Freezing-induced acidification of sea ice brine

• Published in: Science of The Total Environment
• Main Authors: Veselý, L., Štůsek, R., Mikula, O., Yang, X., Heger, D.
• Format: Article in Journal/Newspaper
• Language: unknown
• Published: Elsevier 2024
• Subjects: Sea ice
• Online Access: http://nora.nerc.ac.uk/id/eprint/537655/; https://www.sciencedirect.com/science/article/pii/S0048969724043420?via%3Dihub

The acidity of sea ice and snow plays a key role in the chemistry of the cryosphere; an important example lies in the photochemical catalytic release of reactive bromine in polar regions, facilitated at pHs below 6.5. We apply in-situ acid-base indicators to probe the microscopic acidity of the brine within the ice matrix in artificial sea water at a range of concentrations (0.35–70 PPT) and initial pHs (6–9). The results are supported by analogous measurements of the most abundant salts in seawater: NaCl, Na2SO4, and CaCO3. In the research herein, the acidity is expressed in terms of the Hammett acidity function, H2−. The obtained results show a pronounced acidity increase in sea water after freezing at −15 °C and during the subsequent cooling down to −50 °C. Importantly, we did not observe any significant hysteresis; the values of acidity upon warming markedly resembled those at the corresponding temperatures at cooling. The acidity increase is attributed to the minerals' crystallization, which is accompanied by a loss of the buffering capacity. Our observations show that lower salinity sea water samples (≤ 3.5 PPT) reach pH values below 6.5 at the temperature of −15 °C, whereas higher salinity ices attain such values only at −30 °C. The ensuing implications for polar chemistry and the relevance to the field measurements are discussed.