Trichlorofluoromethane (CCl₃F; CFC-11) and dichlorodifluoromethane (CCl₂F₂; CFC-12) have been widely used as tracers of oceanic circulation and mixing on decadal timescales. In order to estimate their transfer rate across the air-sea interface, liquid-phase diffusion coefficients are needed In this study the diffusivities of CFC-11 and CFC-12 in pure water were measured over the temperature range 0.6–30°C. Diffusivities of CFC-11 in pure water ranged from (5.24±0.25)×10⁻⁶ cm²S⁻¹ at 0.6°C to (1.13±0.05)×10⁻⁵ cm²S⁻¹ at 30.3°C and a fit to the data yielded the equation D _CFC-11 = 0.015 exp (−18.1/RT), where R is the universal gas constant in kJ mol⁻¹ K⁻¹ and T is the temperature in Kelvin. Diffusivities of CFC-12 in pure water ranged from (5.38±0.22)×10⁻⁶ cm² s⁻¹ at 0.6°C to (1.26±0.05)×10⁻⁵ cm² s⁻¹at 30.3°C and the temperature dependence can be expressed as D_CFC-12= 0.036 exp (−20.1/RT). The estimated uncertainty in both equations is <3%. Experiments were also carried out in seawater for each compound. For CFC-11 the diffusivity in seawater was not significantly different from that in pure water. However, the diffusivity of CFC-12 in seawater was found to be 7.2±3.0% lower than that in pure water. Schmidt numbers for both CFC-11 and CFC-12 in pure water and seawater were estimated from the data.

Measurements of seawater dimethylsulfide (DMS), atmospheric dimethylsulfide, and sulfur dioxide (SO₂) were made on board the R/VDiscoverer in the Southern Ocean, southeast of Australia, as part of the First Aerosol Characterization Experiment (ACE 1). The measurements covered a latitude range of 40°S–55°S during November-December 1995. Seawater DMS concentrations ranged from 0.4 to 6.8 nM, with a mean of 1.7±1.1 nM (1σ). The highest DMS concentrations were found in subtropical convergence zone waters north of 44°S, and the lowest were found in polar waters south of 49°S. In general, seawater DMS concentrations increased during the course of the study, presumably due to the onset of austral spring warming. Atmospheric DMS concentrations ranged from 24 to 350 parts per trillion by volume (pptv), with a mean of 112±61 pptv (1σ). Atmospheric SO₂ was predominantly of marine origin with occasional anthropogenic input, as evidenced by correlation with elevated ²²²Rn and air mass trajectories. Concentrations ranged from 3 to 1000 pptv with a mean of 48.8± 49 pptv (1σ) and a median 15.8 pptv. The mean SO₂ concentration observed in undisturbed marine air was 11.9±7.6 pptv (1σ), and the mean DMS to SO₂ ratio in these conditions was 13±9 (1σ). Diurnal variations in SO₂ were observed, with a daytime maximum and early morning minimum in agreement with model simulations of DMS oxidation in the marine boundary layer. Steady state calculations and photochemical box model simulations suggest that the DMS to SO₂ conversion efficiency in this region is 30–50%. Comparison of these results with results from warmer regions suggests that the DMS to SO₂ conversion efficiency has a positive temperature dependence.

We present a detailed evaluation of the atmospheric sulfur cycle simulated in the Georgia Tech/Goddard Global Ozone Chemistry Aerosol Radiation and Transport (GOCART) model. The model simulations of SO₂, sulfate, dimethylsulfide (DMS), and methanesulfonic acid (MSA) are compared with observations from different regions on various timescales. The model agrees within 30% with the regionally averaged sulfate concentrations measured over North America and Europe but overestimates the SO₂ concentrations by more than a factor of 2 there. This suggests that either the emission rates are too high, or an additional loss of SO₂ which does not lead to a significant sulfate production is needed. The average wintertime sulfate concentrations over Europe in the model are nearly a factor of 2 lower than measured values, a discrepancy which may be attributed largely to the sea-salt sulfate collected in the data. The model reproduces the sulfur distributions observed over the oceans in both long-term surface measurements and short-term aircraft campaigns. Regional budget analyses show that sulfate production from SO₂ oxidation is 2 to 3 times more efficient and the lifetimes of SO₂ and sulfate are nearly a factor of 2 longer over the ocean than over the land. This is due to a larger free tropospheric fraction of SO₂ column over the ocean than over the land, hence less loss to the surface. The North Atlantic and northwestern Pacific regions are heavily influenced by anthropogenic activities, with more than 60% of the total SO₂ originating from anthropogenic sources. The average production efficiency of SO₂ from DMS oxidation is estimated at 0.87 to 0.91 in most oceanic regions.