1,4-Dioxane (dioxane) is an emerging groundwater contaminant that has significant regulatory implications and potential remediation costs, but our current understanding of its occurrence and behavior is limited. This study used intensive data mining to identify and evaluate >2000 sites in California where groundwater has been impacted by chlorinated solvents and/or dioxane. Dioxane was detected at 194 of these sites, with 95% containing one or more chlorinated solvents. Dioxane frequently co-occurs with 1,1,1-trichloroethene (1,1,1-TCA) (76% of the study sites), but despite this, no dioxane analyses were conducted at 332 (67%) of the sites where 1,1,1-TCA was detected. At sites where dioxane has been identified, plumes are dilute but not large (median maximal concentration of 365 μg/L; median plume length of 269 m) and have been delineated to a similar extent as typically co-occurring chlorinated solvents. Furthermore, at sites where dioxane and chlorinated solvents co-occur, dioxane plumes are frequently shorter than the chlorinated solvent plumes (62%). The results suggest that dioxane has not migrated beyond chlorinated solvent plumes and existing monitoring networks at the majority of sites, and that the primary risk is the large number of sites where dioxane is likely to be present but has yet to be identified.

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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.

This column reviews the general features of PHT3D Version 2, a reactive multicomponent transport model that couples the geochemical modeling software PHREEQC-2 (Parkhurst and Appelo 1999) with three-dimensional groundwater flow and transport simulators MODFLOW-2000 and MT3DMS (Zheng and Wang 1999). The original version of PHT3D was developed by Henning Prommer and Version 2 by Henning Prommer and Vincent Post (Prommer and Post 2010). More detailed information about PHT3D is available at the website http://www.pht3d.org.The review was conducted separately by two reviewers. This column is presented in two parts.