Improved Polycyclic Aromatic Hydrocarbon and n‑Alkane Determination in Speleothems through Cleanroom Sample Processing

Interest in paleoenvironmental reconstructions from biomarkers in speleothems is increasing, thanks in part to the capacity of speleothems to grow continuously and to resist postdepositional alteration. In particular, the possibility exists to link high-resolution and accurately dated fire and vegetation records with isotopic data of climatic and paleoenvironmental interactions at the local and regional scale. However, the scarcity of existing methods for the quantification of organic molecules in stalagmites, together with the issues of sample availability, contamination, and low concentrations, complicate this approach. In this work, we developed a novel method for the simultaneous determination of 18 polycyclic aromatic hydrocarbons (PAHs) and 26 n-alkanes (C10−C35) and then tested it on “clean” calcite and aragonite stalagmite samples from cave KNI-51 in the Australian tropics. The method involves subsampling by using a hand-held drill, complete dissolution of the matrix in hydrochloric acid, then liquid−liquid extraction, and GC-MS analysis. Sample preparation was carried out in a 10 000 class clean room built entirely in stainless steel to avoid contamination. Detection limits were 0.3−9 ng for PAHs and 6−44 ng for n-alkanes. Measurable concentrations of fire-derived PAH compounds, namely, phenanthrene, pyrene, benzo(e)pyrene, and indeno(123-cd)pyrene, were detected in only one sample, which dates to the year ∼2004 CE, when a fire burned vegetation over the cave; n-alkanes were detected in all samples in the range C23−C35, with no odd−even preference.