The New England Air Quality Forecasting Pilot Program: development of an evaluation protocol and performance benchmark

The National Oceanic and Atmospheric Administration recently sponsored the New England Forecasting Pilot Program to serve as a "test bed" for chemical forecasting by providing all of the elements of a National Air Quality Forecasting System, including the development and implementation of an evaluation protocol. This Pilot Program enlisted three regional-scale air quality models, serving as prototypes, to forecast ozone (O3) concentrations across the northeastern United States during the summer of 2002. A suite of statistical metrics was identified as part of the protocol that facilitated evaluation of both discrete forecasts (observed versus modeled concentrations) and categorical forecasts (observed versus modeled exceedances/nonexceedances) for both the maximum 1-hr (125 ppb) and 8-hr (85 ppb) forecasts produced by each of the models. Implementation of the evaluation protocol took place during a 25-day period (August 5-29), utilizing hourly O3 concentration data obtained from over 450 monitors from the U.S. Environment Protection Agency's Air Quality System network.     

The effects of roadside structures on the transport and dispersion of ultrafine particles from highways

Understanding local-scale transport and dispersion of pollutants emitted from traffic sources is important for urban planning and air quality assessments. Predicting pollutant concentration patterns in complex environments depends on accurate representations of local features (e.g., noise barriers, trees, buildings) affecting near-field air flows. This study examined the effects of roadside barriers on the flow patterns and dispersion of pollutants from a high-traffic highway in Raleigh, North Carolina, USA. The effects of the structures were analyzed using the Quick Urban & Industrial Complex (QUIC) model, an empirically based diagnostic tool which simulates fine-scale wind field and dispersion patterns around obstacles. Model simulations were compared with the spatial distributions of ultrafine particles (UFP) from vehicular emissions measured using a passenger van equipped with a Differential Mobility Analyzer/Condensation Particle Counter. The field site allowed for an evaluation of pollutant concentrations in open terrain, with a noise barrier present near the road, and with a noise barrier and vegetation present near the road.Results indicated that air pollutant concentrations near the road were generally higher in open terrain situations with no barriers present; however, concentrations for this case decreased faster with distance than when roadside barriers were present. The presence of a noise barrier and vegetation resulted in the lowest downwind pollutant concentrations, indicating that the plume under this condition was relatively uniform and vertically well-mixed. Comparison of the QUIC model with the mobile UFP measurements indicated that QUIC reasonably represented pollutant transport and dispersion for each of the study configurations.     

Influence of air flow rate on emission of DEHP from vinyl flooring in the emission cell FLEC: Measurements and CFD simulation

The emission of di-(2-ethylhexyl)phthalate (DEHP) from one type of vinyl flooring with ～15% (w/w) DEHP as plasticizer was measured at 22 °C in five FLECs + one blank FLEC (Field and Laboratory Emission Cell). Initially, the flow through all FLECs was 450 ml min^?1. After 689 days the flows were changed to 1000 ml min^?1, 1600 ml min^?1, 2300 ml min^?1, and 3000 ml min^?1, respectively, in four FLECs, and kept at 450 ml min^?1 in one FLEC. Air samples were collected from the effluent air at regular intervals. After 1190 days the experiments were terminated and the interior surfaces of all six FLECs were rinsed with methanol to estimate the internal surface concentrations of DEHP. The DEHP air concentration and specific emission rate (SER) at steady state was estimated for the five different flow rates. The steady-state concentrations decreased slightly with increasing air flow with only the two highest flow rates resulting in significantly lower concentrations. In contrast, the SERs increased significantly. Despite large variation, the internal surface concentrations appeared to decrease slightly with increasing FLEC flow. Computational fluid dynamic (CFD) simulations suggest that the interior gas and surface concentrations were roughly uniform for the low flow case (450 ml min^?1), under which, the partitioning between the FLEC internal surface and chamber air was examined. Although paired t-tests showed no difference between CFD and experimental results for DEHP air concentrations and SERs at steady-state conditions, CFD indicated that the experimental DEHP surface concentrations in the FLECs were underestimated. In conclusion, the experiments showed that the emission of DEHP from vinyl flooring is subject to “external” control and that the SER is strongly and positively dependent on the air exchange rate. However, the increased SER almost compensates for the decrease in gas-phase concentration caused by the increased air exchange.     

Direct wet and dry deposition of ammonia,nitric acid,ammonium and nitrate to the Tampa Bay Estuary,FL, USA

The average total (wet plus dry) nitrogen deposition to the Tampa Bay Estuary was 7.3 (±1.3) kg-N ha⁻¹ yr⁻¹ or 760 (±140) metric tons-N yr⁻¹ for August 1996–July 1999, estimated as a direct deposition rate to the 104,000-ha water surface. This nitrogen flux estimate accounted for ammonia exchange at the air–sea interface. The uncertainty estimate was based on measurement error. Wet deposition was 56% of the total nitrogen deposition over this period, with an average 0.78 ratio of dry-to-wet deposition. Wet nitrogen deposition rates varied considerably, from near zero to 1.3 kg-N ha⁻¹ month⁻¹. About 40% of the total nitrogen flux occurred during the summer months of June, July and August when rainfall was the highest, except for 1997–1998 when the El Niño phenomenon brought unseasonal rainfall. Ammonia/ammonium contributed to 58%, and nitric acid/nitrate 42%, of the total nitrogen deposition over the 3-yr period. In one summer as waters of Tampa Bay warmed above 28°C and ammonium concentrations reached 0.03 mg l⁻¹, the estimated net flux of ammonia was from the Bay waters to the atmosphere.     

MNEQA,an emissions model for photochemical simulations

This study focuses on a new emissions model, Numerical Emissions Model for Air Quality (MNEQA), to be used in photochemical simulations and emission control strategies relating to tropospheric ozone pollutants. MNEQA processes available local information from external files and is easily adaptable to any desired spatial resolution. Top-down and bottom-up methodologies are combined to calculate emissions at the required resolution for photochemical simulations. It was used in conjunction with the MM5-CMAQ air quality modelling system and was applied to an episode of high ozone levels in June 2003. Emission results are widely analysed showing a difference of ?8.8% with EMEP NOx emissions, and ?18.7% with EMEP VOC emissions. Related to ozone simulations, comparative results between measurements and simulations indicated good behaviour of the model in reproducing diurnal ozone concentrations, as statistical values fall within the EPA and EU regulatory frameworks.     

Bench-scale studies on the simultaneous formation of PCBs and PCDD/Fs from combustion systems

The presence of endocrine disrupting chemicals (EDCs) in the environment has wide-ranging potential ecological and health impacts on animals and humans. A significant amount of experimental and theoretical work has been performed the examining formation and control of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs), which account for only part of the EDCs being emitted from combustion devices. Generally accepted mechanistic theories for PCDD/F formation propose heterogeneous reactions in the cooler regions of the combustor involving gas-phase organic precursors (such as chlorobenzenes or chlorophenols), a chlorine donor [such as hydrogen chloride (HCl)], and a flyash-bound metallic catalyst (such as copper chloride). There is evidence that some other proposed EDCs, including polychlorinated biphenyls (PCBs), are formed through a similar mechanistic pathway as PCDD/Fs. In addition, there is evidence that certain important steps in the catalytic reaction between the copper catalyst and the organic precursors may suggest a common rate limiting step for the heterogeneous formation of the previously mentioned EDCs. This paper reports on a bench-scale experimental study to characterize a newly built reactor system that was built to: produce levels and distributions of PCDD/F production similar to those achieved by previous researchers; verify similar responses to changes in independent variables; examine the hypothesis that PCB formation rates exhibit trends similar to PCDD/F formation rates as reactor variables are changed; and begin to explore the dependence of PCB formation on temperature and precursor type. The reactor system has been built, and initial reactor characterization studies have been performed. Initial experiments yielded results that support the hypothesis of a similar formation mechanism of PCBs and PCDD/Fs in combustors. Initial experiments uncovered potential deficiencies with the reactor system and the experimental procedures and have suggested corrective action to improve the experimental system.     

Inorganic PM2.5 at a U.S. agricultural site

In this study, we present approximately two years (January 1999-December 2000) of atmospheric NH3, NH4+, HCl, Cl-, HNO3, NO3-, SO2, and SO4= concentrations measured by the annular denuder/filter pack method at an agricultural site in eastern North Carolina. This site is influenced by high NH3 emissions from animal production and fertilizer use in the surrounding area and neighboring counties. The two-year mean NH3 concentration is 5.6 (+/-5.13) microg m(-3). The mean concentration of total inorganic PM2.5, which includes SO4=, NO3-, NH4+, and Cl-, is 8.0 (+/-5.84) microg m(-3). SO4=, NO3-, NH4+, and Cl- represent, respectively, 53, 24, 22, and 1% of measured inorganic PM2.5. NH3 contributes 72% of total NH3 + NH4+, on an average. Equilibrium modeling of the gas+aerosol NH3/H2SO4/HNO3 system shows that inorganic PM2.5 is more sensitive to reductions in gas + aerosol concentrations of sulfate and nitrate relative to NH3.     

Retained nitrate, hydrated sulfates, and carbonaceous mass in federal reference method fine particulate matter for six eastern U.S. cities

Material balance of fine particulate matter (PM2.5) measured with the Federal Reference Method (FRM) is developed for one rural and five urban locations in the eastern half of the United States using routine Speciation Trends Network (STN) and FRM chemical measurements and thermodynamic models. The Aerosol Inorganics Model is used to estimate retained particle bound water, and an ammonium nitrate evaporation model is used to estimate nitrate concentrations retained on the Teflon-membrane filter of the FRM. To address large uncertainties in carbonaceous mass calculated from STN carbon measurements, retained carbonaceous mass is derived by material balance between PM2.5 FRM mass and estimates of its non-carbon constituents. The resulting sulfate, adjusted nitrate, derived water, inferred carbonaceous material balance approach (SANDWICH) is compared with reconstructed fine mass (RCFM) using the Interagency Monitoring of Protected Visual Environments monitoring program equation. For this study, the SANDWICH method resulted in approximately 21-27% higher sulfate mass and approximately 24-85% lower nitrate mass. The combined mass associated with sulfates and nitrates, however, are well within +/- 10% of the proportion derived using the more traditional RCFM method. The discrepancies between SANDWICH and measurement-derived carbonaceous mass vary from -21% to +56% on an annual basis and are attributed in part to urban-rural source influences and uncertainties in estimating FRM-retained carbonaceous mass.     

Performance and diagnostic evaluation of ozone predictions by the Eta-Community Multiscale Air Quality Forecast System during the 2002 New England Air Quality Study

A real-time air quality forecasting system (Eta-Community Multiscale Air Quality [CMAQ] model suite) has been developed by linking the National Centers for Environmental Estimation Eta model to the U.S. Environmental Protection Agency (EPA) CMAQ model. This work presents results from the application of the Eta-CMAQ modeling system for forecasting ozone (O3) over the Northeastern United States during the 2002 New England Air Quality Study (NEAQS). Spatial and temporal performance of the Eta-CMAQ model for O3 was evaluated by comparison with observations from the EPA Air Quality System (AQS) network. This study also examines the ability of the model to simulate the processes governing the distributions of tropospheric O3 on the basis of the intensive datasets obtained at the four Atmospheric Investigation, Regional Modeling, Analysis, and Estimation (AIRMAP) and Harvard Forest (HF) surface sites. The episode analysis reveals that the model captured the buildup of O3 concentrations over the northeastern domain from August 11 and reproduced the spatial distributions of observed O3 very well for the daytime (8:00 p.m.) of both August 8 and 12 with most of normalized mean bias (NMB) within +/- 20%. The model reproduced 53.3% of the observed hourly O3 within a factor of 1.5 with NMB of 29.7% and normalized mean error of 46.9% at the 342 AQS sites. The comparison of modeled and observed lidar O3 vertical profiles shows that whereas the model reproduced the observed vertical structure, it tended to overestimate at higher altitude. The model reproduced 64-77% of observed NO2 photolysis rate values within a factor of 1.5 at the AIRMAP sites. At the HF site, comparison of modeled and observed O3/nitrogen oxide (NOx) ratios suggests that the site is mainly under strongly NOx-sensitive conditions (>53%). It was found that the modeled lower limits of the O3 production efficiency values (inferred from O3-CO correlation) are close to the observations.