Seasonal and short-term variability in dimethyl sulfide, sulfur dioxide and biogenic sulfur and sea salt aerosol particles in the arctic marine boundary layer during summer and autumn

Abstract

The International Arctic Ocean Expedition (IAOE), lasting from August to mid-October 1991, provided a unique opportunity to characterize and quantify relationships within the natural sulfur cycle in the marine boundary layer under conditions of limited anthropogenic influence. Concentrations of dimethyl sulfide, sulfur dioxide, and submicrometer aerosol concentrations of methane sulfonate, non-sea-salt sulfate, ammonium and elemental carbon ranged from 17 to 0.05 nmol m³ (380–1 ppt(v)), 1.7–0.04 nmol m³ (38–0.9 ppt(v)), 1.4–0.002 nmol m^-3 (31–0.05 ppt(v), 6.9–0.03 nmol m^-3 (155–0.7 ppt(v)), 3.9–0.03 nmol m^-3 (90–0.7 ppt(v)) and 0.51–0.009 nmol m^-3 (11–0.2 ppt(v)), respectively. Observations showed a seasonal variation of concentrations with highest values for all the marine biogenic sulfur gas-aerosol parametres along the ice edge zone in August and lowest values over the pack ice in late September On average concentrations fell with a decline rate of about 20–40% per week. A similar seasonal change was also reflected in particulate ammonium. This therefore indicates links between the different sulfur compounds as well as between the biogenic sulfur and nitrogen cycles. Concentrations over the pack ice region were generally lower than over the open waters at the ice edge with an estimated net loss rate of roughly 35% per day of transport over the pack ice. Contrary to earlier marine sulfur studies performed outside the Arctic region, a constant methane sulfonate to non-sea-salt sulfate molar ratio was found in the submicrometer size fraction for samples with a minimal influence from fog and anthropogenic sources. This ratio had a value of 0.22 in spite of large seasonal changes in temperature and concentrations of methane sulfonate and non-sea-salt sulfate. Thus we conclude that the sum of the proceses controlling the measured particle properties do not exhibit a net temperature dependence. The one to one molar ratio of ammonium to non-sea-salt sulfate indicated a partly neutralised ammoniated sulfate aerosol. This was further verified by single particle analysis. Measurements of non-sea-salt sulfate and ammonium revealed a bimodal size distribution with about 70% of their mass found in the submicrometer size fraction. Methane sulfonate was mainly associated with submicrometer particles, with less than 8% of the mass observed in the largest particles. We have also shown that the interchange of air between the surface mixed layer and clouds, caused by atmospheric wave motions, dominated the short time variations in atmospheric DMS and submicrometer aerosol concentrations. This interchange will have a strong influence on the chemical and physical processes that control the properties of the aerosol, and deserves more attention in future work.