Model Simulations on the Variability of Particulate MSA to Non-Sea-Salt Sulfate Ratio in the Marine Environment

A box model was constructed to investigate connections between the particulate MSA to non-sea-salt sulfate ratio, R, and DMS chemistry in a clean marine boundary layer. The simulations demonstrated that R varies widely with particle size, which must be taken into account when interpreting field measurements or comparing them with each other. In addition to DMS gas-phase chemistry, R in the submicron size range was shown to be sensitive to the factors dictating sulfate production via cloud processing, to the removal of SO₂ from the boundary layer by dry deposition and sea-salt oxidation, to the entrainment of SO₂ from the free troposphere, to the relative concentration of sub- and supermicron particles, and to meteorology. Three potential explanations for the increase of R toward high-latitudes during the summer were found: larger MSA yields from DMS oxidation at high latitudes, larger DMSO yields from DMS oxidation followed by the conversion of DMSO to MSA at high latitudes, or lower ambient H₂O₂ concentrations at high latitudes leading to less efficient sulfate production in clouds. Possible reasons for the large seasonal amplitude of R at mid and high latitudes include seasonal changes in the partitioning of DMS oxidation to the OH and NO₃ initiated pathways, seasonal changes in the concentration of species participating the DMS-OH reaction pathway, or the existence of a SO₂ source other than DMS oxidation in the marine boundary layer. Even small anthropogenic perturbations were shown to have a potential to alter the MSA to non-sea-salt sulfate ratio.     

Sources,transport, and sinks of SO<Subscript>2</Subscript> over the equatorial Pacific during the Pacific Atmospheric Sulfur Experiment

The Pacific Atmospheric Sulfur Experiment (PASE) is the first sulfur-budget field experiment to feature simultaneous flux measurements of DMS marine emissions and SO₂ deposition to the ocean surface. We make use of these data to constrain a 1-D chemical transport model to study the production and loss pathways for DMS and SO₂ over the equatorial Pacific. Model results suggest that OH is the main sink for DMS in the boundary layer (BL), and the average DMS-to-SO₂ conversion efficiency is ~73%. In an exploratory run involving the addition of 1 pptv of BrO as a second oxidant, a 14% increase in the DMS flux is needed beyond that based on OH oxidation alone. This BrO addition also reduces the DMS-to-SO₂ conversion efficiency from 73% to 60%. The possibility of non-DMS sources of marine sulfur influencing the estimated conversion efficiency was explored and found to be unconvincing. For BL conditions, SO₂ losses consist of 48% dry deposition, while transport loss to the BuL and aerosol scavenging each account for another 19%. The conversion of SO₂ to H₂SO₄ consumes the final 14%. In the BuL, cloud scavenging removes 85% of the SO₂, thus resulting in a decreasing vertical profile for SO₂. The average SO₂ dry deposition velocity from direct measurements (i.e., 0.36 cm sec⁻¹) is approximately 50% of what is calculated from the 1-D model and the global GEOS-Chem model. This suggests that the current generation of global models may be significantly overestimating SO₂ deposition rates over some tropical marine areas. Although the specific mechanism cannot be determined, speculation here is that the dry deposition anomalous results may point to the presence of a micro-surface chemical phenomenon involving partial saturation with either S(IV) and/or S(VI) DMS oxidation products. This could also appear as a pH drop in the ocean’s surface microfilm layer in this region. Finally, we propose that the enhanced SO₂ level observed in the lower free troposphere versus that in the upper BuL during PASE is most likely the result of transported DMS/SO₂-rich free-tropospheric air parcels from the east of the PASE sampling area, rather than an inadequate representation in the model of local convection.     

A global three-dimensional model of the tropospheric sulfur cycle

The tropospheric part of the atmospheric sulfur cycle has been simulated in a global three-dimensional model. The model treats the emission, transport, chemistry, and removal processes for three sulfur components; DMS (dimethyl sulfide), SO₂ and SO₄ ^2– (sulfate). These processes are resolved using an Eulerian transport model, the MOGUNTIA model, with a horizontal resolution of 10° longitude by 10° latitude and with 10 layers in the vertical between the surface and 100 hPa. Advection takes place by climatological monthly mean winds. Transport processes occurring on smaller space and time scales are parameterized as eddy diffusion except for transport in deep convective clouds which is treated separately. The simulations are broadly consistent with observations of concentrations in air and precipitation in and over polluted regions in Europe and North America. Oxidation of DMS by OH radicals together with a global emission of 16 Tg DMS-S yr^–1 from the oceans result in DMS concentrations consistent with observations in the marine boundary layer. The average turn-over times were estimated to be 3, 1.2–1.8, and 3.2–6.1 days for DMS, SO₂, and SO₄ ^2– respectively.     

Dimethylsulfide oxidation and the ratio of methanesulfonate to non sea-salt sulfate in the marine aerosol

A box model of DMS oxidation in the clean, low-NO _x marine atmospheric boundary layer has been used to predict the latitude dependence of the aerosol methanesulfonate to non sea-salt sulfate ratio. The observed latitude dependence of this ratio in the Southern Hemisphere can be reproduced reasonably well if the full suite of reactions proposed by Yin et al. (1990a) is employed, and a strong temperature dependence is specified in the rates of decomposition of CH₃SO₂ and CH₃SO₃ radicals.     

DMS and SO2 Measurements in the Tropical Marine Boundary Layer

Dimethyl sulfide (DMS) and sulfur dioxide (SO₂) mixing ratios were measured in the boundary layer on Oahu, Hawaii in April and May 2000. Average DMS and SO₂ levels were 22 ± 7 (n = 488) pmol/mol and 23 ± 7 (n = 471) pmol/mol respectively. Anti-correlated DMS and SO₂ diurnal cycles, consistent with DMS + OH oxidation were observed on most days. Photochemical box model simulations suggest that the yield of SO₂ and total SO₂ sink are ∼85% and ∼2 × 10⁴ molec cm^{− 3} s^{− 1} respectively. On several days the rate of decrease in DMS and increase in SO₂ levels in the early morning were larger that predicted by the model. Dynamical and chemical causes for the anomalous early morning data are explored.     

Sulfur dioxide in the tropical marine boundary layer: dry deposition and heterogeneous oxidation observed during the Pacific Atmospheric Sulfur Experiment

Research flights with the National Center for Atmospheric Research (NCAR) C-130 airborne laboratory were conducted over the equatorial ocean during the Pacific Atmospheric Sulfur Experiment (PASE). The focused, repetitive flight plans provided a unique opportunity to explore the principal pathways of sulfur processing in remote marine environments in close detail. Fast airborne measurements of SO₂ using the Drexel University APIMS (Atmospheric Pressure Ionization Mass Spectrometer) instrument further provided unprecedented insight into the complete budget of this important sulfur gas. In general, turbulent mixing in the marine boundary layer (MBL) continuously depletes SO₂ due to the shallow convection of the tropical trade wind regime by venting the gas into the buffer layer (BuL) above. However, on nearly one-third of the flights a net import of SO₂ into the MBL from the BuL was observed. Concurrent measurements of the DMS budget allowed for a heterogeneous S(IV) oxidation rate to be inferred from the SO₂ budget residual. The average heterogeneous loss rate was found to be 0.05 h⁻¹, which taken in conjunction with the observed aerosol surface area distributions and O₃ levels indicates that the supermicron aerosols maintain a near neutral pH. The average dry deposition velocity of SO₂ was found to be 0.4 cm s⁻¹, about 30% lower than predicted by standard parameterizations. The yield of SO₂ from DMS oxidation was found to be near unity. The mission averages indicate that approximately 57% of the SO₂ in the MBL is lost to aerosols, 27% is subject to dry deposition, 7% is mixed into the BuL, and 10% is oxidized by OH.     

DMS and SO2 at Baring Head, New Zealand: Implications for the Yield of SO2 from DMS

Atmospheric dimethyl sulfide (DMS) and sulfur dioxide (SO₂) concentrations were measured at Baring Head, New Zealandduring February and March 2000. Anti-correlated DMS and SO₂ diurnalcycles, consistent with the photochemical production of SO₂ from DMS, were observed in clean southerly air off the ocean. The data is used to infer a yield of SO₂ from DMS oxidation. The estimated yields are highly dependent on assumptions about the DMS oxidation rate. Fitting the measured data in a photochemical box model using model-generated OH levels and the Hynes et al. (1986) DMS + OH rate constant suggests that theSO₂ yield is 50–100%, similar to current estimates for the tropical Pacific.However, the observed amplitude of the DMS diurnal cycle suggests that the oxidation rate is higher than that used by the model, and therefore, that theSO₂ yield is lower in the range of 20–40%.     

Numerical study of the oxidation process of dimethylsulfide in the marine atmosphere

A box model, involving simple heterogeneous reaction processes associated with the production of non-sea-salt sulfate (nss-SO ₄ ^2– ) particles, is used to investigate the oxidation processes of dimethylsulfide (DMS or CH₃SCH₃) in the marine atmosphere. The model is applied to chemical reactions in the atmospheric surface mixing layer, at intervals of 15 degrees latitude between 60° N and 60° S. Given that the addition reaction of the hydroxyl radical (OH) to the sulfur atom in the DMS molecule is faster at lower temperature than at higher temperature and that it is the predominant pathway for the production of methanesulfonic acid (MSA or CH₃SO₃H), the results can well explain both the increasing tendency of the molar ratio of MSA to nss-SO ₄ ^2– toward higher latitudes and the uniform distribution with latitude of sulfur dioxide (SO₂). The predicted production rate of MSA increases with increasing latitude due to the elevated rate constant of the addition reaction at lower temperature. Since latitudinal distributions of OH concentration and DMS reaction rate with OH are opposite, a uniform production rate of SO₂ is realized over the globe. The primary sink of DMS in unpolluted air is caused by the reaction with OH. Reaction of DMS with the nitrate radical (NO₃) also reduces DMS concentration but it is less important compared with that of OH. Concentrations of SO₂, MSA, and nss-SO ₄ ^2– are almost independent of NO _x concentration and radiation field. If dimethylsulfoxide (DMSO or CH₃S(O)CH₃) is produced by the addition reaction and further converted to sulfuric acid (H₂SO₄) in an aqueous solution of cloud droplets, the oxidation process of DMSO might be important for the production of aerosol particles containing nss-SO ₄ ^2– at high latitudes.     

A Study of DMS Oxidation in the Tropics: Comparison of Christmas Island Field Observations of DMS, SO2, and DMSO with Model Simulations

This study reports comparisonsbetween model simulations, based on current sulfurmechanisms, with the DMS, SO₂ and DMSOobservational data reported by Bandy et al.(1996) in their 1994 Christmas Island field study. For both DMS and SO₂, the model results werefound to be in excellent agreement with theobservations when the observations were filtered so asto establish a common meteorological environment. Thisfiltered DMS and SO₂ data encompassedapproximately half of the total sampled days. Basedon these composite profiles, it was shown thatoxidation of DMS via OH was the dominant pathway withno more than 5 to 15% proceeding through Cl atoms andless than 3% through NO₃. This analysis wasbased on an estimated DMS sea-to-air flux of 3.4 ×10⁹ molecs cm^-2 s^-1. The dominant sourceof BL SO₂ was oxidation of DMS, the overallconversion efficiency being evaluated at 0.65 ± 0.15. The major loss of SO₂ was deposition to theocean's surface and scavenging by aerosol. Theresulting combined first order k value was estimated at 1.6 × 10^-5 s^-1. In contrast to the DMSand SO₂ simulations, the model under-predictedthe observed DMSO levels by nearly a factor of 50. Although DMSO instrument measurement problems can notbe totally ruled out, the possibility of DMSO sourcesother than gas phase oxidation of DMS must beseriously considered and should be explored in futurestudies.     

Sulfur dioxide and dimethyl sulfide in the central Pacific troposphere

Boundary-layer and free-troposphere measurements of sulfur dioxide, dimethyl sulfide, and carbon disulfide were made during transits of the central and southern Pacific Ocean between Hawaii and Australia. Sulfur dioxide was generally less than 100 pptv and highly variable with no correlation with respect to geographic location or altitude. Dimethyl sulfide in the boundary layer had a concentration range of <10 to 200 pptv. Highest concentrations of DMS were in the equatorial region of the southern hemisphere although the concentrations were dependent on location and meteorological regime. In the region of the Fiji Islands several boundary layer samples had SO₂, DMS, and CS₂. In 1989, additional SO₂ measurements were made between Hawaii and the equator and to the west of Hawaii downwind of the Kilauea volcano plumes.Paper submitted to the 7th International Symposium of the Commission for Atmospheric Chemistry and Global Pollution on the Chemistry of the Global Atmosphere held in Chamrousse, France, from 5 to 11 September 1990.     

Field study of dimethylsulfide oxibation in the boundary layer: Variations of dimethylsulfide,methanesulfonic acid,sulfur dioxide,non-sea-salt sulfate and aitken nuclei at a coastal site

Measurements of atmospheric dimethylsulfide (DMS) and its oxidation products, sulfur dioxide (SO₂), methanesulfonic acid (MSA) and non-sea-salt sulfate (nss-SO₄ ^2-) were monitored during the period June 9–26, 1989 at a coastal site in Brittany. As indicated by the radon (Rn-222) activities and the high concentrations of NOx the air masses, for most of the experiment, were continental in origin. The observed concentrations range from 1.9 to 65 nmol/m³ for DMS (n=157), 0.6 to 94.2 nmol/m³ for SO₂ (n=50), 0.6 to 11.6 nmol/m³ for MSA (n=44) and 42 to 350 nmol/m³ for nss-SO₄ ^2- (n=44). Aitken nuclei reached values as high as 4.5 × 10⁵ particles/m³. When continental conditions predominated, the measured SO₂ concentrations were lower than those expected from a consideration of the observed DMS concentrations and the existence of SO₂ background of the continental air masses. Similarly, compared to the MSA/DMS ratio in the marine atmosphere, higher concentrations of MSA were observed than those expected from the measured levels of DMS. The presence of enhanced levels of MSA was also endorsed by the observation that the measured mean MSA/nss-SO₄ ^2- ratio of 6±3% was similar to the mean value of 6.9% observed in the marine atmosphere. These above observations are in line with recent laboratory findings by Barnes et al. (1988), which show an increase of the MSA/DMS yield with a simultaneous decrease of the SO₂/DMS yield in the presence of NOx.     

Covariations in oceanic dimethyl sulfide,its oxidation products and rain acidity at Amsterdam Island in the Southern Indian Ocean

Simultaneous measurements of rain acidity and dimethyl sulfide (DMS) at the ocean surface and in the atmosphere were performed at Amsterdam Island over a 4 year period. During the last 2 years, measurements of sulfur dioxide (SO₂) in the atmosphere and of methane sulfonic acid (MSA) and non-sea-salt-sulfate (nss-SO₄ ^2-) in rainwater were also performed. Covariations are observed between the oceanic and atmospheric DMS concentrations, atmospheric SO₂ concentrations, wet deposition of MSA, nss-SO₄ ^2-, and rain acidity. A comparable summer to winter ratio of DMS and SO₂ in the atmosphere and MSA in precipitation were also observed. From the chemical composition of precipitation we estimate that DMS oxidation products contribute approximately 40% of the rain acidity. If we consider the acidity in excess, then DMS oxidation products contribute about 55%.     

Low Ozone Episodes at Amphitrite Point Marine Boundary Layer Observatory,British Columbia,Canada

At Amphitrite Point, ozone (O₃) mixing ratios are observed to drop steadily to 5–15?ppb over a period of 12 hours or less with a frequency approaching one event per week (with highest frequencies occurring in summer and fall). Analysis of 47 such O₃ depletion events reveals that low O₃ episodes are a predominantly nocturnal phenomenon associated with anticyclonic conditions characterized by light onshore or alongshore winds and an absence of fog and mist. Back-trajectories show air carried to the Amphitrite Point Observatory (APO) during depletion events remains in the marine boundary layer and is not brought to the surface from aloft. There is no strong correlation with other “criteria” pollutants (CO, NO_x, SO₂, PM_2.5) that might be indicative of a mechanism for O₃ destruction linked to human, terrestrial, or marine pollutant sources. However, CO₂ mixing ratios are observed to increase, coincident with O₃ depletion. Together, these results point to a natural marine boundary layer phenomenon in which O₃ destruction dominates O₃ production and/or replenishment by vertical mixing. While there are several candidate mechanisms, the conditions for O₃ depletion (and CO₂ buildup) to occur are set by meteorology and, in particular, development of a stable marine boundary layer in which vertical mixing is suppressed. Support for this interpretation is provided by simultaneous increases in CO₂ in the stable marine boundary that are indicative of an important role played by marine biogenic processes (respiration). Future research should be directed at elucidating the chemical mechanisms responsible for O₃ destruction in the coastal zone, which means that there would be a need for a much broader range of measurements at APO (including halogenated species) as well as offshore measurements of both chemical and marine boundary layer meteorological variables.     

Pacific Atmospheric Sulfur Experiment (PASE): dynamics and chemistry of the south Pacific tropical trade wind regime

The Pacific Atmospheric Sulfur Experiment (PASE) was a comprehensive airborne study of the chemistry and dynamics of the tropical trade wind regime (TWR) east of the island of Kiritibati (Christmas Island, 157º, 20?? W, 2º 52?? N). Christmas Island is located due south of Hawaii. Geographically it is in the northern hemisphere yet it is 6?C12º south of the intertropical convergence zone (ITCZ) which places it in the southern hemisphere meteorologically. Christmas Island trade winds in August and September are from east south east at 3?C15 ms^?1. Clouds, if present, are fair weather cumulus located in the middle layer of the TWR which is frequently labeled the buffer layer (BuL). PASE provided clear support for the idea that small particles (80 nm) were subsiding into the tropical trade wind regime (TWR) where sulfur chemistry transformed them to larger particles. Sulfur chemistry promoted the growth of some of these particles until they were large enough to activate to cloud drops. This process, promoted by sulfur chemistry, can produce a cooling effect due to the increase in cloud droplet density and changes in cloud droplet size. These increases in particle size observed in PASE promote additional cooling due to direct scattering from the aerosol. These potential impacts on the radiation balance in the TWR are enhanced by the high solar irradiance and ocean albedo of the TWR. Finally because of the large area involved there is a large factional impact on earth??s radiation budget. The TWR region near Christmas Island appears to be similar to the TWR that persists in August and September, from southwest of the Galapagos to at least Christmas Island. Transport in the TWR between the Galapagos and Christmas involves very little precipitation which could have removed the aerosol thus explaining at least in part the high concentrations of CCN (??300 at 0.5% supersaturation) observed in PASE. As expected the chemistry of sulfur in the trade winds was found to be initiated by the emission of DMS into the convective boundary layer (BL, the lowest of three layers). However, the efficiency with which this DMS is converted to SO₂ has been brought into further question by this study. This unusual result has come about as result of our using two totally different approaches for addressing this long standing question. In the first approach, based on accepted kinetic rate constants and detailed steps for the oxidation of DMS reflecting detailed laboratory studies, a DMS to SO₂ conversion efficiency of 60?C73% was determined. This range of values lies well within the uncertainties of previous studies. However, using a completely different approach, involving a budget analysis, a conversion value of 100% was estimated. The latter value, to be consistent with all other sulfur studies, requires the existence of a completely independent sulfur source which would emit into the atmosphere at a source strength approximately half that measured for DMS under tropical Pacific conditions. At this time, however, there is no credible scientific observation that identifies what this source might be. Thus, the current study has opened for future scientific investigation the major question: is there yet another major tropical marine source of sulfur? Of equal importance, then, is the related question, is our global sulfur budget significantly in error due to the existence of an unknown marine source of sulfur? Pivotal to both questions may be gaining greater insight about the intermediate DMS oxidation species, DMSO, for which rather unusual measurements have been reported in previous marine sulfur studies. The 3 pptv bromine deficit observed in PASE must be lost over the lifetime of the aerosol which is a few days. This observation suggests that the primary BrO production rate is very small. However, considering the uncertainties in these observations and the possible importance of secondary production of bromine radicals through aerosol surface reactions, to completely rule out the importance of bromine chemistry under tropical conditions at this time cannot be justified. This point has been brought into focus from prior work that even at levels of 1 pptv, the effect of BrO oxidation on DMS can still be quite significant. Thus, as in the case of DMS conversion to SO₂, future studies will be needed. In the latter case there will need to be a specific focus on halogen chemistry. Such studies clearly must involve specific measurements of radical species such as BrO.     

Airborne measurements of dimethylsulfide,sulfur dioxide,and aerosol ions over the Southern Ocean South of Australia

Vertical distributions of dimethylsulfide (DMS), sulfur dioxide (SO₂), aerosol methane-sulfonate (MSA), non-sea-salt sulfate (nss-SO₄ ^2-), and other aerosol ions were measured in maritime air west of Tasmania (Australia) during December 1986. A few cloudwater and rainwater samples were also collected and analyzed for major anions and cations. DMS concentrations in the mixed layer (ML) were typically between 15–60 ppt (parts per trillion, 10^–12; 24 ppt=1 nmol m^–3 (20°C, 1013 hPa)) and decreased in the free troposphere (FT) to about <1–2.4 ppt at 3 km. One profile study showed elevated DMS concentrations at cloud level consistent with turbulent transport (cloud pumping) of air below convective cloud cells. In another case, a diel variation of DMS was observed in the ML. Our data suggest that meteorological rather than photochemical processes were responsible for this behavior. Based on model calculations we estimate a DMS lifetime in the ML of 0.9 days and a DMS sea-to-air flux of 2–3 mol m^–2 d^–1. These estimates pertain to early austral summer conditions and southern mid-ocean latitudes. Typical MSA concentrations were 11 ppt in the ML and 4.7–6.8 ppt in the FT. Sulfur-dioxide values were almost constant in the ML and the lower FT within a range of 4–22 ppt between individual flight days. A strong increase of the SO₂ concentration in the middle FT (5.3 km) was observed. We estimate the residence time of SO₂ in the ML to be about 1 day. Aqueous-phase oxidation in clouds is probably the major removal process for SO₂. The corresponding removal rate is estimated to be a factor of 3 larger than the rate of homogeneous oxidation of SO₂ by OH. Model calculations suggest that roughly two-thirds of DMS in the ML are converted to SO₂ and one-third to MSA. On the other hand, MSA/nss-SO₄ ^2- mole ratios were significantly higher compared to values previously reported for other ocean areas suggesting a relatively higher production of MSA from DMS oxidation over the Southern Ocean. Nss-SO₄ ^2- profiles were mostly parallel to those of MSA, except when air was advected partially from continental areas (Africa, Australia). In contrast to SO₂, nss-SO₄ ^2- values decreased significantly in the middle FT. NH₄ ⁺/nss-SO₄ ^2- mole ratios indicate that most non-sea-salt sulfate particles in the ML were neutralized by ammonium.     

Observation of DMSO and CH3S(O)OH from the gas phase reaction between DMS and OH

Products and mechanisms have been investigated for the reactions between dimethylsulfide (DMS) and dimethylsulfoxide (DMSO) and the hydroxyl radical (OH) in the presence of NO_x. All of the experiments were performed in a 480 L reaction chamber, applying Fourier transform infrared spectroscopy (FT-IR) and ion chromatography as the analytical techniques.In addition to the sulfur containing products that are known to be produced from the gas phase reaction between DMS and OH (SO₂, dimethylsulfone, methylsulfonyl peroxynitrate, methanesulfonic acid, H₂SO₄), DMSO and methanesulfinic acid (CH₃S(O)OH) were also observed as products. Only SO₂, DMSO₂ and methylsulfonyl peroxynitrate were found as sulfur containing products in the reaction between DMSO and OH. Based on these new results we propose a mechanism for the atmospheric oxidation of DMS and DMSO by OH radical.     

Seasonal variations of atmospheric sulfur dioxide and dimethylsulfide concentrations at Amsterdam Island in the southern Indian Ocean

Daily measurements of atmospheric sulfur dioxide (SO₂) concentrations were performed from March 1989 to January 1991 at Amsterdam Island (37°50 S–77°30 E), a remote site located in the southern Indian Ocean. Long-range transport of continental air masses was studied using Radon (²²²Rn) as continental tracer. Average monthly SO₂ concentrations range from less than 0.2 to 3.9 nmol m^-3 (annual average = 0.7 nmol m^-3) and present a seasonal cycle with a minimum in winter and a maximum in summer, similar to that described for atmospheric DMS concentrations measured during the same period. Clear diel correlation between atmospheric DMS and SO₂ concentrations is also observed during summer. A photochemical box model using measured atmospheric DMS concentrations as input data reproduces the seasonal variations in the measured atmospheric SO₂ concentrations within ±30%. Comparing between computed and measured SO₂ concentrations allowed us to estimate a yield of SO₂ from DMS oxidation of about 70%.     

Shipboard measurements of atmospheric dimethylsulfide and hydrogen sulfide in the Caribbean and Gulf of Mexico

Simultaneous shipboard measurements of atmospheric dimethylsulfide and hydrogen sulfide were made on three cruises in the Gulf of Mexico and the Caribbean. The cruise tracks include both oligotrophic and coastal waters and the air masses sampled include both remote marine air and air masses heavily influenced by terrestrial or coastal inputs. Using samples from two north-south Caribbean transects which are thought to represent remote subtropical Atlantic air, mean concentrations of DMS and H₂S were found to be 57 pptv (74 ng S m^-3, =29 pptv, n=48) and 8.5 pptv (11 ng S m^-3, =5.3 pptv, n=36), respectively. The ranges of measured concentrations for all samples were 0–800 pptv DMS and 0–260 pptv H₂S. Elevated concentrations were found in coastal regions and over some shallow waters. Statistical analysis reveals slight nighttime maxima in the concentrations of both DMS and H₂S in the remote marine atmosphere. The diurnal nature of the H₂S data is only apparent after correcting the measurements for interference due to carbonyl sulfide. Calculations using the measured ratio of H₂S to DMS in remote marine air suggest that the oxidation of H₂S contributes only about 11% to the excess (non-seasalt) sulfate in the marine boundary layer.     

Vertical distribution of dimethylsulfide,sulfur dioxide,aerosol ions,and radon over the Northeast Pacific Ocean

Dimethylsulfide (DMS), sulfur dioxide (SO₂), methanesulfonate (MSA), nonsea-salt sulfate (nss-SO₄ ^2–), sodium (Na⁺), ammonium (NH₄ ⁺), and nitrate (NO₃ ^–) were determined in samples collected by aircraft over the open ocean in postfrontal maritime air masses off the northwest coast of the United States (3–12 May 1985). Measurements of radon daughter concentrations and isentropic trajectory calculations suggested that these air masses had been over the Pacific for 4–8 days since leaving the Asian continent. The DMS and MSA profiles showed very similar structures, with typical concentrations of 0.3–1.2 and 0.25–0.31 nmol m^–3 (STP) respectively in the mixed layer, decreasing to 0.01–0.12 and 0.03–0.13 nmol m^–3 (STP) at 3.6 km. These low atmospheric DMS concentrations are consistent with low levels of DMS measured in the surface waters of the northeastern Pacific during the study period.The atmospheric SO₂ concentrations always increased with altitude from <0.16–0.25 to 0.44–1.31 nmol m^–3 (STP). The nonsea-salt sulfate (ns-SO₄ ^2–) concentrations decreased with altitude in the boundary layer and increased again in the free troposphere. These data suggest that, at least under the conditions prevailing during our flights, the production of SO₂ and nss-SO₄ ^2– from DMS oxidation was significant only within the boundary layer and that transport from Asia dominated the sulfur cycle in the free troposphere. The existence of a sea-salt inversion layer was reflected in the profiles of those aerosol components, e.g., Na⁺ and NO₃ ^–, which were predominantly present as coarse particles. Our results show that long-range transport at mid-tropospheric levels plays an important role in determining the chemical composition of the atmosphere even in apparently remote northern hemispheric regions.     

Uncertainty and sensitivity analyses of OH-initiated dimethyl sulphide (DMS) oxidation kinetics

A numerical experiment has been conducted on the OH-initiated tropospheric oxidation of DMS. This involved the selection of a set of reactions describing the OH-initiated oxidation kinetics and the conversion of the present level of uncertainty of the system into uncertainty ranges and distributions for the relevant system parameters (kinetic constants and initial concentrations). Uncertainties have been propagated through the model onto the output variables of interest. This has allowed (a) the uncertainty in model prediction to be quantified and compared with observations (uncertainty analysis) and (b) the relative importance of each input parameter in determining the output uncertainty to be quantified (sensitivity analysis). Output considered were the ratio of MSA/(SO₂ + H₂SO₄) concentration at a given time, the ratio SO₂/H₂SO₄, the total peroxynitrate species concentrations and the relative fraction of SO₂ and H₂SO₄ formed through the various pathways. Conditional upon the model and data assumptions underlying the experiment, the following main conclusions were drawn:

1. The possibility of direct formation of SO₃ without SO₂ as intermediate as suggested by Bandyet al. (1992) and Yinet al. (1990), involving direct thermal decomposition of CH₃SO₃ · does not seem to play a major role in the overall generation of sulphate. This is relevant to the issue of gas to particle conversion over remote areas.
2. Reaction of CH₃SOO · intermediate may be the most important pathway to the formation of SO₂.
3. The dominating peroxynitrate is CH₃S(O)₂O₂NO₂.

Through sensitivity analysis the kinetic constants have been identified which — because of their uncertainty and of their impact on the output — mostly contribute to the output uncertainty.