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  • 1
    Electronic Resource
    Electronic Resource
    [s.l.] : Nature Publishing Group
    Nature 442 (2006), S. 145-146 
    ISSN: 1476-4687
    Source: Nature Archives 1869 - 2009
    Topics: Biology , Chemistry and Pharmacology , Medicine , Natural Sciences in General , Physics
    Notes: [Auszug] In an impressive feat of endurance and analytical skill, Rohrer and Berresheim have obtained a five-year record of the atmospheric concentration of the hydroxyl free radical, OH, at a research station in southern Germany (page 184 of this issue). This is remarkable because, although OH ...
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1476-4687
    Source: Nature Archives 1869 - 2009
    Topics: Biology , Chemistry and Pharmacology , Medicine , Natural Sciences in General , Physics
    Notes: [Auszug] Molecular hydrogen (H2) is the second most abundant trace gas in the atmosphere after methane (CH4). In the troposphere, the D/H ratio of H2 is enriched by 120‰ relative to the world's oceans. This cannot be explained by the sources of H2 ...
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  • 3
    Electronic Resource
    Electronic Resource
    [s.l.] : Macmillan Magazines Ltd.
    Nature 397 (1999), S. 299-301 
    ISSN: 1476-4687
    Source: Nature Archives 1869 - 2009
    Topics: Biology , Chemistry and Pharmacology , Medicine , Natural Sciences in General , Physics
    Notes: [Auszug] Bromine free radicals are emerging as important players in the photochemistry of the lower atmosphere, at least on local scales. Earlier this month, Hebestreit et al. described the discovery of air laden with bromine monoxide (BrO) wafting off the salt pans near the Dead Sea. And on page 338 ...
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  • 4
    Publication Date: 2022-05-25
    Description: Author Posting. © American Meteorological Society, 2013. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Climate 26 (2013): 4447–4475, doi:10.1175/JCLI-D-12-00589.1.
    Description: Changes in atmospheric CO2 variability during the twenty-first century may provide insight about ecosystem responses to climate change and have implications for the design of carbon monitoring programs. This paper describes changes in the three-dimensional structure of atmospheric CO2 for several representative concentration pathways (RCPs 4.5 and 8.5) using the Community Earth System Model–Biogeochemistry (CESM1-BGC). CO2 simulated for the historical period was first compared to surface, aircraft, and column observations. In a second step, the evolution of spatial and temporal gradients during the twenty-first century was examined. The mean annual cycle in atmospheric CO2 was underestimated for the historical period throughout the Northern Hemisphere, suggesting that the growing season net flux in the Community Land Model (the land component of CESM) was too weak. Consistent with weak summer drawdown in Northern Hemisphere high latitudes, simulated CO2 showed correspondingly weak north–south and vertical gradients during the summer. In the simulations of the twenty-first century, CESM predicted increases in the mean annual cycle of atmospheric CO2 and larger horizontal gradients. Not only did the mean north–south gradient increase due to fossil fuel emissions, but east–west contrasts in CO2 also strengthened because of changing patterns in fossil fuel emissions and terrestrial carbon exchange. In the RCP8.5 simulation, where CO2 increased to 1150 ppm by 2100, the CESM predicted increases in interannual variability in the Northern Hemisphere midlatitudes of up to 60% relative to present variability for time series filtered with a 2–10-yr bandpass. Such an increase in variability may impact detection of changing surface fluxes from atmospheric observations.
    Description: The CESM project is supported by the National Science Foundation and the Office of Science (BER) of the U.S. Department of Energy. Computing resources were provided by the Climate Simulation Laboratory at NCAR’s Computational and Information Systems Laboratory (CISL), sponsored by the National Science Foundation and other agencies. G.K.A. acknowledges support of a NOAA Climate and Global Change postdoctoral fellowship. J.T.R., N.M.M., S.C.D., K.L., and J.K.M. acknowledge support of Collaborative Research: Improved Regional and Decadal Predictions of the Carbon Cycle (NSF AGS-1048827, AGS-1021776,AGS-1048890). TheHIPPO Programwas supported byNSF GrantsATM-0628575,ATM-0628519, and ATM-0628388 to Harvard University, University of California (San Diego), and by University Corporation for Atmospheric Research, University of Colorado/ CIRES, by the NCAR and by the NOAAEarth System Research Laboratory. Sunyoung Park, Greg Santoni, Eric Kort, and Jasna Pittman collected data during HIPPO. The ACME project was supported by the Office of Biological and Environmental Research of the U.S. Department of Energy under Contract DE-AC02- 05CH11231 as part of the Atmospheric Radiation Measurement Program (ARM), the ARM Aerial Facility, and the Terrestrial EcosystemScience Program. TCCON measurements at Eureka were made by the Canadian Network for Detection of Atmospheric Composition Change (CANDAC) with additional support from the Canadian Space Agency. The Lauder TCCON program was funded by the New Zealand Foundation for Research Science and Technology contracts CO1X0204, CO1X0703, and CO1X0406. Measurements at Darwin andWollongong were supported by Australian Research Council Grants DP0879468 and DP110103118 and were undertaken by David Griffith, Nicholas Deutscher, and Ronald Macatangay. We thank Pauli Heikkinen, Petteri Ahonen, and Esko Kyr€o of the Finnish Meteorological Institute for contributing the Sodankyl€a TCCON data. Measurements at Park Falls, Lamont, and Pasadena were supported byNASAGrant NNX11AG01G and the NASA Orbiting Carbon Observatory Program. Data at these sites were obtained by Geoff Toon, Jean- Francois Blavier, Coleen Roehl, and Debra Wunch.
    Description: 2014-01-01
    Keywords: Carbon cycle ; Carbon dioxide ; Aircraft observations ; In situ atmospheric observations ; Remote sensing ; Tracers
    Repository Name: Woods Hole Open Access Server
    Type: Article
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  • 5
    Publication Date: 2022-05-25
    Description: Recent measurements of methane (CH4) by the Mars Science Laboratory (MSL) now confront us with robust data that demand interpretation. Thus far, the MSL data have revealed a baseline level of CH4 (∼0.4 parts per billion by volume [ppbv]), with seasonal variations, as well as greatly enhanced spikes of CH4 with peak abundances of ∼7 ppbv. What do these CH4 revelations with drastically different abundances and temporal signatures represent in terms of interior geochemical processes, or is martian CH4 a biosignature? Discerning how CH4 generation occurs on Mars may shed light on the potential habitability of Mars. There is no evidence of life on the surface of Mars today, but microbes might reside beneath the surface. In this case, the carbon flux represented by CH4 would serve as a link between a putative subterranean biosphere on Mars and what we can measure above the surface. Alternatively, CH4 records modern geochemical activity. Here we ask the fundamental question: how active is Mars, geochemically and/or biologically? In this article, we examine geological, geochemical, and biogeochemical processes related to our overarching question. The martian atmosphere and surface are an overwhelmingly oxidizing environment, and life requires pairing of electron donors and electron acceptors, that is, redox gradients, as an essential source of energy. Therefore, a fundamental and critical question regarding the possibility of life on Mars is, "Where can we find redox gradients as energy sources for life on Mars?" Hence, regardless of the pathway that generates CH4 on Mars, the presence of CH4, a reduced species in an oxidant-rich environment, suggests the possibility of redox gradients supporting life and habitability on Mars. Recent missions such as ExoMars Trace Gas Orbiter may provide mapping of the global distribution of CH4. To discriminate between abiotic and biotic sources of CH4 on Mars, future studies should use a series of diagnostic geochemical analyses, preferably performed below the ground or at the ground/atmosphere interface, including measurements of CH4 isotopes, methane/ethane ratios, H2 gas concentration, and species such as acetic acid. Advances in the fields of Mars exploration and instrumentation will be driven, augmented, and supported by an improved understanding of atmospheric chemistry and dynamics, deep subsurface biogeochemistry, astrobiology, planetary geology, and geophysics. Future Mars exploration programs will have to expand the integration of complementary areas of expertise to generate synergistic and innovative ideas to realize breakthroughs in advancing our understanding of the potential of life and habitable conditions having existed on Mars. In this spirit, we conducted a set of interdisciplinary workshops. From this series has emerged a vision of technological, theoretical, and methodological innovations to explore the martian subsurface and to enhance spatial tracking of key volatiles, such as CH4.
    Description: Published
    Description: 6A. Geochimica per l'ambiente e geologia medica
    Description: JCR Journal
    Keywords: Methane, Mars
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 6
    Publication Date: 2022-05-26
    Description: Author Posting. © American Geophysical Union, 2007. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research 112 (2007): D10314, doi:10.1029/2006JD007659.
    Description: Precision requirements are determined for space-based column-averaged CO2 dry air mole fraction (XCO2) data. These requirements result from an assessment of spatial and temporal gradients in XCO2, the relationship between XCO2 precision and surface CO2 flux uncertainties inferred from inversions of the XCO2 data, and the effects of XCO2 biases on the fidelity of CO2 flux inversions. Observational system simulation experiments and synthesis inversion modeling demonstrate that the Orbiting Carbon Observatory mission design and sampling strategy provide the means to achieve these XCO2 data precision requirements.
    Description: This work was supported by the Orbiting Carbon Observatory (OCO) project through NASA’s Earth System Science Pathfinder (ESSP) program. SCO and JTR were supported by a NASA IDS grant (NAG5-9462) to JTR.
    Repository Name: Woods Hole Open Access Server
    Type: Article
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  • 7
    Publication Date: 2019-05-20
    Description: The hydroxyl radical (OH) fuels tropospheric ozone production and governs the lifetime of methane and many other gases. Existing methods to quantify global OH are limited to annual and global-to-hemispheric averages. Finer resolution is essential for isolating model deficiencies and building process-level understanding. In situ observations from the Atmospheric Tomography (ATom) mission demonstrate that remote tropospheric OH is tightly coupled to the production and loss of formaldehyde (HCHO), a major hydrocarbon oxidation product. Synthesis of this relationship with satellite-based HCHO retrievals and model-derived HCHO loss frequencies yields a map of total-column OH abundance throughout the remote troposphere (up to 70% of tropospheric mass) over the first two ATom missions (August 2016 and February 2017). This dataset offers unique insights on near-global oxidizing capacity. OH exhibits significant seasonality within individual hemispheres, but the domain mean concentration is nearly identical for both seasons (1.03 ± 0.25 × 106 cm−3), and the biseasonal average North/South Hemisphere ratio is 0.89 ± 0.06, consistent with a balance of OH sources and sinks across the remote troposphere. Regional phenomena are also highlighted, such as a 10-fold OH depression in the Tropical West Pacific and enhancements in the East Pacific and South Atlantic. This method is complementary to budget-based global OH constraints and can help elucidate the spatial and temporal variability of OH production and methane loss.
    Print ISSN: 0027-8424
    Electronic ISSN: 1091-6490
    Topics: Biology , Medicine , Natural Sciences in General
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  • 8
    Publication Date: 2017-04-17
    Description: Methane is the second strongest anthropogenic greenhouse gas and its atmospheric burden has more than doubled since 1850. Methane concentrations stabilized in the early 2000s and began increasing again in 2007. Neither the stabilization nor the recent growth are well understood, as evidenced by multiple competing hypotheses in recent literature. Here we use a multispecies two-box model inversion to jointly constrain 36 y of methane sources and sinks, using ground-based measurements of methane, methyl chloroform, and the C13/C12 ratio in atmospheric methane (δ13CH4) from 1983 through 2015. We find that the problem, as currently formulated, is underdetermined and solutions obtained in previous work are strongly dependent on prior assumptions. Based on our analysis, the mathematically most likely explanation for the renewed growth in atmospheric methane, counterintuitively, involves a 25-Tg/y decrease in methane emissions from 2003 to 2016 that is offset by a 7% decrease in global mean hydroxyl (OH) concentrations, the primary sink for atmospheric methane, over the same period. However, we are still able to fit the observations if we assume that OH concentrations are time invariant (as much of the previous work has assumed) and we then find solutions that are largely consistent with other proposed hypotheses for the renewed growth of atmospheric methane since 2007. We conclude that the current surface observing system does not allow unambiguous attribution of the decadal trends in methane without robust constraints on OH variability, which currently rely purely on methyl chloroform data and its uncertain emissions estimates.
    Print ISSN: 0027-8424
    Electronic ISSN: 1091-6490
    Topics: Biology , Medicine , Natural Sciences in General
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  • 9
    Publication Date: 2017-12-18
    Description: Gas-phase autoxidation—regenerative peroxy radical formation following intramolecular hydrogen shifts—is known to be important in the combustion of organic materials. The relevance of this chemistry in the oxidation of organics in the atmosphere has received less attention due, in part, to the lack of kinetic data at relevant temperatures. Here, we combine computational and experimental approaches to investigate the rate of autoxidation for organic peroxy radicals (RO2) produced in the oxidation of a prototypical atmospheric pollutant, n-hexane. We find that the reaction rate depends critically on the molecular configuration of the RO2 radical undergoing hydrogen transfer (H-shift). RO2 H-shift rate coefficients via transition states involving six- and seven-membered rings (1,5 and 1,6 H-shifts, respectively) of α-OH hydrogens (HOC-H) formed in this system are of order 0.1 s−1 at 296 K, while the 1,4 H-shift is calculated to be orders of magnitude slower. Consistent with H-shift reactions over a substantial energetic barrier, we find that the rate coefficients of these reactions increase rapidly with temperature and exhibit a large, primary, kinetic isotope effect. The observed H-shift rate coefficients are sufficiently fast that, as a result of ongoing NOx emission reductions, autoxidation is now competing with bimolecular chemistry even in the most polluted North American cities, particularly during summer afternoons when NO levels are low and temperatures are elevated.
    Print ISSN: 0027-8424
    Electronic ISSN: 1091-6490
    Topics: Biology , Medicine , Natural Sciences in General
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  • 10
    Publication Date: 2010-09-01
    Print ISSN: 0034-6748
    Electronic ISSN: 1089-7623
    Topics: Electrical Engineering, Measurement and Control Technology , Physics
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