We use the adjoint of a global 3‐D chemical transport model (GEOS‐Chem) to optimize ammonia (NH3) emissions in the U.S., European Union, and China by inversion of 2005–2008 network data for NH4+ wet ...deposition fluxes. Optimized emissions are derived on a 2° × 2.5° grid for individual months and years. Error characterization in the optimization includes model errors in precipitation. Annual optimized emissions are 2.8 Tg NH3−N a−1 for the contiguous U.S., 3.1 Tg NH3−N a−1 for the European Union, and 8.4 Tg NH3−N a−1 for China. Comparisons to previous inventories for the U.S. and European Union show consistency (∼±15%) in annual totals but some large spatial and seasonal differences. We develop a new global bottom‐up inventory of NH3 emissions (Magnitude And Seasonality of Agricultural Emissions model for NH3 (MASAGE_NH3)) to interpret the results of the adjoint optimization. MASAGE_NH3 provides information on the magnitude and seasonality of NH3 emissions from individual crop and livestock sources on a 0.5° × 0.5° grid. We find that U.S. emissions peak in the spring in the Midwest due to corn fertilization and in the summer elsewhere due to manure. The seasonality of European emissions is more homogeneous with a well‐defined maximum in spring associated with manure and mineral fertilizer application. There is some evidence for the effect of European regulations of NH3 emissions, notably a large fall decrease in northern Europe. Emissions in China peak in summer because of the summertime application of fertilizer for double cropping.
Key Points
Adjoint‐based inversion of ammonium wet deposition in the U.S., Europe, and ChinaMuch larger spatial and temporal variability of U.S. emission than in the a prioriNew model of NH3 emissions reproduces the patterns of the optimized emissions
Stringent controls have reduced U.S. SO2 emissions by over 60% since the late 1990s. These controls have been more effective at reducing surface
SO42− in summer (June, July, and August) than in ...winter (December, January, and February (DJF)), a seasonal contrast that is not robustly captured by Climate Model Intercomparison Project 5 global models. We use the Geophysical Fluid Dynamics Laboratory AM3 chemistry‐climate model to show that oxidant limitation during winter causes
SO42− (DJF) to be sensitive to primary
SO42− emissions, in‐cloud titration of H2O2, and in‐cloud oxidation by O3. The observed contrast in the seasonal response of
SO42− to decreasing SO2 emissions is best explained by the O3 reaction, whose rate coefficient has increased over the past decades as a result of increasing NH3 emissions and decreasing SO2 emissions, both of which lower cloud water acidity. The fraction of SO2 oxidized to
SO42− is projected to keep increasing in future decades, delaying improvements in wintertime air quality.
Plain Language Summary
All observing stations in the Eastern US show that sulfate aerosols are decreasing more slowly in winter than in summer in response to sulfur dioxide emission reductions. We suggest that this seasonal contrast has a photochemical origin, namely the increase of the in‐cloud oxidation of sulfur dioxide by ozone (O3). This reaction is very sensitive to cloud pH and has only become important in recent years following the decrease of sulfur dioxide emissions (from fossil fuel) and the increase of ammonia emissions (from farming), both of which lower cloud acidity. Our model predicts that the ozone reaction could delay improvements in wintertime air quality from the continuing decrease of sulfur dioxide emissions.
Key Points
Observed weaker decline of sulfate in DJF than in JJA in response to SO2 emission controls in the U.S. is not well captured by CMIP5 models
This seasonal contrast results from faster in‐cloud oxidation of SO2 by ozone, promoted by diminishing cloud acidity
Anthropogenic ammonia indirectly reduces the effectiveness of SO2 emission controls in decreasing sulfate in winter
Peroxyacetyl nitrate (PAN) formed in the atmospheric oxidation of non-methane volatile organic compounds (NMVOCs) is the principal tropospheric reservoir for nitrogen oxide radicals (NO
= NO + NO
). ...PAN enables the transport and release of NO
to the remote troposphere with major implications for the global distributions of ozone and OH, the main tropospheric oxidants. Simulation of PAN is a challenge for global models because of the dependence of PAN on vertical transport as well as complex and uncertain NMVOC sources and chemistry. Here we use an improved representation of NMVOCs in a global 3-D chemical transport model (GEOS-Chem) and show that it can simulate PAN observations from aircraft campaigns worldwide. The immediate carbonyl precursors for PAN formation include acetaldehyde (44% of the global source), methylglyoxal (30 %), acetone (7 %), and a suite of other isoprene and terpene oxidation products (19 %). A diversity of NMVOC emissions is responsible for PAN formation globally including isoprene (37 %) and alkanes (14 %). Anthropogenic sources are dominant in the extratropical Northern Hemisphere outside the growing season. Open fires appear to play little role except at high northern latitudes in spring, although results are very sensitive to plume chemistry and plume rise. Lightning NO
is the dominant contributor to the observed PAN maximum in the free troposphere over the South Atlantic.
Formic acid (HCOOH) is one of the most abundant acids in the atmosphere, with an important influence on precipitation chemistry and acidity. Here we employ a chemical transport model (GEOS-Chem CTM) ...to interpret recent airborne and ground-based measurements over the US Southeast in terms of the constraints they provide on HCOOH sources and sinks. Summertime boundary layer concentrations average several parts-per-billion, 2-3 larger than can be explained based on known production and loss pathways. This indicates one or more large missing HCOOH sources, and suggests either a key gap in current understanding of hydrocarbon oxidation or a large, unidentified, direct flux of HCOOH. Model-measurement comparisons implicate biogenic sources (e.g., isoprene oxidation) as the predominant HCOOH source. Resolving the unexplained boundary layer concentrations based (i) solely on isoprene oxidation would require a 3 increase in the model HCOOH yield, or (ii) solely on direct HCOOH emissions would require approximately a 25 increase in its biogenic flux. However, neither of these can explain the high HCOOH amounts seen in anthropogenic air masses and in the free troposphere. The overall indication is of a large biogenic source combined with ubiquitous chemical production of HCOOH across a range of precursors. Laboratory work is needed to better quantify the rates and mechanisms of carboxylic acid production from isoprene and other prevalent organics. Stabilized Criegee intermediates (SCIs) provide a large model source of HCOOH, while acetaldehyde tautomerization accounts for ~ 15% of the simulated global burden. Because carboxylic acids also react with SCIs and catalyze the reverse tautomerization reaction, HCOOH buffers against its own production by both of these pathways. Based on recent laboratory results, reaction between CH3O2 and OH could provide a major source of atmospheric HCOOH; however, including this chemistry degrades the model simulation of CH3OOH and NOx : CH3OOH. Developing better constraints on SCI and RO2 + OH chemistry is a high priority for future work. The model neither captures the large diurnal amplitude in HCOOH seen in surface air, nor its inverted vertical gradient at night. This implies a substantial bias in our current representation of deposition as modulated by boundary layer dynamics, and may indicate an HCOOH sink underestimate and thus an even larger missing source. A more robust treatment of surface deposition is a key need for improving simulations of HCOOH and related trace gases, and our understanding of their budgets.
Current global inventories of ammonia emissions identify the ocean as the largest natural source. This source depends on seawater pH, temperature, and the concentration of total seawater ammonia ...(NHx(sw)), which reflects a balance between remineralization of organic matter, uptake by plankton, and nitrification. Here we compare NHx(sw) from two global ocean biogeochemical models (BEC and COBALT) against extensive ocean observations. Simulated NHx(sw) are generally biased high. Improved simulation can be achieved in COBALT by increasing the plankton affinity for NHx within observed ranges. The resulting global ocean emissions is 2.5 TgN a−1, much lower than current literature values (7–23 TgN a−1), including the widely used Global Emissions InitiAtive (GEIA) inventory (8 TgN a−1). Such a weak ocean source implies that continental sources contribute more than half of atmospheric NHx over most of the ocean in the Northern Hemisphere. Ammonia emitted from oceanic sources is insufficient to neutralize sulfate aerosol acidity, consistent with observations. There is evidence over the Equatorial Pacific for a missing source of atmospheric ammonia that could be due to photolysis of marine organic nitrogen at the ocean surface or in the atmosphere. Accommodating this possible missing source yields a global ocean emission of ammonia in the range 2–5 TgN a−1, comparable in magnitude to other natural sources from open fires and soils.
Key Points
New observational constraints on the ocean atmosphere ammonia flux
Ocean NH3 flux to the atmosphere is lower than previous estimates
Photolysis of organic N may contribute to the release of N from the ocean
Bidirectional air–surface exchange of ammonia (NH3) has been neglected in many air quality models. In this study, we implement the bidirectional exchange of NH3 in the GEOS-Chem global chemical ...transport model. We also introduce an updated diurnal variability scheme for NH3 livestock emissions and evaluate the recently developed MASAGE_NH3 bottom-up inventory. While updated diurnal variability improves comparison of modeled-to-hourly in situ measurements in the southeastern USA, NH3 concentrations decrease throughout the globe, up to 17 ppb in India and southeastern China, with corresponding decreases in aerosol nitrate by up to 7 μg m−3. The ammonium (NH4+) soil pool in the bidirectional exchange model largely extends the NH3 lifetime in the atmosphere. Including bidirectional exchange generally increases NH3 gross emissions (7.1 %) and surface concentrations (up to 3.9 ppb) throughout the globe in July, except in India and southeastern China. In April and October, it decreases NH3 gross emissions in the Northern Hemisphere (e.g., 43.6 % in April in China) and increases NH3 gross emissions in the Southern Hemisphere. Bidirectional exchange does not largely impact NH4+ wet deposition overall. While bidirectional exchange is fundamentally a better representation of NH3 emissions from fertilizers, emissions from primary sources are still underestimated and thus significant model biases remain when compared to in situ measurements in the USA. The adjoint of bidirectional exchange has also been developed for the GEOS-Chem model and is used to investigate the sensitivity of NH3 concentrations with respect to soil pH and fertilizer application rate. This study thus lays the groundwork for future inverse modeling studies to more directly constrain these physical processes rather than tuning bulk unidirectional NH3 emissions.
The ozone (O3) dry depositional sink and its contribution to observed variability in tropospheric O3 are both poorly understood. Distinguishing O3 uptake through plant stomata versus other pathways ...is relevant for quantifying the O3 influence on carbon and water cycles. We use a decade of O3, carbon, and energy eddy covariance (EC) fluxes at Harvard Forest to investigate interannual variability (IAV) in O3 deposition velocities (
vd,O3). In each month, monthly mean
vd,O3 for the highest year is twice that for the lowest. Two independent stomatal conductance estimates, based on either water vapor EC or gross primary productivity, vary little from year to year relative to canopy conductance. We conclude that nonstomatal deposition controls the substantial observed IAV in summertime
vd,O3 during the 1990s over this deciduous forest. The absence of obvious relationships between meteorology and
vd,O3 implies a need for additional long‐term, high‐quality measurements and further investigation of nonstomatal mechanisms.
Key Points
Observed factor of 2 in interannual variability (IAV) of ozone dry deposition velocities, dominated by nonstomatal processes
Stomatal conductance estimates from two observation‐driven independent models show similar but weak IAV
High‐quality, long‐term measurements needed to identify processes driving IAV in ozone dry deposition
Tropical tropospheric ozone affects Earth's radiative forcing and the oxidative capacity of the atmosphere. Considerable work has been devoted to the study of the processes controlling its budget. ...Yet, large discrepancies between simulated and observed tropical tropospheric ozone remain. Here, we characterize some of the mechanisms by which the photochemistry of isoprene impacts the budget of tropical ozone. At the regional scale, we use forward sensitivity simulation to explore the sensitivity to the representation of isoprene nitrates. We find that isoprene nitrates can account for up to 70% of the local NOx = NO+NO2 sink. The resulting modulation of ozone can be well characterized by their net modulation of NOx. We use adjoint sensitivity simulations to demonstrate that the oxidation of isoprene can affect ozone outside of continental regions through the transport of NOx over near-shore regions (e.g., South Atlantic) and the oxidation of isoprene outside of the boundary layer far from its emissions regions. The latter mechanism is promoted by the simulated low boundary-layer oxidative conditions. In our simulation, ~20% of the isoprene is oxidized above the boundary layer in the tropics. Changes in the interplay between regional and global effect are discussed in light of the forecasted increase in anthropogenic emissions in tropical regions.
Rapid Asian industrialization has led to increased downwind atmospheric nitrogen deposition threatening the marine environment. We present an analysis of the sources and processes controlling ...atmospheric nitrogen deposition to the northwestern Pacific, using the GEOS-Chem global chemistry model and its adjoint model at 1/2 degree 2/3 degree horizontal resolution over East Asia and its adjacent oceans. We focus our analyses on the marginal seas: the Yellow Sea and the South China Sea. Asian nitrogen emissions in the model are 28.6 Tg N a-1 as NH3 and 15.7 Tg N a-1 as NOx. China has the largest sources with 12.8 Tg N a-1 as NH3 and 7.9 Tg N a-1 as NOx; the high-NH3 emissions reflect its intensive agricultural activities. We find Asian NH3 emissions are a factor of 3 higher in summer than winter. The model simulation for 2008-2010 is evaluated with NH3 and NO2 column observations from satellite instruments, and wet deposition flux measurements from surface monitoring sites. Simulated atmospheric nitrogen deposition to the northwestern Pacific ranges 0.8-20 kg N ha-1 a-1, decreasing rapidly downwind of the Asian continent. Deposition fluxes average 11.9 kg N ha-1 a-1 (5.0 as reduced nitrogen NHx and 6.9 as oxidized nitrogen NOy) to the Yellow Sea, and 5.6 kg N ha-1 a-1 (2.5 as NHx and 3.1 as NOy) to the South China Sea. Nitrogen sources over the ocean (ship NOx and oceanic NH3) have little contribution to deposition over the Yellow Sea, about 7 % over the South China Sea, and become important (greater than 30 %) further downwind. We find that the seasonality of nitrogen deposition to the northwestern Pacific is determined by variations in meteorology largely controlled by the East Asian monsoon and in nitrogen emissions. The model adjoint further estimates that nitrogen deposition to the Yellow Sea originates from sources over China (92 % contribution) and the Korean peninsula (7 %), and by sectors from fertilizer use (24 %), power plants (22 %), and transportation (18 %). Deposition to the South China Sea shows source contribution from mainland China (66 %), Taiwan (20 %), and the rest (14 %) from the southeast Asian countries and oceanic NH3 emissions. The adjoint analyses also indicate that reducing Asian NH3 emissions would increase NOy dry deposition to the Yellow Sea (28 % offset annually), limiting the effectiveness of NH3 emission controls on reducing nitrogen deposition to the Yellow Sea.
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