Elucidating the Composition and Distribution of Trace Metals in Corals

Abstract:

Coral reefs host a plethora of marine life and thereby provide a wealth of aesthetic and economic benefits to coastal countries. Anthropogenic influences, including local coastal water contamination, however threaten the health of these delicate ecosystems. Metal incorporation into carbonate minerals, the backbone of coral reefs, is known to have a large yet variable impact on carbonate structure and solubility. Yet, trace metal influences on the structure, porosity, composition, and solubility of coral skeletons is largely unknown. Here, we coupled synchrotron-based micro-X-ray fluorescence (u-XRF) mapping and X-ray absorption near edge structure (XANES) spectroscopy with micro-X-ray diffraction (XRD) to explore the distribution and speciation of trace metals associated with corals and their impact on the carbonate structure of corals obtained from reefs varying in anthropogenic influence – Florida Keys, FL USA and the Federated States of Micronesia. Iron and copper were the most abundant metals in the biological tissue, while in some areas zinc was observed in the tissue, overlapping with the skeleton. Trace metals were not detectable in the aragonite skeletons; in fact, the distributions of Ca and Fe were anti-correlated. XANES spectra show that the iron is primarily Fe(III), likely as the poorly crystalline iron oxide ferrihydrite structure or trapped within ferretin proteins. The same trace metals were observed in corals of different species and from different environments. This in situ investigation corroborates previous studies that corals tend to incorporate iron into the biological components but not into the aragonite skeleton. Given the dominant partitioning of metals within the biological tissue rather than the coral skeleton, the specific carbon molecules responsible for metal attenuation and their fate under changing geochemical conditions and following coral death require exploration.