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Peroxynitrates are responsible for global scale transport of reactive nitrogen. Recent laboratory observations suggest that they may also play an important role in delivery of nutrients to plant canopies. We measured eddy covariance fluxes of total peroxynitrates (ΣPNs) and three individual peroxynitrates (APNs ≡ PAN + PPN + MPAN) over a ponderosa pine forest during the Biosphere Effects on AeRosols and Photochemistry EXperiment 2009 (BEARPEX 2009). Concentrations of these species were also measured at multiple heights above and within the canopy. While the above-canopy daytime concentrations are nearly identical for ΣPNs and APNs, we observed the downward flux of ΣPNs to be 30–60% slower than the flux of APNs. The vertical concentration gradients of ΣPNs and APNs vary with time of day and exhibit different temperature dependencies. These differences can be explained by the production of peroxynitrates other than PAN, PPN, and MPAN within the canopy (presumably as a consequence of biogenic VOC emissions) and upward fluxes of these PN species. The impact of this implied peroxynitrate flux on the interpretation of NOx fluxes and ecosystem N exchange is discussed.

We describe the effects of nitrogen oxide (NOx) and organic reactivity reductions on the frequency of high ozone days in California's San Joaquin Valley. We use sixteen years of observations of ozone, nitrogen oxides, and temperature at sites upwind, within, and downwind of three cities to assess the probability of exceeding the California 8-h average ozone standard of 70.4 ppb at each location. The comprehensive data records in the region and the steep decreases in emissions over the last decade are sufficient to constrain the relative import of NOx and organic reactivity reductions on the frequency of violations. We show that high ozone has a large component that is due to local production, as the probability of exceeding the state standard is lowest for each city at the upwind site, increases in the city center, is highest at downwind locations, and then decreases at the receptor city to the south. We see that reductions in organic reactivity have been very effective in the central and northern regions of the San Joaquin but less so in the southern portion of the Valley. We find evidence for two distinct categories of reactivity sources: one source that has decreased and dominates at moderate temperatures, and a second source that dominates at high temperatures, particularly in the southern San Joaquin, and has not changed over the last twelve years. We show that NOx reductions are already effective or are poised to become so in the southern and central Valley, where violations are most frequent, as conditions in these regions have or are transitioning to NOx-limited chemistry when temperatures are hottest and high ozone most probable.

Soils have been identified as a major source (~15%) of global nitrogen oxide (NOx) emissions. Parameterizations of soil NOx emissions (SNOx ) commonly used in the current generation of chemical transport models were designed to capture mean seasonal behaviour. These parameterizations do not, however, respond quantitatively to the meteorological triggers that are observed to result in pulsed SNOx . Here we present a new parameterization of SNOx implemented within a global chemical transport model (GEOS-Chem). The parameterization represents available nitrogen (N) in soils using biome specific emission factors, online wet- and dry-deposition of N, and fertilizer and manure N derived from a spatially explicit dataset, distributed using seasonality derived from data obtained by the Moderate Resolution Imaging Spectrometer. Moreover, it represents the functional form of emissions derived from point measurements and ecosystem scale experiments including pulsing following soil wetting by rain or irrigation, and emissions that are a smooth function of soil moisture as well as temperature between 0 and 30 °C. This parameterization yields global above-soil SNOx of 10.7 Tg N yr−1, including 1.8 Tg N yr−1 from fertilizer N input (1.5% of applied N) and 0.5 Tg N yr−1 from atmospheric N deposition. Over the United States (US) Great Plains region, SNOx are predicted to comprise 15–40% of the tropospheric NO2 column and increase column variability by a factor of 2–4 during the summer months due to chemical fertilizer application and warm temperatures. SNOx enhancements of 50–80% of the simulated NO2 column are predicted over the African Sahel during the monsoon onset (April–June). In this region the day-to-day variability of column NO2 is increased by a factor of 5 due to pulsed-N emissions. We evaluate the model by comparison with observations of NO2 column density from the Ozone Monitoring Instrument (OMI). We find that the model is able to reproduce the observed interannual variability of NO2 (induced by pulsed-N emissions) over the US Great Plains. We also show that the OMI mean (median) NO2 observed during the overpass following first rainfall over the Sahel is 49% (23%) higher than in the five days preceding. The measured NO2 on the day after rainfall is still 23% (5%) higher, providing a direct measure of the pulse's decay time of 1–2 days. This is consistent with the pulsing representation used in our parameterization and much shorter than 5–14 day pulse decay length used in current models.

Using measurements from the NASA Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) experiment, we show that methyl peroxy nitrate (CH3O2NO2) is present in concentrations of ~5–15 pptv in the springtime arctic upper troposphere. We investigate the regional and global effects of CH3O2NO2 by including its chemistry in the GEOS-Chem 3-D global chemical transport model. We find that at temperatures below 240 K inclusion of CH3O2NO2 chemistry results in decreases of up to ~20 % in NOx, ~20 % in N2O5, ~5 % in HNO3, ~2 % in ozone, and increases in methyl hydrogen peroxide of up to ~14 %. Larger changes are observed in biomass burning plumes lofted to high altitude. Additionally, by sequestering NOx at low temperatures, CH3O2NO2 decreases the cycling of HO2 to OH, resulting in a larger upper tropospheric HO2 to OH ratio. These results may impact some estimates of lightning NOx sources as well as help explain differences between models and measurements of upper tropospheric composition.

The formation of organic nitrates and secondary organic aerosol (SOA) were monitored during the NO3 + limonene reaction in the atmosphere simulation chamber SAPHIR at Research Center Jülich. The 24-h run began in a purged, dry, particle-free chamber and comprised two injections of limonene and oxidants, such that the first experiment measured SOA yield in the absence of seed aerosol, and the second experiment yields in the presence of 10 μg m−3 seed organic aerosol. After each injection, two separate increases in aerosol mass were observed, corresponding to sequential oxidation of the two limonene double bonds. Analysis of the measured NO3, limonene, product nitrate concentrations, and aerosol properties provides mechanistic insight and constrains rate constants, branching ratios and vapor pressures of the products. The organic nitrate yield from NO3 + limonene is ≈30%. The SOA mass yield was observed to be 25–40%. The first injection is reproduced by a kinetic model. PMF analysis of the aerosol composition suggests that much of the aerosol mass results from combined oxidation by both O3 and NO3, e.g., oxidation of NO3 + limonene products by O3. Further, later aerosol nitrate mass seems to derive from heterogeneous uptake of NO3 onto unreacted aerosol alkene.

We examine the interannual variability in the NO2 column over North America measured by the Ozone Monitoring Instrument (OMI) in 2005–2008. By comparison to a model of soil NOx emissions driven by the North American Regional Reanalysis precipitation and 0–10 cm soil temperature fields, we show the source of this observed interannual variability over much of the central United States in June is fertilizer application. We find that dry, warm conditions followed by convective precipitation induces pulsed emissions of NOx over the agricultural Great Plains. In June 2006 we infer a 50% increase in soil NOx emission and a 30% increase in the tropospheric NO2 column relative to the June 2005–2008 mean. In a case-study of fertilized corn and soybean fields over SE South Dakota, we find an associated rain-induced pulsing event reaching 4.6×1015 molec cm−2, equivalent to a surface concentration of ~2 ppbv. We calculate that soil NOx emissions resulted in a mean daily maximum 8-h ozone enhancement over the agricultural Great Plains of 5 ppbv in June 2006 (with predicted events reaching 16 ppbv) compared with a mean enhancement of 3 ppbv for soil NOx in the years 2005–2008.

Alkyl and multifunctional nitrates (RONO2, Sigma ANs) have been observed to be a significant fraction of NOy in a number of different chemical regimes. Their formation is an important free radical chain termination step ending production of ozone and possibly affecting formation of secondary organic aerosol. Sigma ANs also represent a potentially large, unmeasured contribution to OH reactivity and are a major pathway for the removal of nitrogen oxides from the atmosphere. Numerous studies have investigated the role of nitrate formation from biogenic compounds and in the remote atmosphere. Less attention has been paid to the role Sigma ANs may play in the complex mixtures of hydrocarbons typical of urban settings. Measurements of total alkyl and multifunctional nitrates, NO2, total peroxy nitrates (Sigma PNs), HNO3 and a representative suite of hydrocarbons were obtained from the NASA DC-8 aircraft during spring of 2006 in and around Mexico City and the Gulf of Mexico. Sigma ANs were observed to be 10-20% of NOy in the Mexico City plume and to increase in importance with increased photochemical age. We describe three conclusions: (1) Correlations of Sigma ANs with odd-oxygen (O-x) indicate a stronger role for Sigma ANs in the photochemistry of Mexico City than is expected based on currently accepted photochemical mechanisms, (2) Sigma AN formation suppresses peak ozone production rates by as much as 40% in the near-field of Mexico City and (3) Sigma ANs play a significant role in the export of NOy from Mexico City to the Gulf Region.

The Sulfur Transport and dEposition Model (STEM) is applied to the analysis of observations obtained during the Intercontinental Chemical Transport Experiment-Phase B (INTEX-B), conducted over the eastern Pacific Ocean during spring 2006. Predicted trace gas and aerosol distributions over the Pacific are presented and discussed in terms of transport and source region contributions. Trace species distributions show a strong west (high) to east (low) gradient, with the bulk of the pollutant transport over the central Pacific occurring between similar to 20 degrees N and 50 degrees N in the 2-6 km altitude range. These distributions are evaluated in the eastern Pacific by comparison with the NASA DC-8 and NSF/NCAR C-130 airborne measurements along with observations from the Mt. Bachelor (MBO) surface site. Thirty different meteorological, trace gas and aerosol parameters are compared. In general the meteorological fields are better predicted than gas phase species, which in turn are better predicted than aerosol quantities. PAN is found to be significantly overpredicted over the eastern Pacific, which is attributed to uncertainties in the chemical reaction mechanisms used in current atmospheric chemistry models in general and to the specifically high PAN production in the SAPRC-99 mechanism used in the regional model. A systematic underprediction of the elevated sulfate layer in the eastern Pacific observed by the C-130 is another issue that is identified and discussed. Results from source region tagged CO simulations are used to estimate how the different source regions around the Pacific contribute to the trace gas species distributions. During this period the largest contributions were from China and from fires in South/Southeast and North Asia. For the C-130 flights, which operated off the coast of the Northwest US, the regional CO contributions range as follows: China (35%), South/Southeast Asia fires (35%), North America anthropogenic (20%), and North Asia fires (10%). The transport of pollution into the western US is studied at MBO and a variety of events with elevated Asian dust, and periods with contributions from China and fires from both Asia and North America are discussed. The role of heterogeneous chemistry on the composition over the eastern Pacific is also studied. The impacts of heterogeneous reactions at specific times can be significant, increasing sulfate and nitrate aerosol production and reducing gas phase nitric acid levels appreciably (similar to 50%).

Air quality in the outflow from urban centers affects millions of people, as well as, natural and managed ecosystems downwind. In locations where there are large sources of biogenic VOCs downwind of urban centers, the outflow is characterized by a high VOC reactivity due to biogenic emissions and low NOx. However most field and chamber studies have focused on limiting cases of high NOx or of near zero NOx. Recent measurements of a wide suite of VOCs, O3 and meteorological parameters at several locations within the Sacramento urban plume have provided a detailed benchmark for testing our understanding of chemistry in a plume transitioning from high NOx to low NOx and high VOC reactivity. As an additional simplification, the strong mountain valley circulation in the region makes this urban plume a physical realization of a nearly idealized Lagrangian plume. Here, we describe a model of this plume. We use a Lagrangian model representing chemistry based on the Master Chemical Mechanism (MCM) v3.1 along with mixing and deposition. We discuss the effects of entrainment of background air, the branching ratio for the production of isoprene nitrates and the effects of soil NOx emissions on the composition of the evolving plume. The model predicts that after 2–3 h of chemical processing only 45% of the peroxynitrates (ΣPNs) are PAN and that most (69%) RONO2 are secondary alkyl nitrate products of the reaction of OH with RONO2. We find the model is more consistent with the observations if: a) the yield of ΣPNs from large and multi-functional aldehydes is close to zero; and b) the reaction between OH and RONO2 produces multifunctional nitrates as opposed to either HNO3 or NO2 as is typical in most currently adopted reaction mechanisms. Model results also show that adding NOx emissions throughout the transect increases the available NOx in the downwind regions, but modeled ozone concentrations were little affected by the increased NOx.

In-situ airborne measurements of trace gases, aerosol size distributions, chemistry and optical properties were conducted over Mexico and the Eastern North Pacific during MILAGRO and INTEX-B. Heterogeneous reactions between secondary aerosol precursor gases and mineral dust lead to sequestration of sulfur, nitrogen and chlorine in the supermicrometer particulate size range. Simultaneous measurements of aerosol size distributions and weak-acid soluble calcium result in an estimate of 11 wt% of CaCO3 for Asian dust. During transport across the North Pacific, ~5–30% of the CaCO3 is converted to CaSO4 or Ca(NO3)2 with an additional ~4% consumed through reactions with HCl. The 1996 to 2008 record from the Mauna Loa Observatory confirm these findings, indicating that, on average, 19% of the CaCO3 has reacted to form CaSO4 and 7% has reacted to form Ca(NO3)2 and ~2% has reacted with HCl. In the nitrogen-oxide rich boundary layer near Mexico City up to 30% of the CaCO3 has reacted to form Ca(NO3)2while an additional 8% has reacted with HCl. These heterogeneous reactions can result in a ~3% increase in dust solubility which has an insignificant effect on their optical properties compared to their variability in-situ. However, competition between supermicrometer dust and submicrometer primary aerosol for condensing secondary aerosol species led to a 25% smaller number median diameter for the accumulation mode aerosol. A 10–25% reduction of accumulation mode number median diameter results in a 30–70% reduction in submicrometer light scattering at relative humidities in the 80–95% range. At 80% RH submicrometer light scattering is only reduced ~3% due to a higher mass fraction of hydrophobic refractory components in the dust-affected accumulation mode aerosol. Thus reducing the geometric mean diameter of the submicrometer aerosol has a much larger effect on aerosol optical properties than changes to the hygroscopic:hydrophobic mass fractions of the accumulation mode aerosol. In the presence of dust, nitric acid concentrations are reduced to 85% to 60–80% in the presence of dust. These observations support previous model studies which predict irreversible sequestration of reactive nitrogen species through heterogeneous reactions with mineral dust during long-range transport.

Formation of isoprene nitrates (INs) is an important free radical chain termination step ending production of ozone and possibly affecting formation of secondary organic aerosol. Isoprene nitrates also represent a potentially large, unmeasured contribution to OH reactivity and are a major pathway for the removal of nitrogen oxides from the atmosphere. Current assessments indicate that formation rates of isoprene nitrates are uncertain to a factor of 2-3 and the subsequent fate of isoprene nitrates remains largely unconstrained by laboratory, field or modeling studies. Measurements of total alkyl and multifunctional nitrates (Sigma ANs), NO2, total peroxy nitrates (Sigma PNs), HNO3, CH2O, isoprene and other VOC were obtained from the NASA DC-8 aircraft during summer 2004 over the continental US during the INTEX-NA campaign. These observations represent the first characterization of Sigma ANs over a wide range of land surface types and in the lower free troposphere. Sigma ANs were a significant, 12-20%, fraction of NOy throughout the experimental domain and Sigma ANs were more abundant when isoprene was high. We use the observed hydrocarbon species to calculate the relative contributions of Sigma AN precursors to their production. These calculations indicate that isoprene represents at least three quarters of the Sigma AN source in the summertime continental boundary layer of the US. An observed correlation between Sigma ANs and CH2O is used to place constraints on nitrate yields from isoprene oxidation, atmospheric lifetimes of the resulting nitrates and recycling efficiencies of nitrates during subsequent oxidation. We find reasonable fits to the data using sets of production rates, lifetimes and recycling efficiencies of INs as follows (4.4%, 16 h, 97%), (8%, 2.5h, 79%) and (12%, 95 min, 67%). The analysis indicates that the lifetime of Sigma ANs as a pool of compounds is considerably longer than the lifetime of the individual isoprene nitrates to reaction with OH, implying that the organic nitrate functionality is at least partially maintained through a second oxidation cycle.

The yields of organic nitrates and of secondary organic aerosol (SOA) particle formation were measured for the reaction NO3+β-pinene under dry and humid conditions in the atmosphere simulation chamber SAPHIR at Research Center Jülich. These experiments were conducted at low concentrations of NO3 (NO3+N2O5

The measurement of OH reactivity, the inverse of the OH lifetime, provides a powerful tool to investigate atmospheric photochemistry. A new airborne OH reactivity instrument was designed and deployed for the first time on the NASA DC-8 aircraft during the second phase of Intercontinental Chemical Transport Experiment-B (INTEX-B) campaign, which was focused on the Asian pollution outflow over Pacific Ocean and was based in Hawaii and Alaska. The OH reactivity was measured by adding OH, generated by photolyzing water vapor with 185 nm UV light in a moveable wand, to the flow of ambient air in a flow tube and measuring the OH signal with laser induced fluorescence. As the wand was pulled back away from the OH detector, the OH signal decay was recorded; the slope of -Delta 1n(signal)/Delta time was the OH reactivity. The overall absolute uncertainty at the 2 sigma confidence levels is about 1 s(-1) at low altitudes (for decay about 6 s(-1)), and 0.7 s(-1) at high altitudes (for decay about 2 s(-1)). From the median vertical profile obtained in the second phase of INTEX-B, the measured OH reactivity (4.0 +/- 1.0 s(-1)) is higher than the OH reactivity calculated from assuming that OH was in steady state (3.3 +/- 0.8 s(-1)), and even higher than the OH reactivity that was calculated from the total measurements of all OH reactants (1.6 +/- 0.4 s(-1)). Model calculations show that the missing OH reactivity is consistent with the over-predicted OH and under-predicted HCHO in the boundary layer and lower troposphere. The over-predicted OH and under-predicted HCHO suggest that the missing OH sinks are most likely related to some highly reactive VOCs that have HCHO as an oxidation product.

The evaporation rate of D2O has been determined by Raman thermometry of a droplet train (12–15 μm diameter) injected into vacuum (~10-5 torr). The cooling rate measured as a function of time in vacuum was fit to a model that accounts for temperature gradients between the surface and the core of the droplets, yielding an evaporation coefficient (γe) of 0.57±0.06. This is nearly identical to that found for H2O (0.62±0.09) using the same experimental method and model, and indicates the existence of a kinetic barrier to evaporation. The application of a recently developed transition-state theory (TST) model suggests that the kinetic barrier is due to librational and hindered translational motions at the liquid surface, and that the lack of an isotope effect is due to competing energetic and entropic factors. The implications of these results for cloud and aerosol particles in the atmosphere are discussed.

The first direct in situ measurements of HO2NO2 in the upper troposphere were performed from the NASA DC-8 during the Intercontinental Chemical Transport Experiment–North America 2004 with a chemical ionization mass spectrometer (CIMS). These measurements provide an independent diagnostic of HOx chemistry in the free troposphere and complement direct observations of HOx, because of the dual dependency of HO2NO2 on HOx and NOx. On average, the highest HO2NO2 mixing ratio of 76 pptv (median = 77 pptv,σ = 39 pptv) was observed at altitudes of 8–9 km. Simple steady state calculations of HO2NO2, constrained by measurements of HOx, NOx, and J values, are in good agreement (slope = 0.90, R2 = 0.60, and z = 5.5–7.5 km) with measurements in the midtroposphere where thermal decomposition is the major loss process. Above 8 km the calculated steady state HO2NO2 is in poor agreement with observed values (R2 = 0.20) and is typically larger by a factor of 2.4. Conversely, steady state calculations using model-derived HOx show reasonable agreement with the observed HO2NO2 in both the midtroposphere (slope = 0.96, intercept = 7.0, and R2 = 0.63) and upper troposphere (slope = 0.80, intercept = 32.2, and R2 = 0.58). These results indicate that observed HO2 and HO2NO2 are in poor agreement in the upper troposphere but that HO2NO2 levels are consistent with current photochemical theory.

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 240 K, 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 (SigmaPNsequivalent toHO(2)NO(2)+CH3O2NO2+PAN+PPN+...) aboard the NCAR C-130 research aircraft. We infer the sum of HO2NO2 and CH3O2NO2 as the difference between SigmaPN 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 230 K, 15% of NOy at 240 K, and

In situ measurements of hydrogen, nitrogen, and chlorine radicals obtained through sunrise and sunset in the lower stratosphere during SPADE are compared to results from a photochemical model constrained by observed concentrations of radical precursors and environmental conditions. Models allowing for heterogeneous hydrolysis of N2O5 on sulfate aerosols agree with measured concentrations of NO, NO2, and ClO throughout the day, but fail to account for high concentrations of OH and HO2 observed near sunrise and sunset. The morning burst of [OH] and [HO2] coincides with the rise of [NO] from photolysis of NO2, suggesting a new source of HOxthat photolyzes in the near UV (350 to 400 nm) spectral region. A model that allows for the heterogeneous production of HNO2 results in an excellent simulation of the diurnal variations of [OH] and [HO2].

The situ observations were used to evaluate the primary mechanisms that control NOx-HNO3 exchange and to understand their control over the partitioning between NO2 and HNO3 in regions of continuous sunlight. The steady-state description of NOx-HNO3 exchange reveals the significant influence of the tight correlation between the photolysis rate of HNO3 and [OH] established in situ measurements throughout the lower stratosphere.

In situ observations of OH and HO2 from the Airborne Southern Hemisphere Ozone Experiment/Measurements for Assessing the Effects of Stratospheric Aircraft (ASHOE/MAESA), Stratospheric TRacers of Atmospheric Transport (STRAT), and Polar Ozone Loss in the Arctic Region in Summer (POLARIS) NASA ER-2 field campaigns are used to examine the partitioning of HOx in the lower stratosphere (tropopause to ~21 km) and upper troposphere. The concentration of HO2 depends on [OH], which, to first order, was observed to be a simple function of the solar zenith angle in the lower stratosphere.

The extensive measurement campaigns by the NASA ER-2 research aircraft have obtained a nearly pole-to-pole database of the species that control HOx (OH + HO2) chemistry. The measurements in the lower stratosphere shows a remarkably tight correlation of OH concentration with the solar zenith angle (SZA).