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At least 19 records

Photochemistry of biogenic gases

The relationship between the biosphere and the atmosphere is examined, emphasizing the composition and photochemistry and chemistry of the troposphere and stratosphere. The reactions of oxygen, ozone, and hydroxyl are reviewed and the fate of the biogenic gases ammonia, methane, reduced sulfur species, reduced halogen species, carbon monoxide, nitric oxide, nitrous oxide, nitrogen, and carbon dioxide are described. A list is given of the concentration and sources of the various gases.

Levine, Joel S.↗

The photochemistry of biogenic gases in the early and present atmosphere

The distribution of gases in the prebiologial paleoatmosphere is investigated using photochemical models. A chart of the photochemical and chemical reactions and reaction rates for CH4, NH3, H2S, N2O, and CO atmospheric gases is given. Mixing ratios and surface mixing ratios for CH4, NH3, CO, and N2O are obtained using thermodynamic equilibrium calculations; an increase in CH4 and N2O is observed. The reactions, which explain the photochemistry of the gases studied, are presented. The sources of these gases and their concentration with regards to altitude are examined. Graphs of the vertical distribution of CH4, NH3, H2S, CO, O2, and N2O in prebiological paleoatmosphere are provided. The data reveals the presence of only N2, CO2, and N2O in the early atmosphere; with the evolution of life, sources of atmospheric gases increased and their influence on the photochemistry of the troposphere and stratosphere increased.

Levine, J. S.↗

A search for biogenic trace gases in the atmosphere of Mars

The detection of certain trace gases in the atmosphere of Mars may serve as a possible indicator of microbial life on the surface of Mars. Candidate biogenic gases include methane CH4, ammonia NH3, nitrous oxide N2O, and several reduced sulfur species. Chemical thermodynamic equilibrium and photochemical calculations preclude the presence of these gases in any measurable concentrations in the atmosphere of Mars in the absence of biogenic production. A search for these gases utilizing either high resolution (spectral and spatial) spectroscopy from a Mars orbiter, such as the Observer, and or in situ measurements from a Mars lander or rover, is proposed.

Levine, Joel S.↗

Emissions of biogenic sulfur gases from Alaskan tundra

Fluxes of the biogenic sulfur gases carbonyl sulfide (COS), dimethyl sulfide (DMS), methyl mercaptan (MeSH), and carbon disulfide (CS2) were determined for several freshwater and coastal marine tundra habitats using a dynamic enclosure method and gas chromatography. In the freshwater tundra sites, highest emissions, with a mean of 6.0 nmol/m(sup -2)H(sup -1) (1.5-10) occurred in the water-saturated wet meadow areas inhabited by grasses, sedges, and Sphagnum mosses. In the drier upland tundra sites, highest fluxes occurred in areas inhabited by mixed vegetation and labrador tea at 3.0 nmol/m(sup -2)h(sup -1) (0-8.3) and lowest fluxes were from lichen-dominated areas at 0.9 nmol/m(sup -2)h(sup -1). Sulfur emissions from a lake surface were also low at 0.8 nmol/m(sup -2)h(sup -1). Of the compounds measured, DMS was the dominant gas emitted from all of these sites. Sulfure emissions from the marine sites were up to 20-fold greater than fluxes in the freshwater habitats and were also dominated by DMS. Emissions of DMS were highest from intertidal soils inhabited by Carex subspathacea (150-250 nmol/m(sup -2)h(sup -1)). This Carex sp. was grazed thoroughly by geese and DMS fluxes doubled when goose feces were left within the flux chamber. Emissions were much lower from other types of vegetation which were more spatially dominant. Sulfure emissions from tundra were among the lowest reported in the literature. When emission data were extrapolated to include all tundra globally, the global flux of biogenic sulfur from this biome is 2-3 x 10(exp 8) g/yr. This represents less than 0.001 percent of the estimated annual global flux (approximately 50 Tg) of biogenic sulfur and less than 0.01 percent of the estimated terrestrial flux. The low emissions are attributed to the low availability of sulfate, certain hydrological characteristics of tundra, and the tendency for tundra to accumulate organic matter.

Hines, Mark E.↗

Open-path tunable diode laser absorption for eddy correlation flux measurements of atmospheric trace gases

Biogenic emissions from and dry deposition to terrestrial surfaces are important processes determining the trace gas composition of the atmosphere. An instrument has been developed for flux measurements of gases such as CH4, N2O, and O3 based on the eddy correlation technique which combines trace gas fluctuation measurements with simultaneous windfield measurements. The instrument combines a tunable diode laser infrared light source with an open-path multipass absorption cell in order to provide the fast time response and short base pathlength required for the eddy correlation method. Initial field tests using the instrument to measure methane emissions from a local wetland demonstrate the capability for high precision eddy correlation flux measurements.

Anderson, Stuart M.↗

Process Considerations for the Production of Hydrogen via Steam Reforming of Oxygenated Gases from Biomass Pyrolysis and Other Conversion Processes

Abstract In 2021, average CO 2 emissions was 9.7 g CO 2 /g H 2 produced, primarily based on steam methane reforming (SMR) technology that currently dominates hydrogen production. The substitution of natural gas (NG) and other fossil feedstocks in SMRs with renewable gases may be considered as an option for reducing greenhouse gas emissions. This analysis explores process impacts and constraints associated with the potential introduction of biogenic gases into SMRs. The results indicate that replacing NG in the fuel train of the SMR, followed by partial replacement of NG in the feed train may be a feasible approach. For the CO‐ and CO 2 ‐rich gas compositions assumed in this analysis the results indicate that feed train may accommodate up to 25 mole % of biogenic gases using allowances in existing designs and/or with small modifications, while maintaining similar hydrogen output. NG substitution in higher proportions require more major changes because of increased flow rates and heat exchange requirements in the system. Biogenic gases with lower CO 2 and higher calorific values are advantageous for NG substitution, and dry reforming using the CO 2 present in the feed gas can reduce steam consumption and increase process efficiency within limits where coking does not become a new constraint.

08 HYDROGEN↗

Emissions of biogenic sulfur gases from northern bogs and fens

Sulfur gases are important components of the global cycle of S. They contribute to the acidity of precipitation and they influence global radiation balance and climate. The role of terrestrial sources of biogenic S and their effect on atmospheric chemistry remain as major unanswered questions in our understanding of the natural S cycle. The role of northern wetlands as sources and sinks of gaseous S by measuring rates of S gas exchange as a function of season, hydrologic conditions, and gradients in tropic status was investigated. Experiments were conducted in wetlands in New Hampshire, particularly a poor fen, and in Mire 239, a poor fen at the Experimental Lakes Area (ELA) in Ontario. Emissions were determined using Teflon enclosures, gas cryotrapping methods and gas chromatography (GC) with flame photometric detection. Dynamic (sweep flow) and static enclosures were employed which yielded similar results. Dissolved S gases and methane were determined by gas stripping followed by GC.

Demello, William Zamboni↗

Emissions of biogenic sulfur gases from Alaskan tundra

Results of sulfur emission measurements made in freshwater and marine wetlands in Alaskan tundra during the Arctic Boundary Layer Expedition 2A (ABLE 3A) in July 1988 are presented. The data indicate that this type of tundra emits very small amounts of gaseous sulfur and, when extrapolated globally, accounts for a very small percentage of the global flux of biogenic sulfur to the atmosphere. Sulfur emissions from marine sites are up to 20-fold greater than fluxes from freshwater habitats and are dominated by dimethyl sulfide (DMS). Highest emissions, with a mean of 6.0 nmol/sq m/h, occurred in water-saturated wet meadow areas. In drier upland tundra sites, highest fluxes occurred in areas inhabited by mixed vegetation and labrador tea at 3.0 nmol/sq m/h and lowest fluxes were from lichen-dominated areas at 0.9 nmol/sq m/h. DMS was the dominant gas emitted from all these sites. Emissions of DMS were highest from intertidal soils inhabited by Carex subspathacea.

Hines, Mark E.↗

Modern Microbial Ecosystems are a Key to Understanding Our Biosphere's Early Evolution and its Contributions To The Atmosphere and Rock Record

The survival of our early biosphere depended upon efficient coordination anion- diverse microbial populations. Microbial mats exhibit a 3.46-billion-year fossil record, thus they are the oldest known ecosystems. Photosynthetic microbial mats were key because, today, sunlight powers more than 99 percent of global primary productivity. Thus photosynthetic ecosystems have affected the atmosphere profoundly and have created the most pervasive, easily-detected fossils. Photosynthetic biospheres elsewhere will be most detectible via telescopes or spacecraft. As a part of the Astrobiology Institute, our Ames Microbial Ecosystems group examines the roles played by ecological processes in the early evolution of our biosphere, as recorded in geologic fossils and in the macromolecules of living cells: (1) We are defining the microbial mat microenvironment, which was an important milieu for early evolution. (2) We are comparing mats in contrasting environments to discern strategies of adaptation and diversification, traits that were key for long-term survival. (3) We have selected sites that mimic key environmental attributes of early Earth and thereby focus upon evolutionary adaptations to long-term changes in the global environment. (4) Our studies of gas exchange contribute to better estimates of biogenic gases in Earth's early atmosphere. This group therefore directly addresses the question: How have the Earth and its biosphere influenced each other over time Our studies strengthen the systematics for interpreting the microbial fossil record and thereby enhance astrobiological studies of martian samples. Our models of biogenic gas emissions will enhance models of atmospheres that might be detected on inhabited extrasolar planets. This work therefore also addresses the question: How can other biospheres be recogniZed" Our choice of field sites helps us explore Earth's evolving early environment. For example, modern mats that occupy thermal springs and certain freshwater environments experience conditions such as low O2 and sulfate and high inorganic carbon and sulfide levels that resemble those of ancient marine environments. Later in history, both biologically-induced carbonate precipitation and the trapping and binding of suspended grains of carbonate became a dominant mechanism for carbonate deposition. Modern marine carbonate platforms and alkaline offer good examples of microbiologically-induced calcification. Both marine platforms and solar salterns illustrate microbially-driven trapping and binding. We are also exploring the effects of water composition upon the exchange of biogenic gases with the atmosphere.

DesMarais, David J.↗

Photosynthesis and Astrobiology: Looking for Life Elsewhere

Photosynthesis produces signs of life we can see from space: the absorbance spectrum of surface photosynthetic pigments and, with oxygenic photosynthesis, atmospheric oxygen. Since the first discovery of a planet in another solar system in 1989, there has been an explosion in the detection of exoplanets (over 1849 as of 7 November 2014) and we are getting ever closer to finding that Goldilocks planet that might harbour life. With telescope observations of these planets, oxygenic photosynthesis has been considered our most robust target 'biosignature' that would not appear on a lifeless planet. Since anoxygenic photosynthetic organisms do not produce unambiguously biogenic gases, there is interest in their pigments serving as spectral indicators of life. But will they look the same as on Earth, can we distinguish them from the abiotic, and what will dominate on another planet? Examples from Earth provide us with the potential to extrapolate some rules for photosynthesis to predict its signature on another planet, but there are yet things we must answer about life here to improve our confidence. In particular, given the combination of the available stellar spectrum and molecular constraints on photon energy use, can we predict the pigment spectral features that will dominate, which reductant will match, and what biogenic gases would result? We take clues from the diversity of anoxygenic photosynthetic metabolisms and three very recent examples of oxygenic photosynthesis utilizing other reaction centre (RC) chlorophylls in addition to chlorophyll a (Chl a).

Pigments↗

A preliminary study of the variability and magnitude of the flux of biogenic sulfur gases from a New Hampshire salt marsh

Salt marshes have highly variable spatial and temporal fluxes of hydrogen sulfide, carbonyl sulfide, methane thiol, dimethyl sulfide, and carbon disulfide (H2S, COS, MeSH, DMS, and CS2, respectively). This variability was tested at nine emission sites in a New Hampshire, USA salt marsh: three replicates in each of three vegetation zones, Spartina alterniflora, S. patens, and a transition zone. Three sites were sampled simultaneously, either within or across vegetation zones, using a dynamic flux chamber technique. Difficulties with calibration and field equipment resulted in fluxes with maximum absolute uncertainties of greater than plus or minus 200 percent. However, the relative uncertainty between subsequent samples was closer to plus or minus 20 percent. Chambers are expected to affect the natural flux of gases by altering the humidity, temperature, and composition of the gas inside the chamber. Summertime fluxes are highest for all gases except COS which demonstrated evidence of a springtime peak. A summertime background flux of 5 to 100 x 10(exp -9) g S/m(sup -2) min was observed for all gases, while S alternifora fluxes of MeSH and DMS were approximately 8 fold and approximately 100 fold higher than S. patens, respectively. DMS and MeSH fluxes were higher during the day than at night. Evidence of COS uptake by plants was observed. CS2 appeared to be the quantitatively least important sulfur gas emitted. Improved laboratory and sample collection techniques and further data collection in the field will yield information on the details of salt marsh variability, will improve estimates of the error associated with single flux measurements, and will allow a more accurate estimation of sulfur fluxes from salt marshes based on vegetation and area coverage data. Inability to control the temperature and humidity inside of the chamber remain significant problems with the chamber design.

Morrison, Michael Cope↗

Ecosystem Modeling of Biological Processes to Global Budgets

From an ecological perspective, the search for life on distant planets begins from several key assumptions. The first of these is that, viewed from a remote location in space, the signature of life on a distant planet will be the result of net gas exchange of organisms with their environment. On the basis of extensive biogeochemical measurements and biogenic trace gas fluxes in modem Earth environments, it is probable that certain groups of organisms both produce and consume the same trace gas(es) within a single bioprofile of Solid (porous) substrate or surface water. The net gas exchange rate with the atmosphere measured at the living surface is frequently the result of competing metabolic reactions, which may carried out by different functional groups of organisms located at dissimilar 'climatic' or chemical microsites within the same bioprofile. Biogenic gases produced at one (deep) level of a bioprofile may be consumed by another functional group of organisms located closer to the level of surface exchange with the atmosphere. A second key assumption is that the net biogenic fluxes of atmospheric gases on Earth can be used to infer relative abundance and functional composition of the major organisms on a distant planet. Examples of this principle include the presence of methanogenic microorganisms abundant today in freshwater ecosystems worldwide, which are major source of atmospheric methane and its seasonal variability in Earth's atmosphere. A third assumption is that scaling up biogenic gas fluxes from a single biological community to the planetary level requires flux measurements at the whole ecosystem level. This implies that measurements of biogenic gas exchange with the global atmosphere cannot be easily inferred from measurements of gas production rates of single organisms, which may have been isolated in some manner from the setting of their native ecosystem. Hence, the unit of biological organization used in modern Earth Science for scaling up to biosphere effects on atmospheric composition is the ecosystem level. These assumptions are the foundation for developing modern emission budgets for biogenic gases such as carbon dioxide, methane, carbon monoxide, isoprene, nitrous and nitric oxide, and ammonia. Such emission budgets commonly include information on seasonal flux patterns, typical diurnal profiles, and spatial resolution of at least one degree latitude/longitude for the globe. On the basis of these budgets, it is possible to compute 'base emission rates' for the major biogenic trace gases from both terrestrial and ocean sources, which may be useful benchmarks for defining the gas production rates of organisms, especially those from early Earth history, which are required to generate a detectable signal on a global atmosphere. This type of analysis is also the starting point for evaluation of the 'biological processes to global gas budget' extrapolation procedure described above for early Earth ecosystems.

Christopher, Potter S.↗

Rn-222 tracing and stable isotope measurements of biogenic gas fluxes from methane saturated sediments

Transport of reduced biogenic gases from anoxic sediments and soils to the atmosphere can be quantitatively studied through measurement of radon-222/radium-226 disequilibrium. In previous work, seasonal variations in biogenic gas transport mechanisms, net fluxes and overall composition were documented. Now presented are direct field measurements of radon-222 activity in gases exiting organic rich sediments which show their usefulness for tracing of the stripping of dissolved biogenic gases from within the sediment column and transport via bubble ebullition. Methane is depleted in deuterium during the summer as compared with winter months and is in general lighter than in most marine sediments signaling the probable importance of acetate as an important precursor molecule. The significant seasonal isotopic variations observed illustrate the importance of understanding mechanisms and rates of biogenic gas production in order to interpret observed tropospheric isotopic data.

Martens, Christopher S.↗

Observed Relationships Between Cloud Droplet Effective Radius and Biogenic Gas Concentrations in Summertime Marine Stratocumulus Over the Eastern North Atlantic

Abstract Biogenic gases are a prominent component of the summertime marine boundary layer (MBL) over the Eastern North Atlantic. One of these gases, dimethyl sulfide (DMS), can produce sulfate cloud condensation nuclei (CCN) that, in theory, can brighten clouds through photolysis, and produces a reaction product, methane sulfonic acid (MSA). It is also possible that DMS can interact with sea‐salt or other marine aerosols changing their CCN activation spectrum, which could also modify cloud microphysical structure. Data collected aboard the G1 aircraft during the Aerosol Cloud Experiment Eastern North Atlantic (ACE‐ENA) in well‐mixed and decoupled marine boundary layers (MBLs) were used to examine relationships between the cloud droplet effective radii, , and the concentrations of DMS and MSA in constant cloud liquid water content (LWC) bins. A weak but statistically significant negative correlation was observed between CCN concentration and in most LWC bins, regardless of the source of the CCN, while a weak but statistically significant positive correlation between and DMS was observed. No correlation between the cloud droplet number concentration and DMS was found. The presence of MSA indicated that DMS‐to‐sulfate photolysis was likely occurring, but data sparsity prevented a statistically significant conclusion regarding the relationship between MSA and . Data sparsity in decoupled conditions also prevented statistically significant conclusions. To properly address biogenic gas impacts on cloud microphysics, it is recommended that aircraft data be supplemented by long‐term biogenic gas measurements at the surface in marine locations with appropriate remote and in‐situ cloud sensing capabilities, and the analysis limited to well‐mixed MBL's.

54 ENVIRONMENTAL SCIENCES↗

Trace gases in the atmosphere of Mars - An indicator of microbial life

The detection of certain trace gases in the atmosphere of Mars would indicate the presence of microbial life on the surface. Candidate biogenic gases include CH4, NH3, N2O, and several reduced sulfur species. Chemical thermodynamic equilibrium and photochemical calculations preclude the presence of these gases in any measurable concentrations in the atmosphere of Mars in the absence of biogenic production. A search for these gases utilizing either high-resolution (spectral and spatial) spectroscopy from a Mars orbiter, such as the Mars Observer orbiter, and/or in situ measurements from a Mars lander or rover is proposed.

Levine, Joel S.↗

Changes in Physical Properties of Everglades Peat Soils Induced by Increased Salinity at the Laboratory Scale: Implications for Changes in Biogenic Gas Dynamics

Abstract Saltwater intrusion due to sea level rise is a major concern for the Florida Everglades because it may induce shifts in ecosystem productivity and physical soil properties. However, the effects of saline water intrusion into the current carbon gas dynamics of the Everglades (particularly in terms of biogenic gas production and emissions, i.e., CH 4 and CO 2 ) are still uncertain. In this work, we present a laboratory‐based study to simulate how sea level rise may alter the physical properties (i.e., hydraulic conductivity) of peat soils from the Everglades and consequently affect the accumulation and release of biogenic gases within the peat matrix. Peat monoliths collected from the Everglades were subjected to progressive increases in salinity from a NaCl solution, and changes to the biogenic gas dynamics regime were simultaneously monitored using a combination of time‐lapse ground‐penetrating radar measurements, manometers, time‐lapse photography, and gas traps. Physical changes to the peat matrix at each salinity interval were assessed using constant head permeameter tests. Consistent with previous research, results show that a progressive increase in salinity (from fresh to saltwater) results in (1) a progressive increase in hydraulic conductivity and (2) a progressive decrease in gas content within the peat matrix (i.e., production) and gas releases. This work has implications for better understanding the potential effects of saltwater intrusion into freshwater peatland systems in the Everglades, particularly in terms of carbon gas dynamics.

Sirianni, Matthew J.↗

Remote sensing of tidal wetlands - Mapping and beyond

Remote sensing, by means of aerial photography, is an accepted method for the mapping and inventory of tidal wetlands, enjoying considerable advantages in speed, flexibility and cost per area mapped over conventional techniques. Initially employed for the identification of wetlands and their boundaries, new applications concern the effective sensing of functional processes within the wetlands environment, such as plant biomass and the production of biogenic gases. The availability of accurate hand-held radiometers has produced increased efforts to quantitatively relate remote measurements to environmental parameters for these processes, expanding the information derivable from aerial and orbital multispectral scanners.

Bartlett, D. S.↗

Planetary ecology; Proceedings of the Sixth International Symposium on Environmental Biogeochemistry, Santa Fe, NM, October 10-14, 1983

Topics presented include biological evolution and planetary chemistry; C-1 compounds; transport, deposition, and weathering; sulfur transformations; ground water; transformation processes for nitrogen oxides; and soils. Papers are presented on immunological studies on the organic matrix of recent and fossil invertebrate shells; biogenic gases in sediments deposited since Miocene times on the Walvis Ridge, South Atlantic Ocean; aspects of the biogeochemistry of Big Soda Lake, NV; mesophilic manganese-oxidizing bacteria from hydrothermal discharge areas at 21 deg North on the East Pacific Rise; and autotrophic growth and iron oxidation and inhibition kinetics of Leptospirillum ferrooxidans. Consideration is also given to thermophilic archaebacteria occurring in submarine hydrothermal areas; fate of sulfate in a soft-water, acidic lake; geochemical conditions in the ground water environment; microbial transformations as sources and sinks for nitrogen oxides; and the biogeochemistry of soil phosphorus.

Caldwell, D. E.↗