The enigma of reactive nitrogen in volcanic emissions

Martin, R.S.; Ilyinskaya, Evgenia; Oppenheimer, Clive

doi:10.1016/j.gca.2012.07.027

Cited by 27 publications

(32 citation statements)

References 73 publications

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“…Palaeogeochemists have in the past come up with a series of mechanisms for the large-scale production of nitric oxide from atmospheric N 2 and CO 2 ranging from volcanism through bolide impacts to lightning [20,59]. The energy necessary to activate the relatively inert gases N 2 and CO 2 in all these cases comes from either heat or electrical discharge, or both.…”

Section: (B) Likelihood Of Oxidants On the Early Earthmentioning

confidence: 99%

Beating the acetyl coenzyme A-pathway to the origin of life

Nitschke

Russell

2013

Phil. Trans. R. Soc. B

118

174

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Attempts to draft plausible scenarios for the origin of life have in the past mainly built upon palaeogeochemical boundary conditions while, as detailed in a companion article in this issue, frequently neglecting to comply with fundamental thermodynamic laws. Even if demands from both palaeogeochemistry and thermodynamics are respected, then a plethora of strongly differing models are still conceivable. Although we have no guarantee that life at its origin necessarily resembled biology in extant organisms, we consider that the only empirical way to deduce how life may have emerged is by taking the stance of assuming continuity of biology from its inception to the present day. Building upon this conviction, we have assessed extant types of energy and carbon metabolism for their appropriateness to conditions probably pertaining in those settings of the Hadean planet that fulfil the thermodynamic requirements for life to come into being. Wood–Ljungdahl (WL) pathways leading to acetyl CoA formation are excellent candidates for such primordial metabolism. Based on a review of our present understanding of the biochemistry and biophysics of acetogenic, methanogenic and methanotrophic pathways and on a phylogenetic analysis of involved enzymes, we propose that a variant of modern methanotrophy is more likely than traditional WL systems to date back to the origin of life. The proposed model furthermore better fits basic thermodynamic demands and palaeogeochemical conditions suggested by recent results from extant alkaline hydrothermal seeps.

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Section: (B) Likelihood Of Oxidants On the Early Earthmentioning

confidence: 99%

Beating the acetyl coenzyme A-pathway to the origin of life

Nitschke

Russell

2013

Phil. Trans. R. Soc. B

118

174

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“…Following Seinfeld and Pandis (2006) a crystallisation humidity of 40 % for sulphate-containing particles is assumed in the model, but other studies suggest sulphate-containing particles to be liquid for lower relative humidities (e.g. Martin et al, 2003).…”

Section: Speciesmentioning

confidence: 99%

Quantification of the depletion of ozone in the plume of Mount Etna

et al. 2015

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Volcanoes are an important source of inorganic halogen species into the atmosphere. Chemical processing of these species generates oxidised, highly reactive, halogen species which catalyse considerable O3 destruction within volcanic plumes. A campaign of ground-based in situ O3, SO2 and meteorology measurements was undertaken at the summit of Mount Etna volcano in July/August 2012. At the same time, spectroscopic measurements were made of BrO and SO2 columns in the plume downwind. Depletions of ozone were seen at all in-plume measurement locations, with average O3 depletions ranging from 11-35 nmol mol-1 (15-45%). Atmospheric processing times of the plume were estimated to be between 1 and 4 min. A 1-D numerical model of early plume evolution was also used. It was found that in the early plume O3 was destroyed at an approximately constant rate relative to an inert plume tracer. This is ascribed to reactive halogen chemistry, and the data suggests the majority of the reactive halogen that destroys O3 in the early plume is generated within the crater, including a substantial proportion generated in a high-temperature "effective source region" immediately after emission. The model could approximately reproduce the main measured features of the ozone chemistry. Model results show a strong dependence of the near-vent bromine chemistry on the presence or absence of volcanic NOx emissions and suggest that near-vent ozone measurements can be used as a qualitative indicator of NOx emission

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“…In descending order of typical abundance (which varies with volcano setting, magma redox conditions, and eruptive style) volcanic gas emissions consist of: H 2 O, CO 2 , SO 2 , HCl, HF, H 2 S, OCS, CO, and HBr, as well as other trace species e.g., metals. Observations of volcanic plumes identify several additional species (e.g., NO, NO 2 , HNO 3 , BrO, OClO, SO 4 2− , HO 2 NO 2 , and H 2 O 2 ), (Allen et al, 2000;Mather et al, 2004b;Bobrowski et al, 2007;Oppenheimer et al, 2010;Carn et al, 2011;Martin et al, 2012;Kern and Lyons, 2018). These species are formed by oxidizing chemical reactions as the magmatic gases mix with air, first at high temperatures near to the source and then at low temperatures as the cooled plume disperses further into the background atmosphere.…”

Section: Introductionmentioning

confidence: 99%

Reaction Rates Control High-Temperature Chemistry of Volcanic Gases in Air

2019

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When volcanic gases enter the atmosphere, they encounter a drastically different chemical and physical environment, triggering a range of rapid processes including photochemistry, oxidation, and aerosol formation. These processes are critical to understanding the reactivity and evolution of volcanic emissions in the atmosphere yet are typically challenging to observe directly due to the nature of volcanic activity. Inferences are instead drawn largely from observations of volcanic plumes as they drift across a crater's edge and further downwind, and the application of thermodynamic models that neglect reaction kinetics as gas and air mix and thermally equilibrate. Here, we foreground chemical kinetics in simulating this critical zone. Volcanic gases are injected into a chain-of-reactors model that simulates time-resolved high-temperature chemistry in the dispersing plume. Boundary conditions of decreasing temperature and increasing proportion of air interacting with volcanic gases are specified with time according to an offline plume dynamics model. In contrast to equilibrium calculations, our chemical kinetics model predicts that CO is only partially oxidized, consistent with observed CO in volcanic plumes downwind from source. Formation of sulfate precursor SO 3 at SO 3 /SO 2 = 10 −3 mol/mol is consistent with the range of reported sulfate aerosol to SO 2 ratios observed close to crater rims. High temperature chemistry also forms oxidants OH, HO 2 , and H 2 O 2. The H 2 O 2 will likely augment volcanic sulfate yields by reacting with SO 2(aq) in the cooled-condensed plume. Calculations show that hightemperature OH will react with volcanic halogen halides (HBr and HCl) to yield reactive halogens (Br and Cl) in the young plume. Strikingly, high-temperature production of radical oxidants (including HO x) is enhanced by volcanic emissions of reduced gases (CO, H 2 , and H 2 S) due to chemical feedback mechanisms, although the kinetics of some reactions are uncertain, especially regarding sulfur. Our findings argue strongly that the chemistry of the hot near-source plume cannot be captured by equilibrium model assumptions, and highlight the need for development of more sophisticated, kinetics-based, high-temperature CHONS-halogen reaction models.

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The enigma of reactive nitrogen in volcanic emissions

Cited by 27 publications

References 73 publications

Beating the acetyl coenzyme A-pathway to the origin of life

Beating the acetyl coenzyme A-pathway to the origin of life

Quantification of the depletion of ozone in the plume of Mount Etna

Reaction Rates Control High-Temperature Chemistry of Volcanic Gases in Air

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