Abstract

An effective, specific and accurate method is presented for the quantification of 13 markers of anthropogenic contaminants in water using solid phase extraction (SPE) followed by high performance liquid chromatography (HPLC) tandem mass spectrometry (MS/MS). Validation was conducted according to the International Conference on Harmonisation (ICH) guidelines. Method recoveries ranged from 77 to 114% and limits of quantification between 0.75 and 4.91 ng/L. A study was undertaken to quantify the concentrations and loadings of the selected contaminants in 6 sewage treatment works (STW) effluent discharges as well as concentrations in 5 rain-driven street runoffs and field drainages. Detection frequencies in STW effluent ranged from 25% (ethinylestradiol) to 100% (benzoylecgonine, bisphenol-A (BPA), bisphenol-S (BPS) and diclofenac). Average concentrations of detected compounds in STW effluents ranged from 3.62 ng/L (ethinylestradiol) to 210 ng/L (BPA). Levels of perfluorinated compounds (PFCs) perfluorooctanoic acid (PFOA) and perfluorononanoic acid (PFNA) as well as the plasticiser BPA were found in street runoff at maximum levels of 1160 ng/L, 647 ng/L and 2405 ng/L respectively (8.52, 3.09 and 2.7 times more concentrated than maximum levels in STW effluents respectively). Rain-driven street runoff may have an effect on levels of PFCs and plasticisers in receiving rivers and should be further investigated. Together, this method with the 13 selected contaminants enables the quantification of various markers of anthropogenic pollutants: inter alia pharmaceuticals, illicit drugs and their metabolites from humans and improper disposal of drugs, while the plasticisers and perfluorinated compounds may also indicate contamination from industrial and transport activity (street runoff).

Highlights

  • From the turn of the 21st century, the occurrence, fate and environmental toxicity of pharmaceuticals and other so-called emerging contaminants in the aquatic environment has been the subject of many studies (e.g., Kolpin et al, 2002; Vajda et al, 2008; 2011; Llorca et al 2012) and reviews (e.g., Petrie et al, 2015; Wilkinson et al, 2015)

  • All intra-day relative standard deviation (RSD)-values were below 10% except for methamphetamine at 25 ng/L (10.1% on day 3) and 100 ng/L (12.5% day 1 and 13.7% day 3), acetaminophen at 25 ng/L (12.2% on day 3) and 4’-hydroxyacetophenone at 25 ng/L (10.5% day 2 and 12.3% day 3)

  • The presented method demonstrated that pharmaceuticals are not the only contaminants of ecological concern entering rivers via sewage treatment works (STW) effluent discharge

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Summary

Introduction

From the turn of the 21st century, the occurrence, fate and environmental toxicity of pharmaceuticals and other so-called emerging contaminants in the aquatic environment (rivers, reservoirs, oceans and drinking water) has been the subject of many studies (e.g., Kolpin et al, 2002; Vajda et al, 2008; 2011; Llorca et al 2012) and reviews (e.g., Petrie et al, 2015; Wilkinson et al, 2015). Every human and veterinary pharmaceutical has been detected in the aquatic environment, typically at sub-μg/L concentrations. Residues of pharmaceuticals typically enter the aquatic environment through STW effluent outfalls where many compounds do not completely degrade (Verlicchi et al, 2012). Other anthropogenic contaminants such as musk compounds used in fragrances and lotions, surfactants, and ultraviolet filters in sunscreen are directed to STWs via wastewater (Peck, 2006; Roosens et al, 2007).

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