The spatial distribution of pharmaceuticals, personal care products (PPCPs) and other emerging contaminants (ECs) such as plasticisers, perflourinated compounds (PFCs) and illicit drug metabolites in water and bound to suspended particulate material (SPM) is not well-understood. Here, we quantify levels of thirteen selected contaminants in water (n = 88) and their partition to suspended particulate material (SPM, n = 16) in three previously-unstudied rivers of Greater London and Southern England during a key reproduction/spawning period. Analysis was conducted using an in-house validated method for Solid Phase Extraction followed by High-Performance Liquid Chromatography-Tandem Mass-Spectrometry. Analytes were extracted from SPM using an optimised method for ultrasonic-assisted solvent extraction. Detection frequencies of contaminants dissolved in water ranged from 3% (ethinylestradiol) to 100% (bisphenol-A). Overall mean concentrations in the aqueous-phase ranged from 14.7 ng/L (benzoylecgonine) to 159 ng/L (bisphenol-A). Sewage treatment works (STW) effluent was the predominant source of pharmaceuticals, while plasticisers/perfluorinated compounds may additionally enter rivers via other sources. In SPM, detection frequencies ranged from 44% (PFOA) to 94% (hydroxyacetophenone). Mean quantifiable levels of analytes bound to SPM ranged from 13.5 ng/g dry SPM (0.33 ng bound/L water) perfluorononanoic acid to 2830 ng/g dry SPM (14.3 ng bound/L water) perfluorooctanesulfonic acid. Long chain (> C7) amphipathic and acidic PFCs were found to more preferentially bind to SPM than short chain PFCs and other contaminants (Kd = 34.1–75.5 vs < 5 respectively). Per capita daily contributions of studied contaminants entering rivers ranged from 0.157 μg/person/day of benzoylecgonine (cocaine metabolite) to 58.6 μg/person/day of bisphenol-A. The large sample size of this work (n = 104) enabled ANOVA followed by Tukey HSD post-hoc tests to establish significant trends in PPCP/EC spatial distribution from headwaters through downstream stretches of studied rivers. Novel findings include environmental Kd calculations, the occurrence of contaminants in river headwaters, increases in contaminant metabolite concentrations downstream of STW effluents revealing possible in-river degradation or de-conjugation, the influence of polarity and acidity in the partition of contaminants to particulate-material, among others.
Bibliographical notePublisher Copyright:
- Contaminant partition
- Emerging contaminants
- Pharmaceuticals and personal care products
- Spatial distribution
- Suspended particulate material
- Temporal distribution