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Abstract. Dimethyl sulfide (DMS) is primarily emitted by marine phytoplankton and oxidized in the atmosphere to form methanesulfonic acid (MSA) and sulfate aerosols. Ice cores in regions affected by anthropogenic pollution show an industrial-era decline in MSA, which has previously been interpreted as indicating a decline in phytoplankton abundance. However, a simultaneous increase in DMS-derived sulfate (bioSO4) in a Greenland ice core suggests that pollution-driven oxidant changes caused the decline in MSA by influencing the relative production of MSA versus bioSO4. Here we use GEOS-Chem, a global chemical transport model, and a zero-dimensional box model over three time periods (preindustrial era, peak North Atlantic NOx pollution, and 21st century) to investigate the chemical drivers of industrial-era changes in MSA and bioSO4, and we examine whether four DMS oxidation mechanisms reproduce trends and seasonality in observations. We find that box model and GEOS-Chem simulations can only partially reproduce ice core trends in MSA and bioSO4 and that wide variation in model results reflects sensitivity to DMS oxidation mechanism and oxidant concentrations. Our simulations support the hypothesized increase in DMS oxidation by the nitrate radical over the industrial era, which increases bioSO4 production, but competing factors such as oxidation by BrO result in increased MSA production in some simulations, which is inconsistent with observations. To improve understanding of DMS oxidation, future work should investigate aqueous-phase chemistry, which produces 82 %–99 % of MSA and bioSO4 in our simulations, and constrain atmospheric oxidant concentrations, including the nitrate radical, hydroxyl radical, and reactive halogens. 

This project intends to use the Mount Denali ice core archive to develop the most comprehensive suite of North Pacific fire and summer climate proxy records since about 2500 years before present. Wildfire is a key component of summer climate in the North Pacific where wildfires are projected to increase with continued summer warming. Studies that combine paleorecords of summer climate and wildfire are therefore critically needed, especially in the North Pacific region where fire recurrence rate and decadal-to-centennial scale climate fluctuations occur over longer time periods than are covered by direct observations. The goal of the proposed research is to improve our understanding of relationships between summertime climate and wildfire activity, focusing especially on the Medieval Climate Anomaly (MCA), when regional temperatures were perhaps as warm as the 20th century. Recent advances now permit the measurement of new fire-related (pyrogenic) compounds in ice cores, enabling the development of a robust fire record capable of rigorous comparison with regional paleoclimate reconstructions. 

An industrial-era drop in Greenland ice core methanesulfonic acid (MSA) is thought to herald a collapse in North Atlantic marine phytoplankton stocks related to a weakening of the Atlantic Meridional Overturning Circulation. In contrast, stable levels of marine biogenic sulfur production contradict this interpretation and point to changes in atmospheric oxidation as a potential cause of the MSA decline. However, the impact of oxidation on MSA production has not been quantified, nor has this hypothesis been rigorously tested. Here we present a multi-century MSA record from the Denali, Alaska, ice core, which shows an MSA decline similar in magnitude but delayed by 93 years relative to the Greenland record. Box model results using updated chemical pathways indicate that oxidation by industrial nitrate radicals has suppressed atmospheric MSA production, explaining most of Denali’s and Greenland’s MSA declines without requiring a change in phytoplankton production. The delayed timing of the North Pacific MSA decline, relative to the North Atlantic, reflects the distinct history of industrialization in upwind regions and is consistent with the Denali and Greenland ice core nitrate records. These results demonstrate that multi-decadal trends in industrial-era Arctic ice core MSA reflect rising anthropogenic pollution rather than declining marine primary production.