Quantifying the influence of agricultural fires in northwest India on urban air pollution in Delhi, India

Since at least the 1980s, many farmers in northwest India have switched to mechanized combine harvesting to boost efficiency. This harvesting technique leaves abundant crop residue on the fields, which farmers typically burn to prepare their fields for subsequent planting. A key question is to what extent the large quantity of smoke emitted by these fires contributes to the already severe pollution in Delhi and across other parts of the heavily populated Indo-Gangetic Plain located downwind of the fires. Using a combination of observed and modeled variables, including surface measurements of PM2.5, we quantify the magnitude of the influence of agricultural fire emissions on surface air pollution in Delhi. With surface measurements, we first derive the signal of regional PM2.5 enhancements (i.e. the pollution above an anthropogenic baseline) during each post-monsoon burning season for 2012–2016. We next use the Stochastic Time-Inverted Lagrangian Transport model (STILT) to simulate surface PM2.5 using five fire emission inventories. We reproduce up to 25% of the weekly variability in total observed PM2.5 using STILT. Depending on year and emission inventory, our method attributes 7.0%–78% of the maximum observed PM2.5 enhancements in Delhi to fires. The large range in these attribution estimates points to the uncertainties in fire emission parameterizations, especially in regions where thick smoke may interfere with hotspots of fire radiative power. Although our model can generally reproduce the largest PM2.5 enhancements in Delhi air quality for 1–3 consecutive days each fire season, it fails to capture many smaller daily enhancements, which we attribute to the challenge of detecting small fires in the satellite retrieval. By quantifying the influence of upwind agricultural fire emissions on Delhi air pollution, our work underscores the potential health benefits of changes in farming practices to reduce fires

Sensitivity to grid resolution in the ability of a chemical transport model to simulate observed oxidant chemistry under high-isoprene conditions

Formation of ozone and organic aerosol in continental atmospheres depends on whether isoprene emitted by vegetation is oxidized by the high-NOx pathway (where peroxy radicals react with NO) or by low-NOx pathways (where peroxy radicals react by alternate channels, mostly with HO2). We used mixed layer observations from the SEAC4RS aircraft campaign over the Southeast US to test the ability of the GEOS-Chem chemical transport model at different grid resolutions (0.25°  ×  0.3125°, 2°  ×  2.5°, 4°  ×  5°) to simulate this chemistry under high-isoprene, variable-NOx conditions. Observations of isoprene and NOx over the Southeast US show a negative correlation, reflecting the spatial segregation of emissions; this negative correlation is captured in the model at 0.25°  ×  0.3125° resolution but not at coarser resolutions. As a result, less isoprene oxidation takes place by the high-NOx pathway in the model at 0.25°  ×  0.3125° resolution (54 %) than at coarser resolution (59 %). The cumulative probability distribution functions (CDFs) of NOx, isoprene, and ozone concentrations show little difference across model resolutions and good agreement with observations, while formaldehyde is overestimated at coarse resolution because excessive isoprene oxidation takes place by the high-NOx pathway with high formaldehyde yield. The good agreement of simulated and observed concentration variances implies that smaller-scale non-linearities (urban and power plant plumes) are not important on the regional scale. Correlations of simulated vs. observed concentrations do not improve with grid resolution because finer modes of variability are intrinsically more difficult to capture. Higher model resolution leads to decreased conversion of NOx to organic nitrates and increased conversion to nitric acid, with total reactive nitrogen oxides (NOy) changing little across model resolutions. Model concentrations in the lower free troposphere are also insensitive to grid resolution. The overall low sensitivity of modeled concentrations to grid resolution implies that coarse resolution is adequate when modeling continental boundary layer chemistry for global applications

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

Why do Models Overestimate Surface Ozone in the Southeastern 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 deg. x 0.3125 deg. 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 15 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

Global impact of nitrate photolysis in sea-salt aerosol on NOx, OH, and O3 in the marine boundary layer

Recent field studies have suggested that sea-salt particulate nitrate (NITs) photolysis may act as a significant local source of nitrogen oxides (NOx) over oceans. We present a study of the global impact of this process on oxidant concentrations in the marine boundary layer (MBL) using the GEOS-Chem model, after first updating the model to better simulate observed gas-particle phase partitioning of nitrate in the marine boundary layer. Model comparisons with long-term measurements of NOx from the Cape Verde Atmospheric Observatory (CVAO) in the eastern tropical North Atlantic provide support for an in situ source of NOx from NITs photolysis, with NITs photolysis coefficients about 25-50 times larger than corresponding HNO3 photolysis coefficients. Short-term measurements of nitrous acid (HONO) at this location show a clear daytime peak, with average peak mixing ratios ranging from 3 to 6 pptv. The model reproduces the general shape of the diurnal HONO profile only when NITs photolysis is included, but the magnitude of the daytime peak mixing ratio is under-predicted. This under-prediction is somewhat reduced if HONO yields from NITs photolysis are assumed to be close to unity. The combined NOx and HONO analysis suggests that the upper limit of the ratio of NITs : HNO3 photolysis coefficients is about 100. The largest simulated relative impact of NITs photolysis is in the tropical and subtropical marine boundary layer, with peak local enhancements ranging from factors of 5 to 20 for NOx, 1.2 to 1.6 for OH, and 1.1 to 1.3 for ozone. Since the spatial extent of the sea-salt aerosol (SSA) impact is limited, global impacts on NOx, ozone, and OH mass burdens are small ( ∼ 1-3 %). We also present preliminary analysis showing that particulate nitrate photolysis in accumulation-mode aerosols (predominantly over continental regions) could lead to ppbv-level increases in ozone in the continental boundary layer. Our results highlight the need for more comprehensive long-term measurements of NOx, and related species like HONO and sea-salt particulate nitrate, to better constrain the impact of particulate nitrate photolysis on marine boundary layer oxidant chemistry. Further field and laboratory studies on particulate nitrate photolysis in other aerosol types are also needed to better understand the impact of this process on continental boundary layer oxidant chemistry

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 Niño 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 Indonesia's 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

Effect of sea salt aerosol on tropospheric bromine chemistry

Bromine radicals influence global tropospheric chemistry by depleting ozone and OH, and by oxidizing elemental mercury, sulfur species, and volatile organic compounds. Observations typically indicate a 50&thinsp;% depletion of sea salt aerosol (SSA) bromide relative to seawater composition, implying that SSA debromination could be the dominant global source of tropospheric bromine. However, it has been difficult to reconcile this large source with the relatively low BrO concentrations observed in the marine boundary layer (MBL). Here we present a new mechanistic description of SSA debromination in the GEOS-Chem global atmospheric chemistry model with a detailed representation of halogen (Cl, Br, and I) chemistry. We show, for the first time, observed levels of SSA debromination can be reproduced in a manner consistent with observed BrO concentrations. Bromine radical sinks from the HOBr + S(IV) heterogeneous reactions and from ocean emission of acetaldehyde are found to be critical in moderating tropospheric BrO levels. The resulting HBr is rapidly taken up by SSA and also deposited. We find that the source of bromine radicals is mostly from SSA in the MBL, but from organobromines in the free troposphere. Simulated BrO in the MBL is generally much higher in winter than in summer due to a combination of greater SSA emission and weaker radiation. Outstanding issues are the model underestimate of free tropospheric BrO, driven by the HOBr + S(IV) reactions, and uncertainty regarding HBr uptake by SSA.</p

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