Wastewater-based epidemiology to assess human exposure to personal care and household products - A review of biomarkers, analytical methods, and applications

Abstract

Humans are nowadays exposed to numerous chemicals in our day-to-day life, including parabens, UV filters, phosphorous flame retardants/plasticizers, bisphenols, phthalates and alternative plasticizers, which can have different adverse effects to human health. Estimating human's exposure to these potentially harmful substances is, therefore, of paramount importance. Human biomonitoring (HBM) is the existing approach to assess exposure to environmental contaminants, which relies on the analysis of specific human biomarkers (parent compounds and/or their metabolic products) in biological matrices from individuals. The main drawback is its implementation, which involves complex cohort studies. A novel approach, wastewater-based epidemiology (WBE), involves estimating exposure from the analysis of biomarkers in sewage (a pooled urine and feces sample of an entire population). One of the key challenges of WBE is the selection of biomarkers which are specific to human metabolism, excreted in sufficient amounts, and stable in sewage. So far, literature data on potential biomarkers for estimating exposure to these chemicals are scattered over numerous pharmacokinetic and HBM studies. Hence, this review provides a list of potential biomarkers of exposure to more than 30 widely used chemicals and report on their urinary excretion rates. Furthermore, the potential and challenges of WBE in this particular field is discussed through the review of pioneer WBE studies, which for the first time explored applicability of this novel approach to assess human exposure to environmental contaminants. In the future, WBE could be potentially applied as an "early warning system", which could promptly identify communities with the highest exposure to environmental contaminants.

Keywords: 3−OH-EtP, ethyl protocatechuate; 3−OH-MeP, methyl protocatechuate; 5−OH−OC, 2-ethyl-5-hydroxyhexyl 2-cyano-3,3-diphenyl acrylate; ASE, accelerated solvent extraction; BBOEHEP, bis(2-butoxyethyl) 2-hydroxyethyl phosphate; BBOEP, bis(2-butoxyethyl) phosphate; BP-3, 2,4-dihydroxybenzophenone (Benzophenone-3, Oxybenzone); BPA, bisphenol A; BPA-Glu, bisphenol A glucuronide; BPA-SO4, bisphenol A sulfate; Biomarkers; Bisphenols; CPAA, 2-cyano-3,3-diphenylacrylic acid; DEHA, di-2-ethylhexyl adipate; DEHP, di(2-ethylhexyl) phthalate; DEHTP, di(2-ethylhexyl) terephthalate; DHB, 2,4-dihydroxybenzophenone (Benzophenone-1, BP-1); DHMB, 2,2′-dihydroxy-4-methoxybenzophenone (Benzophenone-8, BP-8); DINCH, di(isononyl)cyclohexane-1,2-dicarboxylate; DNBP, di-n-butyl phosphate; DPHP, di-(2-propylheptyl) phthalate; DPhP, diphenyl phosphate; EHDPhP, 2-ethylhexyldiphenyl phosphate; EHS, 2-ethylhexyl salicylate (Octisalate); EI, electron ionization; ESI, electrospray ionization; EtP, ethylparaben; Excretion rate; Flame retardants; GC–MS, gas chromatography‒mass spectrometry; HBM, human biomonitoring; HPLC-MS/MS, high performance liquid chromatography–tandem mass spectrometry; LC–MS/MS, liquid chromatography‒tandem mass spectrometry; MAE, microwave-assisted extraction; MEHA, mono-2-ethylhexyl adipate; MINCH, Monoisononyl-cyclohexane-1,2-dicarboxylate; MQL, method quantification limit; MRM, multiple reaction monitoring (MRM); MTBSTFA, N-tert-butyldimethylsilyl-N-methyltrifluoroacetamide; MeP, methylparaben; OC, Octocrylene; OH-MINCH, Cyclohexane-1,2-dicarboxylate-mono-(7-hydroxy-4-methyl) octyl ester; PE, primary effluent; PFRs, phosphorous flame retardants/plasticizers; PHBA, p-hydroxybenzoic acid; PHHA, p-hydroxyhippuric acid; Parabens; Phthalates; Plasticizers; PrP, propylparaben; Q-ToF, quadrupole-time-of-flight; QTRAP, quadrupole-ion trap; QqQ, triple quadrupole; RW, raw wastewater; SE, secondary (final) effluent; SIM, selected ion monitoring; SPE, solid-phase extraction; SPM, suspended particulate matter; Sewage chemical information mining; Sewage epidemiology; TBOEP, tris(2-butoxyethyl) phosphate; TPhP, triphenyl phosphate; UAE, ultrasonic-assisted extraction; UHPLC-MS/MS, ultrahigh performance liquid chromatography–tandem mass spectrometry; UV filters; WBE, wastewater-based epidemiology; WWTPs, wastewater treatment plants; bbCID, broadband collision-induced dissociation.