In living organisms, color patterns, behavior, and ecology are closely linked. Thus, detection of fossil pigments may permit inferences about important aspects of ancient animal ecology and evolution. Melanin-bearing melanosomes were suggested to preserve as organic residues in exceptionally preserved fossils, retaining distinct morphology that is associated with aspects of original color patterns. Nevertheless, these oblong and spherical structures have also been identified as fossilized bacteria. To date, chemical studies have not directly considered the effects of diagenesis on melanin preservation, and how this may influence its identification. Here we use time-of-flight secondary ion mass spectrometry to identify and chemically characterize melanin in a diverse sample of previously unstudied extant and fossil taxa, including fossils with notably different diagenetic histories and geologic ages. We document signatures consistent with melanin preservation in fossils ranging from feathers, to mammals, to amphibians. Using principal component analyses, we characterize putative mixtures of eumelanin and phaeomelanin in both fossil and extant samples. Surprisingly, both extant and fossil amphibians generally exhibit melanosomes with a mixed eumelanin/phaeomelanin composition rather than pure eumelanin, as assumed previously. We argue that experimental maturation of modern melanin samples replicates diagenetic chemical alteration of melanin observed in fossils. This refutes the hypothesis that such fossil microbodies could be bacteria, and demonstrates that melanin is widely responsible for the organic soft tissue outlines in vertebrates found at exceptional fossil localities, thus allowing for the reconstruction of certain aspects of original pigment patterns.
Three methods of estimating H20 contents of geologic glasses are compared: (1) ion microprobe analysis (secondary ion mass spectrometry), (2) Fourier-transform infrared spectroscopy (FTIR), and (3) electron microprobe analysis using the Na decay-curve method. Each analytical method has its own advantages under certain conditions, depending on the relative importance of analytical accuracy, precision, sensitivity, spatial resolution, and convenience, and each is capable of providing reasonably accurate estimates of the H20, or total volatile, content of geologic glasses. The accuracy of ion microprobe analyses depends critically on the availability of well-characterized hydrous standard glasses. Precision is often better than 0,2 wt% (10). The method provides good spatial resolution (-15 #m) and the capability to determine simultaneously the abundance of other volatile species of interest (e.g., F, B). FTIR spectroscopy provides excellent analytical sensitivity (-10 ppm), accuracy and precision «0.1 wt%), and the capability to determine the abundance of H20 and C02 species (H20, OH-, C02' eOj-) in analyzed glasses, although the spatial resolution (> 25-35 #m) is not as good as that of the ion microprobe. The main advantages of the estimation of H20 contents of hydrous glasses using the electron microprobe are excellent spatial resolution (-10 #m) and analytical convenience. The disadvantages are that accuracy and precision (>0.5 wt%) are not as good as those associated with the other methods, but, for certain applications, these uncertainties may be acceptable for the estimation of H20 contents of H20-rich (> 1 wt%) samples.
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