Salt effects on ion formation in desorption mass spectrometry: an investigation into the role of alkali chlorides on peak suppression in time-of-flight-secondary ion mass spectrometry.

In secondary ion mass spectrometry, the molecular environment from which a sample is analyzed can influence ion formation, affecting the resulting data. With the recent surge in studies involving examination of biological specimens, a better understanding of constituents commonly found in biological matrixes is necessary. In this article we discuss results from an investigation directed at understanding the role of salts doped as alkali chlorides in a model biological environment, arginine. The data show that addition of salt to the model system causes ion suppression of all the major mass spectral peaks attributed to arginine, with KCl having the largest suppression effect. Potential causes for the suppression effects are briefly discussed in relation to collected data. These theories include sample degradation, formation of salt adduct peaks, and anion neutralization. Investigation of the arginine salt data in comparison with data collected from pure salt systems indicates that suppression of the positive secondary ions is likely caused by a neutralization process involving the salt counteranion, chloride. To address the suppression issue, various procedures were performed on the arginine films such as sample washing with a cleaning solution (ammonium formate, ethanol, water) and analysis of films in a frozen-hydrated state. We present data from the analysis of the frozen-hydrated samples that shows both an ion yield enhancement and a significant amelioration of the salt suppression effects when compared to the samples run under standard conditions, demonstrating that it is a helpful approach to dealing with salt suppression.

Fossilization of melanosomes via sulfurization.

Fossil melanin granules (melanosomes) are an important resource for inferring the evolutionary history of colour and its functions in animals. The taphonomy of melanin and melanosomes, however, is incompletely understood. In particular, the chemical processes responsible for melanosome preservation have not been investigated. As a result, the origins of sulfur-bearing compounds in fossil melanosomes are difficult to resolve. This has implications for interpretations of original colour in fossils based on potential sulfur-rich phaeomelanosomes. Here we use pyrolysis gas chromatography mass spectrometry (Py-GCMS), fourier transform infrared spectroscopy (FTIR) and time of flight secondary ion mass spectrometry (ToF-SIMS) to assess the mode of preservation of fossil microstructures, confirmed as melanosomes based on the presence of melanin, preserved in frogs from the Late Miocene Libros biota (NE Spain). Our results reveal a high abundance of organosulfur compounds and non-sulfurized fatty acid methyl esters in both the fossil tissues and host sediment; chemical signatures in the fossil tissues are inconsistent with preservation of phaeomelanin. Our results reflect preservation via the diagenetic incorporation of sulfur, i.e. sulfurization (natural vulcanization), and other polymerization processes. Organosulfur compounds and/or elevated concentrations of sulfur have been reported from melanosomes preserved in various invertebrate and vertebrate fossils and depositional settings, suggesting that preservation through sulfurization is likely to be widespread. Future studies of sulfur-rich fossil melanosomes require that the geochemistry of the host sediment is tested for evidence of sulfurization in order to constrain interpretations of potential phaeomelanosomes and thus of original integumentary colour in fossils.