Nonmethane hydrocarbons and halocarbons were measured during two Lagrangian experiments conducted in the lower troposphere of the North Atlantic as part of the June 1992, Atlantic Stratosphere Transition Experiment/Marine Aerosol and Gas Exchange (ASTEX/MAGE) expedition. The first experiment was performed in very clean marine air. Meteorological observations indicate that the height of the marine boundary layer rose rapidly, entraining free tropospheric air. However, the free tropospheric and marine boundary layer halocarbon concentrations were too similar to allow this entrainment to be quantified by these measurements. The second Lagrangian experiment took place along the concentration gradient of an aged continental air mass advecting from Europe. The trace gas measurements confirm that the National Center for Atmospheric Research (NCAR) Electra aircraft successfully intercepted the same air mass on consecutive days. Two layers, a surface layer and a mixed layer with chemically distinct compositions, were present within the marine boundary layer. The composition of the free troposphere was very different from that of the mixed layer, making entrainment from the free troposphere evident. Concentrations of the nonmethane hydrocarbons in the Lagrangian surface layer were observed to become depleted relative to the longer‐lived tetrachloroethene. A best fit to the observations was calculated using various combinations of the three parameters, loss by reaction with hydroxyl, loss by reaction with chlorine, and/or dilution from the mixed layer. These calculations provided estimated average concentrations in the surface layer for a 5‐hour period from dawn to 11 UT of 0.3 ± 0.5 × 106 molecules cm−3 for HO, and 3.3 ± 1.1 × 104 molecules cm−3 for Cl. Noontime concentration estimates were 2.6 ± 0.7 × 106 molecules cm−3 for HO and 6.5 ± 1.4 × 104 molecules cm−3 for Cl.

Biogenic lipids and polymers are surveyed for their ability to adsorb at the water-air interfaces associated with bubbles, marine microlayers and particles in the overlying boundary layer. Representative ocean biogeochemical regimes are defined in order to estimate local concentrations for the major macromolecular classes. Surfactant equilibria and maximum excess are then derived based on a network of model compounds. Relative local coverage and upward mass transport follow directly, and specific chemical structures can be placed into regional rank order. Lipids and denatured protein-like polymers dominate at the selected locations. The assigned monolayer phase states are variable, whether assessed along bubbles or at the atmospheric spray droplet perimeter. Since oceanic film compositions prove to be irregular, effects on gas and organic transfer are expected to exhibit geographic dependence as well. Moreover, the core arguments extend across the sea-air interface into aerosol-cloud systems. Fundamental nascent chemical properties including mass to carbon ratio and density depend strongly on the geochemical state of source waters. High surface pressures may suppress the Kelvin effect, and marine organic hygroscopicities are almost entirely unconstrained. While bubble adsorption provides a well-known means for transporting lipidic or proteinaceous material into sea spray, the same cannot be said of polysaccharides. Carbohydrates tend to be strongly hydrophilic so that their excess carbon mass is low despite stacked polymeric geometries. Since sugars are abundant in the marine aerosol, gel-based mechanisms may be required to achieve uplift. Uncertainties distill to a global scale dearth of information regarding

[1] Short-lived halocarbon tracers were used to investigate marine influences on air quality in a coastal region of New England. Atmospheric measurements made at the University of New Hampshire's Observing Station at Thompson Farm (TF) in Durham, New Hampshire, indicate that relatively large amounts of halocarbons are emitted from local estuarine and coastal oceanic regions. Bromine-containing halocarbons of interest in this work include bromoform (CHBr 3 ) and dibromomethane (CH 2 Br 2 ). The mean mixing ratios of CHBr 3 and CH 2 Br 2 from 11 January to 5 March 2002 were 2.6 pptv and 1.6 pptv, and from 1 June to 31 August 2002 mean mixing ratios were 5.9 pptv and 1.4 pptv, respectively. The mean mixing ratio of CHBr 3 was not only highest during summer, but both CHBr 3 and CH 2 Br 2 exhibited large variability in their atmospheric mixing ratios during this season. We attribute the greater variability to increased production combined with faster atmospheric removal rates. Other seasonal characteristics of CHBr 3 and CH 2 Br 2 in the atmosphere, as well as the impact of local meteorology on their distributions at this coastal site, are discussed. Tetrachloroethene (C 2 Cl 4 ) and trichloroethene (C 2 HCl 3 ) were used to identify time periods influenced by urban emissions. Additionally, measurements of CHBr 3, CH 2 Br 2, C 2 Cl 4 , methyl iodide (CH 3 I), and ethyl iodide (C 2 H 5 I) were made at TF and five sites throughout the nearby Great Bay estuarine area between 18 and 19 August 2003. These measurements were used to elucidate the effect of the tidal cycle on the distributions of these gases. The mean mixing ratios of CHBr 3 , CH 2 Br 2 , CH 3 I, and C 2 H 5 I were $82%, 46%, 14%, and 17% higher, respectively, near the coast compared to inland sites, providing evidence for a marine source of short-lived halocarbons at TF. Correlation between the tidal cycle and atmospheric concentrations of marine tracers on the night of 18 August 2003 showed that the highest values for the brominated species occurred $2-3 hours after high tide. Emission fluxes of CHBr 3 , CH 2 Br 2 , CH 3 I, and C 2 H 5 I on this night were estimated to be 26 ± 57, 4.7 ± 5.4, 5.9 ± 4.6, and 0.065 ± 0.20 nmol m À2 h À1 , respectively. Finally, the anthropogenic source strength of CHBr 3 was calculated to determine its impact on atmospheric levels observed in this region. Although our results indicate that anthropogenic contributions could potentially range from 15 to 60% of the total dissolved CHBr 3 in the Great Bay, based on the observed ratio of CH 2 Br 2 /CHBr 3 and surface seawater measurements in the Gulf of Maine, it appears unlikely that anthropogenic activities are a significant source of CHBr 3 in the region.

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