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Peroxyacetyl nitrate (PAN) formed in the atmospheric oxidation of non-methane volatile organic compounds (NMVOCs) is the principal tropospheric reservoir for nitrogen oxide radicals (NOx = NO + NO2). PAN enables the transport and release of NOx 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 NOx is the dominant contributor to the observed PAN maximum in the free troposphere over the South Atlantic.

We use an ensemble of surface (EPA CSN, IMPROVE, SEARCH, AERONET), aircraft (SEAC4RS), and satellite (MODIS, MISR) observations over the southeast US during the summer–fall of 2013 to better understand aerosol sources in the region and the relationship between surface particulate matter (PM) and aerosol optical depth (AOD). The GEOS-Chem global chemical transport model (CTM) with 25 × 25 km2 resolution over North America is used as a common platform to interpret measurements of different aerosol variables made at different times and locations. Sulfate and organic aerosol (OA) are the main contributors to surface PM2.5 (mass concentration of PM finer than 2.5 μm aerodynamic diameter) and AOD over the southeast US. OA is simulated successfully with a simple parameterization, assuming irreversible uptake of low-volatility products of hydrocarbon oxidation. Biogenic isoprene and monoterpenes account for 60 % of OA, anthropogenic sources for 30 %, and open fires for 10 %. 60 % of total aerosol mass is in the mixed layer below 1.5 km, 25 % in the cloud convective layer at 1.5–3 km, and 15 % in the free troposphere above 3 km. This vertical profile is well captured by GEOS-Chem, arguing against a high-altitude source of OA. The extent of sulfate neutralization (f = [NH4+]/(2[SO42−] + [NO3−]) is only 0.5–0.7 mol mol−1 in the observations, despite an excess of ammonia present, which could reflect suppression of ammonia uptake by OA. This would explain the long-term decline of ammonium aerosol in the southeast US, paralleling that of sulfate. The vertical profile of aerosol extinction over the southeast US follows closely that of aerosol mass. GEOS-Chem reproduces observed total column aerosol mass over the southeast US within 6 %, column aerosol extinction within 16 %, and space-based AOD within 8–28 % (consistently biased low). The large AOD decline observed from summer to winter is driven by sharp declines in both sulfate and OA from August to October. These declines are due to shutdowns in both biogenic emissions and UV-driven photochemistry. Surface PM2.5 shows far less summer-to-winter decrease than AOD and we attribute this in part to the offsetting effect of weaker boundary layer ventilation. The SEAC4RS aircraft data demonstrate that AODs measured from space are consistent with surface PM2.5. This implies that satellites can be used reliably to infer surface PM2.5 over monthly timescales if a good CTM representation of the aerosol vertical profile is available.

Atmospheric deposition of Hg(II) represents a major input of mercury to surface environments. The phase of Hg(II) (gas or particle) has important implications for deposition. We use long-term observations of reactive gaseous mercury (RGM, the gaseous component of Hg(II)), particle-bound mercury (PBM, the particulate component of Hg(II)), fine particulate matter (PM2.5), and temperature (T) at five sites in North America to derive an empirical gas-particle partitioning relationship log10(K−1) = (10±1)–(2500±300)/T where K = (PBM/PM2.5)/RGM with PBM and RGM in common mixing ratio units, PM2.5 in μg m−3, and T in K. This relationship is within the range of previous work but is based on far more extensive data from multiple sites. We implement this empirical relationship in the GEOS-Chem global 3-D Hg model to partition Hg(II) between the gas and particle phases. The resulting gas-phase fraction of Hg(II) ranges from over 90 % in warm air with little aerosol to less than 10 % in cold air with high aerosol. Hg deposition to high latitudes increases because of more efficient scavenging of particulate Hg(II) by precipitating snow. Model comparison to Hg observations at the North American surface sites suggests that subsidence from the free troposphere (warm air, low aerosol) is a major factor driving the seasonality of RGM, while elevated PBM is mostly associated with high aerosol loads. Simulation of RGM and PBM at these sites is improved by including fast in-plume reduction of Hg(II) emitted from coal combustion and by assuming that anthropogenic particulate Hg(p) behaves as semi-volatile Hg(II) rather than as a refractory particulate component. We improve the simulation of Hg wet deposition fluxes in the US relative to a previous version of GEOS-Chem; this largely reflects independent improvement of the washout algorithm. The observed wintertime minimum in wet deposition fluxes is attributed to inefficient snow scavenging of gas-phase Hg(II).

Acetone is one of the most abundant carbonyl compounds in the atmosphere and it plays an important role in atmospheric chemistry. The role of the ocean in the global atmospheric acetone budget is highly uncertain, with past studies reaching opposite conclusions as to whether the ocean is a source or sink. Here we use a global 3‐D chemical transport model (GEOS‐Chem) simulation of atmospheric acetone to evaluate the role of air‐sea exchange in the global budget. Inclusion of updated (slower) photolysis loss in the model means that a large net ocean source is not needed to explain observed acetone in marine air. We find that a simulation with a fixed seawater acetone concentration of 15 nM based on observations can reproduce the observed global patterns of atmospheric concentrations and air‐sea fluxes. The Northern Hemisphere oceans are a net sink for acetone while the tropical oceans are a net source. On a global scale the ocean is in near‐equilibrium with the atmosphere. Prescribing an ocean concentration of acetone as a boundary condition in the model assumes that ocean concentrations are controlled by internal production and loss, rather than by air‐sea exchange. An implication is that the ocean plays a major role in controlling atmospheric acetone. This hypothesis needs to be tested by better quantification of oceanic acetone sources and sinks. Key Points We updated the global atmospheric acetone budget using a global model We can reproduce observed marine atmospheric concentrations and air‐sea fluxes The ocean plays a major role in controlling atmospheric acetone

We estimate future area burned in the Alaskan and Canadian forest by the mid-century (2046–2065) based on the simulated meteorology from 13 climate models under the A1B scenario. We develop ecoregion-dependent regressions using observed relationships between annual total area burned and a suite of meteorological variables and fire weather indices, and apply these regressions to the simulated meteorology. We find that for Alaska and western Canada, almost all models predict significant (p < 0.05) increases in area burned at the mid-century, with median values ranging from 150 to 390 %, depending on the ecoregion. Such changes are attributed to the higher surface air temperatures and 500 hPa geopotential heights relative to present day, which together lead to favorable conditions for wildfire spread. Elsewhere the model predictions are not as robust. For the central and southern Canadian ecoregions, the models predict increases in area burned of 45–90 %. Except for the Taiga Plain, where area burned decreases by 50 %, no robust trends are found in northern Canada, due to the competing effects of hotter weather and wetter conditions there. Using the GEOS-Chem chemical transport model, we find that changes in wildfire emissions alone increase mean summertime surface ozone levels by 5 ppbv for Alaska, 3 ppbv for Canada, and 1 ppbv for the western US by the mid-century. In the northwestern US states, local wildfire emissions at the mid-century enhance surface ozone by an average of 1 ppbv, while transport of boreal fire pollution further degrades ozone air quality by an additional 0.5 ppbv. The projected changes in wildfire activity increase daily summertime surface ozone above the 95th percentile by 1 ppbv in the northwestern US, 5 ppbv in the high latitudes of Canada, and 15 ppbv in Alaska, suggesting a greater frequency of pollution episodes in the future atmosphere.

We use observations from the April 2008 NASA ARCTAS aircraft campaign to the North American Arctic, interpreted with a global 3-D chemical transport model (GEOS-Chem), to better understand the sources and cycling of hydrogen oxide radicals (HOx≡H+OH+peroxy radicals) and their reservoirs (HOy≡HOx+peroxides) in the springtime Arctic atmosphere. We find that a standard gas-phase chemical mechanism overestimates the observed HO2 and H2O2 concentrations. Computation of HOx and HOy gas-phase chemical budgets on the basis of the aircraft observations also indicates a large missing sink for both. We hypothesize that this could reflect HO2 uptake by aerosols, favored by low temperatures and relatively high aerosol loadings, through a mechanism that does not produce H2O2. We implemented such an uptake of HO2 by aerosol in the model using a standard reactive uptake coefficient parameterization with γ(HO2) values ranging from 0.02 at 275 K to 0.5 at 220 K. This successfully reproduces the concentrations and vertical distributions of the different HOx species and HOy reservoirs. HO2 uptake by aerosol is then a major HOx and HOy sink, decreasing mean OH and HO2 concentrations in the Arctic troposphere by 32% and 31% respectively. Better rate and product data for HO2 uptake by aerosol are needed to understand this role of aerosols in limiting the oxidizing power of the Arctic atmosphere.

We evaluate the GEOS-Chem atmospheric transport model (v8-02-01) of CO2 over 2003-2006, driven by GEOS-4 and GEOS-5 meteorology from the NASA Goddard Global Modeling and Assimilation Office, using surface, aircraft and space-borne concentration measurements of CO2 . We use an established ensemble Kalman Filter to estimate a posteriori biospheric+biomass burning (BS + BB) and oceanic (OC) CO2 fluxes from 22 geographical regions, following the TransCom-3 protocol, using boundary layer CO2 data from a subset of GLOBALVIEW surface sites. Global annual net BS + BB + OC CO2 fluxes over 2004-2006 for GEOS-4 (GEOS-5) meteorology are -4.4 ± 0.9 (-4.2 ± 0.9), -3.9 ± 0.9 (-4.5 ± 0.9), and -5.2 ± 0.9 (-4.9 ± 0.9) PgC yr-1 , respectively. After taking into account anthropogenic fossil fuel and bio-fuel emissions, the global annual net CO2 emissions for 2004-2006 are estimated to be 4.0 ± 0.9 (4.2 ± 0.9), 4.8 ± 0.9 (4.2 ± 0.9), and 3.8 ± 0.9 (4.1 ± 0.9) PgC yr-1 , respectively. The estimated 3-yr total net emission for GEOS-4 (GEOS-5) meteorology is equal to 12.5 (12.4) PgC, agreeing with other recent top-down estimates (12-13 PgC). The regional a posteriori fluxes are broadly consistent in the sign and magnitude of the TransCom-3 study for 1992-1996, but we find larger net sinks over northern and southern continents. We find large departures from our a priori over Europe during summer 2003, over temperate Eurasia during 2004, and over North America during 2005, reflecting an incomplete description of terrestrial carbon dynamics. We find GEOS-4 (GEOS-5) a posteriori CO2 concentrations reproduce the observed surface trend of 1.91-2.43 ppm yr-1 (parts per million per year), depending on latitude, within 0.15 ppm yr-1 (0.2 ppm yr-1 ) and the seasonal cycle within 0.2 ppm (0.2 ppm) at all latitudes. We find the a posteriori model reproduces the aircraft vertical profile measurements of CO2 over North America and Siberia generally within 1.5 ppm in the free and upper troposphere but can be biased by up to 4-5 ppm in the boundary layer at the start and end of the growing season. The model has a small negative bias in the free troposphere CO2 trend (1.95-2.19 ppm yr-1 ) compared to AIRS data which has a trend of 2.21-2.63 ppm yr-1 during 2004-2006, consistent with surface data. Model CO2 concentrations in the upper troposphere, evaluated using CONTRAIL (Comprehensive Observation Network for TRace gases by AIrLiner) aircraft measurements, reproduce the magnitude and phase of the seasonal cycle of CO2 in both hemispheres. We generally find that the GEOS meteorology reproduces much of the observed tropospheric CO2 variability, suggesting that these meteorological fields will help make significant progress in understanding carbon fluxes as more data become available.

New particle formation contributes significantly to the number concentration of condensation nuclei (CN) as well as cloud CN (CCN), a key factor determining aerosol indirect radiative forcing of the climate system. Using a physics-based nucleation mechanism that is consistent with a range of field observations of aerosol formation, it is shown that projected increases in global temperatures could significantly inhibit new particle, and CCN, formation rates worldwide. An analysis of CN concentrations observed at four NOAA ESRL/GMD baseline stations since the 1970s and two other sites since 1990s reveals long-term decreasing trends that are consistent in sign with, but are larger in magnitude than, the predicted temperature effects. The possible reasons for larger observed long-term CN reductions at remote sites are discussed. The combined effects of rising temperatures on aerosol nucleation rates and other chemical and microphysical processes may imply substantial decreases in future tropospheric particle abundances associated with global warming, delineating a potentially significant feedback mechanism that increases Earth's climate sensitivity to greenhouse gas emissions. Further research is needed to quantify the magnitude of such a feedback process.

The use of global three-dimensional (3-D) models with satellite observations of CO2 in inverse modeling studies is an area of growing importance for understanding Earth's carbon cycle. Here we use the GEOS-Chem model (version 8-02-01) CO2 mode with multiple modifications in order to assess their impact on CO2 forward simulations. Modifications include CO2 surface emissions from shipping (~0.19 Pg C yr-1 ), 3-D spatially-distributed emissions from aviation (~0.16 Pg C yr-1 ), and 3-D chemical production of CO2 (~1.05 Pg C yr-1 ). Although CO2 chemical production from the oxidation of CO, CH4 and other carbon gases is recognized as an important contribution to global CO2 , it is typically accounted for by conversion from its precursors at the surface rather than in the free troposphere. We base our model 3-D spatial distribution of CO2 chemical production on monthly-averaged loss rates of CO (a key precursor and intermediate in the oxidation of organic carbon) and apply an associated surface correction for inventories that have counted emissions of CO2 precursors as CO2 . We also explore the benefit of assimilating satellite observations of CO into GEOS-Chem to obtain an observation-based estimate of the CO2 chemical source. The CO assimilation corrects for an underestimate of atmospheric CO abundances in the model, resulting in increases of as much as 24% in the chemical source during May-June 2006, and increasing the global annual estimate of CO2 chemical production from 1.05 to 1.18 Pg C. Comparisons of model CO2 with measurements are carried out in order to investigate the spatial and temporal distributions that result when these new sources are added. Inclusion of CO2 emissions from shipping and aviation are shown to increase the global CO2 latitudinal gradient by just over 0.10 ppm (~3%), while the inclusion of CO2 chemical production (and the surface correction) is shown to decrease the latitudinal gradient by about 0.40 ppm (~10%) with a complex spatial structure generally resulting in decreased CO2 over land and increased CO2 over the oceans. Since these CO2 emissions are omitted or misrepresented in most inverse modeling work to date, their implementation in forward simulations should lead to improved inverse modeling estimates of terrestrial biospheric fluxes.

Methyl hydroperoxide (MHP) is produced by the CH3O2 + HO2 reaction in the oxidation cascade of volatile organic compounds (VOCs). During KORUS‐AQ (May–June 2016), aircraft observations over Seoul using chemical ionization mass spectrometry reported MHP concentrations exceeding 1 ppb in the planetary boundary layer, four times higher than simulated by the GEOS‐Chem atmospheric chemistry model. We show that this discrepancy can be explained in part by the instrument's positive interference from methanediol (MD) under high‐humidity conditions, where MD is produced in clouds by formaldehyde hydration. Including MD chemistry in GEOS‐Chem increases the global formic acid source by 11% but has otherwise minimal impact on the model chemistry. Observed MHP concentrations in the dry free troposphere are much less sensitive to MD interference and vary with the branching ratio of the CH3O2 reaction with HO2 versus NO, supporting current understanding of low‐NO and high‐NO chemical regimes for VOC oxidation.