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We quantify the stratospheric injection of brominated very short-lived substances (VSLS) based on aircraft observations acquired in winter 2014 above the Tropical Western Pacific during the CONvective TRansport of Active Species in the Tropics (CONTRAST) and the Airborne Tropical TRopopause EXperiment (ATTREX) campaigns. The overall contribution of VSLS to stratospheric bromine was determined to be 5.0 ± 2.1 ppt, in agreement with the 5 ± 3 ppt estimate provided in the 2014 World Meteorological Organization (WMO) Ozone Assessment report (WMO 2014), but with lower uncertainty. Measurements of organic bromine compounds, including VSLS, were analyzed using CFC-11 as a reference stratospheric tracer. From this analysis, 2.9 ± 0.6 ppt of bromine enters the stratosphere via organic source gas injection of VSLS. This value is two times the mean bromine content of VSLS measured at the tropical tropopause, for regions outside of the Tropical Western Pacific, summarized in WMO 2014. A photochemical box model, constrained to CONTRAST observations, was used to estimate inorganic bromine from measurements of BrO collected by two instruments. The analysis indicates that 2.1 ± 2.1 ppt of bromine enters the stratosphere via inorganic product gas injection. We also examine the representation of brominated VSLS within 14 global models that participated in the Chemistry-Climate Model Initiative. The representation of stratospheric bromine in these models generally lies within the range of our empirical estimate. Models that include explicit representations of VSLS compare better with bromine observations in the lower stratosphere than models that utilize longer-lived chemicals as a surrogate for VSLS.

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We derive tropospheric column BrO during the ARCTAS and ARCPAC field campaigns in spring 2008 using retrievals of total column BrO from the satellite UV nadir sensors OMI and GOME-2 using a radiative transfer model and stratospheric column BrO from a photochemical simulation. We conduct a comprehensive comparison of satellite-derived tropospheric BrO column to aircraft in-situ observations of BrO and related species. The aircraft profiles reveal that tropospheric BrO, when present during April 2008, was distributed over a broad range of altitudes rather than being confined to the planetary boundary layer (PBL). Perturbations to the total column resulting from tropospheric BrO are the same magnitude as perturbations due to longitudinal variations in the stratospheric component, so proper accounting of the stratospheric signal is essential for accurate determination of satellite-derived tropospheric BrO. We find reasonably good agreement between satellite-derived tropospheric BrO and columns found using aircraft in-situ BrO profiles, particularly when satellite radiances were obtained over bright surfaces (albedo >0.7), for solar zenith angle

Dry deposition velocities (Vd) for peroxyacetyl nitrate (PAN) calculated using two community dry deposition models with different treatments of both stomatal and nonstomatal uptakes were evaluated using measurements of PAN eddy covariance fluxes over a Loblolly pine forest in July 2003. The observed daytime maximum of Vd(PAN) was ∼1.0 cm s-1 on average, while the estimates by the WRF-Chem dry deposition module (WDDM) and the Noah land surface model coupled with a photosynthesis-based Gas Exchange Model (Noah-GEM) were only 0.2 cm s-1 and 0.6 cm s-1, respectively. The observations also showed considerable PAN deposition at night with typical Vd values of 0.2-0.6 cm s-1, while the estimated values from both models were less than 0.1 cm s-1. Noah-GEM modeled more realistic stomatal resistance (Rs) than WDDM, as compared with observations of water vapor exchange fluxes. The poor performance of WDDM for stomatal uptake is mainly due to its lack of dependence on leaf area index. Thermal decomposition was found to be relatively unimportant for measured PAN fluxes as shown by the lack of a relationship between measured total surface conductance and temperature. Thus, a large part of the underprediction in Vd from both models should be caused by the underestimation of nonstomatal uptake, in particular, the cuticle uptake. Sensitivity tests on both stomatal and nonstomatal resistances terms were conducted and some recommendations were provided. Copyright 2012 by the American Geophysical Union.

An interpretative modeling analysis is conducted to simulate the diurnal variations in OH and HO2 + RO2 observed at Summit, Greenland in 2003. The main goal is to assess the HOx budget and to quantify the impact of snow emissions on ambient HOx as well as on CH2O and H2O2. This analysis is based on composite diurnal profiles of HOx precursors recorded during a 3-day period (July 7-9), which were generally compatible with values reported in earlier studies. The model simulations can reproduce the observed diurnal variation in HO2 + RO2 when they are constrained by observations of H2O2 and CH2O. By contrast, model predictions of OH were about factor of 2 higher than the observed values. Modeling analysis of H2O2 suggests that its distinct diurnal variation is likely controlled by snow emissions and loss by deposition and/or scavenging. Similarly, deposition and/or scavenging sinks are needed to reproduce the observed diel profile in CH2O. This study suggests that for the Summit 2003 period snow emissions contribute similar to 25% of the total CH2O production, while photochemical oxidation of hydrocarbon appears to be the dominant source. A budget assessment of HOx radicals shows that primary production from O(D-1) + H2O and photolysis of snow emitted precursors (i.e., H2O2 and CH2O)are the largest primary HOx sources at Summit, contributing 41% and 40%, respectively. The snow contribution to the HOx budget is mostly in the form of emissions of H2O2. The dominant HO, sink involves the HO2 + HO2 reaction forming H2O2, followed by its deposition to snow. These results differ from those previously reported for the South Pole (SP), in that primary production of HOx was shown to be largely driven by both the photolysis of CH2O and H2O2 emissions (46%) with smaller contributions coming from the oxidation of CH4 and the 0(D-1) + H2O reaction (i.e., 27% each). In sharp contrast to the findings at Summit in 2003, due to the much higher levels of NOx the SP HO, sinks are dominat

It has been shown that sunlit snow and ice plays an important role in processing atmospheric species. Photochemical production of a variety of chemicals has recently been reported to occur in snow/ice and the release of these photochemically generated species may significantly impact the chemistry of the overlying atmosphere. Nitrogen oxide and oxidant precursor fluxes have been measured in a number of snow covered environments, where in some cases the emissions significantly impact the overlying boundary layer. For example, photochemical ozone production (such as that occurring in polluted mid-latitudes) of 3–4 ppbv/day has been observed at South Pole, due to high OH and NO levels present in a relatively shallow boundary layer. Field and laboratory experiments have determined that the origin of the observed NOx flux is the photochemistry of nitrate within the snowpack, however some details of the mechanism have not yet been elucidated. A variety of low molecular weight organic compounds have been shown to be emitted from sunlit snowpacks, the source of which has been proposed to be either direct or indirect photo-oxidation of natural organic materials present in the snow. Although myriad studies have observed active processing of species within irradiated snowpacks, the fundamental chemistry occurring remains poorly understood. Here we consider the nature of snow at a fundamental, physical level; photochemical processes within snow and the caveats needed for comparison to atmospheric photochemistry; our current understanding of nitrogen, oxidant, halogen and organic photochemistry within snow; the current limitations faced by the field and implications for the future.