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At least 163 records · Page 9

In Situ Infrared Spectroscopy of the Gaseous Species Present in a Diamond Chemical Vapor Deposition System

We interfaced a Hot-Filament Chemical Vapor Deposition (HFCVD) system to the emission port of an FT-IR spectrometer, in order to study the gas phase species present during the deposition of diamond thin films. The implementation of the infrared (IR) emission technique in situ allowed the study of various carbon-containing species believed to be crucial in diamond film growth. The two IR-active vibrational fundamentals of methane, v(3)(f2) and v(4)(f2), were observed at three different filament temperatures: 1000, 1500 and 2000 C. However, the net signal of v(3) was emission, while that of v(4) was absorption. These results indicate that the v(4) fundamental is excited beyond equilibrium, while the v(3) fundamental remains mostly in the ground state. This is due to the small concentration of methane, the low energy of v(4) compared to v(3) or to the Hz vibrational mode, and symmetry considerations that forbid interaction among the four fundamentals of methane. Thus, the excitation of v(3) is more likely than its decay under HFCVD conditions, producing a non-equilibrium population. At a filament temperature of 2000 C, the v(3) (sigma(+)(3)) fundamental of acetylene and a band at 1328 cm-l also ascribed to acetylene (v5 (pi(U)) + v4) appear in net absorption. This correlates well with the onset of molecular hydrogen breaking by the filament, which occurs at temperatures around 2000 C and above. The hydrogen atoms produced in this heterogeneous reaction give rise to a chain of reactions that lead to acetylene, among other carbonaceous species.

Morell, G.↗

Gross and Net Soil Methane Flux and Ancillary Data, Edgewater, MD, USA, summer 2022

This data package contains measurements used to quantify methane cycling and environmental conditions in coastal forest soils during the 2022 growing season. It includes time‑series data of soil methane flux, soil respiration, soil temperature, and volumetric water content collected from soil monoliths transplanted along an inundation and salinity gradient. The package also provides one‑time measurements from a stable‑isotope pool‑dilution incubation, including gravimetric water content, methane headspace concentrations, and ¹³CH₄ enrichment over time. Data files are provided in comma‑separated values (CSV) format, with accompanying metadata and readme documentation in PDF and plain‑text formats. All files can be opened with standard software such as R, Python, or spreadsheet programs capable of handling CSV files. The metadata file describes variable definitions, units, processing steps, and the structure of each data table to support reuse and integration with other datasets.

13-C↗

Deacetylation and Mechanical Refining Pathway for the Bioconversion of Sugarcane Bagasse

Advancing lignocellulose biorefining is imperative for the deployment of cellulosic (2G) biofuels. This work investigates the tailoring of the alkaline deacetylation and mechanical refining (DMR) pathway for the bioconversion of sugarcane bagasse. Experiments are conducted at laboratory and pilot scales, varying the pretreatment conditions (70–92 °C; 48–100 g NaOH /kg) and the mechanical refining technologies (PFI and disk refining). The pretreatments selectively solubilize acetyl groups (> 86%) and lignin (10–63%) while mostly preserving structural carbohydrates in the solid phase. Enzymatic hydrolysis generates hydrolysates of clean sugars (glucose and xylose), with sugar yields increasing up to 81% for glucose and 89% for xylose in response to delignification and mechanical refining. Biochemical methane potential assays reveal specific methane productions of up to 568 NmL CH₄ gVS⁻¹ for alkaline liquor monodigestion and 344 NmL CH₄ gVS⁻¹ for co-digestion with sugarcane vinasse from the conventional (1G) sugarcane ethanol, indicating a strong potential for bioenergy recovery from this process stream. Synergies are identified in integrating 1G ethanol, 2G DMR processing of bagasse, and anaerobic co-digestion of 1G vinasse and 2G DMR alkaline liquor. This technology enables sugarcane biorefineries to enhance the co-production of ethanol, methane, and concentrated streams of CO 2 .

09 BIOMASS FUELS↗

Utilizing Earth Observations of Soil Freeze/Thaw Data and Atmospheric Concentrations to Estimate Cold Season Methane Emissions in the Northern High Latitudes

The northern wetland methane emission estimates have large uncertainties. Inversion models are a qualified method to estimate the methane fluxes and emissions in northern latitudes but when atmospheric observations are sparse, the models are only as good as their a priori estimates. Thus, improving a priori estimates is a competent way to reduce uncertainties and enhance emission estimates in the sparsely sampled regions. Here, we use a novel way to integrate remote sensing soil freeze/thaw (F/T) status from SMOS satellite to better capture the seasonality of methane emissions in the northern high latitude. The SMOS F/T data provide daily information of soil freezing state in the northern latitudes, and in this study, the data is used to define the cold season in the high latitudes and, thus, improve our knowledge of the seasonal cycle of biospheric methane fluxes. The SMOS F/T data is implemented to LPX-Bern DYPTOP model estimates and the modified fluxes are used as a biospheric a priori in the inversion model CarbonTracker Europe-CH 4 . The implementation of the SMOS F/T soil state is shown to be beneficial in improving the inversion model’s cold season biospheric flux estimates. Our results show that cold season biospheric CH4 emissions in northern high latitudes are approximately 0.60 Tg lower than previously estimated, which corresponds to 17% reduction in the cold season biospheric emissions. This reduction is partly compensated by increased anthropogenic emissions in the same area (0.23 Tg), and the results also indicates that the anthropogenic emissions could have even larger contribution in cold season than estimated here.

54 ENVIRONMENTAL SCIENCES↗

Factors controlling sulfur gas exchange in Sphagnum-dominated wetlands

Atmosphere-peatland exchange of reduced sulfur gases was determined seasonally in fen in NH, and in an artificially-acidified fen at the Experimental Lakes Area (ELA) in Canada. Dimethyl sulfide (DMS) dominated gas fluxes at rates as high as 400 nmol/m(sup -2)hr(sup -1). DMS fluxes measured using enclosures were much higher than those calculated using a stagnant-film model, suggesting that Sphagnum regulated efflux. Temperature controlled diel and seasonal variability in DMS emissions. Use of differing enclosure techniques indicated that vegetated peatlands consume atmospheric carbonyl sulfide. Sulfate amendments caused DMS and methane thiol concentrations in near-surface pore waters to increase rapidly, but fluxes of these gases to the atmosphere were not affected. However, emission data from sites experiencing large differences in rates of sulfate deposition from the atmosphere suggested that chronic elevated sulfate inputs enhance DMS emissions from northern wetlands.

Demello, William Zamboni↗

Biogenic and anthropogenic trace gases in the atmosphere

This paper illustrates the importance of biogenic and anthropogenic trace gases for the global environment and for the climate system. The paper briefly reviews the currently available estimates of sources and strengths of the biogenic and anthropogenic gases on the global scale. One of the major concerns for the global environment is the rapid increase in the concentration of long-lived trace gases such as CO2, CH4, N2O and the chlorofluorocarbons. The trend in the carbon dioxide concentration, as a result of fossil-fuel burning, is of the order of 0.4 percent per year, and this trend is related to the CO2 uptake by the ocean and by terrestrial ecosystems, which are likely to be modified if the planet warms up in the forthcoming decades. The concentrations of methane and nitrous oxide are increasing by 0.9 and 0.25 percent per year, respectively. In the case of the most widely used chlorofluorocarbons, trends as large as 10 percent per year or more are being measured.

Brasseur, G. P.↗

BOREAS TF-4 CO2 and CH4 Soil Profile Data from the SSA

The BOReal Ecosystem-Atmosphere Study Tower Flux (BOREAS TF-4) team measured distributions of carbon dioxide (CO2) and methane (CH4) concentrations for the upper 5 m of soil and unsaturated zone at the mature stand, upper 6 m at the 20-year-old stand, and the upper 1 m at the 8-year-old stand and clear cut area at the BOREAS Southern Study Area (SSA) during August 1993 to March 1995. Particle size and carbon content of the unsaturated deposits, precipitation, soil temperature and moisture, carbon and oxygen isotopes of soil CO2, and soil water chemistry are also presented. The data are stored in tabular ASCII files.

Striegl, Robert↗

Carbon isotope geochemistry of hydrocarbons in the Cerro Prieto geothermal field, Baja California Norte, Mexico

Hydrocarbon abundances and stable-isotopic compositions were measured in wells M5, M26, M35 and M102, which represent a range of depths (1270-2000 m) and temperatures (275-330 degrees C) in the field. In order to simulate the production of the geothermal hydrocarbons, gases were collected from the pyrolysis of lignite in the laboratory. This lignite was obtained from a well which sampled rock strata which are identical to those occurring in the field, but which have experienced much lower subsurface temperatures. In both the well and the laboratory observations, high-temperature environments favored higher relative concentrations of methane, ethane and benzene and generally higher delta 13C-values in the individual hydrocarbons. The best correlation between the laboratory and well data is obtained when laboratory-produced gases from experiments conducted at lower (400 degrees C) and higher (600 degrees C) temperatures are mixed. This improved correlation suggests that the wells are sampling hydrocarbons produced from a spectrum of depths and temperatures in the sediments.

NASA Center ARC↗

Clouds of Neptune and Uranus

We present results on the bases and concentrations of methane ice, ammonia ice, ammonium hydrosulfide-solid, water ice, and aqueous-ammonia solution (droplet) clouds of Neptune and Uranus, based on an equilibrium cloud condensation model. Due to their similar p-T structures, the model results for Neptune and Uranus are similar. Assuming 30-50x solar enhancement for the condensibles species, as expected from formation models, we find that the base of the droplet cloud is at the 370 bars for 30 solar, and at 500 bars for 50 solar cases. Despite this, entry probes need to be deployed to only 50-100 bars to obtain all the critical information needed to constrain models of the formation of these planets and their atmospheres.

Atreya, Sushil K.↗

Metabolic Potential and Activity in Fluids of the Coast Range Ophiolite Microbial Observatory, California, USA

Metabolic potential and activity associated with hydrogen and carbon monoxide were characterized in fluids sampled from the the Coast Range Ophiolite Microbial Observatory (CROMO). CROMO consists of two clusters of science-dedicated wells drilled to varying depths up to 35m in the actively serpentinizing, Jurassic-age Coast Range Ophiolite of Northern California, along with a suite of pre-existing monitoring wells at the same site. Consistent with the fluid chemistry observed in other serpentinizing systems, CROMO fluids are highly alkaline, with pH up to 12.5, high in methane, with concentrations up 1600 micromolar, and low in dissolved inorganic carbon (DIC), with concentrations of 10's to 100's of micromolar. CROMO is conspicuous for fluid H2 concentrations that are consistently sub-micromolar, orders of magnitude lower than is typical of other systems. However, higher H2 concentrations (10's -100's of micromolar) at an earlier stage of fluid chemical evolution are predicted by, or consistent with: thermodynamic models for fluid chemistry based on parent rock composition equivalent to local peridotite and with water:rock ratio constrained by observed pH; the presence of magnetite at several wt% in CROMO drill cores; and concentrations of formate and carbon monoxide that would require elevated H2 if formed in equilibrium with H2 and DIC. Calculated Gibbs energy changes for reaction of H2 and CO in each of several metabolisms, across the range of fluid composition encompassed by the CROMO wells, range from bioenergetically feasible (capable of driving ATP synthesis) to thermodynamically unfavorable. Active consumption relative to killed controls was observed for both CO and H2 during incubation of fluids from the pre-existing monitoring wells; in incubations of freshly cored solids, consumption was only observed in one sample set (corresponding to the lowest pH) out of three. The specific metabolisms by which H2 and CO are consumed remain to be determined.

Hydrogen↗

An Unusual Inverted Saline Microbial Mat Community in an Interdune Sabkha in the Rub' Alkhali (the Empty Quarter), UAE: an Analog for Habitats on Present Mars

Salt flats (sabkha) are a recognized habitat for microbial life in desert environments and as analogs for habitats for life on Mars. Here we report on the physical setting and microbiology of interdune sabkhas among the large dunes in the Rub' al Khali (the Empty Quarter) in Liwa Oasis, United Arab Emirates. The salt flats, composed of gypsum and halite, between the dunes are moistened by relatively fresh ground water from below. The result is a salinity gradient that is inverted compared to most salt flat communities with the hypersaline layer at the top and freshwater layers below. We describe and characterize a rich photosynthetically-based microbial ecosystem that is protected from the arid outside environment below the translucent salt crust. Gases collected from sediments under shallow ponds in the sabkha contain methane in concentrations as high as 3400 ppm. The salt layer provides environmental protection to the habitat below and could preserve biomarkers and other evidence for life in the salt after it dries out. Chloride-filled depressions have been identified on Mars and although the surface flow of water is unlikely on Mars today, ground water is possible. Such a near surface system with modern groundwater flowing under ancient salt deposits could be present on Mars and could be accessed by surface rovers.

Hypersaline environments in deserts↗

Global Wetland Contribution to 2000-2012 Atmospheric Methane Growth Rate Dynamics

Increasing atmospheric methane (CH4) concentrations have contributed to approximately 20% of anthropogenic climate change. Despite the importance of CH4 as a greenhouse gas, its atmospheric growth rate and dynamics over the past two decades, which include a stabilization period (1999-2006), followed by renewed growth starting in 2007, remain poorly understood. We provide an updated estimate of CH4 emissions from wetlands, the largest natural global CH4 source, for 2000-2012 using an ensemble of biogeochemical models constrained with remote sensing surface inundation and inventory-based wetland area data. Between 2000-2012, boreal wetland CH4 emissions increased by 1.2 Tg yr(sup -1) (-0.2-3.5 Tg yr(sup -1), tropical emissions decreased by 0.9 Tg yr(sup -1) (-3.2-1.1 Tg yr(sup -1), yet globally, emissions remained unchanged at 184 +/- 22 Tg yr(sup -1). Changing air temperature was responsible for increasing high-latitude emissions whereas declines in low-latitude wetland area decreased tropical emissions; both dynamics are consistent with features of predicted centennial-scale climate change impacts on wetland CH4 emissions. Despite uncertainties in wetland area mapping, our study shows that global wetland CH4 emissions have not contributed significantly to the period of renewed atmospheric CH4 growth, and is consistent with findings from studies that indicate some combination of increasing fossil fuel and agriculture-related CH4 emissions, and a decrease in the atmospheric oxidative sink.

Poulter, Benjamin↗

Long term monitoring of methane in the atmosphere by multiplex gas chromatography

Methane is of interest in the study of the Earth's atmosphere because of its implication in the future global warming of the surface. This warming is produced by the absorption of infrared energy by trace gases. It has been estimated that in the next 40 to 50 years, methane could contribute 20 to 25 pct. as much atmospheric warming as that expected from carbon dioxide increases. Studies to examine sources, sinks, and cycles of methane will require analytical methods capable of continuous unattended measurement with temporal resolution of an hour or less for weeks at a time. Gas chromatography (GC) is one of the most practical methods available to conduct the analysis of air, but limitations in this technique still exist which can be alleviated with multiplex GC (MGC). MGC is a technique where many samples are pseudo-randomly introduced to the chromatograph without regard to the length of time required for an analysis. The resulting data must then be reduced using computational methods such as cross correlation. In the technique reported, a tube packed with silver oxide was used at the inlet of the GC column to create concentration pulses of methane in a sample stream of air. By using only one carrier, i.e., ambient air, an effective and accurate method to monitor the variations in concentration of methane in the atmosphere over long periods of time was developed. Methane in ambient air was monitored for an eight day period and an interesting temporal variability was found. This work has shown the utility of a relatively simple MGC for the analysis of a real environmental sample.

Valentin, Jose R.↗

Microbial ecology and biogeochemistry of hypersaline sediments in Orca Basin

In deep ocean hypersaline basins, the combination of high salinity, unusual ionic composition and anoxic conditions represents significant challenges for microbial life. We used geochemical porewater characterization and DNA sequencing based taxonomic surveys to enable environmental and microbial characterization of anoxic hypersaline sediments and brines in the Orca Basin, the largest brine basin in the Gulf of Mexico. Full-length bacterial 16S rRNA gene clone libraries from hypersaline sediments and the overlying brine were dominated by the uncultured halophilic KB1 lineage, Deltaproteobacteria related to cultured sulfate-reducing halophilic genera, and specific lineages of heterotrophic Bacteroidetes. Archaeal clones were dominated by members of the halophilic methanogen genus Methanohalophilus, and the ammonia-oxidizing Marine Group I (MG-I) within the Thaumarchaeota. Illumina sequencing revealed higher phylum- and subphylum-level complexity, especially in lower-salinity sediments from the Orca Basin slope. Illumina and clone library surveys consistently detected MG-I Thaumarchaeota and halotolerant Deltaproteobacteria in the hypersaline anoxic sediments, but relative abundances of the KB1 lineage differed between the two sequencing methods. The stable isotopic composition of dissolved inorganic carbon and methane in porewater, and sulfate concentrations decreasing downcore indicated methanogenesis and sulfate reduction in the anoxic sediments. While anaerobic microbial processes likely occur at low rates near their maximal salinity thresholds in Orca Basin, long-term accumulation of reaction products leads to high methane concentrations and reducing conditions within the Orca Basin brine and sediments.

54 ENVIRONMENTAL SCIENCES↗

One-carbon (bio ?) Geochemistry in Subsurface Waters of the Serpentinizing Coast Range Ophiolite

Serpentinization - the aqueous alteration of ultramafic rocks - typically imparts a highly reducing and alkaline character to the reacting fluids. In turn, these can influence the speciation and potential for metabolism of one-carbon compounds in the system. We examined the aqueous geochemistry and assessed the biological potential of one-carbon compounds in the subsurface of the McLaughlin Natural Reserve (Coast Range Ophiolite, California, USA). Fluids from wells sunk at depths of 25-90 meters have pH values ranging from 9.7 to 11.5 and dissolved inorganic carbon (DIC concentrations) generally below 60 micromolar. Methane is present at concentrations up to 1.3 millimolar (approximately one-atmosphere saturation), and hydrogen concentrations are below 15 nanomolar, suggesting active consumption of H2 and production of CH4. However, methane production from CO2 is thermodynamically unfavorable under these conditions. Additionally, the speciation of DIC predominantly into carbonate at these high pH values creates a problem of carbon availability for any organisms that require CO2 (or bicarbonate) for catabolism or anabolism. A potential alternative is carbon monoxide, which is present in these waters at concentrations 2000-fold higher than equilibrium with atmospheric CO. CO is utilized in a variety of metabolisms, including methanogenesis, and bioavailability is not adversely affected by pH-dependent speciation (as for DIC). Methanogenesis from CO under in situ conditions is thermodynamically favorable and would satisfy biological energy requirements with respect to both Gibbs Energy yield and power.

McLaughlin Natural Reserve↗

Survey of lunar carbon compounds. II - The carbon chemistry of Apollo 11, 12, 14, and 15 samples.

The methane and carbide concentrations of a number of Apollo 11, 12, 14, and 15 samples of fines and breccias have been examined by the deuterated acid dissolution method. Location studies indicate that these carbon compounds are concentrated in the outer surfaces of the fines particles of 48-152 micron diameter; for larger particles a volume-related component may contribute. In individual samples the methane and carbide concentrations correlate with parameters indicative of lunar surface exposure. The data provide further evidence that solar wind implantation is the major source of the methane in the fines and that the carbide originates from both solar wind implantation and meteorite impacts.

Cadogan, P. H.↗

The effects of acid deposition on sulfate reduction and methane production in peatlands

Peatlands, as fens and bods, make up a large percentage of northern latitude terrestrial environments. They are organic rich and support an active community of anaerobic bacteria, such as methanogenic and sulfate-reducing bacteria. The end products of these microbial activities, methane and hydrogen sulfide, are important components in the global biogeochemical cycles of carbon and sulfur. Since these two bacterial groups compete for nutritional substrates, increases in sulfate deposition due to acid rain potentially can disrupt the balance between these processes leading to a decrease in methane production and emission. This is significant because methane is a potent greenhouse gas that effects the global heat balance. A section of Mire 239 in the Experimental Lakes Area, in Northwestern Ontario, was artificially acidified and rates of sulfate reduction and methane production were measured with depth. Preliminary results suggested that methane production was not affected immediately after acidification. However, concentrations of dissolved methane decreased and dissolved sulfide increased greatly after acidification and both took several days to recover. The exact mechanism for the decrease in methane was not determined. Analyses are under way which will be used to determine rates of sulfate reduction. These results will be available by Spring and will be discussed.

Murray, Georgia L.↗

Prospecting for Methane in Arabia Terra, Mars - First Results

Methane has been measured in the Martian atmosphere at concentrations of approx. 10 ppb. Since the photochemical lifetime of this gas is approx. 300 years, it is likely that methane is currently being released from the surface. Possible sources for the methane include 1) hydrothermal activity, 2) serpentinization of basalts and other water-rock interactions, 3) thermal maturation of sedimentary organic matter, and 4) metabolism of living bacteria. Any such discovery would revolutionize our understanding of Mars. Longitudinal variations in methane concentration, as measured by the Planetary Fourier Spectrometer (PFS) on Mars Express, show the highest values over Arabia Terra, Elysium Planum, and Arcadia-Memnonia, suggesting localized areas of methane release. We are using orbital data and methodologies derived from petroleum exploration in an attempt to locate these release points.

Allen, Carlton C.↗