Assessing the Ability of Instantaneous Aircraft and Sonde Measurements to Characterize Climatological Means and Long-Term Trends in Tropospheric Composition

Over four decades of measurements exist that sample the 3-D composition of reactive trace gases in the troposphere from approximately weekly ozone sondes, instrumentation on civil aircraft, and individual comprehensive aircraft field campaigns. An obstacle to using these data to evaluate coupled chemistry-climate models (CCMs)the models used to project future changes in atmospheric composition and climateis that exact space-time matching between model fields and observations cannot be done, as CCMs generate their own meteorology. Evaluation typically involves averaging over large spatiotemporal regions, which may not reflect a true average due to limited or biased sampling. This averaging approach generally loses information regarding specific processes. Here we aim to identify where discrete sampling may be indicative of long-term mean conditions, using the GEOS-Chem global chemical-transport model (CTM) driven by the MERRA reanalysis to reflect historical meteorology from 2003 to 2012 at 2o by 2.5o resolution. The model has been sampled at the time and location of every ozone sonde profile available from the Would Ozone and Ultraviolet Radiation Data Centre (WOUDC), along the flight tracks of the IAGOSMOZAICCARABIC civil aircraft campaigns, as well as those from over 20 individual field campaigns performed by NASA, NOAA, DOE, NSF, NERC (UK), and DLR (Germany) during the simulation period. Focusing on ozone, carbon monoxide and reactive nitrogen species, we assess where aggregates of the in situ data are representative of the decadal mean vertical, spatial and temporal distributions that would be appropriate for evaluating CCMs. Next, we identically sample a series of parallel sensitivity simulations in which individual emission sources (e.g., lightning, biogenic VOCs, wildfires, US anthropogenic) have been removed one by one, to assess where and when the aggregated observations may offer constraints on these processes within CCMs. Lastly, we show results of an additional 31-year simulation from 1980-2010 of GEOS-Chem driven by the MACCity emissions inventory and MERRA reanalysis at 4o by 5o. We sample the model at every WOUDC sonde and flight track from MOZAIC and NASA field campaigns to evaluate which aggregate observations are statistically reflective of long-term trends over the period

Chemical nonlinearities in relating intercontinental ozone pollution to anthropogenic emissions

Model studies typically estimate intercontinental influence on surface ozone by perturbing emissions from a source continent and diagnosing the ozone response in the receptor continent. Since the response to perturbations is non-linear due to chemistry, conclusions drawn from different studies may depend on the magnitude of the applied perturbation. We investigate this issue for intercontinental transport between North America, Europe, and Asia with sensitivity simulations in three global chemical transport models. In each region, we decrease anthropogenic emissions of NOx and nonmethane volatile organic compounds (NMVOCs) by 20% and 100%. We find strong nonlinearity in the response to NOx perturbations outside summer, reflecting transitions in the chemical regime for ozone production. In contrast, we find no significant nonlinearity to NOx perturbations in summer or to NMVOC perturbations year-round. The relative benefit of decreasing NOx vs. NMVOC from current levels to abate intercontinental pollution increases with the magnitude of emission reductions

Summertime cyclones over the Great Lakes Storm Track from 1860–2100: variability, trends, and association with ozone pollution

Prior work indicates that the frequency of summertime mid-latitude cyclones tracking across the Great Lakes Storm Track (GLST, bounded by: 70° W, 90° W, 40° N, and 50° N) are strongly anticorrelated with ozone (O₃) pollution episodes over the Northeastern United States (US). We apply the MAP Climatology of Mid-latitude Storminess (MCMS) algorithm to 6-hourly sea level pressure fields from over 2500 yr of simulations with the GFDL CM3 global coupled chemistry-climate model. These simulations include (1) 875 yr with constant 1860 emissions and forcings (Pre-industrial Control), (2) five ensemble members for 1860–2005 emissions and forcings (Historical), and (3) future (2006–2100) scenarios following the Representative Concentration Pathways (RCP 4.5 and RCP 8.5) and a sensitivity simulation to isolate the role of climate warming from changes in O₃ precursor emissions (RCP 4.5*). The GFDL CM3 Historical simulations capture the mean and variability of summertime cyclones traversing the GLST within the range determined from four reanalysis datasets. Over the 21st century (2006–2100), the frequency of summertime mid-latitude cyclones in the GLST decreases under the RCP 8.5 scenario and in the RCP 4.5 ensemble mean. These trends are significant when assessed relative to the variability in the Pre-industrial Control simulation. In addition, the RCP 4.5* scenario enables us to determine the relationship between summertime GLST cyclones and high-O₃ events (> 95th percentile) in the absence of emission changes. The summertime GLST cyclone frequency explains less than 10% of the variability in high-O₃ events over the Northeastern US in the model, implying that other factors play an equally important role in determining high-O₃ events

Chemical nonlinearities in relating intercontinental ozone pollution to anthropogenic emissions

Model studies typically estimate intercontinental influence on surface ozone by perturbing emissions from a source continent and diagnosing the ozone response in the receptor continent. Since the response to perturbations is non-linear due to chemistry, conclusions drawn from different studies may depend on the magnitude of the applied perturbation. We investigate this issue for intercontinental transport between North America, Europe, and Asia with sensitivity simulations in three global chemical transport models. In each region, we decrease anthropogenic emissions of NOx and nonmethane volatile organic compounds (NMVOCs) by 20% and 100%. We find strong nonlinearity in the response to NOx perturbations outside summer, reflecting transitions in the chemical regime for ozone production. In contrast, we find no significant nonlinearity to NOx perturbations in summer or to NMVOC perturbations year-round. The relative benefit of decreasing NOx vs. NMVOC from current levels to abate intercontinental pollution increases with the magnitude of emission reductions

Changes in the frequency and return level of high ozone pollution events over the eastern United States following emission controls

In order to quantify the impact of recent efforts to abate surface ozone (O3) pollution, we analyze changes in the frequency and return level of summertime (JJA) high surface O₃ events over the eastern United States (US) from 1988–1998 to 1999–2009. We apply methods from extreme value theory (EVT) to maximum daily 8-hour average ozone (MDA8 O₃) observed by the Clean Air Status and Trends Network (CASTNet) and define O₃ extremes as days on which MDA8 O₃ exceeds a threshold of 75 ppb (MDA8 O₃>75). Over the eastern US, we find that the number of summer days with MDA8 O₃>75 declined on average by about a factor of two from 1988–1998 to 1999–2009. The applied generalized Pareto distribution (GPD) fits the high tail of MDA8 O₃ much better than a Gaussian distribution and enables the derivation of probabilistic return levels (describing the probability of exceeding a value x within a time window T) for high O₃ pollution events. This new approach confirms the significant decline in both frequency and magnitude of high O₃ pollution events over the eastern US during recent years reported in prior studies. Our analysis of 1-yr and 5-yr return levels at each station demonstrates the strong impact of changes in air quality regulations and subsequent control measures (e.g., the 'NOₓ SIP Call'), as the 5-yr return levels of the period 1999–2009 correspond roughly to the 1-yr return levels of the earlier time period (1988–1998). Regionally, the return levels dropped between 1988–1998 and 1999–2009 by about 8 ppb in the Mid-Atlantic (MA) and Great Lakes (GL) regions, while the strongest decline, about 13 ppb, is observed in the Northeast (NE) region. Nearly all stations (21 out of 23) have 1-yr return levels well below 100 ppb and 5-yr return levels well below 110 ppb in 1999–2009. Decreases in eastern US O₃ pollution are largest after full implementation of the nitrogen oxide (NOₓ) reductions under the 'NOₓ SIP Call'. We conclude that the application of EVT methods provides a useful approach for quantifying return levels of high O₃ pollution in probabilistic terms, which may help to guide long-term air quality planning

Local and Remote Mean and Extreme Temperature Response to Regional Aerosol Emissions Reductions

The climatic implications of regional aerosol and precursor emissions reductions implemented to protect human health are poorly understood. We investigate the mean and extreme temperature response to regional changes in aerosol emissions using three coupled chemistryclimate models: NOAA GFDL CM3, NCAR CESM1, and NASA GISS-E2. Our approach contrasts a long present-day control simulation from each model (up to 400 years with perpetual year 2000 or 2005 emissions) with 14 individual aerosol emissions perturbation simulations (160240 years each). We perturb emissions of sulfur dioxide (SO2) and/or carbonaceous aerosol within six world regions and assess the statistical significance of mean and extreme temperature responses relative to internal variability determined by the control simulation and across the models. In all models, the global mean surface temperature response (perturbation minus control) to SO2 and/or carbonaceous aerosol is mostly positive (warming) and statistically significant and ranges from +0.17 K (Europe SO2) to -0.06 K (US BC). The warming response to SO2 reductions is strongest in the US and Europe perturbation simulations, both globally and regionally, with Arctic warming up to 1 K due to a removal of European anthropogenic SO2 emissions alone; however, even emissions from regions remote to the Arctic, such as SO2 from India, significantly warm the Arctic by up to 0.5 K. Arctic warming is the most robust response across each model and several aerosol emissions perturbations. The temperature response in the Northern Hemisphere midlatitudes is most sensitive to emissions perturbations within that region. In the tropics, however, the temperature response to emissions perturbations is roughly the same in magnitude as emissions perturbations either within or outside of the tropics. We find that climate sensitivity to regional aerosol perturbations ranges from 0.5 to 1.0 K (W m(exp -2))(exp -1) depending on the region and aerosol composition and is larger than the climate sensitivity to a doubling of CO2 in two of three models. We update previous estimates of regional temperature potential (RTP), a metric for estimating the regional temperature responses to a regional emissions perturbation that can facilitate assessment of climate impacts with integrated assessment models without requiring computationally demanding coupled climate model simulations. These calculations indicate a robust regional response to aerosol forcing within the Northern Hemisphere midlatitudes, regardless of where the aerosol forcing is located longitudinally. We show that regional aerosol perturbations can significantly increase extreme temperatures on the regional scale. Except in the Arctic in the summer, extreme temperature responses largely mirror mean temperature responses to regional aerosol perturbations through a shift of the temperature distributions and are mostly dominated by local rather than remote aerosol forcing

Climate versus emission drivers of methane lifetime against loss by tropospheric OH from 1860–2100

With a more-than-doubling in the atmospheric abundance of the potent greenhouse gas methane (CH₄) since preindustrial times, and indications of renewed growth following a leveling off in recent years, questions arise as to future trends and resulting climate and public health impacts from continued growth without mitigation. Changes in atmospheric methane lifetime are determined by factors which regulate the abundance of OH, the primary methane removal mechanism, including changes in CH₄ itself. We investigate the role of emissions of short-lived species and climate in determining the evolution of methane lifetime against loss by tropospheric OH, (τCH₄_OH), in a suite of historical (1860–2005) and future Representative Concentration Pathway (RCP) simulations (2006–2100), conducted with the Geophysical Fluid Dynamics Laboratory (GFDL) fully coupled chemistry-climate model (CM3). From preindustrial to present, CM3 simulates an overall 5% increase in τCH₄_OH due to a doubling of the methane burden which offsets coincident increases in nitrogen oxide (NOx emissions. Over the last two decades, however, the τCH₄_OH declines steadily, coinciding with the most rapid climate warming and observed slow-down in CH₄ growth rates, reflecting a possible negative feedback through the CH₄ sink. Sensitivity simulations with CM3 suggest that the aerosol indirect effect (aerosol-cloud interactions) plays a significant role in cooling the CM3 climate. The projected decline in aerosols under all RCPs contributes to climate warming over the 21st century, which influences the future evolution of OH concentration and τCH₄_OH. Projected changes in τCH₄_OH from 2006 to 2100 range from −13% to +4%. The only projected increase occurs in the most extreme warming case (RCP8.5) due to the near-doubling of the CH₄ abundance, reflecting a positive feedback on the climate system. The largest decrease occurs in the RCP4.5 scenario due to changes in short-lived climate forcing agents which reinforce climate warming and enhance OH. This decrease is more-than-halved in a sensitivity simulation in which only well-mixed greenhouse gas radiative forcing changes along the RCP4.5 scenario (5% vs. 13%)

Air mass factor formulation for spectroscopic measurements from satellites: Application to formaldehyde retrievals from the Global Ozone Monitoring Experiment

Abstract. We present a new formulation for the air mass factor (AMF) to convert slant column measurements of optically thin atmospheric species from space into total vertical columns. Because of atmospheric scattering, the AMF depends on the vertical distribution of the species. We formulate the AMF as the integral of the relative vertical distribution (shape factor) of the species over the depth of the atmosphere, weighted by altitudedependent coefficients (scattering weights) computed independently from a radiative transfer model. The scattering weights are readily tabulated, and one can then obtain the AMF for any observation scene by using shape factors from a three dimensional (3-D) atmospheric chemistry model for the period of observation. This approach subsequently allows objective evaluation of the 3-D model with the observed vertical columns, since the shape factor and the vertical column in the model represent two independent pieces of information. We demonstrate the AMF method by using slant column measurements of formaldehyde at 346 nm from the Global Ozone Monitoring Experiment satellite instrument over North America during July 1996. Shape factors are computed with the Global Earth Observing System CHEMistry (GEOS-CHEM) global 3-D model and are checked for consistency with the few available aircraft measurements. Scattering weights increase by an order of magnitude from the surface to the upper troposphere. The AMFs are typically 20-40 % less over continents than over the oceans and are approximately half the values calculated in the absence of scattering. Model-induced errors in the AMF are estimated to be • 10%. The GEOS-CHEM model captures 50 % and 60 % of the variances in the observed slant and vertical columns, respectively. Comparison of the simulated and observed vertical columns allows assessment of model bias. 1

Using satellite observed formaldehyde (HCHO) and nitrogen dioxide (NO2) as an indicator of ozone sensitivity in a SIP

Although State Implementation Plans (SIPs) typically rely on observations from ground-based networks and regulatory models, satellite data is increasingly available to state agencies and can also inform and supplement state implementation plans to improve air quality. An advantage of satellite data is that it provides information for a broader area than sampled by ground-based networks. This document provides examples and guidance for using satellite products of formaldehyde (HCHO) and nitrogen dioxide (NO2) to inform ground-level ozone sensitivity to emissions of nitrogen oxides (NOx) versus volatile organic compounds (VOC) in state implementation plans. Analysis of changes in ozone sensitivity over periods where emission controls have been implemented can provide insights into the efficacy of those past strategies and the likely efficacy of proposed future emission control programs

Decadal changes in summertime reactive oxidized nitrogen and surface ozone over the Southeast United States

Widespread efforts to abate ozone (O3) smog have significantly reduced emissions of nitrogen oxides (NOx) over the past 2 decades in the Southeast US, a place heavily influenced by both anthropogenic and biogenic emissions. How reactive nitrogen speciation responds to the reduction in NOx emissions in this region remains to be elucidated. Here we exploit aircraft measurements from ICARTT (July–August 2004), SENEX (June–July 2013), and SEAC4RS (August–September 2013) and long-term ground measurement networks alongside a global chemistry–climate model to examine decadal changes in summertime reactive oxidized nitrogen (RON) and ozone over the Southeast US. We show that our model can reproduce the mean vertical profiles of major RON species and the total (NOy) in both 2004 and 2013. Among the major RON species, nitric acid (HNO3) is dominant (∼ 42–45%), followed by NOx (31%), total peroxy nitrates (ΣPNs; 14%), and total alkyl nitrates (ΣANs; 9–12%) on a regional scale. We find that most RON species, including NOx, ΣPNs, and HNO3, decline proportionally with decreasing NOx emissions in this region, leading to a similar decline in NOy. This linear response might be in part due to the nearly constant summertime supply of biogenic VOC emissions in this region. Our model captures the observed relative change in RON and surface ozone from 2004 to 2013. Model sensitivity tests indicate that further reductions of NOxemissions will lead to a continued decline in surface ozone and less frequent high-ozone events