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Tropospheric ozone is the third strongest greenhouse gas, and has the highest uncertainty in radiative forcing of the top five greenhouse gases. Throughout the troposphere, ozone is produced by radical oxidation of nitrogen oxides (NOx = NO + NO2). In the upper troposphere (8–10 km), current chemical transport models under-estimate nitrogen dioxide (NO2) observations. Improvements to simulated NOx production from lightning have increased NO2 predictions, but the predictions in the upper troposphere remain biased low. The upper troposphere has low temperatures (T < 250 K) that increase the uncertainty of many important chemical reaction rates. This study constrains uncertain reaction rates by combining model predictions with measurements from the Intercontinental Chemical Transport Experiment-North America observational campaign. The results show that the nitric acid formation rate, which is the dominant sink of NO2 and radicals, is currently over-estimated by 22% in the upper troposphere. The results from this study suggest that the temperature sensitivity of nitric acid formation is lower than currently recommended. Since the formation of nitric acid removes nitrogen dioxide and radicals that drive the production of ozone, the revised reaction rate will affect ozone concentrations in upper troposphere impacting climate and air quality in the lower troposphere.

Objectives: To describe the development, cost effectiveness and implementation of a PDA based electronic system to collect, verify and manage data from a multi-site study on HIV/AIDS stigma and pregnancy in a rural, resource-poor area. Methods: We worked within a large prevention of mother-to-child- transmission (PMTCT) program in nine rural health facilities to implement a PDA-based data collection system and to study the feasibility of its use in a multisite HIV research study in rural Kenya. The PDAs were programmed for collecting screening and eligibility data, and responses to structured interviews on HIV/AIDS stigma and violence in three local languages. Results: Between November 2007 and December 2008, nine PDAs were used by Clinic and Community Health Assistants to enrol 1,270 participants on to the PMTCT program. Successes included: capacity-building of interviewers, low cost of implementation, quick turnaround time of data entry with good data quality, and convenience. Conclusion: Our study demonstrated the feasibility of utilizing PDAs for data collection in a multi-site observational study on HIV/AIDS stigma conducted in remote rural health facilities in Kenya. However, appropriate and frequent data backup protocols need to be established and paper forms are still needed as backup tools in resource-poor settings.Keywords: Personal Digital Assistants, Developing countries, multisite studies, feasibility, cost effectivenessAfrican Health Sciences 2011; 11(3): 464 - 473

Nitrous acid (HONO) is an important precursor of the hydroxyl radical (OH) in the lower troposphere. Understanding HONO chemistry, particularly its sources and contribution to HOx (=OH+HO2) production, is very important for understanding atmospheric oxidation processes. A highly sensitive instrument for detecting atmospheric HONO based on aqueous long path absorption photometry (LOPAP) was deployed in the Biosphere Effects on Aerosols and Photochemistry Experiment (BEARPEX) at Blodgett Forest, California in late summer 2007. The median diurnal variation shows minimum HONO levels of about 20–30 pptv during the day and maximum levels of about 60–70 pptv at night, a diurnal pattern quite different from the results at various other forested sites. Measured HONO/NO2 ratios for a 24-h period ranged from 0.05 to 0.13 with a mean ratio of 0.07. Speciation of reactive nitrogen compounds (NOy) indicates that HONO accounted for only ~3% of total NOy. However, due to the fast HONO loss through photolysis, a strong HONO source (1.59 ppbv day−1) existed in this environment in order to sustain the observed HONO levels, indicating the significant role of HONO in NOy cycling. The LOPAP HONO measurements were compared to the HONO measurements made with a Chemical Ionization Mass Spectrometer (CIMS) over a three-day period. Good agreement was obtained between the measurements from the two different techniques. Using the expansive suite of photochemical and meteorological measurements, the contribution of HONO photolysis to HOx budget was calculated to be relatively small (6%) compared to results from other forested sites. The lower HONO mixing ratio and thus its smaller contribution to HOx production are attributed to the unique meteorological conditions and low acid precipitation at Blodgett Forest. Further studies of HONO in this kind of environment are needed to test this hypothesis and to improve our understanding of atmospheric oxidation and nitrogen budget.

International audience; We describe observations of atmospheric reactive nitrogen compounds including NO, NO2, total peroxy nitrates, total alkyl nitrates, and HNO3 and their correlation with temperature. The measurements were made at a rural location 1315 m a.s.l. on the western slope of the Sierra Nevada Mountains in California during summer of 2001. The ratio of HNO3 to its source molecule, NO2, and the ratio of HNO3 to all other higher oxides of nitrogen (NOz) both increase with increasing temperature. Analysis of these increases suggests they are due to a steep increase in OH of between a factor of 2 and 3 over the range 18?32°C. Total peroxy nitrates decrease and total alkyl nitrates increase over the same temperature range. The decrease in the total peroxy nitrates is shown to be much less than expected if the rate of thermal decomposition were the sole important factor. This observation is consistent with the increase in OH inferred from the temperature trends in the HNO3/NO2 ratio.

International audience; Observations of speciated nitrogen oxides, namely NO2, total peroxy nitrates (?PNs), total alkyl nitrates (?ANs), and HNO3 by thermal dissociation laser induced fluorescence (TD-LIF), and supporting chemical and meteorological measurements at Big Hill (1860 m), a high elevation site in California's Sierra Nevada Mountains, are described. From May through October, terrain-driven winds in the region routinely bring air from Sacramento, 100 km southwest of the site, upslope over oak and pine forests to Big Hill during the day, while at night, the site often samples clean, dry air characteristic of the free troposphere. Winter differs mainly in that the meteorology does not favour the buildup of Sacramento's pollution over the Sierra Nevada range, and the urban-influenced air that is seen has been less affected by biogenic VOC emissions, resulting in longer lifetime for NO2 and a predominance of the inorganic forms of nitrogen oxides. Summertime observations at Big Hill can be compared with those from Granite Bay, a Sacramento suburb, and from the University of California's Blodgett Forest Research Station to examine the evolution of nitrogen oxides and ozone within the urban plume. Nitrogen oxide radicals (NO and NO2), which dominate total nitrogen oxides (NOy) at Granite Bay, are rapidly converted into HNO3, ?PNs, and ?ANs, such that these compounds contribute 29, 30, and 21% respectively to the NOy budget in the plume at Big Hill. Nevertheless, the decreasing concentrations of NO2 as the plume is advected to Big Hill lead to decreases in the production rate of HNO3 and ozone. The data also demonstrate the role that temperature plays in sequestering NO2 into peroxy nitrates, effectively decreasing the rate of ozone production. The important contribution of ?ANs to NOy in the region suggests that they should be considered with regards to export of NOy from the boundary layer. Nocturnal observations of airmasses characteristic of the free troposphere showed lower NOy concentrations, which were dominated by HNO3 with a relatively small contribution from the organic nitrates.

International audience; Nitrogen exchange between the atmosphere and biosphere directly influences atmospheric composition. While much is known about mechanisms of NO and N2O emissions, instrumentation for the study of mechanisms contributing to exchange of other major nitrogen species is quite limited. Here we describe the application of a new technique, thermal dissociation-laser induced fluorescence (TD-LIF), to eddy covariance measurements of the fluxes of NO2, total peroxy acyl and peroxy nitrates, total alkyl and multifunctional alkyl nitrates, and nitric acid. The technique offers the potential for investigating mechanisms of exchange of these species at the canopy scale over timescales from days to years. Examples of flux measurements at a ponderosa pine plantation in the mid-elevation Sierra Nevada Mountains in California are reported and used to evaluate instrument performance.

Observations of day-of-week patterns and diurnal profiles of ozone, volatile organic compounds and nitrogen oxides are examined to assess the chemical and dynamical factors governing the daytime ozone accumulation and the distribution of chemically related species in Central California. Isoprene observations show that urban OH concentrations are higher on the weekend whereas rural OH concentrations are lower on the weekend, confirming that NOx concentrations have a direct effect on the rate of photochemical ozone production and that the transition from NOx-saturated (VOC-limited) to NOx-limited chemistry occurs between the city and the downwind rural counties. We quantify the extent to which mixing of ozone and its precursors from aloft contributes to the daytime accumulation of ozone at the surface in Sacramento. Ozone production in the rural Mountain Counties is currently NOx-limited and will decrease in response to NOx emission reductions in the Sacramento Valley. However, NOx emissions reductions of at least 50% (from weekday levels) are necessary to bring about a significant decrease in accumulation of ozone at the surface in the Sacramento Valley. The impact of NOx emission reductions on the frequency of exceeding the federal 8-hour ozone standard at an individual site will depend on the balance between reduced titration and the sign and magnitude of production changes. We further show that HNO3 production, which depends on the product of OH and NO2 mixing ratios, is a constant at high NOx, suggesting that NOx must be reduced below a threshold before nitrate aerosol can be expected to decrease.

International audience; We report in situ measurements of N2O5, NO2, and O3 in Contra Costa County, California during January 2004. Mixing ratios of N2O5, an intermediate compound in the atmosphere's nocturnal cleansing process, ranged up to 200pmol/mol at night. The highest N2O5 concentrations were correlated with low O3 and high NO2 concentrations. The calculated steady state lifetime for N2O5 ranged from 5 to 30min. The total HNO3 produced by N2O5 hydrolysis over a 14h night was comparable to ambient NO2 concentrations, and is estimated to be a factor of nine bigger than the HNO3 produced during the day.

International audience; The chemistry of peroxynitric acid (HO2NO2) and methyl peroxynitrate (CH3O2NO2)is predicted to be particularly important in the upper troposphere where temperatures are frequently low enough that these compounds do not rapidly decompose. At temperatures below 240K, we calculate that about 20% of NOy in the mid- and high-latitude upper troposphere is HO2NO2. Under these conditions, the reaction of OH with HO2NO2 is estimated to account for as much as one third of the permanent loss of hydrogen radicals. During the Tropospheric Ozone Production about the Spring Equinox (TOPSE) campaign, we used thermal dissociation laser-induced fluorescence (TD-LIF) to measure the sum of peroxynitrates (PNs HO2NO2+CH3O2NO2+PAN+PPN+...) aboard the NCAR C-130 research aircraft. We infer the sum of HO2NO2 and CH3O2NO2 as the difference between PN measurements and gas chromatographic measurements of the two major peroxy acyl nitrates, peroxy acetyl nitrate (PAN) and peroxy propionyl nitrate (PPN). Comparison with NOy and other nitrogen oxide measurements confirms the importance of HO2NO2 and CH3O2NO2 to the reactive nitrogen budget and shows that current thinking about the chemistry of these species is approximately correct. During the spring high latitude conditions sampled during the TOPSE experiment, the model predictions of the contribution of (HO2NO2+CH3O2NO2) to NOy are highly temperature dependent: on average 30% of NOy at 230K, 15% of NOy at 240K, and 5% of NOy above 250K. The temperature dependence of the inferred concentrations corroborates the contribution of overtone photolysis to the photochemistry of peroxynitric acid. A model that includes IR photolysis (J=1x10-5s-1) agreed with the observed sum of HO2NO2+CH3O2NO2 to better than 35% below 240K where the concentration of these species is largest.

Reactions that inter-convert OH and HO_2 are directly involved in the catalytic removal of O_3 in the lower stratosphere and in the catalytic production of O_3 in the upper troposphere. The agreement between the measured and modeled [HO_2]/[OH] tests our current understanding of this important chemistry. Recent changes to the recommended rate constants for OH+O_3 and HO_2+O_3 call into question how accurately the chemistry of the stratosphere is understood. [HO_2]/[OH] calculated with the new recommendations is 48% higher than the observations throughout the lower stratosphere, exceeding the uncertainty limits of the observations (20%). The extensive atmospheric data set allows tests of the rates of the individual processes that couple these free radicals. This work shows that the discrepancy is largest when the ratio is controlled by the reactions of OH and HO_2 with ozone.

We examine inorganic chlorine (Cl_y,) partitioning in the summer lower stratosphere using in situ ER-2 aircraft observations made during the Photochemistry of Ozone Loss in the Arctic Region in Summer (POLARIS) campaign. New steady state and numerical models estimate [ClONO_2]/[HCl] using currently accepted photochemistry. These models are tightly constrained by observations with OH (parameterized as a function of solar zenith angle) substituting for modeled HO_2 chemistry. We find that inorganic chlorine photochemistry alone overestimates observed [ClONO_2]/[HCl] by approximately 55–60% at mid and high latitudes. On the basis of POLARIS studies of the inorganic chlorine budget, [ClO]/[ClONO_2], and an intercomparison with balloon observations, the most direct explanation for the model-measurement discrepancy in Cl_y, partitioning is an error in the reactions, rate constants, and measured species concentrations linking HCl and ClO (simulated [ClO]/[HCl] too high) in combination with a possible systematic error in the ER-2 ClONO_2 measurement (too low). The high precision of our simulation (±15% 1σ for [ClONO_2]/[HCl], which is compared with observations) increases confidence in the observations, photolysis calculations, and laboratory rate constants. These results, along with other findings, should lead to improvements in both the accuracy and precision of stratospheric photochemical models.

Measurements of the concentrations of OH and HO_(2) (HO_(x)) in the high-latitude lower stratosphere imply the existence of unknown photolytic sources of HO_(x). The strength of the additional HO_(x) source required to match the observations depends only weakly on solar zenith angle (SZA) for 80° < SZA < 93°. The wavelengths responsible for producing this HO_(x) must be longer than 650 nm because the flux at shorter wavelengths is significantly attenuated at high SZA by scattering and absorption. Provided that the sources involve only a single photon, the strength of the bonds being broken must be < 45 kcal mole^(−1). We speculate that peroxynitric acid (HNO_4) dissociates after excitation to an unknown excited state with an integrated band cross section of 2-3 × 10^(−20) cm^(2) molecule^(−1) nm (650 < λ < 1250 nm).