Solid-phase extraction liquid chromatography–tandem mass spectrometry analytical method for the determination of 2-hydroxy-4-methoxybenzophenone and its metabolites in both human urine and semen

Abstract

2-Hydroxy-4-methoxybenzophenone (HMB), which is one of the most commonly used UV filters in sunscreen cosmetics to protect skin from the deleterious effects of the sun, can be percutaneously absorbed, further metabolized, and finally excreted or bioaccumulated. An analytical method for the sensitive determination of HMB and its three metabolites in both human urine and semen is developed. The presented analytical method is based on a solid-phase extraction (SPE) procedure to clean-up and preconcentrate the target analytes from the urine and semen samples followed by liquid chromatography-tandem mass spectrometry (LC-MS/MS) detection. The methodology was fully validated and the standard addition calibration method was used to quantify the target analytes in order to correct the matrix effects observed. Considering this approach, the accuracy of the method was evaluated and the recoveries ranged from 98% to 115% and from 86% to 111% in urine and semen samples, respectively, depending on the analyte. For urine samples, the limits of detection ranged between 0.027 and 0.103 ng mL(-1) and the repeatability of the method, expressed as relative standard deviation, was in the range of 7.2-9.2%, depending on the analyte. In the case of semen samples, the limits of detection ranged between 1 and 3 ng mL(-1) whereas the repeatability was in the range of 2.2-6.4%, depending on the analyte. The described SPE-LC-MS/MS method was satisfactorily applied to both urine and semen samples from a male volunteer who applied a sunscreen cosmetic product containing HMB. HMB and its metabolites were found and quantified in the low ng mL(-1) range in both urine and semen samples, although at a different extent.

Urinary concentrations of benzophenone-type ultraviolet light filters and semen quality

“…We are aware of one previous paper reporting that BP-3 can be detected and quantified in semen (37). In our previous paper focusing on these same five BP-type UV filters as measured in both partners of the couples participating in the LIFE Study, we found that male partners’ BP-2 concentrations were associated with a significant 31% reduction in couple fecundity resulting in a longer time-to-pregnancy even after adjusting for the female partners concentrations (18).…”

UV Filters Biodegradation by Fungi, Metabolites Identification and Biological Activity Assessment

“…Secondary pathways would be aromatic hydroxylations carried out by the cytochrome P450 leading to the hydroxylatedmetabolites THB and DHMB [59]. Nevertheless, the predominant metabolites in human urine and semen samples during the first 24 h after topic application are the glucuronide conjugates of BP3 and BP1 [63]. None of those compounds, except BP1, were found in the fungal culture.…”

Methods for the determination of biomarkers of exposure to emerging pollutants in human specimens

“…The mobile phases comprise methanol, acetonitrile and water. Besides, solvent modifiers {e.g., ammonium acetate (proton acceptor) [48], formic acid [18] and acetic acid (proton donors) [34]} are added to enhance ionization efficiencies of the target compounds.…”

“…Although some conventional bonded silica sorbents are still in use [18], these are being replaced by hydrophilic-hydrophobic balance polymeric material {e.g., Oasis HLB [36] or Strata XL [43]}. For polar anionic compounds (e.g., OPFRs and PFCs), weak-anion exchange sorbents {e.g., StrataX-AW and Oasis WAX [105]} have proved useful [25].…”

“…The Phase I metabolites include BP-1, BP-8 and 2,3,4-trihydroxybenzophenone [18]. BP-3 or any of its metabolites can potentially be used as biomarkers of exposure to BP-3 [19].…”