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.
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
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.
Nitrous acid (HONO) often plays an important role in tropospheric photochemistry as a major precursor of the hydroxyl radical (OH) in early morning hours and potentially during the day. However, the ...processes leading to formation of HONO and its vertical distribution at night, which can have a considerable impact on daytime ozone formation, are currently poorly characterized by observations and models. Long-path differential optical absorption spectroscopy (LP-DOAS) measurements of HONO during the 2006 TexAQS II Radical and Aerosol Measurement Project (TRAMP), near downtown Houston, TX, show nocturnal vertical profiles of HONO, with mixing ratios of up to 2.2 ppb near the surface and below 100 ppt aloft. Three nighttime periods of HONO, NO2 and O3 observations during TRAMP were used to perform model simulations of vertical mixing ratio profiles. By adjusting vertical mixing and NOx emissions the modeled NO2 and O3 mixing ratios showed very good agreement with the observations. Using a simple conversion of NO2 to HONO on the ground, direct HONO emissions, as well as HONO loss at the ground and on aerosol, the observed HONO profiles were reproduced by the model for 1–2 and 7–8 September in the nocturnal boundary layer (NBL). The unobserved increase of HONO to NO2 ratio (HONO/NO2) with altitude that was simulated by the initial model runs was found to be due to HONO uptake being too small on aerosol and too large on the ground. Refined model runs, with adjusted HONO uptake coefficients, showed much better agreement of HONO and HONO/NO2 for two typical nights, except during morning rush hour, when other HONO formation pathways are most likely active. One of the nights analyzed showed an increase of HONO mixing ratios together with decreasing NO2 mixing ratios that the model was unable to reproduce, most likely due to the impact of weak precipitation during this night. HONO formation and removal rates averaged over the lowest 300 m of the atmosphere showed that NO2 to HONO conversion on the ground was the dominant source of HONO, followed by traffic emission. Aerosol did not play an important role in HONO formation. Although ground deposition was also a major removal pathway of HONO, net HONO production at the ground was the main source of HONO in our model studies. Sensitivity studies showed that in the stable NBL, net HONO production at the ground tends to increase with faster vertical mixing and stronger NOx emission. Vertical transport was found to be the dominant source of HONO aloft.
Total hydroxyl radical (OH) reactivity was measured at the PROPHET (Program for Research on Oxidants: PHotochemistry, Emissions, and Transport) forested field site in northern Michigan during the ...2009 Community Atmosphere–Biosphere INteraction EXperiment (CABINEX). OH reactivity measurements were made with a turbulent-flow reactor instrument at three heights from the forest floor above (21 and 31 m) and below (6 m) the canopy at three different time periods during the CABINEX campaign. In addition to total OH reactivity measurements, collocated measurements of volatile organic compounds (VOCs), inorganic species, and ambient temperature were made at the different heights. These ancillary measurements were used to calculate the total OH reactivity, which was then compared to the measured values. Discrepancies between the measured and calculated OH reactivity, on the order of 1–24 s−1, were observed during the daytime above the canopy at the 21 and 31 m heights, as previously reported for this site. The measured OH reactivity below the canopy during the daytime was generally lower than that observed above the canopy. Closer analysis of the measurements of OH reactivity and trace gases suggests that the missing OH reactivity could come from oxidation products of VOCs. These results suggest that additional unmeasured trace gases, likely oxidation products, are needed to fully account for the OH reactivity measured during CABINEX.
Black carbon (BC) is the dominant absorbing aerosol in the atmosphere, and plays an important role in climate and human health. The optical properties and cloud condensation nuclei (CCN) activity of ...soot depend on the amounts (both relative and absolute) of BC and non-refractory material in the particles. Mixing between these two components is often represented in models by a core / shell coated sphere. The single-particle soot photometer (SP2) is one of, if not the only, instrument capable of reporting distributions of both core size and coating thickness. Most studies combine the SP2's incandescence and 1064 nm scattering data to report coating properties, but to date there is no consistency in the assumed values of density and refractive index of the core that are used in these calculations, which can greatly affect the reported parameters such as coating thickness. Given that such data are providing an important constraint for model comparisons and comparison between large data sets, it is important that this lack of consistency is addressed. In this study we explore the sensitivity of the reported coatings to these parameters. An assessment of the coating properties of freshly emitted, thermodenuded ambient particles demonstrated that a core density of 1.8 g cm−3 and refractive index of (2.26–1.26i) were the most appropriate to use with ambient soot in the Los Angeles area. Using these parameters generated a distribution with median shell / core ratio of 1.02 ± 0.11, corresponding to a median absolute coating thickness of 2 ± 8 nm. The main source of statistical error in the single-particle data was random variation in the incandescence signals. Other than the sensitivity to core refractive index, the incandescence calibration was the main source of uncertainty when optically determining the average coatings. The refractive index of coatings was found to have only a minor influence. This work demonstrates that using this technique the SP2 can accurately determine the average mixing state (externally or internally mixed) of ambient soot within the precision of the instrument calibration. Ambient coatings were measured up to a median shell / core ratio of 1.50 ± 0.11, meaning that this technique is able to resolve absolute changes in mixing state. However, when different core parameters were used, the core / shell ratio and the coating thickness were shown to be offset by amounts that could be larger than the atmospheric variability in these parameters, though the results have a similar precision. For comparison, using the core parameters that resulted in the thickest coatings, on the same thermodenuded fresh particles as before, generated a median shell / core ratio of 1.39 ± 0.11, corresponding to a median absolute coating thickness of 30 ± 8 nm. These results must be taken into account when comparing BC coatings measured using this technique, or if using these data for optical or CCN calculations. We have determined the most appropriate values of BC density and refractive index to use to measure mixing state at 1064 nm where particle morphology has only a minor effect, but appropriate values to use for optical calculations of nonspherical particles at visible wavelengths will also be subject to similar, significant uncertainties. Without similar constraints as those provided here, constraining the behaviour of BC particles in models using field data will be subject to large systematic measurement uncertainties.
Organic aerosols (OA) in Pasadena are characterized using multiple measurements from the California Research at the Nexus of Air Quality and Climate Change (CalNex) campaign. Five OA components are ...identified using positive matrix factorization including hydrocarbon‐like OA (HOA) and two types of oxygenated OA (OOA). The Pasadena OA elemental composition when plotted as H : C versus O : C follows a line less steep than that observed for Riverside, CA. The OOA components from both locations follow a common line, however, indicating similar secondary organic aerosol (SOA) oxidation chemistry at the two sites such as fragmentation reactions leading to acid formation. In addition to the similar evolution of elemental composition, the dependence of SOA concentration on photochemical age displays quantitatively the same trends across several North American urban sites. First, the OA/ΔCO values for Pasadena increase with photochemical age exhibiting a slope identical to or slightly higher than those for Mexico City and the northeastern United States. Second, the ratios of OOA to odd‐oxygen (a photochemical oxidation marker) for Pasadena, Mexico City, and Riverside are similar, suggesting a proportional relationship between SOA and odd‐oxygen formation rates. Weekly cycles of the OA components are examined as well. HOA exhibits lower concentrations on Sundays versus weekdays, and the decrease in HOA matches that predicted for primary vehicle emissions using fuel sales data, traffic counts, and vehicle emission ratios. OOA does not display a weekly cycle—after accounting for differences in photochemical aging —which suggests the dominance of gasoline emissions in SOA formation under the assumption that most urban SOA precursors are from motor vehicles.
Key Points
For the same photochemical ages, SOA to CO ratios do not display a weekly cycle
Organic aerosol is apportioned into five components using PMF
SOA formation/evolution is similar for several urban locations
Recent laboratory and field studies have indicated that glyoxal is a potentially large contributor to secondary organic aerosol mass. We present in situ glyoxal measurements acquired with a recently ...developed, high sensitivity spectroscopic instrument during the CalNex 2010 field campaign in Pasadena, California. We use three methods to quantify the production and loss of glyoxal in Los Angeles and its contribution to organic aerosol. First, we calculate the difference between steady state sources and sinks of glyoxal at the Pasadena site, assuming that the remainder is available for aerosol uptake. Second, we use the Master Chemical Mechanism to construct a two‐dimensional model for gas‐phase glyoxal chemistry in Los Angeles, assuming that the difference between the modeled and measured glyoxal concentration is available for aerosol uptake. Third, we examine the nighttime loss of glyoxal in the absence of its photochemical sources and sinks. Using these methods we constrain the glyoxal loss to aerosol to be 0–5 × 10−5 s−1 during clear days and (1 ± 0.3) × 10−5 s−1 at night. Between 07:00–15:00 local time, the diurnally averaged secondary organic aerosol mass increases from 3.2 μg m−3 to a maximum of 8.8 μg m−3. The constraints on the glyoxal budget from this analysis indicate that it contributes 0–0.2 μg m−3 or 0–4% of the secondary organic aerosol mass.
Key Points
We used a new field instrument to measure glyoxal in Los Angeles during 2010
We constrain glyoxal contribution to aerosol using three methods
During daytime, glyoxal contributes 0–4% of secondary organic aerosol mass
We reanalyze a data set of hydrocarbons in ambient air obtained by gas chromatography‐mass spectrometry at a surface site in Pasadena in the Los Angeles basin during the NOAA California Nexus study ...in 2010. The number of hydrocarbon compounds quantified from the chromatograms is expanded through the use of new peak‐fitting data analysis software. We also reexamine hydrocarbon removal processes. For alkanes, small alkenes, and aromatics, the removal is determined by the reaction with hydroxyl (OH) radicals. For several highly reactive alkenes, the nighttime removal by ozone and nitrate (NO3) radicals is also significant. We discuss how this nighttime removal affects the determination of emission ratios versus carbon monoxide (CO) and show that previous estimates based on nighttime correlations with CO were too low. We analyze model output from the Weather Research and Forecasting‐Chemistry model for hydrocarbons and radicals at the Pasadena location to evaluate our methods for determining emission ratios from the measurements. We find that our methods agree with the modeled emission ratios for the domain centered on Pasadena and that the modeled emission ratios vary by 23% across the wider South Coast basin. We compare the alkene emission ratios with published results from ambient measurements and from tunnel and dynamometer studies of motor vehicle emissions. We find that with few exceptions the composition of alkene emissions determined from the measurements in Pasadena closely resembles that of motor vehicle emissions.
Plain Language Summary
We report new measurements of hydrocarbons in ambient air in the Los Angeles basin. Chemical reactions between hydrocarbons and nitrogen oxides form ozone and fine particles, two important pollutants in Los Angeles smog. It is therefore important to understand hydrocarbon emission sources. In this work, we derive the composition of hydrocarbon emissions using ambient measurements at Pasadena in 2010. The study is complicated due to rapid chemical reactions that remove hydrocarbons in between the time of emission and measurement. After correcting for this chemistry, it is shown that the composition of reactive alkenes agrees closely with those emitted from motor vehicles.
Key Points
An expanded data set of hydrocarbons in ambient air in the Los Angeles basin is presented and analyzed
For reactive alkenes, removal by ozone and nitrate radicals at night is important in addition to their removal by hydroxyl radicals during the day, which complicates determining the composition of emissions
After correction for chemical removal, the composition of reactive alkene emissions is consistent with a source from motor vehicles
Measurements and predictions of ambient ozone (O3), planetary boundary layer (PBL) height, the surface energy budget, wind speed, and other meteorological parameters were made near downtown Houston, ...Texas, and were used to investigate meteorological controls on elevated levels of ground‐level O3. Days during the study period (1 April 2009 to 31 December 2010 for measurements and 15 April 2009 to 17 October 2009 for modeled) were classified into low (LO3) and high ozone (HO3) days. The majority of observed high HO3 days occurred in a postfrontal environment. Observations showed there is not a significant difference in daily maximum PBL heights on HO3 and LO3 days. Modeling results showed large differences between maximum PBL heights on HO3 and LO3 days. Nighttime and early morning observed and modeled PBL heights are consistently lower on HO3 days than on LO3 days. The observed spring LO3 days had the most rapid early morning PBL growth (~350 m h−1) while the fall HO3 group had the slowest (~200 m h−1). The predicted maximum average hourly morning PBL growth rates were greater on HO3 (624 m h−1) days than LO3 days (361 m h−1). Observed turbulent mixing parameters were up to 2–3 times weaker on HO3 days, which indicate large‐scale subsidence associated with high‐pressure systems (leading to clear skies and weak winds) substantially suppresses mixing. Lower surface layer ventilation coefficients were present in the morning on HO3 days in the spring and fall, which promotes the accumulation of O3 precursors near the surface.
Key Points
Observed/modeled PBLHs are lower during nighttime/morning on high ozone days
Observed PBL growth rates are lower during early morning on high ozone days
Observed mixing parameters are 2‐3 times weaker on high ozone days
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