No abstract

No abstract

Colour and pattern are key traits with important roles in camouflage, warning and attraction. Ideally, in order to begin to understand the evolution and ecology of colour in nature, it is important to identify and, where possible, fully characterise pigments using biochemical methods. The phylum Mollusca includes some of the most beautiful exemplars of biological pigmentation, with the vivid colours of sea shells particularly prized by collectors and scientists alike. Biochemical studies of molluscan shell colour were fairly common in the last century, but few of these studies have been confirmed using modern methods and very few shell pigments have been fully characterised. Here, we use modern chemical and multi-modal spectroscopic techniques to identify two porphyrin pigments and eumelanin in the shell of marine snails Clanculus pharaonius and C margaritarius. The same porphyrins were also identified in coloured foot tissue of both species. We use high performance liquid chromatography (HPLC) to show definitively that these porphyrins are uroporphyrin I and uroporphyrin III. Evidence from confocal microscopy analyses shows that the distribution of porphyrin pigments corresponds to the striking pink-red of C. pharaonius shells, as well as pink-red dots and lines on the early whorls of C. margaritarius and yellow-brown colour of later whorls. Additional HPLC results suggest that eumelanin is likely responsible for black spots. We refer to the two differently coloured porphyrin pigments as trochopuniceus (pink-red) and trochoxouthos (yellow-brown) in order to distinguish between them. Trochopuniceus and trochoxouthos were not found in the shell of a third species of the same superfamily, Calliostoma zizyphinum, despite its superficially similar colouration, suggesting that this species has different shell pigments. These findings have important implications for the study of colour and pattern in molluscs specifically, but in other taxa more generally, since this study shows that homology of visible colour cannot be assumed without identification of pigments.

No abstract

Abstract-Thirteen presolar silicon carbide grains-three of supernova (SN) origin and ten of asymptotic giant branch (AGB) star origin-were examined with time-of-flight-secondary ion mass spectrometry (TOF-SIMS). The grains had been extracted from two different meteorites-Murchison and Tieschitz-using different acid residue methods. At high lateral resolution of ~300 nm, isotopic and elemental heterogeneities within the micrometer-sized grains were detected. The trace elemental abundances, when displayed in two-element correlation plots, of Li, Mg, K, and Ca show a clear distinction between the two different meteoritic sources. The different concentrations might be attributed to differences of the host meteorites and/or of extraction methods whereas the stellar source seems to be less decisive. In one SN grain with 26 Mg-enrichment from extinct 26 Al, the acid treatment, as part of the grain separation procedure, affected the Mg/Al ratio in the outer rim and therefore the inferred initial 26 Al/ 27 Al ratio. A second SN grain exhibits a lateral heterogeneity in 26 Al/ 27 Al, which either is due to residual Al-rich contamination on the grain surface or to the condensation chemistry in the SN ejecta.

We present the performance characteristics of a time-of-flight secondary ion mass spectrometer designed for 157 nm laser postionization of sputtered neutrals for high sensitivity elemental and isotopic analyses. The instrument was built with the aim of analyzing rare element abundances in micron to submicron samples such as interstellar grains and cometary dust. Relative sensitivity factors have been determined for secondary ion mass spectrometry which show an exponential dependency against the first ionization potential. This allows elemental abundances to be measured with errors below 25% for most major elements. The accuracy for isotope ratios, where isotopes can be resolved from isobaric interferences, is usually limited only by counting statistics. In laser secondary neutral mass spectrometry, the spatial and temporal overlaps between the laser and sputtered neutral atoms are modeled and predictions of total detection efficiency and isotopic and elemental fractionation are compared with experimental data. Relative sensitivity factors for laser-ionized secondary neutrals from a stainless steel standard are found to vary less than 3% above saturation laser pulse energy enabling more accurate quantification.

In recent years, Au-cluster ions have been successfully used for organic analysis in secondary ion mass spectrometry. Cluster ions, such as Au(2)(+) and Au(3)(+), can produce secondary ion yield enhancements of up to a factor of 300 for high mass organic molecules with minimal sample damage. In this study, the potential for using Au(+), Au(2)(+) and Au(3)(+) primary ions for the analysis of inorganic samples is investigated by analyzing a range of silicate glass standards. Practical secondary ion yields for both Au(2)(+) and Au(3)(+) ions are enhanced relative to those for Au(+), consistent with their increased sputter rates. No elevation in ionization efficiency was found for the cluster primary ions. Relative sensitivity factors for major and trace elements in the standards showed no improvement in quantification with Au(2)(+) and Au(3)(+) ions over the use of Au(+) ions. Higher achievable primary ion currents for Au(+) ions than for Au(2)(+) and Au(3)(+) allow for more precise analyses of elemental abundances within inorganic samples, making them the preferred choice, in contrast to the choice of Au(2)(+) and Au(3)(+) for the analysis of organic samples. The use of delayed secondary ion extraction can also boost secondary ion signals, although there is a loss of overall sensitivity.

Abstract-We report the first measurements of lithium and boron isotope ratios and abundances measured in "gently separated" presolar SiC grains. Almost all analyses of presolar SiC grains since their first isolation in 1987 have been obtained from grains that were separated from their host meteorite by harsh acid dissolution. We recently reported a new method of "gently" separating the grains from meteorites by using freeze-thaw disaggregation, size, and density separation to retain any nonrefractory coatings or alteration to the surfaces of the grains that have been acquired in interstellar space. Nonrefractory coats or amorphized surfaces will almost certainly be removed or altered by the traditional acid separation procedure. High Li/Si and B/Si ratios of up to ~10 -2 were found implanted in the outer 0.5 μm of the grains dropping to ~10 -5 in the core of the grains. 7 Li/ 6 Li and 11 B/ 10 B ratios indistinguishable from solar system average values were found. Analyses obtained from SiC grains from the acid dissolution technique showed isotope ratios that were the same as those of gently separated grains, but depth profiles that were different. These results are interpreted as evidence of implantation of high velocity (1200-1800 km s -1 ) Li and B ions into the grains by shock waves as the grains traveled through star-forming regions some time after their condensation in the outflow of an AGB star that was their progenitor. The results are in line with spectroscopic measurements of Li and B isotope ratios in star-forming regions and may be used to infer abundances and isotopic sources in these regions.