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Micro-X-ray fluorescence-based comparison of skeletal structure and P, Mg, Sr, O and Fe in a fossil of the cold-water coral Desmophyllum sp., NW Pacific

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Abstract

Micro-scale distributions of trace and minor elements in, for example, coral skeletons are crucial as geochemical tracers of past environmental conditions, because they have the inherent advantage of accounting for confounding diagenetic and physiological effects. To extract reproducible paleoceanographic records from coral skeletons, a selective measurement of specific ultrastructures at high spatial resolution is required. Compared to warm-water reef-building corals, such data are limited in cold-water corals and, to the best of the authors’ knowledge, the latter have to date not been examined by means of micro-X-ray fluorescence. This technique was used for micrometer-scale imaging of P, Mg, Sr, O, and Fe intensities (counts per unit time) in a fossil specimen (as yet unknown age) of the cold-water coral Desmophyllum sp. from surface sediments of the NW Pacific. Cross plots confirmed that the micro-XRF signals were associated with corresponding trends in elemental concentration (ppm). Two major structural components of the septum—centers of calcification (COCs) and the surrounding fibrous aragonite portion—differed in composition. The COCs were characterized by higher intensities of P and Mg (650 and 220 counts per 5 s, respectively), and lower intensities of Sr (2,800) and O (580; corresponding values for the fibrous aragonite are 370, 180, 3,300 and 620 counts per 5 s, respectively). Oxygen intensity values were mostly homogeneous, but slightly lower in COCs and substantially higher in a well-defined patch in the fibrous aragonite. The mostly homogeneous P signals in the fibrous aragonite confirm the utility of this structural component and of coral septa in general for tracer studies of oceanic P. Nevertheless, spot occurrences of elevated P (>950 counts per 5 s) spanning tens of micrometers in specific parts of the fibrous region of the septum would cause overestimates of oceanic P, and should evidently not be overlooked in future research. The distribution of Fe showed no correlation with P, indicating no significant contamination in the form of P-bearing diagenetic ferromanganese precipitates. Such hotspots plausibly reflect the presence of other mineral phases, such as crystalline hydroxylapatite inclusions or contamination with organic material. The P signal intensity was positively correlated with Mg (r=0.553, p<0.001), and negatively with Sr (r=–0.489, p<0.001) and O (r=–0.311, p<0.001). There was no discernible evidence of control by water temperature in the Sr distribution pattern. These findings establish micro-X-ray fluorescence as a highly suitable pre-screening tool in cold-water coral sclerochronology, which can serve to refine sampling strategies without sample damage, and complement other micrometer-scale spatial distribution analyses of elements (notably, Ca) based on well-known approaches involving micro-milling, electron microprobes, secondary ion mass spectrometry, and laser ablation.

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Acknowledgements

We express our appreciation to Kosaku Arai and Takuya Itaki of the Geological Survey of Japan (GSJ), AIST for providing coral samples, Yuichiro Tanaka of GSJ and Mana Hikami of AORI for assistance in SEM analysis, and Takashi Toyofuku of JAMSTEC for stereomicroscopy work. Also gratefully acknowledged are Mayuri Inoue of AORI for valuable advice, as well as J. Raddatz, two anonymous reviewers, and the journal editors for insightful and constructive comments. This study was conducted with the approval of the SPring-8 Proposal Review Committee (Proposal 2012A1556 and 2012B1116).

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Correspondence to Toshihiro Yoshimura.

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Yoshimura, T., Suzuki, A., Tamenori, Y. et al. Micro-X-ray fluorescence-based comparison of skeletal structure and P, Mg, Sr, O and Fe in a fossil of the cold-water coral Desmophyllum sp., NW Pacific. Geo-Mar Lett 34, 1–9 (2014). https://doi.org/10.1007/s00367-013-0347-x

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