Beginnings

1 page(s

Evaluating the impact of blowing-snow sea salt aerosol on springtime BrO and O3 in the Arctic

We use the GEOS-Chem chemical transport model to examine the influence of bromine release from blowingsnow sea salt aerosol (SSA) on springtime bromine activation and O3 depletion events (ODEs) in the Arctic lower troposphere. We evaluate our simulation against observations of tropospheric BrO vertical column densities (VCDtropo) from the GOME-2 (second Global Ozone Monitoring Experiment) and Ozone Monitoring Instrument (OMI) spaceborne instruments for 3 years (2007-2009), as well as against surface observations of O3. We conduct a simulation with blowingsnow SSA emissions from first-year sea ice (FYI; with a surface snow salinity of 0.1 psu) and multi-year sea ice (MYI; with a surface snow salinity of 0.05 psu), assuming a factor of 5 bromide enrichment of surface snow relative to seawater. This simulation captures the magnitude of observed March-April GOME-2 and OMI VCDtropo to within 17 %, as well as their spatiotemporal variability (r D 0:76-0.85). Many of the large-scale bromine explosions are successfully reproduced, with the exception of events in May, which are absent or systematically underpredicted in the model. If we assume a lower salinity on MYI (0.01 psu), some of the bromine explosions events observed over MYI are not captured, suggesting that blowing snow over MYI is an important source of bromine activation. We find that the modeled atmospheric deposition onto snow-covered sea ice becomes highly enriched in bromide, increasing from enrichment factors of ~ 5 in September-February to 10-60 in May, consistent with composition observations of freshly fallen snow. We propose that this progressive enrichment in deposition could enable blowing-snow-induced halogen activation to propagate into May and might explain our late-spring underestimate in VCDtropo. We estimate that the atmospheric deposition of SSA could increase snow salinity by up to 0.04 psu between February and April, which could be an important source of salinity for surface snow on MYI as well as FYI covered by deep snowpack. Inclusion of halogen release from blowing-snow SSA in our simulations decreases monthly mean Arctic surface O3 by 4-8 ppbv (15 %-30 %) in March and 8-14 ppbv (30 %-40 %) in April. We reproduce a transport event of depleted O3 Arctic air down to 40 N observed at many sub-Arctic surface sites in early April 2007. While our simulation captures 25 %-40 % of the ODEs observed at coastal Arctic surface sites, it underestimates the magnitude of many of these events and entirely misses 60 %-75 % of ODEs. This difficulty in reproducing observed surface ODEs could be related to the coarse horizontal resolution of the model, the known biases in simulating Arctic boundary layer exchange processes, the lack of detailed chlorine chemistry, and/or the fact that we did not include direct halogen activation by snowpack chemistry

Anthropogenic Influence on Tropospheric Reactive Bromine Since the Pre‐industrial: Implications for Arctic Ice‐Core Bromine Trends

Tropospheric reactive bromine (Bry) influences the oxidation capacity of the atmosphere by acting as a sink for ozone and nitrogen oxides. Aerosol acidity plays a crucial role in Bry abundances through acid-catalyzed debromination from sea-salt-aerosol, the largest global source. Bromine concentrations in a Russian Arctic ice-core, Akademii Nauk, show a 3.5-fold increase from pre-industrial (PI) to the 1970s (peak acidity, PA), and decreased by half to 1999 (present day, PD). Ice-core acidity mirrors this trend, showing robust correlation with bromine, especially after 1940 (r = 0.9). Model simulations considering anthropogenic emission changes alone show that atmospheric acidity is the main driver of Bry changes, consistent with the observed relationship between acidity and bromine. The influence of atmospheric acidity on Bry should be considered in interpretation of ice-core bromine trends

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

Effects of Sea Salt Aerosol Emissions for Marine Cloud Brightening on Atmospheric Chemistry : Implications for Radiative Forcing

Marine cloud brightening (MCB) is proposed to offset global warming by emitting sea salt aerosols to the tropical marine boundary layer, which increases aerosol and cloud albedo. Sea salt aerosol is the main source of tropospheric reactive chlorine (Cly) and bromine (Bry). The effects of additional sea salt on atmospheric chemistry have not been explored. We simulate sea salt aerosol injections for MCB under two scenarios (212–569 Tg/a) in the GEOS-Chem global chemical transport model, only considering their impacts as a halogen source. Globally, tropospheric Cly and Bry increase (20–40%), leading to decreased ozone (−3 to −6%). Consequently, OH decreases (−3 to −5%), which increases the methane lifetime (3–6%). Our results suggest that the chemistry of the additional sea salt leads to minor total radiative forcing compared to that of the sea salt aerosol itself (~2%) but may have potential implications for surface ozone pollution in tropical coastal regions

Heterogeneous Nitrate Production Mechanisms in Intense Haze Events in the North China Plain

Abstract Studies of wintertime air quality in the North China Plain (NCP) show that particulate-nitrate pollution persists despite rapid reduction in NOx emissions. This intriguing NOx-nitrate relationship may originate from non-linear nitrate-formation chemistry, but it is unclear which feedback mechanisms dominate in NCP. In this study, we re-interpret the wintertime observations of 17O excess of nitrate (∆17O(NO3−)) in Beijing using the GEOS-Chem (GC) chemical transport model to estimate the importance of various nitrate-production pathways and how their contributions change with the intensity of haze events. We also analyze the relationships between other metrics of NOy chemistry and [PM2.5] in observations and model simulations. We find that the model on average has a negative bias of −0.9‰ and −3617O(NO3−) and [Ox,major] (≡ [O3] + [NO2] + [p-NO3−]), respectively, while overestimating the nitrogen oxidation ratio ([NO3−]/([NO3−] + [NO2])) by +0.12 in intense haze. The discrepancies become larger in more intense haze. We attribute the model biases to an overestimate of NO2-uptake on aerosols and an underestimate in wintertime O3 concentrations. Our findings highlight a need to address uncertainties related to heterogeneous chemistry of NO2 in air-quality models. The combined assessment of observations and model results suggest that N2O5 uptake in aerosols and clouds is the dominant nitrate-production pathway in wintertime Beijing, but its rate is limited by ozone under high-NOx-high-PM2.5 conditions. Nitrate production rates may continue to increase as long as [O3] increases despite reduction in [NOx], creating a negative feedback that reduces the effectiveness of air pollution mitigation

Decreases in Mercury Wet Deposition over the United States during 2004–2010: Roles of Domestic and Global Background Emission Reductions

atmospher