Formation processes of paper-thin raft and coated bubble: Calcium carbonate deposition at gas-water interface

Travertines are hot spring carbonate deposits that exhibit characteristic fabrics, including a paper-thin raft and a coated bubble formed by the calcification of water and bubble surfaces, respectively. A previous study interpreted that compared with the water surface, the bubble surface displays more active CO2 degassing and resultant active CaCO3 precipitation. However, considering the CO2 partial pressure and the volumes of atmosphere and bubbles, it is possible that more active CO2 degassing occurs on the water surface. In addition, the surfaces of water and bubbles at the travertine-depositing sites are negatively charged, but it is still unclear whether the CaCO3 nucleation on these surfaces occurs via amorphous precursors, like the CaCO3 nucleation on negatively charged organic matter. This study provides a solution to these uncertainties by examining the aragonitic travertines formed in the Nagayu area of Japan. Through field observations, two types of paper-thin rafts were recognized: one with a smooth surface and formed in approximately 1 h, and the other with a rough surface and formed in approximately 3 h. In addition, the bubbles generated on the microbial mat during the daytime were covered with white minerals within an hour, and with ivory-colored minerals over 8 h after sunset, forming firm coated bubbles. Microelectrode measurements revealed that the active CO2 degassing on the water surface significantly increased the CaCO3 saturation state to cause active CaCO3 precipitation. In contrast, less active CO2 degassing on the bubble surface did not increase the saturation state, and moderate CaCO3 precipitation occurred due to the moderately high saturation state of the hot spring water. Various microscopic observations revealed that the smooth-surfaced paper-thin raft comprises a micritic layer of approximately 10-20 mu m, which represents tightly arranged submicron-sized granular aragonite. At the lower surface of this layer, hemispherical aragonite partially grew toward the hot spring water. In addition, the rough-surfaced paper-thin raft and coated bubble comprise bundled and acicular aragonites arranged along the surfaces of water and bubble, from which hemispherical aragonite grew toward the hot spring water. Neither the paper-thin raft nor the coated bubble contains primary amorphous CaCO3. These results suggest that the smooth-surfaced paper-thin raft is formed by active CaCO3 nucleation on the water surface and subsequent crystal growth, and that the water surface is unfavorable for preserving the amorphous precursors potentially involved in the nucleation. The roughsurfaced paper-thin raft and the coated bubble could have been formed by the attachment of externally formed acicular aragonite to the water/bubble surface and subsequent crystal growth. The revealed formation processes of the paper-thin raft and coated bubble provide valuable information for interpreting their formation mechanism in other travertine deposits, including those in the geological past.