Contrasting Reactive Organic Carbon Observations in the Southeast United States (SOAS) and Southern California (CalNex).

Despite the central role of reactive organic carbon (ROC) in the formation of secondary species that impact global air quality and climate, our assessment of ROC abundance and impacts is challenged by the diversity of species that contribute to it. We revisit measurements of ROC species made during two field campaigns in the United States: the 2013 SOAS campaign in forested Centreville, AL, and the 2010 CalNex campaign in urban Pasadena, CA. We find that average measured ROC concentrations are about twice as high in Pasadena (73.8 µgCsm-3) than in Centreville (36.5 µgCsm-3). However, the OH reactivity (OHR) measured at these sites is similar (20.1 and 19.3 s-1). The shortfall in OHR when summing up measured contributions is 31%, at Pasadena and 14% at Centreville, suggesting that there may be a larger reservoir of unmeasured ROC at the former site. Estimated O3 production and SOA potential (defined as concentration × yield) are both higher during CalNex than SOAS. This analysis suggests that the ROC in urban California is less reactive, but due to higher concentrations of oxides of nitrogen and hydroxyl radicals, is more efficient in terms of O3 and SOA production, than in the forested southeastern U.S.

Formaldehyde (HCHO) As a Hazardous Air Pollutant: Mapping Surface Air Concentrations from Satellite and Inferring Cancer Risks in the United States.

Formaldehyde (HCHO) is the most important carcinogen in outdoor air among the 187 hazardous air pollutants (HAPs) identified by the U.S. Environmental Protection Agency (EPA), not including ozone and particulate matter. However, surface observations of HCHO are sparse and the EPA monitoring network could be prone to positive interferences. Here we use 2005-2016 summertime HCHO column data from the OMI satellite instrument, validated with high-quality aircraft data and oversampled on a 5 × 5 km2 grid, to map surface air HCHO concentrations across the contiguous U.S. OMI-derived summertime HCHO values are converted to annual averages using the GEOS-Chem chemical transport model. Results are in good agreement with high-quality summertime observations from urban sites (-2% bias, r = 0.95) but a factor of 1.9 lower than annual means from the EPA network. We thus estimate that up to 6600-12 500 people in the U.S. will develop cancer over their lifetimes by exposure to outdoor HCHO. The main HCHO source in the U.S. is atmospheric oxidation of biogenic isoprene, but the corresponding HCHO yield decreases as the concentration of nitrogen oxides (NOx ≡ NO + NO2) decreases. A GEOS-Chem sensitivity simulation indicates that HCHO levels would decrease by 20-30% in the absence of U.S. anthropogenic NOx emissions. Thus, NOx emission controls to improve ozone air quality have a significant cobenefit in reducing HCHO-related cancer risks.

Radical precursors and related species from traffic as observed and modeled at an urban highway junction.

Nitrous acid (HONO) and formaldehyde (HCHO) are important precursors for radicals and are believed to favor ozone formation significantly. Traffic emission data for both compounds are scarce and mostly outdated. A better knowledge of today's HCHO and HONO emissions related to traffic is needed to refine air quality models. Here the authors report results from continuous ambient air measurements taken at a highway junction in Houston, Texas, from July 15 to October 15, 2009. The observational data were compared with emission estimates from currently available mobile emission models (MOBILE6; MOVES [MOtor Vehicle Emission Simulator]). Observations indicated a molar carbon monoxide (CO) versus nitrogen oxides (NO(x)) ratio of 6.01 +/- 0.15 (r2 = 0.91), which is in agreement with other field studies. Both MOBILE6 and MOVES overestimate this emission ratio by 92% and 24%, respectively. For HCHO/CO, an overall slope of 3.14 +/- 0.14 g HCHO/kg CO was observed. Whereas MOBILE6 largely underestimates this ratio by 77%, MOVES calculates somewhat higher HCHO/CO ratios (1.87) than MOBILE6, but is still significantly lower than the observed ratio. MOVES shows high HCHO/CO ratios during the early morning hours due to heavy-duty diesel off-network emissions. The differences of the modeled CO/NO(x) and HCHO/CO ratios are largely due to higher NO(x) and HCHO emissions in MOVES (30% and 57%, respectively, increased from MOBILE6 for 2009), as CO emissions were about the same in both models. The observed HONO/NO(x) emission ratio is around 0.017 +/- 0.0009 kg HONO/kg NO(x) which is twice as high as in MOVES. The observed NO2/NO(x) emission ratio is around 0.16 +/- 0.01 kg NO2/kg NO(x), which is a bit more than 50% higher than in MOVES. MOVES overestimates the CO/CO2 emission ratio by a factor of 3 compared with the observations, which is 0.0033 +/- 0.0002 kg CO/kg CO2. This as well as CO/NO(x) overestimation is coming from light-duty gasoline vehicles.

Formaldehyde columns from the Ozone Monitoring Instrument: Urban versus background levels and evaluation using aircraft data and a global model.

[1] We combine aircraft measurements (Second Texas Air Quality Study, Megacity Initiative: Local and Global Research Observations, Intercontinental Chemical Transport Experiment: Phase B) over the United States, Mexico, and the Pacific with a 3-D model (GEOS-Chem) to evaluate formaldehyde column (ΩHCHO) retrievals from the Ozone Monitoring Instrument (OMI) and assess the information they provide on HCHO across local to regional scales and urban to background regimes. OMI ΩHCHO correlates well with columns derived from aircraft measurements and GEOS-Chem (R = 0.80). For the full data ensemble, OMI's mean bias is -3% relative to aircraft-derived ΩHCHO (-17% where ΩHCHO > 5 × 1015 molecules cm-2) and -8% relative to GEOS-Chem, within expected uncertainty for the retrieval. Some negative bias is expected for the satellite and model, given the plume sampling of many flights and averaging over the satellite and model footprints. Major axis regression for OMI versus aircraft and model columns yields slopes (95% confidence intervals) of 0.80 (0.62-1.03) and 0.98 (0.73-1.35), respectively, with no significant intercept. Aircraft measurements indicate that the normalized vertical HCHO distribution, required by the satellite retrieval, is well captured by GEOS-Chem, except near Mexico City. Using measured HCHO profiles in the retrieval algorithm does not improve satellite-aircraft agreement, suggesting that use of a global model to specify shape factors does not substantially degrade retrievals over polluted areas. While the OMI measurements show that biogenic volatile organic compounds dominate intra-annual and regional ΩHCHO variability across the United States, smaller anthropogenic ΩHCHO gradients are detectable at finer spatial scales (∼20-200 km) near many urban areas.

Deciphering the role of radical precursors during the Second Texas Air Quality Study.

The Texas Environmental Research Consortium (TERC) funded significant components of the Second Texas Air Quality Study (TexAQS II), including the TexAQS II Radical and Aerosol Measurement Project (TRAMP) and instrumented flights by a Piper Aztec aircraft. These experiments called attention to the role of short-lived radical sources such as formaldehyde (HCHO) and nitrous acid (HONO) in increasing ozone productivity. TRAMP instruments recorded daytime HCHO pulses as large as 32 parts per billion (ppb) originating from upwind industrial activities in the Houston Ship Channel, where in situ surface monitors detected HCHO peaks as large as 52 ppb. Moreover, Ship Channel petrochemical flares were observed to produce plumes of apparent primary HCHO. In one such combustion plume that was depleted of ozone by large emissions of oxides of nitrogen (NOx), the Piper Aztec measured a ratio of HCHO to carbon monoxide (CO) 3 times that of mobile sources. HCHO from uncounted primary sources or ozonolysis of underestimated olefin emissions could significantly increase ozone productivity in Houston beyond previous expectations. Simulations with the CAMx model show that additional emissions of HCHO from industrial flares or mobile sources can increase peak ozone in Houston by up to 30 ppb. Other findings from TexAQS II include significant concentrations of HONO throughout the day, well in excess of current air quality model predictions, with large nocturnal vertical gradients indicating a surface or near-surface source of HONO, and large concentrations of nighttime radicals (approximately30 parts per trillion [ppt] HO2). HONO may be formed heterogeneously on urban canopy or particulate matter surfaces and may be enhanced by organic aerosol of industrial or motor vehicular origin, such as through conversion of nitric acid (HNO3). Additional HONO sources may increase daytime ozone by more than 10 ppb. Improving the representation of primary and secondary HCHO and HONO in air quality models could enhance the simulated effectiveness of control strategies.