National Oceanic and
Atmospheric Administration
United States Department of Commerce


FY 1992

Equilibria of the marine multiphase ammonia system

Quinn, P.K., W.E. Asher, and R.J. Charlson

J. Atmos. Chem., 14(1–4), 11–30, doi: 10.1007/BF00115219 (1992)

A lack of empirical data has made it difficult to ascertain whether ammonia is in equilibrium between the oceanic, atmospheric gas and atmospheric particle phases in the remote marine environment. Reported here are simultaneous measurements of the saturation concentration of ammonia relative to ammonia concentrations in ocean surface waters; total seawater ammonia; atmospheric gas phase ammonia; and atmospheric particulate-phase ammonium, non-seasalt sulfate, methanesulfonate, and nitrate. Sampling was performed in May of 1987 in the northeast Pacific Ocean environment and in April and May of 1988 in the central Pacific Ocean environment. These measurements were used to determine the degree to which ammonia approached equilibrium between the oceanic and atmospheric gas and aerosol particle phases. The experimental atmospheric gas phase ammonia concentrations were compared with calculated equilibrium concentrations assuming a Henry's law type of partitioning between the gas and condensed phases. Characteristic times of the processes controlling the fate of ammonia in the marine environment also were compared. The measured atmospheric gas phase and oceanic concentrations of ammonia indicate that ammonia is not in a Henry's law equilibrium across the air/sea interface. This disequilibrium is a result of the long air/sea exchange equilibration time relative to the lifetime of ammonia in the atmosphere. Comparison of the calculated equilibrium gas phase ammonia concentrations with the measured gas phase ammonia concentrations shows that attainment of equilibrium between the atmospheric gas and particle phases is a strong function of the chemical composition of the aerosol particles. The data suggest that fully neutralized aerosol particles are not in Henry's law equilibrium with the gas phase while equilibrium is observed for particles with an average ammonium to non-seasalt sulfate molar ratio less than 1.8.

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