Evaluation of Standard Methods for the Analysis of Methyl tert-Butyl Ether and Related Oxygenates in Gasoline-Contaminated Groundwater

The U.S. Environmental Protection Agency (EPA) now requires monitoring of oxygenate compounds in groundwater at leaking underground storage tank (LUST) sites nationwide. Three purge-and-trap gas chromatography methods most commonly employed for this purpose were tested, and their performance as a function of total petroleum hydrocarbon (TPH) content of the sample matrix was determined. Tests included a formal method evaluation, a round-robin study, and a split-sample study (424 groundwater samples). Consistently good results were achieved with EPA Method 8240B/60B (mass spectrometry) and ASTM Method D4815 (flame ionization detection) when five oxygenates were monitored in reagent water and gasoline. However, one protocol routinely employed for analysis of LUST samples had serious limitations:  EPA Method 8020A/21B (photoiozination detection) was unfit for monitoring of tert-butyl alcohol (TBA) and frequently yielded false-positive (12−50% of samples) and inaccurate results when ether oxygenates were monitored in aqueous samples containing high concentrations of TPH (>1 000 μg/L). Thus, care should be taken in the analysis of LUST databases populated with EPA Method 8020/21 data because results reported for methyl tert-butyl ether (MTBE) in samples containing high levels of TPH have a high likelihood of being inaccurate or false-positive. For all three methods, detection limits determined in reagent water were sufficiently low for monitoring MTBE at the stringent primary (13 μg/L) and secondary (5 μg/L) action levels set by the state of California.