Methane Isotopologues Research Articles

Clumped isotopologue constraints on the origin of methane at seafloor hot springs

Hot-spring fluids emanating from deep-sea vents hosted in unsedimented ultramafic and mafic rock commonly contain high concentrations of methane. Multiple hypotheses have been proposed for the origin(s) of this methane, ranging from synthesis via reduction of aqueous inorganic carbon (∑CO2) during active fluid circulation to leaching of methane-rich fluid inclusions from plutonic rocks of the oceanic crust. To further resolve the process(es) responsible for methane generation in these systems, we determined the relative abundances of several methane isotopologues (including 13CH3D, a “clumped” isotopologue containing two rare isotope substitutions) in hot-spring source fluids sampled from four geochemically-distinct hydrothermal vent fields (Rainbow, Von Damm, Lost City, and Lucky Strike).Apparent equilibrium temperatures retrieved from methane clumped isotopologue analyses average 310-42+53 °C, with no apparent relation to the wide range of fluid temperatures (96–370 °C) and chemical compositions (pH, [H2], [∑CO2], [CH4]) represented. Combined with very similar bulk stable isotope ratios (13C/12C and D/H) of methane across the suite of hydrothermal fluids, all available geochemical and isotopic data suggest a common mechanism of methane generation at depth that is disconnected from active fluid circulation. Attainment of equilibrium amongst methane isotopologues at temperatures of ca. 270–360 °C is compatible with the thermodynamically-favorable reduction of CO2 to CH4 at temperatures at or below ca. 400 °C under redox conditions characterizing intrusive rocks derived from sub-ridge melts. Collectively, the observations support a model where methane-rich aqueous fluids, known to be trapped in rocks of the oceanic lithosphere, are liberated from host rocks during hydrothermal circulation and perhaps represent the major source of methane venting with thermal waters at unsedimented hydrothermal fields. The results also provide further evidence that water-rock reactions occurring at temperatures lower than 200 °C do not contribute significantly to the quantities of methane venting at mid-ocean ridge hot springs.

Equilibrium and non-equilibrium controls on the abundances of clumped isotopologues of methane during thermogenic formation in laboratory experiments: Implications for the chemistry of pyrolysis and the origins of natural gases

Multiply isotopically substituted molecules (‘clumped’ isotopologues) can be used as geothermometers because their proportions at isotopic equilibrium relative to a random distribution of isotopes amongst all isotopologues are functions of temperature. This has allowed measurements of clumped-isotope abundances to be used to constrain formation temperatures of several natural materials. However, kinetic processes during generation, modification, or transport of natural materials can also affect their clumped-isotope compositions. Herein, we show that methane generated experimentally by closed-system hydrous pyrolysis of shale or nonhydrous pyrolysis of coal yields clumped-isotope compositions consistent with an equilibrium distribution of isotopologues under some experimental conditions (temperature–time conditions corresponding to ‘low,’ ‘mature,’ and ‘over-mature’ stages of catagenesis), but can have non-equilibrium (i.e., kinetically controlled) distributions under other experimental conditions (‘high’ to ‘over-mature’ stages), particularly for pyrolysis of coal. Non-equilibrium compositions, when present, lead the measured proportions of clumped species to be lower than expected for equilibrium at the experimental temperature, and in some cases to be lower than a random distribution of isotopes (i.e., negative Δ18 values). We propose that the consistency with equilibrium for methane formed by relatively low temperature pyrolysis reflects local reversibility of isotope exchange reactions involving a reactant or transition state species during demethylation of one or more components of kerogen. Non-equilibrium clumped-isotope compositions occur under conditions where ‘secondary’ cracking of retained oil in shale or wet gas hydrocarbons (C2-5, especially ethane) in coal is prominent. We suggest these non-equilibrium isotopic compositions are the result of the expression of kinetic isotope effects during the irreversible generation of methane from an alkyl precursor. Other interpretations are also explored. These findings provide new insights into the chemistry of thermogenic methane generation, and may provide an explanation of the elevated apparent temperatures recorded by the methane clumped-isotope thermometer in some natural gases. However, it remains unknown if the laboratory experiments capture the processes that occur at the longer time and lower temperatures of natural gas formation.

The Methane Isotopologues by Solar Occultation (MISO) Nanosatellite Mission: Spectral Channel Optimization and Early Performance Analysis

MISO is an in-orbit demonstration mission that focuses on improving the representation of the methane distribution throughout the upper troposphere and stratosphere, to complement and augment the nadir- and zenith-looking methane observing system for a better understanding of the methane budget. MISO also aims to raise to space mission readiness the concept of laser heterodyne spectro-radiometry (LHR) and associated miniaturization technologies, through demonstration of Doppler-limited atmospheric transmittance spectroscopy of methane from a nanosatellite platform suitable for future constellation deployment. The instrumental and engineering approach to MISO is briefly presented to demonstrate the technical feasibility of the mission. LHR operates using narrow spectral coverage (<1 cm−1) focusing on a few carefully chosen individual ro-vibrational transitions. A line-by-line spectral channel selection methodology is developed and used to optimize spectral channel selection relevant to methane isotopologue sounding from co-registered thermal infrared and short-wave infrared LHR. One of the selected windows is then used to carry out a first performance analysis of methane retrievals based on measurement noise propagation. This preliminary analysis of a single observation demonstrates an ideal instrumental precision of <1% for altitudes in the range 8–20 km, <5% for 20–30 km and <10% up to 37 km on a single isotopologue profile, which leaves a significant reserve for real-world error budget degradation and bodes well for the mission feasibility. MISO could realistically demonstrate methane limb sounding at Doppler-limited spectral resolution, even from a cost-effective 6 dm3 nanosatellite.

A model for 12CH2D2 and 13CH3D as complementary tracers for the budget of atmospheric CH4

AbstractWe present a theoretical model to investigate the potential of 13CH3D and 12CH2D2, the doubly substituted mass‐18 isotopologues of methane, as tools for tracking atmospheric methane sources and sinks. We use electronic structure methods to estimate kinetic isotope fractionations associated with the major sink reactions of methane in air (reactions with OH and Cl radicals) and combine literature data with reconnaissance measurements of the relative abundances of 13CH3D and 12CH2D2 to estimate the compositions of the largest atmospheric sources. This model atmospheric budget is investigated with a simplified box model in which we explore both steady state and dynamical (nonsteady state) conditions triggered by changes in emission or sink fluxes. The steady state model predicts that sink reactions will generate a marked (>100‰) clumped isotope excess in atmospheric Δ12CH2D2 relative to the net source composition. 12CH2D2 measurements may thus be useful for tracing both atmospheric source and sink fluxes. The effect of sinks on Δ13CH3D is much less pronounced, indicating that 13CH3D in air will give a more focused picture of the source composition.

Determination of foreign broadening coefficients for Methane Lines Targeted by the Tunable Laser Spectrometer (TLS) on the Mars Curiosity Rover

Molecular line parameters of foreign- broadening by air, carbon dioxide, and helium gas have been experimentally determined for infrared ro-vibrational spectral lines of methane isotopologues (12CH4 and 13CH4) at 3057cm−1 targeted by the Tunable Laser Spectrometer (TLS) in the Sample Analysis at Mars (SAM) instrument suite on the Mars Science Laboratory (MSL) Curiosity rover. From multi-spectrum analyses with the speed-dependent Voigt line profile with Rosenkrantz line-mixing, speed-dependence and line-mixing effects were quantified for methane spectra at total pressures up to 200 mbar. The fitted air-broadening coefficients deviated from 8–25% to those reported in the HITRAN-2012 database.

Global inverse modeling of CH<sub>4</sub> sources and sinks: an overview of methods

Abstract. The aim of this paper is to present an overview of inverse modeling methods that have been developed over the years for estimating the global sources and sinks of CH4. It provides insight into how techniques and estimates have evolved over time and what the remaining shortcomings are. As such, it serves a didactical purpose of introducing apprentices to the field, but it also takes stock of developments so far and reflects on promising new directions. The main focus is on methodological aspects that are particularly relevant for CH4, such as its atmospheric oxidation, the use of methane isotopologues, and specific challenges in atmospheric transport modeling of CH4. The use of satellite retrievals receives special attention as it is an active field of methodological development, with special requirements on the sampling of the model and the treatment of data uncertainty. Regional scale flux estimation and attribution is still a grand challenge, which calls for new methods capable of combining information from multiple data streams of different measured parameters. A process model representation of sources and sinks in atmospheric transport inversion schemes allows the integrated use of such data. These new developments are needed not only to improve our understanding of the main processes driving the observed global trend but also to support international efforts to reduce greenhouse gas emissions.

Fractionation of the methane isotopologues 13CH4, 12CH3D, and 13CH3D during aerobic oxidation of methane by Methylococcus capsulatus (Bath)

Aerobic oxidation of methane plays a major role in reducing the amount of methane emitted to the atmosphere from freshwater and marine settings. We cultured an aerobic methanotroph, Methylococcus capsulatus (Bath) at 30 and 37°C, and determined the relative abundance of 12CH4, 13CH4, 12CH3D, and 13CH3D (a doubly-substituted, or “clumped” isotopologue of methane) to characterize the clumped isotopologue effect associated with aerobic methane oxidation. In batch culture, the residual methane became enriched in 13C and D relative to starting methane, with D/H fractionation a factor of 9.14 (Dε/13ε) larger than that of 13C/12C. As oxidation progressed, the Δ13CH3D value (a measure of the excess in abundance of 13CH3D relative to a random distribution of isotopes among isotopologues) of residual methane decreased. The isotopologue fractionation factor for 13CH3D/12CH4 was found to closely approximate the product of the measured fractionation factors for 13CH4/12CH4 and 12CH3D/12CH4 (i.e., 13C/12C and D/H). The results give insight into enzymatic reversibility in the aerobic methane oxidation pathway. Based on the experimental data, a mathematical model was developed to predict isotopologue signatures expected for methane in the environment that has been partially-oxidized by aerobic methanotrophy. Measurement of methane clumped isotopologue abundances can be used to distinguish between aerobic methane oxidation and alternative methane-cycling processes.

Real-time analysis of <i>δ</i><sup>13</sup>C- and <i>δ</i>D-CH<sub>4</sub> in ambient air with laser spectroscopy: method development and first intercomparison results

Abstract. In situ and simultaneous measurement of the three most abundant isotopologues of methane using mid-infrared laser absorption spectroscopy is demonstrated. A field-deployable, autonomous platform is realized by coupling a compact quantum cascade laser absorption spectrometer (QCLAS) to a preconcentration unit, called trace gas extractor (TREX). This unit enhances CH4 mole fractions by a factor of up to 500 above ambient levels and quantitatively separates interfering trace gases such as N2O and CO2. The analytical precision of the QCLAS isotope measurement on the preconcentrated (750 ppm, parts-per-million, µmole mole−1) methane is 0.1 and 0.5 ‰ for δ13C- and δD-CH4 at 10 min averaging time. Based on repeated measurements of compressed air during a 2-week intercomparison campaign, the repeatability of the TREX–QCLAS was determined to be 0.19 and 1.9 ‰ for δ13C and δD-CH4, respectively. In this intercomparison campaign the new in situ technique is compared to isotope-ratio mass spectrometry (IRMS) based on glass flask and bag sampling and real time CH4 isotope analysis by two commercially available laser spectrometers. Both laser-based analyzers were limited to methane mole fraction and δ13C-CH4 analysis, and only one of them, a cavity ring down spectrometer, was capable to deliver meaningful data for the isotopic composition. After correcting for scale offsets, the average difference between TREX–QCLAS data and bag/flask sampling–IRMS values are within the extended WMO compatibility goals of 0.2 and 5 ‰ for δ13C- and δD-CH4, respectively. This also displays the potential to improve the interlaboratory compatibility based on the analysis of a reference air sample with accurately determined isotopic composition.

Bond-Selective and Mode-Specific Dissociation of CH3D and CH2D2 on Pt(111).

Infrared laser excitation of partially deuterated methanes (CH3D and CH2D2) in a molecular beam is used to control their dissociative chemisorption on a Pt(111) single crystal and to determine the quantum state-resolved dissociation probabilities. The exclusive detection of C-H cleavage products adsorbed on the Pt(111) surface by infrared absorption reflection spectroscopy indicates strong bond selectivity for both methane isotopologues upon C-H stretch excitation. Furthermore, the dissociative chemisorption of both methane isotopologues is observed to be mode-specific. Excitation of symmetric C-H stretch modes produces a stronger reactivity increase than excitation of the antisymmetric C-H stretch modes, whereas bend overtone excitation has a weaker effect on reactivity. The observed mode specificity and bond selectivity are rationalized by the sudden vector projection model in terms of the overlap of the reactant's normal mode vectors with the reaction coordinate at the transition state.

Distinguishing and understanding thermogenic and biogenic sources of methane using multiply substituted isotopologues

Sources of methane to sedimentary environments are commonly identified and quantified using the stable isotopic compositions of methane. The methane “clumped-isotope geothermometer”, based on the measurement of multiply substituted methane isotopologues (13CH3D and 12CH2D2), shows promise in adding new constraints to the sources and formational environments of both biogenic and thermogenic methane. However, questions remain about how this geothermometer behaves in systems with mixtures of biogenic and thermogenic gases and different biogenic environments. We have applied the methane clumped-isotope thermometer to a mixed biogenic–thermogenic system (Antrim Shale, USA) and to biogenic gas from gas seeps (Santa Barbara and Santa Monica Basin, USA), a pond on the Caltech campus, and methanogens grown in pure culture. We demonstrate that clumped-isotope based temperatures add new quantitative constraints to the relative amounts of biogenic vs. thermogenic gases in the Antrim Shale indicating a larger proportion (∼50%) of thermogenic gas in the system than previously thought. Additionally, we find that the clumped-isotope temperature of biogenic methane appears related to the environmental settings in which the gas forms. In systems where methane generation rates appear to be slow (e.g., the Antrim Shale and gas seeps), microbial methane forms in or near both internal isotopic equilibrium and hydrogen-isotope equilibrium with environmental waters. In systems where methane forms rapidly, microbial methane is neither in internal isotopic equilibrium nor hydrogen-isotope equilibrium with environmental waters. A quantitative model of microbial methanogenesis that incorporates isotopes is proposed to explain these results.

Temperature dependence of the Cl atom reaction with deuterated methanes.

Kinetic isotope effect (KIE) and reaction rate coefficients, k1-k4, for the gas-phase reaction of Cl atoms with (12)CH3D (k1), (12)CH2D2 (k2), (12)CHD3 (k3), and (12)CD4 (k4) over the temperature range 223-343 K in 630 Torr of synthetic air are reported. Rate coefficients were measured using a relative rate technique with (12)CH4 as the primary reference compound. Fourier transform infrared spectroscopy was used to monitor the methane isotopologue loss. The obtained KIE values were (12)CH3D: KIE1(T) = (1.227 ± 0.004) exp((43 ± 5)/T); (12)CH2D2: KIE2(T) = (1.14 ± 0.20) exp((191 ± 60)/T); (12)CHD3: KIE3(T) = (1.73 ± 0.34) exp((229 ± 60)/T); and (12)CD4: KIE4(T) = (1.01 ± 0.3) exp((724 ± 19)/T), where KIEx(T) = kCl+(12)CH4(T)/kx(T). The quoted uncertainties are at the 2σ (95% confidence) level and represent the precision of our data. The following Arrhenius expressions and 295 K rate coefficient values (in units of cm(3) molecule(-1) s(-1)) were derived from the above KIE using a rate coefficient of 7.3 × 10(-12) exp(-1280/T) cm(3) molecule(-1) s(-1) for the reaction of Cl with (12)CH4: k1(T) = (5.95 ± 0.70) × 10(-12) exp(-(1323 ± 50)/T), k1(295 K) = (6.7 ± 0.8) × 10(-14); k2(T) = (6.4 ± 1.3) × 10(-12) exp(-(1471 ± 60)/T), k2(295 K) = (4.4 ± 0.9) × 10(-14); k3(T) = (4.2 ± 1.0) × 10(-12) exp(-(1509 ± 60)/T), k3(295 K) = (2.53 ± 0.6) × 10(-14); and k4(T) = (7.13 ± 2.3) × 10(-12) exp(-(2000 ± 120)/T), k4(295 K) = (0.81 ± 0.26) × 10(-14). The reported uncertainties in the pre-exponential factors are 2σ and include estimated systematic errors in our measurements and the uncertainty in the reference reaction rate coefficient. The results from this study are compared with previously reported room-temperature rate coefficients for each of the deuterated methanes as well as the available temperature dependent data for the Cl atom reactions with CH3D and CD4. A two-dimensional atmospheric chemistry model was used to examine the implications of the present results to the atmospheric lifetime and vertical variation in the loss of the deuterated methane isotopologues. The relative contributions of the reactions of OH, Cl, and O((1)D) to the loss of the isotopologues in the stratosphere were also examined. The results of the calculations are described and discussed.

Combined 13C–D and D–D clumping in methane: Methods and preliminary results

The stable isotopic composition of methane (e.g., δD and δ13C values) is often used as a tracer for its sources and sinks. Conventional δD and δ13C measurements represent the average isotope ratios of all ten isotopologues of methane, though they are effectively controlled by the relative abundances of the three most abundant species: 12CH4, 13CH4, and 12CH3D. The precise relative abundances of the other seven isotopologues remains largely unexplored because these species contain multiple rare isotopes and are thus rare themselves. These multiply substituted (or ‘clumped’) isotopologues each have their own distinctive chemical and physical properties, which could provide additional constraints on the geochemistry of methane. This work focuses on quantifying the abundances of two rare isotopologues, 13CH3D and 12CH2D2, of methane in order to assess their utility as a window into methane’s geochemistry. Specifically, we seek to assess whether clumped isotope distributions might be useful to quantify the temperature at which methane formed and/or equilibrated. To this end, we report the first highly precise combined measurements of the relative abundances of 13CH3D and 12CH2D2 at natural abundances (i.e., unlabeled) via the high-resolution magnetic-sector mass spectrometry of intact methane. We calibrate the use of these measurements as a geothermometer using both theory and experiment, and apply this geothermometer to representative natural samples. The method yields accurate average (i.e., bulk) isotopic ratios based on comparison with conventional techniques. We demonstrate the accuracy and precision of measurements of 13CH3D and 12CH2D2 through analyses of methane driven to high temperature (>200°C) equilibrium in the laboratory. Application of this thermometer to natural samples yields apparent temperatures consistent with their known formation environments and appears to distinguish between biogenic and thermogenic methane.

H/D methane isotopologues dissolved in magmatic fluids: Stable hydrogen isotope fractionations in the Earth's interior

A series of hydrothermal diamond-anvil cell experiments have been conducted to evaluate the role of supercritical water on the isotopic equilibrium between H/D methane isotopologues at 600-800 °C and 409-1622 MPa. Raman spectroscopy was deployed to investigate the distribution of H/D isotopic molecules formed during hydrothermal decomposition of Si5C12H36 in H2O-D2O aqueous solutions. To this end, the intensities of the fundamental vibrational C-H and C-D modes of deuteromethanes were employed to determine the thermodynamic properties of isotope exchange reactions between H/D isotopologues and to constrain the methane D/H molar ratios. By adjusting the initial volume ratios of silane/H2O-D2O, reactions in the CH4-D2O-H2O system were monitored for gaseous and supercritical-water phases. Discreet differences between the equilibrium constants, describing the relationship between the CH3D-CH2D2-CHD3-CH4 species dissolved in supercritical water or present as a homogeneous gas phase, are revealed. The bulk D/H methane composition in the liquid-system is also twice that of the D/H molar ratios recorded in the gas-bearing system. Accordingly, condensedphase isotope effects are inferred to play a key role on the evolution of H/D isotopologues, likely induced by differences in the solubility of the isotopic molecules driven by the excess energy/entropy developed during mixing of non-polar species in the H2O-D2O structure. Our experiments show that isotope fractionation effects need to account for the presence of condensed matter (e.g., melts, magmatic fluids), even at conditions at which theoretical models suggest minimal (or nonexistent) isotope exchange, but comparable to those within the Earth’s interior.

Reactions of d0 tungsten alkylidyne complexes with O2 or H2O. Formation of an oxo siloxy complex through unusual silyl migrations

(Me3SiCH2)3(Me3SiC≡)W←O=PMe3 (1), an adduct between (Me3SiCH2)3W≡CSiMe3 (2) and O=PMe3, reacts with O2 to give O=W(OSiMe3)(CH2SiMe3)3 (3) and CO2. Reaction of 2 with H2O yields 3 and the trimer [(μ-O)W(CH2SiMe3)2(=O)(THF)]3 (4). In the reaction of D2O with 2, 3-d(n) and methane isotopologues CH2D2, CHD3 and CD4 have been observed.

Design and Construction of Absorption Cells for Precision Radial Velocities in the K Band Using Methane Isotopologues

ABSTRACTWe present a method to optimize absorption cells for precise wavelength calibration in the near-infrared. We apply it to design and optimize methane isotopologue cells for precision radial velocity measurements in the K band. We also describe the construction and installation of two such cells for the CSHELL spectrograph at NASA’s IRTF. We have obtained their high-resolution laboratory spectra, which we can then use in precision radial velocity measurements and which can also have other applications. In terms of obtainable RV precision, methane should outperform other proposed cells, such as the ammonia cell () recently demonstrated on CRIRES/VLT. The laboratory spectra of the ammonia and methane cells show strong absorption features in the H band that could also be exploited for precision Doppler measurements. We present spectra and preliminary radial velocity measurements obtained during our first-light run. These initial results show that a precision down to can be obtained using a wavelength interval of only 5 nm in the K band and S/N ∼ 150. This supports the prediction that a precision down to a few meters per second can be achieved on late-M dwarfs using the new generation of NIR spectrographs, thus enabling the detection of terrestrial planets in their habitable zones. Doppler measurements in the NIR can also be used to mitigate the radial velocity jitter due to stellar activity, enabling more efficient surveys on young active stars.

Mass fluxes and isofluxes of methane (CH4) at a New Hampshire fen measured by a continuous wave quantum cascade laser spectrometer

We have developed a mid‐infrared continuous‐wave quantum cascade laser direct‐absorption spectrometer (QCLS) capable of high frequency (≥1 Hz) measurements of 12CH4 and 13CH4 isotopologues of methane (CH4) with in situ 1‐s RMS precision of 1.5 ‰ and Allan‐minimum precision of 0.2 ‰. We deployed this QCLS in a well‐studied New Hampshire fen to compare measurements of CH4 isoflux by eddy covariance (EC) to Keeling regressions of data from automated flux chamber sampling. Mean CH4 fluxes of 6.5 ± 0.7 mg CH4 m−2 hr−1 over two days of EC sampling in July, 2009 were indistinguishable from mean autochamber CH4 fluxes (6.6 ± 0.8 mgCH4 m−2 hr−1) over the same period. Mean composition of emitted CH4 calculated using EC isoflux methods was −71 ± 8 ‰ (95% C.I.) while Keeling regressions of 332 chamber closing events over 8 days yielded a corresponding value of −64.5 ± 0.8 ‰. Ebullitive fluxes, representing ∼10% of total CH4 fluxes at this site, were on average 1.2 ‰ enriched in 13C compared to diffusive fluxes. CH4 isoflux time series have the potential to improve process‐based understanding of methanogenesis, fully characterize source isotopic distributions, and serve as additional constraints for both regional and global CH4 modeling analysis.

Vibrationally bond-selected chemisorption of methane isotopologues on Pt(111) studied by reflection absorption infrared spectroscopy

Reflection absorption infrared spectroscopy (RAIRS) was used to probe for vibrational bond-selectivity in the dissociative chemisorption of three partially deuterated methane isotopologues on a Pt(111) surface. While a combination of incident translational energy and thermal vibrational excitation produces a nearly statistical distribution of C-H and C-D bond cleavage products, we observe that laser excitation of an infrared active C-H stretch normal mode leads to highly selective dissociation of a C-H bond for CHD3, CH2D2, and CH3D. Our results show that vibrational energy redistribution between C-H and C-D stretch modes due to methane/surface interactions is negligible during the sub-picosecond collision time which indicates that vibrational bond-selectivity may be the rule rather than the exception in heterogeneous reactions of small polyatomic molecules.

The absorption spectrum of methane at 80 and 294 K in the icosad (6717–7589 cm −1): Improved empirical line lists, isotopologue identification and temperature dependence

Using a cryogenic cell and a series of Distributed Feed Back (DFB) diode lasers, new high resolution spectra of methane have been recorded at 80 K and room temperature by differential absorption spectroscopy (DAS) between 6717 and 7589 cm −1 (1.49–1.32 μm). The investigated spectral region corresponds to the very congested icosad, which is not tractable by theory. Empirical lists of 19,940 and 24,001 lines were constructed from the 80 K and room temperature spectrum, respectively. The room temperature list adds about 8500 features to the empirical list of 15,375 lines at 296 K adopted in the HITRAN database from the original work of L. Brown (Brown, L. Empirical line parameters of methane from 1.1 to 2.1 μm. JQSRT 2005;96:251–70). A number of relatively strong CH 4 lines located near strong water lines were found missing in the HITRAN line list. The improved sensitivity allowed adding more than 7000 lines to our previous list of about 12,000 transitions at 80 K (Campargue A, Wang L, Kassi S, Mašát M, Votava O. Temperature dependence of the absorption spectrum of CH 4 by high resolution spectroscopy at 81 K: (II) The Icosad region (1.49–1.30 μm). JQSRT 2010;111:1141–51). In order to facilitate identification of the transitions of the different methane isotopologues present in “natural” isotopic abundance, spectra of highly enriched CH 3D and 13CH 4 samples were recorded with the same experimental setup, both at room temperature and at 80 K. From the variation of the line strengths between 80 K and 294 K, the low energy values of about 12,000 transitions were determined. They allow accounting for the temperature dependence of 84 and 93% of the methane absorbance in the region, at room temperature and 80 K, respectively. As a result, we provide as supplementary material two complete line lists at 80 K and 294 K, including CH 3D and 13CH 4 identification and lower state energy values.

Measurement of the isotopic signatures of water on Mars; Implications for studying methane

The recent discovery of methane on Mars has led to much discussion concerning its origin. On Earth, the isotopic signatures of methane vary with the nature of its production. Specifically, the ratios among 12CH 4, 13CH 4, and 12CH 3D differ for biotic and abiotic origins. On Mars, measuring these ratios would provide insights into the origins of methane and measurements of water isotopologues co-released with methane would assist in testing their chemical relationship. Since 1997, we have been measuring HDO and H 2O in Mars’ atmosphere and comparing their ratio to that in Earth’s oceans. We recently incorporated a line-by-line radiative transfer model (LBLRTM) into our analysis. Here, we present a map for [HDO]/[H 2O] along the central meridian (154°W) for L s=50°. From these results, we constructed models to determine the observational conditions needed to quantify the isotopic ratios of methane in Mars’ atmosphere. Current ground-based instruments lack the spectral resolution and sensitivity needed to make these measurements. Measurements of the isotopologues of methane will likely require in situ sampling.

Cryogenic absorption cells operating inside a Bruker IFS-125HR: First results for 13CH 4 at 7 μm

New absorption cells designed specifically to achieve stable temperatures down to 66 K inside the sample compartment of an evacuated Bruker IFS-125HR Fourier transform spectrometer (FTS) were developed at Connecticut College and tested at the Jet Propulsion Laboratory (JPL). The temperature stabilized cryogenic cells with path lengths of 24.29 and 20.38 cm were constructed of oxygen free high conductivity (OFHC) copper and fitted with wedged ZnSe windows using vacuum tight indium seals. In operation, the temperature-controlled cooling by a closed-cycle helium refrigerator achieved stability of ±0.01 K. The unwanted absorption features arising from cryodeposits on the cell windows at low temperatures were eliminated by building an internal vacuum shroud box around the cell which significantly minimized the growth of cryodeposits. The effects of vibrations from the closed-cycle helium refrigerator on the FTS spectra were characterized. Using this set up, several high-resolution spectra of methane isotopologues broadened with nitrogen were recorded in the 1200–1800 cm −1 spectral region at various sample temperatures between 79.5 and 296 K. Such data are needed to characterize the temperature dependence of spectral line shapes at low temperatures for remote sensing of outer planets and their moons. Initial analysis of a limited number of spectra in the region of the R(2) manifold of the ν 4 fundamental band of 13CH 4 indicated that an empirical power law used for the temperature dependence of the N 2-broadened line widths would fail to fit the observed data in the entire temperature range from 80 to 296 K; instead, it follows a temperature-dependence similar to that reported by Mondelain et al. [17,18]. The initial test was very successful proving that a high precision Fourier transform spectrometer with a completely evacuated optical path can be configured for spectroscopic studies at low temperatures relevant to the planetary atmospheres.