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Abstract Tropospheric ozone is an air pollutant and a greenhouse gas whose anthropogenic production is limited principally by the supply of nitrogen oxides (NOx) from combustion. Tropospheric ozone in the northern hemisphere has been rising despite the flattening of NOx emissions in recent decades. Here we propose that this sustained increase could result from the photolysis of nitrate particles (pNO3−) to regenerate NOx. Including pNO3− photolysis in the GEOS‐Chem atmospheric chemistry model improves the consistency with ozone observations. Our simulations show that pNO3− concentrations have increased since the 1960s because of rising ammonia and falling SO2 emissions, augmenting the increase in ozone in the northern extratropics by about 50% to better match the observed ozone trend. pNO3− will likely continue to increase through 2050, which would drive a continued increase in ozone even as NOx emissions decrease. More work is needed to better understand the mechanism and rates of pNO3− photolysis.

Abstract 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.

Abstract Perchlorate has been observed in many environments on Earth and Mars but its sources remain poorly quantified. In this study, we use a global three‐dimensional chemical transport model to simulate perchlorate's gas‐phase photochemical production, atmospheric transport, and deposition on Earth's surface. Model predictions are compared to newly compiled observations of atmospheric concentrations, deposition flux, and oxygen isotopic composition of perchlorate. We find that the modeled gas‐phase production of perchlorate is consistent with reported stratospheric observations. Nevertheless, we show that this mechanism alone cannot explain the high levels of perchlorate observed at many near‐surface sites (aerosol concentrations >0.1 ng m−3 and deposition fluxes >10 g km−2 yr−1) or the low 17O‐excess observed in perchlorate sampled from pristine environments (

Anthropogenic sulfate aerosols are estimated to have offset 60% of greenhouse-gas-induced warming in the Arctic, a region warming four times faster than the rest of the world. However, sulfate radiative forcing estimates remain uncertain because the relative contributions from anthropogenic versus natural sources to total sulfate aerosols are unknown. Here we measure sulfur isotopes of sulfate in a Summit, Greenland ice core from 1850 to 2006 CE to quantify the contribution of anthropogenic sulfur emissions to ice core sulfate. We use a Keeling plot to determine the anthropogenic sulfur isotopic signature (δ ^34 S _anthro = +2.9 ± 0.3 ‰), and compare this result to a compilation of sulfur isotope measurements of oil and coal. Using δ ^34 S _anthro , we quantify anthropogenic sulfate concentration separated from natural sulfate. Anthropogenic sulfate concentration increases to 67 ± 7% of non-sea-salt sulfate (65.1 ± 20.2 µ g kg ^−1 ) during peak anthropogenic emissions from 1960 to 1990 and decreases to 45 ± 11% of non-sea-salt sulfate (25.4 ± 12.8 µ g kg ^−1 ) from 1996 to 2006. These observations provide the first long-term record of anthropogenic sulfate distinguished from natural sources (e.g. volcanoes, dimethyl sulfide), and can be used to evaluate model characterization of anthropogenic sulfate aerosol fraction and radiative forcing over the industrial era.

Abstract 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.

The quasi-biennial oscillation (QBO) and sudden stratospheric warmings (SSWs) during the Last Glacial Maximum (LGM) are investigated in simulations using the Whole Atmosphere Community Climate Model version 6 (WACCM6). We find that the period of QBO, which is 27 months in the preindustrial and modern climate simulations, was 33 months in the LGM simulation using the proxy sea surface temperatures (SSTs) and 41 months using the model-based LGM SSTs. We show that the longer QBO period in the LGM is due to weaker wave forcing. The WACCM6 simulations of the LGM, preindustrial, and modern climates do not support previous modeling work that suggests that the QBO amplitude is smaller (larger) in a warmer (colder) climate. We find that SSWs in the LGM occurred later in the year, as compared to the preindustrial and modern climate, but that time of the final warming was similar. The difference in SSW frequency is inconclusive.