Trace element concentrations as proxies for diagenetic alteration in the African archaeofaunal record: Implications for isotope analysis

Isotope ratio analyses of trace elements are applied to tooth enamel, ostrich eggshell, and other archaeological hard tissues to infer mobility and other aspects of hominin and animal paleoecology. It has been assumed that these highly mineralized tissues are resistant to diagenetic alteration, but this is seldom tested and some studies document diagenetic alteration over brief time spans. Here, we build on existing research on Maximum Threshold Concentrations (MTCs) to develop screening tools for diagenesis that can inform heavy isotopic analyses. The premise of the MTC approach is that archaeological tissues are likely contaminated and unsuitable for isotope ratio analysis when they exceed characteristic modern concentration ranges of trace elements. Furthermore, we propose a new metric called the Maximum Threshold Ratio (MTR) of 85Rb/88Sr or whole element Rb/Sr, which can be measured simultaneously with 87Sr/86Sr during laser ablation (LA) MC-ICP-MS or applied during post hoc screening of specimens. We analyzed 56 enamel samples from modern Kenyan mammals and 34 modern ostrich eggshells from South Africa, Namibia, and the United States by solution ICP-MS, as well as a subset of shells using LA-MC-ICP-MS. Our results indicate that thresholds are consistent across taxa at a single location, but likely vary across locations. Therefore, MTCs and MTRs need to be tissue and locality specific, but not necessarily taxon-specific. Other important differences are observed between the inner and outer surfaces of the eggshells and between LA and solution ICP-MS. This exploratory study provides guidelines for building reference thresholds to screen enamel and eggshell for diagenesis potentially impacting biogenic isotope ratios.