Donna B. Schwede

Ozone and sulfur dioxide dry deposition to forests: Observations and model evaluation

Fluxes and deposition velocities of O3 and SO2 were measured over both a deciduous and a mixed coniferous-deciduous forest for full growing seasons. Fluxes and deposition velocities of O3 were measured over a coniferous forest for a month. Mean deposition velocities of 0.35 to 0.48 cm/s for O3 and 0.6 to 0.72 cm/s for SO2 were observed during the growing seasons of 1997 and 1998. Weekly averages of O3 deposition velocity ranged from 0.25 cm/s at the beginning and end of the season to 1.25 cm/s in late June. SO2 had a smaller seasonal variation, from 0.75 to 1.5 cm/s between the beginning and peak of the season. Because O3 concentrations are higher, the flux of O3 to forests is considerably greater than the flux of SO2. Daytime deposition velocities are very similar at each site, from 0.75 to 0.79 cm/s for O3, and from 1.01 to 1.04 cm/s for SO2. Diurnal cycles for both gases are discussed, as are the impact of some weather events. The peak time for O3 deposition velocity is in midmorning, while it is near midday for SO2. Surface wetness is usually associated with a small increase in deposition velocity, but for some rain events a major increase was noted. Minimum deposition velocities usually occur at night and increase slowly in the predawn hours before light. Comparisons are made between observations of deposition velocity and predictions made with the Meyers multilayer deposition velocity model. While the model is, on average, unbiased for O3, it tends to underpredict the higher deposition velocity values. The model is slightly biased low (underpredicts) for SO2 deposition velocity. The strengths of the model are noted, as are opportunities for improvement.

Increasing importance of deposition of reduced nitrogen in the United States

Significance Human activities have greatly increased emissions of reactive forms of nitrogen to the atmosphere. This perturbation to the nitrogen cycle has produced large increases of nitrogen deposition to sensitive ecosystems. Over recent decades, attention has focused on wet and dry deposition of nitrate stemming from fossil fuel combustion emissions of nitrogen oxides. Successful decreases in nitrogen oxides emissions in the United States have substantially decreased nitrate deposition. By contrast, emissions of ammonia, an unregulated air pollutant, and resulting deposition of ammonium have grown. Expanded observations demonstrate that deposition of reactive nitrogen in the United States has shifted from a nitrate-dominated to an ammonium-dominated condition. Recognition of this shift is critical to formulating effective future policies to protect ecosystems from excess nitrogen deposition. Rapid development of agriculture and fossil fuel combustion greatly increased US reactive nitrogen emissions to the atmosphere in the second half of the 20th century, resulting in excess nitrogen deposition to natural ecosystems. Recent efforts to lower nitrogen oxides emissions have substantially decreased nitrate wet deposition. Levels of wet ammonium deposition, by contrast, have increased in many regions. Together these changes have altered the balance between oxidized and reduced nitrogen deposition. Across most of the United States, wet deposition has transitioned from being nitrate-dominated in the 1980s to ammonium-dominated in recent years. Ammonia has historically not been routinely measured because there are no specific regulatory requirements for its measurement. Recent expansion in ammonia observations, however, along with ongoing measurements of nitric acid and fine particle ammonium and nitrate, permit new insight into the balance of oxidized and reduced nitrogen in the total (wet + dry) US nitrogen deposition budget. Observations from 37 sites reveal that reduced nitrogen contributes, on average, ∼65% of the total inorganic nitrogen deposition budget. Dry deposition of ammonia plays an especially key role in nitrogen deposition, contributing from 19% to 65% in different regions. Future progress toward reducing US nitrogen deposition will be increasingly difficult without a reduction in ammonia emissions.

Modeling the Current and Future Roles of Particulate Organic Nitrates in the Southeastern United States

Organic nitrates are an important aerosol constituent in locations where biogenic hydrocarbon emissions mix with anthropogenic NOx sources. While regional and global chemical transport models may include a representation of organic aerosol from monoterpene reactions with nitrate radicals (the primary source of particle-phase organic nitrates in the Southeast United States), secondary organic aerosol (SOA) models can underestimate yields. Furthermore, SOA parametrizations do not explicitly take into account organic nitrate compounds produced in the gas phase. In this work, we developed a coupled gas and aerosol system to describe the formation and subsequent aerosol-phase partitioning of organic nitrates from isoprene and monoterpenes with a focus on the Southeast United States. The concentrations of organic aerosol and gas-phase organic nitrates were improved when particulate organic nitrates were assumed to undergo rapid (τ = 3 h) pseudohydrolysis resulting in nitric acid and nonvolatile secondary organic aerosol. In addition, up to 60% of less oxidized-oxygenated organic aerosol (LO-OOA) could be accounted for via organic nitrate mediated chemistry during the Southern Oxidants and Aerosol Study (SOAS). A 25% reduction in nitrogen oxide (NO + NO2) emissions was predicted to cause a 9% reduction in organic aerosol for June 2013 SOAS conditions at Centreville, Alabama.

Sensitivity of the National Oceanic and Atmospheric Administration multilayer model to instrument error and parameterization uncertainty

The response of the National Oceanic and Atmospheric Administration multilayer inferential dry deposition velocity model (NOAA-MLM) to error in meteorological inputs and model parameterization is reported. Monte Carlo simulations were performed to assess the uncertainty in NOAA-MLM deposition velocity V d estimates for ozone (O 3 ), sulfur dioxide (SO 2 ), and nitric acid (HNO 3 ) associated with measurements of meteorological variables (including temperature, humidity, radiation, wind speed, wind direction, and leaf area index). Summer daylight scenarios for grass, corn, soybean, oak, and pine were considered. Model sensitivity to uncertainty in the leaf area index (LAI), minimum stomatal resistance, and soil moisture parameterizations was explored. For SO 2 and HNO 3 , instrument error associated with the measurement of wind speed and direction resulted in the greatest V d error. Depending on vegetation type, the most important source of uncertainty due to instrument error for the V d of O 3 was LAI. Of the model parameterizations studied, accurate estimation of temporal aspects of the annual LAI profile and the characterization of soil moisture supply and demand are most important to model-estimated V d uncertainty. Considered individually, these factors can result in SO 2 and HNO 3 V d estimate uncertainty of ±25% and O 3 estimate uncertainty greater than 60%. For single plant species settings, reductions in estimate uncertainty should be possible with minor algorithmic modification, inclusion of more species-appropriate LAI profiles, and careful application of remote sensing technology.

Description and evaluation of the Community Multiscale Air Quality (CMAQ) modeling system version 5.1

The Community Multiscale Air Quality (CMAQ) model is a comprehensive multipollutant air quality modeling system developed and maintained by the US Environmental Protection Agency’s (EPA) Office of Research and Development (ORD). Recently, version 5.1 of the CMAQ model (v5.1) was released to the public, incorporating a large number of science updates and extended capabilities over the previous release version of the model (v5.0.2). These updates include the following: improvements in the meteorological calculations in both CMAQ and the Weather Research and Forecast (WRF) model used to provide meteorological fields to CMAQ, updates to the gas and aerosol chemistry, revisions to the calculations of clouds and photolysis, and improvements to the dry and wet deposition in the model. Sensitivity simulations isolating several of the major updates to the modeling system show that changes to the meteorological calculations result in enhanced afternoon and early evening mixing in the model, periods when the model historically underestimates mixing. This enhanced mixing results in higher ozone (O3) mixing ratios on average due to reduced NO titration, and lower fine particulate matter (PM2.5) concentrations due to greater dilution of primary pollutants (e.g., elemental and organic carbon). Updates to the clouds and photolysis calculations greatly improve consistency between the WRF and CMAQ models and result in generally higher O3 mixing ratios, primarily due to reduced cloudiness and attenuation of photolysis in the model. Updates to the aerosol chemistry result in higher secondary organic aerosol (SOA) concentrations in the summer, thereby reducing summertime PM2.5 bias (PM2.5 is typically underestimated by CMAQ in the summer), while updates to the gas chemistry result in slightly higher O3 and PM2.5 on average in January and July. Overall, the seasonal variation in simulated PM2.5 generally improves in CMAQv5.1 (when considering all model updates), as simulated PM2.5 concentrations decrease in the winter (when PM2.5 is generally overestimated by CMAQ) and increase in the summer (when PM2.5 is generally underestimated by CMAQ). Ozone mixing ratios are higher on average with v5.1 vs. v5.0.2, resulting in higher O3 mean bias, as O3 tends to be overestimated by CMAQ throughout most of the year (especially at locations where the observed O3 is low); however, O3 correlation is largely improved with v5.1. Sensitivity simulations for several hypothetical emission reduction scenarios show that v5.1 tends to be slightly more responsive to reductions in NOx (NO + NO2), VOC and SOx (SO2 + SO4) emissions than v5.0.2, representing an improvement as previous studies have shown CMAQ to underestimate the observed reduction in O3 due to large, widespread reductions in observed emissions.

Sensitivity of continental United States atmospheric budgets of oxidized and reduced nitrogen to dry deposition parametrizations

Reactive nitrogen (Nr) is removed by surface fluxes (air–surface exchange) and wet deposition. The chemistry and physics of the atmosphere result in a complicated system in which competing chemical sources and sinks exist and impact that removal. Therefore, uncertainties are best examined with complete regional chemical transport models that simulate these feedbacks. We analysed several uncertainties in regional air quality model resistance analogue representations of air–surface exchange for unidirectional and bi-directional fluxes and their effect on the continental Nr budget. Model sensitivity tests of key parameters in dry deposition formulations showed that uncertainty estimates of continental total nitrogen deposition are surprisingly small, 5 per cent or less, owing to feedbacks in the chemistry and rebalancing among removal pathways. The largest uncertainties (5%) occur with the change from a unidirectional to a bi-directional NH3 formulation followed by uncertainties in bi-directional compensation points (1–4%) and unidirectional aerodynamic resistance (2%). Uncertainties have a greater effect at the local scale. Between unidirectional and bi-directional formulations, single grid cell changes can be up to 50 per cent, whereas 84 per cent of the cells have changes less than 30 per cent. For uncertainties within either formulation, single grid cell change can be up to 20 per cent, but for 90 per cent of the cells changes are less than 10 per cent.

Impact of Enhanced Ozone Deposition and Halogen Chemistry on Tropospheric Ozone over the Northern Hemisphere.

Fate of ozone in marine environments has been receiving increased attention due to the tightening of ambient air quality standards. The role of deposition and halogen chemistry is examined through incorporation of an enhanced ozone deposition algorithm and inclusion of halogen chemistry in a comprehensive atmospheric modeling system. The enhanced ozone deposition treatment accounts for the interaction of iodide in seawater with ozone and increases deposition velocities by 1 order of magnitude. Halogen chemistry includes detailed chemical reactions of organic and inorganic bromine and iodine species. Two different simulations are completed with the halogen chemistry: without and with photochemical reactions of higher iodine oxides. Enhanced deposition reduces mean summer-time surface ozone by ∼3% over marine regions in the Northern Hemisphere. Halogen chemistry without the photochemical reactions of higher iodine oxides reduces surface ozone by ∼15% whereas simulations with the photochemical reactions of higher iodine oxides indicate ozone reductions of ∼48%. The model without these processes overpredicts ozone compared to observations whereas the inclusion of these processes improves predictions. The inclusion of photochemical reactions for higher iodine oxides leads to ozone predictions that are lower than observations, underscoring the need for further refinement of the halogen emissions and chemistry scheme in the model.

The role of the atmosphere in the provision of ecosystem services.

Solving the environmental problems that we are facing today requires holistic approaches to analysis and decision making that include social and economic aspects. The concept of ecosystem services, defined as the benefits people obtain from ecosystems, is one potential tool to perform such assessments. The objective of this paper is to demonstrate the need for an integrated approach that explicitly includes the contribution of atmospheric processes and functions to the quantification of air-ecosystem services. First, final and intermediate air-ecosystem services are defined. Next, an ecological production function for clean and clear air is described, and its numerical counterpart (the Community Multiscale Air Quality model) is introduced. An illustrative numerical example is developed that simulates potential changes in air-ecosystem services associated with the conversion of evergreen forest land in Mississippi, Alabama and Georgia to commercial crop land. This one-atmosphere approach captures a broad range of service increases and decreases. Results for the forest to cropland conversion scenario suggest that although such change could lead to increased biomass (food) production services, there could also be coincident, seasonally variable decreases in clean and clear air-ecosystem services (i.e., increased levels of ozone and particulate matter) associated with increased fertilizer application. Metrics that support the quantification of these regional air-ecosystem changes require regional ecosystem production functions that fully integrate biotic as well as abiotic components of terrestrial ecosystems, and do so on finer temporal scales than are used for the assessment of most ecosystem services.

Sensitivity of the Industrial Source Complex Model to Input Deposition Parameters

The Industrial Source Complex model has recently been revised to include algorithms for estimating dry and wet deposition of particles in addition to air concentration. This study examines the sensitivity of the maximum model predictions to changes in input parameters controlling deposition, such as the shape of the particle size distribution, resolution of the size distribution, and scavenging coefficients. The modeled deposition values are more sensitive than the concentrations to changes in these parameters. The model is particularly sensitive to the use of the plume depletion option, with deposition values lowered by up to 40% when the depletion option is selected. Changes in the specification of the particle size distribution affected the highest deposition values by as much as 25%. Neither concentration nor deposition seem particularly sensitive to the use of gridded terrain data.

The Impact of Iodide-Mediated Ozone Deposition and Halogen Chemistry on Surface Ozone Concentrations Across the Continental United States

The air quality of many large coastal areas in the United States is affected by the confluence of polluted urban and relatively clean marine airmasses, each with distinct atmospheric chemistry. In this context, the role of iodide-mediated ozone (O3) deposition over seawater and marine halogen chemistry accounted for in both the lateral boundary conditions and coastal waters surrounding the continental U.S. is examined using the Community Multiscale Air Quality (CMAQ) model. Several nested simulations are conducted in which these halogen processes are implemented separately in the continental U.S. and hemispheric CMAQ domains, the latter providing lateral boundary conditions for the former. Overall, it is the combination of these processes within both the continental U.S. domain and from lateral boundary conditions that lead to the largest reductions in modeled surface O3 concentrations. Predicted reductions in surface O3 concentrations occur mainly along the coast where CMAQ typically has large overpredictions. These results suggest that a realistic representation of halogen processes in marine regions can improve model prediction of O3 concentrations near the coast.