Search

Increasing trends in biomass burning emissions significantly impact air quality in North America. Enhanced mixing ratios of ozone (O3) in urban areas during smoke-impacted periods occur through transport of O3 produced within the smoke or through mixing of pyrogenic volatile organic compounds (PVOCs) with urban nitrogen oxides (NOx = NO + NO2) to enhance local O3 production. Here, we analyze a set of detailed chemical measurements, including carbon monoxide (CO), NOx, and speciated volatile organic compounds (VOCs), to evaluate the effects of smoke transported from relatively local and long-range fires on O3 measured at a site in Boulder, Colorado, during summer 2020. Relative to the smoke-free period, CO, background O3, OH reactivity, and total VOCs increased during both the local and long-range smoke periods, but NOx mixing ratios remained approximately constant. These observations are consistent with transport of PVOCs (comprised primarily of oxygenates) but not NOx with the smoke and with the influence of O3 produced within the smoke upwind of the urban area. Box-model calculations show that local O3 production during all three periods was in the NOx-sensitive regime. Consequently, this locally produced O3 was similar in all three periods and was relatively insensitive to the increase in PVOCs. However, calculated NOx sensitivities show that PVOCs substantially increase O3 production in the transition and NOx-saturated (VOC-sensitive) regimes. These results suggest that (1) O3 produced during smoke transport is the main driver for O3 increases in NOx-sensitive urban areas and (2) smoke may cause an additional increase in local O3 production in NOx-saturated (VOC-sensitive) urban areas. Additional detailed VOC and NOx measurements in smoke impacted urban areas are necessary to broadly quantify the effects of wildfire smoke on urban O3 and develop effective mitigation strategies.

Emission inventories are a critical basis for air quality and climate modeling, as well as policy decisions. Non-methane volatile organic compounds (NMVOCs) are key precursor compounds in ozone and secondary organic aerosol formation. Accurately representing NMVOCs in emission inventories is crucial for understanding atmospheric chemistry, the impact of policy measures, and climate projections. Improving NMVOC representation in emission inventories is fraught with challenges, ranging from the lack of (long-term) NMVOC measurements, limited efforts in updating emission factors, to the diversity of NMVOC species reactivity. Here we take an initial step to evaluate the representation of urban NMVOC speciation in an emission inventory (EDGARv4.3.2 and EDGARv6.1) at the global level. To compare the urban measurements of NMVOCs to the emission inventory estimates, ratios of individual NMVOCs to acetylene are used. Owing to limitations in measurement data and grouping of NMVOCs in emission inventories, the comparison includes only a limited number of alkanes, alkenes, and aromatics. Results show little to no agreement between the ratios in the observations and those in the global emission inventory for the species compared (r2 0.01–0.20). This could be related to incorrect speciation profiles and/or spatial allocation of NMVOCs to urban areas. Regional emission inventories show better agreement among the ratios (r2 0.43–0.70). The inclusion of oxygenated species in NMVOC measurements, as well as greater global coverage of measurements could improve representation of NMVOC species in emission inventories, and a mosaic of regional inventories may be a better approach.

The production of crude oil and natural gas is associated with emissions of air pollutants, such as nitrogen oxides (NOx = NO + NO2) and volatile organic compounds, which are precursors for the formation of ground-level ozone. Knowledge of these emissions is critical to the understanding and mitigation of local air quality. NOx emissions from oil and gas production activities are not well described in commonly used emission inventories, and discrepancies of several factors have been found in the past. Here we present an easy and computationally efficient method to quantify NOx emissions from satellite NO2 observations that can be applied to evaluate common emission inventories and provide timely input for chemistry transport models. Using NO2 columns from the TROPOspheric Monitoring Instrument (TROPOMI), we calculated annually averaged NOx emissions from the divergence of NO2 column fluxes for six oil and gas production regions in the United States. Derived NOx emissions for the years 2018 to 2020 range between 4.8 and 81.1 t/day, and observed trends over time are consistent with changes in industrial activity. To evaluate the method, we compared our results with the fuel-based oil and gas NOx inventory (FOG) and performed sensitivity studies using model output from the Weather Research Forecasting model with Chemistry (WRF-Chem). We found that annually averaged NOx emissions from oil and gas production activities can in most cases be calculated within an uncertainty of 50%, while simultaneously derived emission maps show the spatial distribution of NOx emissions with a high level of detail. For future use, this method can easily be applied globally.

Volatile chemical products (VCPs) and other non-combustion-related sources have become important for urban air quality, and bottom-up calculations report emissions of a variety of functionalized compounds that remain understudied and uncertain in emissions estimates. Using a new instrumental configuration, we present online measurements of oxygenated organic compounds in a US megacity over a 10 d wintertime sampling period, when biogenic sources and photochemistry were less active. Measurements were conducted at a rooftop observatory in upper Manhattan, New York City, USA using a Vocus chemical ionization time-of-flight mass spectrometer, with ammonium (NH4+) as the reagent ion operating at 1 Hz. The range of observations spanned volatile, intermediate-volatility, and semi-volatile organic compounds, with targeted analyses of ∼150 ions, whose likely assignments included a range of functionalized compound classes such as glycols, glycol ethers, acetates, acids, alcohols, acrylates, esters, ethanolamines, and ketones that are found in various consumer, commercial, and industrial products. Their concentrations varied as a function of wind direction, with enhancements over the highly populated areas of the Bronx, Manhattan, and parts of New Jersey, and included abundant concentrations of acetates, acrylates, ethylene glycol, and other commonly used oxygenated compounds. The results provide top-down constraints on wintertime emissions of these oxygenated and functionalized compounds, with ratios to common anthropogenic marker compounds and comparisons of their relative abundances to two regionally resolved emissions inventories used in urban air quality models.

We present an updated fuel-based oil and gas (FOG) inventory with estimates of nitrogen oxide (NOx) emissions from oil and natural gas production in the contiguous US (CONUS). We compare the FOG inventory with aircraft-derived ("top-down") emissions for NOx over footprints that account for ∼25% of US oil and natural gas production. Across CONUS, we find that the bottom-up FOG inventory combined with other anthropogenic emissions is on average within ∼10% of top-down aircraft-derived NOx emissions. We also find good agreement in the trends of NOx from drilling- and production-phase activities, as inferred by satellites and in the bottom-up inventory. Leveraging tracer-tracer relationships derived from aircraft observations, methane (CH4) and non-methane volatile organic compound (NMVOC) emissions have been added to the inventory. Our total CONUS emission estimates for 2015 of oil and natural gas are 0.45 ± 0.14 Tg NOx/yr, 15.2 ± 3.0 Tg CH4/yr, and 5.7 ± 1.7 Tg NMVOC/yr. Compared to the US National Emissions Inventory and Greenhouse Gas Inventory, FOG NOx emissions are ∼40% lower, while inferred CH4 and NMVOC emissions are up to a factor of ∼2 higher. This suggests that NMVOC/NOx emissions from oil and gas basins are ∼3 times higher than current estimates and will likely affect how air quality models represent ozone formation downwind of oil and gas fields.

On-road vehicles continue to be a major source of nitrogen oxide (NOx) emissions in the United States and in other countries around the world. The goal of this study is to compare and evaluate emission inventories and long-term trends in vehicular NOx emissions. Taxable fuel sales data and in-use measurements of emission factors are combined to generate fuel-based NOx emission inventories for California and the US over the period 1990-2020. While gasoline and diesel fuel sales increased over the last three decades, total on-road NOx emissions declined by approximately 70% since 1990, with a steeper rate of decrease after 2004 when heavy-duty diesel NOx emission controls finally started to gain traction. In California, additional steps have been taken to accelerate the introduction of new heavy-duty engines equipped with selective catalytic reduction systems, resulting in a 48% decrease in diesel NOx emissions in California compared to a 32% decrease nationally since 2010. California EMFAC model predictions are in good agreement with fuel-based inventory results for gasoline engines and are higher than fuel-based estimates for diesel engines prior to the mid-2010s. Similar to the findings of recent observational and modeling studies, there are discrepancies between the fuel-based inventory and national MOVES model estimates. MOVES predicts a steeper decrease in NOx emissions and predicts higher NOx emissions from gasoline engines over the entire period from 1990 to 2020.

With traffic emissions of volatile organic compounds (VOCs) decreasing rapidly over the last decades, the contributions of the emissions from other source categories, such as volatile chemical products (VCPs), have become more apparent in urban air. In this work, in situ measurements of various VOCs are reported for New York City, Pittsburgh, Chicago, and Denver. The magnitude of different emission sources relative to traffic is determined by measuring the urban enhancement of individual compounds relative to the enhancement of benzene, a known tracer of fossil fuel in the United States. The enhancement ratios of several VCP compounds to benzene correlate well with population density (R2 ∼ 0.6-0.8). These observations are consistent with the expectation that some human activity should correlate better with the population density than transportation emissions, due to the lower per capita rate of driving in denser cities. Using these data, together with a bottom-up fuel-based inventory of vehicle emissions and volatile chemical products (FIVE-VCP) inventory, we identify tracer compounds for different VCP categories: decamethylcyclopentasiloxane (D5-siloxane) for personal care products, monoterpenes for fragrances, p-dichlorobenzene for insecticides, D4-siloxane for adhesives, para-chlorobenzotrifluoride (PCBTF) for solvent-based coatings, and Texanol for water-based coatings. Furthermore, several other compounds are identified (e.g., ethanol) that correlate with population density and originate from multiple VCP sources. Ethanol and fragrances are among the most abundant and reactive VOCs associated with VCP emissions.

We analyze airborne measurements of atmospheric CO concentration from 70 flights conducted over six years (2015-2020) using an inverse model to quantify the CO emissions from the Washington, DC, and Baltimore metropolitan areas. We found that CO emissions have been declining in the area at a rate of ≈-4.5 % a

There have only been a few wintertime studies of heavy-duty vehicle (HDV) NO

Decades of air quality improvements have substantially reduced the motor vehicle emissions of volatile organic compounds (VOCs). Today, volatile chemical products (VCPs) are responsible for half of the petrochemical VOCs emitted in major urban areas. We show that VCP emissions are ubiquitous in US and European cities and scale with population density. We report significant VCP emissions for New York City (NYC), including a monoterpene flux of 14.7 to 24.4 kg ⋅ d(−1) ⋅ km(−2) from fragranced VCPs and other anthropogenic sources, which is comparable to that of a summertime forest. Photochemical modeling of an extreme heat event, with ozone well in excess of US standards, illustrates the significant impact of VCPs on air quality. In the most populated regions of NYC, ozone was sensitive to anthropogenic VOCs (AVOCs), even in the presence of biogenic sources. Within this VOC-sensitive regime, AVOCs contributed upwards of ∼20 ppb to maximum 8-h average ozone. VCPs accounted for more than 50% of this total AVOC contribution. Emissions from fragranced VCPs, including personal care and cleaning products, account for at least 50% of the ozone attributed to VCPs. We show that model simulations of ozone depend foremost on the magnitude of VCP emissions and that the addition of oxygenated VCP chemistry impacts simulations of key atmospheric oxidation products. NYC is a case study for developed megacities, and the impacts of VCPs on local ozone are likely similar for other major urban regions across North America or Europe.

Most countries around the world including the United States took actions to control COVID-19 spread that led to an abrupt shift in human activity. On-road NOx emissions from light and heavy-duty vehicles decreased by 9% to 19% between February and March at the onset of the lockdown period in the middle of March in most of the US;between March and April, the on-road NOx emissions dropped further by 8% to 31% when lockdown measures were the most stringent. These precipitous drops in NOx emissions correlated well (r = 0.75) with tropospheric NO2 column amount observed by the Sentinel 5 Precursor TROPOspheric Monitoring Instrument (S5P TROPOMI). Furthermore, the changes in TROPOMI tropospheric NO2 across the continental US between 2020 and 2019 correlated well with changes in on-road NOx emissions (r = 0.68) but correlated weakly with changes in emissions from the power plants (r = 0.35). At the height of lock-down related unemployment in the second quarter of 2020, the tropospheric NO2 values decreased at the rate of 0.8 µmoles/m2 per unit percentage increase in the unemployment rate. Despite the lifting of lockdown measures, parts of the US continued to have ?20% below normal on-road NOx emissions. To achieve this new normal urban air quality in the US, continuing remote work policies that do not impede economic growth may become one of the many options.

Despite decades of declining air pollution, urban U.S. areas are still affected by summertime ozone and wintertime particulate matter exceedance events. Volatile organic compounds (VOCs) are known precursors of secondary organic aerosol (SOA) and photochemically produced ozone. Urban VOC emission sources, including on-road transportation emissions, have decreased significantly over the past few decades through successful regulatory measures. These drastic reductions in VOC emissions have led to a change in the distribution of urban emissions and noncombustion sources of VOCs such as those from volatile chemical products (VCPs), which now account for a higher fraction of the urban VOC burden. Given this shift in emission sources, it is essential to quantify the relative contribution of VCP and mobile source emissions to urban pollution. Herein, ground site and mobile laboratory measurements of VOCs were performed. Two ground site locations with different population densities, Boulder, CO, and New York City (NYC), NY, were chosen in order to evaluate the influence of VCPs in cities with varying mixtures of VCPs and mobile source emissions. Positive matrix factorization was used to attribute hundreds of compounds to mobile- and VCP-dominated sources. VCP-dominated emissions contributed to 42 and 78% of anthropogenic VOC emissions for Boulder and NYC, respectively, while mobile source emissions contributed 58 and 22%. Apportioned VOC emissions were compared to those estimated from the Fuel-based Inventory of Vehicle Emissions and VCPs and agreed to within 25% for the bulk comparison and within 30% for more than half of individual compounds. The evaluated inventory was extended to other U.S. cities and it suggests that 50 to 80% of emissions, reactivity, and the SOA-forming potential of urban anthropogenic VOCs are associated with VCP-dominated sources, demonstrating their important role in urban U.S. air quality.

Non-methane volatile organic compounds (NMVOCs) are important precursors of ozone (O3) and secondary organic aerosol (SOA), which play key roles in tropospheric chemistry. A huge amount of NMVOCs emissions from solvent use are complicated by a wide spectrum of sources and species. This work presents a long-term NMVOCs emission inventory of solvent use during 2000–2017 in China. Based on a mass (material) balance method, NMVOCs emissions were estimated for six categories, including coatings, adhesives, inks, pesticides, cleaners and personal care products. The results show that NMVOC emissions from solvent use in China increased rapidly from 2000 to 2014 then kept stable after 2014. The total emission increased from 1.6 Tg (1.2–2.2 Tg at 95 % confidence interval) in 2000 to 10.6 Tg (7.7–14.9 Tg) in 2017. The substantial growth is driven by the large demand of solvent products in both industrial and residential activities. However, increasing treatment facilities on the solvent-related factories in China restrained the continued growth of solvent NMVOCs emissions in recent years. Rapidly developing and heavily industrialized provinces such as Jiangsu, Shandong and Guangdong contributed significantly to the solvent use emissions. Oxygenated VOCs, alkanes and aromatics were main components, accounting for 42 %, 28 % and 21 % of total NMVOCs emissions in 2017, respectively. Our results and previous inventories are generally comparable within the estimation uncertainties (−27 %–52 %). However, there exist significant differences in the estimates of sub-categories. Personal care products were a significant and quickly rising source of NMVOCs, which were probably underestimated in previous inventories. Emissions from solvent use were growing faster compared with transportation and combustion emissions which were relatively better controlled in China. Environmentally friendly products can reduce the NMVOCs emissions from solvent use. Supposing all solvent-based products were substituted by water-based products, it would result in 37 %, 41 % and 38 % reduction of emissions, OFP and SOAP, respectively. These results indicate there is still large room for NMVOCs reduction by reducing the utilization of solvent product and end-of-pipe control across industrial sectors.

On March 11th , 2020, the World Health Organization (WHO) characterized the COVID-19 respiratory disease caused by the coronavirus (SARS-CoV-2) as a world wide pandemic which led to a massive slowdown in anthropogenic activity as people attempted to "shelter in place". In response to this slowdown NOAA's Global Monitoring Lab (GML), in collaboration with the National Institute of Standards and Technology (NIST), University of Michigan, University of Maryland, Stony Brook University and NOAA's Chemical Science and Atmospheric Resource Laboratories, launched a campaign to measure CO2, CH4, and CO emissions from five major cities along the northeast corridor of the US (Washington, D.C., Baltimore, MD, Philadelphia, PA, New York, NY, and Boston, MA). The month-long campaign which lasted from April 16 to May 16 of 2020 mirrored a campaign that was completed exactly two years prior in April and May of 2018 and which enabled direct comparison of CO2, CH4, CO emissions from these five cities before and during SARS-CoV-2.In this work, we used a Bayesian multi-resolution tiered inversion framework to quantify the CO2, CH4 and CO emissions from these urban areas. We used the HYSPLIT atmospheric transport and dispersion model to calculate the sensitivity of our aircraft observations to surface fluxes (footprints) using three meteorological drivers (NAM, ERA5 and a custom WRF); using three driver models allowed us to account for uncertainties in the transport. To account for biospheric influences on atmospheric CO2, we used a year-specific VPRM simulation that allowed us to isolate the fossil-fuel contribution and solve for it alone. In addition, we also solved for total CO2 and show that not accounting for biogenic activity in lower latitude urban areas could have led to an overestimation of the observed reduction due to biogenic flux differences between the two years.Results show that systematic reductions in CO2 and CO emissions for the five urban areas occurred in April 2020 with signs of recovery in May 2020, which had larger emissions than April 2020. The observed reductions and evolution are consistent with bottom-up estimations based on mobility metrics, which showed the lowest mobility in April with progressive recovery in May. Fuel use from tax records indicates similar reductions. In addition, we show that changes are not homogeneous in space within the urban metropolitan areas and that CO2 and CO emissions reductions are collocated, showing the largest drops in urban centers and roads. While CO2 and CO estimated reductions and evolution are systematic in all cities, CH4 does not show a clear reduction or consistent pattern among cities during the COVID-19 lock-downs. In fact, all the measured changes for CH4 were lower than the standard errors of the differences, implying that the observed changes in CH4 are not significant. Last, we note that since the same prior emissions, constant in time, were used in all the inversions, the anomalous decrease in posterior emissions and subsequent recovery in CO2 and CO observed during the COVID-19 lock-down period are driven by the atmospheric observations and not by temporal changes in the prior emissions.

The development of horizontal drilling and hydraulic fracturing has led to a steep increase in the U.S. production of natural gas and crude oil from shale formations since the mid 2000s. Associated with this industrial activity are emissions of ground-level ozone precursors such as nitrogen oxides (NOx). Satellite data are important in this context, because surface measurements are limited or non-existent in rural regions, where most U.S. oil and gas production operations take place. Here we use TROPOMI NO2 observations to study NOx emissions coming from oil and natural gas production sites. Applying the divergence method we quantify basin wide emissions from well pad fields and aim to push spatial and temporal resolution of this technique. The divergence was method introduced by Beirle et al. (Science Advances 2019) to quantify point source emissions. It relies on calculating the divergence of the NO2 flux to derive NOx sources and estimating the NO2 lifetime to quantify sinks. Our analysis will include an assessment of different methods to constrain the NO2 lifetime, which becomes particularly important when applying this method to larger areas. Further we will compare our results with bottom-up derived emissions. Here we use the Fuel-based Oil & Gas (FOG) inventory that calculates NOx emissions based on fuel consumption. Initial results show good agreement for the Permian Basin (NM, TX) and we will expand our analysis to other U.S. basins.

The coronavirus-19 (COVID-19) pandemic led to government interventions to limit the spread of the disease that are unprecedented in the last decades. Stay at home orders and other measures led to sudden decreases in atmospheric emissions, most visibly from the transportation sector. We present a review of the current knowledge and understanding of the influence of these emission reductions on atmospheric pollutants concentration and notably air quality with a focus on NO2, PM2.5, and O3 based on more than 200 papers utilizing observations from ground-based and satellite remote sensing instruments. We use the government stringency index as an indicator for the severity of lockdown measures and show how key air pollutants change as the stringency index increases. Changes in NO2 and PM2.5 mass concentration are well-studied globally. The observed decrease of NO2 with increasing stringency index is in general agreement with emission inventories that account for the lockdown. Due to the important influence of atmospheric chemistry on O3 and PM2.5 concentrations, their responses may not be linear with respect to primary pollutants. At most sites, we found O3 increased, whereas PM2.5 decreased slightly, with increasing stringency index. Changes in the PM2.5 composition are found to be understudied and not well-quantified so far. We highlight future research needs for utilizing the emerging data sets covering a full seasonal cycle as a preview of a future state of the atmosphere in a world with targeted permanent reductions of emissions. Finally, we emphasize the need to account for the effects of meteorology, long-term trends, and atmospheric chemistry when determining the lockdown effects on pollutant concentrations, especially on PM2.5.

The emissions of volatile organic compounds (VOCs) from volatile chemical products (VCPs) – specifically personal care products, cleaning agents, coatings, adhesives, and pesticides – are emerging as the largest source of petroleum-derived organic carbon in US cities. Previous work has shown that the ambient concentration of markers for most VCP categories correlates strongly with population density, except for VOCs predominantly originating from solvent- and water-borne coatings (e.g., parachlorobenzotrifluoride (PCBTF) and Texanol®, respectively). Instead, these enhancements were dominated by distinct emission events likely driven by industrial usage patterns, such as construction activity. In this work, the headspace of a variety of coating products was analyzed using a proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS) and a gas chromatography (GC) preseparation front end to identify composition differences for various coating types (e.g., paints, primers, sealers, and stains). Evaporation experiments of several products showed high initial VOC emission rates, and for the length of these experiments, the majority of the VOC mass was emitted during the first few hours following application. The percentage of mass emitted as measured VOCs (<1 % to 83 %) mirrored the VOC content reported by the manufacturer (<5 to 550 g L−1). Ambient and laboratory measurements, usage trends, and ingredients compiled from architectural coatings surveys show that both PCBTF and Texanol account for ∼10 % of the total VOC ingredient sales and, therefore, can be useful tracers for solvent- and water-borne coatings.

Nitrogen oxides (NOx) are air pollutants critical to ozone and fine particle production in the troposphere. Here, we present fuel-based emission inventories updated to 2018, including for mobile source engines using the Fuel-based Inventory of Vehicle Emissions (FIVEs) and oil and gas production using the Fuel-based Oil and Gas (FOG) inventory. The updated FIVE emissions are now consistent with the NEI17 estimates differing within 2% across the contiguous US (CONUS). Tropospheric NO2 columns modeled by the Weather Research and Forecasting with Chemistry model (WRF-Chem) are compared with those observed by TROPOspheric Monitoring Instrument (TROPOMI) and Ozone Monitoring Instrument (OMI) during the summer of 2018. Modeled NO2 columns show strong temporal and spatial correlations with TROPOMI (OMI), identified with biases of −3% (−21%) over CONUS, and +8% (−6%) over point sources plus urban regions. Taking account of the negative bias (∼20%) in early version of TROPOMI over polluted regions, WRF-Chem shows good performance with updated FIVE and FOG emissions. Our model tends to under-predict the tropospheric NO2 columns over background and rural regions (bias of −21% to −3%). Through model sensitivity analyses, we demonstrate the important roles of emissions from soils (11.7% average over CONUS), oil and gas production (4.1%), wildfires (10.6%), and lightning (2.3%) with greater contributions at regional scales. This work provides a roadmap for satellite-based evaluations for emission updates from various sources.

Most countries around the world took actions to control COVID-19 spread that included social distancing, limiting air and ground travel, closing schools, suspending sports leagues, closing factorie...

Anthropogenic secondary organic aerosol (ASOA), formed from anthropogenic emissions of organic compounds, constitutes a substantial fraction of the mass of submicron aerosol in populated areas around the world and contributes to poor air quality and premature mortality. However, the precursor sources of ASOA are poorly understood, and there are large uncertainties in the health benefits that might accrue from reducing anthropogenic organic emissions. We show that the production of ASOA in 11 urban areas on three continents is strongly correlated with the anthropogenic reactivity of specific volatile organic compounds. The differences in ASOA production across different cities can be explained by differences in the emissions of aromatics and intermediate- and semi-volatile organic compounds, indicating the importance of controlling these ASOA precursors. With an improved modeling representation of ASOA driven by the observations, we attribute 340,000 PM2.5 premature deaths per year to ASOA, which is over an order of magnitude higher than prior studies. A sensitivity case with a more recently proposed model for attributing mortality to PM2.5 (the Global Exposure Mortality Model) results up to 900,000 deaths. A limitation of this study is the extrapolation from regions with detailed data to others where data is not available. Comprehensive air quality campaigns in the countries in South and Central America, Africa, South Asia, and the Middle East are needed for further progress in this area.

Consumer, industrial, and commercial product usage is a source of exposure to potentially hazardous chemicals. In addition, cleaning agents, personal care products, coatings, and other volatile chemical products (VCPs), evaporate and react in the atmosphere producing secondary pollutants. Here, we show high air emissions from VCP usage (≥ 14 kg person-1 yr-1, at least 1.7× higher than current operational estimates) are supported by multiple estimation methods and constraints imposed by ambient levels of ozone, hydroxyl radical (OH) reactivity, and the organic component of fine particulate matter (PM2.5) in Pasadena, California. A near-field model, which estimates human chemical exposure during or in the vicinity of product use, indicates these high air emissions are consistent with organic product usage up to ~75 kg person-1 yr-1, and inhalation of consumer products could be a non-negligible exposure pathway. After constraining the PM2.5 yield to 5% by mass, VCPs produce ~41% of the photochemical organic PM2.5 (1.1 ± 0.3 μg m-3) and ~17% of maximum daily 8-hr average ozone (9 ± 2 ppb) in summer Los Angeles. Therefore, both toxicity and ambient criteria pollutant formation should be considered when organic substituents are developed for VCPs in pursuit of safer and sustainable products and cleaner air.

Houston, Texas is a major U.S. urban and industrial area where poor air quality is unevenly distributed and a disproportionate share is located in low-income, non-white, and Hispanic neighborhoods. We have traditionally lacked city-wide observations to fully describe these spatial heterogeneities in Houston and in cities globally, especially for reactive gases like nitrogen dioxide (NO

In this study, we develop an alternative Fuel-based Oil and Gas inventory (FOG) of nitrogen oxides (NOx) from oil and gas production using publicly available fuel use records and emission factors reported in the literature. FOG is compared with the Environmental Protection Agency’s 2014 National Emissions Inventory (NEI) and with new top-down estimates of NOx emissions derived from aircraft and ground-based field measurement campaigns. Compared to our top-down estimates derived in four oil and gas basins (Uinta, UT, Haynesville, TX/LA, Marcellus, PA, and Fayetteville, AR), the NEI overestimates NOx by over a factor of 2 in three out of four basins, while FOG is generally consistent with atmospheric observations. Challenges in estimating oil and gas engine activity, rather than uncertainties in NOx emission factors, may explain gaps between the NEI and top-down emission estimates. Lastly, we find a consistent relationship between reactive odd nitrogen species (NOy) and ambient methane (CH4) across basins w...

Recent studies suggest overestimates in current U.S. emission inventories of nitrogen oxides (NOx = NO + NO2). Here, we expand a previously developed fuel-based inventory of motor-vehicle emissions (FIVE) to the continental U.S. for the year 2013, and evaluate our estimates of mobile source emissions with the U.S. Environmental Protection Agency’s National Emissions Inventory (NEI) interpolated to 2013. We find that mobile source emissions of NOx and carbon monoxide (CO) in the NEI are higher than FIVE by 28% and 90%, respectively. Using a chemical transport model, we model mobile source emissions from FIVE, and find consistent levels of urban NOx and CO as measured during the Southeast Nexus (SENEX) Study in 2013. Lastly, we assess the sensitivity of ozone (O3) over the Eastern U.S. to uncertainties in mobile source NOx emissions and biogenic volatile organic compound (VOC) emissions. The ground-level O3 is sensitive to reductions in mobile source NOx emissions, most notably in the Southeastern U.S. and ...

Decamethylcyclopentasiloxane (D5) is a cyclic volatile methyl siloxane (cVMS) that is widely used in consumer products and commonly observed in urban air. This study quantifies the ambient mixing ratios of D5 from ground sites in two North American cities (Boulder, CO, USA, and Toronto, ON, CA). From these data, we estimate the diurnal emission profile of D5 in Boulder, CO. Ambient mixing ratios were consistent with those measured at other urban locations; however, the diurnal pattern exhibited similarities with those of traffic-related compounds such as benzene. Mobile measurements and vehicle experiments demonstrate that emissions of D5 from personal care products are coincident in time and place with emissions of benzene from motor vehicles. During peak commuter times, the D5/benzene ratio (w/w) is in excess of 0.3, suggesting that the mass emission rate of D5 from personal care product usage is comparable to that of benzene due to traffic. The diurnal emission pattern of D5 is estimated using the meas...

Air pollution evolution Transport-derived emissions of volatile organic compounds (VOCs) have decreased owing to stricter controls on air pollution. This means that the relative importance of chemicals in pesticides, coatings, printing inks, adhesives, cleaning agents, and personal care products has increased. McDonald et al. show that these volatile chemical products now contribute fully one-half of emitted VOCs in 33 industrialized cities (see the Perspective by Lewis). Thus, the focus of efforts to mitigate ozone formation and toxic chemical burdens need to be adjusted. Science , this issue p. 760 ; see also p. 744

Concentrations of atmospheric trace species in the United States have changed dramatically over the past several decades in response to pollution control strategies, shifts in domestic energy policy and economics, and economic development (and resulting emission changes) elsewhere in the world. Reliable projections of the future atmosphere require models to not only accurately describe current atmospheric concentrations, but to do so by representing chemical, physical and biological processes with conceptual and quantitative fidelity. Only through incorporation of the processes controlling emissions and chemical mechanisms that represent the key transformations among reactive molecules can models reliably project the impacts of future policy, energy and climate scenarios. Efforts to properly identify and implement the fundamental and controlling mechanisms in atmospheric models benefit from intensive observation periods, during which collocated measurements of diverse, speciated chemicals in both the gas and condensed phases are obtained. The Southeast Atmosphere Studies (SAS, including SENEX, SOAS, NOMADSS and SEAC4RS) conducted during the summer of 2013 provided an unprecedented opportunity for the atmospheric modeling community to come together to evaluate, diagnose and improve the representation of fundamental climate and air quality processes in models of varying temporal and spatial scales.This paper is aimed at discussing progress in evaluating, diagnosing and improving air quality and climate modeling using comparisons to SAS observations as a guide to thinking about improvements to mechanisms and parameterizations in models. The effort focused primarily on model representation of fundamental atmospheric processes that are essential to the formation of ozone, secondary organic aerosol (SOA) and other trace species in the troposphere, with the ultimate goal of understanding the radiative impacts of these species in the southeast and elsewhere. Here we address questions surrounding four key themes: gas-phase chemistry, aerosol chemistry, regional climate and chemistry interactions, and natural and anthropogenic emissions. We expect this review to serve as a guidance for future modeling efforts.

Significance Emissions of nitrogen oxides (NOx) have a large impact on air quality and climate change as precursors in the formation of ozone and secondary aerosols. We find that NOx emissions have not been decreasing as expected in recent years (2011–2015) when comparing top-down estimates from satellites and surface NO2 measurements to the trends predicted from the US Environmental Protection Agency’s emission inventory data. The discrepancy can be explained by the growing relative contribution of industrial, area, and off-road mobile sources of emissions, decreasing relative contribution of on-road gasoline vehicles, and slower than expected decreases in on-road diesel NOx emissions, with implications for air-quality management., Ground and satellite observations show that air pollution regulations in the United States (US) have resulted in substantial reductions in emissions and corresponding improvements in air quality over the last several decades. However, large uncertainties remain in evaluating how recent regulations affect different emission sectors and pollutant trends. Here we show a significant slowdown in decreasing US emissions of nitrogen oxides (NOx) and carbon monoxide (CO) for 2011–2015 using satellite and surface measurements. This observed slowdown in emission reductions is significantly different from the trend expected using US Environmental Protection Agency (EPA) bottom-up inventories and impedes compliance with local and federal agency air-quality goals. We find that the difference between observations and EPA’s NOx emission estimates could be explained by: (i) growing relative contributions of industrial, area, and off-road sources, (ii) decreasing relative contributions of on-road gasoline, and (iii) slower than expected decreases in on-road diesel emissions.

U.S. oil and natural gas production volumes have grown by up to 100% in key production areas between January 2017 and August 2019. Here we show that recent trends are visible from space and can be attributed to drilling, production, and gas flaring activities. By using oil and gas activity data as predictors in a multivariate regression to satellite measurements of tropospheric NO2 columns, observed changes in NO2 over time could be attributed to NOx emissions associated with drilling, production and gas flaring for three select regions: the Permian, Bakken, and Eagle Ford basins. We find that drilling had been the dominant NOx source contributing around 80% before the downturn in drilling activity in 2015. Thereafter, NOx contributions from drilling activities and combined production and flaring activities are similar. Comparison of our top-down source attribution with a bottom-up fuel-based oil and gas NOx emission inventory shows agreement within error margins.

Mobile sampling studies have revealed enhanced levels of secondary organic aerosol (SOA) in source-rich urban environments. While these enhancements can be from rapidly reacting vehicular emissions, it was recently hypothesized that nontraditional emissions (volatile chemical products and upstream emissions) are emerging as important sources of urban SOA. We tested this hypothesis by using gas and aerosol mass spectrometry coupled with an oxidation flow reactor (OFR) to characterize pollution levels and SOA potentials in environments influenced by traditional emissions (vehicular, biogenic), and nontraditional emissions (e.g., paint fumes). We used two SOA models to assess contributions of vehicular and biogenic emissions to our observed SOA. The largest gap between observed and modeled SOA potential occurs in the morning-time urban street canyon environment, for which our model can only explain half of our observation. Contributions from VCP emissions (e.g., personal care products) are highest in this environment, suggesting that VCPs are an important missing source of precursors that would close the gap between modeled and observed SOA potential. Targeted OFR oxidation of nontraditional emissions shows that these emissions have SOA potentials that are similar, if not larger, compared to vehicular emissions. Laboratory experiments reveal large differences in SOA potentials of VCPs, implying the need for further characterization of these nontraditional emissions.

In California's Central Valley, tule fog frequency increased 85% from 1930 to 1970, then declined 76% in the last 36 winters. Throughout these changes, fog frequency exhibited a consistent north-south trend, with maxima in southern latitudes. We analyzed seven decades of meteorological data and five decades of air pollution data to determine the most likely drivers changing fog, including temperature, dew point depression, precipitation, wind speed, and NOx (oxides of nitrogen) concentration. Climate variables, most critically dew point depression, strongly influence the short-term (annual) variability in fog frequency; however, the frequency of optimal conditions for fog formation show no observable trend from 1980 to 2016. NOx concentration, which has a decreasing north-south concentration gradient, declined continuously over this period, consistent with the long-term temporal and spatial trends in fog. As development in the Central Valley increased direct particle and other pollutant emissions from 1930 to 1970, fog frequency increased. Following the Clean Air Act, particle emissions quickly declined, and NOx emissions declined steadily, reducing the cloud condensation nuclei (CCN) available for fog formation. As a precursor of ammonium nitrate aerosols, which are efficient CCN, we used NOx measurements and emission trends as a proxy for the CCN trend. We conclude that while the short-term fog variability is dominantly driven by climate fluctuations, the longer-term temporal and spatial changes in fog have been driven by changes in air pollution. For conditions close to the dew point, a decrease in fog of 5 days/year per 10 parts per billion NOx decrease occurred across the Central Valley. ©2019. American Geophysical Union. All Rights Reserved.

The COVID-19 pandemic and ensuing lockdown of many US States resulted in rapid changes to motor vehicle traffic and their associated emissions. This presents a challenge for air quality modelling and forecasting during this period, in that transportation emission inventories need to be updated in near real-time. Here, we update the previously developed fuel-based inventory of vehicle emissions (FIVE) to account for changes due to COVID-19 lockdowns. We first construct a 2020 business-as-usual (BAU) case inventory and adjust the emissions for a COVID-19 case using monthly fuel sales information. We evaluate cellular phone-based mobility data products (Google COVID-19 Community Mobility, Apple COVID-19 Mobility Trends) in comparison to embedded traffic monitoring sites in four US cities. We find that mobility datasets tend to overestimate traffic reductions in April 2020 (i.e. lockdown period), while fuel sales adjustments are more similar to changes observed by traffic monitors; for example, mobility-based methods for scaling emissions result in an approximately two-times greater estimate of on-road nitrogen oxide (NO x ) reductions in April 2020 than we find using a fuel-based method. Overall, FIVE estimates a 20%–25% reduction in mobile source NO x emissions in April 2020 versus BAU, and a smaller 6%–7% drop by July. Reductions in April showed considerable spatial heterogeneity, ranging from 6% to 39% at the state level. Similar decreases are found for carbon monoxide (CO) and volatile organic compounds. Decreases to mobile source NO x emissions are expected to lower total US anthropogenic emissions by 9%–12% and 3%–4% in April and July, respectively, with larger relative impacts in urban areas. Changes to diurnal and day-of-week patterns of light- and heavy-duty vehicular traffic are evaluated and found to be relatively minor. Beyond the applicability to modelling air quality in 2020, this work also represents a methodology for quickly updating US transportation inventories and for calibrating mobility-based estimates of emissions.

The majority of anthropogenic CO2 emissions are attributable to urban areas. While the emissions from urban electricity generation often occur in locations remote from consumption, many of the other emissions occur within the city limits. Evaluating the effectiveness of strategies for controlling these emissions depends on our ability to observe urban CO2 emissions and attribute them to specific activities. Cost-effective strategies for doing so have yet to be described. Here we characterize the ability of a prototype measurement network, modeled after the Berkeley Atmospheric CO2 Observation Network (BEACO2N) in California's Bay Area, in combination with an inverse model based on the coupled Weather Research and Forecasting/Stochastic Time-Inverted Lagrangian Transport (WRF-STILT) to improve our understanding of urban emissions. The pseudo-measurement network includes 34 sites at roughly 2 km spacing covering an area of roughly 400 km2. The model uses an hourly 1 × 1 km2 emission inventory and 1 × 1 km2 meteorological calculations. We perform an ensemble of Bayesian atmospheric inversions to sample the combined effects of uncertainties of the pseudo-measurements and the model. We vary the estimates of the combined uncertainty of the pseudo-observations and model over a range of 20 to 0.005 ppm and vary the number of sites from 1 to 34. We use these inversions to develop statistical models that estimate the efficacy of the combined model–observing system in reducing uncertainty in CO2 emissions. We examine uncertainty in estimated CO2 fluxes on the urban scale, as well as for sources embedded within the city such as a line source (e.g., a highway) or a point source (e.g., emissions from the stacks of small industrial facilities). Using our inversion framework, we find that a dense network with moderate precision is the preferred setup for estimating area, line, and point sources from a combined uncertainty and cost perspective. The dense network considered here (modeled after the BEACO2N network with an assumed mismatch error of 1 ppm at an hourly temporal resolution) could estimate weekly CO2 emissions from an urban region with less than 5 % error, given our characterization of the combined observation and model uncertainty.

Long-term atmospheric NOx/CO enhancement ratios in megacities provide evaluations of emission inventories. A fuel-based emission inventory approach that diverges from conventional bottom-up inventory methods explains 1970–2015 trends in NOx/CO enhancement ratios in Los Angeles. Combining this comparison with similar measurements in other U.S. cities demonstrates that motor vehicle emissions controls were largely responsible for U.S. urban NOx/CO trends in the past half century. Differing NOx/CO enhancement ratio trends in U.S. and European cities over the past 25 years highlights alternative strategies for mitigating transportation emissions, reflecting Europe's increased use of light-duty diesel vehicles and correspondingly slower decreases in NOx emissions compared to the U.S. A global inventory widely used by global chemistry models fails to capture these long-term trends and regional differences in U.S. and Europe megacity NOx/CO enhancement ratios, possibly contributing to these models' inability to accurately reproduce observed long-term changes in tropospheric ozone.

We developed a new nitrogen oxide (NOx) and carbon monoxide (CO) emission inventory for the Los Angeles-South Coast Air Basin (SoCAB) expanding the Fuel-based Inventory for motor-Vehicle Emissions and applied it in regional chemical transport modeling focused on the California Nexus of Air Quality and Climate Change (CalNex) 2010 field campaign. The weekday NOx emission over the SoCAB in 2010 is 620 t d−1, while the weekend emission is 410 t d−1. The NOx emission decrease on weekends is caused by reduced diesel truck activities. Weekday and weekend CO emissions over this region are similar: 2340 and 2180 t d−1, respectively. Previous studies reported large discrepancies between the airborne observations of NOx and CO mixing ratios and the model simulations for CalNex based on the available bottom-up emission inventories. Utilizing the newly developed emission inventory in this study, the simulated NOx and CO mixing ratios agree with the observations from the airborne and the ground-based in situ and remote sensing instruments during the field study. The simulations also reproduce the weekly cycles of these chemical species. Both the observations and the model simulations indicate that decreased NOx on weekends leads to enhanced photochemistry and increase of O3 and Ox (=O3 + NO2) in the basin. The emission inventory developed in this study can be extended to different years and other urban regions in the U.S. to study the long-term trends in O3 and its precursors with regional chemical transport models.