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International audience; 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.

[1] 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.

A group of nonpolar organic compounds (NPOCs) in five compound classes including alkanes, polycyclic aromatic hydrocarbons (PAHs), hopanes, steranes, and 1,3,5-triphenylbenzene (TPB), were quantified in PM2.5 samples collected at four sites in the Pearl River Delta (PRD) region, China over a two-year period from 2011 to 2012. The four sites include industrial (Nanhai), urban (Guangzhou), urban outskirt (Dongguan) and suburban (Nansha) locations. Some NPOCs are uniquely emitted from particular combustion sources, and thereby serving as markers in source apportionment. Based on this multi-year and multi-site NPOC data set, spatial and seasonal variations, correlation analysis and ratio-ratio plots were used to investigate the source information and degradation of NPOC tracers. In summer, NPOCs showed distinct local emission characteristics, with urban sites having much higher concentrations than suburban sites. In winter, regional transport was an important influence on NPOC levels, driving up concentrations at all sampling sites and diminishing an urban-suburban spatial gradient. The lighter NPOCs exhibited more prominent seasonal variations. Such spatiotemporal features suggest their particle-phase abundance is more influenced by temperature, which is a critical factor in controlling the extent of semi-volatile organics partitioned into the aerosol phase. The heavier NPOCs, especially PAHs, showed negligible correlation among the four sites, suggesting more influence from local emissions. Ratio-ratio plots indicate photo-degradation and mixing of various sources for the NPOCs in the PRD. A positive matrix factorization (PMF) analysis of this large NPOC data set suggests that heavier NPOCs are more suitable source indicators than lighter NPOCs. Incorporating particle-phase light NPOC concentrations in PMF produces a separate factor, which primarily contains those light NPOCs and likely is not a source factor. Total NPOC concentrations predicted using Pankow partitioning theory were explored as PMF inputs, however, the PMF solution is not able to fully explain the input total concentrations or to give reasonable source profiles, suggesting the need for reliable gas-phase NPOC data before their use in source apportionment studies. In addition, degradation of NPOCs needs to be considered to avoid misinterpretation of PMF source apportionment results.

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.

[1] 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.

Oxalic acid is one of the most abundant dicarboxylic acids in the atmosphere, receiving a great deal of attention due to its potential influence on cloud condensation nucleus activities. In this work, we report 10 months of hourly oxalate measurements in particulate matter of less than 2.5 µm in aerodynamic diameter (PM2.5) by a Monitor for Aerosols and Gases in ambient Air at a suburban coastal site in Hong Kong from April 2012 to February 2013. A total of more than 6000 sets of oxalate and inorganic ion data were obtained. The mean (±SD) oxalate concentration was 0.34 (±0.18) µg m−3, accounting for 2.8% of the total ion mass and 1.5% of the PM2.5 mass. Seasonal variation showed higher concentrations in fall and winter (0.54 and 0.36 µg m−3, respectively) and lower concentrations in spring and summer (~0.26 µg m−3). Different from the inorganic ions, a shallow dip in the oxalate concentration consistently occurred in the morning after sunrise (around 9:00 A.M.) throughout all seasons. Our analysis suggests that this was likely due to photolysis of oxalate-Fe (III) complex under sunlight. In summer, a small daytime peak was discernable for oxalate and nitrate. This characteristic, together with a more evident diurnal variation of O3, indicates comparatively more active photochemical oxidation in summer than other seasons. High correlations were observed between oxalate and non-sea-salt SO42− (NSS) (R2 = 0.63) and Ox (O3 + NO2) (R2 = 0.48), indicating significant commonality in their secondary formation. Positive matrix factorization analysis of oxalate and other real-time gas and particle-phase component data estimates that secondary formation processes, including secondary gas or aqueous oxidation processes (49%), oxidation processes of biomass burning emissions (37%), accounted for the majority of PM2.5 oxalate. A backward trajectories cluster analysis found that higher oxalate/NSS ratios were associated with low pollution samples under the influence of marine air masses while the ratios were lower in high pollution samples that were typically associated with continental air masses passing through areas of high anthropogenic emissions. Isolating the “low pollution marine” aerosols across the entire data set indicates that oxalate production increased in the summer compared to other seasons, suggesting either more active marine emissions of oxalate precursors or stronger photochemical processes in the summer.