Trends in 1,4-Dioxane Analyses: Implications for Identification and Characterization of Contaminated Groundwater Sites

1,4-Dioxane is a contaminant of emerging concern, and there is significant uncertainty about how its environmental occurrence in groundwater is being assessed given the various analytical methods available. This study compiled public sampling records from 2000 to 2019 that included >106,000 analyses of 1,4-dioxane from 822 different U.S. sites. The 1,4-dioxane detection frequency in the entire dataset (including all methods) was 45%, and the median detected concentration was 10 μg/L, highlighting the dilute nature of 1,4-dioxane in environmental media and the importance of selecting methods with adequate sensitivity. The annual distribution of samples analyzed by each method type confirmed a shift towards methods designed for semi-volatile compounds (Method 8270 and Method 8270 SIM) that exhibited consistently lower reporting limits (median reporting limit for each year typically ≤1 μg/L). In contrast, the method designed for volatile compounds (Method 8260) exhibited less sensitivity for 1,4-dioxane (median reporting limit per year between 40 and 100 μg/L) and its use declined significantly over time with increasing use of the moderately sensitive Method 8260 SIM in later years. This shift contributed to an increase in the 1,4-dioxane detection frequency over time, with a strong correlation between the annual detection frequency and the median reporting limit. Sites where 1,4-dioxane was analyzed but not detected overwhelmingly used less-sensitive methods that may not have been adequate for the expected concentration levels. Given the sub-μg/L groundwater criteria issued for 1,4-dioxane by some regulatory agencies, more sensitive and accurate methods will be increasingly needed to assess compliance.