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Direct Two-Dimensional Time Series Observation of pH Distribution around Dissolving Calcium Carbonate Crystals in Aqueous Solution

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posted on 28.06.2019, 00:00 by Jun Kawano, Takashi Toyofuku, Kaede Nishimura, Akiyuki Ueda, Yukiko Nagai, Sachiko Kawada, Henry Teng, Takaya Nagai
Monitoring in situ local pH changes to dissolving/growing crystal surfaces is critical to decipher the related mechanisms. To date, however, reliable techniques to acquire such measurements remain under-developed. Here we report the first successful attempt to observe time-resolved, two-dimensional distribution of pH around crystals dissolving in aqueous solutions. The local pH change around dissolving calcium carbonate polymorphs (calcite and aragonite) was visualized by using the fluorescent probe 8-hydroxypyrene-1,3,6-trisul-fonic acid HPTS under an optical microscope. The observations unambiguously showed that pH increased and saturated rapidly immediately adjacent to the reactive surfaces on the cleavage rhombs of calcite. Approximately 1 mm away, however, the increase slowed down significantly, generating a steep pH gradient at the crystal–water interface. Aragonite, which has rough fractured surfaces in contrast to the well cleaved calcite, dissolved much faster and showed a stronger tendency for the pH profile to trace the outer shape of crystal grains. These results indicate that this technique is sensitive enough to detect small differences in dissolution between polymorphs and surface conditions and may be used as an effective tool to visualize and understand various reactions in aqueous solutions including environmental weathering and material erosion.