Search for: All records

Abstract Tropospheric reactive bromine (Br_y) influences the oxidation capacity of the atmosphere by acting as a sink for ozone and nitrogen oxides. Aerosol acidity plays a crucial role in Br_yabundances 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 Br_ychanges, consistent with the observed relationship between acidity and bromine. The influence of atmospheric acidity on Br_yshould be considered in interpretation of ice‐core bromine trends. 

Abstract Snowpack emissions are recognized as an important source of gas‐phase reactive bromine in the Arctic and are necessary to explain ozone depletion events in spring caused by the catalytic destruction of ozone by halogen radicals. Quantifying bromine emissions from snowpack is essential for interpretation of ice‐core bromine. We present ice‐core bromine records since the pre‐industrial (1750 CE) from six Arctic locations and examine potential post‐depositional loss of snowpack bromine using a global chemical transport model. Trend analysis of the ice‐core records shows that only the high‐latitude coastal Akademii Nauk (AN) ice core from the Russian Arctic preserves significant trends since pre‐industrial times that are consistent with trends in sea ice extent and anthropogenic emissions from source regions. Model simulations suggest that recycling of reactive bromine on the snow skin layer (top 1 mm) results in 9–17% loss of deposited bromine across all six ice‐core locations. Reactive bromine production from below the snow skin layer and within the snow photic zone is potentially more important, but the magnitude of this source is uncertain. Model simulations suggest that the AN core is most likely to preserve an atmospheric signal compared to five Greenland ice cores due to its high latitude location combined with a relatively high snow accumulation rate. Understanding the sources and amount of photochemically reactive snow bromide in the snow photic zone throughout the sunlit period in the high Arctic is essential for interpreting ice‐core bromine, and warrants further lab studies and field observations at inland locations. 

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. 

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. 

Future climate change may bring local benefits or penalties to surface air pollution, resulting from changing temperature, precipitation, and transport patterns, as well as changes in climate-sensitive natural precursor emissions. Here, we estimate the climate penalties and benefits at the end of this century with regard to surface ozone and fine particulate matter (PM ${}_{2.5}$; excluding dust and smoke) using a one-way offline coupling between a general circulation model and a global 3-D chemical-transport model. We archive meteorology for the present day (2005 to 2014) and end of this century (2090 to 2099) for seven future scenarios developed for Phase 6 of the Coupled Model Intercomparison Project. The model isolates the impact of forecasted anthropogenic precursor emission changes versus that of climate-only driven changes on surface ozone and PM ${}_{2.5}$for scenarios ranging from extreme mitigation to extreme warming. We then relate these changes to impacts on human mortality and crop production. We find ozone penalties over nearly all land areas with increasing warming. We find net benefits due to climate-driven changes in PM ${}_{2.5}$in the Northern Extratropics, but net penalties in the Tropics and Southern Hemisphere, where most population growth is forecast for the coming century. 

Abstract. Comprehensive evaluation of the effects of post-depositional processing is a prerequisite for appropriately interpreting ice-core records of nitrate concentration and isotopes. In this study, we developed an inverse model that uses archived snow/ice-core nitrate signals to reconstruct primary nitrate flux (i.e., the deposition flux of nitrate to surface snow that originates from long-range transport or stratospheric input) and its isotopes (δ15N and Δ17O). The model was then applied to two polar sites, Summit, Greenland, and Dome C, Antarctica, using measured snowpack nitrate concentration and isotope profiles in the top few meters. At Summit, the model successfully reproduced the observed atmospheric δ15N(NO3-) and Δ17O(NO3-) and their seasonality. The model was also able to reasonably reproduce the observed snowpack nitrate profiles at Dome C as well as the skin layer and atmospheric δ15N(NO3-) and Δ17O(NO3-) at the annual scale. The calculated Fpri at Summit was 6.9 × 10−6 kgN m2 a−1, and the calculated Δ17O(NO3-) of Fpri is consistent with atmospheric observations in the Northern Hemisphere. However, the calculated δ15N(NO3-) of Fpri displays an opposite seasonal pattern to atmospheric observations in the northern mid-latitudes, but it is consistent with observations in two Arctic coastal sites. The calculated Fpri at Dome C varies from 1.5 to 2.2 × 10−6 kgN m−2 a−1, with δ15N(NO3-) of Fpri varying from 6.2 ‰ to 29.3 ‰ and Δ17O(NO3-) of Fpri varying from 48.8 ‰ to 52.6 ‰. The calculated Fpri at Dome C is close to the previous estimated stratospheric denitrification flux in Antarctica, and the high δ15N(NO3-) and Δ17O(NO3-) of Fpri at Dome C also point towards the dominant role of stratospheric origin of primary nitrate to Dome C.