Coupling between dimethylsulfide emissions and the ocean–atmosphere exchange of ammonia

M. T. Johnson; T. G. Bell

doi:10.1071/EN08030

RESEARCH ARTICLE

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Coupling between dimethylsulfide emissions and the ocean–atmosphere exchange of ammonia

M. T. Johnson ^A ^B and T. G. Bell ^A

+ Author Affiliations

- Author Affiliations

^A School of Environmental Sciences, University of East Anglia, Norwich, NR4 7TJ, UK.

^B Corresponding author. Email: martin.johnson@uea.ac.uk

Environmental Chemistry 5(4) 259-267 https://doi.org/10.1071/EN08030
Submitted: 22 May 2008 Accepted: 15 July 2008 Published: 19 August 2008

Environmental context. Dimethylsulfide (DMS) is recognised as a potentially significant climate-forcing gas, owing to its role in particle and cloud formation in the marine atmosphere, where it is the dominant source of acidity. Ammonia, the dominant naturally occurring base in the atmosphere, plays an important role in neutralising particles formed from DMS oxidation products and may even enhance the formation rate of new particles. A biogeochemical coupling has previously been proposed between DMS and ammonia fluxes from the ocean to the atmosphere, in the form of coproduction of the two gases in seawater. We revise this suggestion by introducing the concept of ‘co-emission’ of the gases, where DMS emission controls the rate of emission of ammonia from the ocean by acidifying the atmosphere.

Abstract. A strong correlation between aerosol ammonium and non-sea salt sulfate is commonly observed in the remote marine boundary layer. It has been suggested that this relationship implies a biogeochemical linkage between the nitrogen (N) and sulfur (S) cycles at the cellular biochemical level in phytoplankton in the ocean, or a linkage in the atmosphere (see P. S. Liss and J. N. Galloway, Interactions of C, N, P and S biogeochemical cycles and global change (Springer, 1993), and P. K. Quinn et al. in J. Geophys. Res. – Atmos. 1990, 95). We argue that an oceanic linkage is unlikely and draw on mechanistic and observational evidence to make the argument that the atmospheric connection is based on simple physical chemistry. Drawing on an established analogous concept in terrestrial trace gas biogeochemistry, we propose that any emission of dimethylsulfide (DMS) from the ocean will indirectly influence the flux of NH₃ from the ocean, through the neutralisation of acidic DMS oxidation products and consequent lowering of the partial pressure of NH₃ in the atmosphere. We present a simple numerical model to investigate this hypothesised phenomenon, using a parameterisation of the rate and thermodynamics of gas-to-particle conversion of NH_x and explicitly modelled ocean–atmosphere NH₃ exchange. The model indicates that emission of acidic sulfur to the atmosphere (e.g. as a product of DMS oxidation) may enhance the marine emission of NH₃. It also suggests that the ratio of ammonium to non-sea salt sulfate in the aerosol phase is strongly dependent on seawater pH, temperature and wind speed – factors that control the ocean–atmosphere ammonia flux. Therefore, it is not necessary to invoke a stoichiometric link between production rates of DMS and ammonia in the ocean to explain a given ammonium to non-sea salt sulfate ratio in the aerosol. We speculate that this mechanism, which can provide a continuous resupply of ammonia to the atmosphere, may be involved in a series of biogeochemical-climate feedbacks.

Acknowledgements

We are indebted to Peter Liss, Tim Jickells, Roland von Glasow, Tim Lenton and Simon Clegg for useful and insightful discussions, help and advice and to the three reviewers of this manuscript, who provided positive and extremely constructive criticism.

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^A Harrison and Kitto^[ ⁵⁰ ^] found kinetic control of aerosol sulfate neutralisation by NH₃ during a ‘connected flow’ study over S.E. England. They observed that the pseudo-first order rate constant (with respect to NH₃) for the reaction decreases with increasing neutralisation (Eqn 1).

where K has units of s^–1. Although these observations were made under a very different biogeochemical regime to that of the remote marine atmosphere, they strongly indicate a decrease in reaction rate towards aerosol neutralisation. Quinn et al.^[ ²² ^] predict exponentially increasing pNH_3(g) over aerosol tending towards neutralisation in their thermo-dynamic model of the atmospheric NH_x system. The authors do not present the details of their model, but we have closely reproduced their findings using the Aerosol Inorganics Model (AIM) described in Clegg et al.^[ ⁴⁹ ^] and in a related model, PITZ93, which is more reliable at near-neutral pH (S. Clegg, pers. comm.). Furthermore, the strong pH dependence of pNH_3(g) over ammonium sulfate aerosols has been observed in laboratory studies.^[ ⁵⁵ ^]

^B In regions where seawater temperatures are low and ambient ammonia fluxes are likely to be from atmosphere to ocean (owing to advection from source regions), the coupling of the fluxes may in fact be via an inhibition of NH₃ flux into the ocean, rather than enhanced emission of NH₃ from the sea surface.

^C Recent modelling studies have suggested that new particle formation is rare or non-existent in the MBL, owing to high temperatures inhibiting particle formation.^[ ⁵⁶ ^] These modelling studies consider only binary homogeneous nucleation between sulfuric acid and water (probably not the only process in new particle formation in the marine atmosphere^[ ¹⁵ ^]) and thus may not be entirely correct. Either way, it has no bearing on our hypothesised process: the co-emitted DMS and ammonia are already spatially and temporally separated owing to the oxidation time for DMS and an extension to this separation while new particles sink back into the MBL is of little consequence at large scales of space and time.