Potential biomarkers for southern African hunter-gatherer arrow poisons applied to ethno-historical and archaeological samples

The detection of complex poison recipes applied to ancient hunting weapons has the potential to provide important insights into traditional pharmacological knowledge systems. Yet, recipes comprising many ingredients can be challenging to decipher, especially in older samples that have undergone biodegradation. We present the results of our attempt to analyze samples of poison collected from nineteenth and twentieth century arrowheads from southern Africa, and from a 1000-year-old archaeological bone point. The arrow poison residues and reference samples were analyzed by Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy (ATR FTIR) and Gas Chromatography Mass Spectrometry (GC–MS). The ATR FTIR analysis is primarily able to separate between different arrow poison binder recipes. The extractives identified by GC–MS analysis consist of a multitude of components from both binders and active substances, confirming and adding to the results from the ATR FTIR analyses. We discuss the results in terms of potential biomarkers for arrow poisons in organic residue analyses of archaeological artefacts; that residues of toxic cardiotonic glycosides can be detected on curated and excavated arrow tips of between about 1000 and 100 years old, serves as proof of concept for working with older materials in the future.