Heterogeneous Reactivity of Nitric Acid with Nascent Sea Spray Aerosol: Large Differences Observed between and within Individual Particles

Abstract

Current climate and atmospheric chemistry models assume that all sea spray particles react as if they are pure NaCl. However, recent studies of sea spray aerosol particles have shown that distinct particle types exist (including sea salt, organic carbon, and biological particles) as well as mixtures of these and, within each particle type, there is a range of single-particle chemical compositions. Because of these differences, individual particles should display a range of reactivities with trace atmospheric gases. Herein, to address this, we study the composition of individual sea spray aerosol particles after heterogeneous reaction with nitric acid. As expected, a replacement reaction of chloride with nitrate is observed; however, there is a large range of reactivities spanning from no reaction to complete reaction between and within individual sea spray aerosol particles. These data clearly support the need for laboratory studies of individual, environmentally relevant particles to improve our fundamental understanding as to the properties that determine reactivity.

Contributions of transported Prudhoe Bay oil field emissions to the aerosol population in Utqiaġvik, Alaska

“…However, few studies have measured PM emitted from oil and gas extraction in the Arctic. Measurements of BC from 1977 to 1997 in Utqiaġvik showed contributions from Russian oil fields year round (Polissar et al, 1999(Polissar et al, , 2001), similar to the recent results of Barrett et al (2015) at Utqiaġvik during December 2012-March 2013 when transported particles from Russian oil fields were observed. Barrett et al (2015) also measured regional Arctic BC from both fossil fuel combustion and biomass burning.…”

“…Measurements of BC from 1977 to 1997 in Utqiaġvik showed contributions from Russian oil fields year round (Polissar et al, 1999(Polissar et al, , 2001), similar to the recent results of Barrett et al (2015) at Utqiaġvik during December 2012-March 2013 when transported particles from Russian oil fields were observed. Barrett et al (2015) also measured regional Arctic BC from both fossil fuel combustion and biomass burning. The Arctic Climate Change, Economy, and Society (ACCESS) aircraft field campaign recently investigated emissions from oil and gas extraction in the Norwegian Arctic and measured increased BC, among other pollutants, compared to the Arctic background while sampling within plumes from oil and gas extraction facilities (Roiger et al, 2015).…”

“…6), consistent with previous Utqiaġvik measurements that demonstrated that SSA comprises approximately 70 % of the summertime Arctic supermicron (1-10 µm) particle mass (Quinn et al, 2002). Approximately 20 % of 0.13-0.4 µm and 40-70 % of 0.4-1 µm particles, by number, were identified as fresh SSA, as determined using CCSEM-EDX, and in agreement with the measured ATOFMS number fraction of 63 ± 5 % for 0.2-1.5 µm particles ( [m/z 81, 83] (Ault et al, 2014;Gard et al, 1998), were present in the ATOFMS SSA mass spectra. The majority of the identified supermicron SSA (> 99 %, by number) also showed little evidence of atmospheric processing through addition of nitrogen or sulfur, identified as nitrate and sulfate using ATOFMS (Fig.…”

Hygroscopic properties of NaCl and NaNO<sub>3</sub> mixture particles as reacted inorganic sea-salt aerosol surrogates

“…This can lead to the formation of partially or fully reacted particles containing NaCl and NaNO 3 over a range of mixing ratios. Indeed, studies of individual marine aerosols have clearly shown the existence of fully or partially reacted SSA particles, and a significant portion of these particles were reported to be mixtures of sodium chloride, nitrate, and/or sulfate (Gard et al, 1998;Ro et al, 2001;Laskin et al, 2003;Ault et al, 2014). Moreover, the further reactive uptake of N 2 O 5 was reported to be dependent on the chloride to nitrate ratio of the reacted SSAs and their phases .…”

Characterization of carbonaceous aerosols over the East China Sea: The impact of the East Asian continental outflow

“…The even carbon number preference of C 12 eC 22 is associated with marine bacteria, fungi and yeast species (Grimalt and Albaiges, 1987), and possible petroleumderived inputs, such as petroleum residue (Harji et al, 2008). It has been suggested that marine aerosols could be derived from the bubble bursting upon breaking waves on the ocean surface, which is also known as sea spray (Ault et al, 2014). Sea spray aerosol (SSA) plays a key role in influencing inorganic and organic aerosol burden over much of the Earth's surface (Salter et al, 2014).…”