A rare bronze sculpture of the male athlete Apoxyomenos, dating from about the second century BCE, was found submerged in the Adriatic Sea off the Croatian coast in 1998. The influence of the specific artificial surface on the crystal phase of encrusted calcareous structures of biomineralizing marine organisms attached to the sculpture was probed. Inductively coupled plasma atomic emission spectroscopy analysis showed all samples to have a high metal content, with the specific metals and their concentrations being consistent with the sculpture as the source rather than normal seawater. No metal-based crystalline phases were found by powder X-ray diffraction apart from the presence of iron and copper hydroxides in one sample that showed a distinctly green coloration. X-ray diffraction analysis indicated that calcite, magnesium calcite, and aragonite were the dominant phases in all cases, with minor or trace phases of albite, microcline, and mineral quartz. The phase compositions of these biomineralized structures were significantly different from those of the same organisms living in putatively unpolluted environments. The accumulation of non-native metals in the calcareous structures of these organisms and the unusual phase compositions of the latter suggest metalinduced changes to the biological pathways controlling the transport of calcium and magnesium and incorporation of heavy metals at inorganic matrix growth sites.
Abstract. Chemical vapour generation by reduction with sodium tetraborohydride and coupled to inductively coupled plasma spectrometry (HG-ICP-AES) was examined for tin analysis in high-content calcium matrix samples. Comparison of calibration curves in aqueous and matrix-matched solution showed good linearity (R 2 = 0.9951 -0.9999) in the observed range of concentration. The effects of added calcium were established as attenuation of emission intensity for 3 % at 224.605 nm and 235.484 nm and only 1 % at 283.999 nm and 189.991 nm of tin lines. The best limit of detection, i.e. 1.9 mg L -1 in aqueous and 2.1 mg L -1 in matrix-matched solution were obtained at 189.991 nm. Method of standard addition was applied for the analysis of laboratory samples of high purity calcite and aragonite shell structures and it gave 0.11 µg g -1 and 0.17 µg g -1 of tin, respectively. The accuracy of method was tested by certified reference material (NRCC, MESS-3) and good recoveries (100.08 %) were obtained in both calibration modes. Tin content was determined by HG-ICP-AES method using matrix-matched calibration in shell samples of Mytilus galloprovinciallis. The obtained values of tin content showed relatively flat distribution in shells along the coast (0.511 -0.718 µg g -1 ). Higher concentrations were measured on several hotspots, especially fishing ports and harbours. (doi: 10.5562/cca2259)
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