The Global Methane Cycle: Isotopes and Mixing Ratios,Sources and Sinks

Abstract

A review of the global cycle of methane is presented with emphasis on its isotopic composition. The history of methane mixing ratios, reconstructed from measurements of air trapped in ice-cores is described. The methane record now extends back to 420 kyr ago in the case of the Vostok ice cores from Antarctica. The trends in mixing ratios and in δ¹³C values are reported for the two Hemispheres. The increase of the atmospheric methane concentration over the past 200 years, and by 1% per year since 1978, reaching 1.7 ppmv in 1990 is underlined.

The various methane sources are presented. Indeed the authors describe the methane emissions by bacterial activity under anaerobic conditions in wet environments (wetlands, bogs, tundra, rice paddies), in ruminant stomachs and termite guts, and that originating from fossil carbon sources, such as biomass burning, coal mining, industrial losses, automobile exhaust, sea floor vent, and volcanic emissions. Furthermore, the main sinks of methane in the troposphere, soils or waters via oxidation are also reported, and the corresponding kinetic isotope effects.     

Tropospheric emission spectrometer (TES) and atmospheric chemistry experiment (ACE) measurements of tropospheric chemistry in tropical southeast Asia during a moderate El Niño in 2006

High spectral resolution Fourier transform spectrometer (FTS) measurements of tropospheric carbon monoxide (CO) distributions show mixing ratios over Indonesia during October 2006 of ∼200 ppbv (10⁻⁹ per unit volume) in the middle troposphere. The elevated emissions were caused by intense and widespread Indonesian peat and forest fire emissions elevated compared to other years by the impact of a moderate El Niño/Soutern Oscillation (ENSO) event, which delayed that year's monsoon season and produced very dry conditions. Moderate resolution imaging spectrometer (MODIS) fire counts, atmospheric chemistry experiment (ACE) measurements of elevated mixing ratios of fire emission products and near infrared extinction, and back trajectory calculations for a sample measurement location near the time of maximum emissions provide additional evidence that the elevated 2006 emissions resulted primarily from the Indonesia fires. Lower CO mixing ratios measured by ACE and fewer MODIS fire counts in Indonesia during October 2005 indicate lower emissions than during 2006. Coincident profiles from the ACE agree within the uncertainties with those from the tropospheric emission spectrometer (TES) for pressure ranges and time periods with good TES sensitivity after accounting for its lower vertical sensitivity compared with the ACE FTS.     

EUV branching ratios for ionized nitrogen and oxygen emissions

Branching ratios of singly ionized atomic nitrogen and oxygen EUV emissions that terminate on the metastable states of the respective ions are presented. The four NII ratios and the 482/515 Å ratio in OII reported represent the first measured values. Details of the wavelength calibration procedures adopted and a brief discussion of two modeling implications of the measured ratios are included.     

An investigation of flame zones and burning velocities of laminar unconfined methane-oxygen premixed flames

Numerical and experimental investigations of unconfined methane-oxygen laminar premixed flames are presented. In a lab-scale burner, premixed flame experiments have been conducted using pure methane and pure oxygen mixtures having different equivalence ratios. Digital photographs of the flames have been captured and the radial temperature profiles at different axial locations have been measured using a thermocouple. Numerical simulations have been carried out with a C2 chemical mechanism having 25 species and 121 reactions and with an optically thin radiation sub-model. The numerical results are validated against the experimental and numerical results for methane-air premixed flames reported in literature. Further, the numerical results are validated against the results from the present methane-oxygen flame experiments. Visible regions in digital flame photographs have been compared with OH isopleths predicted by the numerical model. Parametric studies have been carried out for a range of equivalence ratios, varying from 0.24 to 1.55. The contours of OH, temperature and mass fractions of product species such as CO, CO₂ and H₂O, are presented and discussed for various cases. By using the net methane consumption rate, an estimate of the laminar flame speed has been obtained as a function of equivalence ratio.     

High-resolution infrared polarization spectroscopy and?degenerate four wave mixing spectroscopy of methane

High-resolution infrared polarization spectroscopy (IR-PS) and degenerate four wave mixing (IR-DFWM) spectroscopy of methane using a diode-seeded modeless laser (DSML) system are reported. Mid-infrared radiation around 3.3 μm is generated by difference frequency mixing of the single-mode output of the DSML around 0.634 μm with the frequency-doubled output of a single-mode Nd:YAG pump laser at 0.532 μm. Polarization spectroscopy signals in the forward geometry were generated in methane at around 5 Torr pressure. IR-PS spectra were recorded with a typical signal-to-noise ratio of 150:1 with methane pressures of at least 1 Torr. The line shape of the IR-PS signals was analysed to measure pressure broadening induced by nitrogen buffer gas yielding a value of 6.3±1.5 MHz Torr⁻¹. IR-DFWM spectra of methane were generated in the counter-propagating pump geometry yielding Doppler-free signals with signal-to-noise ratios of typically 650:1. Signals were obtained at methane pressures down to less than 10 mTorr. A comparison of IR-PS and IR-DFWM is made indicating that IR-DFWM has some advantages over IR-PS in this spectral region in terms of sensitivity, signal-to-noise ratio and ease of use. The results illustrate the utility of the DSML for high-resolution nonlinear spectroscopy in the mid infrared.     

Raman intensities of methanes from electrooptical parameters

This paper deals with the calculation of the intensities of Raman active fundamental vibrations of methane and its isotopical derivatives by the electrooptical theory of valence and with the “least squares” refinement of a set of electrooptical parameters from the experimental data. First some general considerations on the electrooptical theory of valence and on the computational method are presented. Then we give the expressions of the Raman intensities and depolarization ratios as functions of the electrooptical parameters and discuss some features of the “least squares” refinement technique. The results of our calculations on methane and deuteroderivatives are then reported. Particular attention has been given to the study of the type and combinations of parameters affecting each intensity.     

Near-field flow and flame dynamics of LOX/methane shear-coaxial injector under supercritical conditions

The mixing and combustion of liquid oxygen (LOX) and gaseous methane of a shear coaxial injector operating under supercritical pressures have been numerically investigated. The near-field flow and flame dynamics are examined in depth, with emphasis placed on the flame-stabilization mechanisms. The model accommodates the full conservation laws and real-fluid thermodynamics and transport phenomena over the entire range of fluid states of concern. The injector flowfield is characterized by the evolution of the three mixing layers originating from the trailing edges of the two concentric tubes of the injector. As a consequence of the strong inertia of the oxygen stream and light density of methane, a diffusion-dominated flame is anchored in the wake of the LOX post and propagates downstream along the boundary of the oxygen stream. The large-scale vortices shedding from the outer rim of the LOX postengulf methane into the wake recirculation region to react with gasified oxygen. The frequencies of vortex shedding match closely those of the flow over a rear-facing step, mainly due to the large density disparity between LOX and gaseous methane. The effects of the momentum-flux ratio of the two streams are also examined. A higher-momentum methane stream enhances mixing and shortens the potential cores of both the LOX and methane jets.     

Chemical and Isotope Investigations in Dissolved Gases of a Meromictic Residual Lake

Abstract

Lake Hufeisen near Halle/Saale has been formed in an old mining pit. Its deepest part is trench shaped and filled with water of sodium chloride content. Due to the density difference strong mixing processes in this part of the water body are prevented all over the year (meromictic lake). Therefore anoxic conditions have been established and the organic matter of the lake sediments is converted to carbon dioxide and methane. Over a period of more than one year gas samples were collected from different water depths. The investigations of the chemical composition (mainly nitrogen, carbon dioxide and methane) and the carbon isotope ratios show different relationships for individual species. The results are discussed with respect to the behaviour of the gases in the water column and to the stability of the density stratification in the saline bottom water.     

Detection of methane in air using diode-laser pumped difference-frequency generation near 3.2 μm

Spectroscopic detection of the methane in natural air using an 800 nm diode laser and a diode-pumped 1064 nm Nd:YAG laser to produce tunable light near 3.2 µm is reported. The lasers were pump sources for ring-cavity-enhanced tunable difference-frequency mixing in AgGaS₂. IR frequency tuning between 3076 and 3183 cm^–1 was performed by crystal rotation and tuning of the extended-cavity diode laser. Feedback stabilization of the IR power reduced intensity noise below the detector noise level. Direct absorption and wavelength-modulation (2f) spectroscopy of the methane in natural air at 10.7 kPa (80 torr) were performed in a 1 m single-pass cell with 1 µW probe power. Methane has also been detected using a 3.2 µm confocal build-up cavity in conjunction with an intracavity absorption cell. The best methane detection limit observed was 12 ppb m (Hz.)^–1/2.     

Spectroscopic detection of methane by use of guided-wave diode-pumped difference-frequency generation

We report spectroscopic gas detection by the use of mid-infrared difference-frequency mixing of two diode lasers in a channel waveguide. The waveguide was fabricated by annealed proton exchange in periodically poled lithium niobate. We generated 3.43-3.73-mum tunable radiation in a single waveguide at room temperature by mixing diode lasers near 780 and 1010 nm. High-resolution spectra of methane were obtained in 2 s with electronically controlled frequency scans of 45 GHz. The use of highly efficient waveguide frequency converters pumped by fiber-coupled diode lasers will permit construction of compact, solid-state, room-temperature mid-infrared sources for use in trace-gas detection.     

A novel combustion system for liquid fuel evaporating and burning

To utilize sustainable biofuel, the current study proposes a novel combustion technique that directly burns liquid ethanol without a spray system. Two swirling air flows are induced by tangentially injected the gas from two concentric tubes at different stages. The liquid ethanol is fed by a liquid tank at the center. At the beginning methane flame assists in preheating the system to vaporize liquid ethanol and ignite the vapor. Thereafter methane is switched off, and liquid ethanol can be continuously vaporized through self-burning released heat. The heat and mass transfer processes are examined to illustrate such self-sustained burning–heating–evaporating system. The ethanol flow rate is gradually increased to provide different heat output. The flame structures, temperature distributions and pollutant emissions are carefully examined. The results show that the ethanol can be steadily burned to provide heat output between 0.7 and 2.5?kW. Generally a blue flame is obtained, and the NO_x and CO concentrations are ultralow. By increasing ethanol flow rate to exceed 8?mL/min, an unsteady, sooting flame is observed owing to incomplete evaporation and poor mixing. A parametric study is conducted to evaluate the influences of liquid tank position, flow rate and tip structure on the combustion characteristics. Additionally, an optimal operation condition is proposed. The current study provides a promising method to burn low-boiling liquid fuel in a clean, efficient and compact way.     

A comparative study on determination of uranium and thorium in their mixed oxides by EDXRF using tube and radioisotope X‐ray sources

Studies on the matrix effects of uranium and thorium on the determinations of each other in their mixed oxides using energy dispersive X‐ray fluorescence (EDXRF) spectrometry with tube and radioisotope excitations of U Lα and Th Lα are reported. An internal standard method for the determination of uranium and thorium in these mixed oxides is found suitable. Comparison of the analytical results of EDXRF determinations of uranium and thorium using tube and radioisotope excitation sources has been made. The analytical methodology involves preparation of mixed oxide calibration/sample mixtures of uranium and thorium oxides, mixing of internal standard yttrium in these mixtures, pelletizing the mixtures after thorough mixing and grinding using boric acid binder and measuring EDXRF spectra of the specimens thus prepared using Rh X‐ray tube as well as ¹⁰⁹Cd radioisotope source. The samples were analyzed for uranium and thorium on the basis of the calibration plots obtained by plotting the intensity ratios of the analyte and internal standard characteristic X‐ray lines and their corresponding amount ratios. An average precision of 1.2% (1 s RSD) was observed for the determination of U and Th and the results deviated from the corresponding expected values by 3% on average. Due to the refractory nature of thorium oxide, comparatively more grinding time was required for thorium determinations. Copyright © 2011 John Wiley & Sons, Ltd.     

Estimating groundwater mixing and origin in an overexploited aquifer in Guanajuato, Mexico, using stable isotopes (strontium-87, carbon-13, deuterium and oxygen-18)

Stable Isotopes (strontium-87, deuterium and oxygen-18, carbon-13) have been used to reveal different sources of groundwater and mixing processes in the aquifer of the Silao-Romita Valley in the state of Guanajuato, Mexico. Calcite dissolution appeared to be the main process of strontium release leading to relatively equal (87)Sr/(86)Sr ratios of 0.7042-0.7062 throughout the study area which could be confirmed by samples of carbonate rocks having similar Sr ratios (0.7041-0.7073). delta(13)C values (-11.91- -6.87 per thousand VPDB) of groundwaters confirmed the solution of carbonates but indicated furthermore influences of soil-CO(2). Deuterium and (18)O contents showed a relatively narrow range of-80.1- -70.0 per thousand VSMOW and -10.2- -8.8 per thousand, VSMOW, respectively but are affected by evaporation and mixing processes. The use of delta(13)C together with (87)Sr/(86)Sr revealed three possible sources: (i) carbonate-controlled waters showing generally higher Sr-concentrations, (ii) fissure waters with low-strontium contents and (iii) infiltrating water which is characterized by low delta(13)C and (87)Sr/(86)Sr ratios. The third component is affected by evaporation processes taking place before and during infiltration which might be increased by extraction and reinfiltration (irrigation return flow).     

Modeling of helicopter-borne tunable TEA CO2 DIAL system employment for detection of methane and ammonia leakages

The characteristics of a helicopter-borne lidar based on tunable TEA CO₂ laser and its third harmonic designed for remote detection of methane and ammonia leakages from pipelines are analyzed numerically. The spectral range near 3 μm was shown to be most promising for remote sensing of methane emissions. Parameters of radiation of the tunable pulse-periodic mini-TEA CO₂ laser and generators of harmonics to be utilized in the helicopter-borne differential absorption lidar are estimated. Emissions of different gas intensities are analyzed for possible detectability at a distance of up to 1 km. The use of the third harmonic of the TEA CO₂ laser allows methane emissions from a pipeline to be detected and measured with mean measurement error from 10% to 15% for methane concentrations varying from the background level to the explosion-hazardous one. The optimal pair and possibilities of the ammonia remote sensing on the base of the first harmonic of TEA CO₂ laser were determined as well.     

Nuclear structure studies of187Ir via on-line nuclear orientation

A more complete level scheme is presented here for the decay of¹⁸⁷Pt, incorporating many new lines and levels up to 2.4 MeV. Emphasis has been placed on the extraction of multipole mixing ratios from nuclear orientation data. Analysis of that data, however, required a more complete understanding of the level structure (including, in particular, branching ratios, conversion coefficients, and level feedings), prompting the collection of new spectroscopy data. The low-lying, positive-parity levels are described in terms of (odd-proton) single-particle Nilsson states coupled to a triaxial core. Multipole mixing ratios are compared to those calculated in the Particle-Plus-Triaxial-Rotor Model.     

Axially phase-matched parametric four- and six-wave mixing in potassium vapor

Systematic experimental observations of axially phase-matched parametric four- and sixwave mixing processes have been made in potassium vapor pumped on or near the 4S–6S two-photon resonance. An IR up-conversion with a beta barium borate crystal was used for the detection of IR emissions. All the predicted processes have been observed. It is found that the excitation spectra of the emissions for those processes observed in this work are quite different from the excitation spectra of similar processes in sodium vapor. A dye-dependence of some emissions generated by the axially phase-matched parametric six-wave mixing processes has been found by using different dyes in the dye laser. The reason for the dye-dependence is discussed.     

Flame acceleration and transition to detonation: Effects of a composition gradient in a mixture of methane and air

The effects of a composition gradient on flame acceleration and transition to detonation in a mixture of methane and air were studied by numerically solving the unsteady, fully compressible, reactive Navier–Stokes equations. The specific problem addressed here is for ignition in a two-dimensional, obstructed channel where there is a spatial gradient of equivalence ratios perpendicular to the propagation direction of the reaction wave. The solution method uses a calibrated, optimized chemical-diffusive model that reproduces correct flame and detonation properties for methane–air mixtures over a range of equivalence ratios. Comparisons were made to a stoichiometric, homogeneous mixture in order to focus on the worst-case scenario for safety concerns. The results showed that the flame speed is smaller and the average total heat release are lower, but the maximum flame surface area is larger in the inhomogeneous mixture. This is because there is more unburned material between obstacles but less energy released from this increased flame surface area in the fuel-lean region, leading to the reduction of the total heat release. The transition to detonation is delayed in the inhomogeneous mixture, because the hot spot forms in the fuel-lean region and the strength of the Mach stem that hits the obstacle is weaker. The detonation front tends to decouple into a shock and a flame earlier in the inhomogeneous mixture, due to the incomplete mixing throughout the entire domain during the detonation propagation process.     

Multiple internal reflections in the cochlea and their effect on DPOAE fine structure

In recent years, evidence has accumulated in support of a two-source model of distortion product otoacoustic emissions (DPOAEs). According to such models DPOAEs recorded in the ear canal are associated with two separate sources of cochlear origin. It is the interference between the contributions from the two sources that gives rise to the DPOAE fine structure (a pseudoperiodic change in DPOAE level or group delay with frequency). Multiple internal reflections between the base of the cochlea (oval window) and the DP tonotopic place can add additional significant components for certain stimulus conditions and thus modify the DPOAE fine structure. DPOAEs, at frequency increments between 4 and 8 Hz, were recorded at fixed f2/f1 ratios of 1.053, 1.065, 1.08, 1.11, 1.14, 1.18, 1.22, 1.26, 1.30, 1.32, 1.34, and 1.36 from four subjects. The resulting patterns of DPOAE amplitude and group delay (the negative of the slope of phase) revealed several previously unreported patterns in addition to the commonly reported log sine variation with frequency. These observed "exotic" patterns are predicted in computational simulations when multiple internal reflections are included. An inverse FFT algorithm was used to convert DPOAE data from the frequency to the "time" domain. Comparison of data in the time and frequency domains confirmed the occurrence of these "exotic" patterns in conjunction with the presence of multiple internal reflections. Multiple internal reflections were observed more commonly for high primary ratios (f2/f1 > or = 1.3). These results indicate that a full interpretation of the DPOAE level and phase (group delay) must include not only the two generation sources, but also multiple internal reflections.     

An efficient analytical approach for calculating line mixing in atmospheric remote sensing applications

Collisional coupling between energy states in a molecule undergoing an optical transition can alter the line shape associated with the transition, an effect known as line mixing. Accounting for this effect in the analysis of remote sensing measurements of Earth's atmosphere by the Atmospheric Chemistry Experiment (ACE) yields reduced residuals, which leads to improved performance in the volume mixing ratio retrievals for some molecules. Analytical expressions are presented for the imaginary components of the polynomial ratios from the Humlicek algorithm, which provides approximate solutions to the complex probability function. These imaginary components are employed in the calculation of line mixing using the Rosenkranz first order approximation. Examples of line mixing in ACE measurements are presented, including a set of CH₄ lines that exhibit both line mixing and speed dependence. An efficient, analytical approach is proposed for calculating line shapes with a combination of line mixing and speed dependence. FORTRAN routines for calculating line mixing effects are provided as a supplement to the paper.