Assessing the flux of different volatile sulfur gases from the ocean to the atmosphere

Kettle, A. J.; Rhee, T.S.; Hobe, Marc von; Poulton, Alex J.; Aiken, J. David; Andreae, Meinrat O.

doi:10.1029/2000jd900630

Cited by 86 publications

(105 citation statements)

References 77 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Rosing et al (2010) asserted that DMS fluxes would be low in the Archean, but there may well have been other biological and chemical sources of the sulphuric acid on which water condenses (DMS is a precursor to this). For example, methyl mercaptan is produced abundantly by bacteria (Kettle et al, 2001). Observations of clouds show that the effective radius rarely becomes larger that 15 µm (Bréon et al, 2002), which implies that regionally low CCN flux does not lead to very large droplets.…”

Section: Discussionmentioning

confidence: 99%

“…The climatic feedbacks involving DMS (Charlson et al, 1987) have been subject of long debate. Whilst DMS is prevalent today due to production by eukaryotes, other biogenic sulphur gases are produced by bacteria, in particular hydrogen sulphide (H 2 S) and methyl mercaptan (CH 3 SH) (Kettle et al, 2001). These will react chemically to form sulphates, which will provide CCN.…”

Section: Cloud Particle Sizementioning

confidence: 99%

See 1 more Smart Citation

Clouds and the Faint Young Sun Paradox

Goldblatt

Zahnle

2011

Clim. Past

View full text Add to dashboard Cite

Abstract. We investigate the role which clouds could play in resolving the Faint Young Sun Paradox (FYSP). Lower solar luminosity in the past means that less energy was absorbed on Earth (a forcing of −50 W m −2 during the late Archean), but geological evidence points to the Earth having been at least as warm as it is today, with only very occasional glaciations. We perform radiative calculations on a single global mean atmospheric column. We select a nominal set of three layered, randomly overlapping clouds, which are both consistent with observed cloud climatologies and reproduced the observed global mean energy budget of Earth. By varying the fraction, thickness, height and particle size of these clouds we conduct a wide exploration of how changed clouds could affect climate, thus constraining how clouds could contribute to resolving the FYSP. Low clouds reflect sunlight but have little greenhouse effect. Removing them entirely gives a forcing of +25 W m −2 whilst more modest reduction in their efficacy gives a forcing of +10 to +15 W m −2 . For high clouds, the greenhouse effect dominates. It is possible to generate +50 W m −2 forcing from enhancing these, but this requires making them 3.5 times thicker and 14 K colder than the standard high cloud in our nominal set and expanding their coverage to 100% of the sky. Such changes are not credible. More plausible changes would generate no more than +15 W m −2 forcing. Thus neither fewer low clouds nor more high clouds can provide enough forcing to resolve the FYSP. Decreased surface albedo can contribute no more than +5 W m −2 forcing. Some models which have been applied to the FYSP do not include clouds at all. These overestimate the forcing due to increased CO 2 by 20 to 25% when pCO 2 is 0.01 to 0.1 bar.

show abstract

Section: Discussionmentioning

confidence: 99%

Section: Cloud Particle Sizementioning

confidence: 99%

Clouds and the Faint Young Sun Paradox

Goldblatt

Zahnle

2011

Clim. Past

View full text Add to dashboard Cite

show abstract

“…The net result is a positive annual mean flux that peaks in high and mid latitude oceans (Kettle et al, 2002;Kjellström, 1998). Response of the oceanic net flux to changing climate would involve a combination of physical factors affecting photochemical production, hydrolysis and air/sea gas exchange, such as solar irradiance, sea surface temperature, wind speed, and mixed layer depth, and also biological changes that influence the production and cycling of dissolved organic matter and biogenic gases (Kettle et al, 2001). It is unlikely that the processes contributing to the oceanic flux of COS will all respond to a changing climate in the same direction.…”

Section: Sourcesmentioning

confidence: 99%

“…The sources of tropospheric COS include direct terrestrial and oceanic emissions of COS and production in the atmosphere from the oxidation of carbon disulfide (CS 2 ) and dimethyl sulfide (DMS) (Barnes et al, 1994;Chin, 1991;Patroescu et al, 1999). The oceans are both a source and sink of atmospheric COS, with strong latitudinal and seasonal dependence, and a net air/sea flux that is a strong source to the atmosphere (Kettle et al, 2001;Ulshöfer et al, 1995;Weiss et al, 1995;Yvon-Lewis and Published by Copernicus Publications on behalf of the European Geosciences Union.…”

Section: Introductionmentioning

confidence: 99%

Carbonyl sulfide in air extracted from a South Pole ice core: a 2000 year record

et al. 2008

View full text Add to dashboard Cite

Abstract. In this study, we present carbonyl sulfide (COS) measurements from an ice core drilled near South Pole, East Antarctica (SPRESSO). The samples are from 135–291 m, with estimated mean COS ages ranging from 278 to 2155 years before present (defined as 2000 C.E.). When combined with the previous records of COS from Antarctic ice cores and firn air, the current data provide a continuous record of COS extending beyond the last two millennia. The general agreement between ice cores, firn air, and modern air measurements supports the idea that polar ice is a valid archive for paleoatmospheric COS. The average COS mixing ratio of the SPRESSO data set is (331±18) ppt (parts per trillion in mol/mol, ±1σ, n=100), excluding 6 outliers. These data confirm earlier firn air and ice core measurements indicating that the late 20th century COS levels of 500 ppt are greatly increased over preindustrial levels and represent the highest atmospheric levels over the past 2000 years. The data also provide evidence of climate-related variability on centennial time-scales, with relative maxima at the peaks of Medieval Climate Anomaly and Little Ice Age. There is evidence for a long-term increasing trend in COS of 1.8 ppt per 100 years. Further ice core studies will be needed to determine whether this trend reflects secular variability in atmospheric COS, or a slow post-depositional chemical loss of COS in the ice core.

show abstract

“…This particular system was chosen because organosulfur compounds, generated from biological processes in the oceans and from agricultural, industrial, and domestic activities (23)(24)(25)(26)(27), form MSA alongside sulfuric acid when oxidized in air (3,28). Although it is known that ammonia and amines enhance particle formation from sulfuric acid (14-19, 29, 30), the effect of amines on MSA chemistry has not been reported.…”

mentioning

confidence: 99%

Simplified mechanism for new particle formation from methanesulfonic acid, amines, and water via experiments and ab initio calculations

Dawson

Varner

Perraud

et al. 2012

Proc. Natl. Acad. Sci. U.S.A.

191

251

View full text Add to dashboard Cite

Airborne particles affect human health and significantly influence visibility and climate. A major fraction of these particles result from the reactions of gaseous precursors to generate low-volatility products such as sulfuric acid and high-molecular weight organics that nucleate to form new particles. Ammonia and, more recently, amines, both of which are ubiquitous in the environment, have also been recognized as important contributors. However, accurately predicting new particle formation in both laboratory systems and in air has been problematic. During the oxidation of organosulfur compounds, gas-phase methanesulfonic acid is formed simultaneously with sulfuric acid, and both are found in particles in coastal regions as well as inland. We show here that: (i) Amines form particles on reaction with methanesulfonic acid, (ii) water vapor is required, and (iii) particle formation can be quantitatively reproduced by a semiempirical kinetics model supported by insights from quantum chemical calculations of likely intermediate clusters.Such an approach may be more broadly applicable in models of outdoor, indoor, and industrial settings where particles are formed, and where accurate modeling is essential for predicting their impact on health, visibility, and climate.kinetics modeling | multi-component nucleation | cluster enthalpy | flow tube reactor | atmospheric nanoparticles U nderstanding how gas phase precursors lead to the formation and growth of new particles that are important for scattering light, for serving as cloud condensation or ice nuclei, and for transport deep into the lung, is one of the most pressing scientific problems (1-5). The most studied system is the conversion of gas-phase SO 2 to sulfuric acid and sulfate particles, but even in this case, models typically underestimate particle formation by an order of magnitude or more (3, 4, 6). However, an accurate predictive capability based on molecular-level understanding is critical for projecting the impacts of particles and developing optimal control strategies.Classical nucleation theory (CNT) has been used for almost a century (7, 8) to predict new particle formation. At its heart, CNT is a thermodynamics approach that assumes that the precursor clusters have bulk liquid properties such as surface tension, and that addition to and evaporation from the clusters occurs via monomers. Modifications to CNT using kinetics approaches have been described (9, 10). More recently, dynamical nucleation theory (11-13) examined intermolecular interactions and used them to obtain rate constants for the individual steps through variational transition-state theory. This theory has been applied to particle formation in relatively simple systems and clusters of relatively few molecules. Recent data from field and laboratory studies, however, suggest that multicomponent systems with multiple reaction steps are likely involved in new particle formation in the atmosphere (14-22).We report here a combination of experimental and theoretical studies of new particle fo...

show abstract

Assessing the flux of different volatile sulfur gases from the ocean to the atmosphere

Cited by 86 publications

References 77 publications

Clouds and the Faint Young Sun Paradox

Clouds and the Faint Young Sun Paradox

Carbonyl sulfide in air extracted from a South Pole ice core: a 2000 year record

Simplified mechanism for new particle formation from methanesulfonic acid, amines, and water via experiments and ab initio calculations

Contact Info

Product

Resources

About