Interlaboratory Comparison of Extractable Organofluorine Measurements in Groundwater and Eel (Anguilla rostrata): Recommendations for Methods Standardization

Research on per- and polyfluoroalkyl substances (PFAS) frequently incorporates organofluorine measurements, particularly because they could support a class-based approach to regulation. However, standardized methods for organofluorine analysis in a broad suite of matrices are currently unavailable, including a method for extractable organofluorine (EOF) measured using combustion ion chromatography (CIC). Here, we report the results of an international interlaboratory comparison. Seven laboratories representing academia, government, and the private sector measured paired EOF and PFAS concentrations in groundwater and eel (Anguilla rostrata) from a site contaminated by aqueous film-forming foam. Among all laboratories, targeted PFAS could not explain all EOF in groundwater but accounted for most EOF in eel. EOF results from all laboratories for at least one replicate extract fell within one standard deviation of the interlaboratory mean for groundwater and five out of seven laboratories for eel. PFAS spike mixture recoveries for EOF measurements in groundwater and eel were close to the criterion (±30%) for standardized targeted PFAS methods. Instrumental operation of the CIC such as replicate sample injections was a major source of measurement uncertainty. Blank contamination and incomplete inorganic fluorine removal may introduce additional uncertainties. To elucidate the presence of unknown organofluorine using paired EOF and PFAS measurements, we recommend that analysts carefully consider confounding methodological uncertainties such as differences in precision between measurements, data processing steps such as blank subtraction and replicate analyses, and the relative recoveries of PFAS and other fluorine compounds.publishedVersio

Characteristics of competitive adsorption between 2-methylisoborneol and natural organic matter on superfine and conventionally sized powdered activated carbons

When treating water with activated carbon, natural organic matter (NOM) is not only a target for adsorptive removal but also an inhibitory substance that reduces the removal efficiency of trace compounds, such as 2-methylisoborneol (MIB), through adsorption competition. Recently, superfine (submicron-sized) activated carbon (SPAC) was developed by wet-milling commercially available powdered activated carbon (PAC) to a smaller particle size. It was reported that SPAC has a larger NOM adsorption capacity than PAC because NOM mainly adsorbs close to the external adsorbent particle surface (shell adsorption mechanism). Thus, SPAC with its larger specific external surface area can adsorb more NOM than PAC. The effect of higher NOM uptake on the adsorptive removal of MIB has, however, not been investigated. Results of this study show that adsorption competition between NOM and MIB did not increase when NOM uptake increased due to carbon size reduction; i.e., the increased NOM uptake by SPAC did not result in a decrease in MIB adsorption capacity beyond that obtained as a result of NOM adsorption by PAC. A simple estimation method for determining the adsorbed amount of competing NOM (NOM that reduces MIB adsorption) is presented based on the simplified equivalent background compound (EBC) method. Furthermore, the mechanism of adsorption competition is discussed based on results obtained with the simplified EBC method and the shell adsorption mechanism. Competing NOM, which likely comprises a small portion of NOM, adsorbs in internal pores of activated carbon particles as MIB does, thereby reducing the MIB adsorption capacity to a similar extent regardless of adsorbent particle size. SPAC application can be advantageous because enhanced NOM removal does not translate into less effective removal of MIB. Molecular size distribution data of NOM suggest that the competing NOM has a molecular weight similar to that of the target compound

Determination of 1,4-Dioxane in the Cape Fear River Watershed by Heated Purge-and-Trap Preconcentration and Gas Chromatography–Mass Spectrometry

Recent U.S. Environmental Protection Agency data show that 1,4-dioxane is frequently detected in U.S. drinking water derived from both groundwater and surface water. 1,4-Dioxane is a likely human carcinogen, and an excess 10^–6 cancer risk is associated with a drinking water concentration of 0.35 μg/L. To support 1,4-dioxane occurrence investigations, source identification and exposure assessment, a rapid and sensitive analytical method capable of quantifying 1,4-dioxane over a wide concentration range in a broad spectrum of aqueous matrices was developed. The fully automated method is based on heated purge-and-trap preconcentration and gas chromatography/mass spectrometry with selected-ion storage and has a reporting limit of 0.15 μg/L. Quantification of 1,4-dioxane was accomplished by isotope dilution using mass-labeled 1,4-dioxane-d8 as internal standard. Matrix spikes yielded recoveries of 86–115% in drinking water, groundwater, surface water, and wastewater treatment plant (WWTP) effluent. Also, 1,3-dioxane can be distinguished from 1,4-dioxane. The method was applied to investigate 1,4-dioxane occurrence and sources in the Cape Fear River watershed of North Carolina. 1,4-Dioxane concentrations ranged from <0.15 μg/L in nonimpacted surface water to 436 μg/L downstream of a WWTP discharge. In WWTP effluent, 1,4-dioxane concentrations varied widely, with a range of 1.3–2.7 μg/L in one community and 105–1,405 μg/L in another. Discharges from three municipal WWTPs were primarily responsible for elevated 1,4-dioxane concentrations in the Cape Fear River watershed