Determination of fluorine distribution in shark teeth by laser-induced breakdown spectroscopy.

Quantifying the chemical composition of fast-growing hard tissues in the environment can shed valuable information in terms of understanding ecosystems both prehistoric and current. Changes in chemical composition can be correlated with environmental conditions and can provide information about the organism's life. Sharks can lose 0.1 to 1.1 teeth/day, depending on species, which offers a unique opportunity to record environmental changes over a short duration of time. Shark teeth contain a biomineral phase that is made up of fluorapatite [Ca5(PO4)3F], and the F distribution within the tooth can be correlated to tooth hardness. Typically, this is determined by bulk acid digestion, energy-dispersive X-ray spectroscopy (EDS), or wavelength-dispersive spectroscopy. Here we present laser-induced breakdown spectroscopy (LIBS) as an alternative and faster approach for determining F distribution within shark teeth. Using a two-volume laser ablation chamber (TwoVol3) with innovative embedded collection optics for LIBS, shark teeth were investigated from sand tiger (Carcharias Taurus), tiger (Galeocerdo Cuvier), and hammerhead sharks (Sphyrnidae). Fluorine distribution was mapped using the CaF 603 nm band (CaF, Β 2Σ+ → X 2Σ+) and quantified using apatite reference materials. In addition, F measurements were cross referenced with EDS analyses to validate the findings. Distributions of F (603 nm), Na (589 nm), and H (656 nm) within the tooth correlate well with the expected biomineral composition and expected tooth hardness. This rapid methodology could transform the current means of determining F distribution, particularly when large sample specimens (350 mm2, presented here) and large quantities of specimens are of interest.

Volcanic glass properties from 1459 C.E. volcanic event in South Pole ice core dismiss Kuwae caldera as a potential source.

A large volcanic sulfate increase observed in ice core records around 1450 C.E. has been attributed in previous studies to a volcanic eruption from the submarine Kuwae caldera in Vanuatu. Both EPMA-WDS (electron microprobe analysis using a wavelength dispersive spectrometer) and SEM-EDS (scanning electron microscopy analysis using an energy dispersive spectrometer) analyses of five microscopic volcanic ash (cryptotephra) particles extracted from the ice interval associated with a rise in sulfate ca. 1458 C.E. in the South Pole ice core (SPICEcore) indicate that the tephra deposits are chemically distinct from those erupted from the Kuwae caldera. Recognizing that the sulfate peak is not associated with the Kuwae volcano, and likely not a large stratospheric tropical eruption, requires revision of the stratospheric sulfate injection mass that is used for parameterization of paleoclimate models. Future work is needed to confirm that a volcanic eruption from Mt. Reclus is one of the possible sources of the 1458 C.E. sulfate anomaly in Antarctic ice cores.