Abundance Of CH Research Articles

Chemical Evolution of Turbulent Multiphase Molecular Clouds

AbstractMolecular clouds are essentially made up of atomic and molecular hydrogen, which in spite of being the simplest molecule in the ISM plays a key role in the chemical evolution of molecular clouds. Since its formation time is very long, the H2 molecules can be transported by the turbulent motions within the cloud toward low density and warm regions, where its enhanced abundance can boost the abundances of molecules with high endothermicities.We present high resolution simulations where we include the evolution of the molecular gas under the effect of the dynamics, and we analyze its impact on the abundance of CH+.

CH AS A MOLECULAR GAS TRACER AND C-SHOCK TRACER ACROSS A MOLECULAR CLOUD BOUNDARY IN TAURUS

ABSTRACT We present new observations of all three ground-state transitions of the methylidyne (CH) radical and all four ground-state transitions of the hydroxyl (OH) radical toward a sharp boundary region of the Taurus molecular cloud. These data were analyzed in conjunction with existing CO and dust images. The derived CH abundance is consistent with previous observations of translucent clouds (0.8 ≤ A v ≤ 2.1 mag). The X(CH)-factor is nearly a constant (1.0 ± 0.06) × 1022 cm−2 K−1 km−1 s in this extinction range, with less dispersion than that of the more widely used molecular tracers CO and OH. CH turns out be a better tracer of total column density in such an intermediate extinction range than CO or OH. Compared with previous observations, CH is overabundant below 1 mag extinction. Such an overabundance of CH is consistent with the presence of a C-shock. CH has two kinematic components, one of which shifts from 5.3 to 6 km s−1, while the other stays at 6.8 km s−1 when moving from outside toward inside of the cloud. These velocity behaviors exactly match previous OH observation. The shifting of the two kinematic components indicates colliding streams or gas flow at the boundary region, which could be the cause of the C-shock.

Greenhouse trace gases in deadwood

Deadwood, long recognized as playing an important role in storing carbon and releasing it as CO2 in forest ecosystems, is more recently drawing attention for its potential role in the cycling of other greenhouse trace gases. Across three Northeastern and Central US forests, mean methane (CH4) concentrations in deadwood were 23 times atmospheric levels (43.0 μL L−1 ± 12.3; mean ± SE), indicating a lower bound, mean radial wood surface area flux of ~6 × 10−4 μmol CH4 m−2 s−1. Site, decay class, log diameter, and species were all highly significant predictors of CH4 abundance in deadwood, and diameter and decay class interacted as important controls limiting CH4 concentrations in the smallest and most decayed logs. Nitrous oxide (N2O) concentrations were negatively correlated with CH4 (r2 = −0.20, p < 0.001) and on average ~25 % lower than ambient (276.9 nL L−1 ± 2.9; mean ± SE), indicating net consumption of nitrous oxide. Oxygen (O2) concentrations were uniformly near anaerobic (355.8 μL L−1 ±1.2; mean ± SE), and CO2 was elevated from atmospheric (9336.9 μL L−1 ± 600.6; mean ± SE). Most notably, our observations that CH4 concentrations were highest in the least decayed wood, may suggest that methanogenesis is not fuelled by structural wood decomposition but rather by consumption of more labile nonstructural carbohydrates.

THE IMPACT OF NON-UNIFORM THERMAL STRUCTURE ON THE INTERPRETATION OF EXOPLANET EMISSION SPECTRA

ABSTRACT The determination of atmospheric structure and molecular abundances of planetary atmospheres via spectroscopy involves direct comparisons between models and data. While varying in sophistication, most model spectra comparisons fundamentally assume one-dimensional (1D) model physics. However, knowledge from general circulation models and of solar system planets suggests that planetary atmospheres are inherently three-dimensional in their structure and composition. We explore the potential biases resulting from standard “1D” assumptions within a Bayesian atmospheric retrieval framework. Specifically, we show how the assumption of a single 1D thermal profile can bias our interpretation of the thermal emission spectrum of a hot Jupiter atmosphere that is composed of two thermal profiles. We retrieve spectra of unresolved model planets as observed with a combination of the Hubble Space Telescope Wide Field Camera 3 (WFC3)+Spitzer Infrared Array Camera (IRAC) as well as the James Webb Space Telescope (JWST) under varying differences in the two thermal profiles. For WFC3+IRAC, there is a significantly biased estimate of CH4 abundance using a 1D model when the contrast is 80%. For JWST, two thermal profiles are required to adequately interpret the data and estimate the abundances when contrast is greater than 40%. We also apply this preliminary concept to the recent WFC3+IRAC phase curve data of the hot Jupiter WASP-43b. We see similar behavior as present in our simulated data: while the abundance determination is robust, CH4 is artificially well-constrained to incorrect values under the 1D assumption. Our work demonstrates the need to evaluate model assumptions in order to extract meaningful constraints from atmospheric spectra and motivates exploration of optimal observational setups.

Physical inversion of the full IASI spectra: Assessment of atmospheric parameters retrievals, consistency of spectroscopy and forward modelling

Spectra observed by the Infrared Atmospheric Sounder Interferometer (IASI) have been used to assess both retrievals and the spectral quality and consistency of current forward models and spectroscopic databases for atmospheric gas line and continuum absorption. The analysis has been performed with thousands of observed spectra over sea surface in the Pacific Ocean close to the Mauna Loa (Hawaii) validation station. A simultaneous retrieval for surface temperature, atmospheric temperature, H2O, HDO, O3 profiles and gas average column abundance of CO2, CO, CH4, SO2, N2O, HNO3, NH3, OCS and CF4 has been performed and compared to in situ observations. The retrieval system considers the full IASI spectrum (all 8461 spectral channels on the range 645–2760cm−1). We have found that the average column amount of atmospheric greenhouse gases can be retrieved with a precision better than 1% in most cases. The analysis of spectral residuals shows that, after inversion, they are generally reduced to within the IASI radiometric noise. However, larger residuals still appear for many of the most abundant gases, namely H2O, CH4 and CO2. The H2O ν2 spectral region is in general warmer (higher radiance) than observations. The CO2ν2 and N2O/CO2ν3 spectral regions now show a consistent behavior for channels, which are probing the troposphere. Updates in CH4 spectroscopy do not seem to improve the residuals. The effect of isotopic fractionation of HDO is evident in the 2500–2760cm−1 region and in the atmospheric window around 1200cm−1.

THE WATER ABUNDANCE OF THE DIRECTLY IMAGED SUBSTELLAR COMPANION κ AND b RETRIEVED FROM A NEAR INFRARED SPECTRUM

ABSTRACT Spectral retrieval has proven to be a powerful tool for constraining the physical properties and atmospheric compositions of extrasolar planet atmospheres based on observed spectra, primarily for transiting objects but also for directly imaged planets and brown dwarfs. Despite its strengths, this approach has been applied to only about a dozen targets. Determining the abundances of the main carbon- and oxygen-bearing compounds in a planetary atmosphere can lead to the C/O ratio of the object, which is crucial for understanding its formation and migration history. We present a retrieval analysis of the published near-infrared spectrum of b, a directly imaged substellar companion to a young B9 star. We fit the emission spectrum model utilizing a Markov Chain Monte Carlo algorithm. We estimate the abundance of water vapor, and its uncertainty, in the atmosphere of the object. In addition, we place an upper limit on the abundance of CH4. We qualitatively compare our results with studies that have applied model retrieval on multiband photometry and emission spectroscopy of hot Jupiters (extrasolar giant planets with orbital periods of several days) and the directly imaged giant planet HR 8799b.

Methane and carbon dioxide total column retrievals from cloudy GOSAT soundings over the oceans

AbstractWe present a novel physics‐based retrieval method to infer total column mixing ratios of methane (XCH4) and carbon dioxide (XCO2) from space‐borne short‐wavelength infrared (SWIR) Earth radiance observations over the cloud‐covered ocean. In nadir observing geometry in the SWIR spectral range, backscattering at the ocean surface is negligible. Hence, space‐borne radiance measurements of ocean scenes generally do not provide sufficient level to retrieve XCO2 and XCH4. Our approach specifically targets cloudy GOSAT ocean soundings to provide sufficient radiance signal in nadir soundings in ocean areas. Currently, exploiting space‐borne SWIR soundings over oceans relies on soundings in Sun glint geometry, observing the specular solar reflection at the ocean surface. The glint observation mode requires cloud‐free conditions and a suitable observation geometry, severely limiting their number and geographical coverage. The proposed method is based on the existing RemoTeC algorithm that is extensively used to retrieve CH4 and CO2 columns from GOSAT SWIR measurements over land. For ocean pixels, we describe light scattering by clouds and aerosols by a single‐layer water cloud with Gaussian height distribution. We infer the height and the geometrical thickness of the cloud layer jointly with the droplet size and the number density and the column abundances of CO2, CH4, and H2O. The CO2 and CH4 column product is validated with ground‐based total column measurements performed at eight stations from the TCCON network that are geographically close to an ocean coastline. For the TCCON site with the most robust statistics (Lauder, New Zealand), we find a retrieval bias of 0.36% for XCH4 combined with a standard deviation of retrieval errors of 1.12%. For XCO2, the bias is 0.51% combined with a standard deviation of 1.03%. Averaged over all TCCON sites, our retrievals are biased −0.01% for XCO2 and −0.32% for XCH4. The standard deviation of station biases amounts to 0.45% for XCO2 and 0.35% for XCH4.

A Data Mining Approach to Predict In Situ Detoxification Potential of Chlorinated Ethenes.

Despite advances in physicochemical remediation technologies, in situ bioremediation treatment based on Dehalococcoides mccartyi (Dhc) reductive dechlorination activity remains a cornerstone approach to remedy sites impacted with chlorinated ethenes. Selecting the best remedial strategy is challenging due to uncertainties and complexity associated with biological and geochemical factors influencing Dhc activity. Guidelines based on measurable biogeochemical parameters have been proposed, but contemporary efforts fall short of meaningfully integrating the available information. Extensive groundwater monitoring data sets have been collected for decades, but have not been systematically analyzed and used for developing tools to guide decision-making. In the present study, geochemical and microbial data sets collected from 35 wells at five contaminated sites were used to demonstrate that a data mining prediction model using the classification and regression tree (CART) algorithm can provide improved predictive understanding of a site's reductive dechlorination potential. The CART model successfully predicted the 3-month-ahead reductive dechlorination potential with 75.8% and 69.5% true positive rate (i.e., sensitivity) for the training set and the test set, respectively. The machine learning algorithm ranked parameters by relative importance for assessing in situ reductive dechlorination potential. The abundance of Dhc 16S rRNA genes, CH4, Fe(2+), NO3(-), NO2(-), and SO4(2-) concentrations, total organic carbon (TOC) amounts, and oxidation-reduction potential (ORP) displayed significant correlations (p < 0.01) with dechlorination potential, with NO3(-), NO2(-), and Fe(2+) concentrations exhibiting precedence over other parameters. Contrary to prior efforts, the power of data mining approaches lies in the ability to discern synergetic effects between multiple parameters that affect reductive dechlorination activity. Overall, these findings demonstrate that data mining techniques (e.g., machine learning algorithms) effectively utilize groundwater monitoring data to derive predictive understanding of contaminant degradation, and thus have great potential for improving decision-making tools. A major need for realizing the predictive capabilities of data mining approaches is a curated, open-access, up-to-date and comprehensive collection of biogeochemical groundwater monitoring data.

Effects of fertilization on microbial abundance and emissions of greenhouse gases (CH4 and N2O) in rice paddy fields

This study is to explore effects of nitrogen application and straw incorporation on abundance of relevant microbes and CH 4 and N2O fluxes in a midseason aerated rice paddy field. Fluxes of CH 4 and N2O were recorded, and abundance of relevant soil microbial functional genes was determined during rice-growing season in a 6-year-long fertilization experiment field in China. Results indicate that application of urea significantly changed the functional microbial composition, while the influence of straw incorporation was not significant. Application of urea significantly decreased the gene abundances of archaeal amoA and mcrA, but it significantly increased the gene abundances of bacterial amoA. CH 4 emission was significantly increased by fresh straw incorporation. Incorporation of burnt straw tended to increase CH 4 emission, while the urea application had no obvious effect on CH 4 emission. N2O emission was significantly increased by urea application, while fresh or burnt straw incorporation tended to decrease N2O emission. The functional microbial composition did not change significantly over time, although the abundances of pmoA, archaeal amoA, nirS, and nosZ genes changed significantly. The change of CH 4 emission showed an inverse trend with the one of the N2O emissions over time. To some extent, the abundance of some functional genes in this study can explain CH 4 and N2O emissions. However, the correlation between CH 4 and N2O emissions and the abundance of related functional genes was not significant. Environmental factors, such as soil Eh, may be more related to CH 4 and N2O emissions.

The compositional evolution of C/2012 S1 (ISON) from ground-based high-resolution infrared spectroscopy as part of a worldwide observing campaign

Volatile production rates, relative abundances, rotational temperatures, and spatial distributions in the coma were measured in C/2012 S1 (ISON) using long-slit high-dispersion (λ/Δλ∼2.5×104) infrared spectroscopy as part of a worldwide observing campaign. Spectra were obtained on UT 2013 October 26 and 28 with NIRSPEC at the W.M. Keck Observatory, and UT 2013 November 19 and 20 with CSHELL at the NASA IRTF. H2O was detected on all dates, with production rates increasing markedly from (8.7±1.5)×1027moleculess−1 on October 26 (Rh=1.12AU) to (3.7±0.4)×1029moleculess−1 on November 20 (Rh=0.43AU). Short-term variability of H2O production is also seen as observations on November 19 show an increase in H2O production rate of nearly a factor of two over a period of about 6h. C2H6, CH3OH and CH4 abundances in ISON are slightly depleted relative to H2O when compared to mean values for comets measured at infrared wavelengths. On the November dates, C2H2, HCN and OCS abundances relative to H2O appear to be within the range of mean values, whereas H2CO and NH3 were significantly enhanced. There is evidence that the abundances with respect to H2O increased for some species but not others between October 28 (Rh=1.07AU) and November 19 (Rh=0.46AU). The high mixing ratios of H2CO/CH3OH and C2H2/C2H6 on November 19, and changes in the mixing ratios of some species with respect to H2O between October 28 to November 19, indicates compositional changes that may be the result of a transition from sampling radiation-processed outer layers in this dynamically new comet to sampling more pristine natal material as the outer processed layer was increasingly eroded and the thermal wave propagated into the nucleus as the comet approached perihelion for the first time. On November 19 and 20, the spatial distribution for dust appears asymmetric and enhanced in the antisolar direction, whereas spatial distributions for volatiles (excepting CN) appear symmetric with their peaks slightly offset in the sunward direction compared to the dust. Spatial distributions for H2O, HCN, C2H6, C2H2, and H2CO on November 19 show no definitive evidence for significant contributions from extended sources; however, broader spatial distributions for NH3 and OCS may be consistent with extended sources for these species. Abundances of HCN and C2H2 on November 19 and 20 are insufficient to account for reported abundances of CN and C2 in ISON near this time. Differences in HCN and CN spatial distributions are also consistent with HCN as only a minor source of CN in ISON on November 19 as the spatial distribution of CN in the coma suggests a dominant distributed source that is correlated with dust and not volatile release. The spatial distributions for NH3 and NH2 are similar, suggesting that NH3 is the primary source of NH2 with no evidence of a significant dust source of NH2; however, the higher production rates derived for NH3 compared to NH2 on November 19 and 20 remain unexplained. This suggests a more complete analysis that treats NH2 as a distributed source and accounts for its emission mechanism is needed for future work.

Low temperature rate coefficients of the H + CH+ → C+ + H2 reaction: New potential energy surface and time-independent quantum scattering

The observed abundances of the methylidyne cation, CH(+), in diffuse molecular clouds can be two orders of magnitude higher than the prediction of the standard gas-phase models which, in turn, predict rather well the abundances of neutral CH. It is therefore necessary to investigate all the possible formation and destruction processes of CH(+) in the interstellar medium with the most abundant species H, H2, and e(-). In this work, we address the destruction process of CH(+) by hydrogen abstraction. We report a new calculation of the low temperature rate coefficients for the abstraction reaction, using accurate time-independent quantum scattering and a new high-level ab initio global potential energy surface including a realistic model of the long-range interaction between the reactants H and CH(+). The calculated thermal rate coefficient is in good agreement with the experimental data in the range 50 K-800 K. However, at lower temperatures, the experimental rate coefficient takes exceedingly small values which are not reproduced by the calculated rate coefficient. Instead, the latter rate coefficient is close to the one given by the Langevin capture model, as expected for a reaction involving an ion and a neutral species. Several recent theoretical works have reported a seemingly good agreement with the experiment below 50 K, but an analysis of these works show that they are based on potential energy surfaces with incorrect long-range behavior. The experimental results were explained by a loss of reactivity of the lowest rotational states of the reactant; however, the quantum scattering calculations show the opposite, namely, a reactivity enhancement with rotational excitation.

The CH+abundance in turbulent, diffuse molecular clouds

The intermittent dissipation of interstellar turbulence is an important energy source in the diffuse ISM. Though on average smaller than the heating rates due to cosmic rays and the photoelectric effect on dust grains, the turbulent cascade can channel large amounts of energy into a relatively small fraction of the gas that consequently undergoes significant heating and chemical enrichment. In particular, this mechanism has been proposed as a solution to the long-standing problem of the high abundance of CH+ along diffuse molecular sight lines, which steady-state, low temperature models under-produce by over an order of magnitude. While much work has been done on the structure and chemistry of these small-scale dissipation zones, comparatively little attention has been paid to relating these zones to the properties of the large-scale turbulence. In this paper, we attempt to bridge this gap by estimating the temperature and CH+ column density along diffuse molecular sight-lines by post-processing 3-dimensional MHD turbulence simulations. Assuming reasonable values for the cloud density (30 / cm^3), size (20 pc), and velocity dispersion (2.3 km / s), we find that our computed abundances compare well with CH+ column density observations, as well as with observations of emission lines from rotationally excited H2 molecules.

Application of portable FTIR spectrometers for detecting greenhouse gas emissions of the major city Berlin

Abstract. Five portable Bruker EM27/SUN FTIR (Fourier transform infrared) spectrometers have been used for the accurate and precise observation of column-averaged abundances of CO2 and CH4 around the major city Berlin. In the work by Frey et al. (2015), a calibration procedure is developed and applied to the set of spectrometers used for the Berlin campaign. Here, we describe the observational setup of the campaign and aspects of the data analysis, and we present the recorded time series of XCH4 and XCO2. We demonstrate that the CO2 emissions of Berlin can be clearly identified in the observations. A simple dispersion model is applied which indicates a total strength of the Berlin source of about 0.8 t CO2 s−1. In the Supplement of this work, we provide the measured data set and auxiliary data. We hope that the model community will exploit this unique data set for state-of-the art inversion studies of CO2 and CH4 sources in the Berlin area.

METHYL ACETATE AND ITS SINGLY DEUTERATED ISOTOPOMERS IN THE INTERSTELLAR MEDIUM

Methyl acetate (CH_3COOCH_3) has been recently observed by IRAM 30 m radio telescope in Orion though the presence of its deuterated isotopomers is yet to be confirmed. We therefore study the properties of various forms of methyl acetate, namely, CH_3COOCH_3, CH_2DCOOCH_3 and CH_3COOCH_2D. Our simulation reveals that these species could be produced efficiently both in gas as well as in ice phases. Production of methyl acetate could follow radical-radical reaction between acetyl (CH_3CO) and methoxy (CH_3O) radicals. To predict abundances of CH_3COOCH_3 along with its two singly deuterated isotopomers and its two isomers (ethyl formate and hydroxyacetone), we prepare a gas-grain chemical network to study chemical evolution of these molecules. Since gas phase rate coefficients for methyl acetate and its related species were unknown, either we consider similar rate coefficients for similar types of reactions (by following existing data bases) or we carry out quantum chemical calculations to estimate the unknown rate coefficients. For the surface reactions, we use adsorption energies of reactants from some earlier studies. Moreover, we perform quantum chemical calculations to obtain spectral properties of methyl acetate in infrared and sub-millimeter regions. We prepare two catalog files for the rotational transitions of CH_2DCOOCH_3 and CH_3COOCH_2D in JPL format, which could be useful for their detection in regions of interstellar media where CH_3COOCH_3 has already been observed.

New constraints on the CH4vertical profile in Uranus and Neptune fromHerschelobservations

Dedicated line observations of CH4 rotational lines performed with Herschel /PACS and HIFI in 2009–2011 provide new inferences of the mean methane profile in the upper tropospheres and stratospheres of Uranus and Neptune. At Uranus, CH4 is found to be near saturation, with a ~9 × 10-4 tropopause/lower stratosphere mole fraction. This is nominally six times larger than inferred from Spitzer in 2007, although reconciliation may be possible if the CH4 abundance decreases sharply from ~100 to 2 mbar. This unexpected situation might reflect heterogeneous conditions in Uranus’ stratosphere, with local CH4 depletions and heating associated with downwelling motions. Higher CH4 abundances compared to values inferred under solstitial conditions by Voyager in 1989 suggest that atmospheric mixing is effectively subdued at high latitudes and/or is time-variable. At Neptune, the mid-stratosphere CH4 abundance is (1.15 ± 0.10) × 10-3 , in agreement with earlier determinations and indicative of either leakage through a warmer polar region or upwelling at low or middle latitudes. On both planets, spatially resolved observations of temperature and methane in the stratosphere are needed to further identify the physical processes at work.

CH(+) Destruction by Reaction with H: Computing Quantum Rates To Model Different Molecular Regions in the Interstellar Medium.

A detailed analysis of an ionic reaction that plays a crucial role in the carbon chemistry of the interstellar medium (ISM) is carried out by computing ab initio reactive cross sections with a quantum method and by further obtaining the corresponding CH(+) destruction rates over a range of temperatures that shows good overall agreement with existing experiments. The differences found between all existing calculations and the very-low-T experiments are discussed and explored via a simple numerical model that links these cross section reductions to collinear approaches where nonadiabatic crossing is expected to dominate. The new rates are further linked to a complex chemical network that models the evolution of the CH(+) abundance in the photodissociation region (PDR) and molecular cloud (MC) environments of the ISM. The abundances of CH(+) are given by numerical solutions of a large set of coupled, first-order kinetics equations that employs our new chemical package krome. The analysis that we carry out reveals that the important region for CH(+) destruction is that above 100 K, hence showing that, at least for this reaction, the differences with the existing laboratory low-T experiments are of essentially no importance within the astrochemical environments discussed here because, at those temperatures, other chemical processes involving the title molecule are taking over. A detailed analysis of the chemical network involving CH(+) also shows that a slight decrease in the initial oxygen abundance might lead to higher CH(+) abundances because the main chemical carbon ion destruction channel is reduced in efficiency. This might provide an alternative chemical route to understand the reason why general astrochemical models fail when the observed CH(+) abundances are matched with the outcomes of their calculations.

INFRARED SPECTRA AND OPTICAL CONSTANTS OF ELUSIVE AMORPHOUS METHANE

New and accurate laboratory results are reported for amorphous methane (CH4) ice near 10 K for the study of the interstellar medium (ISM) and the outer Solar System. Near- and mid-infrared (IR) data, including spectra, band strengths, absorption coefficients, and optical constants, are presented for the first time for this seldom-studied amorphous solid. The apparent IR band strength near 1300 cm(exp −1) (7.69 micrometer) for amorphous CH4 is found to be about 33% higher than the value long used by IR astronomers to convert spectral observations of interstellar CH4 into CH4 abundances. Although CH4 is most likely to be found in an amorphous phase in the ISM, a comparison of results from various laboratory groups shows that the earlier CH4 band strength at 1300 cm(exp −1) (7.69 micrometer) was derived from IR spectra of ices that were either partially or entirely crystalline CH4 Applications of the new amorphous-CH4 results are discussed, and all optical constants are made available in electronic form.

Implications of RCP emissions for future changes in vegetative exposure to ozone in the western U.S.

AbstractFuture changes in anthropogenic emissions of ozone precursors will likely impact seasonal vegetative ozone exposure, W126, in the western U.S. To investigate this, source‐receptor relationships are calculated with the GEOS‐Chem adjoint model and are separated by location, species, and sector. These are used to project changes in W126 through midcentury following representative concentration pathway (RCP) emissions. The overall behavior of W126 is governed by declining domestic emissions. However, foreign emissions of NOx, non‐methane volatile organic compounds, and CO and CH4 abundance can either slow or enhance this trend, depending on scenario. The relative importance of foreign emissions increases as U.S. emissions decline, and, in some cases, the contribution of foreign sources exceeds that of domestic as early as 2020. In 2050, W126 in the western U.S. contributed by Chinese emissions alone, dominated by the industrial sector, is up to 15% higher than in 2000, although such estimates are strongly dependent on scenario.

Methane oxidation pathways and associated methanotrophic communities in the water column of a tropical lake

We examined methane (CH4) oxidation pathways and associated methanotrophic communities in the water column of Lake Kivu using abundance and isotopic compositions of CH4 and phospholipid fatty acids (PLFA), distributions of glycerol dialkyl glycerol tetraethers, and catalyzed reporter deposition fluorescence in situ hybridization (CARD–FISH) analysis. The carbon isotopic data of CH4 indicate that aerobic CH4 oxidation is the predominant pathway of microbial CH4 consumption with an isotopic fractionation factor (α) of 1.022–1.038. A small amount of CH4 is oxidized anaerobically, with an α of 1.002–1.006. Aerobic CH4 oxidation is mediated by type II methane–oxidizing bacteria (type II MOB) based on the 13C depletion (δ13C of −40.5‰ to −43.7‰) of diagnostic C18:1ω7 fatty acids in the surface waters. CARD–FISH images and PLFA components C16:1ω7 and C16:1ω5 indicate the presence of type I MOB in the methane and nutrient–rich deep–water region. 13C depletion of C16:1ω7 and C16:1ω5 (δ13C, ∼ −40‰ to −50.6‰) in the lake water below 52 m suggests the involvement of type I MOB in methane oxidation in the anoxic deep–water regions of the lake. A novel cluster of anaerobic methane–oxidizing archaea (ANME) rather than the known ANME–1 and ANME–2 appear to be involved in anaerobic oxidation of methane (AOM). Sulfate reducing bacteria are associated with AOM in the lake based on the 13C depletion (δ13C, −38.2‰ to −45.0‰) of anteiso–methyl–C15:0 fatty acid. Methane constitutes an important carbon and energy source (up to 38%) for the heterotrophic and autotrophic communities in the lake.

Mapping CH&amp;lt;sub&amp;gt;4&amp;lt;/sub&amp;gt; : CO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt; ratios in Los Angeles with CLARS-FTS from Mount Wilson, California

Abstract. The Los Angeles megacity, which is home to more than 40% of the population in California, is the second largest megacity in the United States and an intense source of anthropogenic greenhouse gases (GHGs). Quantifying GHG emissions from the megacity and monitoring their spatiotemporal trends are essential to be able to understand the effectiveness of emission control policies. Here we measure carbon dioxide (CO2) and methane (CH4) across the Los Angeles megacity using a novel approach – ground-based remote sensing from a mountaintop site. A Fourier transform spectrometer (FTS) with agile pointing optics, located on Mount Wilson at 1.67 km above sea level, measures reflected near-infrared sunlight from 29 different surface targets on Mount Wilson and in the Los Angeles megacity to retrieve the slant column abundances of CO2, CH4 and other trace gases above and below Mount Wilson. This technique provides persistent space- and time-resolved observations of path-averaged dry-air GHG concentrations, XGHG, in the Los Angeles megacity and simulates observations from a geostationary satellite. In this study, we combined high-sensitivity measurements from the FTS and the panorama from Mount Wilson to characterize anthropogenic CH4 emissions in the megacity using tracer–tracer correlations. During the period between September 2011 and October 2013, the observed XCH4 : XCO2 excess ratio, assigned to anthropogenic activities, varied from 5.4 to 7.3 ppb CH4 (ppm CO2)−1, with an average of 6.4 ± 0.5 ppb CH4 (ppm CO2)−1 compared to the value of 4.6 ± 0.9 ppb CH4 (ppm CO2)−1 expected from the California Air Resources Board (CARB) bottom-up emission inventory. Persistent elevated XCH4 : XCO2 excess ratios were observed in Pasadena and in the eastern Los Angeles megacity. Using the FTS observations on Mount Wilson and the bottom-up CO2 emission inventory, we derived a top-down CH4 emission of 0.39 ± 0.06 Tg CH4 year−1 in the Los Angeles megacity. This is 18–61% larger than the state government's bottom-up CH4 emission inventory and consistent with previous studies.