Abstract

Due to the high consumption and incorrect disposal of pharmaceutical active compounds (PhACs), they are recognized as contaminants of emerging concern. Wastewater treatment plants (WWTPs) may be inefficient in removing PhACs, therefore discharging them into surface waters. The removal efficiencies of five WWTPs located in the south of Portugal (Alentejo) were evaluated in 2020. Twenty-six PhACs were analyzed in wastewater influents, effluents, and surface waters, upstream and downstream of the WWTPs by solid-phase extraction (SPE) and ultra-performance liquid chromatography coupled with tandem mass detection (UPLC-MS/MS). The most representative PhACs in influents were acetaminophen, caffeine, naproxen, ibuprofen, and diclofenac with minimum-maximum concentrations of 49–225 µg/L, 26–46 µg/L, 5.9–13 µg/L, 5.2–22 µg/L, and 1.3–2.5 µg/L, respectively. For effluents, it was acetaminophen, caffeine, and diclofenac with minimum-maximum concentrations of 0.054–7.8 µg/L, 0.084–4.8 µg/L, and 0.28–3.3 µg/L, respectively. The highest removal efficiencies were observed for acetaminophen, sulfadiazine, cortisone, testosterone, metoprolol, and propranolol (100%). The lowest removal efficiencies were observed for carbamazepine (2.7%) and diclofenac (−13.2%). The risk quotient of sulfamethoxazole and diclofenac were higher than 1 for receiving waters, indicating they probably pose high risks to aquatic organisms.

Highlights

  • Introduction published maps and institutional affilAnthropogenic pressures and climate change are currently responsible for extreme changes in raw water availability and quality as well as the degradation of water sources.Regarding anthropogenic pressures, there has been growing concern about several biologically active environmental contaminants in the aquatic environment, mainly regarding the group of so-called contaminants of emerging concern (CECs)

  • All figures and tables show the pharmaceutical active compounds (PhACs) grouped by acid and basic chromatographic runs, and in each method, they are grouped by their retention time

  • Acetaminophen was the prevalent PhAC measured in WWTPs, ranging from 27 to

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Summary

Reagents and Standards

The target PhACs were chosen considering the Portuguese data consumption provided by Infarmed (Portuguese Authority of Medicines and Health) and the compounds proposed in the Water Framework Directive [21,22]. All standards of PhACs are of analytical grade (purity ≥ 95%), suitable for chromatographic analysis. The standards of acetaminophen, clofibric acid, atenolol, bezafibrate, carbamazepine, cortisone, diclofenac, erythromycin, estrone, fluoxetine, ibuprofen, naproxen, propranolol, sulfadiazine, sulfamethoxazole, sulfapyridine, clarithromycin, and azithromycin were provided by Sigma-Aldrich (Steinheim, Germany), caffeine, and testosterone by Fluka (Buchs, Switzerland), and gestodene and metoprolol by LGC (Teddington, UK). Individual stock solutions of PhACs were prepared in methanol and stored at −20 ± 3 ◦ C in the absence of light. Methanol was LC/MS purity grade (J.T. Baker, Deventer, the Netherlands). Formic acid (liquid chromatography grade, ≥98%) and ammonium acetate (98%, p.a.) were provided by Merck (Darmstadt, Germany).

Material and Apparatus
Removal Efficiency and Environmental Risk Assessment
Water Analysis
Method Performance
Occurrence of PhACs in the Five WWTPs and Surface Waters
Acidic Method
Composition profilesofofPhACs
Removal Efficiencies of PhACs by WWTPs
Environmental Risks of Target PhACs
Conclusions
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