Atmospheric sulfur chemistry and cloud condensation nuclei (CCN) concentrations over the northeastern Pacific Coast

Abstract

Correlated measurements of dimethylsulfide (DMS), gas phase dimethylsulfoxide (DMSO), methane‐sulfonic acid (MSA)(g), sulfuric acid (H2SO4), and cloud condensation nuclei (CCN) were conducted in April 1991 at a Pacific coastal site in northern Washington. Measurements of SO2, aerosol methanesulfonate (MSA)(p), and non‐sea‐salt sulfate (nss‐SO4) concentrations were also included. Maximum DMS concentrations between 100 and 240 pptv were observed when the measurement site (480 m above sea level) was embedded in clouds and air from the marine boundary layer was flowing upslope to the site. DMS levels measured in continental air and/or above the mixed layer were typically less than 20 pptv. The sulfur gases DMSO, H2SO4, and MSA(g) were measured in real time on a continuous basis (once every 60–150 s) using selected ion chemical ionization mass spectrometry. Corresponding concentrations ranged between <0.5–3.2 pptv, 0.001–1.19 pptv, and 0.002–0.19 pptv, respectively. All three sulfur gases showed significant diel variations mostly in phase with each other. Their corresponding lifetimes in the marine atmosphere are estimated to be of the order of a few hours. The results in connection with recent laboratory studies and model calculations suggest that dimethylsulfone (DMSO2) was the dominant end product of DMS oxidation under the present conditions. CCN concentrations measured in marine air ranged roughly between 10–200 cm−3 and 200–400 cm−3 at 0.3% and 0.9% supersaturation, respectively. A statistical analysis using only data obtained in predominantly marine air and during non‐fog/non‐precipitation periods showed significant correlations between individual sulfur species and between CCN (0.3% ss) and H2SO4, and CCN (0.3% ss) and nss‐SO4. The results indirectly support a relationship between DMS and CCN concentrations. However, other observations also suggest that at higher supersaturations (0.9%), compounds less soluble than sulfate may become important in marine CCN formation.