In this paper, we describe a simple method for sampling, pre-concentrating, and separating volatile and
semi-volatile components from two different cave atmospheres. Sampling is performed by capturing a
volume of cave atmosphere in a Tedlar bag or Suma canister for sample storage and transport back to
the laboratory. Loading a portion of the sample on a multi-bed sorption trap allows for sample preconcentration
prior to separation and detection of components on a comprehensive two-dimensional
gas chromatograph (GCGC). Comparison of two Texas caves reveals the power of comprehensive
two-dimensional gas chromatography (GCGC) for volatile separation and detection, and to our
knowledge marks the first use of GCGC for the analysis of cave atmospheres. Analysis of the results
revealed 138 and 146 chromatographic signals over an S/N threshold of 500 and direct comparison of
the two samples revealed 50 identical chromatographic signals. This study is a first step toward demonstrating
the ability of GCGC to separate the complex volatiles and semi-volatiles in the cave atmosphere
as a fingerprinting tool.