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 potentialto provide important insights into traditional pharmacological knowledge systems. Yet, recipescomprising many ingredients can be challenging to decipher, especially in older samples that haveundergone biodegradation. We present the results of our attempt to analyze samples of poisoncollected from nineteenth and twentieth century arrowheads from southern Africa, and from a1000-year-old archaeological bone point. The arrow poison residues and reference samples wereanalyzed by Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy (ATR FTIR) andGas Chromatography Mass Spectrometry (GC–MS). The ATR FTIR analysis is primarily able to separatebetween different arrow poison binder recipes. The extractives identified by GC–MS analysis consistof a multitude of components from both binders and active substances, confirming and adding to theresults from the ATR FTIR analyses. We discuss the results in terms of potential biomarkers for arrowpoisons in organic residue analyses of archaeological artefacts; that residues of toxic cardiotonicglycosides can be detected on curated and excavated arrow tips of between about 1000 and 100 yearsold, serves as proof of concept for working with older materials in the future.