Raman analysis of octocoral carbonate ion structural disorder along a natural depth gradient, Kona coast, Hawai'i

Both environmental and physiological factors cause carbonate ion structural disorder in biogenic Mg-calcites. A major component of this disorder is driven by the incorporation of Mg through environmental forcing and growth rate kinetics although non-Mg factors (e.g., other cation/anion impurities, organic molecules) also contribute. Understanding the drivers of Mg content in biogenic calcite and its effects on disorder has implications for octocoral Mg paleo-proxies and the stability and diagenetic alteration of their calcitic skeletons. However, prior studies of biogenic Mg-calcites have often been complicated by sampling inconsistencies over space and time and potential intra-sample Mg variability. This study aims to analyze the relative contributing factors of octocoral Mg-calcite structural disorder along gradients of both depth and growth rate. Calcitic octocorals (Coralliidae and Keratoisididae, N = 28) were collected from 221-823 m depths across a natural gradient in biogeochemical parameters (pH: 7.4-7.9, T: 5-16 ?) off the Kona coast of Hawai'i Island and were analyzed using Raman spectroscopy. Samples were collected during the same month, controlling for potential seasonal variability. Raman spectral parameters from the ?(1) peak quantified total carbonate ion structural disorder (full-width at half maximum height [FWHM] of ?(1)) and Mg content (?(1) position, Raman shift). The total structural disorder was then partitioned into Mg-driven and non-Mg driven components (residual ?(1) FWHM). The total structural disorder and Mg content decreased significantly with increasing depth, correlating with temperature and carbonate system parameters. The Mg-temperature relationships from this study were also consistent with prior studies. Non-Mg structural disorder did not correlate to any environmental parameters. When measured across an intra-sample gradient of ontogenetic growth rate, total structural disorder, Mg content, and non-Mg structural disorder increased with growth rate for all but one taxon, demonstrating the kinetic effect of growth rate as well as potential taxon-specific physiological effects. These results provide insight into how environmental and growth rate kinetic effects independently afect different components of carbonate ion structural disorder (Mg content and non-Mg factors). These findings also suggest that Raman spectroscopy may be helpful in quantifying solubility within biogenic calcites.