[1] A ship emission plume experiment was conducted about 100 km off the California coast during the NOAA Intercontinental Transport and Chemical Transformation (ITCT) 2K2 airborne field campaign. Measurements of chemical species were made from the NOAA WP-3D aircraft in eight consecutive transects of a ship plume around midday during 2.5 hours of flight. The measured species include NO x , HNO 3 , peroxyacetylnitrate (PAN), SO 2 , H 2 SO 4 , O 3 , CO, CO 2 , nonmethane hydrocarbons (NMHC), and particle number and size distributions. Observations demonstrate a NO x lifetime of $1.8 hours inside the ship plume compared to $6.5 hours (at noontime) in the moderately polluted background marine boundary layer of the experiment. This confirms the earlier hypothesis of highly enhanced in-plume NO x destruction. Consequently, one would expect the impact of ship emissions is much less severe than those predicted by global models that do not include rapid NO x destruction. Photochemical model calculations suggest that more than 80% of the NO x loss was due to the NO 2 + OH reaction; the remainder was by PAN formation. The model underestimated in-plume NO x loss rate by about 30%. In addition, a comparison of measured to predicted H 2 SO 4 in the plumes suggests that the photochemical model predicts OH variability reasonably well but may underestimate actual values. Predictions of in-plume O 3 production agree well with the observations, suggesting that model-predicted peroxy radical (HO 2 + RO 2 ) levels are reasonable. The model estimated ozone production efficiency ranges from 6 to 30. The largest model bias was seen in the comparison with measured HNO 3 . The model overestimated in-plume HNO 3 by about a factor of 6. This is most likely caused by underestimated HNO 3 sinks possibly involving particle scavenging. However, limited data availability precluded a conclusive test of this possible loss process.

Abstract. In situ measurements of ozone, photochemically active bromine compounds, and other trace gases over the Arctic Ocean in April 2008 are used to examine the chemistry and geographical extent of ozone depletion in the arctic marine boundary layer (MBL). Data were obtained from the NOAA WP-3D aircraft during the Aerosol, Radiation, and Cloud Processes affecting Arctic Climate (ARCPAC) study and the NASA DC-8 aircraft during the Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) study. Fast (1 s) and sensitive (detection limits at the low pptv level) measurements of BrCl and BrO were obtained from three different chemical ionization mass spectrometer (CIMS) instruments, and soluble bromide was measured with a mist chamber. The CIMS instruments also detected Br 2 . Subsequent laboratory studies showed that HOBr rapidly converts to Br 2 on the Teflon instrument inlets. This detected Br 2 is identified as active bromine and represents a lower limit of the sum HOBr + Br 2 . The measured active bromine is shown to likely be HOBr during daytime flights in the arctic. In the MBL over the Arctic Ocean, soluble bromide and active bromine were consistently elevated and ozone was depleted. Ozone depletion and active bromine enhancement were confined to the MBL that was capped by a temperature inversion at 200-500 m altitude. In ozonedepleted air, BrO rarely exceeded 10 pptv and was always substantially lower than soluble bromide that was as high as 40 pptv. BrCl was rarely enhanced above the 2 pptv detection limit, either in the MBL, over Alaska, or in the arctic free troposphere.

[1] Inorganic bromine plays a critical role in ozone and mercury depletions events (ODEs and MDEs) in the Arctic marine boundary layer. Direct observations of bromine species other than bromine oxide (BrO) during ODEs are very limited. Here we report the first direct measurements of hypobromous acid (HOBr) as well as observations of BrO and molecular bromine (Br 2 ) by chemical ionization mass spectrometry at Barrow, Alaska in spring 2009 during the Ocean-Atmospheric-Sea Ice-Snowpack (OASIS) campaign. Diurnal profiles of HOBr with maximum concentrations near local noon and no significant concentrations at night were observed. The measured average daytime HOBr mixing ratio was 10 pptv with a maximum value of 26 pptv. The observed HOBr was reasonably well correlated (R 2 = 0.57) with predictions from a simple steady state photochemical model constrained to observed BrO and HO 2 at wind speeds <6 m s À1 . However, predicted HOBr levels were considerably higher than observations at higher wind speeds. This may be due to enhanced heterogeneous loss of HOBr on blowing snow coincident with higher wind speeds. BrO levels were also found to be higher at elevated wind speeds. Br 2 was observed in significant mixing ratios (maximum = 46 pptv; average = 13 pptv) at night and was strongly anti-correlated with ozone. The diurnal speciation of observed gas phase inorganic bromine species can be predicted by a time-dependent box model that includes efficient heterogeneous recycling of HOBr, hydrogen bromide (HBr), and bromine nitrate (BrONO 2 ) back to more reactive forms of bromine.

The first measurements of OH, H2SO4, and MSA performed at the South Pole as part of the Investigation of Sulfur Chemistry in the Antarctic Troposphere (ISCAT) study are presented. OH concentrations were found to be quite elevated for such a dry environment, with average values of 2x106 molecule cm−3. Model simulations suggest that much of the observed OH is a result of unexpectedly high NO concentrations. Concentrations of H2SO4 and MSA were generally low with average values of 2.5x105 and 1x105 molecule cm−3, respectively. Major variations in the concentration levels of the above species were found to have a high correlation with changes in the polar mixing layer as estimated from the measured temperature difference from 22 to 2m above the snow surface. Chemical details are discussed.

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[1] Airborne measurements of aerosol and cloud condensation nuclei (CCN) were conducted aboard the National Oceanic and Atmospheric Administration WP-3D platform during the 2006 Texas Air Quality Study/Gulf of Mexico Atmospheric Composition and Climate Study (TexAQS/GoMACCS). The measurements were conducted in regions influenced by industrial and urban sources. Observations show significant local variability of CCN activity (CCN/CN from 0.1 to 0.5 at s = 0.43%), while variability is less significant across regional scales (∼100 km × 100 km; CCN/CN is ∼0.1 at s = 0.43%). CCN activity can increase with increasing plume age and oxygenated organic fraction. CCN measurements are compared to predictions for a number of mixing state and composition assumptions. Mixing state assumptions that assumed internally mixed aerosol predict CCN concentrations well. Assuming organics are as hygroscopic as ammonium sulfate consistently overpredicted CCN concentrations. On average, the water-soluble organic carbon (WSOC) fraction is 60 ± 14% of the organic aerosol. We show that CCN closure can be significantly improved by incorporating knowledge of the WSOC fraction with a prescribed organic hygroscopicity parameter ( = 0.16 or effective ∼ 0.3). This implies that the hygroscopicity of organic mass is primarily a function of the WSOC fraction. The overall aerosol hygroscopicity parameter varies between 0.08 and 0.88. Furthermore, droplet activation kinetics are variable and 60% of particles are smaller than the size characteristic of rapid droplet growth.

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