The antiquity of the use of hunting poisons has received much attention in recent years. In this paper
we present the results of a pilot study designed to detect the presence of organic compounds, typically
of less than 1200 Da, from poisonous plants that may have been used as hunting poisons in the past.
We used ultra-performance liquid chromatography connected to a Synapt G2 high-resolution MS-QTOF
mass spectrometer (UPLC-QTOF-MS) to provisionally identify plant-based toxins present in (1) extracts
of fresh plant material, (2) a blind control recipe consisting of three plant ingredients and (3) a Hei||om
arrow poison of unknown ingredients. Although not all expected toxic compounds were identified, those
that were identified compared favourably with those reported in the literature and confirmed through
databases, specifically the Dictionary of Natural Products and ChemSpider. MS/MS fragmentation
patterns and accurate mass were used for tentative identification of compounds because archaeological
residues usually contain insufficient material for unambiguous identification using nuclear magnetic
resonance. We highlight the potential of this method for accurately identifying plant-based toxins present
on archaeological artefacts and unique (albeit non-toxic) chemical markers that may allow one to infer
the presence of toxic plant ingredients in arrow poisons. Any chemical study of archaeological material
should consider the unique environmental degradative factors and be sensitive to the oxidative byproducts
of toxic compounds.
Methodology is presented for the identification of ancient plant-based arrow poisons.
J.B. and M.L. conceptualised the project; M.W. and D.K. prepared and
ran the samples; V.M. interpreted the results; M.W., J.B. and V.M. wrote
the paper; D.K. and M.W. prepared the figures; D.K., L.W. and M.L.
provided academic input; and L.W. and L.P. provided conceptual input
and read the draft manuscript.
Most of the plant material was supplied by the South African National
Biodiversity Institute and we thank Andrew Hankey of the Walter
Sisulu National Botanical Gardens for his assistance in this regard.
Diana Wall of Museum Africa provided access to the Fourie Collection
and other poisoned arrows.