Comparing targeted and non-targeted high-resolution mass spectrometric approaches for assessing advanced oxidation...

High resolution mass spectrometry (HR-MS) offers the opportunity to track large numbers of non-target analytes through water treatment processes, providing a more comprehensive view of reactor performance than targeted evaluation. Both approaches were used to evaluate the performance of a pilot scale advanced oxidation process (AOP) employing ultraviolet light and hydrogen peroxide (UV/H₂O₂) to treat municipal wastewater effluent. Twelve pharmaceuticals and personal care products were selected as target compounds and added to reactor influent. Target compound removal over a range of flow rates and hydrogen peroxide addition levels was assessed using a liquid chromatograph combined with a quadrupole time-of-flight mass spectrometer (LC-qTOF-MS). Target compound removals were used to determine hydroxyl radical concentrations and UV fluence under pilot scale conditions. The experiments were also analyzed using a nontarget approach, which identified "molecular features" in either reactor influent or effluent. Strong correlation (r = 0.94) was observed between target compound removals calculated using the targeted and non-targeted approaches across the range of reactor conditions tested. The two approaches also produced consistent rankings of the performance of the various reactor operating conditions, although the distribution of compound removal efficiencies was usually less favorable with the broader, nontarget approach. For example, in the UV only treatment 8.3% of target compounds and 2.2% of non-target compounds exhibited removals above 50%, while 100% of target compounds and 74% of non-target compounds exhibited removals above 50% in the best condition tested. These results suggest that HR-MS methods can provide more holistic evaluation of reactor performance, and may reduce biases caused by selection of a limited number of target compounds. HR-MS methods also offer insights into the composition of poorly removed compounds and the formation of transformation products, which were widely detected.