We report measurements of the product yield for nitryl chloride (ClNO2) production following the reactive uptake of dinitrogen pentoxide (N2O5) to a wide variety of ambient seawater samples as well as seawater mimics. The ClNO2 yield, as measured for ambient seawater collected from both coastal and open ocean waters, was found to be both insensitive to chlorophyll-a, a marker for biological activity, and significantly lower (0.16-0.30) than that expected for equivalent salt-containing solutions (0.82 ± 0.05). Suppression in the ClNO2 yield can be induced by the addition of aromatic organic compounds (e.g., phenol and humic acid) to synthetic seawater matrices. In the case of phenol, surface tension measurements reveal that the surface phenol:chloride ratio can be enhanced by more than a factor of 100 as compared to bulk ratios for subtle changes in surface tension (<1.5 mN m(-1)), providing a mechanism to suppress ClNO2 production at low bulk phenol concentrations. We interpret measurements of the dependence of the ClNO2 yield on phenol using a kinetic model, where we confine the surface enhancement in phenol to the top 1 nm of the interface. Our results are most consistent with a model where N2O5 is ionized within the first three water monolayers (<1 nm), where the product nitronium ions react rapidly with interfacial phenol molecules. These results suggest that ClNO2 may not be formed at the air-sea interface at the yield expected for NaCl, and that the reactive uptake of N2O5 and the subsequent product yield of ClNO2 may serve as a unique probe for the composition of the interfacial region of the sea surface microlayer.

Previous laboratory measurements and field observations have suggested that the reactive uptake of N 2 O 5 to sea spray aerosol particles is a complex function of particle chemical composition and phase, where surface active organics can suppress the reactive uptake by up to a factor of 60. To date, there are no direct studies of the reactive uptake of N 2 O 5 to nascent sea spray aerosol that permit assessment of the role that organic molecules present in sea spray aerosol (SSA) may play in suppressing or enhancing N 2 O 5 uptake kinetics. In this study, SSA was generated from ambient seawater and artificial seawater matrices using a Marine Aerosol Reference Tank (MART), capable of producing nascent SSA representative of ambient conditions. The reactive uptake coefficient of N 2 O 5 (γ(N 2 O 5 )) on nascent SSA was determined using an entrained aerosol flow reactor coupled to a chemical ionization mass spectrometer for measurement of surface area dependent heterogeneous loss rates. Population averaged measurements of γ(N 2 O 5 ) for SSA generated from salt water sequentially doped with representative organic molecular mimics, or from ambient seawater, do not deviate statistically from that observed for sodium chloride (γ(N 2 O 5 ) NaCl = 0.01−0.03) for relative humidity (RH) ranging between 50 and 65%. The results are consistent with measurements made under clean marine conditions at the Scripps Institution of Oceanography Pier and those conducted on nascent SSA generated in the marine aerosol reference tank. The results presented here suggest that organic films present on nascent SSA (at RH greater than 50%) likely do not significantly limit N 2 O 5 reactive uptake.

Abstract. Benzene cluster cations were revisited as a sensitive and selective reagent ion for the chemical ionization of dimethyl sulfide (DMS) and a select group of volatile organic compounds (VOCs). Laboratory characterization was performed using both a new set of compounds (i.e., DMS, β-caryophyllene) as well as previously studied VOCs (i.e., isoprene, α-pinene). Using a field deployable chemical-ionization time-of-flight mass spectrometer (CIToFMS), benzene cluster cations demonstrated high sensitivity (> 1 ncps ppt −1 ) to DMS, isoprene, and α-pinene standards. Parallel measurements conducted using a chemicalionization quadrupole mass spectrometer, with a much weaker electric field, demonstrated that ion-molecule reactions likely proceed through a combination of ligandswitching and direct charge transfer mechanisms. Laboratory tests suggest that benzene cluster cations may be suitable for the selective ionization of sesquiterpenes, where minimal fragmentation (< 25 %) was observed for the detection of β-caryophyllene, a bicyclic sesquiterpene. The in-field stability of benzene cluster cations using CI-ToFMS was examined in the marine boundary layer during the High Wind Gas Exchange Study (HiWinGS). The use of benzene cluster cation chemistry for the selective detection of DMS was validated against an atmospheric pressure ionization mass spectrometer, where measurements from the two instruments were highly correlated (R 2 > 0.95, 10 s averages) over a wide range of sampling conditions.

No abstract