Patrick S. Kim

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 8±13 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.

Public health impacts of the severe haze in Equatorial Asia in September-October 2015: demonstration of a new framework for informing fire management strategies to reduce downwind smoke exposure

In September–October 2015, El Nino and positive Indian Ocean Dipole conditions set the stage for massive fires in Sumatra and Kalimantan (Indonesian Borneo), leading to persistently hazardous levels of smoke pollution across much of Equatorial Asia. Here we quantify the emission sources and health impacts of this haze episode and compare the sources and impacts to an event of similar magnitude occurring under similar meteorological conditions in September–October 2006. Using the adjoint of the GEOS-Chem chemical transport model, we first calculate the influence of potential fire emissions across the domain on smoke concentrations in three receptor areas downwind—Indonesia, Malaysia, and Singapore—during the 2006 event. This step maps the sensitivity of each receptor to fire emissions in each grid cell upwind. We then combine these sensitivities with 2006 and 2015 fire emission inventories from the Global Fire Assimilation System (GFAS) to estimate the resulting population-weighted smoke exposure. This method, which assumes similar smoke transport pathways in 2006 and 2015, allows near real-time assessment of smoke pollution exposure, and therefore the consequent morbidity and premature mortality, due to severe haze. Our approach also provides rapid assessment of the relative contribution of fire emissions generated in a specific province to smoke-related health impacts in the receptor areas. We estimate that haze in 2015 resulted in 100 300 excess deaths across Indonesia, Malaysia and Singapore, more than double those of the 2006 event, with much of the increase due to fires in Indonesias South Sumatra Province. The model framework we introduce in this study can rapidly identify those areas where land use management to reduce and/or avoid fires would yield the greatest benefit to human health, both nationally and regionally.

Fire emissions and regional air quality impacts from fires in oil palm, timber, and logging concessions in Indonesia

Fires associated with agricultural and plantation development in Indonesia impact ecosystem services and release emissions into the atmosphere that degrade regional air quality and contribute to greenhouse gas concentrations. In this study, we estimate the relative contributions of the oil palm, timber (for wood pulp and paper), and logging industries in Sumatra and Kalimantan to land cover change, fire activity, and regional population exposure to smoke concentrations. Concessions for these three industries cover 21% and 49% of the land area in Sumatra and Kalimantan respectively, with the highest overall area in lowlands on mineral soils instead of more carbon-rich peatlands. In 2012, most remaining forest area was located in logging concessions for both islands, and for all combined concessions, there was higher remaining lowland and peatland forest area in Kalimantan (45% and 46%, respectively) versus Sumatra (20% and 27%, respectively). Emissions from all combined concessions comprised 41% of total fire emissions (within and outside of concession boundaries) in Sumatra and 27% in Kalimantan for the 2006 burning season, which had high fire activity relative to decadal emissions. Most fire emissions were observed in concessions located on peatlands and non-forested lowlands, the latter of which could include concessions that are currently under production, cleared in preparation for production, or abandoned lands. For the 2006 burning season, timber concessions from Sumatra (47% of area and 88% of emissions) and oil palm concessions from Kalimantan (33% of area and 67% of emissions) contributed the most to concession-related fire emissions from each island. Although fire emissions from concessions were higher in Kalimantan, emissions from Sumatra contributed 63% of concession-related smoke concentrations for the population-weighted region because fire sources were located closer to population centers. In order to protect regional public health, our results highlight the importance of limiting the use of fire by the timber and oil palm industries, particularly on concessions that contain peatlands and non-forest, by such methods as improving monitoring systems, local-level management, and enforcement of existing fire bans.

Organic nitrate chemistry and its implications for nitrogen budgets in an isoprene- and monoterpene-rich atmosphere: constraints from aircraft (SEAC 4 RS) 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 × 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.

Observing atmospheric formaldehyde (HCHO) from space: validation and intercomparison of six retrievals from four satellites (OMI, GOME2A, GOME2B, OMPS) with SEAC4RS aircraft observations over the southeast US

Formaldehyde (HCHO) column data from satellites are widely used as a proxy for emissions of volatile organic compounds (VOCs) but validation of the data has been extremely limited. Here we use highly accurate HCHO aircraft observations from the NASA SEAC4RS campaign over the Southeast US in August-September 2013 to validate and intercompare six retrievals of HCHO columns from four different satellite instruments (OMI, GOME2A, GOME2B and OMPS) and three different research groups. The GEOS-Chem chemical transport model is used as a common intercomparison platform. All retrievals feature a HCHO maximum over Arkansas and Louisiana, consistent with the aircraft observations and reflecting high emissions of biogenic isoprene. The retrievals are also interconsistent in their spatial variability over the Southeast US (r=0.4-0.8 on a 0.5°×0.5° grid) and in their day-to-day variability (r=0.5-0.8). However, all retrievals are biased low in the mean by 20-51%, which would lead to corresponding bias in estimates of isoprene emissions from the satellite data. The smallest bias is for OMI-BIRA, which has high corrected slant columns relative to the other retrievals and low scattering weights in its air mass factor (AMF) calculation. OMI-BIRA has systematic error in its assumed vertical HCHO shape profiles for the AMF calculation and correcting this would eliminate its bias relative to the SEAC4RS data. Our results support the use of satellite HCHO data as a quantitative proxy for isoprene emission after correction of the low mean bias. There is no evident pattern in the bias, suggesting that a uniform correction factor may be applied to the data until better understanding is achieved.

Quantifying sources and sinks of reactive gases in the lower atmosphere using airborne flux observations

Atmospheric composition is governed by the interplay of emissions, chemistry, deposition, and transport. Substantial questions surround each of these processes, especially in forested environments with strong biogenic emissions. Utilizing aircraft observations acquired over a forest in the southeast U.S., we calculate eddy covariance fluxes for a suite of reactive gases and apply the synergistic information derived from this analysis to quantify emission and deposition fluxes, oxidant concentrations, aerosol uptake coefficients, and other key parameters. Evaluation of results against state-of-the-science models and parameterizations provides insight into our current understanding of this system and frames future observational priorities. As a near-direct measurement of fundamental process rates, airborne fluxes offer a new tool to improve biogenic and anthropogenic emissions inventories, photochemical mechanisms, and deposition parameterizations.

Regional air quality impacts of future fire emissions in Sumatra and Kalimantan

Fire emissions associated with land cover change and land management contribute to the concentrations of atmospheric pollutants, which can affect regional air quality and climate. Mitigating these impacts requires a comprehensive understanding of the relationship between fires and different land cover change trajectories and land management strategies. We develop future fire emissions inventories from 2010–2030 for Sumatra and Kalimantan (Indonesian Borneo) to assess the impact of varying levels of forest and peatland conservation on air quality in Equatorial Asia. To compile these inventories, we combine detailed land cover information from published maps of forest extent, satellite fire radiative power observations, fire emissions from the Global Fire Emissions Database, and spatially explicit future land cover projections using a land cover change model. We apply the sensitivities of mean smoke concentrations to Indonesian fire emissions, calculated by the GEOS-Chem adjoint model, to our scenario-based future fire emissions inventories to quantify the different impacts of fires on surface air quality across Equatorial Asia. We find that public health impacts are highly sensitive to the location of fires, with emissions from Sumatra contributing more to smoke concentrations at population centers across the region than Kalimantan, which had higher emissions by more than a factor of two. Compared to business-as-usual projections, protecting peatlands from fires reduces smoke concentrations in the cities of Singapore and Palembang by 70% and 40%, and by 60% for the Equatorial Asian region, weighted by the population in each grid cell. Our results indicate the importance of focusing conservation priorities on protecting both forested (intact or logged) peatlands and non-forested peatlands from fire, even after considering potential leakage of deforestation pressure to other areas, in order to limit the impact of fire emissions on atmospheric smoke concentrations and subsequent health effects.

Incomplete sulfate aerosol neutralization despite excess ammonia in the eastern US: a possible role of organic aerosol

Acid-base neutralization of sulfate aerosol (S(VI) ≡ H 2 SO 4 (aq) + HSO 4 - + SO 4 2- ) by ammonia (NH 3 ) has important implications for aerosol mass, hygroscopicity, and acidity. Surface network and aircraft observations across the eastern US show that sulfate aerosol is not fully neutralized even in the presence of excess ammonia, at odds with thermodynamic equilibrium models. The sulfate aerosol 15