Abstract
Quantifying the saturation state of aragonite (ΩAr) within
the calcifying fluid of corals is critical for understanding their
biomineralization process and sensitivity to environmental changes including
ocean acidification. Recent advances in microscopy, microprobes, and isotope
geochemistry enable the determination of calcifying fluid pH and
[CO32−], but direct quantification of ΩAr (where
ΩAr = [CO32−][Ca2+]∕Ksp) has proved
elusive. Here we test a new technique for deriving ΩAr based
on Raman spectroscopy. First, we analysed abiogenic aragonite crystals
precipitated under a range of ΩAr from 10 to 34, and we
found a strong dependence of Raman peak width on ΩAr with no
significant effects of other factors including pH, Mg∕Ca partitioning,
and temperature. Validation of our Raman technique for corals is difficult
because there are presently no direct measurements of calcifying fluid
ΩAr available for comparison. However, Raman analysis of the
international coral standard JCp-1 produced ΩAr of
12.3 ± 0.3, which we demonstrate is consistent with published skeletal
Mg∕Ca, Sr∕Ca, B∕Ca, δ11B, and δ44Ca
data. Raman measurements are rapid ( ≤ 1 s), high-resolution
( ≤ 1 µm), precise (derived ΩAr ± 1 to
2 per spectrum depending on instrument configuration), accurate ( ±2 if
ΩAr < 20), and require minimal sample preparation, making
the technique well suited for testing the sensitivity of coral calcifying
fluid ΩAr to ocean acidification and warming using samples
from natural and laboratory settings. To demonstrate this, we also show a
high-resolution time series of ΩAr over multiple years of
growth in a Porites skeleton from the Great Barrier Reef, and we
evaluate the response of ΩAr in juvenile Acropora
cultured under elevated CO2 and temperature.
Citation
ID:
185905
Ref Key:
decarlo2017biogeosciencescoral