Hydroxyl radical (OH) is an important oxidant in atmospheric aqueous phases such as cloud and fog drops and water-containing aerosol particles. We find that numerical models nearly always overestimate aqueous hydroxyl radical concentrations because they overpredict its rate of formation and, more significantly, underpredict its sinks. To address this latter point, we examined OH sinks in atmospheric drops and aqueous particles using both new samples and an analysis of published data. Although the molecular composition of organic carbon, the dominant sink of OH, is extremely complex and poorly constrained, this sink behaves very similarly in different atmospheric waters and even in surface waters. Thus, the sink for aqueous OH can be estimated as the concentration of dissolved organic carbon multiplied by a general scavenging rate constant [kC,OH = (3.8 ± 1.9) × 10(8) L (mol C)(-1) s(-1)], a simple process that should significantly improve estimates of OH concentrations in atmospheric drops and aqueous particles.

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We studied photoformation of Fe(II) in the water-soluble fractions (WSFs) of bulk aerosol particles collected in Okinawa, Japan, using radiation at wavelengths of 313, 334, 366, and 405 nm. Fe(II) photoformation quickly reached a steady state within 5 min of irradiation at all wavelengths. The steady-state Fe(II) concentrations were 85+/-13% (n = 39) of the total dissolved Fe (TDFe) concentrations in the WSF solutions. Apparent quantum yields of Fe(II) photoformation were determined based on total absorbance of the WSF solutions, and the means (+/-1 S.D.) were 0.019 (+/-0.034), 0.021 (+/-0.031), 0.014 (+/-0.023), and 0.010 (+/-0.025) at 313, 334, 366, and 405 nm, respectively. Comparison of the observed rates of Fe(II) photoformation for the WSF solutions and the calculated rates from the known Fe(II)-forming compounds suggested that Fe(oxalate)2- could account for the observed Fe(II) photoformation rates if the Fe(oxalate)2- concentration is sufficiently high (>20% of [Fe(III)]o). Furthermore, our study showed that the calculated wavelength dependence of Fe(ll) photoformation from Fe(oxalate)2- was consistent with that of Fe(II) photoformation observed in the WSF solutions. The results obtained here have implications to daytime Fe(III)/ Fe(II) cycles in the atmospheric water droplet.

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