Three-dimensional Air Quality Model Research Articles

Differences of Three Methods in Determining Ozone Sensitivity in Nanjing

In recent years， ozone （O3） has become an increasingly important air pollutant in China. Identifying the sensitivity of O3 to the precursors volatile organic compounds （VOCs） and nitrogen oxides （NOx） can help make effective abatement strategies. This study compared three methods for determining O3-VOCs-NOx sensitivity： simulated photochemical indicator values and sensitivity coefficients derived from a three-dimensional air quality model and an observation-based model （OBM）， with a case study involving an O3 pollution event that occurred in Nanjing in late July 2017. The results showed that O3 sensitivity based on the photochemical indicator and sensitivity coefficients demonstrated similar spatial variations （over 50% of the grid cells of Nanjing exhibiting identical O3 sensitivity）. However， sensitivity coefficients identified a larger number of areas within a transitional O3 sensitivity regime， as opposed to the VOCs- or NOx-limited regime identified by the photochemical indicator. The determination of the latter was affected by the adopted threshold values. The OBM relied on the quality of the observational data. For example， positive biases in observed NO2 could lead to an underestimation of O3 sensitivity to NOx with the OBM. During the high pollution period， the three methods exhibited significant disparities. The photochemical indicator tended to suggest the VOCs-limited condition， whereas the OBM and sensitivity coefficients indicated the NOx-limited or transitional regimes.

Source apportionment of ambient concentration and population exposure to elemental carbon in South Korea using a three-dimensional air quality model

We quantified the foreign and domestic contributions to annual mean elemental carbon (EC) concentration over South Korea in 2016 using the Primary Carbon Appointment tool in the community multiscale air quality model. The individual domestic contributions were further examined by emission source category (area, mobile, and point) in each sub-region (i.e., Seoul Metropolitan Area (SMA), Gangwon, Chungcheong, Youngnam, and Honam). EC contribution and population-weighted exposure contribution (PWEC) for each emission source were calculated. Two indicators were compared and adjusted considering uncertainties of emissions from sub-regions. Based on the results of this analysis, the primary EC emission sources that need to be managed to alleviate the concentrations and PWECs were classified, and the cost-effectiveness was compared with contribution rates for EC and PWEC. The modeled annual mean EC concentration in South Korea was 0.6 µg/m3, of which 54% was contributed by foreign sources (0.3 µg/m3). However, the quarterly foreign contribution differed by up to five times depending on the monsoon, while the domestic contribution did not. Simultaneously, spatial variations of the annual mean EC contributions are smaller than those of the foreign contributions. Regardless of the uncertainty of emissions, domestic PWEC was 20% higher than the domestic concentration as domestic EC emissions were concentrated in densely populated areas. It implies that EC emission control has more significant meaning not only to improve concentration but also to improve population exposure. In addition, the contribution rate showed greater variation between sub-regions than the EC emission source categories within a region. Considering this, if the cost used to reduce a unit EC emission is the same, the cost effect can be expected when EC emissions are reduced in the sub-regions with a large contribution rate regardless of EC emission source category.

Comparison of three aerosol representations of NHM-Chem (v1.0) for the simulations of air quality and climate-relevant variables

Abstract. This study provides comparisons of aerosol representation methods incorporated into a regional-scale nonhydrostatic meteorology–chemistry model (NHM-Chem). Three options for aerosol representations are currently available: the five-category non-equilibrium (Aitken, soot-free accumulation, soot-containing accumulation, dust, and sea salt), three-category non-equilibrium (Aitken, accumulation, and coarse), and bulk equilibrium (submicron, dust, and sea salt) methods. The three-category method is widely used in three-dimensional air quality models. The five-category method, the standard method of NHM-Chem, is an extensional development of the three-category method and provides improved predictions of variables relating to aerosol–cloud–radiation interaction processes by implementing separate treatments of light absorber and ice nuclei particles, namely, soot and dust, from the accumulation- and coarse-mode categories (implementation of aerosol feedback processes to NHM-Chem is still ongoing, though). The bulk equilibrium method was developed for operational air quality forecasting with simple aerosol dynamics representations. The total CPU times of the five-category and three-category methods were 91 % and 44 % greater than that of the bulk method, respectively. The bulk equilibrium method was shown to be eligible for operational forecast purposes, namely, the surface mass concentrations of air pollutants such as O3, mineral dust, and PM2.5. The simulated surface concentrations and depositions of bulk chemical species of the three-category method were not significantly different from those of the five-category method. However, the internal mixture assumption of soot/soot-free and dust/sea salt particles in the three-category method resulted in significant differences in the size distribution and hygroscopicity of the particles. The unrealistic dust/sea salt complete mixture of the three-category method induced significant errors in the prediction of the mineral dust-containing cloud condensation nuclei (CCN), which alters heterogeneous ice nucleation in cold rain processes. The overestimation of soot hygroscopicity by the three-category method induced errors in the BC-containing CCN, BC deposition, and light-absorbing aerosol optical thickness (AAOT). Nevertheless, the difference in AAOT was less pronounced with the three-category method because the overestimation of the absorption enhancement was compensated by the overestimation of hygroscopic growth and the consequent loss due to in-cloud scavenging. In terms of total properties, such as aerosol optical thickness (AOT) and CCN, the results of the three-category method were acceptable.

Characteristics of regional transport during two-year wintertime haze episodes in North China megacities

A three-dimensional air quality model coupled with an on-line source-tagged module was adopted to investigate the source-receptor relationship in North China during the winter of 2017 and 2018. The total contribution of cities located along transport pathway (the “2 + 26” cities) accounts for most of the fine particulate matter (PM2.5) across this region both on average and during haze episodes. Regional joint prevention and control strategies are crucial to both routine and emergency environmental governance. Compared to primary PM2.5, secondary compounds may be transported across greater distances and impose notable effects in downstream areas. In regard to the secondary inorganic aerosols (SIA) in Beijing during haze episodes, regional transport plays a more important role than do local emissions. The contribution of the transport of particle-phase secondary pollutants is comparable to that of the transport of gas-phase precursors during haze episodes. Control measurements of gas-phase precursors in upstream areas are also important, and they benefit the reduction in the total PM2.5 level.

Modeling the effect of non-ideality, dynamic mass transfer and viscosity on SOA formation in a 3-D air quality model

Abstract. In this study, assumptions (ideality and thermodynamic equilibrium) commonly made in three-dimensional (3-D) air quality models were reconsidered to evaluate their impacts on secondary organic aerosol (SOA) formation over Europe. To investigate the effects of non-ideality, dynamic mass transfer and aerosol viscosity on the SOA formation, the Secondary Organic Aerosol Processor (SOAP) model was implemented in the 3-D air quality model Polyphemus. This study presents the first 3-D modeling simulation which describes the impact of aerosol viscosity on the SOA formation. The model uses either the equilibrium approach or the dynamic approach with a method specially designed for 3-D air quality models to efficiently solve particle-phase diffusion when particles are viscous. Sensitivity simulations using two organic aerosol models implemented in Polyphemus to represent mass transfer between gas and particle phases show that the computation of the absorbing aerosol mass strongly influences the SOA formation. In particular, taking into account the concentrations of inorganic aerosols and hydrophilic organic aerosols in the absorbing mass of the aqueous phase increases the average SOA concentration by 5 % and 6 %, respectively. However, inorganic aerosols influence the SOA formation not only because they constitute an absorbing mass for hydrophilic SOA, but also because they interact with organic compounds. Non-ideality (short-, medium- and long-range interactions) was found to influence SOA concentrations by about 30 %. Concerning the dynamic mass transfer for the SOA formation, if the viscosity of SOA is not taken into account and if ideality of aerosols is assumed, the dynamic approach is found to give generally similar results to the equilibrium approach (indicating that equilibrium is an efficient hypothesis for inviscid and ideal aerosols). However, when a non-ideal aerosol is assumed, taking into account the dynamic mass transfer leads to a decrease of concentrations of the hydrophilic compounds (compared to equilibrium). This decrease is due to differences in the values of activity coefficients, which are different between values computed for bulk aerosols and those for each size section. This result indicates the importance of non-ideality on the dynamic evolution of SOA. For viscous aerosols, assuming a highly viscous organic phase leads to an increase in SOA concentrations during daytime (by preventing the evaporation of the most volatile organic compounds). The partitioning of nonvolatile compounds is not affected by viscosity, but the aging of more volatile compounds (that leads to the formation of the less volatile compounds) slows down as the evaporation of those compounds is stopped due to the viscosity of the particle. These results imply that aerosol concentrations may deviate significantly from equilibrium as the gas–particle partitioning could be higher than predicted by equilibrium. Furthermore, although a compound evaporates in the simulation using the equilibrium approach, the same compound can condense in the simulation using the dynamic approach if the particles are viscous. The results of this study emphasize the need for 3-D air quality models to take into account the effect of non-ideality on SOA formation and the effect of aerosol viscosity for the more volatile fraction of semi-volatile organic compounds.

Simulated sensitivity of secondary organic aerosol in the South Coast Air Basin of California to nitrogen oxides and other chemical parameters

ABSTRACTSensitivity of secondary organic aerosol (SOA) concentrations in the South Coast Air Basin (SoCAB) of California to nitrogen oxide (NOx) emission is simulated using gas-phase chemistry and gas-particle partitioning modules. These modules are implemented into a three-dimensional air quality model applied for high-pollution summer meteorology and 2008 emissions. To test sensitivity, NOx emissions in all locations and at all times are scaled by factors ranging from 0.1 to 10.0 in separate model runs. The basin-wide average SOA concentration exhibits a ‘turnover’ NOx emission multiplicative factor, above and below which the average SOA concentration decreases. For the entire SoCAB, this critical NOx emission factor is ∼0.3; while the magnitude of SOA concentrations changes with time, this peak value (∼0.2–0.3) appears to be relatively independent of the hour of the simulated day. When considering individual locations within the SoCAB, this peak factor shows a slightly broader range. Projected emission...

Explaining the spatiotemporal variation of fine particle number concentrations over Beijing and surrounding areas in an air quality model with aerosol microphysics

In this study, a three-dimensional air quality model with detailed aerosol microphysics (NAQPMS + APM) was applied to simulate the fine particle number size distribution and to explain the spatiotemporal variation of fine particle number concentrations in different size ranges over Beijing and surrounding areas in the haze season (Jan 15 to Feb 13 in 2006). Comparison between observations and the simulation indicates that the model is able to reproduce the main features of the particle number size distribution. The high number concentration of total particles, up to 26600 cm−3 in observations and 39800 cm−3 in the simulation, indicates the severity of pollution in Beijing. We find that primary particles with secondary species coating and secondary particles together control the particle number size distribution. Secondary particles dominate particle number concentration in the nucleation mode. Primary and secondary particles together determine the temporal evolution and spatial pattern of particle number concentration in the Aitken mode. Primary particles dominate particle number concentration in the accumulation mode. Over Beijing and surrounding areas, secondary particles contribute at least 80% of particle number concentration in the nucleation mode but only 10–20% in the accumulation mode. Nucleation mode particles and accumulation mode particles are anti-phased with each other. Nucleation or primary emissions alone could not explain the formation of the particle number size distribution in Beijing. Nucleation has larger effects on ultrafine particles while primary particles emissions are efficient in producing large particles in the accumulation mode. Reduction in primary particle emissions does not always lead to a decrease in the number concentration of ultrafine particles. Measures to reduce fine particle pollution in terms of particle number concentration may be different from those addressing particle mass concentration.

Influence of tree crown characteristics on the local PM10 distribution inside an urban street canyon in Antwerp (Belgium): A model and experimental approach

Apart from influencing the amount of leaf-deposited particles, tree crown morphology will influence the local distribution of atmospheric particles. Nevertheless, tree crowns are often represented very rudimentary in three-dimensional air quality models. Therefore, the influence of tree crown representation on the local ambient PM10 concentration and resulting leaf-deposited PM10 mass was evaluated, using the three-dimensional computational fluid dynamics (CFD) model ENVI-met® and ground-based LiDAR imaging. The modelled leaf-deposited PM10 mass was compared to gravimetric results within three different particle size fractions (0.2–3, 3–10 and >10μm), obtained at 20 locations within the tree crown. Modelling of the LiDAR-derived tree crown resulted in altered atmospheric PM10 concentrations in the vicinity of the tree crown. Although this model study was limited to a single tree and model configuration, our results demonstrate that improving tree crown characteristics (shape, dimensions and LAD) affects the resulting local PM10 distribution in ENVI-met. An accurate tree crown representation seems, therefore, of great importance when aiming at modelling the local PM distribution.

Source attribution and quantification of benzene event emissions in a Houston ship channel community based on real-time mobile monitoring of ambient air

ABSTRACTA mobile laboratory equipped with a proton transfer reaction mass spectrometer (PTR-MS) operated in Galena Park, Texas, near the Houston Ship Channel during the Benzene and other Toxics Exposure Study (BEE-TEX). The mobile laboratory measured transient peaks of benzene of up to 37 ppbv in the afternoon and evening of February 19, 2015. Plume reconstruction and source attribution were performed using the four-dimensional (4D) variational data assimilation technique and a three-dimensional (3D) micro-scale forward and adjoint air quality model based on mobile PTR-MS data and nearby stationary wind measurements at the Galena Park Continuous Air Monitoring Station (CAMS). The results of inverse modeling indicate that significant pipeline emissions of benzene may at least partly explain the ambient concentration peaks observed in Galena Park during BEE-TEX. Total pipeline emissions of benzene inferred within the 16-km2 model domain exceeded point source emissions by roughly a factor of 2 during the observational episode. Besides pipeline leaks, the model also inferred significant benzene emissions from marine, railcar, and tank truck loading/unloading facilities, consistent with the presence of a tanker and barges in the Kinder Morgan port terminal during the afternoon and evening of February 19. Total domain emissions of benzene exceeded corresponding 2011 National Emissions Inventory (NEI) estimates by a factor of 2–6.Implications: Port operations involving petrochemicals may significantly increase emissions of air toxics from the transfer and storage of materials. Pipeline leaks, in particular, can lead to sporadic emissions greater than in emission inventories, resulting in higher ambient concentrations than are sampled by the existing monitoring network. The use of updated methods for ambient monitoring and source attribution in real time should be encouraged as an alternative to expanding the conventional monitoring network.

Application of photochemical indicators to evaluate ozone nonlinear chemistry and pollution control countermeasure in China

Ozone sensitivity in China was investigated by using a comprehensive three-dimensional air quality model system WRF-CALGRID. A real case and two cases with 35% emission reduction for either NOx or VOC were conducted for the period of March in 2010. The simulation results of O3 agreed fairly well with the observation data. Based on the meaning of O3 sensitivity, the ratio Ra was defined, with the transition value of 1 to distinguish NOx-sensitive region from VOC-sensitive region. With the aid of Ra, VOC- and NOx-sensitive regions in China were preliminary located. The transition ranges for some photochemical indicators were quantified. Only those of H2O2/NOz and H2O2/HNO3 met the requirement that the 95th percentile VOC-sensitive value should be equal to or lower than the 5th percentile NOx-sensitive value. 0.16–0.40 for H2O2/HNO3 and 0.14–0.28 for H2O2/NOz were adopted to distinguish different O3 sensitivity in China. The results showed that the VOC-sensitive regions are primarily distributed over the urban centers and the developed industrial areas in eastern and southern China, while the NOx-sensitive regions are mainly located in the remote areas of northern and western China. High correlation between Ra and indicators was found, and a new approach to quantify the transition values of indicators was proposed. These indicators can play an important role in the air complex pollution control of urban clusters over East Asia.

Impacts of uncertainty in AVOC emissions on the summer ROx budget and ozone production rate in the three most rapidly-developing economic growth regions of China

High levels of uncertainty in non-methane volatile organic compound (NMVOC) emissions in China could lead to significant variation in the budget of the sum of hydroxyl (OH) and peroxy (HO2, RO2) radicals (ROx = OH + HO2 + RO2) and the ozone production rate [P(O3)], but few studies have investigated this possibility, particularly with three-dimensional air quality models. We added diagnostic variables into the WRF-Chem model to assess the impact of the uncertainty in anthropogenic NMVOC (AVOC) emissions on the ROx budget and P(O3) in the Beijing-Tianjin-Hebei region, Yangtze River Delta, and Pearl River Delta of China. The WRF-Chem simulations were compared with satellite and ground observations, and previous observation-based model studies. Results indicated that 68% increases (decreases) in AVOC emissions produced 4%–280% increases (2%–80% decreases) in the concentrations of OH, HO2, and RO2 in the three regions, and resulted in 35%–48% enhancements (26%–39% reductions) in the primary ROx production and ∼ 65% decreases (68%–73% increases) of the P(O3) in Beijing, Shanghai, and Guangzhou. For the three cities, the two largest contributors to the ROx production rate were the reaction of O1D + H2O and photolysis of HCHO, ALD2, and others; the reaction of OH + NO2 (71%–85%) was the major ROx sink; and the major contributor to P(O3) was the reaction of HO2 + NO (∼ 65%). Our results showed that AVOC emissions in 2006 from Zhang et al. (2009) have been underestimated by ∼ 68% in suburban areas and by 〉 68% in urban areas, implying that daily and hourly concentrations of secondary organic aerosols and inorganic aerosols could be substantially underestimated, and cloud condensation nuclei could be underestimated, whereas local and regional radiation was overestimated.

The Ozone–Climate Penalty: Past, Present, and Future

Climate change is expected to increase global mean temperatures leading to higher tropospheric ozone (O3) concentrations in already polluted regions, potentially eroding the benefits of expensive emission controls. The magnitude of the "O3-climate penalty" has generally decreased over the past three decades, which makes future predictions for climate impacts on air quality uncertain. Researchers attribute historical reductions in the O3-climate penalty to reductions in NOx emissions but have so far not extended this theory into a quantitative prediction for future effects. Here, we show that a three-dimensional air quality model can be used to map the behavior of the O3-climate penalty under varying NOx and VOC emissions in both NOx-limited and NOx-saturated conditions in Central and Southern California, respectively. Simulations suggest that the planned emissions control program for O3 precursors will not diminish the O3-climate penalty to zero as some observational studies might imply. The results further demonstrate that in a NOx-limited air basin, NOx control strategies alone are sufficient to both decrease the O3-climate penalty and mitigate O3 pollution, while in a NOx-saturated air basin, a modified emissions control plan that carefully chooses reductions in both NOx and VOC emissions may be necessary to eliminate the O3-climate penalty while simultaneously reducing base case O3 concentrations to desired levels. Additional modeling is needed to determine the behavior of the O3-climate penalty as NOx and VOC emissions evolve in other regions.

Comparison of Exposure Estimation Methods for Air Pollutants

Background and Aims: Ambient monitors are often used to estimate air pollution exposure for epidemiological studies. This approach is efficient and economical but has limitations, including restricted coverage and resolution. Although three-dimensional air quality modeling has its own limitations, this emerging exposure approach has the potential to address some challenges of monitoring networks. We evaluated differences in exposure estimates obtained using monitoring data and simulation results based on the Community Multi-scale Air Quality (CMAQ) modeling system. Methods: Spatially-aggregated (county-level) exposure estimates for PM2.5 were calculated for the eastern two-thirds of the U.S. for years 2002-2006 from three sources: (1) 24hr ambient monitoring data; (2) 12 x 12 km gridded CMAQ simulation results; and (3) concentration estimates from a Bayesian space-time downscaler model “fusing” PM2.5 monitoring data with 12-km gridded CMAQ output (i.e., downscaler-derived exposures). Results: Exposure estimates generated from CMAQ and the downscaler provide greater spatial and temporal coverage compared to estimates from monitor data. The CMAQ and CMAQ-downscaler exposure estimates included 2818 counties and the monitoring approach produced estimates for 190 counties, which contain ~51% of the population within the CMAQ domain. Exposure estimates derived from CMAQ results underestimated PM2.5 levels (normalized mean bias [NMB]=-4.0%), while downscaler-derived exposures slightly overestimated observed PM2.5 (NMB=1.0%). Across time, correlation between monitor-derived exposure estimates and CMAQ- and downscaler-derived exposure estimates were 0.62 and 0.97, respectively. Conclusions: The downscaler approach had superior performance based on several metrics. Epidemiology may benefit from use of regional air quality models, with improved spatial and temporal coverage and ability to study populations far from monitors that may differ from those near monitors.

Measurements and simulation of speciated PM2.5 in south-west Europe

Chemically speciated concentrations of PM2.5 (sulphate, ammonium, nitrate, elemental and organic carbon) were simulated in south-west Europe using the three-dimensional air quality model CAMx driven by the MM5 meteorological model. The inner domain covered the south-west region of Spain with a high spatial (2 km × 2 km) and temporal resolution (1 h). The simulation results were evaluated against experimental data obtained in four intensive field campaigns performed in 2008 and 2009 at urban and rural sites. PM2.5 measurements of secondary inorganic compounds and carbonaceous aerosol plus a suite of major and trace elements were determined. High time resolution (10 min) measurements of Black Carbon (BC) were also conducted. The model captured the variability in the ammonium concentrations in both summer and winter periods, although it tended to underestimate the magnitude of concentrations, while for sulphate the performance was better during the summer periods. Particulate ammonium nitrate was only simulated in significant concentrations in the wintertime campaign. This was found to be consistent with the measured composition of PM2.5 where most of nitrate (79–94%) and a significant fraction of sulphate (24–37%) were estimated to be present as non-ammonium salts. These non-ammonium nitrate salts were attributed to the formation of NaNO3. The model PM2.5 primary elemental carbon simulations, evaluated with hourly resolution, captured the diurnal and seasonal variability of PM2.5 BC concentrations at the urban site while poorer performance was observed at the rural site. A large underestimation was observed for simulated PM2.5 organic carbon concentrations during all campaigns. Scenarios of pollution events linked to emissions from south-west Spain, shipping and contributions from more distant emission sources such as Portugal were identified. These results highlight how the distinct features of PM2.5 composition in southern Europe regions, such as the large contribution of non-ammonium salts, need to be taken into account both in model evaluation and in future implementation of aerosol modelling systems.

Environmental Risk Assessment: Comparison of Receptor and Air Quality Models for Source Apportionment

ABSTRACT Source apportionment of particulate matter has been commonly performed using receptor models, but studies suggest that the assumptions in receptor models limit the accuracy of results. An alternative approach is the use of three-dimensional source-oriented air quality models. Here, a comparison is conducted between the PM2.5 apportioned from the Chemical Mass Balance (CMB) receptor model using organic tracers as molecular markers with those from the source-based Community Multiscale Air Quality (CMAQ) model. Source apportionment was conducted at sites in the southeastern United States for July 2001 and January 2002. PM2.5 source apportionment results had moderate discrepancies, which originate from different spatial scales, fundamental limitations, and uncertainties of the two models. Results from CMB fluctuated temporally more than real variation due to measurement and source profile errors and uncertainties, whereas those from CMAQ could not capture daily variation well. In addition, results from CMB are mass contributions for the monitoring location, whereas those from CMAQ represent the average mass contributions of the model's grid. It is difficult to assess which approach is “better.” Indeed, both models have strengths and limitations, and each model's strengths can be utilized to help overcome the other model's limitations.

Secondary organic aerosol formation from naphthalene roadway emissions in the South Coast Air Basin of California

Naphthalene is the simplest and most abundant polycyclic aromatic hydrocarbon (PAH) in California fuels, with concentrations of up to 2,600 mg L–1 in gasoline and 1,600 mg L–1 in diesel fuel. In this work, naphthalene emission factors for gasoline and diesel vehicles are combined with an activity-based automobile inventory to characterise anthropogenic naphthalene emissions in the South Coast Air Basin of California (SoCAB). A three-dimensional air quality model is used to examine transport and chemical reaction losses of naphthalene in the SoCAB. Inclusion of naphthalene emissions from on-road gasoline and diesel vehicles was found to increase modelled SOA growth by up to 10%. Hence, reductions of naphthalene from both gasoline and diesel fuels may be an effective means of reducing the emissions of an important SOA-forming precursor to the atmosphere of large urban centres with characteristics similar to the SoCAB. The implications of these findings are discussed.

Aerosol effects on ozone concentrations in Beijing: A model sensitivity study

AbstractMost previous O3 simulations were based only on gaseous phase photochemistry. However, some aerosol-related processes, namely, heterogeneous reactions occurring on the aerosol surface and photolysis rate alternated by aerosol radiative influence, may affect O3 photochemistry under high aerosol loads. A three-dimensional air quality model, Models-3/Community Multi-scale Air Quality-Model of Aerosol Dynamics, Reaction, Ionization, and Dissolution, was employed to simulate the effects of the above-mentioned processes on O3 formation under typical high O3 episodes in Beijing during summer. Five heterogeneous reactions, i.e., NO2, NO3, N2O5, HO2, and O3, were individually investigated to elucidate their effects on O3 formation. The results showed that the heterogeneous reactions significantly affected O3 formation in the urban plume. NO2 heterogeneous reaction increased O3 to 90 ppb, while HO2 heterogeneous reaction decreased O3 to 33 ppb. In addition, O3 heterogeneous loss decreased O3 to 31 ppb. The effects of NO2, NO3, and N2O5 heterogeneous reactions showed opposite O3 concentration changes between the urban and extra-urban areas because of the response of the reactions to the two types of O3 formation regimes. When the aerosol radiative influence was included, the photolysis rate decreased and O3 decreased significantly to 73 ppb O3. The two aerosol-related processes should be considered in the study of O3 formation because high aerosol concentration is a ubiquitous phenomenon that affects the urban- and regional air quality in China.

Mobile Source and Livestock Feed Contributions to Regional Ozone Formation in Central California

A three-dimensional air quality model with 8 km horizontal resolution was applied to estimate the summertime ozone (O(3)) production from mobile sources and fermented livestock feed in California's San Joaquin Valley (SJV) during years 2000, 2005, 2010, 2015, and 2020. Previous studies have estimated that animal feed emissions of volatile organic compounds (VOCs) have greater O(3) formation potential than mobile-source VOC emissions when averaging across the entire SJV. The higher spatial resolution in the current study shows that the proximity of oxides of nitrogen (NO(x)) and VOC emissions from mobile sources enhances their O(3) formation potential. Livestock feed VOC emissions contributed 3-4 ppb of peak O(3) (8-h average) in Tulare County and 1-2 ppb throughout the remainder of the SJV during the CCOS 2000 July-August episode. In total, livestock feed contributed ~3.5 tons of the ground level peak O(3) (8 h average) in the SJV region, and mobile VOC contributed ~12 tons in this episode. O(3) production from mobile sources is declining over time in response to emissions control plans that call for cleaner fuels and engines with advanced emissions controls. Projecting forward to the year 2020, mobile-source VOC emissions are predicted to produce ~3 tons of the ground level peak O(3)(8-h average) and livestock feed VOC emissions are predicted to contribute ~2.5 tons making these sources nearly equivalent.

Application of WRF/Chem-MADRID for real-time air quality forecasting over the Southeastern United States

PM2.5 WRF/Chem-MADRID abstract A Real-Time Air Quality Forecast (RT-AQF) system that is based on a three-dimensional air quality model provides a powerful tool to forecast air quality and advise the public with proper preventive actions. In this work, a new RT-AQF system is developed based on the online-coupled Weather Research and Forecasting model with Chemistry (WRF/Chem) with the Model of Aerosol Dynamics, Reaction, Ioniza- tion, and Dissolution (MADRID) (referred to as WRF/Chem-MADRID) and deployed in the southeastern U.S. during MayeSeptember, 2009. Max 1-h and 8-h average ozone (O3) and 24-h average fine particulate matter (PM2.5) are evaluated against surface observations from the AIRNow database in terms of spatial distribution, temporal variation, and domain-wide and region-specific discrete and categorical perfor- mance statistics. WRF/Chem-MADRID demonstrates good forecasting skill that is consistent with current RT-AQF models. The overpredictions of O3 and underprediction of PM2.5 are likely due to uncertainties in emissions such as those of biogenic volatile organic compounds (BVOCs) and ammonia, inaccuracies in simulated meteorological variables such as 2-m temperature, 10-m wind speed, and precipitation, and uncertainties in the boundary conditions. Sensitivity simulations show that the use of the online BVOC emissions can improve PM2.5 forecast in areas with high BVOC emissions and adjusting lateral bound- aries can improve domain-wide O3 and PM2.5 predictions. Several limitations and uncertainties are identified to further improve the model's forecasting skill.

Multi-day ozone production potential of volatile organic compounds calculated with a tagging approach

Calculation of the ozone production potential of Volatile Organic Compounds (VOC) has traditionally been performed using so-called incremental reactivity techniques, requiring multiple photochemical model runs in which the combined direct and indirect effects on ozone from slight perturbations to each VOC are investigated in turn. A new approach to this problem is presented here using an extensively tagged chemical mechanism, in which the direct effects of VOC on ozone are calculated using a single model run. The results of this approach are consistent with previous work, but deliver much more detailed information about the VOC intermediate oxidation products involved in the production of ozone. We show that different classes of VOC exhibit very different temporal evolution in their ozone production potential, with alkenes and reactive aromatic VOC producing ozone rapidly, while the ozone production potential of alkanes increases in the day after they are emitted. We suggest that this is related to the rate at which these different classes of compounds are able to produce very small oxidation fragments. This multi-day ozone production potential has implications for emission control strategies for the management of air quality in polluted regions. We also relate the ozone production potential of VOC to the OH reactivity of the VOC oxidation intermediates, and show that the early oxidation products of alkenes and reactive aromatics are more efficient at producing ozone in their subsequent reactions with OH than similarly reactive alkanes. While this study examines idealised chemical conditions in a box model, the techniques employed here could potentially be adapted to the study of a wider range of atmospheric conditions using three-dimensional air quality models.