Abiotic and Biotic Processes Controlling Deposition of Calcite and Hydrotalcite Calcretes on Niue Island, Southwest Pacific

Calcretes are indurated terrestrial carbonates that are widespread in arid and semi-arid settings and serve as important archives of present and past environments. Here, we use geochemical tools to explore the nature and origin of calcretes documented from tropical Niue Island in the Southwest Pacific. The study recognizes two types of calcretes that differ in their mineral assemblage, microfabrics, elemental chemistry, and carbon and oxygen isotopes. The calcretes common in the paleo-lagoon soils consist of 90% low-Mg calcite and ~10% highly weathered Mg-Al silicates. These pedogenic calcretes formed in the soil profiles within the vadose zone bear the following distinctions: (i) Fe/Al ratio of 0.75, identical to the ratio in soils (Fe/Al = 0.76 ± 0.5), substantiating the link between the calcretes and soils; (ii) presence of rhizoliths, root voids, micritic nodules, and clasts, which are consistent with a pedogenic calcrete fabric; and (iii) 13C and 18O depletions of −10.6‰ and −5.3‰, respectively, which are compatible with carbon sources from microbial and root respiration, as well as formation in oxygen isotope equilibrium with vadose waters. Unlike the pedogenic calcrete, a rare calcrete from the coastal terrace contains an exceptionally rare hydrotalcite [Mg6Al2(CO3)(OH)16(H2O)4] mineral (65%) coated by microbial films. We contend that the hydrotalcite-rich calcrete was deposited through interaction of dolomite with seawater, similar to the method of producing hydrotalcite in the laboratory. 13C and 18O enrichments of 0.8 to 1.7‰ and −1.0 to −1.6‰, respectively, are in agreement with (i) mixed carbon sources consisting of microbial CO2 degassing, seawater HCO3, and dolomite dissolution, and (ii) oxygen isotope equilibration with seawater-derived fluid.