A gap in emission inventories of urban volatile organic compound (VOC) sources, which contribute to regional ozone and aerosol burdens, has increased as transportation emissions in the United States ...and Europe have declined rapidly. A detailed mass balance demonstrates that the use of volatile chemical products (VCPs)-including pesticides, coatings, printing inks, adhesives, cleaning agents, and personal care products-now constitutes half of fossil fuel VOC emissions in industrialized cities. The high fraction of VCP emissions is consistent with observed urban outdoor and indoor air measurements. We show that human exposure to carbonaceous aerosols of fossil origin is transitioning away from transportation-related sources and toward VCPs. Existing U.S. regulations on VCPs emphasize mitigating ozone and air toxics, but they currently exempt many chemicals that lead to secondary organic aerosols.
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BFBNIB, NMLJ, NUK, ODKLJ, PNG, SAZU, UL, UM, UPUK
A fully coupled “online” Weather Research and Forecasting/Chemistry (WRF/Chem) model has been developed. The air quality component of the model is fully consistent with the meteorological component; ...both components use the same transport scheme (mass and scalar preserving), the same grid (horizontal and vertical components), and the same physics schemes for subgrid-scale transport. The components also use the same timestep, hence no temporal interpolation is needed. The chemistry package consists of dry deposition (“flux-resistance” method), biogenic emission as in Simpson et al., 1995. Journal of Geophysical Research 100D, 22875–22890; Guenther et al., 1994. Atmospheric Environment 28, 1197–1210, the chemical mechanism from RADM2, a complex photolysis scheme (Madronich scheme coupled with hydrometeors), and a state of the art aerosol module (MADE/SORGAM aerosol parameterization).
The WRF/Chem model is statistically evaluated and compared to MM5/Chem and to detailed photochemical data collected during the summer 2002 NEAQS field study. It is shown that the WRF/Chem model is statistically better skilled in forecasting O
3 than MM5/Chem, with no appreciable differences between models in terms of bias with the observations. Furthermore, the WRF/Chem model consistently exhibits better skill at forecasting the O
3 precursors CO and NO
y
at all of the surface sites. However, the WRF/Chem model biases of these precursors and of other gas-phase species are persistently higher than for MM5/Chem, and are most often biased high compared to observations. Finally, we show that the impact of other basic model assumptions on these same statistics can be much larger than the differences caused by model differences. An example showing the sensitivity of various statistical measures with respect to the treatment of biogenic volatile organic compounds emissions illustrates this impact.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK
The United States is now experiencing the most rapid expansion in oil and gas production in four decades, owing in large part to implementation of new extraction technologies such as horizontal ...drilling combined with hydraulic fracturing. The environmental impacts of this development, from its effect on water quality to the influence of increased methane leakage on climate, have been a matter of intense debate. Air quality impacts are associated with emissions of nitrogen oxides (NOx = NO + NO2) and volatile organic compounds (VOCs), whose photochemistry leads to production of ozone, a secondary pollutant with negative health effects. Recent observations in oil- and gas-producing basins in the western United States have identified ozone mixing ratios well in excess of present air quality standards, but only during winter. Understanding winter ozone production in these regions is scientifically challenging. It occurs during cold periods of snow cover when meteorological inversions concentrate air pollutants from oil and gas activities, but when solar irradiance and absolute humidity, which are both required to initiate conventional photochemistry essential for ozone production, are at a minimum. Here, using data from a remote location in the oil and gas basin of northeastern Utah and a box model, we provide a quantitative assessment of the photochemistry that leads to these extreme winter ozone pollution events, and identify key factors that control ozone production in this unique environment. We find that ozone production occurs at lower NOx and much larger VOC concentrations than does its summertime urban counterpart, leading to carbonyl (oxygenated VOCs with a C = O moiety) photolysis as a dominant oxidant source. Extreme VOC concentrations optimize the ozone production efficiency of NOx. There is considerable potential for global growth in oil and gas extraction from shale. This analysis could help inform strategies to monitor and mitigate air quality impacts and provide broader insight into the response of winter ozone to primary pollutants.
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DOBA, IJS, IZUM, KILJ, KISLJ, NUK, PILJ, PNG, SAZU, SIK, UILJ, UKNU, UL, UM, UPUK
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.
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BFBNIB, NMLJ, NUK, PNG, SAZU, UL, UM, UPUK
Total 550 nm aerosol optical depth (AOD) retrievals from Moderate Resolution Imaging Spectroradiometer (MODIS) sensors and surface fine particulate matter (PM2.5) observations were assimilated with ...the National Centers for Environmental Prediction (NCEP) Gridpoint Statistical Interpolation (GSI) three‐dimensional variational (3DVAR) data assimilation (DA) system. Parallel experiments assimilated AOD and surface PM2.5observations both individually and simultaneously. New 3DVAR aerosol analyses were produced every 6 h between 0000 UTC 01 June and 1800 UTC 14 July 2010 over a domain encompassing the continental United States. The analyses initialized Weather Research and Forecasting‐Chemistry (WRF‐Chem) model forecasts. Assimilating AOD, either alone or in conjunction with PM2.5 observations, produced better AOD forecasts than a control experiment that did not perform DA. Additionally, individual assimilation of both AOD and PM2.5 improved surface PM2.5 forecasts compared to when no DA occurred. However, the best PM2.5 forecasts were produced when both AOD and PM2.5 were assimilated. Considering the goodness of both AOD and PM2.5 forecasts, the results unequivocally show that concurrent DA of PM2.5 and AOD observations produced the best overall forecasts, illustrating how simultaneous DA of different aerosol observations can work synergistically to improve aerosol forecasts.
Key Points
Simultaneous 3DVAR data assimilation of MODIS AOD and surface PM2.5 observations
Aerosol data assimilation substantially improves aerosol forecasts
Forecasts are best when both AOD and surface PM2.5 are assimilated concurrently
Recent studies suggest overestimates in current U.S. emission inventories of nitrogen oxides (NO x = 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 NO x 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 NO x 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 NO x emissions and biogenic volatile organic compound (VOC) emissions. The ground-level O3 is sensitive to reductions in mobile source NO x emissions, most notably in the Southeastern U.S. and during O3 exceedance events, under the revised standard proposed in 2015 (>70 ppb, 8 h maximum). This suggests that decreasing mobile source NO x emissions could help in meeting more stringent O3 standards in the future.
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IJS, KILJ, NUK, PNG, UL, UM
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.
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The Green Ocean Amazon experiment – GoAmazon 2014–2015 – explored the interactions between natural biogenic forest emissions from central Amazonia and urban air pollution from Manaus. Previous ...GoAmazon 2014–2015 studies showed that nitrogen oxide (NOx = NO + NO2) and sulfur oxide (SOx) emissions from Manaus strongly interact with biogenic volatile organic compounds (BVOCs), affecting secondary organic aerosol (SOA) formation. In previous studies, ground-based and aircraft measurements provided evidence of SOA formation and strong changes in aerosol composition and properties. Aerosol optical properties also evolve, and their impacts on the Amazonian ecosystem can be significant. As particles age, some processes, such as SOA production, black carbon (BC) deposition, particle growth and the BC lensing effect change the aerosol optical properties, affecting the solar radiation flux at the surface. This study analyzes data and models SOA formation using the Weather Research and Forecasting with Chemistry (WRF-Chem) model to assess the spatial variability in aerosol optical properties as the Manaus plumes interact with the natural atmosphere. The following aerosol optical properties are investigated: single scattering albedo (SSA), asymmetry parameter (gaer), absorption Ångström exponent (AAE) and scattering Ångström exponent (SAE). These simulations were validated using ground-based measurements at three experimental sites, namely the Amazon Tall Tower Observatory – ATTO (T0a), downtown Manaus (T1), Tiwa Hotel (T2) and Manacapuru (T3), as well as the U.S. Department of Energy (DOE) Gulfstream 1 (G-1) aircraft flights. WRF-Chem simulations were performed over 7 d during March 2014. Results show a mean biogenic SOA (BSOA) mass enrichment of 512 % at the T1 site, 450 % in regions downwind of Manaus, such as the T3 site, and 850 % in areas north of the T3 site in simulations with anthropogenic emissions. The SOA formation is rather fast, with about 80 % of the SOA mass produced in 3–4 h. Comparing the plume from simulations with and without anthropogenic emissions, SSA shows a downwind reduction of approximately 10 %, 11 % and 6 % at the T1, T2 and T3 sites, respectively. Other regions, such as those further downwind of the T3 site, are also affected. The gaer values increased from 0.62 to 0.74 at the T1 site and from 0.67 to 0.72 at the T3 site when anthropogenic emissions are active. During the Manaus plume-aging process, a plume tracking analysis shows an increase in SSA from 0.91 close to Manaus to 0.98 160 km downwind of Manaus as a result of SOA production and BC deposition.
A statistical regression method is presented for estimating hourly anthropogenic heat flux (AHF) using an anthropogenic pollutant emission inventory for use in mesoscale meteorological and ...air-quality modeling. Based on bottom-up AHF estimated from detailed energy consumption data and anthropogenic pollutant emissions of carbon monoxide (CO) and nitrogen oxides (NOx) in the US National Emission Inventory year 2005 (NEI-2005), a robust regression relation between the AHF and the pollutant emissions is obtained for Houston. This relation is a combination of two power functions (Y = aXb) relating CO and NOx emissions to AHF, giving a determinant coefficient (R2) of 0.72. The AHF for Houston derived from the regression relation has high temporal (R = 0.91) and spatial (R = 0.83) correlations with the bottom-up AHF. Hourly AHF for the whole US in summer is estimated by applying the regression relation to the NEI-2005 summer pollutant emissions with a high spatial resolution of 4-km. The summer daily mean AHF range 10–40 W m−2 on a 4 × 4 km2 grid scale with maximum heat fluxes of 50–140 W m−2 for major US cities. The AHFs derived from the regression relations between the bottom-up AHF and either CO or NOx emissions show a small difference of less than 5% (4.7 W m−2) in city-scale daily mean AHF, and similar R2 statistics, compared to results from their combination. Thus, emissions of either species can be used to estimate AHF in the US cities. An hourly AHF inventory at 4 × 4 km2 resolution over the entire US based on the combined regression is derived and made publicly available for use in mesoscale numerical modeling.
•A new methodology for anthropogenic heat flux (AHF) estimation is suggested.•The AHF over the entire US regions is estimated at 4-km and 1-h resolution.•The gridded AHF dataset is publicly available via a ftp site.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK
The global Flow-following finite-volume Icosahedral Model (FIM), which was developed in the Global Systems Laboratory (GSL) of NOAA, has been
coupled inline with aerosol and gas-phase chemistry ...schemes of different complexity using the chemistry and aerosol packages from WRF-Chem v3.7,
named FIM-Chem v1. The three chemistry schemes include (1) the simple aerosol modules from the Goddard Chemistry Aerosol Radiation and Transport
model that includes only simplified sulfur chemistry, black carbon (BC), organic carbon (OC), and sectional dust and sea salt modules (GOCART);
(2) the photochemical gas phase of the Regional Atmospheric
Chemistry Mechanism (RACM) coupled to GOCART to determine the impact of more realistic gas-phase chemistry on the GOCART
aerosol simulations (RACM_GOCART); and (3) a further sophistication within the aerosol modules by replacing GOCART with a modal aerosol scheme
that includes secondary organic aerosols (SOAs) based on the volatility basis set (VBS) approach (RACM_SOA_VBS). FIM-Chem is able to simulate aerosol, gas-phase chemical
species, and SOA at various spatial resolutions with different levels of complexity and quantify the impact of aerosol on numerical weather
prediction (NWP). We compare the results of RACM_GOCART and GOCART schemes which use the default climatological model fields for OH,
H2O2, and NO3. We find significant reductions of sulfate that are on the order of 40 % to 80 % over the eastern US
and are up to 40 % near the Beijing region over China when using the RACM_GOCART scheme. We also evaluate the model performance by comparing it
with the Atmospheric Tomography Mission (ATom-1) aircraft measurements in the summer of 2016. FIM-Chem shows good performance in capturing the aerosol and
gas-phase tracers. The model-predicted vertical profiles of biomass burning plumes and dust plumes off western Africa are also reproduced
reasonably well.
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IZUM, KILJ, NUK, PILJ, PNG, SAZU, UL, UM, UPUK
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