Date Published: February 23, 2019
Publisher: Springer Berlin Heidelberg
Author(s): Natalie Sims, Jack Rice, Barbara Kasprzyk-Hordern.
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-PGF2β), 8-nitroguanine (8-NO2Gua) 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-PGF2β. In contrast, 8-NO2Gua 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-PGF2β 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.
Wastewater-based epidemiology is a rapidly developing and innovative technique that analyses human metabolic excretion products in the wastewater of a defined population . The wastewater of a community is an incredibly valuable, yet traditionally under-estimated, source of knowledge. The analysis of targeted aspects of biological and chemical information wastewater contains can offer a unique reflection of health upon the population that contributes. The concept of WBE has already experienced enormous successes from communities to international scales to evaluate and compare trends in illicit drug usage [2–4], pharmaceuticals , alcohol [6–8] and tobacco consumption [9–11]. Recently the potential for WBE to evaluate and monitor community-wide public health has been highlighted by analysing endogenous urinary biomarkers of human health and disease [12–14].
To conclude, we have reported, for the first time, the development of an analytical method using SPE and UHPLC-MS/MS techniques for the detection and quantification of four biomarkers of oxidative stress in wastewater. 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 for HNE-MA, 8-OHdG and 8-iso-PGF2β. In contrast, 8-NO2Gua was found to be less stable in wastewater (68% and 10% of the concentration spiked at t 0 h remaining at 24 h respectively at 4 °C and 17 °C), which affected its method performance: accuracy (> 63%), precision (> 91%), method quantification limits (85.3 ng L−1). All four biomarkers were detected within wastewater samples but full quantification of only HNE-MA was carried out. HNE-MA was quantified in wastewater at levels averaging at 48.9 ± 4.1 mg/1000/people/day. 8-iso-PGF2β was detected within the broad series of peaks as previously mentioned; further work is required in order to investigate separation. 8-OHdG was detected, albeit at < MQL due to relatively low MQL for this biomarker. To the authors’ knowledge, HNE-MA has never been observed and quantified successfully in wastewater before. Further work is required to fully evaluate suitability of 8-NO2Gua as a biomarker due to its low stability. More extensive sample preparation utilising sorbents of higher selectivity and higher concentration factor should be also considered to allow for full quantification of 8-OHdG and 8-iso-PGF2β. Source: http://doi.org/10.1007/s00216-019-01667-8