Deuterium Enrichment In Water Research Articles

Plant water resource partitioning and xylem-to-leaf deuterium enrichment in Lanzhou, northwest China

AbstractLanzhou lies at the western Loess Plateau, China, and has a typical semi-arid temperate continental climate. Plants in this area are exposed to a prolonged dry season. In this study, we measured the stable isotopes of hydrogen (δD) and oxygen (δ18O) of the local precipitation, river water, soil water, plant xylem water, and leaf water at four sampling sites during the 2016 growing season. Our results showed that plants relied mostly on wet season precipitation at sites N1, N2, and N3 because this recharged the soil after the long dry season. Leaf phenology had a significant effect on evaporation distance (ED) value, and evergreen plants have adapted to water tapping from deep soil water sources during the dry season. The ED values of trees and shrubs were quite different in the dry season, indicating water competition among different plant species was mitigated due to water resource partitioning. Moreover, plants at site N4 relied on a water source admixed with river water throughout the whole growing season. The mean value of xylem-to-leaf water deuterium enrichment (ɛl/x) was −0.91 ± 0.36‰ over all plant species, seasons, and sampling sites. Plant species, leaf phenology, and seasons were found to be the primary factors influencing the ɛl/x, while growth form and elevation had negligible effects.

DYNAMIC DEUTERIUM ENRICHMENT IN COMETARY WATER VIA ELEY–RIDEAL REACTIONS

ABSTRACT The deuterium-to-hydrogen ratio (D/H) in water found in the coma of Jupiter family comet (JFC) 67P/Churyumov–Gerasimenko was reported to be (5.3 ± 0.7) × 10−4, the highest among comets and three times the value for other JFCs with an ocean-like ratio. This discrepancy suggests the diverse origins of JFCs and clouds the issue of the origin of Earth’s oceanic water. Here we demonstrate that Eley–Rideal reactions between accelerated water ions and deuterated cometary surface analogs can lead to instantaneous deuterium enrichment in water scattered from the surface. The reaction proceeds with H2O+ abstracting adsorbed D atoms, forming an excited H2DO* state, which dissociates subsequently to produce energetic HDO. Hydronium ions are also produced readily by the abstraction of H atoms, consistent with H3O+ detection and abundance in various comets. Experiments with water isotopologs and kinematic analysis on deuterated platinum surfaces confirmed the dynamic abstraction mechanism. The instantaneous fractionation process is independent of the surface temperature and may operate on the surface of cometary nuclei or dust grains, composed of deuterium-rich silicates and carbonaceous chondrites. The requisite energetic water ions have been detected in the coma of 67P in two populations. This dynamic fractionation process may temporarily increase the water D/H ratio, especially as the comet gets closer to the Sun. The magnitude of the effect depends on the water ion energy-flux and the deuterium content of the exposed cometary surfaces.

Plant water resource partitioning and isotopic fractionation during transpiration in a seasonally dry tropical climate

Abstract. Lake Chala (3°19′ S, 37°42′ E) is a steep-sided crater lake situated in equatorial East Africa, a tropical semiarid area with a bimodal rainfall pattern. Plants in this region are exposed to a prolonged dry season, and we investigated if (1) these plants show spatial variability and temporal shifts in their water source use; (2) seasonal differences in the isotopic composition of precipitation are reflected in xylem water; and (3) plant family, growth form, leaf phenology, habitat and season influence the xylem-to-leaf water deuterium enrichment. In this study, the δ2H and δ18O of precipitation, lake water, groundwater, plant xylem water and plant leaf water were measured across different plant species, seasons and plant habitats in the vicinity of Lake Chala. We found that plants rely mostly on water from the short rains falling from October to December (northeastern monsoon), as these recharge the soil after the long dry season. This plant-available, static water pool is only slightly replenished by the long rains falling from February to May (southeastern monsoon), in agreement with the two water worlds hypothesis, according to which plants rely on a static water pool while a mobile water pool recharges the groundwater. Spatial variability in water resource use exists in the study region, with plants at the lakeshore relying on a water source admixed with lake water. Leaf phenology does not affect water resource use. According to our results, plant species and their associated leaf phenology are the primary factors influencing the enrichment in deuterium from xylem water to leaf water (εl/x), with deciduous species giving the highest enrichment, while growth form and season have negligible effects. Our observations have important implications for the interpretation of δ2H of plant leaf wax n-alkanes (δ2Hwax) from paleohydrological records in tropical East Africa, given that the temporal variability in the isotopic composition of precipitation is not reflected in xylem water and that leaf water deuterium enrichment is a key factor in shaping δ2Hwax. The large interspecies variability in xylem–leaf enrichment (24 ± 28 ‰) is potentially troublesome, taking into account the likelihood of changes in species assemblage with climate shifts.

Application of gas chromatography-tandem mass spectrometry (GC/MS/MS) for the analysis of deuterium enrichment of water.

Incorporation of deuterium from deuterium oxide ((2) H2 O) into biological components is a commonly used approach in metabolic studies. Determining the dilution of deuterium in the body water (BW) pool can be used to estimate body composition. We describe three sensitive GC/MS/MS methods to measure water enrichment in BW. Samples were reacted with NaOH and U-(13) C3 -acetone in an autosampler vial to promote deuterium exchange with U-(13) C3 -acetone hydrogens. Headspace injections were made of U-(13) C3 -acetone-saturated air onto a 30-m DB-1MS column in electron impact-mode. Subjects ingested 30 ml (2) H2 O, and plasma samples were collected. BW was determined by standard equation. Dual-energy X-ray absorptiometry scans were performed to calculate body mass, body volume and bone mineral content. A four-compartmental model was used to estimate body composition (fat and fat free mass). Full-scan experiments generated an m/z 45 peak and to a lesser extent an m/z 61 peak. Product fragment ions further monitored included 45 and 46 using selected ion monitoring (Method1), the 61 > 45 and 62 > 46 transition using multiple reaction monitoring (MRM; Method2) and the neutral loss, 62 > 45, transition (Method3). MRM methods were optimized for collision energy (CE) and collision-induced dissociation (CID) argon gas pressure with 6 eV CE and 1.5 mTorr CID gas being optimal. Method2 was used for final determination of (2) H2 O enrichment of subjects because of lower natural background. We have developed a sensitive method to determine (2) H2 O enrichment in BW to enable measurement of FM and FFM.

Water deuterium fractionation in the low-mass protostar NGC1333-IRAS2A

Context. Although deuterium enrichment of water may provide an essential piece of information in the understanding of the formation of comets and protoplanetary systems, only a few studies up to now have aimed at deriving the HDO/H2O ratio in low-mass star forming regions. Previous studies of the molecular deuteration toward the solar-type class 0 protostar, IRAS 16293-2422, have shown that the D/H ratio of water is significantly lower than other grain-surface-formed molecules. It is not clear if this property is general or particular to this source.

Temperature effect on leaf water deuterium enrichment and isotopic fractionation during leaf lipid biosynthesis: Results from controlled growth of C 3 and C 4 land plants

The hydrogen isotopic ratios ( 2H/ 1H) of land plant leaf water and the carbon-bound hydrogen of leaf wax lipids are valuable indicators for climatic, physiological, metabolic and geochemical studies. Temperature will exert a profound effect on the stable isotopic composition of leaf water and leaf lipids as it directly influences the isotopic equilibrium (IE) during leaf water evaporation and cellular water dissociation. It is also expected to affect the kinetics of enzymes involved in lipid biosynthesis, and therefore the balance of hydrogen inputs along different biochemical routes. We conducted a controlled growth experiment to examine the effect of temperature on the stable hydrogen isotopic composition of leaf water and the biological and biochemical isotopic fractionations during lipid biosynthesis. We find that leaf water 2H enrichment at 20 °C is lower than that at 30 °C. This is contrary to the expectation that at lower temperatures leaf water should be more enriched in 2H due to a larger equilibrium isotope effect associated with evapotranspiration from the leaf if all other variables are held constant. A hypothesis is presented to explain the apparent discrepancy whereby lower temperature-induced down-regulation of available aquaporin water channels and/or partial closure of transmembrane water channel forces water flow to “detour” to a more convoluted apoplastic pathway, effectively increasing the length over which diffusion acts against advection as described by the Péclet effect ( Farquhar and Lloyd, 1993) and decreasing the average leaf water enrichment. The impact of temperature on leaf water enrichment is not reflected in the biological isotopic fractionation or the biochemical isotopic fractionation during lipid biosynthesis. Neither the biological nor biochemical fractionations at 20 °C are significantly different from that at 30 °C, implying that temperature has a negligible effect on the isotopic fractionation during lipid biosynthesis.

Metabolic precursors of surfactant disaturated-phosphatidylcholine in preterms with respiratory distress

Our objective was to study the metabolic precursors of surfactant disaturated-phosphatidylcholine (DSPC) in preterm infants with respiratory distress syndrome (RDS) on mechanical ventilation. We performed 46 DSPC kinetic studies in 23 preterms on fat-free parenteral nutrition and mechanical ventilation (birth weight = 1167 +/- 451 g, gestational age = 28.5 +/- 2.0 weeks). Eight infants received a simultaneous intravenous infusion of U(13)C-glucose and [16,16,16](2)H-palmitate, eight infants received U(13)C-glucose and (2)H(2)O, and seven received U(13)C-palmitate and (2)H(2)O. Surfactant DSPC kinetics were calculated from the isotopic enrichments of DSPC-palmitate from sequential tracheal aspirates and its metabolic precursors in plasma or urine. DSPC fractional synthesis rate (FSR) was 17 +/- 11, 21 +/- 16, and 15 +/- 6%/day from glucose, palmitate, and body water, respectively (P = 0.36). DSPC-FSR from U(13)C-glucose and (2)H(2)O were significantly correlated and yielded similar estimates (difference of -0.1 +/- 3%) (P = 0.91). The difference in the 15 infants receiving palmitate versus (2)H(2)O or palmitate versus glucose was +6.0 +/- 12%/day (P = 0.21). There was a significant correlation between DSPC-FSRs from plasma glucose and plasma FFA. The contribution of glucose versus palmitate to DSPC-FSR was 49 +/- 20% versus 51 +/- 20%, respectively. Plasma glucose and FFA showed similar contributions to DSPC-FSR in infants with RDS and fat-free parenteral nutrition. FSRs from (2)H(2)O or glucose were highly correlated.

The Peculiar Volatile Composition of Comet 8P/Tuttle: A Contact Binary of Chemically Distinct Cometesimals?

We report measurements of eight native (i.e., released directly from the comet nucleus) volatiles (H2O, HCN, CH4, C2H2, C2H6, CO, H2CO, and CH3OH) in comet 8P/Tuttle using NIRSPEC at Keck 2. Comet Tuttle reveals a truly unusual composition, distinct from that of any comet observed to date at infrared wavelengths. The prominent enrichment of methanol relative to water contrasts the depletions of other molecules, especially C2H2 and HCN. We suggest that the nucleus of 8P/Tuttle may contain two cometesimals characterized by distinct volatile composition. The relative abundances C2/CN, C2/OH, and CN/OH in 8P/Tuttle (measured at optical/near-UV wavelengths) differ substantially from the mixing ratios of their potential parents (C2H2/HCN, C2H2/H2O, and HCN/H2O) found in this work. Based on this comparison, our results do not support C2H2 and HCN being the principal precursors for respectively C2 and CN in Tuttle. The peculiar native composition observed in 8P/Tuttle (compared to other comets) provides new strong evidence for chemical diversity in the volatile materials stored in comet nuclei. We discuss the implications of this diversity for expected variations in the deuterium enrichment of water among comets.

Isomers of conjugated linoleic acids are synthesized via different mechanisms in ruminal digesta and bacteria

Digesta samples from the ovine rumen and pure ruminal bacteria were incubated with linoleic acid (LA) in deuterium oxide-containing buffer to investigate the mechanisms of the formation of conjugated linoleic acids (CLAs). Rumenic acid (RA; cis-9,trans-11-18:2), trans-9,trans-11-18:2, and trans-10,cis-12-18:2 were the major CLA intermediates formed from LA in ruminal digesta, with traces of trans-9,cis-11-18:2, cis-9,cis-11-18:2, and cis-10,cis-12-18:2. Mass spectrometry indicated an increase in the n+1 isotopomers of RA and other 9,11-CLA isomers, as a result of labeling at C-13, whereas 10,12 isomers contained minimal enrichment. In pure culture, Butyrivibrio fibrisolvens and Clostridium proteoclasticum produced mostly RA with minor amounts of other 9,11 isomers, all labeled at C-13. Increasing the deuterium enrichment in water led to an isotope effect, whereby (1)H was incorporated in preference to (2)H. In contrast, the type strain and a ruminal isolate of Propionibacterium acnes produced trans-10,cis-12-18:2 and other 10,12 isomers that were minimally labeled. Incubations with ruminal digesta provided no support for ricinoleic acid (12-OH,cis-9-18:1) as an intermediate of RA synthesis. We conclude that geometric isomers of 10,12-CLA are synthesized by a mechanism that differs from the synthesis of 9,11 isomers, the latter possibly initiated by hydrogen abstraction on C-11 catalyzed by a radical intermediate enzyme.

Constraints on the Formation of Comets from D/H Ratios Measured in H 2O and HCN

This report is the follow-up of the paper of A. Drouart et al. (1999, Icarus 140, 129) in which it was demonstrated that appropriate models of the solar nebula permit us to interpret the deuterium enrichment in water with respect to the protosolar D/H ratio measured in LL3 meteorites and comets. In the present report, we show that the models selected by Drouart et al. are also able to explain D/H in HCN measured in Comet C/1995 O1 (Hale–Bopp). We find that the D/H ratio in HCN entering the nebula is ∼4×10 −3, which is significantly less than values measured in cold dark clouds, but consistent with values found in hot molecular cores. Both H 2O and HCN ices infalling from the presolar cloud onto the nebula discoid evaporated in the turbulent part of the nebula, isotopically exchanged with hydrogen, and mixed with water vapor coming from the inner part of the nebula. Subsequently, H 2O and HCN ices with D/H ratios measured in Comet Hale–Bopp condensed, agglomerated and were incorporated in cometesimals. In the light of these results, we discuss the story of molecules detected in comets coming from Oort cloud. Most molecules detected in Comet Hale–Bopp originated from ices embedded in the presolar cloud. Ices vaporized prior to entering into the nebula or in the early nebula, and subsequently recondensed, except highly volatile molecules. According to A. Kouchi et al. (1994, Astron. Astrophys. 290, 1009), water ice condensed in crystalline form. We discuss the possibility that the most volatile species were then trapped in the form of clathrate hydrates. The oversolar C/N ratio and the strong depletion of Ne/O with respect to the solar abundance observed in comets are in agreement with the theory of clathrate hydrates of J. I. Lunine and D. J. Stevenson (1985, Astrophys. suppl. Ser. 58, 493). Comets formed in the Kuiper belt may contain amorphous water ice and have kept the isotopic signature of the presolar cloud. New published models of interiors of Uranus and Neptune permit us to calculate that the D/H ratios in proto-uranian and proto-neptunian water ices are in agreement with those measured in comets. This confirms the current assumption that cometesimals and planetesimals that formed the cores of Uranus and Neptune had similar compositions.

Comparison of deuterium incorporation and mass isotopomer distribution analysis for measurement of human cholesterol biosynthesis

To compare endogenous cholesterol biosynthesis measured by deuterium incorporation (DI) and mass isotopomer distribution analysis (MIDA), cholesterol fractional and absolute synthetic rates were measured simultaneously by both techniques under identical physiological conditions. Twelve subjects (22 to 39 years of age) underwent a dual stable isotope protocol, involving oral deuterium oxide administration and measurement of incorporation of deuterium into cholesterol coincident with constant infusion of sodium [1-(13)C]acetate and measurement of the mass isotopomer distribution pattern of newly synthesized cholesterol. Synthesis was determined over 24 h with a 7-h feeding period. Both methods yielded similar measurements of fractional cholesterol synthesis (7.8 +/- 2.5% day(-)(1) for DI vs. 6.9 +/- 2.2% day(-)(1) for MIDA). Correlation of fractional synthesis across techniques was strong (r = 0.84, P = 0.0007). Absolute synthesis rates were also not different at 24 h (13.4 +/- 4.3 mg kg(-)(1) day(-)(1) for DI vs. 11.9 +/- 3.6 mg kg(-)(1) day(-)(1) for MIDA, r = 0.79, P < 0.002). We conclude that despite different assumptions and analytical requirements, deuterium incorporation and MIDA yield similar rates of cholesterogenesis in humans when measurements are made over 24 h. The decision as to which method to adopt depends on available clinical and analytical facilities

Assay of Low Deuterium Enrichment of Water by Isotopic Exchange with [U-13C3]Acetone and Gas Chromatography–Mass Spectrometry

A sensitive assay of the2H-enrichment of water based on the isotopic exchange between the hydrogens of water and of acetone in alkaline medium is described and validated. For low2H-enrichments (0.008 to 0.5%), the sample is spiked with [U-13C3]acetone and NaOH. After exchange,2H-enriched [U-13C3]acetone is extracted with chloroform and assayed by gas chromatography–mass spectrometry. With some instruments, ion–molecule reactions, resulting in increased baseline enrichment, are minimized by lowering the electron ionization energy from the usual 70 to 10 eV. The2H-enrichment of water is amplified nearly sixfold in the M4/M3 ratio of [U-13C3]acetone. For high2H-enrichments (0.25 to 100%), the use of unlabeled acetone suffices. After exchange, the mass isotopomer distribution of acetone is analyzed, yielding the2H-enrichment of water. The assay with [U-13C3]acetone allows measuring the2H-enrichment of water even in biological samples containing acetone. This technique is more rapid and economical than the classical isotope ratio mass spectrometric assay of the enrichment of hydrogen gas derived from the reduction of water.

Hydrogen isotope exchange reaction rates: Origin of water in the inner solar system

Rate constants for hydrogen isotope exchange between molecular hydrogen and water ( k( T) H 2- HDO ) and hydrogen and methane ( k( T) H 2- CH 3 D ) have been determined experimentally. The temperature dependence of the constants can be expressed by: with k( T) in cm 3/sec. Catalytic effects on charcoal, silica, phyllosilicates, and iron were found to be negligible. A model describing the evolution (with time) of the hydrogen isotopic composition of water in the solar nebula is proposed: while the temperature is decreasing in the gas, isotope exchange between H 2 and H 2O yields a deuterium enrichment in water. Using Cameron's numerical models (1972, 1978, 1985) of the solar nebula, we show that the observed difference between the protosolar and the carbonaceous chondrite D/H ratios (i.e., between 30 and 150 10 −6, respectively) is well accounted for by our model, provided that (1) water was accreted as ice at a temperature of ≤ 160 K. and (2) the hydrogen pressure was higher than 10 −5 atm somewhere between 1 and 3 AU. In such conditions, the calculations show that meteoritic phyllosilicates did not form in the gas phase, by reactions between water vapour and silicate grains, but by the subsequent circulation of liquid water, originally condensed as ice. Water on Earth ( D/ H = 155 · 10 −6) also results from such a cold nebula chemistry.

Measurement of fractional lipid synthesis using deuterated water (2H2O) and mass isotopomer analysis.

Fractional biosynthesis of palmitate, stearate, and cholesterol was determined with deuterated water (2H2O) using mass isotopomer analysis in Hep G2 and MCA sarcoma cells in culture. The method employed differs from previous ones in that the number of deuterium atoms from 2H2O incorporated into newly synthesized molecules was determined and not assumed. After correction for background natural abundances, the isotopomer distribution due to deuterium incorporation in fatty acids and cholesterol was shown to follow a simple binomial distribution depending on the deuterium enrichment in water (p) and the maximum number of deuterium atoms incorporated per molecule (N). Under a wide range of 2H2O enrichments, N could be determined to be 17 for palmitate, 20 for stearate, and 20 for cholesterol by regression analysis or from a series of consecutive mass isotopomer ratios. The fraction derived from de novo synthesis was given by the ratio of the observed to the theoretical deuterium enrichment, which is the product (N x p). The new synthesized fraction of palmitate and stearate by Hep G2 cells for the length of the experiment was found to be 77 and 65%, respectively. These values were confirmed by experiments with [U-13C]glucose as the precursor. In MCA sarcoma cells grown in lipid-poor medium, the average values for fractional synthesis of palmitate, stearate, and cholesterol were 70, 35, and 70%, respectively. This approach should be generally applicable to the simultaneous determined of fractional synthesis of a number of compounds with either deuterium or 13C tracers. Its application is only limited by the accuracy of mass spectrometric analysis.

Association between apolipoprotein E phenotype and endogenous cholesterol synthesis as measured by deuterium uptake

The aim was to determine if central pool cholesterol formation rate is related to apo E phenotype in healthy normolipidaemic males. Subjects consumed a fixed composition diet for 5 d and at 07:00 hours on d 5 drank 0.7 g deuterium oxide (D2O).kg-1 body water. Over d 5 body water deuterium enrichment was maintained by ingestion of labelled drinking water. The fractional synthetic rate of the central pool free cholesterol was determined over two consecutive 12 h intervals by the incorporation of deuterium from body water into plasma unesterified cholesterol. Participants were healthy male volunteers, mean age 26.4 years. They were divided into E2/(2 or 3) and E4/(4 or 3) alleles, n = 9 in each group. Subjects with E2/- showed lower fractional synthetic rates than E4/- subjects, at 0.070(SEM 0.007) v 0.097(0.009) d-1 over the 24 h period (p less than 0.05). Cholesterol fractional synthetic rate was higher during the night than during the day (p less than 0.05). These findings suggest an increased central pool free cholesterol synthesis in individuals possessing the apo epsilon-4 versus epsilon-2 allele. Apo E related regulation of whole body de novo cholesterol synthesis may therefore contribute to observed variations in plasma cholesterol levels.

Product isotope effects on in vivo methanogenesis by Methanobacterium thermoautotrophicum.

The hydrogen in methane produced by cultures of Methanobacterium thermoautotrophicum originates from water. In H2O/D2O mixtures, a methane product isotope effect is observed that increases rapidly as the water deuterium enrichment approaches 100%. This effect is due to the intracellular production of protons from H2, catalyzed by hydrogenase, which occurs at 12% the rate of water diffusion through the cell membrane. We estimate that water diffusion through the thick cell membrane of M. thermoautotrophicum is retarded by a factor of 10(6) over the free diffusion rate. The intracellular production of H+ suggests that either (1) hydrogenase is not directly involved in the production of a chemiosmotic proton gradient or (2) if it is involved, the proton gradient exists between the cytosol and the interior of vesicles observed in this bacterium. The intrinsic deutrium product isotope effect in methanogenesis is 1.20 +/- 0.1, comparable to anabolic deuterium product isotope effects in other autotrophs. An algebraic model incorporating the intracellular H2 to H+ flux accurately predicts the distribution of deuterated methane species at all levels of water deuterium enrichment.

Hydrogeological Processes and Chemical Reactions at a Landfill.

Chemical and isotopic analyses were made of water from wells in and downgradient from a landfill to determine chemical and isotopic effects of generation and migration of leachate on ground water. The distribution and wide concentration range of oxygen and methane permit the delineation of an anaerobic zone, a regional oxygenated zone and an intermediate zone. The ratio of reduced nitrogen to nitrate indicates location of reducing fronts as the leachate migrates. The pH of the native ground water is low (≥5.0) primarily because of the low pH of rainfall and the lack of calcareous or other soluble minerals in the aquifer material. The pH is higher (∼6.6) in the leachate because of generation of carbon dioxide, ammonia, and methane. The native ground water has a low TDS (80 mg/l) while the leachate has an average TDS of 2800 mg/l and is primarily a NaHCO3 type water. Sulfate concentrations are extremely low and H2 S was not detected. We suggest that a major source of cations may be their exchange from the clays by the ammonium generated in the leachate. High concentrations of Fe and Mn are attributed to a source in the refuse but more important to reduction of oxide cements and coatings resulting from degradation of organic matter. The main source of bicarbonate is from organic degradation with minimal CO2 from the soil zone. At one landfill site 52% of the total alkalinity is attributed to organic compounds, mainly organic acid anions. The δ13 C of bicarbonate in the leachate is exceedingly heavy (+18.400 /00 ) which results from fractionation during the formation of methane. The 10 per mil deuterium enrichment of water may be due to decomposition of deuterium-enriched compounds and bacterial processes that preferentially consume the lighter hydrogen isotope.