An ultra-high-performance liquid chromatography tandem mass spectrometry method for oxidative stress biomarker analysis in wastewater

Reported herein is the development of an analytical method for the detection of four oxidative stress biomarkers in wastewater using ultra-high-performance liquid chromatography coupled with tandem mass spectrometry (UHPLC-MS/MS) and solid phase extraction (SPE). The following four biomarkers of oxidative stress and lipid peroxidation have been investigated: hydroxynonenal-mercapturic acid (HNE-MA), 8-iso-prostglandin F2beta (8-iso-PGF(2 beta)), 8-nitroguanine (8-NO(2)Gua) and 8-hydroxy-2-deoxyguanosine (8-OHdG). The method showed very good performance: accuracy (>87%), precision (>90%), method quantification limits (1.3-3.0 ng L-1) and biomarker stability in wastewater in the case of HNE-MA, 8-OHdG and 8-iso-PGF(2 beta). In contrast, 8-NO(2)Gua was found to be less stable in wastewater, which affected its method performance: accuracy (>63%), precision (>91%) and method quantification limits (85.3 ng L-1). Application of the developed method resulted in, for the first time, HNE-MA being successfully observed and quantified within wastewater over a study period of a week (displayed average daily loads per capita of 48.9 +/- 4.1 mg/1000/people/day). 8-iso-PGF(2 beta) was detected with good intensity but could not be quantified due to co-elution with other isomers. 8-OHdG was detected, albeit at < MQL. This study demonstrates the potential for expanding on the possible endogenous biomarkers of health used in urban water fingerprinting to aid in measuring health in near-real time on a community-wide scale.