Total organic fluorine (TOF) analysis by completely converting TOF into fluoride with vacuum ultraviolet

Quantifying total organic fluorine (TOF) in water is vital in monitoring the occurrence and persistence of all fluorine-containing organic compounds in the environment, while currently most studies focus on analyzing individual fluorine-containing organic compounds. To fill the technology gap, we herein proposed to convert TOF completely into fluoride with vacuum ultraviolet (VUV) photolysis, followed by analysis of fluoride with ion chromatography. Results showed that the tailored VUV photoreactor achieved satisfying recoveries of fluorine from ten model TOF compounds not only in ultrapure water (83.9 ± 2.0% to 109.4 ± 0.8%) but also in real water samples (92.1 ± 1.0%–106.2 ± 15.7%). Unlike other ultraviolet-based processes that favor alkaline conditions, this VUV process preferred either neutral or acidic conditions to defluorinate selected compounds. While the mechanisms remain to be explored in the future, it has been evidenced that the photo-degradation and photo-defluorination rates of these TOF compounds varied significantly among compounds and operation conditions. The method obtained a method detection limit (MDL) of 0.15 μg-F/L, which is lower than the MDLs of many other TOF analytical methods, along with excellent calibration curves for concentrations ranging from 0.01 to 10.0 mg-F/L. Notably, minimizing fluoride in sample prior to photoconversion was necessary to avoid subtraction-induced errors for TOF measurement, especially when the fluoride/TOF ratio was high. The robust VUV is also green for sample pretreatment due to its unreliance of chemicals or additives.