Oceanic Dimethyl Sulfide Research Articles

Enhanced Production of Oceanic Dimethylsulfide Resulting from CO2-Induced Grazing Activity in a High CO2 World

Oceanic dimethylsulfide (DMS) released to the atmosphere affects the Earth's radiation budget through the production and growth of cloud condensation nuclei over the oceans. However, it is not yet known whether this negative climate feedback mechanism will intensify or weaken in oceans characterized by high CO(2) levels and warm temperatures. To investigate the effects of two emerging environmental threats (ocean acidification and warming) on marine DMS production, we performed a perturbation experiment in a coastal environment. Two sets of CO(2) and temperature conditions (a pCO(2) of ∼900 ppmv at ambient temperature conditions, and a pCO(2) of ∼900 ppmv at a temperature ∼3 °C warmer than ambient) significantly stimulated the grazing rate and the growth rate of heterotrophic dinoflagellates (ubiquitous marine microzooplankton). The increased grazing rate resulted in considerable DMS production. Our results indicate that increased grazing-induced DMS production may occur in high CO(2) oceans in the future.

A first appraisal of prognostic ocean DMS models and prospects for their use in climate models

Ocean dimethylsulfide (DMS) produced by marine biota is the largest natural source of atmospheric sulfur, playing a major role in the formation and evolution of aerosols, and consequently affecting climate. Several dynamic process‐based DMS models have been developed over the last decade, and work is progressing integrating them into climate models. Here we report on the first international comparison exercise of both 1D and 3D prognostic ocean DMS models. Four global 3D models were compared to global sea surface chlorophyll and DMS concentrations. Three local 1D models were compared to three different oceanic stations (BATS, DYFAMED, OSP) where available time series data offer seasonal coverage of chlorophyll and DMS variability. Two other 1D models were run at one site only. The major point of divergence among models, both within 3D and 1D models, relates to their ability to reproduce the summer peak in surface DMS concentrations usually observed at low to mid‐ latitudes. This significantly affects estimates of global DMS emissions predicted by the models. The inability of most models to capture this summer DMS maximum appears to be constrained by the basic structure of prognostic DMS models: dynamics of DMS and dimethylsulfoniopropionate (DMSP), the precursor of DMS, are slaved to the parent ecosystem models. Only the models which include environmental effects on DMS fluxes independently of ecological dynamics can reproduce this summer mismatch between chlorophyll and DMS. A major conclusion of this exercise is that prognostic DMS models need to give more weight to the direct impact of environmental forcing (e.g., irradiance) on DMS dynamics to decouple them from ecological processes.

Quantification of DMS aerosol-cloud-climate interactions using the ECHAM5-HAMMOZ model in a current climate scenario

Abstract. The contribution of ocean dimethyl sulfide (DMS) emissions to changes in cloud microphysical properties is quantified seasonally and globally for present day climate conditions using an aerosol-chemistry-climate general circulation model, ECHAM5-HAMMOZ, coupled to a cloud microphysics scheme. We evaluate DMS aerosol-cloud-climate linkages over the southern oceans where anthropogenic influence is minimal. The changes in the number of activated particles, cloud droplet number concentration (CDNC), cloud droplet effective radius, cloud cover and the radiative forcing are examined by analyzing two simulations: a baseline simulation with ocean DMS emissions derived from a prescribed climatology and one in which the ocean DMS emissions are switched off. Our simulations show that the model realistically simulates the seasonality in the number of activated particles and CDNC, peaking during Southern Hemisphere (SH) summer coincident with increased phytoplankton blooms and gradually declining with a minimum in SH winter. In comparison to a simulation with no DMS, the CDNC level over the southern oceans is 128% larger in the baseline simulation averaged over the austral summer months. Our results also show an increased number of smaller sized cloud droplets during this period. We estimate a maximum decrease of up to 15–18% in the droplet radius and a mean increase in cloud cover by around 2.5% over the southern oceans during SH summer in the simulation with ocean DMS compared to when the DMS emissions are switched off. The global annual mean top of the atmosphere DMS aerosol all sky radiative forcing is −2.03 W/m2, whereas, over the southern oceans during SH summer, the mean DMS aerosol radiative forcing reaches −9.32 W/m2.

A chemical ionization mass spectrometer for continuous underway shipboard analysis of dimethylsulfide in near-surface seawater

Abstract. A compact, low-cost atmospheric pressure, chemical ionization mass spectrometer ("mini-CIMS") has been developed for continuous underway shipboard measurements of dimethylsulfide (DMS) in seawater. The instrument was used to analyze DMS in air equilibrated with flowing seawater across a porous Teflon membrane equilibrator. The equilibrated gas stream was diluted with air containing an isotopically-labeled internal standard. DMS is ionized at atmospheric pressure via proton transfer from water vapor, then declustered, mass filtered via quadrupole mass spectrometry, and detected with an electron multiplier. The instrument described here is based on a low-cost residual gas analyzer (Stanford Research Systems), which has been modified for use as a chemical ionization mass spectrometer. The mini-CIMS has a gas phase detection limit of 220 ppt DMS for a 1 min averaging time, which is roughly equivalent to a seawater DMS concentration of 0.1 nM DMS at 20°C. The mini-CIMS has the sensitivity, selectivity, and time response required for underway measurements of surface ocean DMS over the full range of oceanographic conditions. The simple, robust design and relatively low cost of the instrument are intended to facilitate use in process studies and surveys, with potential for long-term deployment on research vessels, ships of opportunity, and large buoys.

On the relationship between ocean DMS and solar radiation

[1] Biologically produced dimethylsulfide (DMS) is an important source of sulfur to the marine atmosphere that may affect cloud formation and properties. DMS is involved in a complex set of biochemical transformations and ecological exchanges so its global distribution is influenced by numerous factors, including oxidative stress from UV radiation. We re-examine correlations between global surface DMS concentrations and mixed layer solar radiation dose (SRD), and find that SRD accounts for only a very small fraction (14%) of total variance in DMS measurements when using minimal aggregation methods. Moreover this relationship arises in part from the fact that when mixed layers deepen, both SRD and DMS decrease. When we control for this confounding effect, the correlation between DMS and SRD is reduced even further. These results indicate that factors other than solar irradiance play a leading role in determining global DMS emissions.

Open ocean DMS air/sea fluxes over the eastern South Pacific Ocean

Abstract. Air/sea fluxes of dimethylsulfide (DMS) were measured by eddy correlation over the Eastern South Pacific Ocean during January 2006. The cruise track extended from Manzanillo, Mexico, along 110° W, to Punta Arenas, Chile. Bulk air and surface ocean DMS levels were also measured and gas transfer coefficients (kDMS) were computed. Air and seawater DMS measurements were made using chemical ionization mass spectrometry (API-CIMS) and a gas/liquid membrane equilibrator. Mean surface seawater DMS concentrations were 3.8±2.2 nM and atmospheric mixing ratios were 340±370 ppt. The air/sea flux of DMS was uniformly out of the ocean, with an average value of 12±15 μmol m−2 d−1. Sea surface concentration and flux were highest around 15° S, in a region influenced by shelf waters and lowest around 25° S, in low chlorophyll gyre waters. The DMS gas transfer coefficient exhibited a linear wind speed-dependence over the wind speed range of 1 to 9 m s−1. This relationship is compared with previously measured estimates of k from DMS, CO2, and dual tracer data from the Atlantic and Pacific Ocean, and with the NOAA/COARE gas transfer model. The model generated slope of k vs. wind speed is at the low end of those observed in previous DMS field studies.

Influence of oceanic dimethyl sulfide emissions on cloud condensation nuclei concentrations and seasonality over the remote Southern Hemisphere oceans: A global model study

We use a global chemical transport model with size‐resolved aerosol microphysics to investigate the sources of cloud condensation nuclei (CCN) in the Southern Hemisphere remote marine boundary layer (MBL). Long‐term observations of CCN number at Cape Grim (40°41′S, 144°41′E) show a clear seasonal cycle with a 2–3 times higher concentration in summer than in winter, which has been attributed to seasonal changes in the dimethyl sulfide (DMS) ocean‐to‐atmosphere flux. We find that this cycle at Cape Grim and also throughout the 30°–45°S latitude band is caused mostly by changes in the regional‐scale DMS ocean water concentration. In this latitude band, DMS emissions increase the simulated CCN concentrations from November to April, with a maximum effect of 46% in January (calculated at 0.23% supersaturation). Farther south, the impact of DMS on CCN is apparent only from December to February and increases the CCN concentration at most by 18% at 45°–60°S and by 40% at 60°–75°S. These model‐derived contributions of DMS to Southern Ocean summertime CCN are smaller than the 80% derived from correlations between satellite‐observed chlorophyll and column CCN, which we explain in terms of nonlinear behavior of CCN from the free troposphere (FT). We show that the main microphysical pathway of DMS influence on CCN number is nucleation of DMS‐derived H2SO4 in the FT and subsequent growth of formed particles by condensation and coagulation during entrainment into the MBL. Our simulations suggest that >90% of the increase in MBL CCN when DMS is added to the model is formed in this way. The growth of ultrafine sea spray particles to CCN sizes due to condensation of DMS‐derived H2SO4 in the MBL affects the simulated CCN concentrations by less than 6%. Overall, entrainment of nucleated sulfate aerosol into the MBL from the FT accounts for 43–65% of the summer zonal mean CCN concentrations but only 7–20% of the winter CCN over the Southern Hemisphere oceans.

Weak response of oceanic dimethylsulfide to upper mixing shoaling induced by global warming

The solar radiation dose in the oceanic upper mixed layer (SRD) has recently been identified as the main climatic force driving global dimethylsulfide (DMS) dynamics and seasonality. Because DMS is suggested to exert a cooling effect on the earth radiative budget through its involvement in the formation and optical properties of tropospheric clouds over the ocean, a positive relationship between DMS and the SRD supports the occurrence of a negative feedback between the oceanic biosphere and climate, as postulated 20 years ago. Such a natural feedback might partly counteract anthropogenic global warming through a shoaling of the mixed layer depth (MLD) and a consequent increase of the SRD and DMS concentrations and emission. By applying two globally derived DMS diagnostic models to global fields of MLD and chlorophyll simulated with an Ocean General Circulation Model coupled to a biogeochemistry model for a 50% increase of atmospheric CO(2) and an unperturbed control run, we have estimated the response of the DMS-producing pelagic ocean to global warming. Our results show a net global increase in surface DMS concentrations, especially in summer. This increase, however, is so weak (globally 1.2%) that it can hardly be relevant as compared with the radiative forcing of the increase of greenhouse gases. This contrasts with the seasonal variability of DMS (1000-2000% summer-to-winter ratio). We suggest that the "plankton-DMS-clouds-earth albedo feedback" hypothesis is less strong a long-term thermostatic system than a seasonal mechanism that contributes to regulate the solar radiation doses reaching the earth's biosphere.

Substrate kinetics of DMSP-lyases in axenic cultures and mesocosm populations of Emiliania huxleyi

Most oceanic dimethyl sulphide (DMS) is produced through the enzymatic cleavage of dimethylsulphoniopropionate (DMSP), a process governed by the activity of DMSP-lyases in algae and bacteria. Laboratory and field experiments with the DMS-producing coccolithophorid Emiliania huxleyi have advanced our understanding of algal DMSP lyases. However, despite their central role in the global biogeochemical cycle of sulphur, little is known about the physiological and biochemical properties of this group of isozymes. Here we investigate the apparent substrate kinetic properties of two axenic E. huxleyi cultures (CCMP 373 and CCMP 379) under two light conditions and a mesocosm assemblage dominated by this species. Assays of in vivo and in vitro DMSP-lyase activity (DLA) were used to estimate the kinetic parameters Km and Vmax. Whereas in vivo DLA was not detected in CCMP 379, both laboratory cultures showed high DLA during in vitro tests. The mesocosm population was initially characterised by low substrate affinity (low Vmax and high Km), but shifted to a high affinity community when more dissolved DMSP became available after the collapse of the E. huxleyi bloom. At natural DMSP concentrations, DMS production is probably more affected by changes in Km than Vmax and future studies should include further investigations of the kinetic properties of DMSP-lyases.

Interannual variability of dimethylsulfide in air and seawater and its atmospheric oxidation by‐products (methanesulfonate and sulfate) at Dumont d'Urville, coastal Antarctica (1999–2003)

A multiple year‐round study of atmospheric dimethyl sulfide (DMS) (from December 1998 to April 2003) as well as sulfur‐derived aerosols (methanesulfonic acid (MSA) and non‐sea‐salt sulfate) (from March 1991 to February 2003) was conducted at Dumont d'Urville, coastal Antarctica. The three sulfur‐derived species exhibit a seasonal cycle characterized by maxima in midsummer (January). Whereas the interannual variability of winter levels remains low, a strong interannual variability is shown in summer, particularly for DMS and MSA, and to a lesser extent for non‐sea‐salt sulfate. Over the 1998–2003 time period, January 2002 stands out with high values for all sulfur species. These interannual variabilities of atmospheric summer levels are examined in the light of seawater chlorophyll a content derived from Sea‐viewing Wide Field‐of‐view Sensor (SeaWiFS) data (themselves compared to field measurements made south of 60°S), oceanic DMS levels estimated from chlorophyll a SeaWiFS data, and various sea‐ice indices.

Eddy correlation measurements of the air/sea flux of dimethylsulfide over the North Pacific Ocean

Shipboard measurements of air/sea fluxes and sea surface concentrations of dimethylsulfide (DMS) were made over the tropical and midlatitude North Pacific Ocean. Atmospheric pressure chemical ionization mass spectrometry was used to measure DMS levels in ambient air and in air equilibrated with surface seawater drawn from a depth of 5 m. Air/sea fluxes were obtained using eddy covariance. Corrections and uncertainties involved in the calculation of fluxes from shipboard data are discussed. The surface ocean DMS concentrations measured during this study ranged from 1 to 10 nM, and atmospheric mixing ratios ranged from 20 to 1000 ppt. Air/sea fluxes ranged from 0.47 to 39 μmol m−2 d−1. Most of the variance in the fluxes can be accounted for by variations in sea surface concentration (37%) and wind speed (19%). Gas transfer coefficients derived from the measurements are generally consistent with those derived from deliberate inert gas tracer experiments and eddy covariance measurements of CO2. The gas transfer coefficients exhibit wind speed dependence, but the variance in the data is sufficiently large that they do not constrain the functionality of the wind speed dependence of gas exchange.

What controls the oceanic dimethylsulfide (DMS) cycle? A modeling approach

We implemented a process‐based DMS module into the global carbon cycle ocean model (HAMOCC5) which includes a simple module for plankton dynamics and investigated the regional and seasonal variations of the marine sulfur cycle. The turnover rates within the DMS cycle are only poorly known. Therefore we developed, on the basis of a global DMS data set, an optimization routine for the free parameters controlling DMS production and removal. The resulting seasonal and regional distributions of DMS concentration are fully consistent with the underlying hydrodynamical and biogeochemical processes. We investigated a series of DMS model approaches with various complexities. The distinction between different DMS producing phytoplankton species and the consideration of the regionally and seasonally varying bacterial activity on converting dDMSP to DMS and on DMS consumption appears to have a crucial effect on the quality of the results in the given model conception.

Establishment of Long-Term Preservation for Dimethyl Sulfide by the Solid-Phase Microextraction Method

Dimethyl sulfide (DMS) derived from marine biological activity affects radiative forcing of the climate. The general analytical technique for DMS in seawater (purge and trap analytical method, P&T) is complex onboard ship. Thus it is difficult to obtain sufficient data for a comprehensive understanding of the spatiotemporal variability of DMS in the sea surface layer. On the other hand, a new analytical method for DMS using SPME (solid-phase microextraction) has recently been developed as an alternative method to P&T. This method is simpler than P&T because no special or complex apparatus is needed. If it is possible to preserve DMS for an extended period in excess of the duration of the cruise, the SPME method is a promising method for measuring DMS in seawater. We assessed an analytical method which can allow us to preserve DMS on the long-term scale using SPME. In liquid nitrogen (-196 degrees C), as preserved environment, for a period of 20 days after sampling, we found the preservation rate of DMS to be 94.7 +/- 4.4% (n = 6) in this study. Furthermore, estimating the distribution coefficient with respect to the effect of salinity on SPME, we found that DMS changed by 0.1 nM/% sal, suggesting that salinity has only a minor influence on oceanic DMS measurements in the open ocean because the minimal change of the open ocean salinity is within 2 %. Applying the SPME method to open ocean samples, we found that there were no significant differences in DMS between the unpreserved and preserved samples (r = 0.99, n = 26, SE = 0.01, p < 0.0001), showing the SPME method has potential for use for open ocean surveys.

What controls CCN seasonality in the Southern Ocean? A statistical analysis based on satellite‐derived chlorophyll and CCN and model‐estimated OH radical and rainfall

A 3‐year time series set (from January 2002 to December 2004) of monthly means of satellite‐derived chlorophyll (CHL) and cloud condensation nuclei (CCN), as well as model outputs of hydroxyl radical (OH), rainfall amount (RAIN), and wind speed (WIND) for the Southern Ocean (SO, 40°S–60°S) is analyzed in order to explain CCN seasonality. Chlorophyll is used as a proxy for oceanic dimethylsulfide (DMS) emissions since both climatological aqueous DMS and atmospheric methanesulfonate (MSA) concentrations are tightly coupled with chlorophyll seasonality over the Southern Ocean. OH is included as the main atmospheric oxidant of DMS to produce CCN, and rainfall amount as the main loss factor for CCN through aerosol scavenging. Wind speed is used as a proxy for sea salt (SS) particles production. The CCN concentration seasonality is characterized by a clear pattern of higher values during austral summer and lower values during austral winter. Linear and multiple regression analyses reveal high significant correlations between CCN and the product of chlorophyll and OH (in phase) and rainfall amount (in antiphase). Also, CCN concentrations are anticorrelated with wind speed, which shows very little variability and a slight wintertime increase, in agreement with the sea salt seasonality reported in the literature. Finally, the fraction of the total aerosol optical depth contributed by small particles (ETA) exhibits a seasonality with a 3.5‐fold increase from austral winter to austral summer. The biogenic contribution to CCN is estimated to vary between 35% (winter) and 80% (summer). Sea salt particles, although contributing an important fraction of the CCN burden, do not play a role in controlling CCN seasonality over the SO. These findings support the central role of biogenic DMS emissions in controlling not only the number but also the variability of CCN over the remote ocean.

Seasonal and regional comparison of oceanic and atmospheric dimethylsulfide in the northern North Pacific: Dilution effects on its concentration during winter

Concentrations of dimethylsulfide (DMS) in the mixed layer depth (MLD) and in the atmospheric boundary layer (ABL) and carbon disulfide (CS2) and carbonyl sulfide (COS) in the ABL were measured in the northern North Pacific during summer (July–September 1997) and autumn‐winter (November–December 1998). Seasonal and regional variability in sea surface DMS was roughly explained by a simple dilution model (DMS × MLD = constant). Temporal and spatial comparison of COS and CS2 suggests that during autumn‐winter, there would be strong perturbation by transport of terrestrial polluted air masses from the free troposphere (FT) into the ABL. The seasonal difference in the DMS budget in the ABL was assessed by the time series mass‐balance model. This calculation showed that during autumn‐winter, most DMS supplied from the ocean should have escaped from the ABL, while during summer, most DMS should be oxidized in the ABL. Our results suggest the possibility that the strong seasonality of oceanic and atmospheric DMS might be produced mainly by dilution effects due to strong mixing during winter.

Behaviour of the ocean DMS(P) pools in the Sargasso Sea viewed in a coupled physical-biogeochemical ocean model

The dimethylsulfide (DMS) production model NODEM (Northern Oceans DMS Emission Model) was coupled with the water column ocean model GOTM (General Ocean Turbulence Model) that includes a two-equation k–ε turbulence scheme. This coupled physical-biogeochemical ocean model represents a significant improvement over the previous uncoupled version of NODEM that was driven by a diagnostic vertical mixing scheme. Using the same set of biogeochemical parameters, the coupled model is used to simulate the annual cycles of 1992 and 1993 at Hydrostation S in the Sargasso Sea. The better reproduction of the turbulent mixing environment corrects some deficiencies in nitrogen cycling, especially in the seasonal evolution of the nutrient concentrations. Hence, the coupled model captures the late-winter chlorophyll- and DMS(P)-rich blooms. It is also more adept at reproducing the vertical distribution of chlorophyll and DMS(P) in summer. Moreover, the DMS pool becomes less dependent on parameters controlling the nitrogen cycle and relatively more sensitive to parameters related to the sulfur cycle. Finally, the coupled model reproduces some of the observed differences in DMS(P) pools between 1992 and 1993, the latter being an independent data set not used in calibrating the initial version of NODEM.

Assessment of a global climatology of oceanic dimethylsulfide (DMS) concentrations based on SeaWiFS imagery (1998-2001)

A method is developed to estimate sea-surface particulate dimethylsulfoniopropionate (DMSPp) and dimethylsulfide (DMS) concentrations from sea-surface concentrations of chlorophyll a (Chl a). When compared with previous studies, the 1° × 1° global climatology of oceanic DMS concentrations computed from 4 years (1998–2001) of Chl a measurements derived from SeaWiFS (satellite-based, sea-viewing wide field of view sensor) exhibits lower seasonal variability in the southern hemisphere than in the northern hemisphere. A first evaluation of the method shows that it reasonably well represents DMSPp and DMS in the North Atlantic subtropical gyre, in large blooms of mixed populations of diatoms and Phaeocystis spp., and in massive blooms of Phaeocystis spp. but fails for large, almost pure blooms of diatoms. DMSPp and DMS concentrations derived from SeaWiFS were also compared with spatially and temporally coincident in situ measurements acquired independently in the Atlantic between 39°N and 45°N and in subtropical and subantarctic Indian Ocean surface waters. Moderate spring and summer phytoplankton blooms there exhibited similar trends in DMSPp and DMS levels vs. moderate blooms of mixed populations of prymnesiophytes and dinoflagellates investigated by others. Measured DMS largely exceeded simulated DMS concentrations, whereas measured and simulated DMSPp levels were in close agreement. DMS accumulation is tentatively attributed to dinoflagellate DMSP lyase activity.

DMS atmospheric concentrations and sulphate aerosol indirect radiative forcing: a sensitivity study to the DMS source representation and oxidation

Abstract. The global sulphur cycle has been simulated using a general circulation model with a focus on the source and oxidation of atmospheric dimethylsulphide (DMS). The sensitivity of atmospheric DMS to the oceanic DMS climatology, the parameterisation of the sea-air transfer and to the oxidant fields have been studied. The importance of additional oxidation pathways (by O3 in the gas- and aqueous-phases and by BrO in the gas phase) not incorporated in global models has also been evaluated. While three different climatologies of the oceanic DMS concentration produce rather similar global DMS fluxes to the atmosphere at 24-27 Tg S yr -1, there are large differences in the spatial and seasonal distribution. The relative contributions of OH and NO3 radicals to DMS oxidation depends critically on which oxidant fields are prescribed in the model. Oxidation by O3 appears to be significant at high latitudes in both hemispheres. Oxidation by BrO could be significant even for BrO concentrations at sub-pptv levels in the marine boundary layer. The impact of such refinements on the DMS chemistry onto the indirect radiative forcing by anthropogenic sulphate aerosols is also discussed.

The sulfur cycle at high‐southern latitudes in the LMD‐ZT General Circulation Model

This modeling study was motivated by the recent publication of year‐round records of dimethylsulfide (DMS) and dimethylsulfoxide (DMSO) in Antarctica, completing the available series of sulfate and methanesulfonic acid (MSA). Sulfur chemistry has been incorporated in the Laboratoire de Météorologie Dynamique‐Zoom Tracers (LMD‐ZT) Atmospheric General Circulation Model (AGCM), with high‐resolution and improved physics at high‐southern latitudes. The model predicts the concentration of six major sulfur species through emissions, transport, wet and dry deposition, and chemistry in both gas and aqueous phases. Model results are broadly realistic when compared with measurements in air and snow or ice, as well as to results of other modeling studies, at high‐ and middle‐southern latitudes. Atmospheric MSA concentrations are underestimated and DMSO concentrations are overestimated in summer, reflecting the lack of a DMSO heterogeneous sink leading to MSA. Experiments with various recently published estimates of the rate of this sink are reported. Although not corrected in this work, other defects are identified and discussed: DMS concentrations are underestimated in winter, MSA and non‐sea‐salt (nss) sulfate concentrations may be underestimated at the South Pole, the deposition scheme used in the model may not be adapted to polar regions, and the model does not adequately reproduces interannual variability. Oceanic DMS sources have a major contribution to the variability of sulfur in these regions. The model results suggest that in a large part of central Antarctica ground‐level atmospheric DMS concentrations are larger in winter than in summer. At high‐southern latitudes, high loads of DMS and DMSO are found and the main chemical sink of sulfur dioxide (SO2) is aqueous oxidation by ozone (O3), whereas oxidation by hydrogen peroxide (H2O2) dominates at the global scale. A comprehensive modeled sulfur budget of Antarctica is provided.

Influence of wind speed averaging on estimates of dimethylsulfide emission fluxes

The effect of various wind speed averaging periods on calculated dimethylsulfide (DMS) emission fluxes is quantitatively assessed. A global climate model and an emission flux module were run in stand‐alone mode for a full year. Twenty‐minute instantaneous surface wind speeds and related variables generated by the climate model were archived, and corresponding 1‐hour, 6‐hour, daily, and monthly averaged quantities were calculated. These various time‐averaged, model‐derived quantities were used as inputs in the emission flux module, and DMS emissions were calculated using two expressions for the mass transfer velocity commonly used in atmospheric models [Liss and Merlivat, 1986; Nightingale et al., 2000]. Results indicate that the time period selected for averaging wind speeds can affect the magnitude of calculated DMS emission fluxes. A number of individual marine cells within the global grid show DMS emissions fluxes that are 10–60% higher when emissions are calculated using 20‐min instantaneous model time step winds rather than monthly averaged wind speeds, and at some locations the differences exceed 200%. Many of these cells are located in the Southern Hemisphere where anthropogenic sulfur emissions are low and changes in oceanic DMS emissions may significantly affect calculated aerosol concentrations and aerosol radiative forcing.