HO_x chemistry during INTEX-A 2004: Observation, model calculation, and comparison with previous studies

OH and HO_2 were measured with the Airborne Tropospheric Hydrogen Oxides Sensor (ATHOS) as part of a large measurement suite from the NASA DC-8 aircraft during the Intercontinental Chemical Transport Experiment-A (INTEX-A). This mission, which was conducted mainly over North America and the western Atlantic Ocean in summer 2004, was an excellent test of atmospheric oxidation chemistry. The HOx results from INTEX-A are compared to those from previous campaigns and to results for other related measurements from INTEX-A. Throughout the troposphere, observed OH was generally 0.95 of modeled OH; below 8 km, observed HO_2 was generally 1.20 of modeled HO_2. This observed-to-modeled comparison is similar to that for TRACE-P, another midlatitude study for which the median observed-to-modeled ratio was 1.08 for OH and 1.34 for HO_2, and to that for PEM-TB, a tropical study for which the median observed-to-modeled ratio was 1.17 for OH and 0.97 for HO_2. HO_2 behavior above 8 km was markedly different. The observed-to-modeled HO_2 ratio increased from ∼1.2 at 8 km to ∼3 at 11 km with the observed-to-modeled ratio correlating with NO. Above 8 km, the observed-to-modeled HO_2 and observed NO were both considerably greater than observations from previous campaigns. In addition, the observed-to-modeled HO_2/OH, which is sensitive to cycling reactions between OH and HO_2, increased from ∼1.5 at 8 km to almost 3.5 at 11 km. These discrepancies suggest a large unknown HO_x source and additional reactants that cycle HO_x from OH to HO_2. In the continental planetary boundary layer, the observed-to-modeled OH ratio increased from 1 when isoprene was less than 0.1 ppbv to over 4 when isoprene was greater than 2 ppbv, suggesting that forests throughout the United States are emitting unknown HO_x sources. Progress in resolving these discrepancies requires a focused research activity devoted to further examination of possible unknown OH sinks and HO_x sources

HOx Observation and Model Comparison During INTEX-A 2004

OH and HO2 were measured with the Airborne Tropospheric Hydrogen Oxides Sensor (ATHOS) as part of a large measurement suite from the NASA DC-8 aircraft during the Intercontinental Chemical Transport Experiment - A (INTEX-A). This mission, which was conducted mainly over North America and the western Atlantic Ocean in summer 2004, was an excellent test of atmospheric oxidation chemistry. Throughout the troposphere, observed OH was generally 0.60 of the modeled OH; below 8 km, observed HO2 was generally 0.78 of modeled HO2. If the over-prediction of tropospheric OH is not due to an instrument calibration error, then it implied less global tropospheric oxidation capacity and longer lifetimes for gases like methane and methyl chloroform than currently thought. This discrepancy falls well outside uncertainties in both the OH measurement and rate coefficients for known reactions and points to a large unknown OH loss. If the modeled OH is forced to agree with observed values by introducing of an undefined OH loss that removed HOx (HOx=OH+HO2), the observed and modeled HO2 and HO2/OH ratios are largely reconciled within the measurement uncertainty. HO2 behavior above 8 km was markedly different. The observed-to-modeled ratio correlating with NO. The observed-to-modeled HO2 ratio increased from approximately 1 at 8 km to more than approximately 2.5 at 11 km with the observed-to-modeled ratio correlating with NO. The observed-to-modeled HO2 and NO were both considerably greater than observations from previous campaigns. In addition, the observed-to-modeled HO2/OH, which is sensitive to cycling reactions between OH and HO2, increased from approximately 1.2 at 8 km to almost 4 above 11 km. In contrast to the lower atmosphere, these discrepancies above 8 km suggest a large unknown HOx source and additional reactants that cycle HOx from OH to HO2. In the continental planetary boundary layer, the OH observed-to-modeled ratio increased from 0.6 when isoprene was less than 0.1 ppbv to over 3 when isoprene was greater than 2 ppbv, suggesting that forests throughout the United States are emitting unknown HOx sources. Progress in resolving these discrepancies requires further examinations of possible unknown OH sinks and HOx sources and a focused research activity devoted to ascertaining the accuracy of the OH and HO2 measurements

Direct Measurements of the Convective Recycling of the Upper Troposphere

We present a statistical representation of the aggregate effects of deep convection on the chemistry and dynamics of the Upper Troposphere (UT) based on direct aircraft observations of the chemical composition of the UT over the Eastern United States and Canada during summer. These measurements provide new and unique observational constraints on the chemistry occurring downwind of convection and the rate at which air in the UT is recycled, previously only the province of model analyses. These results provide quantitative measures that can be used to evaluate global climate and chemistry models

Relationship between photolysis frequencies derived from spectroscopic measurements of actinic fluxes and irradiances during the IPMMI campaign

[1] The relationship between photolysis frequencies derived from spectroscopic measurements of actinic fluxes and irradiances was determined during a coordinated measurement campaign (International Photolysis Frequency Measurement and Modeling Intercomparison campaign (IPMMI)). When differences in viewing geometries are taken into account, the measurements are in close agreement. An empirical relationship, which is useful for high sun (noon) conditions or for daily integrals, was found to convert irradiance data to photolysis frequencies. For low-sun conditions (large solar zenith angle), model calculations were shown to improve the accuracy. However, the input parameters to the model are site specific and the conversion depends on diffuse/direct ratios. During cloudy conditions, significant improvements in the conversion can be achieved by assuming the radiation field to comprise entirely diffuse isotropic radiation when the UVA transmission by cloud is less than 0.8. Changing cloud conditions remain the greatest limitation, but they tend to bias the results away from the clear-sky case in a systematic way. Furthermore, although the cloud effects on the photolysis rates of nitrogen dioxide (J(NO2)) are rather large, they are much smaller for ozone photolysis (J(O-3 --> O(D-1))), which is of prime importance in tropospheric chemistry. The study shows the potential for deriving historical and geographical differences in actinic fluxes from the extensive records of ground-based measurements of spectral irradiance

Springtime photochemistry at northern mid and high latitudes

Physical and chemical properties of the atmosphere at 0–8 km were measured during the Tropospheric Ozone Production about the Spring Equinox (TOPSE) experiments from February to May 2000 at mid (40°–60°N) and high latitudes (60°–80°N). The observations were analyzed using a diel steady state box model to examine HOx and O3 photochemistry during the spring transition period. The radical chemistry is driven primarily by photolysis of O3 and the subsequent reaction of O(1D) and H2O, the rate of which increases rapidly during spring. Unlike in other tropospheric experiments, observed H2O2 concentrations are a factor of 2–10 lower than those simulated by the model. The required scavenging timescale to reconcile the model overestimates shows a rapid seasonal decrease down to 0.5–1 day in May, which cannot be explained by known mechanisms. This loss of H2O2 implies a large loss of HOx resulting in decreases in O3 production (10–20%) and OH concentrations (20–30%). Photolysis of CH2O, either transported into the region or produced by unknown chemical pathways, appears to provide a significant HOx source at 6–8 km at high latitudes. The rapid increase of in situ O3 production in spring is fueled by concurrent increases of the primary HOx production and NO concentrations. Long‐lived reactive nitrogen species continue to accumulate at mid and high latitudes in spring. There is a net loss of NOx to HNO3 and PAN throughout the spring, suggesting that these long‐term NOx reservoirs do not provide a net source for NOx in the region. In situ O3 chemical loss is dominated by the reaction of O3 and HO2, and not that of O(1D) and H2O. At midlatitudes, there is net in situ chemical production of O3 from February to May. The lower free troposphere (1–4 km) is a region of significant net O3 production. The net production peaks in April coinciding with the observed peak of column O3 (0–8 km). The net in situ O3 production at midlatitudes can explain much of the observed column O3 increase, although it alone cannot explain the observed April maximum. In contrast, there is a net in situ O3 loss from February to April at high latitudes. Only in May is the in situ O3 production larger than loss. The observed continuous increase of column O3 at high latitudes throughout the spring is due to transport from other tropospheric regions or the stratosphere not in situ photochemistry