A Future Multi-Platform Atmospheric Chemistry Measurement Campaign to Study Oxidation in Mixed Anthropogenic-Biogenic Air Masses

<p>It is well known that the high population density of urban regions leads to significant degradation of the quality of the air because of the emissions of pollutants that are by-products of energy production, transportation, and industry. The composition and chemistry of urban air has been studied for many decades and these studies have led to detailed understanding of the factors controlling, for example, the formation of ozone, peroxyacetyl nitrate and other secondary species. In the last 20 to 30 years, significant progress has been made in reducing emissions of volatile organic compounds (VOCs) and oxides of nitrogen (NO<sub>x</sub>) in urban atmospheres. Substantial reductions in the abundance of secondary compounds, though, have been more elusive.</p><p>Research has continued to reveal more and more details of the complex processes involved in the atmospheric degradation of wide varieties of volatile organic compounds (VOCs) of anthropogenic and biospheric (BVOCs) origins. BVOCs include isoprene, monoterpenes and sesquiterpenes, and oxygenated VOCs (OVOCs, such as small alcohols). Emissions of BVOCs depend on several factors such as plant or tree species, temperature, and photosynthetically active radiation. They consist almost exclusively of unsaturated compounds with chemistry somewhat different from those of typical urban organic compound emissions. Oxidation of VOCs can lead to molecules of low volatility that are prone to uptake into the aerosol phase.</p><p>Recent studies conducted in megacities such as Paris, Mexico City, Los Angeles and those in China have led to significant advances in our understanding of the chemical evolution of urban plumes. However, important scientific questions remain on how mixing of anthropogenic and biogenic air masses modifies the composition of urban plumes and hence their impacts. Indeed, the proximity of cites to areas of strong biogenic emissions is not unusual. Many major cities at mid-latitudes are surrounded by forested areas.</p><p>ACROSS (Atmospheric ChemistRy Of the Suburban foreSt) is an integrative, innovative, multi-scale project awarded under the “Make Our Planet Great Again” (MOPGA) framework that seeks to definitively improve understanding of the impacts of mixing urban and biogenic air masses on the oxidation of atmospheric VOCs. The ACROSS working hypothesis is that this leads to changes in the production of oxygenated VOCs whose properties (e.g. vapor pressures) alter their importance in incorporation into SOA and their roles in production of ozone and other secondary species. Changes are also expected in the efficiency of radical recycling affecting the atmospheric oxidative capacity. Particularly important is NO<sub>x</sub> transport to suburban biogenic environments and the resulting modification of key chemical processes.</p><p>A key highlight of ACROSS is an intensive, multi-platform measurement campaign in the summer of 2022. It will use instruments staged on an airborne platform, a tower in the Rambouillet Forest near Paris, and other ground sites. The data collected from this campaign will be analyzed and studied to extract information about tropospheric oxidation chemistry generally, but also changes observed in the situation of mixed urban and biogenic air masses.</p><p>This presentation will summarize plans for the ACROSS campaign.</p>

Tropospheric HONO distribution and chemistry in the southeastern US

Here we report the measurement results of nitrous acid (HONO) and a suite of relevant parameters on the NCAR C-130 research aircraft in the southeastern US during the NOMADSS 2013 summer field study. The daytime HONO concentration ranged from low parts per trillion by volume (pptv) in the free troposphere (FT) to mostly within 5–15 pptv in the background planetary boundary layer (PBL). There was no discernible vertical HONO gradient above the lower flight altitude of 300 m in the PBL, and the transport of ground surface HONO was not found to be a significant contributor to the tropospheric HONO budget. The total in situ HONO source mean (±1 SD) was calculated as 53 (±21) pptv h−1 during the day. The upper-limit contribution from NOx-related reactions was 10 (±5) pptv h−1, and the contribution from photolysis of particulate nitrate (pNO3) was 38 (±23) pptv h−1, based on the measured pNO3 concentrations and the median pNO3 photolysis rate constant of 2.0 × 10−4 s−1 determined in the laboratory using ambient aerosol samples. The photolysis of HONO contributed to less than 10 % of the primary OH source. However, a recycling NOx source via pNO3 photolysis was equivalent to ∼ 2.3 × 10−6 mol m−2 h−1 in the air column within the PBL, a considerable supplementary NOx source in the low-NOx background area. Up to several tens of parts per trillion by volume of HONO were observed in power plant and urban plumes during the day, mostly produced in situ from precursors including NOx and pNO3. Finally, there was no observable accumulation of HONO in the nocturnal residual layer and the nocturnal FT in the background southeastern US, with an increase in the HONO ∕ NOx ratio of ≤ 3 × 10−4 h−1 after sunset.

A multi-model approach to monitor emissions of CO₂ and CO from an urban–industrial complex

Monitoring urban–industrial emissions is often challenging because observations are scarce and regional atmospheric transport models are too coarse to represent the high spatiotemporal variability in the resulting concentrations. In this paper we apply a new combination of an Eulerian model (Weather Research and Forecast, WRF, with chemistry) and a Gaussian plume model (Operational Priority Substances – OPS). The modelled mixing ratios are compared to observed CO2 and CO mole fractions at four sites along a transect from an urban–industrial complex (Rotterdam, the Netherlands) towards rural conditions for October–December 2014. Urban plumes are well-mixed at our semi-urban location, making this location suited for an integrated emission estimate over the whole study area. The signals at our urban measurement site (with average enhancements of 11 ppm CO2 and 40 ppb CO over the baseline) are highly variable due to the presence of distinct source areas dominated by road traffic/residential heating emissions or industrial activities. This causes different emission signatures that are translated into a large variability in observed ΔCO : ΔCO2 ratios, which can be used to identify dominant source types. We find that WRF-Chem is able to represent synoptic variability in CO2 and CO (e.g. the median CO2 mixing ratio is 9.7 ppm, observed, against 8.8 ppm, modelled), but it fails to reproduce the hourly variability of daytime urban plumes at the urban site (R2 up to 0.05). For the urban site, adding a plume model to the model framework is beneficial to adequately represent plume transport especially from stack emissions. The explained variance in hourly, daytime CO2 enhancements from point source emissions increases from 30 % with WRF-Chem to 52 % with WRF-Chem in combination with the most detailed OPS simulation. The simulated variability in ΔCO : ΔCO2 ratios decreases drastically from 1.5 to 0.6 ppb ppm−1, which agrees better with the observed standard deviation of 0.4 ppb ppm−1. This is partly due to improved wind fields (increase in R2 of 0.10) but also due to improved point source representation (increase in R2 of 0.05) and dilution (increase in R2 of 0.07). Based on our analysis we conclude that a plume model with detailed and accurate dispersion parameters adds substantially to top–down monitoring of greenhouse gas emissions in urban environments with large point source contributions within a ∼ 10 km radius from the observation sites.

A multi-model approach to monitor emissions of CO₂ and CO from an urban-industrial complex

Monitoring urban-industrial emissions is often challenging, because observations are scarce and regional atmospheric transport models are too coarse to represent the high spatiotemporal variability in the resulting concentrations. In this paper we apply a new combination of a Eulerian model (WRF with chemistry) and a Gaussian plume model (OPS). The modelled mixing ratios are compared to observed CO2 and CO mole fractions at four sites along a transect from an urban-industrial complex (Rotterdam, Netherlands) towards rural conditions for October–December 2014. Urban plumes are well-mixed at our semi-urban location, making this location suited for an integrated emission estimate over the whole study area. The signals at our urban measurement site (with average enhancements of 11 ppm CO2 and 40 ppb CO over the baseline) are highly variable due to the presence of distinct source areas dominated by road traffic/residential heating emissions or industrial activities. This causes different emission signatures that are translated into a large variability in observed ΔCO : ΔCO2 ratios, which can be used to identify dominant source types. We find that WRF-Chem is able to represent synoptic variability in CO2 and CO (e.g. the median CO2 mixing ratio is 9.7 ppm (observed) against 8.7 ppm (modelled)) , but it fails to reproduce the hourly variability of daytime urban plumes at the urban site (R2 up to 0.05). For the urban site, a plume model should be added to the model framework to adequately represent plume transport especially from stack emissions. The explained variance in hourly, daytime CO2 enhancements from point source emissions increases from 30 % with WRF-Chem to 52 % with WRF-Chem in combination with the most detailed OPS simulation. The simulated variability in ΔCO : ΔCO2 ratios decreases drastically from 1.5 to 0.6 ppb ppm−1 which agrees better with the observed standard deviation of 0.4 ppb ppm−1. This is partly due to improved wind fields (increase in R2 of 0.10), but also due to improved point source representation (increase in R2 of 0.05) and dilution (increase in R2 of 0.07). Based on our analysis we conclude that a plume model with detailed and accurate dispersion parameters is inevitable for top-down monitoring of greenhouse gas emissions in urban environments with large point source contributions within a ~ 10 km radius from the observation sites.

Effects of daily meteorology on the interpretation of space-based remote sensing of NO₂

Retrievals of tropospheric NO2 columns from UV–visible observations of reflected sunlight require a priori vertical profiles to account for the variation in sensitivity of the observations to NO2 at different altitudes. These profiles vary in space and time but are usually approximated using models that do not resolve the full details of this variation. Currently, no operational retrieval simulates these a priori profiles at both high spatial and high temporal resolution. Here we examine the additional benefits of daily variations in a priori profiles for retrievals already simulating a priori NO2 profiles at sufficiently high spatial resolution to identify variations of NO2 within urban plumes. We show the effects of introducing daily variation into a priori profiles can be as large as 40 % and 3 × 1015 molec. cm−2 for an individual day and lead to corrections as large as −13 % for a monthly average in a case study of Atlanta, GA, USA. Additionally, we show that NOx emissions estimated from space-based remote sensing using daily, high-spatial-resolution a priori profiles are ∼ 100 % greater than those of a retrieval using spatially coarse a priori profiles, and 26–40 % less than those of a retrieval using monthly averaged high-spatial-resolution profiles.

Ozone production chemistry in the presence of urban plumes

Ozone pollution affects human health, especially in urban areas on hot sunny days. Its basic photochemistry has been known for decades and yet it is still not possible to correctly predict the high ozone levels that are the greatest threat. The CalNex_SJV study in Bakersfield CA in May/June 2010 provided an opportunity to examine ozone photochemistry in an urban area surrounded by agriculture. The measurement suite included hydroxyl (OH), hydroperoxyl (HO2), and OH reactivity, which are compared with the output of a photochemical box model. While the agreement is generally within combined uncertainties, measured HO2 far exceeds modeled HO2 in NOx-rich plumes. OH production and loss do not balance as they should in the morning, and the ozone production calculated with measured HO2 is a decade greater than that calculated with modeled HO2 when NO levels are high. Calculated ozone production using measured HO2 is twice that using modeled HO2, but this difference in calculated ozone production has minimal impact on the assessment of NOx-sensitivity or VOC-sensitivity for midday ozone production. Evidence from this study indicates that this important discrepancy is not due to the HO2 measurement or to the sampling of transported plumes but instead to either emissions of unknown organic species that accompany the NO emissions or unknown photochemistry involving nitrogen oxides and hydrogen oxides, possibly the hypothesized reaction OH + NO + O2 → HO2 + NO2.

Chemistry of new particle growth in mixed urban and biogenic emissions – insights from CARES

Regional new particle formation and growth events (NPEs) were observed on most days over the Sacramento and western Sierra foothills area of California in June 2010 during the Carbonaceous Aerosols and Radiative Effect Study (CARES). Simultaneous particle measurements at both the T0 (Sacramento, urban site) and the T1 (Cool, rural site located ~40 km northeast of Sacramento) sites of CARES indicate that the NPEs usually occurred in the morning with the appearance of an ultrafine mode at ~15 nm (in mobility diameter, Dm, measured by a mobility particle size spectrometer operating in the range 10-858 nm) followed by the growth of this modal diameter to ~50 nm in the afternoon. These events were generally associated with southwesterly winds bringing urban plumes from Sacramento to the T1 site. The growth rate was on average higher at T0 (7.1 ± 2.7 nm h−1) than at T1 (6.2 ± 2.5 nm h−1), likely due to stronger anthropogenic influences at T0. Using a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS), we investigated the evolution of the size-resolved chemical composition of new particles at T1. Our results indicate that the growth of new particles was driven primarily by the condensation of oxygenated organic species and, to a lesser extent, ammonium sulfate. New particles appear to be fully neutralized during growth, consistent with high NH3 concentration in the region. Nitrogen-containing organic ions (i.e., CHN+, CH4N+, C2H3N+, and C2H4N+) that are indicative of the presence of alkyl-amine species in submicrometer particles enhanced significantly during the NPE days, suggesting that amines might have played a role in these events. Our results also indicate that the bulk composition of the ultrafine mode organics during NPEs was very similar to that of anthropogenically influenced secondary organic aerosol (SOA) observed in transported urban plumes. In addition, the concentrations of species representative of urban emissions (e.g., black carbon, CO, NOx, and toluene) were significantly higher whereas the photo-oxidation products of biogenic VOCs (volatile organic compounds) and the biogenically influenced SOA also increased moderately during the NPE days compared to the non-event days. These results indicate that the frequently occurring NPEs over the Sacramento and Sierra Nevada regions were mainly driven by urban plumes from Sacramento and the San Francisco Bay Area, and that the interaction of regional biogenic emissions with the urban plumes has enhanced the new particle growth. This finding has important implications for quantifying the climate impacts of NPEs on global scale.

Chemistry of new particle growth in mixed urban and biogenic emissions – insights from CARES

Regional new particle formation and growth events (NPE) were observed on most days over the Sacramento and western Sierra Foothills area of California in June 2010 during the Carbonaceous Aerosols and Radiative Effect Study (CARES). Simultaneous particle measurements at both the T0 (Sacramento, urban site) and the T1 (Cool, rural site located ~40 km northeast of Sacramento) sites of CARES indicate that the NPE usually occurred in the morning with the appearance of an ultrafine mode centered at ~15 nm (in mobility diameter, Dm, measured by a scanning mobility particle sizer operating in the range 10–858 nm) followed by the growth of this mode to ~50 nm in the afternoon. These events were generally associated with southwesterly winds bringing urban plumes from Sacramento to the T1 site. The growth rate was on average higher at T0 (7.1 ± 2.7 nm h−1) than at T1 (6.2 ± 2.5 nm h−1), likely due to stronger anthropogenic influences at T0. Using a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS), we investigated the evolution of the size-resolved chemical composition of new particles at T1. Our results indicate that the growth of new particles was driven primarily by the condensation of oxygenated organic species and, to a lesser extent, ammonium sulfate. New particles appear to be fully neutralized during growth, consistent with high NH3 concentration in the region. Nitrogen-containing organic ions (i.e., CHN+, CH4N+, C2H3N+, and C2H4N+) that are indicative of the presence of alkyl-amine species in submicrometer particles enhanced significantly during the NPE days, suggesting that amines might have played a role in these events. Our results also indicate that the bulk composition of the ultrafine mode organics during NPE was very similar to that of anthropogenically-influenced secondary organic aerosol (SOA) observed in transported urban plumes. In addition, the concentrations of species representative of urban emissions (e.g., black carbon, CO, NOx, and toluene) were significantly higher whereas the photo-oxidation products of biogenic VOC and the biogenically-influenced SOA also increased moderately during the NPE days compared to the non-event days. These results indicate that the frequently occurring NPE over the Sacramento and Sierra Nevada regions were mainly driven by urban plumes from Sacramento and that the interaction of regional biogenic emissions with the urban plumes has enhanced the new particle growth. This finding has important implication for quantifying the climate impacts of NPE on global scale.