Transition Metal-Catalyzed Oxidation of Atmospheric Sulfur: Global Implications for the Sulfur Budget

We use observations of the oxygen-17 excess $(Δ^{17}O)$ of sulfate in the Arctic to quantify the sulfate source from aqueous $SO_2 (S(IV))$ oxidation by $O_2$ catalyzed by transition metals. Due to the lack of photochemically produced OH and $H_2O_2$ in high latitudes during winter, combined with high anthropogenic $SO_2$ emissions in the Northern Hemisphere, oxidation by $O_3$ is predicted to dominate sulfate formation during winter in this region. However, $Δ^{17}O$ measurements of sulfate aerosol collected in Alert, Canada, are not consistent with $O_3$ as the dominant oxidant and indicate that a S(IV) oxidant with near-zero $Δ^{17}O$ values $(O_2)$ is important during winter. We use a global chemical transport model to interpret quantitatively the Alert observations and assess the global importance of sulfate production by Fe(III)- and Mn(II)-catalyzed oxidation of S(IV) by $O_2$. We scale anthropogenic and natural atmospheric metal concentrations to primary anthropogenic sulfate and dust concentrations, respectively. The solubility and oxidation state of these metals is determined by cloud liquid water content, source, and sunlight. By including metal-catalyzed S(IV) oxidation, the model is consistent with the $Δ^{17}O$ magnitudes in the Alert data during winter. Globally, we find that this mechanism contributes 9–17% to sulfate production. The inclusion of metal-catalyzed oxidation does not resolve model discrepancies with surface SO2 and sulfate observations in Europe. Oxygen isotope measurements of sulfate aerosols collected near anthropogenic and dust sources of metals would help to verify the importance of this sulfur oxidation pathway.Engineering and Applied Science

Transpacific Transport of Asian Anthropogenic Aerosols and its Impact on Surface Air Quality in the United States

We use satellite (MODIS) observations of aerosol optical depths (AODs) over the North Pacific, together with surface aerosol measurements at a network of remote U.S. sites (IMPROVE), to improve understanding of the transpacific transport of Asian aerosol pollution and assess the ability of a global 3-D chemical transport model (GEOS-Chem CTM) to quantify Asian aerosol enhancements in U.S. surface air. The MODIS observations show the strongest transpacific transport occurring in spring at 40–55°N. This transport in the model takes place mainly in the lower free troposphere (900–700 hPa) because of scavenging during transport either in the boundary layer or during lifting to the upper troposphere. The preferential altitude of aerosol transpacific transport results in direct impact on the elevated terrain of the NW United States. Sulfate observations in the NW United States in spring 2001 show higher concentrations on the days of model-predicted maximum Asian influence (1.04 μg m−3) than seasonal mean values (0.69 μg m−3). No such Asian enhancements are observed for nitrate or for organic carbon (OC) aerosol. Distinct Asian sulfate episodes correlated with dust events are observed in the NW United States and simulated with the model. The mean Asian pollution enhancement in that region in spring is 0.16 μg m−3 with a 50% estimated uncertainty. This is higher than the estimated natural concentration of 0.09 μg m−3 presently used as objective for regulation of visibility in U.S. wilderness areas.Earth and Planetary SciencesEngineering and Applied Science

Surface Ozone Background in the United States: Canadian and Mexican Pollution Influences

We use a global chemical transport model (GEOS-Chem) with 1° × 1° horizontal resolution to quantify the effects of anthropogenic emissions from Canada, Mexico, and outside North America on daily maximum 8-hour average ozone concentrations in US surface air. Simulations for summer 2001 indicate mean North American and US background concentrations of 26 ± 8 ppb and 30 ± 8 ppb, as obtained by eliminating anthropogenic emissions in North America vs. in the US only. The US background never exceeds 60 ppb in the model. The Canadian and Mexican pollution enhancement averages 3 ± 4 ppb in the US in summer but can be occasionally much higher in downwind regions of the northeast and southwest, peaking at 33 ppb in upstate New York (on a day with 75 ppb total ozone) and 18 ppb in southern California (on a day with 68 ppb total ozone). The model is successful in reproducing the observed variability of ozone in these regions, including the occurrence and magnitude of high-ozone episodes influenced by transboundary pollution. We find that exceedances of the 75 ppb US air quality standard in eastern Michigan, western New York, New Jersey, and southern California are often associated with Canadian and Mexican pollution enhancements in excess of 10 ppb. Sensitivity simulations with 2020 emission projections suggest that Canadian pollution influence in the Northeast US will become comparable in magnitude to that from domestic power plants.Engineering and Applied Science

Evaluation of simulated O-3 production efficiency during the KORUS-AQ campaign: Implications for anthropogenic NOx emissions in Korea

We examine O3 production and its sensitivity to precursor gases and boundary layer mixing in Korea by using a 3-D global chemistry transport model and extensive observations during the KORea-US cooperative Air Quality field study in Korea, which occurred in May–June 2016. During the campaign, observed aromatic species onboard the NASA DC-8 aircraft, especially toluene, showed high mixing ratios of up to 10 ppbv, emphasizing the importance of aromatic chemistry in O3 production. To examine the role of VOCs and NOx in O3 chemistry, we first implement a detailed aromatic chemistry scheme in the model, which reduces the normalized mean bias of simulated O3 mixing ratios from –26% to –13%. Aromatic chemistry also increases the average net O3 production in Korea by 37%. Corrections of daytime PBL heights, which are overestimated in the model compared to lidar observations, increase the net O3 production rate by ~10%. In addition, increasing NOx emissions by 50% in the model shows best performance in reproducing O3 production characteristics, which implies that NOx emissions are underestimated in the current emissions inventory. Sensitivity tests show that a 30% decrease in anthropogenic NOx emissions in Korea increases the O3 production efficiency throughout the country, making rural regions ~2 times more efficient in producing O3 per NOx consumed. Simulated O3 levels overall decrease in the peninsula except for urban and other industrial areas, with the largest increase (~6 ppbv) in the Seoul Metropolitan Area (SMA). However, with simultaneous reductions in both NOx and VOCs emissions by 30%, O3 decreases in most of the country, including the SMA. This implies the importance of concurrent emission reductions for both NOx and VOCs in order to effectively reduce O3 levels in Korea

Air-Sea Exchange in the Global Mercury Cycle

We present results from a new global atmospheric mercury model coupled with a mixed layer slab ocean. The ocean model describes the interactions of the mixed layer with the atmosphere and deep ocean, as well as conversion between elemental, divalent, and nonreactive mercury species. Our global mean aqueous concentrations of 0.07 pM elemental, 0.80 pM reactive, and 1.51 pM total mercury agree with observations. The ocean provides a 14.1 Mmol yr−1 source of mercury to the atmosphere, at the upper end of previous estimates. Re-emission of previously deposited mercury constitutes 89% of this flux. Ocean emissions are largest in the tropics and downwind of industrial regions. Midlatitude ocean emissions display a large seasonal cycle induced by biological productivity. Oceans contribute 54% (36%) of surface atmospheric mercury in the Southern (Northern) Hemisphere. We find a large net loss of mercury to the deep ocean (8.7 Mmol yr−1), implying a ∼0.7%/year increase in deep ocean concentrations.Earth and Planetary SciencesEngineering and Applied Science

Sulfate Formation in Sea-Salt Aerosols: Constraints from Oxygen Isotopes

We use observations of the mass-independent oxygen isotopic composition (Δ17O) of sulfate in the marine boundary layer (MBL) to quantify the sulfate source from aqueous SO2 (S(IV)) oxidation by O3 in alkaline sea-salt aerosols. Oxidation by O3 imparts a large Δ17O signature to the resulting sulfate (8.8‰) relative to oxidation by H2O2 (0.9‰) or by OH or O2 (0‰). Ship data from two Indian Ocean Experiment (INDOEX) cruises in the Indian Ocean indicate Δ17O values usually 70%) and increases MBL sulfate concentrations by typically >10% (up to 30%). Globally, this mechanism contributes 9% of atmospheric sulfate production and 1% of the sulfate burden. The impact on H2SO4 (g) formation and implications for the potential formation of new particles in the MBL warrants inclusion in models examining the radiative effects of sulfate aerosols.Earth and Planetary SciencesEngineering and Applied Science

A Large Organic Aerosol Source in the Free Troposphere Missing from Current Models

Aircraft measurements of organic carbon (OC) aerosol by two independent methods over the NW Pacific during the ACE-Asia campaign reveal unexpectedly high concentrations in the free troposphere (FT). Concentrations average 4 μg sm−3 in the 2–6.5 km column with little vertical gradient. These values are 10–100 times higher than computed with a global chemical transport model (CTM) including a standard 2-product simulation of secondary organic aerosol (SOA) formation based on empirical fits to smog chamber data. The same CTM reproduces the observed vertical profiles of sulfate and elemental carbon aerosols, which indicate sharp decreases from the boundary layer to the FT due to wet scavenging. Our results suggest a large, sustained source of SOA in the FT from oxidation of long-lived volatile organic compounds. We find that this SOA is the dominant component of aerosol mass in the FT, with implications for intercontinental pollution transport and radiative forcing of climate.Earth and Planetary SciencesEngineering and Applied Science

North American Pollution Outflow and the Trapping of Convectively Lifted Pollution by Upper-Level Anticyclone

We examine the major outflow pathways for North American pollution to the Atlantic in summer by conducting a 4-year simulation with the GEOS-CHEM global chemical transport model, including a coupled ozone-aerosol simulation with 1° × 1° horizontal resolution for summer 2000. The outflow is driven principally by cyclones tracking eastward across North America at 45–55°N, every 5 days on average. Anthropogenic and fire effluents from western North America are mostly transported north and east, eventually merging with the eastern U.S. pollution outflow to the Atlantic. A semipermanent upper-level anticyclone traps the convective outflow and allows it to age in the upper troposphere over the United States for several days. Rapid ozone production takes place in this outflow, driven in part by anthropogenic and lightning NO x and in part by HO x radicals produced from convectively lifted CH2O that originates from biogenic isoprene. This mechanism could explain ozonesonde observations of elevated ozone in the upper troposphere over the southeastern United States. Asian and European pollution influences in the North American outflow to the Atlantic are found to be dispersed into the background and do not generate distinct plumes. Satellite observations of CO columns from MOPITT and of aerosol optical depths (AODs) from MODIS provide useful mapping of outflow events, despite their restriction to clear-sky scenes.Earth and Planetary Science

Possible link between Arctic Sea ice and January PM10 concentrations in South Korea

In this study, we investigated the possible teleconnection between PM10 concentrations in South Korea and Arctic Sea ice concentrations at inter-annual time scales using observed PM10 data from South Korea, NCEP R2 data, and NOAA Sea Ice Concentration (SIC) data from 2001 to 2018. From the empirical orthogonal function (EOF) analysis, we found that the first mode (TC1) was a large-scale mode for PM10 in South Korea and explained about 27.4% of the total variability. Interestingly, the TC1 is more dominantly influenced by the horizontal ventilation effect than the vertical atmospheric stability effect. The pollution potential index (PPI), which is defined by the weighted average of the two ventilation effects, is highly correlated with the TC1 of PM10 at a correlation coefficient of 0.75, indicating that the PPI is a good measure for PM10 in South Korea at inter-annual time scales. Regression maps show that the decrease of SIC over the Barents Sea is significantly correlated with weakening of high pressure over the Ural mountain range region, the anomalous high pressure at 500 hPa over the Korean peninsula, and the weakening of the Siberian High and Aleutian low. Moreover, these patterns are similar to the correlation pattern with the PPI, suggesting that the variability of SIC over the Barents Sea may play an important role in modulating the variability of PM10 in South Korea through teleconnection from the Barents Sea to the Korean peninsula via Eurasia

Observations of Reactive Gaseous Mercury in the Free Troposphere at the Mount Bachelor Observatory

We measured gaseous elemental mercury (GEM), particulate mercury (PHg), and reactive gaseous mercury (RGM), along with CO, ozone, and aerosol scatter at the Mount Bachelor Observatory (2.7 km above sea level), Oregon, from May to August 2005. The mean mercury concentrations (at standard conditions) were 1.54 ng/m3 (GEM), 5.2 pg/m3 (PHg), and 43 pg/m3 (RGM). RGM enhancements, up to 600 pg/m3, occurred at night and were linked to a diurnal pattern of upslope and downslope flows that mixed in boundary layer air during the day and free tropospheric air at night. During the night, RGM was inversely correlated (P < 0.0001) with CO (r = −0.36), GEM (r = −0.73), and H2O (r = −0.44), was positively correlated with ozone (r = 0.38), and could not be linked to recent anthropogenic emissions from local sources or long-range transport. Principal component analysis and a composite of change in RGM versus change in GEM during RGM enhancements indicate that a nearly quantitative shift in speciation is associated with increases in ozone and decreases in water vapor and CO. This argues that high concentrations of RGM are present in the free troposphere because of in situ oxidation of GEM to RGM. A global chemical transport model reproduces the RGM mean and diurnal pattern but underestimates the magnitude of the largest observed enhancements. Since the only modeled, in situ RGM production mechanisms are oxidation of GEM by ozone and OH, this implies that there are faster reaction rates or additional RGM production mechanisms in the free troposphere.Earth and Planetary SciencesEngineering and Applied Science