Alice B. Gilliland

Surface and Lightning Sources of Nitrogen Oxides over the United States: Magnitudes, Chemical Evolution, and Outflow

[1] We use observations from two aircraft during the ICARTT campaign over the eastern United States and North Atlantic during summer 2004, interpreted with a global 3-D model of tropospheric chemistry (GEOS-Chem) to test current understanding of regional sources, chemical evolution, and export of NOx. The boundary layer NOx data provide top-down verification of a 50% decrease in power plant and industry NOx emissions over the eastern United States between 1999 and 2004. Observed NOx concentrations at 8–12 km altitude were 0.55 ± 0.36 ppbv, much larger than in previous U.S. aircraft campaigns (ELCHEM, SUCCESS, SONEX) though consistent with data from the NOXAR program aboard commercial aircraft. We show that regional lightning is the dominant source of this upper tropospheric NOx and increases upper tropospheric ozone by 10 ppbv. Simulating ICARTT upper tropospheric NOx observations with GEOS-Chem requires a factor of 4 increase in modeled NOx yield per flash (to 500 mol/ flash). Observed OH concentrations were a factor of 2 lower than can be explained from current photochemical models, for reasons that are unclear. A NOy-CO correlation analysis of the fraction f of North American NOx emissions vented to the free troposphere as NOy (sum of NOx and its oxidation products) shows observed f = 16 ± 10% and modeled f = 14 ± 9%, consistent with previous studies. Export to the lower free troposphere is mostly HNO3 but at higher altitudes is mostly PAN. The model successfully simulates NOy export efficiency and speciation, supporting previous model estimates of a large U.S. anthropogenic contribution to global tropospheric ozone through PAN export.

A preliminary synthesis of modeled climate change impacts on U.S. regional ozone concentrations.

This paper provides a synthesis of results that have emerged from recent modeling studies of the potential sensitivity of U.S. regional ozone (O3) concentrations to global climate change (ca. 2050). This research has been carried out under the auspices of an ongoing U.S. Environmental Protection Agency (EPA) assessment effort to increase scientific understanding of the multiple complex interactions among climate, emissions, atmospheric chemistry, and air quality. The ultimate goal is to enhance the ability of air quality managers to consider global change in their decisions through improved characterization of the potential effects of global change on air quality, including O3 The results discussed here are interim, representing the first phase of the EPA assessment. The aim in this first phase was to consider the effects of climate change alone on air quality, without accompanying changes in anthropogenic emissions of precursor pollutants. Across all of the modeling experiments carried out by the differe...

Seasonal NH3 emission estimates for the eastern United States based on ammonium wet concentrations and an inverse modeling method

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A comparison of CMAQ‐based aerosol properties with IMPROVE, MODIS, and AERONET data

[1] Evaluation of concentrations predicted by air quality models is needed to ensure that model results are compatible with observations. In this study aerosol properties derived from the Community Multiscale Air Quality (CMAQ) model-simulated aerosol mass concentrations are compared with routine data from NASA satellite-borne Moderate Resolution Imaging Spectroradiometer (MODIS) sensor aboard the Sun-synchronous Terra satellite, NASA’s ground-based Aerosol Robotic Network (AERONET), and the ground-based Interagency Monitoring of Protected Visual Environment (IMPROVE) network. The motivation for this analysis is to determine how best to use these parameters in evaluating model-predicted PM2.5 concentrations. CMAQ surface extinction estimates due to scattering at 550 nm wavelength are compared with the IMPROVE nephelometer data obtained from 25 sites within the United States. It is found that model-predicted surface extinctions bear high correlations with nephelometer measured data. Sulfate fractional aerosol optical depth (AOD) is found to dominate in the northeastern part of the United States; hence ground-based measurement of sulfate concentrations have been compared with time series of columnar AOD as observed by the MODIS instrument and also with the CMAQ-predicted tropospheric column values obtained during the June– August period of 2001. CMAQ surface extinctions are found to be relatively higher than the IMPROVE nephelometer observations; however, there is a good agreement between CMAQ AOD trends and AERONET and MODIS data, obtained at the seven AERONET sites located in the eastern United States. CMAQ is also found to capture the day-to-day variability in the spatial AOD patterns. Monthly average satellite AOD estimates are found to be higher than the AOD data obtained using the CMAQ-predicted aerosol concentrations. Seasonal variation of satellite-measured aerosol intensive property ‘‘Angstrom exponent’’ (a gross indicator of the aerosol size distribution) is presented for four selected sites: one each in the eastern and central parts, and two in the western part of the continental United States. Variability of Angstrom exponent at these four selected sites is analyzed in conjunction with the variation of summertime AOD (observed and modeled), mass concentration (observed and modeled) and modeled SO4 average concentrations during the summer (June–August) period of the year 2001. Annual time series of Angstrom exponent data at the four selected sites show a large east-west variation.

Observation-Based Assessment of the Impact of Nitrogen Oxides Emissions Reductions on Ozone Air Quality over the Eastern United States

Abstract Ozone is produced by chemical interactions involving nitrogen oxides (NOx) and volatile organic compounds in the presence of sunlight. At high concentrations, ground-level ozone has been shown to be harmful to human health and to the environment. It has been recognized that ozone is a regional-scale problem and that regionwide control strategies would be needed to improve ozone air quality in the eastern United States. To mitigate interstate transport of ozone and its precursors, the U.S. Environmental Protection Agency issued a regional rule in 1998 known as the “NOx State Implementation Plan (SIP) Call,” requiring 21 states in the eastern United States to reduce their summertime NOx emissions by 30 May 2004. In this paper, the effectiveness of the new emission control measures mandated by the NOx SIP Call is assessed by quantifying the changes that occurred in the daily maximum 8-h ozone concentrations measured at nearly 50 locations, most of which are rural (33 sites of the Clean Air Status an...

The triple value model: a systems approach to sustainable solutions

Abstract The unintended environmental impacts of economic development threaten the continued availability of ecosystem services that are critical to human well-being. An integrated systems approach is needed to characterize sustainability problems and evaluate potential solutions. The Triple Value Model is an innovative framework that depicts the dynamic linkages and resource flows among industrial, societal, and environmental systems. The U.S. EPA has begun using this model to support transdisciplinary research projects that focus upon water resources, communities, and other broad sustainability themes. One recent application addresses opportunities for mitigation of nutrient impairment in the Narragansett Bay watershed, and has produced a policy simulation tool that enables evaluation of alternative sustainable solutions.

Daily Simulation of Ozone and Fine Particulates over New York State: Findings and Challenges

Abstract This study investigates the potential utility of the application of a photochemical modeling system in providing simultaneous forecasts of ozone (O3) and fine particulate matter (PM2.5) over New York State. To this end, daily simulations from the Community Multiscale Air Quality (CMAQ) model for three extended time periods during 2004 and 2005 have been performed, and predictions were compared with observations of ozone and total and speciated PM2.5. Model performance for 8-h daily maximum O3 was found to be similar to other forecasting systems and to be better than that for the 24-h-averaged total PM2.5. Both pollutants exhibited no seasonal differences in model performance. CMAQ simulations successfully captured the urban–rural and seasonal differences evident in observed total and speciated PM2.5 concentrations. However, total PM2.5 mass was strongly overestimated in the New York City metropolitan area, and further analysis of speciated observations and model predictions showed that most of th...

Modeling analyses of the effects of changes in nitrogen oxides emissions from the electric power sector on ozone levels in the eastern United States.

Abstract In this paper, we examine the changes in ambient ozone concentrations simulated by the Community Multiscale Air Quality (CMAQ) model for summer 2002 under three different nitrogen oxides (NOx) emission scenarios. Two emission scenarios represent best estimates of 2002 and 2004 emissions; they allow assessment of the impact of the NOx emissions reductions imposed on the utility sector by the NOx State Implementation Plan (SIP) Call. The third scenario represents a hypothetical rendering of what NOx emissions would have been in 2002 if no emission controls had been imposed on the utility sector. Examination of the modeled median and 95th percentile daily maximum 8-hr average ozone concentrations reveals that median ozone levels estimated for the 2004 emission scenario were less than those modeled for 2002 in the region most affected by the NOx SIP Call. Comparison of the “no-control” with the “2002” scenario revealed that ozone concentrations would have been much higher in much of the eastern United States if the utility sector had not implemented NOx emission controls; exceptions occurred in the immediate vicinity of major point sources where increased NO titration tends to lower ozone levels.

Monthly and annual bias in weekly (NADP/NTN) versus daily (AIRMoN) precipitation chemistry data in the Eastern USA

Abstract Previous comparisons of the data from the National Atmospheric Deposition Program, National Trends Network (NTN) against collocated event sampled data and daily sampled data suggest a substantial bias in the concentration of ammonium [NH 4 + ] and concentrations of several base cations, while the comparability of other ion concentrations ranges among the studies. Eight years of collocated data from five NTN and Atmospheric Integrated Research and Monitoring Network (AIRMoN) sites are compared here. Unlike previous analyses, the data from these two data sets were analyzed in the same laboratory using the same analytical methods; therefore, factors that influence concentration differences can be isolated to sampling frequency and sample preservation techniques. For comparison, the relative biases for these data have been calculated using both median value and volume-weighted mean concentrations, following two different approaches in the literature. The results suggest a relative bias of about 10% in [NH 4 + ] (NTN less than AIRMoN), which is smaller than previous estimates that included the influence of inter-laboratory comparisons. The annual relative bias of [H + ] increases over the analysis period, which results in a larger total relative bias for [H + ] than found in a previous analysis of AIRMoN and NTN data. When comparing NTN and AIRMoN data on monthly time scales, strong seasonal variations are evident in the relative bias for [H + ], [NH 4 + ], and [SO 4 2− ]. Large biases in [SO 4 2− ] (NTN greater than AIRMoN) on monthly times scales have not been detected in previous analyses where data for all seasons were considered together.

A sensitivity study of the discrete Kalman filter (DKF) to initial condition discrepancies

In several previous studies the discrete Kalman filter (DKF) has been used in an adaptive-iterative mode to deduce time-varying air quality emissions. While it is not expressly stated in previous literature on this method, the DKF assumes that the initial modeled and observed concentrations are equal. Careful consideration of this assumption is critical for urban or regional scale air quality models because agreement of initial concentrations with observations is not always a requirement or priority when using these models. The purpose of this paper is to clarify the initial condition assumption in the DKF and to investigate potential implications when the assumption is violated. We focus on the adaptive-iterative implementation of the DKF since we are specifically interested in deducing time-varying air quality emissions. A complete description of the adaptive-iterative DKF as implemented by other authors is provided. A case study in the form of a pseudodata test or identical twin experiment is presented to show that if the initial condition assumption is violated, the adaptive-iterative DKF can produce biased emissions to compensate for the initial modeled and observed concentration differences. The magnitude and longevity of the resulting compensating error depends on the influence of the initial concentrations, as the error is removed more quickly for highly reactive species than for less reactive species (e.g., isoprene versus CO).