Comprehensive investigation of a wide range of pharmaceuticals and personal care products in urban and hospital wastewaters in Greece

https://doi.org/10.1016/j.scitotenv.2019.07.371Get rights and content

Highlights

  • The protocol can analyze large number of PPCPs (138 analytes).

  • Extensive monitoring survey of PPCPs in four WWTPs in three Greek cities

  • NSAIDs, antibiotics, anti-hypertensives and psychiatrics were the most frequently detected.

  • The removal rates varied between the different therapeutic groups.

  • Risk was assessed by RQ approach and cumulative RQ for the classes of PPCPs.

Abstract

Detection and quantification of Pharmaceutical and Personal care products (PPCPs) in wastewaters and aqueous samples is crucial in terms of environmental monitoring and risk assessment for these emerging contaminants in the environment. The majority of the studies on PPCPs in wastewaters involve analysis only of representative compounds for each class, while few studies reported for the analysis of several compounds from multiple classes of PPCPs in samples. In this light, the aim of this work was to develop a multiresidue analytical protocol based on solid phase extraction (SPE) coupled to liquid chromatography combined with tandem mass spectrometer-(LC-MS/MS) for simultaneous determination of 138 substances including 37 different classes of PPCPs that can be used for monitoring in wastewater. Hence, an extensive monitoring survey of PPCPs in four wastewater treatment plants (WWTPs) in three cities of North (Thessaloniki) and Central (Larisa, Volos) Greece region has been conducted. In addition, the occurrence of the target compounds in raw waters of effluents from two medium-size hospitals located in the Larisa Region was investigated. Analgesics-anti-inflammatories (paracetamol, diclofenac, ibuprofen, salicylic acid), diuretic (furosemide), antibiotics (amoxicillin, ampicillin, clarithromycin, azithromycin), anti-hypertensives (valsartan, irbesartan, telmisartan), psychiatric drugs (carbamazepine, venlafaxine, citalopram), stimulant (caffeine) and beta blockers (atenolol, metoprolol, pindolol) were among the most frequently detected compounds. The removal rates varied between the different therapeutic groups, as well within each therapeutic group, important variations in removal were observed, going from not eliminated to 100%. Mass loading distribution in the different WWTPs was also evaluated. Finally, the risk quotient approach (RQ) for single substances and the cumulative RQ for the classes of the target PPCPs was used in order to identify the potential ecotoxicological risk posed in the tree trophic levels of aquatic organisms.

Introduction

In the current decade dozens of extensive studies have recognized the problems that our society confronts with pharmaceutical and personal care products (PPCPs) (Evgenidou et al., 2015; Yang et al., 2017). PPCPs originate from pharmaceutical production facilities, anthropogenic and agriculture uses (Rivera-Jaimes et al., 2018). Due to the use, a wide range of PPCPs are released; end up in wastewaters and are transported mainly in Waste Water Treatment Plants (WWTPs) or disposed untreated in surface and groundwater (Papageorgiou et al., 2016). Despite their low concentrations, the ubiquity of pharmaceuticals in the aquatic environment along with their persistent biological activities explains the concern over this specific group (Kosma et al., 2014).

In spite of the increasing number of studies on PPCPs, data regarding the concentrations of a wide range of PPCPs in the environment exhibit great variability. This is due to many factors, including usage, operating parameters of the wastewater treatment plants and physicochemical properties of these compounds, which contribute to their widespread presence and complex behavior/synergistic effects, particularly in the aquatic environment (Verlicchi and Zambello, 2015).

Monitoring campaigns remain the most useful tool which can give information of the up to date situation, especially in the cases where detailed data from the consumed PPCPs from the companies and the national or/and international organizations are scarce, like in Greece (Iatrou et al., 2014). Thus, analyzing monitoring data, the actual performance of the WWTPs and the situation of the aquatic aquifer can be evaluated facilitating the process for prioritizing candidates that must be monitored and consequently regulated in-terms of emissions. In monitoring studies, the use of rapid and effective analytical methods can play a vital role since medical products and the number of PPCPs that need to be monitored keep increasing. Hence, the detection of as many PPCP compounds as possible in multiresidue analysis has always been a critical and ongoing challenge for scientists and analysts.

Based on the above, the main objective of the present study was to develop a multiresidue screening method for simultaneous analysis of a wide range of PPCPs (138 compounds) to be used, for the first time, for an extensive monitoring study in urban wastewaters from WWTPs at locations (Three cities; Thessaloniki, Larisa, Volos) in North and Central Greece. In detail, we determined the levels of PPCPs in influents and effluents of WWTPs as well as in raw waters of effluents from two medium-sized hospitals located in the region of Larisa. The Greek WWTPs monitored in this study were large facilities located in North and Central region of the country. These WWTPs were selected as they represent typical urban sewage treatment facilities in Greece. Although some recent works described the occurrence of PPCPs in Greek aquatic environment (Arditsoglou and Voutsa, 2010; Dasenaki and Thomaidis, 2015; Ibáñez et al., 2017; Kosma et al., 2014; Kosma et al., 2015; Koutsouba et al., 2003; Samaras et al., 2013; Stamatis and Konstantinou, 2013; Stasinakis et al., 2013; Alygizakis et al., 2016; Ibáñez et al., 2017), very little data are currently available in localized areas of Central Makedonia and Thessaly (Papageorgiou et al., 2016) on the concentrations of PPCPs in wastewaters. Furthermore, given the growing number of PPCPs, gaps in the data are inevitable. For example, data and systematic survey for some classes such as antihypertensives, antineoplastics, anesthetics or even antibiotics and hormones are missing or are scarce in Greek aquatic environment. Hence, research including a wide scope monitoring of high number of PPCPs and risk assessment at environmentally relevant concentrations are required for a better assessment of the potential environmental impact of these compounds. Particular attention has been paid to compounds with limited data (i.e. antihypertensives (valsartan, irbersatan, telmisartan, losartan) etc.) and compounds with relative concern about their impact in the environment (i.e. antineoplastics (cytarabine, 5-Fluorouracil, viblastine, etoposide) etc.). This study also compared the results obtained from our previous study conducted in WWTP of Volos (Papageorgiou et al., 2016). A total of 84 new compounds were added in the present study in comparison with our previous one for more comprehensive overview on the concentrations of PPCPs, expanding the final list to 138 substances. For the rest three WWTPs in Thessaloniki and Larisa, this is the first time to report the results of a monitoring for evaluation of the occurrence of these compounds. Other specific objectives of the present study were: (i) to establish the removal of these target compounds during wastewater treatment, (ii) to estimate theirs mass loadings in the influents and the effluents and to evaluate the environmental risk assessment based on the concentrations of PPCPs detected in effluents, (iii) to have better knowledge on the PPCPs present in effluent wastewater that potentially reaches the surface waters receiving discharges from the investigated WWTPs.

Section snippets

Sampling sites and sampling campaigns

The study was carried out in Central and Northern Greece. Thessaloniki is the second largest city in Greece, located in Central Macedonia. WWTP-S located in the west part of Thessaloniki and serves 1,333,000 citizens, while the WWTP-A is located in the southeast coastal part of Thessaloniki and serves 50,264 citizens. Both WWTPs receive urban wastewaters (domestic and storm waters) and the samples were collected after secondary treatment with disinfection treatment. WWTP-S serves the main

Occurrence comparison of PPCPs between WWTP-S and WWTP-A

The detected concentrations of the target compounds detected in influents and effluents from the two WWTPs of the city of Thessaloniki are summarized in Tables SD5-SD8 in SM. In a general point of view, among the therapeutic groups of pharmaceuticals, analgesics/anti-inflammatories antihypertensive, antibiotics, diuretics, antihistamines, beta-blockers, anti-vertigo and psychiatrics were those most frequently detected and at higher concentration levels, in both influents and effluents of

Conclusions

In the current study, a solid-phase extraction-LC–MS/MS method was optimized and successfully applied to wastewater samples for a comprehensive investigation of a wide range of compounds (138 analytes) belonging in 37 different classes of PPCPs in four urban WWTPs and in raw waters of effluents from two medium-size hospitals in Greece was investigated. Special attention was given to classes that are not frequently included in monitoring campaigns such as thyroid hormone, antineoplastics,

Acknowledgments

This research has been co-financed by the European Union (European Social Fund — ESF) and Greek national funds through the Operational Program “Education and Lifelong Learning” of the National Strategic Reference Framework (NSRF) — Research Funding Program “Excellence II (Aristeia II)”, Research Grant, No 4199, which is gratefully acknowledged. Myrsini Papageorgiou acknowledges the institution State Scholarships Foundation (IKY) for the “Scholarship Program for postgraduate studies second

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