Tropospheric nitrogen dioxide from satellite measurements: SCIAMACHY limb/nadir matching and multi-instrument trend analysis

Tropospheric NO2, a key air pollutant particularly in cities, has been measured from space since the mid-1990s by the GOME, SCIAMACHY, OMI, and GOME-2 instruments. These data provide a unique global long-term dataset of tropospheric pollution. The focus of this thesis is twofold: When these satellite measurements are to be used for assessing tropospheric emissions and pollution, it is necessary to separate the stratospheric from the tropospheric signal. This thesis develops a new unique technique for this separation by using the measurements performed by SCIAMACHY in limb geometry. The stratospheric NO2 measurements from SCIAMACHY are shown to be in very good agreement with NO2 fields modeled by the Oslo CTM2. However, both stratospheric datasets need to be adjusted to the level of the nadir measurements, because a time- and latitude-dependent bias to the measured nadir columns can be observed over clean regions. By combining measurements of total and stratospheric air masses taken by the same instrument, the uncertainties commonly introduced by unjustified assumptions and spatial averaging and smoothing can be significantly reduced, leading to the best dataset of tropospheric NO2 slant columns currently available. The tropospheric columns can then be used to assess the level of air pollution on a regional and even local scale. However, the observations of the four instruments differ in spatial resolution, local time of measurement, viewing geometry, and other details, and all these factors can severely impact the retrieved NO2 columns. Therefore, the analysis of temporal changes in troposheric NO2 abundances using these measurements is challenging and not straightforward. In the second part of this thesis, several methods to account for these instrumental differences are developed and applied to the analysis of trends in tropospheric NO2 columns over megacities. The first method is based on spatial averaging of the measured SCIAMACHY earthshine spectra and extraction of a spatial pattern of the resolution effect. Furthermore, two empirical corrections, which summarize all instrumental differences by including instrument-dependent offsets in a fitted trend function, are developed. These methods are applied to data from GOME and SCIAMACHY separately, to the combined time series, and to an extended dataset comprising also OMI and GOME-2 measurements. All approaches show consistent trends of tropospheric NO2 for a selection of areas on both regional and city scales, for the first time allowing consistent trend analysis of the full time series at high spatial resolution. Measured tropospheric NO2 columns have been strongly increasing over China, the Middle East, and India, with values over east-central China tripling from 1996 to 2011. All parts of the developed world, including Western Europe, the United States, and Japan, show significantly decreasing NO2 amounts in the same time period. On a megacity level, individual trends can be as large as 27.2 ± 3.9 % / yr and 20.7 ± 1.9 % / yr in Dhaka and Baghdad, respectively, while Los Angeles shows a very strong decrease of −6.00 ± 0.72 % / yr. Most megacities in China, India, and the Middle East show NO2 columns increasing by 5 to 10 % / yr, which leads to a doubling to tripling within the study period

Global deposition of total reactive nitrogen oxides from 1996 to 2014 constrained with satellite observations of NO2 columns

Reactive nitrogen oxides (NOy) are a major constituent of the nitrogen deposited from the atmosphere, but observational constraints on their deposition are limited by poor or nonexistent measurement coverage in many parts of the world. Here we apply NO2 observations from multiple satellite instruments (GOME, SCIAMACHY, and GOME-2) to constrain the global deposition of NOy over the last two decades. We accomplish this by producing top-down estimates of NOx emissions from inverse modeling of satellite NO2 columns over 1996–2014, and including these emissions in the GEOS-Chem chemical transport model to simulate chemistry, transport, and deposition of NOy. Our estimates of long-term mean wet nitrate (NO3−) deposition are highly consistent with available measurements in North America, Europe, and East Asia combined (r = 0.83, normalized mean bias = −7 %, N = 136). Likewise, our calculated trends in wet NO3− deposition are largely consistent with the measurements, with 129 of the 136 gridded model-data pairs sharing overlapping 95 % confidence intervals. We find that global mean NOy deposition over 1996–2014 is 56.0 Tg N yr−1, with a minimum in 2006 of 50.5 Tg N and a maximum in 2012 of 60.8 Tg N. Regional trends are large, with opposing signs in different parts of the world. Over 1996 to 2014, NOy deposition decreased by up to 60 % in eastern North America, doubled in regions of East Asia, and declined by 20 % in parts of Western Europe. About 40 % of the global NOy deposition occurs over oceans, with deposition to the North Atlantic Ocean declining and deposition to the northwestern Pacific Ocean increasing. Using the residual between NOx emissions and NOy deposition over specific land regions, we investigate how NOx export via atmospheric transport has changed over the last two decades. Net export from the continental United States decreased substantially, from 2.9 Tg N yr−1 in 1996 to 1.5 Tg N yr−1 in 2014. On the other hand, export from China more than tripled between 1996 and 2011 (from 1.0 Tg N yr−1 to 3.5 Tg N yr−1), before a striking decline to 2.5 Tg N yr−1 by 2014. We find that declines in NOx export from some Western European countries have counteracted increases in emissions from neighbouring countries to the east. A sensitivity study indicates that simulated NOy deposition is robust to uncertainties in NH3 emissions with a few exceptions. Our novel long-term study provides timely context on the rapid redistribution of atmospheric nitrogen transport and subsequent deposition to ecosystems around the world.https://www.atmos-chem-phys-discuss.net/acp-2016-1100/acp-2016-1100.pdfhttps://www.atmos-chem-phys-discuss.net/acp-2016-1100/acp-2016-1100.pdfhttps://www.atmos-chem-phys-discuss.net/acp-2016-1100/acp-2016-1100.pdfPublished versionPublished versio

Global deposition of total reactive nitrogen oxides from 1996 to 2014 constrained with satellite observations of NO2 columns

Reactive nitrogen oxides (NOy) are a major constituent of the nitrogen deposited from the atmosphere, but observational constraints on their deposition are limited by poor or nonexistent measurement coverage in many parts of the world. Here we apply NO2 observations from multiple satellite instruments (GOME, SCIAMACHY, and GOME-2) to constrain the global deposition of NOy over the last 2 decades. We accomplish this by producing top-down estimates of NOx emissions from inverse modeling of satellite NO2 columns over 1996–2014, and including these emissions in the GEOS-Chem chemical transport model to simulate chemistry, transport, and deposition of NOy. Our estimates of long-term mean wet nitrate (NO3−) deposition are highly consistent with available measurements in North America, Europe, and East Asia combined (r = 0.83, normalized mean bias  = −7%, N = 136). Likewise, our calculated trends in wet NO3− deposition are largely consistent with the measurements, with 129 of the 136 gridded model–data pairs sharing overlapping 95% confidence intervals. We find that global mean NOy deposition over 1996–2014 is 56.0TgNyr−1, with a minimum in 2006 of 50.5TgN and a maximum in 2012 of 60.8TgN. Regional trends are large, with opposing signs in different parts of the world. Over 1996 to 2014, NOy deposition decreased by up to 60% in eastern North America, doubled in regions of East Asia, and declined by 20% in parts of western Europe. About 40% of the global NOy deposition occurs over oceans, with deposition to the North Atlantic Ocean declining and deposition to the northwestern Pacific Ocean increasing. Using the residual between NOx emissions and NOy deposition over specific land regions, we investigate how NOx export via atmospheric transport has changed over the last 2 decades. Net export from the continental United States decreased substantially, from 2.9TgNyr−1 in 1996 to 1.5TgNyr−1 in 2014. Export from China more than tripled between 1996 and 2011 (from 1.0 to 3.5TgNyr−1), before a striking decline to 2.5TgNyr−1 by 2014. We find that declines in NOx export from some western European countries have counteracted increases in emissions from neighboring countries to the east. A sensitivity study indicates that simulated NOy deposition is robust to uncertainties in NH3 emissions with a few exceptions. Our novel long-term study provides timely context on the rapid redistribution of atmospheric nitrogen transport and subsequent deposition to ecosystems around the world.This work was supported by NSERC and Environment and Climate Change Canada. We acknowledge the free use of tropospheric NO2 column data from the GOME, SCIAMACHY, and GOME-2 sensors from www.temis.nl. We further acknowledge the NADP, CAPMoN, EMEP, and EANET regional monitoring networks as well as the World Data Centre for Precipitation Chemistry for access to wet deposition data. (NSERC; Environment and Climate Change Canada)https://www.atmos-chem-phys.net/17/10071/2017/acp-17-10071-2017.pdfhttps://www.atmos-chem-phys.net/17/10071/2017/acp-17-10071-2017.pdfhttps://www.atmos-chem-phys.net/17/10071/2017/acp-17-10071-2017.pdfPublished versionPublished versio

Stratosphere-troposphere separation of nitrogen dioxide columns from the TEMPO geostationary satellite instrument

Separating the stratospheric and tropospheric contributions in satellite retrievals of atmospheric NO2 column abundance is a crucial step in the interpretation and application of the satellite observations. A variety of stratosphere–troposphere separation algorithms have been developed for sun-synchronous instruments in low Earth orbit (LEO) that benefit from global coverage, including broad clean regions with negligible tropospheric NO2 compared to stratospheric NO2. These global sun-synchronous algorithms need to be evaluated and refined for forthcoming geostationary instruments focused on continental regions, which lack this global context and require hourly estimates of the stratospheric column. Here we develop and assess a spatial filtering algorithm for the upcoming TEMPO geostationary instrument that will target North America. Developments include using independent satellite observations to identify likely locations of tropospheric enhancements, using independent LEO observations for spatial context, consideration of diurnally varying partial fields of regard, and a filter based on stratospheric to tropospheric air mass factor ratios. We test the algorithm with LEO observations from the OMI instrument with an afternoon overpass, and from the GOME-2 instrument with a morning overpass. We compare our TEMPO field of regard algorithm against an identical global algorithm to investigate the penalty resulting from the limited spatial coverage in geostationary orbit, and find excellent agreement in the estimated mean daily tropospheric NO2 column densities (R2=0.999, slope=1.009 for July and R2=0.998, slope=0.999 for January). The algorithm performs well even when only small parts of the continent are observed by TEMPO. The algorithm is challenged the most by east coast morning retrievals in the wintertime (e.g., R2=0.995, slope=1.038 at 14:00 UTC). We find independent global LEO observations (corrected for time of day) provide important context near the field-of-regard edges. We also test the performance of the TEMPO algorithm without these supporting global observations. Most of the continent is unaffected (R2=0.924 and slope=0.973 for July and R2=0.996 and slope=1.008 for January), with 90 % of the pixels having differences of less than ±0.2×1015 molecules cm−2 between the TEMPO tropospheric NO2 column density and the global algorithm. For near-real-time retrieval, even a climatological estimate of the stratospheric NO2 surrounding the field of regard would improve this agreement. In general, the additional penalty of a limited field of regard from TEMPO introduces no more error than normally expected in most global stratosphere–troposphere separation algorithms. Overall, we conclude that hourly near-real-time stratosphere–troposphere separation for the retrieval of NO2 tropospheric column densities by the TEMPO geostationary instrument is both feasible and robust, regardless of the diurnally varying limited field of regard.The authors are grateful to Kelly Chance, Xiong Liu, John Houck, Peter Zoogman, and other members of the TEMPO trace gas retrieval team for their input in preparation of this paper. Work at Dalhousie University was supported by Environment and Climate Change Canada. The authors also gratefully acknowledge the free use of TEMIS NO2 data from the GOME-2 sensor provided by http://www.temis.nl, last access: 12 November 2018, and the NASA Standard Product NO2 data from OMI provided by https://disc.gsfc.nasa.gov/datasets/OMNO2_V003/summary, last access: 9 November 2018. (Environment and Climate Change Canada)https://www.atmos-meas-tech.net/11/6271/2018/Published versio

Why do models overestimate surface ozone in the Southeast United States

Ozone pollution in the Southeast US involves complex chemistry driven by emissions of anthropogenic nitrogen oxide radicals (NOx  ≡  NO + NO2) and biogenic isoprene. Model estimates of surface ozone concentrations tend to be biased high in the region and this is of concern for designing effective emission control strategies to meet air quality standards. We use detailed chemical observations from the SEAC4RS aircraft campaign in August and September 2013, interpreted with the GEOS-Chem chemical transport model at 0.25°  ×  0.3125° horizontal resolution, to better understand the factors controlling surface ozone in the Southeast US. We find that the National Emission Inventory (NEI) for NOx from the US Environmental Protection Agency (EPA) is too high. This finding is based on SEAC4RS observations of NOx and its oxidation products, surface network observations of nitrate wet deposition fluxes, and OMI satellite observations of tropospheric NO2 columns. Our results indicate that NEI NOx emissions from mobile and industrial sources must be reduced by 30–60 %, dependent on the assumption of the contribution by soil NOx emissions. Upper-tropospheric NO2 from lightning makes a large contribution to satellite observations of tropospheric NO2 that must be accounted for when using these data to estimate surface NOx emissions. We find that only half of isoprene oxidation proceeds by the high-NOx pathway to produce ozone; this fraction is only moderately sensitive to changes in NOx emissions because isoprene and NOx emissions are spatially segregated. GEOS-Chem with reduced NOx emissions provides an unbiased simulation of ozone observations from the aircraft and reproduces the observed ozone production efficiency in the boundary layer as derived from a regression of ozone and NOx oxidation products. However, the model is still biased high by 6 ± 14 ppb relative to observed surface ozone in the Southeast US. Ozonesondes launched during midday hours show a 7 ppb ozone decrease from 1.5 km to the surface that GEOS-Chem does not capture. This bias may reflect a combination of excessive vertical mixing and net ozone production in the model boundary layer

Interannual variability of tropospheric composition:the influence of changes in emissions, meteorology and clouds

We have run a chemistry transport model (CTM) to systematically examine the drivers of interannual variability of tropospheric composition during 1996-2000. This period was characterised by anomalous meteorological conditions associated with the strong El Nino of 1997-1998 and intense wildfires, which produced a large amount of pollution. On a global scale, changing meteorology (winds, temperatures, humidity and clouds) is found to be the most important factor driving interannual variability of NO2 and ozone on the timescales considered. Changes in stratosphere-troposphere exchange, which are largely driven by meteorological variability, are found to play a particularly important role in driving ozone changes. The strong influence of emissions on NO2 and ozone interannual variability is largely confined to areas where intense biomass burning events occur. For CO, interannual variability is almost solely driven by emission changes, while for OH meteorology dominates, with the radiative influence of clouds being a very strong contributor. Through a simple attribution analysis for 1996-2000 we conclude that changing cloudiness drives 25% of the interannual variability of OH over Europe by affecting shortwave radiation. Over Indonesia this figure is as high as 71%. Changes in cloudiness contribute a small but non-negligible amount (up to 6%) to the interannual variability of ozone over Europe and Indonesia. This suggests that future assessments of trends in tropospheric oxidizing capacity should account for interannual variability in cloudiness, a factor neglected in many previous studies

Global inventory of nitrogen oxide emissions constrained by space-based observations of NO2 columns

sions (37.7 Tg N yr #1 ) agrees closely with the GEIAbased a priori (36.4) and with the EDGAR 3.0 bottom-up inventory (36.6), but there are significant regional differences. A posteriori NO x emissions are higher by 50 -- 100% in the Po Valley, Tehran, and Riyadh urban areas, and by 25 -- 35% in Japan and South Africa. Biomass burning emissions from India, central Africa, and Brazil are lower by up to 50%; soil NO x emissions are appreciably higher in the western United States, the Sahel, and southern Europe

Assessment of ozone photochemistry in the western North Pacific as inferred from PEM-West A observations during the fall 1991

This study examines the influence of photochemical processes on ozone distributions in the western North Pacific. The analysis is based on data generated during NASA's western Pacific Exploratory Mission (PEM-West A) during the fall of 1991. Ozone trends were best described in terms of two geographical domains: the western North Pacific rim (WNPR) and the western tropical North Pacific (WTNP). For both geographical regions, ozone photochemical destruction, D(O3), decreased more rapidly with altitude than did photochemical formation, F(O3). Thus the ozone tendency, P(O3), was typically found to be negative for z <6 km and positive for z > 6-8 km. For nearly all altitudes and latitudes, observed nonmethane hydrocarbon (NMHC) levels were shown to be of minor importance as ozone precursor species. Air parcel types producing the largest positive values of P(O3) included fresh continental boundary layer (BL) air and high-altitude (z > 7 km) parcels influenced by deep convection/lightning. Significant negative P(O3) values were found when encountering clean marine BL air or relatively clean lower free-tropospheric air. Photochemical destruction and formation fluxes for the Pacific rim region were found to exceed average values cited for marine dry deposition and stratospheric injection in the northern hemisphere by nearly a factor of 6. This region was also found to be in near balance with respect to column-integrated O3 photochemical production and destruction. By contrast, for the tropical regime column-integrated O3 showed photochemical destruction exceeding production by nearly 80%. Both transport of O3 rich midlatitude air into the tropics as well as very high-altitude (10-17 km) photochemical O3 production were proposed as possible additional sources that might explain this estimated deficit. Results from this study further suggest that during the fall time period, deep convection over Asia and Malaysia/Indonesia provided a significant source of high-altitude NOx to the western Pacific. Given that the high-altitude NOx lifetime is estimated at between 3 and 9 days, one would predict that this source added significantly to high altitude photochemical O3 formation over large areas of the western Pacific. When viewed in terms of strong seasonal westerly flow, its influence would potentially span a large part of the Pacific. Copyright 1996 by the American Geophysical Union