Anthropogenic Nitrogen Oxides Research Articles

The Atmospheric Chemistry and Canopy Exchange Simulation System (ACCESS): model description and application to a temperate deciduous forest canopy

Abstract. Forest canopies are primary emission sources of biogenic volatile organic compounds (BVOCs) and have the potential to significantly influence the formation and distribution of secondary organic aerosol (SOA) mass. Biogenically-derived SOA formed as a result of emissions from the widespread forests across the globe may affect air quality in populated areas, degrade atmospheric visibility, and affect climate through direct and indirect forcings. In an effort to better understand the formation of SOA mass from forest emissions, a 1-D column model of the multiphase physical and chemical processes occurring within and just above a vegetative canopy is being developed. An initial, gas-phase-only version of this model, the Atmospheric Chemistry and Canopy Exchange Simulation System (ACCESS), includes processes accounting for the emission of BVOCs from the canopy, turbulent vertical transport within and above the canopy and throughout the height of the planetary boundary layer (PBL), near-explicit representation of chemical transformations, mixing with the background atmosphere and bi-directional exchange between the atmosphere and canopy and the atmosphere and forest floor. The model formulation of ACCESS is described in detail and results are presented for an initial application of the modeling system to Walker Branch Watershed, an isoprene-emission-dominated forest canopy in the southeastern United States which has been the focal point for previous chemical and micrometeorological studies. Model results of isoprene profiles and fluxes are found to be consistent with previous measurements made at the simulated site and with other measurements made in and above mixed deciduous forests in the southeastern United States. Sensitivity experiments are presented which explore how canopy concentrations and fluxes of gas-phase precursors of SOA are affected by background anthropogenic nitrogen oxides (NOx). Results from these experiments suggest that the level of ambient NOx influences the pathways by which SOA is formed by affecting the relative magnitudes and fluxes of isoprene oxidation products emitted from the canopy. Future versions of the ACCESS model are planned to be multiphase, including gas- and aerosol-phase chemical and physical processes, to more fully explore these preliminary results.

Global air quality and climate

Emissions of air pollutants and their precursors determine regional air quality and can alter climate. Climate change can perturb the long-range transport, chemical processing, and local meteorology that influence air pollution. We review the implications of projected changes in methane (CH(4)), ozone precursors (O(3)), and aerosols for climate (expressed in terms of the radiative forcing metric or changes in global surface temperature) and hemispheric-to-continental scale air quality. Reducing the O(3) precursor CH(4) would slow near-term warming by decreasing both CH(4) and tropospheric O(3). Uncertainty remains as to the net climate forcing from anthropogenic nitrogen oxide (NO(x)) emissions, which increase tropospheric O(3) (warming) but also increase aerosols and decrease CH(4) (both cooling). Anthropogenic emissions of carbon monoxide (CO) and non-CH(4) volatile organic compounds (NMVOC) warm by increasing both O(3) and CH(4). Radiative impacts from secondary organic aerosols (SOA) are poorly understood. Black carbon emission controls, by reducing the absorption of sunlight in the atmosphere and on snow and ice, have the potential to slow near-term warming, but uncertainties in coincident emissions of reflective (cooling) aerosols and poorly constrained cloud indirect effects confound robust estimates of net climate impacts. Reducing sulfate and nitrate aerosols would improve air quality and lessen interference with the hydrologic cycle, but lead to warming. A holistic and balanced view is thus needed to assess how air pollution controls influence climate; a first step towards this goal involves estimating net climate impacts from individual emission sectors. Modeling and observational analyses suggest a warming climate degrades air quality (increasing surface O(3) and particulate matter) in many populated regions, including during pollution episodes. Prior Intergovernmental Panel on Climate Change (IPCC) scenarios (SRES) allowed unconstrained growth, whereas the Representative Concentration Pathway (RCP) scenarios assume uniformly an aggressive reduction, of air pollutant emissions. New estimates from the current generation of chemistry-climate models with RCP emissions thus project improved air quality over the next century relative to those using the IPCC SRES scenarios. These two sets of projections likely bracket possible futures. We find that uncertainty in emission-driven changes in air quality is generally greater than uncertainty in climate-driven changes. Confidence in air quality projections is limited by the reliability of anthropogenic emission trajectories and the uncertainties in regional climate responses, feedbacks with the terrestrial biosphere, and oxidation pathways affecting O(3) and SOA.

Application of satellite observations for timely updates to global anthropogenic NOxemission inventories

[1] Anthropogenic emissions of nitrogen oxides (NOx) can change rapidly due to economic growth or control measures. Bottom-up emissions estimated using source-specific emission factors and activity statistics require years to compile and can become quickly outdated. We present a method to use satellite observations of tropospheric NO2 columns to estimate changes in NOx emissions. We use tropospheric NO2 columns retrieved from the SCIAMACHY satellite instrument for 2003–2009, the response of tropospheric NO2 columns to changes in NOx emissions determined from a global chemical transport model (GEOS-Chem), and the bottom-up anthropogenic NOx emissions for 2006 to hindcast and forecast the inventories. We evaluate our approach by comparing bottom-up and hindcast emissions for 2003. The two inventories agree within 6.0% globally and within 8.9% at the regional scale with consistent trends in western Europe, North America, and East Asia. We go on to forecast emissions for 2009. During 2006–2009, anthropogenic NOx emissions over land increase by 9.2% globally and by 18.8% from East Asia. North American emissions decrease by 5.7%.

Sensitivity of the NOy budget over the United States to anthropogenic and lightning NOx in summer

We examine the implications of new estimates of the anthropogenic and lightning nitrogen oxide (NOx) source for the budget of oxidized nitrogen (NOy) over the United States in summer using a 3‐D global chemical transport model (Model of Ozone and Related Tracers‐4). As a result of the Environmental Protection Agency (EPA) State Implementation call, power plant NOx emissions over the eastern United States decreased significantly, as reflected by a 23% decrease in summer surface emissions from the 1999 U.S. EPA National Emissions Inventory to our 2004 inventory. We increase the model lightning NOx source over northern midlatitude continents (by a factor of 10) and the fraction emitted into the free troposphere (FT, from 80% to 98%) to better match the recent observation‐based estimates. While these NOx source updates improve the simulation of NOx and O3 compared to the Intercontinental Chemical Transport Experiment‐North America aircraft observations, a bias in the partitioning between nitric acid (HNO3) and peroxyacetylnitrate (PAN) remains especially above 8 km, suggesting gaps in the current understanding of upper tropospheric processes. We estimate a model NOy export efficiency of 4%−14% to the North Atlantic in the FT, within the range of previous plume‐based estimates (3%−20%) and lower than the 30% exported directly from the continental boundary layer. Lightning NOx contributes 24%−43% of the FT NOy export from the U.S. to the North Atlantic and 28%−34% to the NOy wet deposition over the United States, with the ranges reflecting different assumptions. Increasing lightning NOx decreases the fractional contribution of PAN to total NOy export, increases the O3 production in the northern extratropical FT by 33%, and decreases the regional mean ozone production efficiency per unit NOx (OPE) by 30%. If models underestimate the lightning NOx source, they would overestimate the background OPE in the FT and the fractional contribution of PAN to NOy export. Therefore, a model underestimate of lightning NOx would likely lead to an overestimate of the downwind O3 production due to anthropogenic NOx export. Better constraints on the lightning NOx source are required to more confidently assess the impacts of anthropogenic emissions and their changes on air quality over downwind regions.

Effect of regional precursor emission controls on long-range ozone transport – Part 2: Steady-state changes in ozone air quality and impacts on human mortality

Abstract. Large-scale changes in ozone precursor emissions affect ozone directly in the short term, and also affect methane, which in turn causes long-term changes in ozone that affect surface ozone air quality. Here we assess the effects of changes in ozone precursor emissions on the long-term change in surface ozone via methane, as a function of the emission region, by modeling 10% reductions in anthropogenic nitrogen oxide (NOx) emissions from each of nine world regions. Reductions in NOx emissions from all world regions increase methane and long-term surface ozone. While this long-term increase is small compared to the intra-regional short-term ozone decrease, it is comparable to or larger than the short-term inter-continental ozone decrease for some source-receptor pairs. The increase in methane and long-term surface ozone per ton of NOx reduced is greatest in tropical and Southern Hemisphere regions, exceeding that from temperate Northern Hemisphere regions by roughly a factor of ten. We also assess changes in premature ozone-related human mortality associated with regional precursor reductions and long-range transport, showing that for 10% regional NOx reductions, the strongest inter-regional influence is for emissions from Europe affecting mortalities in Africa. Reductions of NOx in North America, Europe, the Former Soviet Union, and Australia are shown to reduce more mortalities outside of the source regions than within. Among world regions, NOx reductions in India cause the greatest number of avoided mortalities per ton, mainly in India itself. Finally, by increasing global methane, NOx reductions in one hemisphere tend to cause long-term increases in ozone concentration and mortalities in the opposite hemisphere. Reducing emissions of methane, and to a lesser extent carbon monoxide and non-methane volatile organic compounds, alongside NOx reductions would avoid this disbenefit.

Effect of regional precursor emission controls on long-range ozone transport – Part 1: Short-term changes in ozone air quality

Abstract. Observations and models demonstrate that ozone and its precursors can be transported between continents and across oceans. We model the influences of 10% reductions in anthropogenic nitrogen oxide (NOx) emissions from each of nine world regions on surface ozone air quality in that region and all other regions. In doing so, we quantify the relative importance of long-range transport between all source-receptor pairs, for direct short-term ozone changes. We find that for population-weighted concentrations during the three-month "ozone-season", the strongest inter-regional influences are from Europe to the Former Soviet Union, East Asia to Southeast Asia, and Europe to Africa. The largest influences per unit of NOx reduced, however, are seen for source regions in the tropics and Southern Hemisphere, which we attribute mainly to greater sensitivity to changes in NOx in the lower troposphere, and secondarily to increased vertical convection to the free troposphere in tropical regions, allowing pollutants to be transported further. Results show, for example, that NOx reductions in North America are ~20% as effective per unit NOx in reducing ozone in Europe during summer, as NOx reductions from Europe itself. Reducing anthropogenic emissions of non-methane volatile organic compounds (NMVOCs) and carbon monoxide (CO) by 10% in selected regions, can have as large an impact on long-range ozone transport as NOx reductions, depending on the source region. We find that for many source-receptor pairs, the season of greatest long-range influence does not coincide with the season when ozone is highest in the receptor region. Reducing NOx emissions in most source regions causes a larger decrease in export of ozone from the source region than in ozone production outside of the source region.

Intercontinental Impacts of Ozone Pollution on Human Mortality

Ozone exposure is associated with negative health impacts, including premature mortality. Observations and modeling studies demonstrate that emissions from one continent influence ozone air quality over other continents. We estimate the premature mortalities avoided from surface ozone decreases obtained via combined 20% reductions of anthropogenic nitrogen oxide, nonmethane volatile organic compound, and carbon monoxide emissions in North America (NA), EastAsia (EA), South Asia (SA), and Europe (EU). We use estimates of ozone responses to these emission changes from several atmospheric chemical transportmodels combined with a health impactfunction. Foreign emission reductions contribute approximately 30%, 30%, 20%, and >50% of the mortalities avoided by reducing precursor emissions in all regions together in NA, EA, SA and EU, respectively. Reducing emissions in NA and EU avoids more mortalities outside the source region than within, owing in part to larger populations in foreign regions. Lowering the global methane abundance by 20% reduces mortality mostin SA,followed by EU, EA, and NA. For some source-receptor pairs, there is greater uncertainty in our estimated avoided mortalities associated with the modeled ozone responses to emission changes than with the health impact function parameters.

Satellite‐observed U.S. power plant NOx emission reductions and their impact on air quality

Nitrogen oxide (NOx) emissions resulting from fossil fuel combustion lead to unhealthy levels of near‐surface ozone (O3). One of the largest U.S. sources, electric power generation, represented about 25% of the U.S. anthropogenic NOx emissions in 1999. Here we show that space‐based instruments observed declining regional NOx levels between 1999 and 2005 in response to the recent implementation of pollution controls by utility companies in the eastern U.S. Satellite‐retrieved summertime nitrogen dioxide (NO2) columns and bottom‐up emission estimates show larger decreases in the Ohio River Valley, where power plants dominate NOx emissions, than in the northeast U.S. urban corridor. Model simulations predict lower O3 across much of the eastern U.S. in response to these emission reductions.

Global distribution pattern of anthropogenic nitrogen oxide emissions: Correlation analysis of satellite measurements and model calculations

Nitrogen oxides play a key role in tropospheric chemistry; to study the distribution patterns of the corresponding anthropogenic emissions (fossil, industrial, waste), we use three independent data sources: GOME measurements of the tropospheric NO2 column density fields, the EDGAR 3 emission inventory as an estimation of the anthropogenic NOx emissions and nighttime images of worldwide human settlements seen by the DMSP OLS satellite instrument as a proxy for these emission patterns. The uncertainties are not known precisely for any of the fields. Using the MOZART‐2 CTM, tropospheric column density fields are calculated from the emission estimates, and transformations are developed to turn the GOME columns into anthropogenic emission fields. Assuming the errors of the three data sources (GOME, EDGAR, lights) to be independent, we are able to determine ranges for the pattern errors of the column density fields and values for the pattern errors of the source fields by a correlation analysis that connects relative error (co)variances and correlation coefficients. That method was developed for this investigation but can generally be used to calculate relative error variances of data sets, if the errors of at least three of them can be assumed to be independent. We estimate the pattern error of the EDGAR 3 anthropogenic NOx emission field as (27 ± 5)%, which can be reduced by combining all fields to (15 ± 3)%. By determining outliers, we identify locations with high uncertainty that need further examination.

Ozone: Unrealistic Scenarios

Knowlton et al. (2004) argued that increasing temperatures associated with climate change will increase urban ozone and related health risks. They have disregarded important factors in reaching this conclusion. During the last 20 years, nationwide exceedances of the federal 1-hr ozone standard declined 90%, and the June–August average of daily 1-hr peak ozone levels declined 10% (Schwartz et al., in press), presumably with ensuing declines in ozone-related mortality. Ozone declined despite a roughly 1°C increase in urban temperatures during the last few decades (Karl et al. 1988). Knowlton et al. (2004) did not explain why we should expect the future to be the opposite of the past. Knowlton et al. (2004) used ozone-precursor [nitrogen oxides (NOx) and volatile organic compound (VOC)] emissions estimates for 1996 to predict ozone levels in the 2050s. However, even current emissions are substantially lower than 1996 levels, while, as shown below, already-adopted U.S. Environmental Protection Agency (EPA) requirements will eliminate most remaining ozone-precursor emissions, even after accounting for growth. The U.S. EPA (2003) estimated that between 1996 and 2001, total emissions of NOx and VOC declined, 10 and 14%, respectively. [The U.S. EPA updated its trend estimates in November 2004 (U.S. EPA 2004a) and now believes the decline was even steeper, although these new estimates were obviously not available to Knowlton et al.] During 2003 and 2004, the U.S. EPA capped total NOx from coal-fired power plants and industrial boilers at 60% below 2000 levels (U.S. EPA 1998a, 2004b). A range of emissions data show the average automobile’s NOx emissions rate declined 4–9% per year between 1995 and 2001, with greater improvements for vehicles up to 4 years old (Pokharel et al. 2003; Schwartz 2003). Total driving is increasing < 2% per year, resulting in large net NOx declines (Texas Transportation Institute 2004). Data on heavy-duty diesel vehicles are sparse, but there is every reason to believe that diesel NOx has also declined. The U.S. EPA has tightened NOx standards for new on- and off-road diesels several times over the last 15 years, and also recently required additional NOx reductions from in-use 1993–1998 model year trucks (U.S. EPA 2002a, 2004c, 2004d). VOCs have declined far more than NOx and far more than U.S. EPA estimates. The U.S. EPA’s official VOC inventory understates significantly the gasoline-vehicle contribution to total VOCs (Watson et al. 2001). Real-world data show the average automobile’s VOC emission rate is declining 11–15% per year, again much more rapidly than driving is increasing, and with a more rapid decline for recent models (Pokharel et al. 2003; Schwartz 2003). The U.S. EPA also recently implemented VOC reductions for other sources (U.S. EPA 1998b, 2002b, 2004e). Overall, between 1996 and 2004, anthropogenic NOx and VOC emissions likely declined, respectively, at least 25 and 50%—declines overlooked by Knowlton et al. (2004). Emission declines will continue. For example, a vehicle fleet meeting the U.S. EPA’s “Tier 2” automobile standards, implemented in 2004, on-road diesel standards set for 2007, and off-road diesel standards set for 2010, will emit 90% less NOx and VOCs per mile over their lifetime than the current average vehicle, resulting in huge emissions declines, even with predicted increases in driving (Schwartz 2003; U.S. EPA 2000a, 2000b, 2004c). Knowlton et al. (2004) assume ozone-precursor emissions several times greater than any plausible future scenario. Their projections of future ozone and related health impacts are therefore unrealistically high. Heat-related mortality has also declined, by 70% nationwide since the 1960s, despite warming urban climates, with the hottest and most humid cities achieving the greatest risk reductions (Davis et al. 2003). These health improvements resulted from a range of adaptive technologies and processes, including increased air conditioning, changes in building design, physiologic adaptations, and improved emergency medicine. Nevertheless, because of a single major blackout on a warm day in 2003, Knowlton et al. (2004) maintain that “air conditioning may not really be an appropriate ‘fix’ for adapting to climate change.” Air conditioning is clearly a vital adaptive technology that has saved countless lives. One study reported a relative risk of death on hot days of 1.7 for people with no air conditioning compared to those with central air (Rogot et al. 1992). The nondiscriminating reader might be impressed by the downscaling of a general circulation model using a regional mesoscale model to predict localized differences in future air-pollution related mortality, but the complexity of the models is irrelevant in the face of Knowlton et al.’s failure to temper their theoretical exercise with real-world data. Had Knowlton et al. (2004) accounted for observed historical health and pollution trends and future emission-reduction requirements, they would have arrived at a markedly different story.

Ozone response to precursor controls in very complex terrains: Use of photochemical indicators to assess O3‐NOx‐VOC sensitivity in the northeastern Iberian Peninsula

The kinetics of ozone (O3) chemistry and its two main precursors, nitrogen oxides (NOx) and volatile organic compounds (VOC), represents an important field of uncertainty in atmospheric chemistry and photochemical modeling. This uncertainty affects the design of control strategies to reduce tropospheric O3 production. The effect of controlling ozone precursors on sensitivity regimes was evaluated by performing simulations with MM5‐EMICAT2000‐CMAQ model to represent O3 formation in the northeastern Iberian Peninsula with baseline emission rates for VOC and NOx, and reducing anthropogenic VOC and NOx emissions on a 35%. Three different scenarios were considered in order to assess chemical sensitivity in urban, industrial, and background domains. Areas downwind of the city of Barcelona benefit from NOx reductions (reduction of 10 ppb in ground‐level O3), while the same reduction causes an important increment of O3 in Barcelona (9 ppb) and the area downwind of Tarragona (18 ppb), with a high industrial influence. The city of Barcelona benefits from VOC reductions (10 ppb of O3) as well as the industrial zone of Alcover (20 ppb). The rest of the domain is practically insensitive to VOC reductions. Diverse photochemical species derived from the air quality model were used as indicators in order to establish the chemical sensitivity regime existing in the areas, analyzing whether O3 values reacted consistently to similar changes in emissions. Results showed that NOy (total reactive nitrogen) and O3/NOy are the indicators involving a lower uncertainty when assessing sensitivity, according to the narrow transition regime between NOx‐ and VOC‐sensitive chemistry and the low uncertainty observed. Indicators performed better in VOC‐sensitive than in NOx‐sensitive domains. H2O2‐ and HNO3‐ derived indicators entailed higher uncertainties since transition regimes between NOx and VOC sensitivity covered a wide range. The extent of reaction also performed as a good indicator to separate NOx‐ and VOC‐sensitive regimes. This sensitivity analysis provides a tool for establishing hypothetical control policies for O3 precursor emissions through a comparison of simulated correlation between the species.

Mobile Source Emission Inventories—Monthly or Annual Average Inputs to MOBILE6?

In many urban areas, on-road vehicles are the biggest contributing source category of volatile organic compounds (VOCs) and nitrogen oxides (NOx). Based on a recently completed emission inventory study for three counties in central Florida, the major source by far of anthropogenic VOCs and NOx was on-road mobile sources, even though other sources (such as construction equipment, lawn and garden equipment, and various point sources) were also significant. Although there is specific guidance for conducting an ozone-season inventory for mobile sources, there is a lack of detailed guidance as to how to employ the U.S. Environmental Protection Agency's (EPA) latest mobile source emission factor program, MOBILE6, for an annual inventory. Several of the MOBILE6 inputs that significantly influence emission factors (e.g., temperature) can vary widely throughout the year, and the annual average value may not be appropriate. Rather, it may be better to utilize monthly values of these parameters. This paper investigated the sensitivity of the annual emission inventory results to using annual or monthly values of temperature, Reid Vapor Pressure of gasoline, and humidity. The results show that, for a three-county area in central Florida representing metropolitan Orlando, the annual emission inventory based on the sum of individual monthly averages is not significantly different from that calculated using one set of annual average inputs to MOBILE6.

Evidence that nitric acid increases relative humidity in low-temperature cirrus clouds.

In situ measurements of the relative humidity with respect to ice (RHi) and of nitric acid (HNO3) were made in both natural and contrail cirrus clouds in the upper troposphere. At temperatures lower than 202 kelvin, RHi values show a sharp increase to average values of over 130% in both cloud types. These enhanced RHi values are attributed to the presence of a new class of HNO3-containing ice particles (Delta-ice). We propose that surface HNO3 molecules prevent the ice/vapor system from reaching equilibrium by a mechanism similar to that of freezing point depression by antifreeze proteins. Delta-ice represents a new link between global climate and natural and anthropogenic nitrogen oxide emissions. Including Delta-ice in climate models will alter simulated cirrus properties and the distribution of upper tropospheric water vapor.

Role of anthropogenic volatile organic compounds and nitrogen oxides as ozone precursors in the wintertime over East Asia

As an exercise in model sensitivity, the Models-3 Community Multiscale Air Quality (CMAQ) modeling system with meteorological fields from the Regional Atmospheric Modeling System (RAMS) was applied to study the response of photochemical oxidants to systematic increases in anthropogenic volatile organic compounds (VOC) and nitrogen oxides (NOx) emissions in January 1997 over East Asia. Three simulations-one base case and two sensitivity simulations were carried out. Two sensitivity simulations were performed by assuming a 35% separate increase in anthropogenic VOC and NOx emissions comparing with the base case. Biogenic VOC emissions were held constant across the sensitivity simulations. To evaluate the model performance, ozone mixing ratios (O3) from the base case simulation were compared with surface observations at five remote sites in Japan, and it was found that the model reproduces most of the important features in the observations. Monthly average O3 concentrations in the daytime were examined to gain an understanding of how the increase in anthropogenic emissions affected the overall chemical system for each sensitivity simulation.

Anthropogenic nitrogen oxide transport and deposition in Eastern North America

Anthropogenic nitrogen oxide transport and deposition in Eastern North America

Anthropogenic nitrogen oxide transport and deposition in Eastern North America

A long-range atmospheric transport and transformation model is presented for nitrogen oxides emitted by man-made sources. The model parameters are optimized by matching the model output—annual average nitrate (NO − 3) wet deposition—to observed deposition at 109 precipitation sampling stations in eastern N America that operated continuously in the years 1980–1982. The root-mean-square residual between observations and predictions is 2.9 kg NO − 3 ha −1 y −1 or 19.7% of the root-mean-square observed value. The trend of estimated annual average NO − 3 concentrations in precipitation at Hubbard Brook, New Hampshire compares well with the observations from 1964 to 1981. Transfer coefficients decay nearly exponentially with distance with length scales of 200–800 km, depending on source-receptor orientation with respect to the resultant annual wind direction. The model is used for source apportionment of NO − 3 wet deposition at several receptors and for estimating a nitrogen budget for eastern N America, including the transboundary fluxes between the U.S. and Canada.

Aspects of the chemistry of ozone depletion

The conversion of stratospheric ozone and atomic oxygen back to molecular oxygen is catalysed by a number of atmospheric trace species such as nitrogen oxides (NO, NO 2 ), halogen (Cl, ClO) and hydrogen (H, HO, HO 2 ) radicals. The concentrations of these species are interrelated by a complex series of chemical reactions where those of hydroperoxy (HO 2 ) are the least well understood. Recent direct laboratory studies of the reactions of HO 2 have a considerable effect on estimates of ozone depletion by anthropogenic nitrogen oxides and halogen compounds.