20). The main pathway of thiophenes formation throughout the experiments is by the thermal cracking pathway. In the hydrous experiments, water promotes the synthetic pathway that generated thiols and retarded the thermal cracking pathway that forms thiophenes, but had no significant impact on δ34S values of individual VOSCs, δ13C and δ2H values of gaseous hydrocarbons. Therefore, combining with carbon and hydrogen isotopic compositions of gaseous hydrocarbons, molecular and sulfur isotopic compositions of individual VOSCs in the gas phase can provide valuable clues for petroleum systems in sedimentary basins including gas sources, generation pathways, thermal maturity levels and petroleum secondary transformations, such as thermochemical sulfate reduction in the subsurface reservoirs.

Hydrogen isotopic evidence for nebular pre-hydration and the limited role of parent-body processes in CM chondrites

The conditions and environments in which hydrated phases in unequilibrated meteorites formed remain debated. Among carbonaceous chondrites, Mighei-type chondrites (CMs) display a large range in the degree of aqueous alteration, and thus record different stages of hydration and alteration. Here, we report the bulk H, C, and N contents, H and C isotopic compositions, and thermogravimetric signatures of the most- and least-altered CMs known so far, Kolang and Asuka 12236, respectively. We also report in-situ SIMS measurements of the hydrogen isotopic compositions of water in both chondrites. Compared to other CMs, Asuka 12236 has the lowest bulk water content (3.3 wt.% H2O) and the most D-rich water and bulk isotopic compositions (δD = 180‰ and 280‰, respectively). Combined with literature data, our results show that phyllosilicate-bearing CMs altered to varying degrees accreted water-ice grains with similar isotopic compositions. These results demonstrate that the hydrogen isotopic variations in CM chondrites (i) are not controlled by secondary alteration processes and (ii) were mostly shaped by interactions between the protoplanetary disk and the molecular cloud that episodically fed the disk over several million years. The minimally altered CM chondrites Paris and Asuka 12236 display peculiar, D-rich, hydrogen isotopic compositions that imply the presence of another H-bearing component in addition to insoluble organic matter and phyllosilicates. This component is most likely the hydrated amorphous silicates that are ubiquitous in these chondrites. CM bulk H and O isotopic compositions are linearly correlated, implying that (i) amorphous silicates in CM matrices were already hydrated by disk processes before the onset of CM parent-body alteration, and (ii) the quest for a hypothetically water-free CM3 is illusory.

Vacuum extraction of high-salinity water for the determination of oxygen and hydrogen isotopic compositions using cavity ring-down spectroscopy

Tracking the hydrogen and oxygen isotopic compositions of water samples can aid in understanding the water cycle. Compared to that of fresh water, analyzing the hydrogen and oxygen isotopic composition of high-salinity water is still a challenging task owing to the influence of dissolved salts. In this study, desalination was achieved by vacuum extraction, and the oxygen and hydrogen isotope ratios (δ18O and δ2H) were measured using cavity ring-down spectroscopy (CRDS). Different solutions of the individual salts (NaCl, KCl, MgCl2, and CaCl2) were prepared with deionized water (DI) having a known stable isotopic composition. After vacuum extraction, the maximum differences in isotopic composition was no more than 0.09‰ for δ18O and 0.30‰ for δ2H at 4 mol/L NaCl and KCl and 1 mol/L MgCl2 and CaCl2. The isotopic compositions of two high-salinity samples (IAPSO standard seawater and brine water) were determined by the proposed procedure as well as thermal conversion/elemental analyzer-isotope ratio mass spectrometry for comparison. The δ18O and δ2H results obtained using the two methods were consistent. The influence of isotope-salts was completely overcome by the proposed vacuum extraction desalination procedure. Thus, the method enables the rapid extraction of a large number of samples, regardless of the type and origin of the salt solutions, provided the concentrations of MgCl2 and CaCl2 are below 1.0 mol/L.

Seasonality in groundwater recharge in Coastal Southwestern India and its hydrological implications based on stable isotopes (δ18O, δD)

This study observes and interprets the spatio-temporal variation in the oxygen and hydrogen isotopic composition (δ18O, δD) of shallow groundwater in the Southwestern Coastal state of India, Kerala, in terms of seasonally varying rainfall, physiography, and hydrogeological settings of this region. This study identifies effective groundwater recharge sources and their relative contributions and provides first-order estimates of submarine groundwater discharge by interpreting the spatio-temporal variations in the stable isotopes of oxygen and hydrogen in groundwater, collected from 225 locations for pre-monsoon and post-monsoon seasons in conjunction with the isotopic composition of rainfall. Spatio-temporal variations in the δ18O and d-excess, with other hydrogeological data, reveals that: (1) ∼4.9 Billion Cubic Meter (BCM) of fresh water from rainfall during May to October mixes with ∼5.9 BCM of residual pre-monsoon groundwater across Kerala. (2) ∼ 11% area of Kerala is additionally recharged by the NE monsoon rainfall. (3) The annual groundwater recharge varies physiographically from ∼2.2 BCM in the lowland to ∼1.5 BCM in the midland and ∼1.2 BCM in highland regions. (4) On an annual basis, 41% of replenishable groundwater is drained as SGD into the Arabian Sea.

A solar wind-derived water reservoir on the Moon hosted by impact glass beads

The past two decades of lunar exploration have seen the detection of substantial quantities of water on the Moon’s surface. It has been proposed that a hydrated layer exists at depth in lunar soils, buffering a water cycle on the Moon globally. However, a reservoir has yet to be identified for this hydrated layer. Here we report the abundance, hydrogen isotope composition and core-to-rim variations of water measured in impact glass beads extracted from lunar soils returned by the Chang’e-5 mission. The impact glass beads preserve hydration signatures and display water abundance profiles consistent with the inward diffusion of solar wind-derived water. Diffusion modelling estimates diffusion timescales of less than 15 years at a temperature of 360 K. Such short diffusion timescales suggest an efficient water recharge mechanism that could sustain the lunar surface water cycle. We estimate that the amount of water hosted by impact glass beads in lunar soils may reach up to 2.7 × 1014 kg. Our direct measurements of this surface reservoir of lunar water show that impact glass beads can store substantial quantities of solar wind-derived water on the Moon and suggest that impact glass may be water reservoirs on other airless bodies.

Water sources used by artificial Salix psammophila in stands of different ages based on stable isotope analysis in northeastern Mu Us Sandy Land

Understanding the water use pattern of artificially restored vegetation is important to provide reasonable water management strategies. However, the characteristics, controls and differences of water sources of planted Salix psammophila at different developmental stages remain poorly understood. In this study, the hydrogen and oxygen isotope compositions of xylem water, soil water, and rainwater were measured and coupled with the MixSIAR model to investigate the variations and controls of water use patterns of different aged S. psammophila in a semi-arid region in northeastern Mu Us Sandy Land. Results showed that >60% of water used by 6-yr S. psammophila derived from 0 to 120 cm soil layer throughout the growing season due to the relatively shallow roots (0–100 cm). In contrast, water sources used by 12- and 18-yr S. psammophila differed markedly between the dry and rainy seasons, which were attributed to the developed dimorphic root systems and seasonal changes in soil water profile. In the dry season, 12- and 18-yr S. psammophila extracted 71.93% and 68.91% of water from 120 to 300 cm and 40–200 cm soil layer, respectively; in the rainy season, however, they both shifted main water sources to 0–120 cm soil layer (65.09% and 56.14%). The severe soil desiccation and dead roots observed in the 18-yr stand decreased the ability of old S. psammophila to extract water from the deep soil layer (200–300 cm) in the dry season. Thus, changes in the vertical distribution of roots and soil water contents controlled the seasonal water use pattern of different aged S. psammophila. Our study demonstrates that the age-dependent water use pattern of S. psammophila should be considered to implement the corresponding management measures in future afforestation plans to avoid overuse of water and maintain sustainable vegetation restoration in the water-limited desert regions.

Genesis of the world-class Dachang gold deposit, northern Qinghai-Tibet Plateau: A multiproxy approach

Dachang is a world-class gold deposit that occurs in the Bayan Har Terrane, northern Qinghai-Tibet Plateau, with Au resources of 121 t at an average grade of 3.0 g/t. Although this deposit was investigated in some previous studies, its genesis remains debated. The deposit is controlled by the Gande-Maduo anticlinorium and thrust fault zone, and the orebodies occur in subsidiary interlayer faults or fractures in thin-bedded, stratatoid, lenticular and vein forms. The host strata belong to the Lower Triassic Bayan Har Shan Group consisting of metasandstone, metasiltstone, slate, and carbonaceous slate interlayered with phyllite. The mineralization of Dachang can be divided into the following four stages. Stage 1 gold-sulfide-quartz veins, stage 2 gold-sulfide-carbonate-quartz veins, stage 3 stibnite-quartz veins and stage 4 quartz-carbonate veins. There are two types of ores: altered rocks and quartz veins. The main ore minerals are pyrite, arsenopyrite, stibnite and native gold, with trace amounts of tetrahedrite, chalcopyrite, galena and sphalerite. The wallrock alteration comprises mainly sulfidation, silicification, carbonatization, and sericitization. The element association is As, Sb, Au, Te, Bi, Ag, W and Pb in order of enrichment factors, whereas Cu, Mo, and Sn are depleted relative to their crustal abundances.In this study, we identified three types of primary fluid inclusions in quartz from veins of the four mineralization stages as follows: type 1 liquid-dominated two-phase aqueous inclusions; type 2 aqueous-carbonic inclusions, including aqueous-dominated (type 2a) and carbonic-dominated inclusions (type 2b); and type 3 two-phase hydrocarbon inclusions. Microthermometric measurements of fluid inclusion assemblages (FIAs) and bulk fluid inclusion analyses show that the ore-forming fluids had similar low-salinity compositions (1.7 to 6.9 wt% NaCl equiv.) in the H2O-CO2-N2 system with trace amounts of hydrocarbons. The mineralization temperatures range from 150 to 200 °C, and estimated depths are approximately 5 to 6.5 km. Fluid/wallrock reactions and immiscibility or boiling during mineralization in response to pressure fluctuations in a brittle faults were the main triggers for gold precipitation at Dachang.The hydrogen, oxygen, carbon and He-Ar isotopic compositions indicate that the ore-forming fluids originated from metamorphic devolatilization of immediate- and deep-level country rocks and no meteoric water or mantle volatiles were involved. The organic carbon proportions account for 42 to 53% of the total carbon in ore-forming fluid, and carbon fractions from sedimentary carbonates range from 47 to 58%. The gold mineralization followed immediately after the regional metamorphism (240–225 Ma) and occurred when the host rocks had exhumated into a brittle environment. The Dachang deposit is an epizonal orogenic gold deposit.

Ecohydrological niche segregation among desert shrubs in a gypsum-calcareous formation, north-western Iran

ABSTRACT Background Xerophilic subshrubs exhibit multiple functional types and frequently show hydrological niche segregation. In the poorly studied Irano-Turanian gypsum deserts, knowledge of the ecohydrological strategies of different plant species is essential to understand community complexity in these vulnerable ecosystems. Aim We studied the ecohydrological strategies of five co-existing subshrub members of Caryophyllales, ascertaining if their rooting architecture, gypsum affinity or photosynthetic pathway determined their water uptake, and if gypsum crystallisation water could be a relevant water source for plants in different seasons. Methods We conducted soil and xylem sampling for isotope analyses in spring and summer and extracted water by cryogenic vacuum distillation. Oxygen and hydrogen isotope compositions were determined and compared with visual representation and Bayesian Mixing Models to determine species ecohydrological strategies. Results Species – season interactions were related to differences in xylem sap isotopic composition. Three basic strategies relying on contrasting the use of free topsoil moisture and deep soil water could be detected and were in part explained by rooting architecture. Plant gypsum affinity and photosynthetic pathways did not have a significant effect on the water sources used by the plants. Conclusions Ecohydrological niche segregation was explained partly by rooting architecture and species-specific traits. Gypsum crystallisation water was not used in summer by the studied species.

The relationship between Carlin-type Au mineralization and magmatism in the Youjiang Basin-a case study from the Mingshan gold deposit in northwest Guangxi, China

The Youjiang Basin in Southwest (SW) China is the second-largest Carlin-type goldfield in the world after Nevada, USA; however, the spatial, temporal, and genetic links between Carlin-type Au mineralization and magmatism in SW China remain controversial compared with those in Nevada. The Mingshan gold deposit is one of the few Carlin-type gold deposits that exhibits a close spatial relationship between gold orebodies and magmatic rocks in the Youjiang Basin. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) uranium-lead (U-Pb) dating of magmatic zircons from quartz porphyry dikes and hydrothermal apatite associated with gold yields the intrusive and gold mineralization ages of 96.34 ± 0.89 and 139.9 ± 4.8 Ma, respectively, indicating that the magmatism was much younger than the gold mineralization at Mingshan. Petrography and microthermometry of the fluid inclusions from ore-stage quartz and calcite suggest a low to moderate temperature (140–240 °C), low salinity (3–8 wt% NaCleqv), and moderate to low density fluid. The hydrogen and oxygen isotope compositions of the ore-stage quartz indicate a metamorphic fluid source of the ore fluid. Thus, we propose that the close spatial contact between the gold orebodies and igneous dikes could have resulted from the same NWW-trending fault space during the Early Cretaceous precipitation of ore fluid and the Late Cretaceous intrusion of the quartz porphyry dikes. However, the genetic link between the quartz porphyry and Carlin-type Au mineralization was not observed at Mingshan. The primary metamorphic fluid associated with Early Cretaceous gold mineralization in the Youjiang Basin was derived from syn-orogenic shortening deformation and metamorphism in the compressional tectonic setting caused by the subduction of the Paleo-Pacific Plate. Subsequent post-orogenic extension during the rollback of the subducted Pacific slab led to significant extensional faults and intrusions of Early Cretaceous concealed granites, which may have provided heat, materials, and energy for the transport of ore fluid. The ore fluid was transported through permeable extensional structures from the deep crust and reacted with the carbonaceous and Fe-rich host rocks in the shallow crust, resulting in the Early Cretaceous gold mineralization event in the Youjiang Basin.

Land-use-based freshwater sediment source fingerprinting using hydrogen isotope compositions of long-chain fatty acids

Rapidly changing land use patterns and frequent extreme weather events have resulted in an increased sediment flux to freshwater systems globally, highlighting the need for land-use-based sediment source fingerprinting. Application of variability in hydrogen isotope compositions (δ2H values) of vegetation-specific biomarkers from soils and sediments is relatively underexplored for land-use-based freshwater suspended sediment (SS) source fingerprinting, but has the potential to complement the information from routinely applied carbon isotope analysis and provide new insights. We analysed δ2H values of long-chain fatty acids (LCFAs) as vegetation-specific biomarkers in source soils and SS collected from the mixed land use Tarland catchment (74 km2) in NE Scotland, to identify stream SS sources and quantify their contributions to SS. Plant growth form was the primary control on source soils LCFAs (n-C26:0, n-C28:0, n-C30:0) δ2H variability, while the isotopic composition of source water had no significant control. Forest and heather moorland soils covered with dicotyledonous and gymnosperm species were differentiated from arable land and grasslands soils covered with monocotyledonous species. SS samples collected for fourteen months from the Tarland catchment with a nested sampling approach showed monocot-based land use (cereal crops, grassland) to be the major source of SS with 71 ± 11% contribution on catchment-wide scale averaged throughout the sampling period. Storm events after a dry summer period and sustained high flow conditions in the streams during autumn and early winter suggested enhanced connectivity of more distant forest and heather moorland land uses covering relatively steep topography. This was shown by an increased contribution (44 ± 8%) on catchment-wide scale from dicot and gymnosperm-based land uses during the corresponding period. Our study demonstrated successful application of vegetation-specificity in δ2H values of LCFAs for land-use-based freshwater SS source fingerprinting in a mesoscale catchment where δ2H values of LCFAs were primarily controlled by plant growth forms.

Authenticating Tibetan pork in China by tracing the species and geographical features based on stable isotopic and multi-elemental fingerprints

A potential tool for authenticating Tibetan pork based on species and geographical origins was investigated by isotopic and multi-elemental fingerprints to compare Tibetan pork and plain pork from various regions in China. In this study, carbon, nitrogen, hydrogen and oxygen isotope compositions and concentrations of 50 elements of a total of 93 pork samples (Tibetan pork from Tibet and Sichuan, Jilin pork from Jilin and DLY pork from Liaoning) were determined and subjected to multivariate analysis, including linear discriminant analysis (LDA), partial least squares discriminant analysis (PLS-DA) and correlation analysis. The trace elements Fe, Cu, Rb, Mo, Cs, Ir, Co, Sr, Sm and four stable isotopes were determined as potential markers for identifying Tibetan pork. The discriminant model revealed good discrimination among pork samples based on species and regions, and the high accuracies of K-fold cross-validation (95.74% and 97.84%) indicated the reliability and stability of classification models. This study has demonstrated the efficiency of isotopic and multi-elemental technology in identifying Chinese high-altitude indigenous pigs. • Tibetan pork from different regions was discriminated compared to plain pork. • Multi-elements and stable isotopes combined with chemometrics as effective tools. • High cross-validation accuracy for tracing species and origins. • Fe, Cu and δ 13 C are indicators for discriminating high-altitude pork samples.

Hydrogen Isotope Exchange between Trichloroethene and Water under Mild Environmental Conditions─Implications for the Use of Hydrogen CSIA in Contaminated Site Assessment

Trichloroethylene (TCE) is a key legacy environmental contaminant and a major target for contaminant remediation projects. Hydrogen compound-specific isotope analysis (CSIA) of halocarbons is a relatively recent technique, predominantly used as a line of evidence for apportionment of TCE sources. To date, no published data addressed the potential for hydrogen exchange between TCE and hydroxide in a water solution under typical groundwater pH conditions. In this study, we determined the pH- and temperature-dependent rates of exchange in controlled experiments to constrain the scope of applications of hydrogen CSIA at field sites contaminated by TCE. Relatively high rates of the exchange were associated with above-neutral pH typical of carbonate aquifers (half-lives of years to decades) and slower, but not negligible, rates were associated with sub-neutral pH. Hydrogen exchange alters the hydrogen isotope composition of TCE in solution, masking initial source signatures or degradation signatures over environmentally relevant time scales. In effect, the TCE–water exchange restricts the classical applications of hydrogen CSIA data to a subset of distinctly acidic environments. On the other hand, as the rates of the exchange can be predicted for specific combinations of pH and temperature, the process could be potentially utilized in age-dating of TCE contamination.

A fluid inclusion and stable-isotope study of hydrothermal vein mineralization, Schwarzwald district, Germany

A combined fluid inclusion and stable isotope study has been carried out on over 180 individual samples from 89 post-Variscan hydrothermal veins (Pb-Zn-Cu-bearing fluorite-barite-quartz veins, Co-Ni-Ag-Bi-U-bearing barite-fluorite-quartz veins and barren barite-fluorite-quartz veins) from the Schwarzwald district, Germany. The salinities of fluid inclusions in post-Variscan primary fluorite, calcite, barite and quartz are in the range of 22–25 wt.% equivalent (eqv.) NaCl, and the eutectic temperatures range between –57 and –45°C, indicating the presence of H2O-NaCl-CaCl2 fluids. Homogenization temperatures vary from 130 to 180°C. A low-salinity fluid (0 to 15 wt.% eqv. NaCl) was observed in some late stage fluorite, calcite and quartz samples, which were trapped similar temperature, range of high salinity fluids.&#x0D; Raman microprobe analyses show that the only detectable volatile in the vapour is CO2. Almost all δ18O (n=86) measurements of quartz from the fluorite-bearing post-Variscan veins range between +11.1 and +20.9 ‰. The calculated δ18OH2O values are between –11.0 and +4.4 ‰, using known quartz-water fractionation and fluid inclusion homogenization temperatures. The δ18OH2O values of directly extracted fluid inclusion water of fluorites range from –11.6 to +1.1 ‰, very consistent with the calculated values. The δD values of fluid inclusion water in calcites (extracted from primary and late calcite samples) lie in a narrower range between –26 and –15 ‰. The extracted fluid inclusion water from quartz samples has significantly more variable δD values between –63 and +9 ‰. The δ13C and δ18O values of fluid inclusion gas (CO2) range between –21.4 and –6.7 ‰ and between –16.3 to –7.1 ‰, respectively.&#x0D; Calculations for fluorite-barite-quartz veins combining oxygen isotope equilibria with microthermometric data result in quartz precipitation temperatures of 120–170°C at pressures between 0.3 to 0.5 kbar. The δ18OH2O and δD data, particularly the observed wide range in hydrogen isotopic compositions, indicate that the hydrothermal mineralization formed through large-scale mixing of a basement-derived saline NaCl-CaCl2 brine with meteoric water.

Hydrogeochemical characteristics and the genesis of the No. Lu 32 well in the Jiaodong Peninsula, China

The No. Lu 32 well is a seismic observation well situated on the easternmost tip of the Penglai–Weihai fault zone in the Jiaodong Peninsula. It is necessary to reveal the genetic mechanism of the water in this well for earthquake forecasting along the Penglai–Weihai fault zone. Water samples were collected from the No. Lu 32 well, neighboring wells, and seawater to measure the hydrochemical composition and main hydrogen and oxygen isotopic compositions. The water type of the No. Lu 32 well is Cl–Na, which may be due to the influence of seawater intrusion. Hydrogen and oxygen isotopes indicate that the No. Lu 32 well and adjacent wells are mainly influenced by meteoric water, that the high salinity in the water is mainly from the mixing of modern seawater, and that the proportion of seawater there is approximately 5%. Observation of water temperature data in the No. Lu 32 well over several years shows regular annual variations. This comprehensive study shows that the well is greatly affected by seawater backflow infiltration and shallow water. The results of this paper provide an important reference for exploring the hydrogeochemical characteristics and genesis of wells in other coastal zones.