Sensitivity of tropospheric oxidants to biomass burning emissions: implications for radiative forcing

Biomass burning is one of the largest sources of trace gases and aerosols to the atmosphere and has profound influence on tropospheric oxidants and radiative forcing. Using a fully coupled chemistry-climate model (GFDL AM3), we find that co-emission of trace gases and aerosol from present-day biomass burning increases the global tropospheric ozone burden by 5.1% and decreases global mean OH by 6.3%. Gas and aerosol emissions combine to increase CH4 lifetime nonlinearly. Heterogeneous processes are shown to contribute partly to the observed lower ΔO3/ΔCO ratios in northern high latitudes versus tropical regions. The radiative forcing from biomass burning is shown to vary nonlinearly with biomass burning strength. At present-day emission levels, biomass burning produces a net radiative forcing of −0.19 W/m2 (−0.29 from short-lived species, mostly aerosol direct and indirect effects, +0.10 from CH4- and CH4-induced changes in O3 and stratospheric H2O) but increases emissions to over 5 times present levels would result in a positive net forcing

Impact of preindustrial to present-day changes in short-lived pollutant emissions on atmospheric composition and climate forcing

We describe and evaluate atmospheric chemistry in the newly developed Geophysical Fluid Dynamics Laboratory chemistry-climate model (GFDL AM3) and apply it to investigate the net impact of preindustrial (PI) to present (PD) changes in short-lived pollutant emissions (ozone precursors, sulfur dioxide, and carbonaceous aerosols) and methane concentration on atmospheric composition and climate forcing. The inclusion of online troposphere-stratosphere interactions, gas-aerosol chemistry, and aerosol-cloud interactions (including direct and indirect aerosol radiative effects) in AM3 enables a more complete representation of interactions among short-lived species, and thus their net climate impact, than was considered in previous climate assessments. The base AM3 simulation, driven with observed sea surface temperature (SST) and sea ice cover (SIC) over the period 1981–2007, generally reproduces the observed mean magnitude, spatial distribution, and seasonal cycle of tropospheric ozone and carbon monoxide. The global mean aerosol optical depth in our base simulation is within 5% of satellite measurements over the 1982–2006 time period. We conduct a pair of simulations in which only the short-lived pollutant emissions and methane concentrations are changed from PI (1860) to PD (2000) levels (i.e., SST, SIC, greenhouse gases, and ozone-depleting substances are held at PD levels). From the PI to PD, we find that changes in short-lived pollutant emissions and methane have caused the tropospheric ozone burden to increase by 39% and the global burdens of sulfate, black carbon, and organic carbon to increase by factors of 3, 2.4, and 1.4, respectively. Tropospheric hydroxyl concentration decreases by 7%, showing that increases in OH sinks (methane, carbon monoxide, nonmethane volatile organic compounds, and sulfur dioxide) dominate over sources (ozone and nitrogen oxides) in the model. Combined changes in tropospheric ozone and aerosols cause a net negative top-of-the-atmosphere radiative forcing perturbation (−1.05 W m−2) indicating that the negative forcing (direct plus indirect) from aerosol changes dominates over the positive forcing due to ozone increases, thus masking nearly half of the PI to PD positive forcing from long-lived greenhouse gases globally, consistent with other current generation chemistry-climate models

Observational Constraints on Glyoxal Production from Isoprene Oxidation and Its Contribution to Organic Aerosol over the Southeast United States

We use a 0-D photochemical box model and a 3-D global chemistry-climate model, combined with observations from the NOAA Southeast Nexus (SENEX) aircraft campaign, to understand the sources and sinks of glyoxal over the Southeast United States. Box model simulations suggest a large difference in glyoxal production among three isoprene oxidation mechanisms (AM3ST, AM3B, and Master Chemical Mechanism (MCM) v3.3.1). These mechanisms are then implemented into a 3-D global chemistry-climate model. Comparison with field observations shows that the average vertical profile of glyoxal is best reproduced by AM3ST with an effective reactive uptake coefficient gamma(sub glyx) of 2 x 10(exp -3) and AM3B without heterogeneous loss of glyoxal. The two mechanisms lead to 0-0.8micrograms m(exp -3) secondary organic aerosol (SOA) from glyoxal in the boundary layer of the Southeast U.S. in summer. We consider this to be the lower limit for the contribution of glyoxal to SOA, as other sources of glyoxal other than isoprene are not included in our model. In addition, we find that AM3B shows better agreement on both formaldehyde and the correlation between glyoxal and formaldehyde (RGF[GLYX]/[HCHO]), resulting from the suppression of delta-isoprene peroxy radicals (delta-ISOPO2). We also find that MCM v3.3.1 may underestimate glyoxal production from isoprene oxidation, in part due to an underestimated yield from the reaction of isoprene epoxydiol (IEPOX) peroxy radicals with HO2. Our work highlights that the gas-phase production of glyoxal represents a large uncertainty in quantifying its contribution to SOA

Ozone and organic nitrates over the eastern United States: Sensitivity to isoprene chemistry

We implement a new isoprene oxidation mechanism in a global 3-D chemical transport model (GEOS-Chem). Model results are evaluated with observations for ozone, isoprene oxidation products, and related species from the International Consortium for Atmospheric Research on Transport and Transformation aircraft campaign over the eastern United States in summer 2004. The model achieves an unbiased simulation of ozone in the boundary layer and the free troposphere, reflecting canceling effects from recent model updates for isoprene chemistry, bromine chemistry, and HO2 loss to aerosols. Simulation of the ozone-CO correlation is improved relative to previous versions of the model, and this is attributed to a lower and reversible yield of isoprene nitrates, increasing the ozone production efficiency per unit of nitrogen oxides (NO_x ≡ NO + NO_2). The model successfully reproduces the observed concentrations of organic nitrates (∑ANs) and their correlations with HCHO and ozone. ∑ANs in the model is principally composed of secondary isoprene nitrates, including a major contribution from nighttime isoprene oxidation. The correlations of ∑ANs with HCHO and ozone then provide sensitive tests of isoprene chemistry and argue in particular against a fast isomerization channel for isoprene peroxy radicals. ∑ANs can provide an important reservoir for exporting NO_x from the U.S. boundary layer. We find that the dependence of surface ozone on isoprene emission is positive throughout the U.S., even if NO_x emissions are reduced by a factor of 4. Previous models showed negative dependences that we attribute to erroneous titration of OH by isoprene

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

HO_x chemistry during INTEX-A 2004: Observation, model calculation, and comparison with previous studies

OH and HO_2 were measured with the Airborne Tropospheric Hydrogen Oxides Sensor (ATHOS) as part of a large measurement suite from the NASA DC-8 aircraft during the Intercontinental Chemical Transport Experiment-A (INTEX-A). This mission, which was conducted mainly over North America and the western Atlantic Ocean in summer 2004, was an excellent test of atmospheric oxidation chemistry. The HOx results from INTEX-A are compared to those from previous campaigns and to results for other related measurements from INTEX-A. Throughout the troposphere, observed OH was generally 0.95 of modeled OH; below 8 km, observed HO_2 was generally 1.20 of modeled HO_2. This observed-to-modeled comparison is similar to that for TRACE-P, another midlatitude study for which the median observed-to-modeled ratio was 1.08 for OH and 1.34 for HO_2, and to that for PEM-TB, a tropical study for which the median observed-to-modeled ratio was 1.17 for OH and 0.97 for HO_2. HO_2 behavior above 8 km was markedly different. The observed-to-modeled HO_2 ratio increased from ∼1.2 at 8 km to ∼3 at 11 km with the observed-to-modeled ratio correlating with NO. Above 8 km, the observed-to-modeled HO_2 and observed NO were both considerably greater than observations from previous campaigns. In addition, the observed-to-modeled HO_2/OH, which is sensitive to cycling reactions between OH and HO_2, increased from ∼1.5 at 8 km to almost 3.5 at 11 km. These discrepancies suggest a large unknown HO_x source and additional reactants that cycle HO_x from OH to HO_2. In the continental planetary boundary layer, the observed-to-modeled OH ratio increased from 1 when isoprene was less than 0.1 ppbv to over 4 when isoprene was greater than 2 ppbv, suggesting that forests throughout the United States are emitting unknown HO_x sources. Progress in resolving these discrepancies requires a focused research activity devoted to further examination of possible unknown OH sinks and HO_x sources

HOx Observation and Model Comparison During INTEX-A 2004

OH and HO2 were measured with the Airborne Tropospheric Hydrogen Oxides Sensor (ATHOS) as part of a large measurement suite from the NASA DC-8 aircraft during the Intercontinental Chemical Transport Experiment - A (INTEX-A). This mission, which was conducted mainly over North America and the western Atlantic Ocean in summer 2004, was an excellent test of atmospheric oxidation chemistry. Throughout the troposphere, observed OH was generally 0.60 of the modeled OH; below 8 km, observed HO2 was generally 0.78 of modeled HO2. If the over-prediction of tropospheric OH is not due to an instrument calibration error, then it implied less global tropospheric oxidation capacity and longer lifetimes for gases like methane and methyl chloroform than currently thought. This discrepancy falls well outside uncertainties in both the OH measurement and rate coefficients for known reactions and points to a large unknown OH loss. If the modeled OH is forced to agree with observed values by introducing of an undefined OH loss that removed HOx (HOx=OH+HO2), the observed and modeled HO2 and HO2/OH ratios are largely reconciled within the measurement uncertainty. HO2 behavior above 8 km was markedly different. The observed-to-modeled ratio correlating with NO. The observed-to-modeled HO2 ratio increased from approximately 1 at 8 km to more than approximately 2.5 at 11 km with the observed-to-modeled ratio correlating with NO. The observed-to-modeled HO2 and NO were both considerably greater than observations from previous campaigns. In addition, the observed-to-modeled HO2/OH, which is sensitive to cycling reactions between OH and HO2, increased from approximately 1.2 at 8 km to almost 4 above 11 km. In contrast to the lower atmosphere, these discrepancies above 8 km suggest a large unknown HOx source and additional reactants that cycle HOx from OH to HO2. In the continental planetary boundary layer, the OH observed-to-modeled ratio increased from 0.6 when isoprene was less than 0.1 ppbv to over 3 when isoprene was greater than 2 ppbv, suggesting that forests throughout the United States are emitting unknown HOx sources. Progress in resolving these discrepancies requires further examinations of possible unknown OH sinks and HOx sources and a focused research activity devoted to ascertaining the accuracy of the OH and HO2 measurements

Can a “state of the art” chemistry transport model simulate Amazonian tropospheric chemistry?

We present an evaluation of a nested high-resolution Goddard Earth Observing System (GEOS)-Chem chemistry transport model simulation of tropospheric chemistry over tropical South America. The model has been constrained with two isoprene emission inventories: (1) the canopy-scale Model of Emissions of Gases and Aerosols from Nature (MEGAN) and (2) a leaf-scale algorithm coupled to the Lund-Potsdam-Jena General Ecosystem Simulator (LPJ-GUESS) dynamic vegetation model, and the model has been run using two different chemical mechanisms that contain alternative treatments of isoprene photo-oxidation. Large differences of up to 100 Tg C yr^(−1) exist between the isoprene emissions predicted by each inventory, with MEGAN emissions generally higher. Based on our simulations we estimate that tropical South America (30–85°W, 14°N–25°S) contributes about 15–35% of total global isoprene emissions. We have quantified the model sensitivity to changes in isoprene emissions, chemistry, boundary layer mixing, and soil NO_x emissions using ground-based and airborne observations. We find GEOS-Chem has difficulty reproducing several observed chemical species; typically hydroxyl concentrations are underestimated, whilst mixing ratios of isoprene and its oxidation products are overestimated. The magnitude of model formaldehyde (HCHO) columns are most sensitive to the choice of chemical mechanism and isoprene emission inventory. We find GEOS-Chem exhibits a significant positive bias (10–100%) when compared with HCHO columns from the Scanning Imaging Absorption Spectrometer for Atmospheric Chartography (SCIAMACHY) and Ozone Monitoring Instrument (OMI) for the study year 2006. Simulations that use the more detailed chemical mechanism and/or lowest isoprene emissions provide the best agreement to the satellite data, since they result in lower-HCHO columns

Organic nitrate chemistry and its implications for nitrogen budgets in an isoprene- and monoterpene-rich atmosphere: constraints from aircraft (SEAC4RS) and ground-based (SOAS) observations in the Southeast US

Formation of organic nitrates (RONO2) during oxidation of biogenic volatile organic compounds (BVOCs: isoprene, monoterpenes) is a significant loss pathway for atmospheric nitrogen oxide radicals (NOx), but the chemistry of RONO2 formation and degradation remains uncertain. Here we implement a new BVOC oxidation mechanism (including updated isoprene chemistry, new monoterpene chemistry, and particle uptake of RONO2) in the GEOS-Chem global chemical transport model with  ∼  25  x  25 km2 resolution over North America. We evaluate the model using aircraft (SEAC4RS) and ground-based (SOAS) observations of NOx, BVOCs, and RONO2 from the Southeast US in summer 2013. The updated simulation successfully reproduces the concentrations of individual gas- and particle-phase RONO2 species measured during the campaigns. Gas-phase isoprene nitrates account for 25-50 % of observed RONO2 in surface air, and we find that another 10 % is contributed by gas-phase monoterpene nitrates. Observations in the free troposphere show an important contribution from long-lived nitrates derived from anthropogenic VOCs. During both campaigns, at least 10 % of observed boundary layer RONO2 were in the particle phase. We find that aerosol uptake followed by hydrolysis to HNO3 accounts for 60 % of simulated gas-phase RONO2 loss in the boundary layer. Other losses are 20 % by photolysis to recycle NOx and 15 % by dry deposition. RONO2 production accounts for 20 % of the net regional NOx sink in the Southeast US in summer, limited by the spatial segregation between BVOC and NOx emissions. This segregation implies that RONO2 production will remain a minor sink for NOx in the Southeast US in the future even as NOx emissions continue to decline