A single-point modeling approach for the intercomparison and evaluation of ozone dry deposition across chemical transport models (Activity 2 of AQMEII4).

A primary sink of air pollutants and their precursors is dry deposition. Dry deposition estimates differ across chemical transport models, yet an understanding of the model spread is incomplete. Here, we introduce Activity 2 of the Air Quality Model Evaluation International Initiative Phase 4 (AQMEII4). We examine 18 dry deposition schemes from regional and global chemical transport models as well as standalone models used for impact assessments or process understanding. We configure the schemes as single-point models at eight Northern Hemisphere locations with observed ozone fluxes. Single-point models are driven by a common set of site-specific meteorological and environmental conditions. Five of eight sites have at least 3 years and up to 12 years of ozone fluxes. The interquartile range across models in multiyear mean ozone deposition velocities ranges from a factor of 1.2 to 1.9 annually across sites and tends to be highest during winter compared with summer. No model is within 50 % of observed multiyear averages across all sites and seasons, but some models perform well for some sites and seasons. For the first time, we demonstrate how contributions from depositional pathways vary across models. Models can disagree with respect to relative contributions from the pathways, even when they predict similar deposition velocities, or agree with respect to the relative contributions but predict different deposition velocities. Both stomatal and nonstomatal uptake contribute to the large model spread across sites. Our findings are the beginning of results from AQMEII4 Activity 2, which brings scientists who model air quality and dry deposition together with scientists who measure ozone fluxes to evaluate and improve dry deposition schemes in the chemical transport models used for research, planning, and regulatory purposes.

Impact of Biomass Burning Organic Aerosol Volatility on Smoke Concentrations Downwind of Fires.

Biomass burning particulate matter (BBPM) affects regional air quality and global climate, with impacts expected to continue to grow over the coming years. We show that studies of North American fires have a systematic altitude dependence in measured BBPM normalized excess mixing ratio (NEMR; ΔPM/ΔCO), with airborne and high-altitude studies showing a factor of 2 higher NEMR than ground-based measurements. We report direct airborne measurements of BBPM volatility that partially explain the difference in the BBPM NEMR observed across platforms. We find that when heated to 40-45 °C in an airborne thermal denuder, 19% of lofted smoke PM1 evaporates. Thermal denuder measurements are consistent with evaporation observed when a single smoke plume was sampled across a range of temperatures as the plume descended from 4 to 2 km altitude. We also demonstrate that chemical aging of smoke and differences in PM emission factors can not fully explain the platform-dependent differences. When the measured PM volatility is applied to output from the High Resolution Rapid Refresh Smoke regional model, we predict a lower PM NEMR at the surface compared to the lofted smoke measured by aircraft. These results emphasize the significant role that gas-particle partitioning plays in determining the air quality impacts of wildfire smoke.

Compositional Constraints are Vital for Atmospheric PM2.5 Source Attribution over India.

India experiences some of the highest levels of ambient PM2.5 aerosol pollution in the world. However, due to the historical dearth of in situ measurements, chemical transport models that are often used to estimate PM2.5 exposure over the region are rarely evaluated. Here, we conduct a novel model comparison with speciated airborne measurements of fine aerosol, revealing large biases in the ammonium and nitrate simulations. To address this, we incorporate process-level changes to the model and use satellite observations from the Cross-track Infrared Sounder (CrIS) and the TROPOspheric Monitoring Instrument (TROPOMI) to constrain ammonia and nitrogen oxide emissions. The resulting simulation demonstrates significantly lower bias (NMBModified: 0.19; NMBBase: 0.61) when validated against the airborne aerosol measurements, particularly for the nitrate (NMBModified: 0.08; NMBBase: 1.64) and ammonium simulation (NMBModified: 0.49; NMBBase: 0.90). We use this validated simulation to estimate a population-weighted annual PM2.5 exposure of 61.4 µg m-3, with the RCO (residential, commercial, and other) and energy sectors contributing 21% and 19%, respectively, resulting in an estimated 961,000 annual PM2.5-attributable deaths. Regional exposure and sectoral source contributions differ meaningfully in the improved simulation (compared to the baseline simulation). Our work highlights the critical role of speciated observational constraints in developing accurate model-based PM2.5 aerosol source attribution for health assessments and air quality management in India.

Impacts of Sugarcane Fires on Air Quality and Public Health in South Florida.

BACKGROUND: Preharvest burning of sugarcane is a common agricultural practice in Florida, which produces fine particulate matter [particulate matter (PM) with aerodynamic diameter ≤2.5µm (PM2.5)] that is associated with higher mortality. OBJECTIVES: We estimated premature mortality associated with exposure to PM2.5 from sugarcane burning in people age 25 y and above for 20 counties in South Florida. METHODS: We combined information from an atmospheric dispersion model, satellites, and surface measurements to quantify PM2.5 concentrations in South Florida and the fraction of PM2.5 from sugarcane fires. From these concentrations, estimated mortalities attributable to PM2.5 from sugarcane fires were calculated by census tract using health impact functions derived from literature for six causes of death linked to PM2.5. Confidence intervals (CI) are provided based on Monte Carlo simulations that propagate uncertainty in the emissions, dispersion model, health impact functions, and demographic data. RESULTS: Sugarcane fires emitted an amount of primary PM2.5 similar to that of motor vehicles in Florida. PM2.5 from sugarcane fires is estimated to contribute to mortality rates within the Florida Sugarcane Growing Region (SGR) by 0.4 death per 100,000 people per year (95% CI: 0.3, 1.6 per 100,000). These estimates imply 2.5 deaths per year across South Florida were associated with PM2.5 from sugarcane fires (95% CI: 1.2, 6.1), with 0.16 in the SGR (95% CI: 0.09, 0.6) and 0.72 in Palm Beach County (95% CI: 0.17, 2.2). DISCUSSION: PM2.5 from sugarcane fires was estimated to contribute to mortality risk across South Florida, particularly in the SGR. This is consistent with prior studies that documented impacts of sugarcane fire on air quality but did not quantify mortality. Additional health impacts of sugarcane fires, which were not quantified here, include exacerbating nonfatal health conditions such as asthma and cardiovascular problems. Harvesting sugarcane without field burning would likely reduce PM2.5 and health burdens in this region. https://doi.org/10.1289/EHP9957.

Airborne Emission Rate Measurements Validate Remote Sensing Observations and Emission Inventories of Western U.S. Wildfires.

Carbonaceous emissions from wildfires are a dynamic mixture of gases and particles that have important impacts on air quality and climate. Emissions that feed atmospheric models are estimated using burned area and fire radiative power (FRP) methods that rely on satellite products. These approaches show wide variability and have large uncertainties, and their accuracy is challenging to evaluate due to limited aircraft and ground measurements. Here, we present a novel method to estimate fire plume-integrated total carbon and speciated emission rates using a unique combination of lidar remote sensing aerosol extinction profiles and in situ measured carbon constituents. We show strong agreement between these aircraft-derived emission rates of total carbon and a detailed burned area-based inventory that distributes carbon emissions in time using Geostationary Operational Environmental Satellite FRP observations (Fuel2Fire inventory, slope = 1.33 ± 0.04, r2 = 0.93, and RMSE = 0.27). Other more commonly used inventories strongly correlate with aircraft-derived emissions but have wide-ranging over- and under-predictions. A strong correlation is found between carbon monoxide emissions estimated in situ with those derived from the TROPOspheric Monitoring Instrument (TROPOMI) for five wildfires with coincident sampling windows (slope = 0.99 ± 0.18; bias = 28.5%). Smoke emission coefficients (g MJ-1) enable direct estimations of primary gas and aerosol emissions from satellite FRP observations, and we derive these values for many compounds emitted by temperate forest fuels, including several previously unreported species.

Understanding the Evolution of Smoke Mass Extinction Efficiency Using Field Campaign Measurements.

Aerosol mass extinction efficiency (MEE) is a key aerosol property used to connect aerosol optical properties with aerosol mass concentrations. Using measurements of smoke obtained during the Fire Influence on Regional to Global Environments and Air Quality (FIREX-AQ) campaign we find that mid-visible smoke MEE can change by a factor of 2-3 between fresh smoke (<2 hr old) and one-day-old smoke. While increases in aerosol size partially explain this trend, changes in the real part of the aerosol refractive index (real(n)) are necessary to provide closure assuming Mie theory. Real(n) estimates derived from multiple days of FIREX-AQ measurements increase with age (from 1.40 - 1.45 to 1.5-1.54 from fresh to one-day-old) and are found to be positively correlated with organic aerosol oxidation state and aerosol size, and negatively correlated with smoke volatility. Future laboratory, field, and modeling studies should focus on better understanding and parameterizing these relationships to fully represent smoke aging.

Ozone chemistry in western U.S. wildfire plumes.

Wildfires are a substantial but poorly quantified source of tropospheric ozone (O3). Here, to investigate the highly variable O3 chemistry in wildfire plumes, we exploit the in situ chemical characterization of western wildfires during the FIREX-AQ flight campaign and show that O3 production can be predicted as a function of experimentally constrained OH exposure, volatile organic compound (VOC) reactivity, and the fate of peroxy radicals. The O3 chemistry exhibits rapid transition in chemical regimes. Within a few daylight hours, the O3 formation substantially slows and is largely limited by the abundance of nitrogen oxides (NOx). This finding supports previous observations that O3 formation is enhanced when VOC-rich wildfire smoke mixes into NOx-rich urban plumes, thereby deteriorating urban air quality. Last, we relate O3 chemistry to the underlying fire characteristics, enabling a more accurate representation of wildfire chemistry in atmospheric models that are used to study air quality and predict climate.

Technical note: AQMEII4 Activity 1: evaluation of wet and dry deposition schemes as an integral part of regional-scale air quality models.

We present in this technical note the research protocol for phase 4 of the Air Quality Model Evaluation International Initiative (AQMEII4). This research initiative is divided into two activities, collectively having three goals: (i) to define the current state of the science with respect to representations of wet and especially dry deposition in regional models, (ii) to quantify the extent to which different dry deposition parameterizations influence retrospective air pollutant concentration and flux predictions, and (iii) to identify, through the use of a common set of detailed diagnostics, sensitivity simulations, model evaluation, and reduction of input uncertainty, the specific causes for the current range of these predictions. Activity 1 is dedicated to the diagnostic evaluation of wet and dry deposition processes in regional air quality models (described in this paper), and Activity 2 to the evaluation of dry deposition point models against ozone flux measurements at multiple towers with multiyear observations (to be described in future submissions as part of the special issue on AQMEII4). The scope of this paper is to present the scientific protocols for Activity 1, as well as to summarize the technical information associated with the different dry deposition approaches used by the participating research groups of AQMEII4. In addition to describing all common aspects and data used for this multi-model evaluation activity, most importantly, we present the strategy devised to allow a common process-level comparison of dry deposition obtained from models using sometimes very different dry deposition schemes. The strategy is based on adding detailed diagnostics to the algorithms used in the dry deposition modules of existing regional air quality models, in particular archiving diagnostics specific to land use-land cover (LULC) and creating standardized LULC categories to facilitate cross-comparison of LULC-specific dry deposition parameters and processes, as well as archiving effective conductance and effective flux as means for comparing the relative influence of different pathways towards the net or total dry deposition. This new approach, along with an analysis of precipitation and wet deposition fields, will provide an unprecedented process-oriented comparison of deposition in regional air quality models. Examples of how specific dry deposition schemes used in participating models have been reduced to the common set of comparable diagnostics defined for AQMEII4 are also presented.

Novel Analysis to Quantify Plume Crosswind Heterogeneity Applied to Biomass Burning Smoke.

We present a novel method, the Gaussian observational model for edge to center heterogeneity (GOMECH), to quantify the horizontal chemical structure of plumes. GOMECH fits observations of short-lived emissions or products against a long-lived tracer (e.g., CO) to provide relative metrics for the plume width (wi/wCO) and center (bi/wCO). To validate GOMECH, we investigate OH and NO3 oxidation processes in smoke plumes sampled during FIREX-AQ (Fire Influence on Regional to Global Environments and Air Quality, a 2019 wildfire smoke study). An analysis of 430 crosswind transects demonstrates that nitrous acid (HONO), a primary source of OH, is narrower than CO (wHONO/wCO = 0.73-0.84 ± 0.01) and maleic anhydride (an OH oxidation product) is enhanced on plume edges (wmaleicanhydride/wCO = 1.06-1.12 ± 0.01). By contrast, NO3 production [P(NO3)] occurs mainly at the plume center (wP(NO3)/wCO = 0.91-1.00 ± 0.01). Phenolic emissions, highly reactive to OH and NO3, are narrower than CO (wphenol/wCO = 0.96 ± 0.03, wcatechol/wCO = 0.91 ± 0.01, and wmethylcatechol/wCO = 0.84 ± 0.01), suggesting that plume edge phenolic losses are the greatest. Yet, nitrophenolic aerosol, their oxidation product, is the greatest at the plume center (wnitrophenolicaerosol/wCO = 0.95 ± 0.02). In a large plume case study, GOMECH suggests that nitrocatechol aerosol is most associated with P(NO3). Last, we corroborate GOMECH with a large eddy simulation model which suggests most (55%) of nitrocatechol is produced through NO3 in our case study.

Rapid cloud removal of dimethyl sulfide oxidation products limits SO2 and cloud condensation nuclei production in the marine atmosphere.

Oceans emit large quantities of dimethyl sulfide (DMS) to the marine atmosphere. The oxidation of DMS leads to the formation and growth of cloud condensation nuclei (CCN) with consequent effects on Earth's radiation balance and climate. The quantitative assessment of the impact of DMS emissions on CCN concentrations necessitates a detailed description of the oxidation of DMS in the presence of existing aerosol particles and clouds. In the unpolluted marine atmosphere, DMS is efficiently oxidized to hydroperoxymethyl thioformate (HPMTF), a stable intermediate in the chemical trajectory toward sulfur dioxide (SO2) and ultimately sulfate aerosol. Using direct airborne flux measurements, we demonstrate that the irreversible loss of HPMTF to clouds in the marine boundary layer determines the HPMTF lifetime (τHPMTF < 2 h) and terminates DMS oxidation to SO2 When accounting for HPMTF cloud loss in a global chemical transport model, we show that SO2 production from DMS is reduced by 35% globally and near-surface (0 to 3 km) SO2 concentrations over the ocean are lowered by 24%. This large, previously unconsidered loss process for volatile sulfur accelerates the timescale for the conversion of DMS to sulfate while limiting new particle formation in the marine atmosphere and changing the dynamics of aerosol growth. This loss process potentially reduces the spatial scale over which DMS emissions contribute to aerosol production and growth and weakens the link between DMS emission and marine CCN production with subsequent implications for cloud formation, radiative forcing, and climate.

Variability and Time of Day Dependence of Ozone Photochemistry in Western Wildfire Plumes.

Understanding the efficiency and variability of photochemical ozone (O3) production from western wildfire plumes is important to accurately estimate their influence on North American air quality. A set of photochemical measurements were made from the NOAA Twin Otter research aircraft as a part of the Fire Influence on Regional to Global Environments and Air Quality (FIREX-AQ) experiment. We use a zero-dimensional (0-D) box model to investigate the chemistry driving O3 production in modeled plumes. Modeled afternoon plumes reached a maximum O3 mixing ratio of 140 ± 50 ppbv (average ± standard deviation) within 20 ± 10 min of emission compared to 76 ± 12 ppbv in 60 ± 30 min in evening plumes. Afternoon and evening maximum O3 isopleths indicate that plumes were near their peak in NOx efficiency. A radical budget describes the NOx volatile - organic compound (VOC) sensitivities of these plumes. Afternoon plumes displayed a rapid transition from VOC-sensitive to NOx-sensitive chemistry, driven by HOx (=OH + HO2) production from photolysis of nitrous acid (HONO) (48 ± 20% of primary HOx) and formaldehyde (HCHO) (26 ± 9%) emitted directly from the fire. Evening plumes exhibit a slower transition from peak NOx efficiency to VOC-sensitive O3 production caused by a reduction in photolysis rates and fire emissions. HOx production in evening plumes is controlled by HONO photolysis (53 ± 7%), HCHO photolysis (18 ± 9%), and alkene ozonolysis (17 ± 9%).

Mercury Wet Scavenging and Deposition Differences by Precipitation Type.

We analyze the effect of precipitation type on mercury wet deposition using a new database of individual rain events spanning the contiguous United States. Measurements from the Mercury Deposition Network (MDN) containing single rainfall events were identified and classified into six precipitation types. Mercury concentrations in surface precipitation follow a power law of precipitation depth that is modulated by precipitation system morphology. After controlling for precipitation depth, the highest mercury deposition occurs in supercell thunderstorms, with decreasing deposition in disorganized thunderstorms, quasi-linear convective systems (QLCS), extratropical cyclones, light rain, and land-falling tropical cyclones. Convective morphologies (supercells, disorganized, and QLCS) enhance wet deposition by a factor of at least 1.6 relative to nonconvective morphologies. Mercury wet deposition also varies by geographic region and season. After controlling for other factors, we find that mercury wet deposition is greater over high-elevation sites, seasonally during summer, and in convective precipitation.

Thunderstorms Increase Mercury Wet Deposition.

Mercury (Hg) wet deposition, transfer from the atmosphere to Earth's surface by precipitation, in the United States is highest in locations and seasons with frequent deep convective thunderstorms, but it has never been demonstrated whether the connection is causal or simple coincidence. We use rainwater samples from over 800 individual precipitation events to show that thunderstorms increase Hg concentrations by 50% relative to weak convective or stratiform events of equal precipitation depth. Radar and satellite observations reveal that strong convection reaching the upper troposphere (where high atmospheric concentrations of soluble, oxidized mercury species (Hg(II)) are known to reside) produces the highest Hg concentrations in rain. As a result, precipitation meteorology, especially thunderstorm frequency and total rainfall, explains differences in Hg deposition between study sites located in the eastern United States. Assessing the fate of atmospheric mercury thus requires bridging the scales of global transport and convective precipitation.

Mercury in tropical and subtropical coastal environments.

Anthropogenic activities influence the biogeochemical cycles of mercury, both qualitatively and quantitatively, on a global scale from sources to sinks. Anthropogenic processes that alter the temporal and spatial patterns of sources and cycling processes are changing the impacts of mercury contamination on aquatic biota and humans. Human exposure to mercury is dominated by the consumption of fish and products from aquaculture operations. The risk to society and to ecosystems from mercury contamination is growing, and it is important to monitor these expanding risks. However, the extent and manner to which anthropogenic activities will alter mercury sources and biogeochemical cycling in tropical and sub-tropical coastal environments is poorly understood. Factors as (1) lack of reliable local/regional data; (2) rapidly changing environmental conditions; (3) governmental priorities and; (4) technical actions from supra-national institutions, are some of the obstacles to overcome in mercury cycling research and policy formulation. In the tropics and sub-tropics, research on mercury in the environment is moving from an exploratory "inventory" phase towards more process-oriented studies. Addressing biodiversity conservation and human health issues related to mercury contamination of river basins and tropical coastal environments are an integral part of paragraph 221 of the United Nations document "The Future We Want" issued in Rio de Janeiro in June 2012.

Global source-receptor relationships for mercury deposition under present-day and 2050 emissions scenarios.

Global policies regulating anthropogenic mercury require an understanding of the relationship between emitted and deposited mercury on intercontinental scales. Here, we examine source-receptor relationships for present-day conditions and four 2050 IPCC scenarios encompassing a range of economic development and environmental regulation projections. We use the GEOS-Chem global model to track mercury from its point of emission through rapid cycling in surface ocean and land reservoirs to its accumulation in longer lived ocean and soil pools. Deposited mercury has a local component (emitted Hg(II), lifetime of 3.7 days against deposition) and a global component (emitted Hg(0), lifetime of 6 months against deposition). Fast recycling of deposited mercury through photoreduction of Hg(II) and re-emission of Hg(0) from surface reservoirs (ice, land, surface ocean) increases the effective lifetime of anthropogenic mercury to 9 months against loss to legacy reservoirs (soil pools and the subsurface ocean). This lifetime is still sufficiently short that source-receptor relationships have a strong hemispheric signature. Asian emissions are the largest source of anthropogenic deposition to all ocean basins, though there is also regional source influence from upwind continents. Current anthropogenic emissions account for only about one-third of mercury deposition to the global ocean with the remainder from natural and legacy sources. However, controls on anthropogenic emissions would have the added benefit of reducing the legacy mercury re-emitted to the atmosphere. Better understanding is needed of the time scales for transfer of mercury from active pools to stable geochemical reservoirs.

Uncertainties in climate assessment for the case of aviation NO.

Nitrogen oxides emitted from aircraft engines alter the chemistry of the atmosphere, perturbing the greenhouse gases methane (CH(4)) and ozone (O(3)). We quantify uncertainties in radiative forcing (RF) due to short-lived increases in O(3), long-lived decreases in CH(4) and O(3), and their net effect, using the ensemble of published models and a factor decomposition of each forcing. The decomposition captures major features of the ensemble, and also shows which processes drive the total uncertainty in several climate metrics. Aviation-specific factors drive most of the uncertainty for the short-lived O(3) and long-lived CH(4) RFs, but a nonaviation factor dominates for long-lived O(3). The model ensemble shows strong anticorrelation between the short-lived and long-lived RF perturbations (R(2)=0.87). Uncertainty in the net RF is highly sensitive to this correlation. We reproduce the correlation and ensemble spread in one model, showing that processes controlling the background tropospheric abundance of nitrogen oxides are likely responsible for the modeling uncertainty in climate impacts from aviation.

An improved global model for air-sea exchange of mercury: high concentrations over the North Atlantic.

We develop an improved treatment of the surface ocean in the GEOS-Chem global 3-D biogeochemical model for mercury (Hg). We replace the globally uniform subsurface ocean Hg concentrations used in the original model with basin-specific values based on measurements. Updated chemical mechanisms for Hg°/Hg(II) redox reactions in the surface ocean include both photochemical and biological processes, and we improved the parametrization of particle-associated Hg scavenging. Modeled aqueous Hg concentrations are consistent with limited surface water observations. Results more accurately reproduce high-observed MBL concentrations over the North Atlantic (NA) and the associated seasonal trends. High seasonal evasion in the NA is driven by inputs from Hg enriched subsurface waters through entrainment and Ekman pumping. Globally, subsurface waters account for 40% of Hg inputs to the ocean mixed layer, and 60% is from atmospheric deposition. Although globally the ocean is a net sink for 3.8 Mmol Hg y⁻¹, the NA is a net source to the atmosphere, potentially due to enrichment of subsurface waters with legacy Hg from historical anthropogenic sources.