Atmospheric Dimethylsulfide Concentrations Research Articles

The sensitivity of Southern Ocean atmospheric dimethyl sulfide (DMS) to modeled oceanic DMS concentrations and emissions

Abstract. The biogeochemical formation of dimethyl sulfide (DMS) from the Southern Ocean is complex, dynamic, and driven by physical, chemical, and biological processes. Such processes, produced by marine biogenic activity, are the dominant source of sulfate aerosol over the Southern Ocean. Using an atmosphere-only configuration of the United Kingdom Earth System Model (UKESM1-AMIP), we performed eight 10-year simulations for the recent past (2009–2018) during austral summer. We tested the sensitivity of atmospheric DMS to four oceanic DMS datasets and three DMS transfer velocity parameterizations. One oceanic DMS dataset was developed here from satellite chlorophyll a. We find that the choice of oceanic DMS dataset has a larger influence on atmospheric DMS than the choice of DMS transfer velocity. Simulations with linear transfer velocity parameterizations show a more accurate representation of atmospheric DMS concentration than those using quadratic relationships. This work highlights that the oceanic DMS and DMS transfer velocity parameterizations currently used in climate models are poorly constrained for the Southern Ocean region. Simulations using oceanic DMS derived from satellite chlorophyll a data, and when combined with a recently developed linear transfer velocity parameterization for DMS, show better spatial variability than the UKESM1 configuration. We also demonstrate that capturing large-scale spatial variability can be more important than large-scale interannual variability. We recommend that models use a DMS transfer velocity parameterization that was developed specifically for DMS and improvements to oceanic DMS spatial variability. Such improvements may provide a more accurate process-based representation of oceanic and atmospheric DMS, and therefore sulfate aerosol, in the Southern Ocean region.

High-resolution distribution and emission of dimethyl sulfide and its relationship with pCO2 in the Northwest Pacific Ocean

Ocean-derived dimethyl sulfide (DMS) is widely concerning because of its hypothesized influence on global climate change. This study aims to explore the distribution characteristics and influencing factors of DMS and partial pressure of carbon dioxide (pCO2) in the Northwest Pacific Ocean, as well as the potential relationship between DMS and pCO2. A high-resolution, underway, shipboard measurement device was used to determine the DMS and pCO2 of the surface seawater and atmosphere in the Northwest Pacific and its marginal seas during November 2019. The result show that atmospheric and surface seawater DMS concentrations ranged from 3 to 125 pptv and 0.63 to 2.28 nmol L-1, respectively, with mean values of 46 ± 19 pptv and 1.08 ± 0.34 nmol L-1. The average sea surface pCO2 was 371 ± 16 μatm (range from 332 to 401 μatm). The trends in the surface seawater DMS in different current systems were primarily associated with phytoplankton abundance and composition. Biological activity and physical processes such as cooling jointly influenced the sea surface pCO2. A cold eddy along the transect in the Northwest Pacific Ocean increased DMS at the sea surface by 10% and CO2 uptake by 3%. We found a significant negative correlation between DMS and pCO2 in the Northwest Pacific Ocean at the 0.1° resolution [DMS]seawater = -0.0161[pCO2]seawater + 7.046 (R2 = 0.569, P < 0.01). The DMS and pCO2 sea-air fluxes were estimated to range from 0.04 to 25.3 μmol m-2·d-1 and from -27.0 to 4.22 mmol m-2·d-1 throughout the survey area. The Northwest Pacific Ocean, especially the Oyashio Current, is an important sink of CO2 and a source of DMS.

Modelling the influence of coral-reef-derived dimethylsulfide on the atmosphere of the Great Barrier Reef, Australia

Marine dimethylsulfide (DMS) is an important source of natural sulfur to the atmosphere, with potential implications for the Earth’s radiative balance. Coral reefs are important regional sources of DMS, yet their contribution is not accounted for in global DMS climatologies or in model simulations. This study accounts for coral-reef-derived DMS and investigates its influence on the atmosphere of the Great Barrier Reef (GBR), Australia, using the Australian Community Climate and Earth System Simulator Atmospheric Model version 2 (ACCESS-AM2). A climatology of seawater surface DMS (DMSw) concentration in the GBR and an estimate of direct coral-to-air DMS flux during coral exposure to air at low tide are incorporated into the model, increasing DMS emissions from the GBR region by 0.02 Tg yr-1. Inclusion of coral-reef-derived DMS increased annual mean atmospheric DMS concentration over north-eastern Australia by 29%, contributing to an increase in gas-phase sulfate aerosol precursors of up to 18% over the GBR. The findings suggest that the GBR is an important regional source of atmospheric sulfur, with the potential to influence local-scale aerosol-cloud processes. However, no influence on sulfate aerosol mass or number concentration was detected, even with a reduction in anthropogenic sulfur dioxide emissions, indicating that DMS may not significantly influence the regional atmosphere at monthly, annual or large spatial scales. Further research is needed to improve the representation of coral-reef-derived DMS in climate models and determine its influence on local, sub-daily aerosol-cloud processes, for which observational studies suggest that DMS may play a more important role.

Atmospheric dimethyl sulfide and its significant influence on the sea-to-air flux calculation over the Southern Ocean

Our understanding about the atmospheric dimethyl sulfide (DMS) and its influence to sea-to-air flux calculation in the Southern Ocean is still limited due to insufficient investigations. Herein, high-resolution shipboard underway simultaneous surface seawater and atmospheric DMS measurements were conducted in the Southern Ocean from February 23 to March 31, 2018. A larger variation of DMS levels was found in atmosphere compared with that in seawater. Remarkably, a large-scale area with high seawater and atmospheric DMS concentrations up to 27.9 nM and 3.92 ppbv, respectively, was investigated outside of Ross Sea sector. Atmospheric DMS levels were strongly impacted by wind speed and air mass convection. The relationship between atmospheric DMS and air mass exposure to oceanic chlorophyll varied greatly depending on the area of investigation. Some other regions with high DMS production capacity were examined as well beside those along the cruise tracks based on the results of positive correlations with high slopes and back trajectories. Moreover, significant uncertainty of sea-to-air DMS flux over the Southern Ocean could be caused by follows: (1) the selecting of different gas transfer coefficients; (2) the negative flux values calculated under high atmospheric DMS levels together with low seawater DMS concentrations; and (3) the greatly overestimated flux, approximately 47.1–76.9%, without considering the atmospheric DMS. This study highlights the urgent demand of high-resolution observations of atmospheric DMS over the Southern Ocean to estimate DMS emission with high accuracy.

Quantification of dimethyl sulfide (DMS) production in the sea anemone <i>Aiptasia</i> sp. to simulate the sea-to-air flux from coral reefs

Abstract. The production of dimethyl sulfide (DMS) is poorly quantified in tropical reef environments but forms an essential process that couples marine and terrestrial sulfur cycles and affects climate. Here we quantified net aqueous DMS production and the concentration of its cellular precursor dimethylsulfoniopropionate (DMSP) in the sea anemone Aiptasia sp., a model organism to study coral-related processes. Bleached anemones did not show net DMS production whereas symbiotic anemones produced DMS concentrations (mean ± standard error) of 160.7 ± 44.22 nmol g−1 dry weight (DW) after 48 h incubation. Symbiotic and bleached individuals showed DMSP concentrations of 32.7 ± 6.00 and 0.6 ± 0.19 µmol g−1 DW, respectively. We applied these findings to a Monte Carlo simulation to demonstrate that net aqueous DMS production accounts for only 20 % of gross aqueous DMS production. Monte Carlo-based estimations of sea-to-air fluxes of gaseous DMS showed that reefs may release 0.1 to 26.3 µmol DMS m−2 coral surface area (CSA) d−1 into the atmosphere with 40 % probability for rates between 0.5 and 1.5 µmol m−2 CSA d−1. These predictions were in agreement with directly quantified fluxes in previous studies. Conversion to a flux normalised to sea surface area (SSA) (range 0.1 to 17.4, with the highest probability for 0.3 to 1.0 µmol DMS m−2 SSA d−1) suggests that coral reefs emit gaseous DMS at lower rates than the average global oceanic DMS flux of 4.6 µmol m−2 SSA d−1 (19.6 Tg sulfur per year). The large difference between simulated gross and quantified net aqueous DMS production in corals suggests that the current and future potential for its production in tropical reefs is critically governed by DMS consumption processes. Hence, more research is required to assess the sensitivity of DMS-consumption pathways to ongoing environmental change in order to address the impact of predicted degradation of coral reefs on DMS production in tropical coastal ecosystems and its impact on future atmospheric DMS concentrations and climate.

Direct night-time ejection of particle-phase reduced biogenic sulfur compounds from the ocean to the atmosphere.

The influence of oceanic biological activity on sea spray aerosol composition, clouds, and climate remains poorly understood. The emission of organic material and gaseous dimethyl sulfide (DMS) from the ocean represents well-documented biogenic processes that influence particle chemistry in marine environments. However, the direct emission of particle-phase biogenic sulfur from the ocean remains largely unexplored. Here we present measurements of ocean-derived particles containing reduced sulfur, detected as elemental sulfur ions (e.g., (32)S(+), (64)S2(+)), in seven different marine environments using real-time, single particle mass spectrometry; these particles have not been detected outside of the marine environment. These reduced sulfur compounds were associated with primary marine particle types and wind speeds typically between 5 and 10 m/s suggesting that these particles themselves are a primary emission. In studies with measurements of seawater properties, chlorophyll-a and atmospheric DMS concentrations were typically elevated in these same locations suggesting a biogenic source for these sulfur-containing particles. Interestingly, these sulfur-containing particles only appeared at night, likely due to rapid photochemical destruction during the daytime, and comprised up to ∼67% of the aerosol number fraction, particularly in the supermicrometer size range. These sulfur-containing particles were detected along the California coast, across the Pacific Ocean, and in the southern Indian Ocean suggesting that these particles represent a globally significant biogenic contribution to the marine aerosol burden.

Quantifying the impacts of an updated global dimethyl sulfide climatology on cloud microphysics and aerosol radiative forcing

AbstractOne of the critical parameters in assessing the global impacts of dimethyl sulfide (DMS) on cloud properties and the radiation budget is the estimation of phytoplankton‐induced ocean emissions, which are derived from prescribed, climatological surface seawater DMS concentrations. The most widely used global ocean DMS climatology was published 15 years ago and has recently been updated using a much larger database of observations. The updated climatology displays significant differences in terms of the global distribution and regional monthly averages of sea surface DMS. In this study, we use the ECHAM5‐HAMMOZ aerosol‐chemistry‐climate general circulation model to quantify the influence of the updated DMS climatology in computed atmospheric properties, namely, the spatial and temporal distributions of atmospheric DMS concentration, sulfuric acid concentration, sulfate aerosols, number of activated aerosols, cloud droplet number concentration, and the aerosol radiative forcing at the top of the atmosphere. Significant differences are observed for all the modeled variables. Comparison with observations of atmospheric DMS and total sulfate also shows that in places with large DMS emissions, the updated climatology shows a better match with the observations. This highlights the importance of using the updated climatology for projecting future impacts of oceanic DMS emissions, especially considering that the relative importance of the natural sulfur fluxes is likely to increase due to legislation to “clean up” anthropogenic emissions. The largest estimated differences are in the Southern Ocean, Indian Ocean, and parts of the Pacific Ocean, where the climatologies differ in seasonal concentrations over large geographical areas. The model results also indicate that the former DMS climatology underestimated the effect of DMS on the globally averaged annual aerosol radiative forcing at the top of the atmosphere by about 20%.

Variation of dimethylsulfide mixing ratio over the Southern Ocean from 36°S to 70°S

Atmospheric dimethylsulfide (DMS) was measured to investigate the variation in its concentration over sea ice free oceans and sea ice regions of the Southern Ocean, using a proton transfer reaction-mass spectrometer (PTR-MS) on board the icebreaker Shirase from 1 December 2009 to 16 March 2010. In general, DMS concentrations over sea ice regions were very low compared with those over the sea ice free ocean. However, abrupt increases in DMS concentrations occurred over sea ice regions while the ship was moving and crushing the sea ice. Undoubtedly, the elevated DMS concentrations were caused by large DMS emissions from gaps in the ice made by the ship. During the period when Shirase had anchored off Syowa Station (69°00.4′S, 39°35.3′E), Antarctica, DMS concentrations were not detected. At this time, the surrounding sea of East Ongul island, on which Syowa Station is located, was completely covered with multi-year fast ice. Sea ice probably inhibits DMS emission from the ocean to the atmosphere. In addition, there was no evidence that chlorophyll a concentration in the sea water or wind speed above the sea surface affect atmospheric DMS concentrations over the sea ice free ocean regions.

Relating atmospheric and oceanic DMS levels to particle nucleation events in the Canadian Arctic

[1] Measurements of ocean surface and atmospheric dimethyl sulfide (DMS) and particle size distributions were made in the Canadian Arctic Archipelago during the fall of 2007 and the late summer of 2008 aboard the Canadian Coast Guard Ship Amundsen. Nucleation-mode particles were observed during the 2008 cruise, which took place in the eastern Arctic from August to September when the atmosphere and ocean were more photo-active as compared to the October 2007 transit in the Beaufort Sea during which no nucleation/growth events were observed. The observed nucleation periods in 2008 coincided with high atmospheric and ocean surface DMS concentrations, suggesting that the particles originated from marine biogenic sources. An aerosol microphysics box model was used to simulate nucleation given the measured conditions in the marine boundary layer. Although other sources may have contributed, we find that the newly formed particles can be accounted for by a marine biogenic DMS source for combinations of the following parameters: [OH] ≥ 3 × 105 molecules cm−3, DMS mixing ratio is ≥ 100 pptv, the activation coefficient is ≤ 10−7 and the background particle concentration is ≤ 100 cm−3.

Vertical variability of seawater DMS in the South Pacific Ocean and its implication for atmospheric and surface seawater DMS

Shipboard measurements of atmospheric dimethylsulfide (DMS) and sea surface water DMS were performed aboard the R/V Onnuri across the South Pacific from Santiago, Chile to Fiji in February 2000. Hydrographic profiles of DMS, dissolved dimethylsulfoniopropionate (DMSP d), and particulate DMSP p in the upper 200 m were obtained at 16 stations along the track. Atmospheric and sea surface water DMS concentrations ranged from 3 to 442 pptv and from 0.1 to 19.9 nM, respectively; the mean values of 61 pptv and 2.1 nM, respectively, were comparable to those from previous studies in the South Pacific. The South Pacific Gyre was distinguished by longitudinal-vertical distributions of DMS, DMSP d, and DMSP p, which was thought to be associated with the characteristic modification of biological activities that occurs mainly due to significant change in water temperature. The averaged DMS maximum appeared at 40 m depth, whereas DMSP p and DMSP d maxima coincided with that of dissolved oxygen content at 60–80 m. The sea-to-air fluxes of DMS were estimated to be 0.4–11.3 μmol d −1 m −2 (mean = 2.8 μmol d −1 m −2). A fairly good correlation between atmospheric DMS and sea-to-air DMS flux indicated that atmospheric DMS concentration was more sensitive to change in physical parameters than its photochemical removal process or surface seawater DMS concentrations.

Atmospheric trace gas measurements during SEEDS-II over the northwestern pacific

Abstract Atmospheric trace gas measurements were conducted during SEEDS-II. Atmospheric dimethylsulfide (DMS) was continuously measured by GC-MS during the R/V Hakuho cruise. Further, ambient air was sampled into canisters (42 samples) and analyzed by GC-MS and GC-FID for various biogenic and anthropogenic volatile organic compounds (VOCs) after the cruise. CO, O3, SO2, and NOx were monitored continuously aboard the ship. A fertilization experiment was conducted in a high-nitrate, low-chlorophyll (HNLC) region (48°N, 165°E). The atmospheric concentrations inside a patch (fertilized area) were compared with those outside it (natural area); however, clear differences were not observed for biogenic trace gasses (DMS, CH3Cl, CH3I, isoprene, and alkenes) in the atmosphere. However, a high DMS concentration was observed over the northwestern Pacific Ocean. The fertilized area was also observed by R/V Kilo Moana, and DMS was measured by GC-FPD. A good agreement was observed between the results of the measurements made aboard the two independent ships by different measurement methods. The atmospheric SO2 concentration was compared with the atmospheric DMS concentration. The SO2 concentration was found to vary with the atmospheric DMS concentration. A diurnal variation of the atmospheric DMS concentration was observed around the fertilized region. The DMS content tends to increase during the night and decrease during the day. A box model calculation was conducted to explain the diurnal variation of the atmospheric DMS. Since there was no diurnal variation of the wind speed, a constant DMS flux from the ocean surface was assumed. Further, the atmospheric OH radical concentration was assumed to be dependent on sunlight. The box model can roughly reproduce the atmospheric DMS diurnal variation mainly caused by its removal reaction with OH radicals.

Responses of DMS in the seawater and atmosphere to iron enrichment in the subarctic western North Pacific (SEEDS-II)

Abstract Simultaneous measurements of dimethylsulfide (DMS) in the seawater and atmosphere were conducted during SEEDS-II to investigate the responses of DMS to iron (Fe) fertilization in the subarctic North Pacific. No significant increases in the seawater DMS (DMSw) concentration were observed inside the fertilized patch compared to those outside the patch, while particulate dimethylsulfoniopropionate (DMSPp) concentration inside the patch increased 2-fold compared to those outside the patch in the phytoplankton bloom of major DMSP producers such as prasinophytes, cryptophytes, diatoms and prymnesiophytes. In the decline phase of the bloom, maximum DMSw was observed both inside the patch (ca. 6.2 nM) and outside the patch (ca. 9.3 nM). In this period, increases in mesozooplankton and decreases in the DMSP producers (prymnesiophytes and diatoms) were observed both sides of the patch, but larger inside the patch than outside the patch. Large decreases in the DMSPp inside the patch, which was probably related to the large increases in mesozooplankton inside the patch, did not result in increases in the DMSw concentration. Considering biological and nonbiological parameters, we discussed these results, although they could not be completely explained. Unfortunately, the impact of Fe fertilization on the atmospheric DMS (DMSa) concentration was not detected due to no significant changes in DMSw. However, it is noted that DMSa concentrations were dependent on the sea–air DMS flux in the air from higher latitudes and/or the Eurasian continent, though the DMS flux was a minor role to the budget of DMSw. Therefore if DMSw were significantly changed by Fe fertilization, DMSa might be affected through changes in the sea-air flux in this condition.

Parameter sensitivities in a 1-D model for DMS and sulphur cycling in the upper ocean

We have developed a marine DMS (dimethylsulfide) module and implemented it in a 1-D coupled atmosphere-ocean-biogeochemical model. In developing the marine sulphur model we have found that several parameters used in the model are not known to even an order of magnitude. Our approach is used to test the model's sensitivity to these parameters. A parameter change of ± 25 % is applied to test the respective range of changes in the DMS fluxes. The model is run for a 3-year time period as well as for the time period of the Subarctic Ecosystem Response to Iron Enrichment Study (SERIES) in July 2002. The simulated seasonal cycle is in agreement with available observations: Near surface DMS concentrations vary from 1.5 nmol L - 1 in winter to 13.5 nmol L - 1 in summer. Simulated DMS production is found to be most sensitive to variations of the S:N ratio and the bacterial consumption rate of DMS. Implementing light or UV limited bacterial activity shows a negligible effect in winter and increases DMS concentrations by 0.2– 0.6 nmol L - 1 in summer. Similarly a yield increase under UV stress increases summer values by 1– 2 nmol L - 1 . The simulated diel cycle in surface DMS concentration is no more than 2.5 nmol L - 1 , even when light-dependent changes in bacterial activity are considered. Simulating the DMS response to iron fertilization with the standard run leads to overestimation during an initial bloom of small phytoplankton. While implementing light-dependent bacterial activity has a minor effect, the implementation of yields that depend on nutrient availability significantly improves the results. The model confirms earlier results showing the importance of including atmospheric DMS concentrations in gas flux calculations when there are high surface concentrations and small atmospheric boundary layer heights. Simulated summer concentrations in the upper layer can be underestimated by 2 nmol L - 1 or more if the atmospheric concentration is set to zero. Our study shows that inclusion of mechanistic DMS modules in comprehensive climate models requires better knowledge of the variation of key parameters in the marine sulphur cycle. Even though there are still open questions, the model reasonably reproduces the mean annual cycle; and including variable DMS yield improves the simulation of the DMS response to iron fertilization during SERIES.

Spatial distributions of volatile sulfur compounds in surface seawater and overlying atmosphere in the northwestern Pacific Ocean, eastern Indian Ocean, and Southern Ocean

Distributions of volatile sulfur compounds (carbonyl sulfide (COS), carbon disulfide (CS2), hydrogen sulfide (H2S), dimethyl sulfide (DMS)) in surface seawater and overlying atmosphere were measured in the northwestern Pacific, eastern Indian, and Southern Oceans (40°N–66°S, 40°E–140°E) in November–December 1996 during the 38th Japanese Antarctic Research Expedition cruise. Seawater measurements revealed that DMS was the dominant sulfur compound, with concentrations of 0.5–15.8 nM. High values were found in the Southern Ocean's marginal ice zone (84°E–63°E, 59°S–63°S), suggesting that the area during the bloom acts as an important source of atmospheric DMS. Atmospheric concentrations were 456–471 pptv for OCS, n.d. (not detected level) −13 pptv for CS2, n.d. −17 pptv for H2S, and n.d. −755 pptv for DMS. Concentrations of OCS were nearly constant. Concentrations of CS2 and H2S were high in terrigenic air masses and low in those of oceanic origin. Comparison of atmospheric DMS data and a steady state box model using sea‐to‐air fluxes of DMS and assumed OH radical concentrations revealed that atmospheric DMS concentrations in the equatorial region and most of the Southern Ocean were balanced with local oceanic emission residues and photochemical oxidation. Simultaneous measurements in the atmosphere showed DMS was the dominant sulfur gas that was oxidized rapidly to sulfate aerosols in the marine atmosphere.

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.

Chemical Assessment of Oceanic and Terrestrial Sulfur in the Marine Boundary Layer over the Northern North Pacific during Summer

Dimethylsulfide (DMS) in surface seawater and the air, methanesulfonic acid (MSA) and non-sea-salt sulfate (nss-SO4 2−) in aerosol, and radon-222 (Rn-222) were measured in the northern North Pacific, including the Bering Sea, during summer (13 July – 6 September 1997). The mean atmospheric DMS concentrations in the eastern region (21.0 ± 5.8 nmole/m3 (mean ± S.D.), n=30) and Bering Sea (19.9 ± 9.8 nmole/m3, n=10) were higher than that in the western region (11.1 ± 6.4 nmole/m3, n=31) (p<0.05), although these regions did not significantly differ in the mean DMS concentration in surface seawater. Mean sea-to-air DMS flux in the eastern region (21.0 ± 10.4 μ mole/m2/day, n=19) was larger than those in the western region (11.3 ± 16.9 μ mole /m2/day, n=22) and Bering Sea (11.2 ± 7.8 μ mole/m2/day, n=7) (p<0.05). This suggests that the longitudinal difference in atmospheric DMS was produced by that in DMS flux owing to wind speed, while the possible causes of the higher DMS concentrations in the Bering Sea include (1) later DMS oxidation rates, (2) lower heights of the marine boundary layer, and (3) more inactive convection. The mean MSA concentrations in the eastern region (1.18 ± 0.84 nmole/m3, n=35) and Bering Sea (1.17 ± 0.87 nmole/m3, n=13) were higher than that in the western region (0.49 ± 0.25 nmole/m3, n=28) (p < 0.05). Thus the distribution of MSA was similar to that of DMS, while the nss-SO4 2− concentrations were higher near the continent. This suggests that nss-SO4 2− concentrations were regionally influenced by anthropogenic sulfur input, because the distribution of nss-SO4 2− was similar to that of Rn-222 used as a tracer of continental air masses.

Seasonal variation of dimethylsulfide in the gas phase and of methanesulfonate and non-sea-salt sulfate in the aerosols phase in the Eastern Mediterranean atmosphere

The seasonal variation of gaseous dimethylsulfide (DMS) and its oxidation products (non-sea-salt sulfate (nss-SO 4 2−) and methanesulfonic acid (MSA) have been investigated at a remote coastal location in the Eastern Mediterranean. Daytime atmospheric DMS concentrations were measured in the range 0.3–8.9 nmol m −3 (with an average of 2.35±1.38 nmol m −3, 1 σ uncertainty) and present a well distinguished seasonal cycle with higher values in summer. The seasonal variation of atmospheric DMS is in line with that of seawater DMS concurrently measured in the Cretan Sea. Monthly atmospheric DMS concentrations are significantly correlated with sea-surface temperature. By the mean of a 0-D model based on atmospheric DMS observations, the DMS flux calculated for spring and summer is in reasonable agreement with the fluxes deduced from the seawater DMS data and the wind speed. The diurnal variation of atmospheric DMS was investigated during a 4-day intensive campaign in September 1997 and shows a nighttime minimum, which could be explained by the presence of NO 3 radicals, which are highly reactive towards DMS. Aerosol MSA concentrations varied seasonally from below detection limit (0.04) to 0.99 (average of 0.27±0.15 nmol m −3, 1 σ uncertainty). Similarly aerosol nss-SO 4 2− varied from 0.6 to 123.9 (average of 41.0±17.4 nmol m −3, 1 σ uncertainty). Based on the measured MSA, nss-SO 4 2− and their ratio, the biogenic contribution to nss-SO 4 2− was found to exhibit a well-established seasonal pattern ranging from 1% during winter to 17% during summer.

Diurnal and seasonal variation of atmospheric dimethylsulfoxide at Amsterdam Island in the southern Indian Ocean

Atmospheric dimethylsulfoxide (DMSO), an important dimethylsulfide (DMS) oxidation by‐product, has been monitored on a daily basis at Amsterdam Island in the southern Indian Ocean during three periods (January–September 1997, January–June 1998, and January–October, 1999). In addition, during an intensive experiment carried out in January 1998, DMSO diurnal variation has been studied in conjunction with parallel measurements of atmospheric DMS. Monthly average atmospheric DMSO mixing ratios range from 0.3 to 5.8 parts per trillion by volume and present a well‐distinguished seasonal cycle with a minimum in winter and a maximum in summer similar to that observed for atmospheric DMS simultaneously measured. DMSO presents also a well‐distinguished diurnal variation with maximum values around 0900 and minimum during night. A photochemical box model using measured atmospheric DMS concentrations as input data reproduces quite well the diurnal variation of DMSO when assuming a 50% yield from the DMS+OH addition channel [Hynes and Wine, 1996]. However, in absolute terms the simulated DMSO concentrations were about a factor of 2 higher than those measured. Photochemically driven heterogeneous losses of DMSO on aerosol and/or clouds could account for this difference.

Spatial and temporal variability of atmospheric sulfur‐containing gases and particles during the Albatross campaign

To investigate the oxidation chemistry of dimethylsulfide (DMS) in the marine atmosphere, atmospheric DMS, SO2, as well as several DMS oxidation products in aerosol phase such as non‐sea‐salt sulfate (nss‐SO4), methanesulfonate (MSA), and dimethylsulfoxide (DMSOp) have been measured during the Albatross campaign in the Atlantic Ocean from October 9 to November 2, 1996. Long‐range transport, local sea‐to‐air flux of DMS (FDMS), marine boundary layer (MBL) height variation, and photochemistry were found to be the major factors controlling atmospheric DMS concentration which ranged from 29 to 396 parts per trillion by volume (pptv) (mean of 120±68 pptv) over the cruise. The spatial variability of MSA and DMSOp follows the latitudinal variations of FDMS. A 2‐day period of intensive photochemistry associated with quite stable atmospheric conditions south of the equator allowed the observation of anticorrelated diurnal variations between DMS and its main oxidation products. A chemical box model describing sulfur chemistry in the marine atmosphere was used to reproduce these variations and investigate coherence of experimentally calculated fluxes FDMS with observed DMS atmospheric concentrations. The model results reveal that the measured OH levels are not sufficient to explain the observed DMS daytime variation. Oxidizing species other than OH, probably BrO, must be involved in the oxidation of DMS to reproduce the observed data.

Flux estimation of oceanic dimethyl sulfide around North America

Simultaneous measurements of atmospheric and surface water dimethyl sulfide (DMS) concentrations were taken aboard the icebreaker USCGC Polar Sea from July to October 1994, as part of a joint Canada/United States circumnavigation of North America, an expedition with a unique Arctic Ocean transect. Atmospheric DMS concentrations around North America varied between 0.25 and 50 nmol m−3 (mean = 5.1 nmol m−3, σ = 8.5 nmol m−3, n = 89) with highest values occurring near (south of) the Arctic ice edge. Surface water DMS concentrations ranged between 0.1 and 12.6 nmol L−1 (mean = 2.2 nmol L−1, σ = 2.7 nmol L−1, n = 46) with highest values in the western Arctic Ocean and off the U.S. east coast, near the Sargasso sea. In the Arctic Ocean, maximum concentrations in air and water were found along the ice edge in the Chukchi Sea region. Atmospheric DMS decay rates of 68% per day and 38% per day were deduced from observations between 70° and 76°N (continental shelf and slope of Chukchi Sea) on the west side and between 80° and 90°N (central Arctic Ocean) for the east side of the Arctic Ocean, respectively. Ocean to atmosphere flux estimates of DMS were determined using the Liss‐Merlivat empirical dependence of exchange coefficient on wind speed, DMS air concentrations, Henry's law constants, and DMS water concentrations. DMS fluxes varied between 0.0017 and 30 μmol m−2 d−1, respectively, with higher fluxes in regions with open water. The Arctic Ocean contributed 0.063 Tg S (DMS) (0.4% of DMS from the world oceans) during the summer of 1994. A simple one‐dimensional (1‐D) photochemical box model, applied to six case studies, showed that the atmospheric lifetime of DMS in the high Arctic was 2.5 to 8 days, whereas at 16°–33°N it was 1 to 2 days. Modeled DMS decay rates for these regions, using the 1‐D model, accounted for only 33% of the measured decay rate. This result also suggests that halogen chemistry, reactions with Br/BrO, may be an important sink for DMS in the Arctic atmosphere.