Verification of a source-oriented externally mixed air quality model during a severe photochemical smog episode

The CIT/UCD three-dimensional source-oriented externally mixed air quality model is tested during a severe photochemical smog episode (Los Angeles, 7–9 September 1993) using two different chemical mechanisms that describe the formation of ozone and secondary reaction products. The first chemical mechanism is the secondary organic aerosol mechanism (SOAM) that is based on SAPRC90 with extensions to describe the formation of condensable organic products. The second chemical mechanism is the caltech atmospheric chemistry mechanism (CACM) that is based on SAPRC99 with more detailed treatment of organic oxidation products.The predicted ozone concentrations from the CIT/UCD/SOAM and the CIT/UCD/CACM models agree well with the observations made at most monitoring sites with a mean normalized error of approximately 0.4–0.5. Good agreement is generally found between the predicted and measured NO_x concentrations except during morning rush hours of 6–10 am when NO_x concentrations are under-predicted at most locations. Total VOC concentrations predicted by the two chemical mechanisms agree reasonably well with the observations at three of the four sites where measurements were made. Gas-phase concentrations of phenolic compounds and benzaldehyde predicted by the UCD/CIT/CACM model are higher than the measured concentrations whereas the predicted concentrations of other aromatic compounds approximately agree with the measured values.The fine airborne particulate matter mass concentrations (PM_2.5) predicted by the UCD/CIT/SOAM and UCD/CIT/CACM models are slightly greater than the observed values during evening hours and lower than observed values during morning rush hours. The evening over-predictions are driven by an excess of nitrate, ammonium ion and sulfate. The UCD/CIT/CACM model predicts higher nighttime concentrations of gaseous precursors leading to the formation of particulate nitrate than the UCD/CIT/SOAM model. Elemental carbon and total organic mass are under-predicted by both models during morning rush hour periods. When this latter finding is combined with the NO_x under-predictions that occur at the same time, it suggests a systematic bias in the diesel engine emissions inventory. The mass of particulate total organic carbon is under-predicted by both the UCD/CIT/SOAM and UCD/CIT/CACM models during afternoon hours. Elemental carbon concentrations generally agree with the observations at this time. Both the UCD/CIT/SOAM and UCD/CIT/CACM models predict low concentrations of secondary organic aerosol (SOA) (<3.5 μg m⁻³) indicating that both models could be missing SOA formation pathways. The representation of the aerosol as an internal mixture vs. a source-oriented external mixture did not significantly affect the predicted concentrations during the current study.     

Source apportionment of wintertime secondary organic aerosol during the California regional PM10/PM2.5 air quality study

The UCD/CIT air quality model with the Caltech Atmospheric Chemistry Mechanism (CACM) was used to predict source contributions to secondary organic aerosol (SOA) formation in the San Joaquin Valley (SJV) from December 15, 2000 to January 7, 2001. The predicted 24-day average SOA concentration had a maximum value of 4.26 μg m^?3 50 km southwest of Fresno. Predicted SOA concentrations at Fresno, Angiola, and Bakersfield were 2.46 μg m^?3, 1.68 μg m^?3, and 2.28 μg m^?3, respectively, accounting for 6%, 37%, and 4% of the total predicted organic aerosol. The average SOA concentration across the entire SJV was 1.35 μg m^?3, which accounts for approximately 20% of the total predicted organic aerosol. Averaged over the entire SJV, the major SOA sources were solvent use (28% of SOA), catalyst gasoline engines (25% of SOA), wood smoke (16% of SOA), non-catalyst gasoline engines (13% of SOA), and other anthropogenic sources (11% of SOA). Diesel engines were predicted to only account for approximately 2% of the total SOA formation in the SJV because they emit a small amount of volatile organic compounds relative to other sources. In terms of SOA precursors within the SJV, long-chain alkanes were predicted to be the largest SOA contributor, followed by aromatic compounds. The current study identifies the major known contributors to the SOA burden during a winter pollution episode in the SJV, with further enhancements possible as additional formation pathways are discovered.     

Estimates of heterogeneous formation of secondary organic aerosol during a wood smoke episode in Houston,Texas

Observational data, collected during a wood smoke episode in Houston, Texas, were used to assess the extent to which acid-catalyzed reactions of carbonyls might contribute to secondary organic aerosol (SOA) formation. The wood smoke episode was chosen for this analysis because of relatively high concentrations of acidic aerosol, coupled with high concentrations of SOA precursors during the episode. Photochemical modeling, coupled with ambient measurements, indicated that acid aerosol-mediated organic aerosol formation reactions, not accounted for in most current photochemical models, may have led to SOA formation of up to a few μg m⁻³. In photochemical simulations, acid-mediated organic aerosol formation was modeled by calculating the rate of impingement of aldehyde molecules on acidic particles, and then assuming that a fraction of the impingements resulted in reaction. For reaction probabilities on the order of 0.005–0.0005, the model predicted SOA concentrations were consistent with estimates of SOA based on observations. In addition, observed concentrations of particulate phase ammonium during the episode were consistent with high concentrations of the types of organic acids that would be formed through acid-catalyzed reactions of carbonyls. Although there are substantial uncertainties in the estimates of heterogeneous SOA formation, collectively, these data and modeling analyses provide evidence for the importance of acid-catalyzed SOA formation reactions.     

Temperature dependence of secondary organic aerosol

Temperature was found to have a dramatic effect on secondary organic aerosol formation from two ozonolysis systems, cyclohexene and α-pinene. Isothermal experiments were conducted for both systems where the lowest temperature, 278 K, formed approximately 2.5–3 times and 5–6 times the SOA formed at 300 K and 318 K, respectively. Changing the cyclohexene system temperature to a different isothermal experimental set point after completion of SOA formation did not lead to sufficient condensation/evaporation to reproduce the SOA formation at other temperature set points. When the system temperature was cycled between two set points at the end of an experiment, the α-pinene system showed reversibility between the initial temperature 318 K and 300 K. For temperature cycles between the initial temperature of 300 K–318 K, an irreversible loss of mass is observed after the first heating cycle with reversibility observed between subsequent temperature cycles. The SOA formed at 278 K was reversible over a 22 K range but was unable to evaporate sufficiently to match the SOA mass formed at 300 K. Hygroscopicity measurements, taken after the completion of SOA formation, indicate that hygroscopicity of the aerosol is also a function of temperature and that the aerosol does not continue to be oxidized after initial growth is complete. The differing hygroscopicity of the semi-volatile component of the aerosol is evident during system temperature changes after completion of the experiment.     

Source apportionment of Phoenix PM2.5 aerosol with the Unmix receptor model

The multivariate receptor model Unmix has been used to analyze a 3-yr PM2.5 ambient aerosol data set collected in Phoenix, AZ, beginning in 1995. The analysis generated source profiles and overall average percentage source contribution estimates (SCEs) for five source categories:gasoline engines (33 +/- 4%), diesel engines (16 +/- 2%), secondary SO4(2-) (19 +/- 2%), crustal/soil (22 +/- 2%), and vegetative burning (10 +/- 2%). The Unmix analysis was supplemented with scanning electron microscopy (SEM) of a limited number of filter samples for information on possible additional low-strength sources. Except for the diesel engine source category, the Unmix SCEs were generally consistent with an earlier multivariate receptor analysis of essentially the same data using the Positive Matrix Factorization (PMF) model. This article provides the first demonstration for an urban area of the capability of the Unmix receptor model.     

Measurements of gaseous hydrogen peroxide in southern England during a photochemical episode

Simultaneous measurements of gaseous hydrogen peroxide and ozone made in southern England are reported. The hydrogen peroxide measurements are the first reported for the United Kingdom and show clear diurnal trends and correlate with ozone measurements. Measurements were made during a photochemical episode when a peak hydrogen peroxide concentration of 2.5 microg m(-3) was recorded with a simultaneous peak of 168 microg m(-3) in the ozone concentration. From observations on the rate of decay in the measured concentrations, an evening-time deposition velocity of 0.28 cm s(-1) was derived for hydrogen peroxide.     

The evolution of photochemical smog in a power plant plume

The evolution of photochemical smog in a plant plume was investigated with the aid of an instrumented helicopter. Air samples were taken in the plume of the Cumberland Power Plant, located in central Tennessee, during the afternoon of 16 July 1995 as part of the Southern Oxidants Study – Nashville Middle Tennessee Ozone Study. Twelve cross-wind air sampling traverses were made at six distance groups from 35 to 116 km from the source. During the sampling period the winds were from the west–northwest and the plume drifted towards the city of Nashville TN. Ten of the traverses were made upwind of the city, where the power plant plume was isolated, and two traverses downwind of the city when the plumes were possibly mixed. The results revealed that even six hours after the release, excess ozone production was limited to the edges of the plume. Only when the plume was sufficiently dispersed, but still upwind of Nashville, was excess ozone (up to 109 ppbv, 50–60 ppbv above background levels) produced in the center of the plume. The concentrations image of the plume and a Lagrangian particle model suggests that portions of the power plant plume mixed with the urban plume. The mixed urban power plant plume began to regenerate O₃ that peaked at 120 ppbv at a short distance (15–25 km) downwind of Nashville. Ozone productivity (the ratio of excess O₃ to NO_y and NO_z) in the isolated plume was significantly lower compared with that found in the city plume. The production of nitrate, a chain termination product, was significantly higher in the power plant plume compared to the mixed plume, indicating shorter chain length of the photochemical smog chain reaction mechanism.     

Source apportionment of primary and secondary organic aerosols using positive matrix factorization (PMF) of molecular markers

Monthly average ambient concentrations of more than eighty particle-phase organic compounds, as well as total organic carbon (OC) and elemental carbon (EC), were measured from March 2004 through February 2005 in five cities in the Midwestern United States. A multi-variant source apportionment receptor model, positive matrix factorization (PMF), was applied to explore the average source contributions to the five sampling sites using molecular markers for primary and secondary organic aerosols (POA, SOA). Using the molecular makers in the model, POA and SOA were estimated for each month at each site. Three POA factors were derived, which were dominated by primary molecular markers such as EC, hopanes, steranes, and polycyclic aromatic hydrocarbons (PAHs), and which represented the following POA sources: urban primary sources, mobile sources, and other combustion sources. The three POA sources accounted for 57% of total average ambient OC. Three factors, characterized by the presence of reaction products of isoprene, α-pinene and β-caryophyllene, and displaying distinct seasonal trends, were consistent with the characteristics of SOA. The SOA factors made up 43% of the total average measured OC. The PMF-derived results are in good agreement with estimated SOA concentrations obtained from SOA to tracer yield estimates obtained from smog chamber experiments. A linear regression comparing the smog chamber yield estimates and the PMF SOA contributions had a regression slope of 1.01 ± 0.07 and an intercept of 0.19 ± 0.10 μg OC m^?3 (adjusted R² of 0.763, n = 58).     

On the influence of meteorological input on photochemical modelling of a severe episode over a coastal area

The modelling reconstruction of the processes determining the transport and mixing of ozone and its precursors in complex terrain areas is a challenging task, particularly when local-scale circulations, such as sea breeze, take place. Within this frame, the ESCOMPTE European campaign took place in the vicinity of Marseille (south-east of France) in summer 2001. The main objectives of the field campaign were to document several photochemical episodes, as well as to constitute a detailed database for chemistry transport models intercomparison.CAMx model has been applied on the largest intense observation periods (IOP) (June 21–26, 2001) in order to evaluate the impacts of two state-of-the-art meteorological models, RAMS and MM5, on chemical model outputs. The meteorological models have been used as best as possible in analysis mode, thus allowing to identify the spread arising in pollutant concentrations as an indication of the intrinsic uncertainty associated to the meteorological input.Simulations have been deeply investigated and compared with a considerable subset of observations both at ground level and along vertical profiles. The analysis has shown that both models were able to reproduce the main circulation features of the IOP. The strongest discrepancies are confined to the Planetary Boundary Layer, consisting of a clear tendency to underestimate or overestimate wind speed over the whole domain.The photochemical simulations showed that variability in circulation intensity was crucial mainly for the representation of the ozone peaks and of the shape of ozone plumes at the ground that have been affected in the same way over the whole domain and all along the simulated period. As a consequence, such differences can be thought of as a possible indicator for the uncertainty related to the definition of meteorological fields in a complex terrain area.     

Evaluation of secondary organic aerosol formation in winter

Three different methods are used to predict secondary organic aerosol (SOA) concentrations in the San Joaquin Valley of California during the winter of 1995–1996 [Integrated Monitoring Study, (IMS95)]. The first of these methods estimates SOA by using elemental carbon as a tracer of primary organic carbon. The second method relies on a Lagrangian trajectory model that simulates the formation, transport, and deposition of secondary organic aerosol. The model includes a recently developed gas–particle partitioning mechanism. Results from both methods are in good agreement with the chemical speciation of organic aerosol during IMS95 and suggest that most of the OC measured during IMS95 is of primary origin. Under suitable conditions (clear skies, low winds, low mixing heights) as much as 15–20 μg C m⁻³ of SOA can be produced, mainly due to oxidation of aromatics. The low mixing heights observed during the winter in the area allow accumulation of SOA precursors and the acceleration of SOA formation. Clouds and fog slow down the production of secondary compounds, reducing their concentrations by a factor of two or three from the above maximum levels. In addition, it appears that there is significant diurnal variation of SOA concentration. A strong dependence of SOA concentrations on temperature is observed, along with the existence of an optimal temperature for SOA formation.     

Source apportionment of airborne particulate matter using organic compounds as tracers

A chemical mass balance receptor model based on organic compounds has been developed that relates source contributions to airborne fine particle mass concentrations. Source contributions to the concentrations of specific organic compounds are revealed as well. The model is applied to four air quality monitoring sites in southern California using atmospheric organic compound concentration data and source test data collected specifically for the purpose of testing this model. The contributions of up to nine primary particle source types can be separately identified in ambient samples based on this method, and approximately 85% of the organic fine aerosol is assigned to primary sources on an annual average basis. The model provides information on source contributions to fine mass concentrations, fine organic aerosol concentrations and individual organic compound concentrations. The largest primary source contributors to fine particle mass concentrations in Los Angeles are found to include diesel engine exhaust, paved road dust, gasoline-powered vehicle exhaust, plus emissions from food cooking and wood smoke, with smaller contribution from tire dust, plant fragments, natural gas combustion aerosol, and cigarette smoke. Once these primary aerosol source contributions are added to the secondary sulfates, nitrates and organics present, virtually all of the annual average fine particle mass at Los Angeles area monitoring sites can be assigned to its source.     

Model evidence for a significant source of secondary organic aerosol from isoprene

We investigate how a recently suggested pathway for production of secondary organic aerosol (SOA) affects the consistency of simulated organic aerosol (OA) mass in a global three-dimensional model of oxidant-aerosol chemistry (GEOS-Chem) versus surface measurements from the interagency monitoring of protected visual environments (IMPROVE) network. Simulations in which isoprene oxidation products contribute to SOA formation, with a yield of 2.0% by mass reduce a model bias versus measured OA surface mass concentrations. The resultant increase in simulated OA mass concentrations during summer of 0.6–1.0 μg m⁻³ in the southeastern United States reduces the regional RMSE to 0.88 μg m⁻³ from 1.26 μg m⁻³. Spring and fall biases are also reduced, with little change in winter when isoprene emissions are negligible.     

Comparative analysis of chemical reaction mechanisms for photochemical smog

Six chemical reaction mechanisms for photochemical smog are analyzed to determine why, under identical conditions, they predict different maximum ozone concentrations. Answers to previously inaccessible questions such as the relative contributions of individual organic species to photochemical ozone formation are obtained. Based on the results of the analysis we have identified specific aspects of each mechanism that are responsible for the discrepancies with other mechanisms and with an explicit mechanism based on the latest understanding of atmospheric chemistry. For each mechanism critical areas are identified that when altered bring the predictions of the various mechanisms into much closer agreement. Thus, we identify why the predictions of the mechanisms are different, and have recommended research efforts that are needed to eliminate many of the discrepancies.     

A mechanism describing the photochemical oxidation of toluene in smog

The photo-oxidation of toluene/NO_x exhibits several features that distinguish it from olefin and paraffin smog systems: highly photolytic products, a relatively low production rate of peroxy radicals, and strong sinks for NO_x. The underlying chemical behavior of the toluene smog system is discussed and a kinetic simulation mechanism is presented. The mechanism simulates toluene smog chamber experiments conducted at two facilities: the University of California at Riverside evacuable chamber, and the outdoor smog chamber at the University of North Carolina.     

The influence of aerosols on photochemical smog in Mexico City

Aerosols in the Mexico City atmosphere can have a non-negligible effect on the ultraviolet radiation field and hence on the formation of photochemical smog. We used estimates of aerosol optical depths from sun photometer observations in a detailed radiative transfer model, to calculate photolysis rate coefficients (J_NO2) for the key reaction NO₂+hν→NO+O (λ<430 nm). The calculated values are in good agreement with previously published measurements of J_NO2at two sites in Mexico City: Palacio de Minerı́a (19°25′59″N, 99°07′58″W, 2233 masl), and IMP (19°28′48″N, 99°11′07″W, 2277 masl) and in Tres Marias, a town near Mexico City (19°03′N, 99°14′W, 2810 masl). In particular, the model reproduces very well the contrast between the two urban sites and the evidently much cleaner Tres Marias site. For the measurement days, reductions in surface J_NO2 by 10–30% could be attributed to the presence of aerosols, with considerable uncertainty due largely to lack of detailed data on aerosol optical properties at ultraviolet wavelengths (esp. the single scattering albedo). The potential impact of such large reductions in photolysis rates on surface ozone concentrations is illustrated with a simple zero-dimensional photochemical model.     

Insights into the nature of secondary organic aerosol in Mexico City during the MILAGRO experiment 2006

This study targets understanding the secondary sources of organic aerosol in Mexico City during the Megacities Impact on Regional and Global Environment (MIRAGE) 2006 field campaign. Ambient PM_2.5 was collected daily at urban and peripheral locations. Particle-phase secondary organic aerosol (SOA) products of anthropogenic and biogenic precursor gases were measured by gas chromatography mass spectrometry. Ambient concentrations of SOA tracers were used to estimate organic carbon (OC) from secondary origins (SOC). Anthropogenic SOC was estimated as 20–25% of ambient OC at both sites, while biogenic SOC was less abundant, but was relatively twice as important at the peripheral site. The OC that was not attributed secondary sources or to primary sources in a previous study showed temporal consistency with biomass-burning events, suggesting the importance of secondary processing of biomass-burning emissions in the region. The best estimate of biomass-burning-related SOC was in the range of 20–30% of ambient OC during peak biomass burning events. Low-molecular weight (MW) alkanoic and alkenoic dicarboxylic acids (C₂–C₅) were also measured, of which oxalic acid was the most abundant. The spatial and temporal trends of oxalic acid differed from tracers for primary and secondary sources, suggesting that it had different and/or multiple sources in the atmosphere.