Determination of benzophenone derivatives in wastewater by GC–MS/MS combined with in‐port derivatization

The analysis of UV filters (UVFs) in water has become increasingly important due to their adverse effects on aquatic organisms and humans. This study describes a method for the determination of benzophenone derivatives UVF in wastewater samples. The selected UVFs are 2‐hydroxy‐4‐methoxybenzophenone (BP‐3), 2,4‐dihydroxybenzophenone (BP‐1), 4‐hydroxybenzophenone (4HB), 2,2′‐dihydroxy‐4‐methoxybenzophenone (DHMB) and lastly, 4,4′‐dihydroxybenzophenone (4DHB). The method includes solid‐phase extraction (SPE) of analytes from wastewater followed by on‐line derivatization with bis(trimethylsilyl)trifluoroacetamide (BSTFA) and analysis with GC‐MS/MS. Method validation studies resulted in good recoveries (86–112%), relative standard deviation RSD = 0.8 and 7.3%, the limits of detection LODs = 1.00–10.8 ng/L, and the limits of quantification LOQs = 3.00–32.3 ng/L. The method was successfully applied to domestic wastewater samples collected from influent and effluent of touristic hotels’ biological wastewater treatment plants. BP‐3 (24–1765 ng/L), BP‐1 (8–703 ng/L), 4HB (26–96 ng/L), and 4DHB (20–22 ng/L) were the common benzophenone derivatives in the influent wastewater while effluent contained mainly BP‐1 (8–32 ng/L), 4HB (12–57 ng/L) and 4DHB (20–102 ng/L). These results indicate that BP‐3 and BP‐1 are biodegraded in the treatment processes. However, 4HB and 4DHB are resistant to degradation and they are the main benzophenone metabolites discharged to receiving media. Graphical : Benzophenone‐type UV filters are endocrine‐disrupting micropollutants with adverse effects on organisms. Reliable analytical methods are needed to monitor them in the environment. This study developed a sensitive method for simultaneous analysis of parent compounds and their metabolites in wastewater. The method includes solid‐phase extraction and GC–MS/MS coupled with on‐line derivatization, which is applicable to determine these micro‐concentration pollutants in wastewater.