Potassium and other minor elements in Porites corals: implications for skeletal geochemistry and paleoenvironmental reconstruction

Abstract

We investigated how the K/Ca, Na/Ca, Mg/Ca, and Sr/Ca ratios of powders ground from Porites coral skeletons are changed by cumulative chemical treatments to the powders: first with distilled/deionized water (DDW), next with 30 % H2O2 and then with 0.004 mol l−1 HNO3. The K/Ca, Na/Ca, and Mg/Ca ratios were decreased with the DDW treatment and then increased with the H2O2 and HNO3 treatments; the Sr/Ca ratio was slightly decreased through the cumulative treatments, suggesting fine-scale (tens of μm or less) elemental heterogeneities in the skeleton—K, Na, and Mg are significantly enriched at the skeletal surface and also at the center of calcification (COC); in contrast, the heterogeneity of Sr is very small. We suggest that the principal mechanisms of K incorporation into coral skeleton are (1) ion incorporation into lattice defects/distortions and (2) ion adsorption onto crystal discontinuities (including crystal–organic matter interfaces) as forms of K+ and KSO4−. Furthermore, we measured the element/Ca ratios of a modern Porites coral skeleton along its growth direction at 2-mm intervals. Results showed that all the element/Ca ratios displayed annual cycles, that the K/Ca and Na/Ca ratios covaried with each other, and that the annual-minimum K/Ca and Na/Ca ratios coincided with the annual high-density band in the skeleton. It is unclear what environmental factors may cause the covarying annual cycles of the K/Ca and Na/Ca ratios; however, as a possible explanation, the cycles may be due not to environmental factors, but to a combined effect of (1) the K and Na enrichment at the COC, (2) annual bands of high- and low-density skeleton, and (3) mm-scale element/Ca measurements along the skeletal growth direction. This kind of effect on geochemical proxies of which the concentrations significantly differ between the COC and surrounding skeleton may generate false or distorted paleoenvironmental signals.