D/H equilibrium fractionation between H2O and H2 as a function of the salinity of aqueous solutions

Martineau, François; Fourel, François; Bodergat, Anne‐Marie; Lécuyer, Christophe

doi:10.1016/j.chemgeo.2011.10.017

Cited by 12 publications

(14 citation statements)

References 25 publications

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“…while Lecuyer et al 2009found a significant offset between the measurement of the freshwater and the NaCl solution. For the NaCl effect on δ 2 H, the two available studies of Sofer and Gat (1975) and Martineau et al (2012) also provide rather differing results (albeit with a large scatter). Bourg et al (2001) evaluated the sea-salt effect using a solution composed of a mixture of the different marine salts with a chemical composition proportional to seawater.…”

Section: Salt Effect With Irmsmentioning

confidence: 98%

“…Three other studies have been undertaken with the aim of providing artificial saline solutions with lower salinities in order to evaluate the salt effect especially for sea water (Lecuyer et al, 2009, Martineau et al, 2012, Bourg et al, 2001 Figure 1, we show the δ 18 O results based on the sea salt marsh of Guerande (no pure NaCl solution available), while for δ 2 H we show the results from the pure NaCl solution. In the following, we consider the results from Lecuyer et al 2009, as being the approximate effect on the single salt NaCl.…”

Section: Salt Effect With Irmsmentioning

confidence: 99%

“…The Y-axis is the difference between the freshwater reference and the artificial sea water (=the salt effect).Note that Lecuyer et al (2009) did not use a pure solution of NaCl but a sea salt from natural sea salt marsh of Guerande (France) (see composition in theirTable 1). The data fromMartineau et al (2012) is the average of their two different runs presented inFigure 1(pure NaCl solution). The error bar represents a 95% confidence interval.…”

mentioning

confidence: 99%

“…However, the chemical composition given in theirTable 1 indicates that this commercial table saltis mainly composed of NaCl and is therefore not similar to typical sea water composition. In addition to the table salt from Guerande,Martineau et al (2012) also measured…”

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confidence: 99%

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Inter-comparison of salt effect correction for δ18O and δ2H measurements in seawater by CRDS and IRMS using the gas-H2O equilibration method

et al. 2017

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The isotope composition of seawater is an efficient method for detecting mixing between water masses. To measure long term or large scale hydrological processes at the ocean surface, it is necessary to be able to precisely compare datasets produced by different laboratories. The oxygen and hydrogen isotope (δ 18 O and δ 2 H) composition of marine waters can be measured using isotope ratio mass spectrometry (IRMS) and near-infrared laser absorption spectroscopy (LS) techniques. The IRMS and equilibration method is thought to provide results on the activity scale, while LS provides results on the concentration scale. However, the effect of dissolved seawater salts on the measurement is not sufficiently assessed and seems sometimes contradictory in the literature. For this purpose, we made artificial seawater and a pure NaCl solution from a freshwater of known isotope composition. The solutions were measured by four different laboratories allowing us to compare the two techniques. We show that minor corrections are necessary to correct seawater measurements for the salt effect and report them on the concentration scale. Interestingly, seawater measurements using LS (type Picarro) coupled to a liner are not on the concentration scale and require a correction of ~0.09‰ for δ 18 O, while the correction is relatively less significant for δ 2 H (~0.13‰). Moreover, we found for IRMS measurements that the salt effect can differ between different laboratories but seems reproducible for a given laboratory. A natural sea water sample was then analyzed by the different laboratories participating in the study. We found that applying the corrections increases the reproducibility of the isotope measurement significantly, with inter-laboratory standard deviation decreasing from 0.06 to 0.02‰ and 0.55 to 0.23‰ for δ 18 O and δ 2 H, respectively. Thus, comparing or merging sea water datasets produced in different laboratories requires that each laboratory carries out its own calibration with artificial seawater and presents measurements on the concentration scale.

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Section: Salt Effect With Irmsmentioning

confidence: 98%

Section: Salt Effect With Irmsmentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

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Inter-comparison of salt effect correction for δ18O and δ2H measurements in seawater by CRDS and IRMS using the gas-H2O equilibration method

et al. 2017

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“…Note that measured values for δD of H 2 O in fluids from Lost City are +2 to +7‰ (Proskurowski et al, 2006) and thus the equilibrium values for CH 4 and H 2 at Lost City are slightly (~5‰) higher than those indicated by the curves; this difference is small compared to the uncertainty in equilibrium fractionation factor calibrations at the temperatures of these fluids (~30 to 90°C (Horita and Wesolowski, 1994). The model neglects the effects of elevated pressure and salinity (Horita, 2005;Martineau et al, 2012), and ignores potential isotopic exchange with hydrous minerals Saccocia et al, 2009;Méheut et al, 2010).] The initial δD was taken to be 0‰ (dashed lines) for seawater-derived H, or −60‰ (solid lines) for mantle-derived H (Clog et al, 2013) (Lyon and Hulston, 1984;Lécluse and Robert, 1994;Horibe and Craig, 1995).…”

Section: Hydrogen Exchange and The Origin Of Hydrogen In Chmentioning

confidence: 89%

The geochemistry of methane isotopologues

Wang¹

2017

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This thesis documents the origin, distribution, and fate of methane and several of its isotopic forms on Earth. Using observational, experimental, and theoretical approaches, I illustrate how the relative abundances of 12 CH 4 , 13 CH 4 , 12 CH 3 D, and 13 CH 3 D record the formation, transport, and breakdown of methane in selected settings.Chapter 2 reports precise determinations of 13 CH 3 D, a "clumped" isotopologue of methane, in samples collected from various settings representing many of the major sources and reservoirs of methane on Earth. The results show that the information encoded by the abundance of 13 CH 3 D enables differentiation of methane generated by microbial, thermogenic, and abiogenic processes. A strong correlation between clumped-and hydrogen-isotope signatures in microbial methane is identified and quantitatively linked to the availability of H 2 and the reversibility of microbially-mediated methanogenesis in the environment. Determination of 13 CH 3 D in combination with hydrogen-isotope ratios of methane and water provides a sensitive indicator of the extent of C-H bond equilibration, enables fingerprinting of methane-generating mechanisms, and in some cases, supplies direct constraints for locating the waters from which migrated gases were sourced. Chapter 3 applies this concept to constrain the origin of methane in hydrothermal fluids from sediment-poor vent fields hosted in mafic and ultramafic rocks on slow-and ultraslow-spreading mid-ocean ridges. The data support a hypogene model whereby methane forms abiotically within plutonic rocks of the oceanic crust at temperatures above ca. 300• C during respeciation of magmatic volatiles, and is subsequently extracted during active, convective hydrothermal circulation. Chapter 4 presents the results of culture experiments in which methane is oxidized in the presence of O 2 by the bacterium Methylococcus capsulatus strain Bath. The results show that the clumped isotopologue abundances of partially-oxidized methane can be predicted from knowledge of 13 C/ 12 C and D/H isotope fractionation factors alone.: Shuhei Ono, Ph.D. Acknowledgments I fear that this section will not do justice to the people I have not the space to thank individually. Alas, here goes. To those whose names are not specifically listed here, thank you too. I wish first to thank Shuhei Ono. The work this thesis represents could not have happened without his bold vision and the license to explore and question that working in his lab afforded. His unbridled optimism, breadth of scientific curiosity, personal integrity, and accessibility to his personnel are traits I one day hope to emulate. I thank him for his nonjudgmental yet appropriately measured support of many of my ideas-even those that led nowhere-, for believing in me even when I found it difficult to do so myself, and for teaching me to change pump oil, build vacuum lines, and drink Icelandic vodka.I also wish to thank my thesis committee members Jeff Seewald, Roger Summons, and John Pohlman, for their in...

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Stable Isotope Tracking: Water Cycles and Climates of the Past

Lécuyer¹

2013

Water on Earth

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D/H equilibrium fractionation between H2O and H2 as a function of the salinity of aqueous solutions

Cited by 12 publications

References 25 publications

Inter-comparison of salt effect correction for δ18O and δ2H measurements in seawater by CRDS and IRMS using the gas-H2O equilibration method

Inter-comparison of salt effect correction for δ18O and δ2H measurements in seawater by CRDS and IRMS using the gas-H2O equilibration method

The geochemistry of methane isotopologues

Stable Isotope Tracking: Water Cycles and Climates of the Past

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