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            The melting behavior of Ruddlesden-Popper type hybrid improper ferroelectric Sr3Zr2O7 phase in the ZrO2–SrO pseudo-binary system was investigated, and its single crystals were successfully grown. A series of the slowcooling floating zone experiments revealed that Sr3Zr2O7 melts incongruently into SrZrO3 phase and a liquid and that the compositional range where Sr3Zr2O7 and a liquid coexist is located around 70 mol% SrO composition. Based on the results, we attempted to grow Sr3Zr2O7 single crystals by the traveling solvent floating zone method using SrO-excess solvent and feed. Consequently, many small single crystals of Sr3Zr2O7 phase with several millimeters in size were discovered in the as-grown boules covered with SrO phase. The phase transition behavior of the grown crystals was investigated by differential thermal analysis with polarizing optical microscopy as well as by optical second harmonic generation measurements. We directly observed a reconstruction of orthorhombic twin domains in Sr3Zr2O7 single crystals accompanied by the first-order ferroelectric transition at about 410 ◦C.more » « less
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            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 Bryabundances 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 Brychanges, consistent with the observed relationship between acidity and bromine. The influence of atmospheric acidity on Bryshould be considered in interpretation of ice‐core bromine trends.more » « less
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            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.more » « less
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