Evaluation of the SAPRC-07 mechanism against CSIRO smog chamber data

The updated SAPRC-07 mechanism was evaluated against data from experiments performed in the CSIRO smog chamber. The mechanism predictions have been compared to experimental results as well as predictions by SAPRC-99.Experiments were performed using either toluene or m-xylene in the presence of NO_x at sub-0.1 ppmv concentrations. For the majority of m-xylene experiments, the modelled Δ(O₃–NO) concentration was within 20% of observed values for both SAPRC mechanisms. However during the oxidation of toluene the production of radicals was poorly predicted, with final Δ(O₃–NO) concentration under-predicted by up to 60%. The predictions of major oxidants from isoprene oxidation were in good agreement with observed values. For the NO_x-limited conditions however, the ozone concentration predicted by both mechanisms were under-predicted by approximately 20% in the five experiments tested.The performance of the SAPRC-07 mechanism was also evaluated against twelve evaporated fuel experiments. Two types of evaporative mode experiments were performed: headspace evaporated fuel and wholly evaporated fuel. The major difference was a significantly higher concentration of aromatic hydrocarbons and larger alkane products in wholly evaporated fuels. For headspace evaporated fuel experiments both SAPRC mechanisms were in good agreement with experimental results. For wholly evaporated experiments the average Δ(O₃–NO) model error was ?25% with SAPRC-07 compared to less than ?5% for SAPRC-99. Updates to the photolysis data for dicarbonyls, the light source used and the experimental conditions under which these experiments were performed are possible causes for the discrepancy between SAPRC-99 and -07 predictions for wholly evaporated experiments.     

Condensed atmospheric photooxidation mechanisms for isoprene

Two condensed mechanisms for the atmospheric reactions of isoprene, which differ in the number of species used to represent isoprene's reactive products, have been developed for use in ambient air quality modehng. They are based on a detailed isoprene mechanism that has recently been developed and extensively evaluated against environmental chamber data. The new condensed mechanisms give very close predictions to those of the detailed mechanism for ozone, OH radicals, nitric acid, H₂O₂, formaldehyde, total PANS, and for incremental effects of isoprene on ozone formation in one day simulations. The effects of the condensations become somewhat greater in multi-day simulations, particularly in cases where NO₃ reactions are important at nighttime, but the ozone predictions are still very close. On the other hand, the SAPRC-90, RADM-2, and Carbon Bond IV isoprene mechanisms give quite different predictions of these quantities. It is recommended that the new mechanisms replace those currently used in airshed simulations where isoprene emissions are important.     

Development of the SAPRC-07 chemical mechanism

An updated version of the SAPRC-99 gas-phase atmospheric chemical mechanism, designated SAPRC-07, is described. The rate constants and reactions have been updated based on current data and evaluations, the aromatics mechanisms have been reformulated and are less parameterized, chlorine chemistry has been added, the method used to represent peroxy reactions has been reformulated to be more appropriate for modeling gas-phase secondary organic aerosol precursors, and representations for many types of VOCs have been added or improved. This mechanism was evaluated against the result of ～2400 environmental chamber experiments carried out in 11 different environmental chambers, including experiments to test mechanisms for over 110 types of VOCs. The performance in simulating the chamber data was generally satisfactory for most types of VOCs but some biases were seen in simulations of some types of experiments. The mechanism was used to derive updated MIR and other ozone reactivity scales for almost 1100 types of VOCs, though in most cases the changes in MIR values relative to SAPRC-99 were not large. This mechanism update results in somewhat lower predictions of ozone in one-day ambient model scenarios under low VOC/NO_x conditions. The files needed to implement the mechanism and additional documentation is available at the SAPRC mechanism web site at http://www.cert.ucr.edu/～carter/SAPRC.     

A comparison of chemical mechanisms based on TRAMP-2006 field data

A comparison of a model using five widely known mechanisms (RACM, CB05, LaRC, SAPRC-99, SAPRC-07, and MCMv3.1) has been conducted based on the TexAQS II Radical and Aerosol Measurement Project (TRAMP-2006) field data in 2006. The concentrations of hydroxyl (OH) and hydroperoxy (HO₂) radicals were calculated by a zero-dimensional box model with each mechanism and then compared with the OH and HO₂ measurements. The OH and HO₂ calculated by the model with different mechanisms show similarities and differences with each other and with the measurements. First, measured OH and HO₂ are generally greater than modeled for all mechanisms, with the median modeled-to-measured ratios ranging from about 0.8 (CB05) to about 0.6 (SAPRC-99). These differences indicate that either measurement errors, the effects of unmeasured species or chemistry errors in the model or the mechanisms, with some errors being independent of the mechanism used. Second, the modeled and measured ratios of HO₂/OH agree when NO is about 1 ppbv, but the modeled ratio is too high when NO was less and too low when NO is more, as seen in previous studies. Third, mechanism–mechanism HO_x differences are sensitive to the environmental conditions – in more polluted conditions, the mechanism–mechanism differences are less. This result suggests that, in polluted conditions, the mechanistic details are less important than in cleaner conditions, probably because of the dominance of reactive nitrogen chemistry under polluted conditions.     

Modelling the photooxidation of ULP,E5 and E10 in the CSIRO smog chamber

The photooxidation of fuel vapour was investigated in a smog chamber and simulated using three chemical mechanisms, the Master Chemical Mechanism (MCMv3.1), SAPRC-99 and the Carbon Bond chemical mechanism (CB05). Three varieties of fuel were used, unleaded petrol (ULP) and two ULP-ethanol blends which contained 5% and 10% ethanol (E5, E10). The fuel vapours were introduced into the chamber using two methods, by injecting the vapours from wholly evaporated fuel directly, and by injecting the headspace vapour from fuel equilibrated at 38 °C. The chamber experiments were simulated using the selected mechanisms and comparisons made with collected experimental data.The SAPRC-99 mechanism reproduced Δ(O₃–NO) more accurately for almost all fuel types and injection modes, with negligible model error for both injection modes. The average model error for MCM simulations was ?16% and for CB05 the average model error was ?34%. The predictions for the CB05 mechanism varied depending on injection mode, the Δ(O₃–NO) model error for wholly evaporated experiments was ?44%, compared to ?24% for headspace vapour experiments. The difference in aromatic content between experiments of different injection modes was likely to be the cause of the difference in model error for CB05. The model error for all headspace experiments was dependent upon the initial carbon monoxide concentrations.The results for Δ(O₃–NO) were matched by the prediction of other key products, with formaldehyde predicted to within 20% by both SAPRC and the MCM. The addition of ethanol to the base SAPRC mechanism altered the predictions of Δ(O₃–NO) by less than 2%. Changes observed in the concentrations of formaldehyde and acetaldehyde were consistent with the expected yields from ethanol oxidation.     

A detailed mechanism for the gas-phase atmospheric reactions of organic compounds

A gas-phase reaction mechanism for the atmospheric photooxidations of over 100 alkanes, alkenes, aromatic hydrocarbons, alcohols, ethers and other compounds representative of the range of reactive organics emitted into polluted atmospheres is described. Most of these organic species are represented using generalized reactions with variable rate constants and product yield coefficients for which individual assignments were made or estimated. This mechanism employs 19 species to represent the reactive oxygenated and organic nitrate products, and includes the gas-phase reactions of SO₂, but does not include heterogeneous or liquid-phase reactions. The evaluation of this mechanism, by comparison of its predictions against the results of over 500 environmental chamber experiments, is described in a separate paper. This detailed mechanism can be used in assessments of relative atmospheric reactivities of organic compounds, and can provide the basis for the derivation of more condensed mechanisms for use in air quality simulation models.     

A new condensed toluene mechanism for Carbon Bond: CB05-TU

Toluene is ubiquitous in urban atmospheres and is a precursor to tropospheric ozone and aerosol (smog). An important characteristic of toluene chemistry is the tendency of some degradation products (e.g., cresols and methyl-catechols) to form organic nitro and nitrate compounds that sequester NOx (NO and NO₂) from active participation in smog formation. Explaining the NOx sinks in toluene degradation has made mechanism development more difficult for toluene than for many other organic compounds. Another challenge for toluene is explaining sources of radicals early in the degradation process. This paper describes the development of a new condensed toluene mechanism consisting of 26 reactions, and evaluates the performance of CB05 with this new toluene scheme (Toluene Update, TU) against 38 chamber experiments at 7 different environmental chambers, and provides recommendations for future developments. CB05 with the current toluene mechanism (CB05-Base) under-predicted the maximum O₃ and O₃ production rate for many of these toluene–NOx chamber experiments, especially under low-NOx conditions ([NOx]_t=0 < 100 ppb). CB05 with the new toluene mechanism (CB05-TU) includes changes to the yields and reactions of cresols and ring-opening products, and showed better performance than CB05-Base in predicting the maximum O₃, O₃ formation rate, NOx removal rate and cresol concentration. Additional environmental chamber simulations with xylene–NOx experiments showed that the TU mechanism updates tended to improve mechanism performance for xylene.     

Evaluation of the Community Multiscale Air Quality (CMAQ) model version 4.5: Sensitivities impacting model performance: Part I—Ozone

This study examines ozone (O₃) predictions from the Community Multiscale Air Quality (CMAQ) model version 4.5 and discusses potential factors influencing the model results. Daily maximum 8-h average O₃ levels are largely underpredicted when observed O₃ levels are above 85 ppb and overpredicted when they are below 35 ppb. Using a clustering approach, model performance was examined separately for several different synoptic regimes. Under the most common synoptic conditions of a typical summertime Bermuda High setup, the model showed good overall performance for O₃, while associations have been identified here between other, less frequent, synoptic regimes and the O₃ overprediction and underprediction biases. A sensitivity test between the CB-IV and CB05 chemical mechanisms showed that predictions of daily maximum 8-h average O₃ using CB05 were on average 7.3% higher than those using CB-IV. Boundary condition (BC) sensitivity tests show that the overprediction biases at low O₃ levels are more sensitive to the BC O₃ levels near the surface than BC concentrations aloft. These sensitivity tests also show the model performance for O₃ improved when using the global GEOS-CHEM BCs instead of default profiles. Simulations using the newest version of the CMAQ model (v4.6) showed a small improvement in O₃ predictions, particularly when vertical layers were not collapsed. Collectively, the results suggest that key synoptic weather patterns play a leading role in the prediction biases, and more detailed study of these episodes are needed to identify further modeling improvements.     

Modeling alkene chemistry using condensed mechanisms for conditions relevant to southeast Texas,USA

Alkenes are important in photochemical smog formation in southeast Texas due to their high emissions, especially from industrial sources in and around Houston, and their high reactivities. Therefore, properly characterizing the chemistry of alkenes in condensed mechanisms used in regional photochemical models is important in understanding the formation of ozone and other photochemical air pollutants in Houston. The performance of three versions of the SAPRC condensed chemical mechanism family, for predicting ozone and radical formation, was compared. Simulations were compared to environmental chamber data and ambient data. The analyses showed that separately modeling individual alkenes reactions (especially propene for southeast Texas) has the potential to lead to more accurate simulations of alkene chemistry. Caution must be exercised in un-lumping, however. Testing with different formulations of the 1-butene + O₃ reaction demonstrated the complexity and interconnectedness in choices of stoichiometric parameters for un-lumped species and the extent to which lumped mechanisms are un-lumped.     

Application of Artificial Neural Networks to Modeling and Prediction of Ambient Ozone Concentrations

ABSTRACT

The deterministic modeling of ambient O₃ concentrations is difficult because of the complexity of the atmospheric system in terms of the number of chemical species; the availability of accurate, time-resolved emissions data; and the required rate constants. However, other complex systems have been successfully approximated using artificial neural networks (ANNs). In this paper, ANNs are used to model and predict ambient O₃ concentrations based on a limited number of measured hydrocarbon species, NO_x compounds, temperature, and radiant energy. In order to examine the utility of these approaches, data from the Coastal Oxidant Assessment for Southeast Texas (COAST) program in Houston, TX, have been used. In this study, 53 hydrocarbon compounds, along with O₃, nitrogen oxides, and meteorological data were continuously measured during summer 1993. Steady-state ANN models were developed to examine the ability of these models to predict current O₃ concentrations from measured VOC and NO concentrations. To predict the future concentrations of O₃, dynamic models were also explored and were used for extraction of chemical information such as reactivity estimations for the VOC species.

The steady-state model produced an approximation of O₃ data and demonstrated the functional relationship between O₃ and VOC-NO_x concentrations. The dynamic models were able to the adequately predict the O₃ concentration and behavior of VOC-NO_x-O₃ system a number of hourly intervals into the future. For 3 hr into the future, O₃ concentration could be predicted with a root-mean squared error (RMSE) of 8.21 ppb. Extending the models further in time led to an RMSE of 11.46 ppb for 5-hr-ahead values. This prediction capability could be useful in determining when control actions are needed to maintain measured concentrations within acceptable value ranges.     

An important pathway for ozonolysis of alpha-pinene and beta-pinene in aqueous phase and its atmospheric implications

The aqueous ozonolysis of α-pinene and β-pinene was conducted under simulated tropospheric conditions at different pHs and temperatures. Three kinds of products, peroxides, carbonyl compounds, and organic acids, were well characterized, and the detection of these products provides effective evidence for understanding the atmospheric aqueous reaction pathway. We have two interesting findings: (1) the unexpected formation of methacrolein (MACR), with a yield of ～40%, in the α-pinene–O₃ aqueous reaction indicates a potentially new SOA formation pathway, because MACR is one of the important precursors of SOA; and (2) the surprisingly high yields of H₂O₂, ～60% for the α-pinene–O₃ reaction and ～100% for the β-pinene–O₃ reaction, indicates that H₂O₂ can be a significant contributor to the origin and transformation of oxidants in the atmosphere, especially in the humid regions. Moreover, we have determined the rate constant for aqueous reaction between MACR and H₂O₂ in pH 2 to 7 and obtained its upper limit as 0.13 M L^?1 s^?1. A mechanism concerning the formation of the species mentioned above is proposed, and it differs from that in the gas-phase reaction. We suggest that water plays a key role in the mechanism, by participating in the reactions as a direct reactant and by removing the excess energy of intermediates formed in the reactions.     

A new environmental chamber for evaluation of gas-phase chemical mechanisms and secondary aerosol formation

A new state-of-the-art indoor environmental chamber facility for the study of atmospheric processes leading to the formation of ozone and secondary organic aerosol (SOA) has been constructed and characterized. The chamber is designed for atmospheric chemical mechanism evaluation at low reactant concentrations under well-controlled environmental conditions. It consists of two collapsible 90 m³ FEP Teflon film reactors on pressure-controlled moveable frameworks inside a temperature-controlled enclosure flushed with purified air. Solar radiation is simulated with either a 200 kW Argon arc lamp or multiple blacklamps. Results of initial characterization experiments, all carried out at 300–305 K under dry conditions, concerning NO_x and formaldehyde offgasing, radical sources, particle loss rates, and background PM formation are described. Results of initial single organic–NO_x and simplified ambient surrogate–NO_x experiments to demonstrate the utility of the facility for mechanism evaluation under low NO_x conditions are summarized and compared with the predictions of the SAPRC-99 chemical mechanism. Overall, the results of the initial characterization and evaluation indicate that this new environmental chamber can provide high quality mechanism evaluation data for experiments with NO_x levels as low as 2 ppb, though the results indicate some problems with the gas-phase mechanism that need further study. Initial evaluation experiments for SOA formation, also carried out under dry conditions, indicate that the chamber can provide high quality secondary aerosol formation data at relatively low hydrocarbon concentrations.     

The relation between ozone,NOx and hydrocarbons in urban and polluted rural environments

Research over the past ten years has created a more detailed and coherent view of the relation between O₃ and its major anthropogenic precursors, volatile organic compounds (VOC) and oxides of nitrogen (NO_x). This article presents a review of insights derived from photochemical models and field measurements. The ozone–precursor relationship can be understood in terms of a fundamental split into a NO_x-senstive and VOC-sensitive (or NO_x-saturated) chemical regimes. These regimes are associated with the chemistry of odd hydrogen radicals and appear in different forms in studies of urbanized regions, power plant plumes and the remote troposphere. Factors that affect the split into NO_x-sensitive and VOC-sensitive chemistry include: VOC/NO_x ratios, VOC reactivity, biogenic hydrocarbons, photochemical aging, and rates of meteorological dispersion. Analyses of ozone–NO_x–VOC sensitivity from 3D photochemical models show a consistent pattern, but predictions for the impact of reduced NO_x and VOC in indivdual locations are often very uncertain. This uncertainty can be identified by comparing predictions from different model scenarios that reflect uncertainties in meteorology, anthropogenic and biogenic emissions. Several observation-based approaches have been proposed that seek to evaluate ozone–NO_x–VOC sensitivity directly from ambient measurements (including ambient VOC, reactive nitrogen, and peroxides). Observation-based approaches have also been used to evaluate emission rates, ozone production efficiency, and removal rates of chemically active species. Use of these methods in combination with models can significantly reduce the uncertainty associated with model predictions.     

Detailed characterization of polar compounds of residual oil in contaminated soil revealed by Fourier transform ion cyclotron resonance mass spectrometry

Effects of remediation technologies on polar compounds of crude oil in contaminated soils have not been well understood when compared to hydrocarbons. In this study, ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) was used to characterize the changes in NSO polar compounds of crude oil and residual oil after long-term natural attenuation, biostimulation and subsequent ozonation following biostimulation of contaminated soils. N₁ and O₁ species, which were abundant in the crude oil, were selectively biodegraded, and species with higher double bond equivalent values and smaller carbon numbers appeared to be more resistant to microbial alteration. O₂-O₆ species were enriched by biodegradation and contained a large number of compounds with a high degree of unsaturation. Ozone could react with a variety of polar compounds in residual oil after biodegradation and showed high reactivity with polar species containing aromatic or multi-aliphatic rings, including the residual N₁ and O₁ species, naphthenic acids and unsaturated O₃-O₆ compounds. Fatty acids and O₃-O₈ species dominated by saturated alkyl compounds were resistant to ozonation or the primarily incomplete ozonation products. Principal component analysis of identified peaks in the FT-ICR MS spectra provided a comprehensive overview of the complex samples at the molecular level and the results were consistent with the detailed analysis. Taken together, these results showed the high complexity of polar compounds in residual oils after biodegradation or ozonation in contaminated soil and would contribute to a better understanding of bioremediation and ozonation processes.     

Air Quality Modeling in the South Coast Air Basin of California: What Do the Numbers Really Mean?

Abstract

This study evaluates air quality model sensitivity to input and to model components. Simulations are performed using the California Institute of Technology (CIT) airshed model. Results show the impacts on ozone (O₃) concentration in the South Coast Air Basin (SCAB) of California because of changes in: (1) input data, including meteorological conditions (temperature, UV radiation, mixing height, and wind speed), boundary conditions, and initial conditions (ICs); and (2) model components, including advection solver and chemical mechanism. O₃ concentrations are strongly affected by meteorological conditions and, in particular, by temperature. ICs also affect O₃ concentrations, especially in the first 2 days of simulation. On the other hand, boundary conditions do not significantly affect the absolute peak O₃ concentration, although they do affect concentrations near the inflow boundaries. Moreover, predicted O₃ concentrations are impacted considerably by the chemical mechanism. In addition, dispersion of pollutants is affected by the advection routine used to calculate its transport. Comparison among CIT, California Photochemical Grid Model (CALGRID), and Urban Airshed Model air quality models suggests that differences in O₃ predictions are mainly caused by the different chemical mechanisms used. Additionally, advection solvers contribute to the differences observed among model predictions. Uncertainty in predicted peak O₃ concentration suggests that air quality evaluation should not be based solely on this single value but also on trends predicted by air quality models using a number of chemical mechanisms and with an advection solver that is mass conservative.     

Modeling smog chamber measurements of incremental reactivities of volatile organic compounds

A series of experiments performed at the GM chamber facility provided useful data for the evaluation of two current chemical mechanisms used in airshed models (SAPRC97 and SAPRC93 mechanisms) and a test of their predictions of maximum incremental reactivities which describe the change in ozone caused by adding a small amount of a compound to a polluted urban mixture under high-NO_x conditions. In general, the SAPRC97 detailed mechanism performed well in simulating the volatile organic compound (VOC) reactivity experiments for most test species; however, it had a tendency to underpredict incremental reactivities. For base-case runs containing a nine-component urban-surrogate mixture under high-NO_x conditions, where maximum concentrations of either O₃ or the smog produced (SP=the initial NO oxidized plus the ozone produced) were not attained during a 12-h irradiation, the SAPRC97 performed well while the SAPRC93 underestimated SP or O₃ significantly. Under low-NO_x conditions where SP or O₃ maximums were attained, the SAPRC97 as well as the SAPRC93 underpredicted SP or O₃ for runs containing the urban-surrogate mixture. Simulations of incremental reactivity experiments and special chamber runs showed that the SAPRC97 mechanism performed poorly for n-octane and some aromatic isomers such as ethylbenzene and p-xylene, while it performed well for other aromatic isomers such as toluene, m-xylene and 1,3,5-trimethylbenzene. Although, additional chamber data for aromatic isomers is needed to further clarify the parameterized chemical mechanisms for aromatic isomers, the newer SAPRC97 mechanism appears to be much improved over the older SAPRC93 mechanism for simulating aromatic chemistry.     

A diagnostic comparison of measured and model-predicted speciated VOC concentrations

This study compares speciated model-predicted concentrations (i.e., mixing ratios) of volatile organic compounds (VOCs) with measurements from the Photochemical Assessment Monitoring Stations (PAMS) network at sites within the northeastern US during June–August of 2006. Measurements of total non-methane organic compounds (NMOC), ozone (O₃), oxides of nitrogen (NO_x) and reactive nitrogen species (NO_y) are used for supporting analysis. The measured VOC species were grouped into the surrogate classes used by the Carbon Bond IV (CB4) chemical mechanism. It was found that the model typically over-predicted all the CB4 VOC species, except isoprene, which might be linked to overestimated emissions. Even with over-predictions in the CB4 VOC species, model performance for daily maximum O₃ was typically within ±15%. Analysis at an urban site in NY, where both NMOC and NO_x data were available, suggested that the reasonable ozone performance may be possibly due to compensating overestimated NO_x concentrations, thus modulating the NMOC/NO_x ratio to be in similar ranges as that of observations.     

A new detailed chemical model for indoor air pollution

A detailed chemical box model has been constructed based on a comprehensive chemical mechanism (the Master Chemical Mechanism) to investigate indoor air chemistry in a typical urban residence in the UK. Unlike previous modelling studies of indoor air chemistry, the mechanism adopted contains no simplifications such as lumping or the use of surrogate species, allowing more insight into indoor air chemistry than previously possible. The chemical mechanism, which has been modified to include the degradation reactions of key indoor air pollutants, contains around 15,400 reactions and 4700 species. The results show a predicted indoor OH radical concentration up to 4.0×10⁵ molecule cm⁻³, only a factor of 10–20 less than typically observed outdoors and sufficient for significant chemical cycling to take place. Concentrations of PAN-type species and organic nitrates are found to be important indoors, reaching concentrations of a few ppb. Sensitivity tests highlight that the most crucial parameters for modelling the concentration of OH are the light-intensity levels and the air exchange rate. Outdoor concentrations of O₃ and NO_X are also important in determining radical concentrations indoors. The reactions of ozone with alkenes and monoterpenes play a major role in producing new radicals, unlike outdoors where photolysis reactions are pivotal radical initiators. In terms of radical propagation, the reaction of HO₂ with NO has the most profound influence on OH concentrations indoors. Cycling between OH and RO₂ is dominated by reaction with the monoterpene species, whilst alcohols play a major role in converting OH to HO₂. Surprisingly, the absolute reaction rates are similar to those observed outdoors in a suburban environment in the UK during the summer. The results from this study highlight the importance of tailoring a model for its particular location and the need for future indoor air measurements of radical species, nitrated species such as PANs and organic nitrates, photolysis rates of key species over the range of wavelengths observed indoors and concurrent measurements of outdoor air pollutant concentrations.     

Modelling annual pasture dynamics: Application to stomatal ozone deposition

Modelling ozone (O₃) deposition for impact risk assessment is still poorly developed for herbaceous vegetation, particularly for Mediterranean annual pastures. High inter-annual climatic variability in the Mediterranean area makes it difficult to develop models characterizing gas exchange behaviour and air pollutant absorption suitable for risk assessment. This paper presents a new model to estimate stomatal conductance (g_s) of Trifolium subterraneum, a characteristic species of dehesa pastures. The MEDPAS (MEDiterranean PAStures) model couples 3 modules estimating soil water content (SWC), vegetation growth and g_s. The g_s module is a reparameterized version of the stomatal component of the EMEP DO₃SE O₃ deposition model. The MEDPAS model was applied to two contrasting years representing typical dry and humid springs respectively and with different O₃ exposures. The MEDPAS model reproduced realistically the g_s seasonal and inter-annual variations observed in the field. SWC was identified as the major driver of differences across years. Despite the higher O₃ exposure in the dry year, meteorological conditions favoured 2.1 times higher g_s and 56 day longer growing season in the humid year compared to the dry year. This resulted in higher ozone fluxes absorbed by T. subterraneum in the humid year. High inter-family variability was found in gas exchange rates, therefore limiting the relevance of single species O₃ deposition flux modelling for dehesa pastures. Stomatal conductance dynamics at the canopy level need to be considered for more accurate O₃ flux modelling for present and future climate scenarios in the Mediterranean area.     

Particulate air quality model predictions using prognostic vs. diagnostic meteorology in central California

Comparisons were made between three sets of meteorological fields used to support air quality predictions for the California Regional Particulate Air Quality Study (CRPAQS) winter episode from December 15, 2000 to January 6, 2001. The first set of fields was interpolated from observations using an objective analysis method. The second set of fields was generated using the WRF prognostic model without data assimilation. The third set of fields was generated using the WRF prognostic model with the four-dimensional data assimilation (FDDA) technique. The UCD/CIT air quality model was applied with each set of meteorological fields to predict the concentrations of airborne particulate matter and gaseous species in central California. The results show that the WRF model without data assimilation over-predicts surface wind speed by ～30% on average and consequently yields under-predictions for all PM and gaseous species except sulfate (S(VI)) and ozone(O₃). The WRF model with FDDA improves the agreement between predicted and observed wind and temperature values and consequently yields improved predictions for all PM and gaseous species. Overall, diagnostic meteorological fields produced more accurate air quality predictions than either version of the WRF prognostic fields during this episode. Population-weighted average PM_2.5 exposure is 40% higher using diagnostic meteorological fields compared to prognostic meteorological fields created without data assimilation. These results suggest diagnostic meteorological fields based on a dense measurement network are the preferred choice for air quality model studies during stagnant periods in locations with complex topography.