At the Rocky Mountain Biogenic Aerosol Study (BEACHON-RoMBAS) field campaign in the Colorado front range, July–August 2011, measurements of gas- and aerosol-phase organic nitrates enabled a study of ...the role of NOx (NOx = NO + NO2) in oxidation of forest-emitted volatile organic compounds (VOCs) and subsequent aerosol formation. Substantial formation of peroxy- and alkyl-nitrates is observed every morning, with an apparent 2.9% yield of alkyl nitrates from daytime RO2 + NO reactions. Aerosol-phase organic nitrates, however, peak in concentration during the night, with concentrations up to 140 ppt as measured by both optical spectroscopic and mass spectrometric instruments. The diurnal cycle in aerosol fraction of organic nitrates shows an equilibrium-like response to the diurnal temperature cycle, suggesting some reversible absorptive partitioning, but the full dynamic range cannot be reproduced by thermodynamic repartitioning alone. Nighttime aerosol organic nitrate is observed to be positively correlated with NO2 × O3 but not with O3. These observations support the role of nighttime NO3-initiated oxidation of monoterpenes as a significant source of nighttime aerosol. Nighttime production of organic nitrates is comparable in magnitude to daytime photochemical production at this site, which we postulate to be representative of the Colorado front range forests.
Measurements of hydroxyl (OH) and hydroperoxy (HO2*) radical concentrations were made at the Pasadena ground site during the CalNex‐LA 2010 campaign using the laser‐induced fluorescence‐fluorescence ...assay by gas expansion technique. The measured concentrations of OH and HO2* exhibited a distinct weekend effect, with higher radical concentrations observed on the weekends corresponding to lower levels of nitrogen oxides (NOx). The radical measurements were compared to results from a zero‐dimensional model using the Regional Atmospheric Chemical Mechanism‐2 constrained by NOx and other measured trace gases. The chemical model overpredicted measured OH concentrations during the weekends by a factor of approximately 1.4 ± 0.3 (1σ), but the agreement was better during the weekdays (ratio of 1.0 ± 0.2). Model predicted HO2* concentrations underpredicted by a factor of 1.3 ± 0.2 on the weekends, while measured weekday concentrations were underpredicted by a factor of 3.0 ± 0.5. However, increasing the modeled OH reactivity to match the measured total OH reactivity improved the overall agreement for both OH and HO2* on all days. A radical budget analysis suggests that photolysis of carbonyls and formaldehyde together accounted for approximately 40% of radical initiation with photolysis of nitrous acid accounting for 30% at the measurement height and ozone photolysis contributing less than 20%. An analysis of the ozone production sensitivity reveals that during the week, ozone production was limited by volatile organic compounds throughout the day during the campaign but NOx limited during the afternoon on the weekends.
Key Points
Measurements of OH and HO2 during CalNex‐LA displayed a weekend effect
Modeled OH and HO2 agreed with measurements after accounting for missing OH reactivity
Ozone production was VOC limited on the weekdays but NOx limited on the weekends
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Recent measurements in Houston show that HONO traffic emissions are 1.7% of NOx emissions, which is about twice the previously estimated value of 0.8% based on tunnel measurements in 2001. The 0.8% ...value is widely used to estimate mobile emissions of HONO for air quality modeling applications. This study applies the newly estimated HONO / NOx ratio in the WRF-SMOKE-CMAQ modeling system and estimates the impact of higher HONO traffic emissions on its mixing ratios. Since applied emission inventory resulted in overestimates of NOx mixing ratios and because HONO emissions and chemical formation depend on the magnitude of NOx, thus, before proceeding with HONO emission modifications emissions of NOx were adjusted to reflect current emission trends. The modeled mixing ratios of NOx were evaluated against measured data from a number of sites in the Houston area. Overall, the NOx mean value dropped from 11.11 ppbv in the base case to 7.59 ppbv in the NOx-adjusted case becoming much closer to the observed mean of 7.76 ppbv. The index of agreement (IOA) is improved in the reduced NOx case (0.71 vs. 0.75) and the absolute mean error (AME) is lowered from 6.76 to 4.94. The modeled mixing ratios of HONO were evaluated against the actual observed values attained at the Moody Tower in Houston. The model could not reproduce the morning HONO peaks when the low HONO / NOx ratio of 0.008 was used to estimate HONO emissions. Doubling HONO emissions from mobile sources resulted in higher mixing ratios, and the mean value increased from 0.30 to 0.41 ppbv becoming closer to the observed mean concentrations of 0.69 but still low; AME was slightly reduced from 0.46 to 0.43. IOA for simulation that used the 2001 emission values is 0.63 while for simulation with higher HONO emission it increased to 0.70. Increased HONO emissions from mobile sources resulted in a 14% increase in OH during morning time at the location of the Moody Tower and 3% when averaged over an urban area. The increase calculated for daytime was 7 and 1% for the Moody Tower and the urban area, respectively. The impact on ozone was found to be marginal. This study results shed light on the underestimated HONO and OH in the morning from global/regional chemical transport models with the typical emission of 0.8% HONO emission out of the total NOx emissions.
Nitrous Acid (HONO) plays an important role in tropospheric chemistry as a precursor of the hydroxyl radical (OH), the most important oxidizing agent in the atmosphere. Nevertheless, the formation ...mechanisms of HONO are still not completely understood. Recent field observations found unexpectedly high daytime HONO concentrations in both urban and rural areas, which point to unrecognized, most likely photolytically enhanced HONO sources. Several gas-phase, aerosol, and ground surface chemistry mechanisms have been proposed to explain elevated daytime HONO, but atmospheric evidence to favor one over the others is still weak. New information on whether HONO formation occurs in the gas-phase, on aerosol, or at the ground may be derived from observations of the vertical distribution of HONO and its precursor nitrogen dioxide, NO2, as well as from its dependence on solar irradiance or actinic flux. Here we present field observations of HONO, NO2 and other trace gases in three altitude intervals (30–70 m, 70–130 m and 130–300 m) using UCLA's long path DOAS instrument, as well as in situ measurements of OH, NO, photolysis frequencies and solar irradiance, made in Houston, TX, during the Study of Houston Atmospheric Radical Precursor (SHARP) experiment from 20 April to 30 May 2009. The observed HONO mixing ratios were often ten times larger than the expected photostationary state with OH and NO. Larger HONO mixing ratios observed near the ground than aloft imply, but do not clearly prove, that the daytime source of HONO was located at or near the ground. Using a pseudo steady-state (PSS) approach, we calculated the missing daytime HONO formation rates, Punknown, on four sunny days. The NO2-normalized Punknown, Pnorm, showed a clear symmetrical diurnal variation with a maximum around noontime, which was well correlated with actinic flux (NO2 photolysis frequency) and solar irradiance. This behavior, which was found on all clear days in Houston, is a strong indication of a photolytic HONO source. HONO/NO2 ratios also showed a clear diurnal profile, with maxima of 2–3% around noon. PSS calculations show that this behavior cannot be explained by the proposed gas-phase reaction of photoexcited NO2 (NO2*) or any other gas-phase or aerosol photolytic process occurring at similar or longer wavelengths than that of HONO photolysis. HONO formation by aerosol nitrate photolysis in the UV also seems to be unlikely. Pnorm correlated better with solar irradiance (average R2 = 0.85/0.87 for visible/UV) than with actinic flux (R2 = 0.76) on the four sunny days, clearly pointing to HONO being formed at the ground rather than on the aerosol or in the gas-phase. In addition, the observed HONO/NO2 diurnal variation can be explained if the formation of HONO depends on solar irradiance, but not if it depends on the actinic flux. The vertical mixing ratio profiles, together with the stronger correlation with solar irradiance, support the idea that photolytically enhanced NO2 to HONO conversion on the ground was the dominant source of HONO in Houston.
Nitrous acid (HONO) acts as a major precursor of the hydroxyl radical (OH) in the urban atmospheric boundary layer in the morning and throughout the day. Despite its importance, HONO formation ...mechanisms are not yet completely understood. It is generally accepted that conversion of NO sub(2) on surfaces in the presence of water is responsible for the formation of HONO in the nocturnal boundary layer, although the type of surface on which the mechanism occurs is still under debate. Recent observations of higher than expected daytime HONO concentrations in both urban and rural areas indicate the presence of unknown daytime HONO source(s). Various formation pathways in the gas phase, and on aerosol and ground surfaces have been proposed to explain the presence of daytime HONO. However, it is unclear which mechanism dominates and, in the cases of heterogeneous mechanisms, on which surfaces they occur. Vertical concentration profiles of HONO and its precursors can help in identifying the dominant HONO formation pathways. In this study, daytime HONO and NO sub(2) vertical profiles, measured in three different height intervals (20-70, 70-130, and 130-300 m) in Houston, TX, during the 2009 Study of Houston Atmospheric Radical Precursors (SHARP) are analyzed using a one-dimensional (1-D) chemistry and transport model. Model results with various HONO formation pathways suggested in the literature are compared to the the daytime HONO and HONO/NO sub(2) ratios observed during SHARP. The best agreement of HONO and HONO/NO sub(2) ratios between model and observations is achieved by including both a photolytic source of HONO at the ground and on the aerosol. Model sensitivity studies show that the observed diurnal variations of the HONO/NO sub(2) ratio are not reproduced by the model if there is only a photolytic HONO source on aerosol or in the gas phase from NO sub(2) super(*) + H sub(2)O. Further analysis of the formation and loss pathways of HONO shows a vertical dependence of HONO chemistry during the day. Photolytic HONO formation at the ground is the major formation pathway in the lowest 20 m, while a combination of gas-phase, photolytic formation on aerosol, and vertical transport is responsible for daytime HONO between 200-300 m a.g.l. HONO removal is dominated by vertical transport below 20 m and photolysis between 200-300 m a.g.l.
Vegetation emits large quantities of biogenic volatile organic compounds (BVOC). At remote sites, these compounds are the dominant precursors to ozone and secondary organic aerosol (SOA) production, ...yet current field studies show that atmospheric models have difficulty in capturing the observed HOx cycle and concentrations of BVOC oxidation products. In this manuscript, we simulate BVOC chemistry within a forest canopy using a one-dimensional canopy-chemistry model (Canopy Atmospheric CHemistry Emission model; CACHE) for a mixed deciduous forest in northern Michigan during the CABINEX 2009 campaign. We find that the base-case model, using fully-parameterized mixing and the simplified biogenic chemistry of the Regional Atmospheric Chemistry Model (RACM), underestimates daytime in-canopy vertical mixing by 50–70% and by an order of magnitude at night, leading to discrepancies in the diurnal evolution of HOx, BVOC, and BVOC oxidation products. Implementing observed micrometeorological data from above and within the canopy substantially improves the diurnal cycle of modeled BVOC, particularly at the end of the day, and also improves the observation-model agreement for some BVOC oxidation products and OH reactivity. We compare the RACM mechanism to a version that includes the Mainz isoprene mechanism (RACM-MIM) to test the model sensitivity to enhanced isoprene degradation. RACM-MIM simulates higher concentrations of both primary BVOC (isoprene and monoterpenes) and oxidation products (HCHO, MACR+MVK) compared with RACM simulations. Additionally, the revised mechanism alters the OH concentrations and increases HO2. These changes generally improve agreement with HOx observations yet overestimate BVOC oxidation products, indicating that this isoprene mechanism does not improve the representation of local chemistry at the site. Overall, the revised mechanism yields smaller changes in BVOC and BVOC oxidation product concentrations and gradients than improving the parameterization of vertical mixing with observations, suggesting that uncertainties in vertical mixing parameterizations are an important component in understanding observed BVOC chemistry.
Analysis of in situ airborne measurements from the CalNex 2010 field experiment (Research at the Nexus of Air Quality and Climate Change) show that ozone in the boundary layer over Southern ...California was increased by downward mixing of air from the free troposphere (FT). The chemical composition, origin, and transport of air upwind and over Los Angeles, California, were studied using measurements of carbon monoxide (CO), ozone, reactive nitrogen species, and meteorological parameters from the National Oceanic and Atmospheric Administration WP‐3D aircraft on 18 research flights in California in May and June 2010. On six flights, multiple vertical profiles from 0.2–3.5 km above ground level were conducted throughout the Los Angeles (LA) basin and over the Pacific Ocean. Gas phase compounds measured in 32 vertical profiles are used to characterize air masses in the FT over the LA basin, with the aim of determining the source of increased ozone observed above the planetary boundary layer (PBL). Four primary air mass influences were observed regularly in the FT between approximately 1 and 3.5 km altitude: upper tropospheric air, long‐range transport of emissions, aged regional emissions, and marine air. The first three air mass types accounted for 89% of the FT observations. Ozone averaged 71 ppbv in air influenced by the upper troposphere, 69 ppbv in air containing emissions transported long distances, and 65 ppbv in air with aged regional emissions. Correlations between ozone and CO, and ozone and nitric acid, demonstrate entrainment of ozone from the FT into the LA PBL. Downward transport of ozone‐rich air from the FT into the PBL contributes to the ozone burden at the surface in this region and makes compliance with air quality standards challenging.
Key Points
Air mass chemical composition over Los Angeles Basin measured from aircraft
Upper tropospheric influence increased ozone in the lower free troposphere
Downward mixing of ozone‐rich air increased ozone in California
Attributing observed CO2 variations to human or natural cause is critical to deducing and tracking emissions from observations. We have used in situ CO2 , CO, and planetary boundary layer height ...(PBLH) measurements recorded during the CalNex-LA (CARB et al., 2008) ground campaign of 15 May-15 June 2010, in Pasadena, CA, to deduce the diurnally varying anthropogenic component of observed CO2 in the megacity of Los Angeles (LA). This affordable and simple technique, validated by carbon isotope observations and WRF-STILT (Weather Research and Forecasting model - Stochastic Time-Inverted Lagrangian Transport model) predictions, is shown to robustly attribute observed CO2 variation to anthropogenic or biogenic origin over the entire diurnal cycle. During CalNex-LA, local fossil fuel combustion contributed up to ~50% of the observed CO2 enhancement overnight, and ~100% of the enhancement near midday. This suggests that sufficiently accurate total column CO2 observations recorded near midday, such as those from the GOSAT or OCO-2 satellites, can potentially be used to track anthropogenic emissions from the LA megacity.
The role of chlorine atoms (Cl) in atmospheric oxidation has been traditionally thought to be limited to the marine boundary layer, where they are produced through heterogeneous reactions involving ...sea salt. However, recent observation of photolytic Cl precursors (ClNO2 and Cl2) formed from anthropogenic pollution has expanded the potential importance of Cl to include coastal and continental urban areas. Measurements of ClNO2 in Los Angeles during CalNex (California Nexus – Research at the Nexus of Air Quality and Climate Change) showed it to be an important primary (first generation) radical source. Evolution of ratios of volatile organic compounds (VOCs) has been proposed as a method to quantify Cl oxidation, but we find no evidence from this approach for a significant role of Cl oxidation in Los Angeles. We use a box model with the Master Chemical Mechanism (MCM v3.2) chemistry scheme, constrained by observations in Los Angeles, to examine the Cl sensitivity of commonly used VOC ratios as a function of NOx and secondary radical production. Model results indicate VOC tracer ratios could not detect the influence of Cl unless the ratio of OH to Cl was less than 200 for at least a day. However, the model results also show that secondary (second generation) OH production resulting from Cl oxidation of VOCs is strongly influenced by NOx, and that this effect obscures the importance of Cl as a primary oxidant. Calculated concentrations of Cl showed a maximum in mid-morning due to a photolytic source from ClNO2 and loss primarily to reactions with VOCs. The OH to Cl ratio was below 200 for approximately 3 h in the morning, but Cl oxidation was not evident from the measured ratios of VOCs. Instead, model simulations show that secondary OH production causes VOC ratio evolution to follow that expected for OH oxidation, despite the significant input of primary Cl from ClNO2 photolysis in the morning. Even though OH is by far the dominant oxidant in Los Angeles, Cl atoms do play an important role in photochemistry there, constituting 9% of the primary radical source. Furthermore, Cl–VOC reactivity differs from that of OH, being more than an order of magnitude larger and dominated by VOCs, such as alkanes, that are less reactive toward OH. Primary Cl is also slightly more effective as a radical source than primary OH due to its greater propensity to initiate radical propagation chains via VOC reactions relative to chain termination via reaction with nitrogen oxides.
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.
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