Development of a miniaturized sample preparation prototype for identification and quantification of trace pharmaceuticals in tap waters

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Publications

Occurrence of chiral bioactive compounds in the aquatic environment: a review

Publication . Ribeiro, Cláudia; Ribeiro, Ana Rita; Maia, Alexandra S.; Tiritan, Maria Elizabeth

In recent decades, the presence of micropollutants in the environment has been extensively studied due to their high frequency of occurrence, persistence and possible adverse effects to exposed organisms. Concerning chiral micropollutants in the environment, enantiomers are frequently ignored and enantiomeric composition often neglected. However, enantioselective toxicity is well recognized, highlighting the need to include enantioselectivity in environmental risk assessment. Additionally, the information about enantiomeric fraction (EF) is crucial since it gives insights about: (i) environmental fate (i.e., occurrence, distribution, removal processes and (bio)degradation); (ii) illicit discharges; (iii) consumption pattern (e.g., illicit drugs, pharmaceuticals used as recreational drugs, illicit use of pesticides); and (iv) enantioselective toxicological effects. Thus, the purpose of this paper is to provide a comprehensive review about the enantioselective occurrence of chiral bioactive compounds in aquatic environmental matrices. These include pharmaceuticals, illicit drugs, pesticides, polychlorinated biphenyls (PCBs) and polycyclic musks (PCMs). Most frequently analytical methods used for separation of enantiomers were liquid chromatography and gas chromatography methodologies using both indirect (enantiomerically pure derivatizing reagents) and direct methods (chiral stationary phases). The occurrence of these chiral micropollutants in the environment is reviewed and future challenges are outlined.

2017Journal article

Open access

Photocatalytic ozonation of urban wastewater and surface water using immobilized TiO2 with LEDs: Micropollutants, antibiotic resistance genes and estrogenic activity

Publication . Moreira, Nuno F.F.; Sousa, José M.; Macedo, Gonçalo; Ribeiro, Ana R.; Barreiros, Luisa; Pedrosa, Marta; Faria, Joaquim L.; Pereira, M. Fernando R.; Castro-Silva, Sérgio; Segundo, Marcela A.; Manaia, Célia M.; Nunes, Olga C.; Silva, Adrián M.T.

Photocatalytic ozonation was employed for the first time in continuous mode with TiO2-coated glass Raschig rings and light emitting diodes (LEDs) to treat urban wastewater as well as surface water collected from the supply area of a drinking water treatment plant (DWTP). Different levels of contamination and types of contaminants were considered in this work, including chemical priority substances (PSs) and contaminants of emerging concern (CECs), as well as potential human opportunistic antibiotic resistant bacteria and their genes (ARB&ARG). Photocatalytic ozonation was more effective than single ozonation (or even than TiO2 catalytic ozonation) in the degradation of typical reaction by-products (such as oxalic acid), and more effective than photocatalysis to remove the parent micropollutants determined in urban wastewater. In fact, only fluoxetine, clarithromycin, erythromycin and 17-alpha-ethinylestradiol (EE2) were detected after photocatalytic ozonation, by using solid-phase extraction (SPE) pre-concentration and LC-MS/MS analysis. In surface water, this treatment allowed the removal of all determined micropollutants to levels below the limit of detection (0.01-0.20 ng L(-1)). The efficiency of this process was then assessed based on the capacity to remove different groups of cultivable microorganisms and housekeeping (16S rRNA) and antibiotic resistance or related genes (intI1, blaTEM, qnrS, sul1). Photocatalytic ozonation was observed to efficiently remove microorganisms and ARGs. Although after storage total heterotrophic and ARB (to ciprofloxacin, gentamicin, meropenem), fungi, and the genes 16S rRNA and intI1, increased to values close to the pre-treatment levels, the ARGs (blaTEM, qnrS and sul1) were reduced to levels below/close to the quantification limit even after 3-days storage of treated surface water or wastewater. Yeast estrogen screen (YES), thiazolyl blue tetrazolium reduction (MTT) and lactate dehydrogenase (LDH) assays were also performed before and after photocatalytic ozonation to evaluate the potential estrogenic activity, the cellular metabolic activity and the cell viability. Compounds with estrogenic effects and significant differences concerning cell viability were not observed in any case. A slight cytotoxicity was only detected for Caco-2 and hCMEC/D3 cell lines after treatment of the urban wastewater, but not for L929 fibroblasts.

2016Journal article

Open access

Fármacos quirais em diferentes matrizes ambientais: ocorrência, remoção e toxicidade

Publication . Ribeiro, Ana R.; Afonso, Carlos; Castro, Paula M. L.; Tiritan, Maria E.

In recent decades, the occurrence of pharmaceuticals in the environment has been widely reported due to their high frequency and recalcitrance in many cases. Concerning the chiral pharmaceuticals (CPs) in environmental matrices, the stereochemistry is often neglected and enantiomers are determined together as unique molecules. However, it is well known that CPs might have enantioselective toxicity, rendering important to assess the occurrence and degradation processes of single enantiomers in the environment, namely during biological treatment in wastewater treatment plants (WWTPs). The development of analytical methods to qualitatively and quantitatively evaluate the enantiomers of CPs is crucial for determining enantiomeric fraction (EF). The EF is the most important parameter in studies involving enantiomers and enantioselective processes and fundamental in biodegradation studies and wastewater monitoring. This review summarizes the analytical methods used to determine EF of CPs in environmental matrices and/or during biodegradation processes. The occurrence of CPs in the environment and their biodegradation are reviewed and future trends in the area outlined.

2016Journal article

Open access

Continuous ozonation of urban wastewater: removal of antibiotics, antibiotic-resistant Escherichia coli and antibiotic resistance genes and phytotoxicity

Publication . Iakovides, I. C.; Michael-Kordatou, I.; Moreira, N. F. F.; Ribeiro, A. R.; Fernandes, T.; Pereira, M. F. R.; Nunes, O. C.; Manaia, C. M.; Silva, A. M. T.; Fatta-Kassinos, D.

This work evaluated the removal of a mixture of eight antibiotics (i.e. ampicillin (AMP), azithromycin (AZM), erythromycin (ERY), clarithromycin (CIA), ofloxacin (OFL), sulfamethoxazole (SMX), trimethoprim (TMP) and tetracycline (TC)) from urban wastewater, by ozonation operated in continuous mode at different hydraulic retention times (HRTs) (i.e. 10, 20, 40 and 60 min) and specific ozone doses (i.e. 0.125, 0.25, 0.50 and 0.75 gO(3) gDOC(-1)). As expected, the efficiency of ozonation was highly ozone dose-and contact time-dependent. The removal of the parent compounds of the selected antibiotics to levels below their detection limits was achieved with HRT of 40 min and specific ozone dose of 0.125 gO(3) gDOC(-1). The effect of ozonation was also investigated at a microbiological and genomic level, by studying the efficiency of the process with respect to the inactivation of Escherichia coli and antibiotic-resistant E. coli, as well as to the reduction of the abundance of selected antibiotic resistance genes (ARG5). The inactivation of total cultivable E. coli was achieved under the experimental conditions of HRT 40 min and 0.25 gO(3) gDOC(-1), at which all antibiotic compounds were already degraded. The regrowth examinations revealed that higher ozone concentrations were required for the permanent inactivation of E. coli below the Limit of Quantification (

2019Journal article

Open access

Anthropogenic pressure in a Portuguese river: endocrine-disrupting compounds, trace elements and nutrients

Publication . Ribeiro, Cláudia M. R.; Maia, Alexandra S.; Ribeiro, Ana R.; Couto, Cristina; Almeida, Agostinho A.; Santos, Mariana; Tiritan, Maria E.

Natural organic compounds such as phytoestrogens and phytosterols found in various plants, as well as mycotoxins produced by fungi, can be found in aquatic environments. The aim of this study was to investigate the occurrence of three different classes of natural estrogenic compounds, i.e., phytoestrogens, phytosterols and mycotoxins, in estuarine water samples from the Ave River estuary. For that, water samples were collected at five sampling points distributed along the estuary at low tide, during 1 year, processed by solid-phase extraction (SPE) and analyzed by gas chromatography coupled to mass spectrometry (GC–MS). To correlate the presence of phytoestrogens and phytosterols in the estuarine water, local flora was collected on riverside. Trace elements content and physicochemical parameters such as nutrients and dissolved oxygen were also determined seasonally at each sampling point, to give insights for the evaluation of water quality and anthropogenic pressure. Both phytoestrogens and phytosterols showed a seasonal variation, with the highest values observed in spring and summer and the lowest in winter. Daidzein (DAID) was found up to 404.0 ng L¡1 in spring and coumestrol (COUM) was found up to 165.0 ng L¡1 in summer. The mycotoxin deoxynivalenol (DON) was ubiquitously determined with values ranging from 59.5 to 642.4 ng L¡1. Nutrients and metals distribution and concentration varied among sampling stations and seasons. This study revealed for the first time the presence of mycotoxins, various classes of phytoestrogens and stigmasterol (STG) in estuarine water from the Ave River (Portugal), and the evaluation of the water quality confirmed that this estuary is still highly impacted by anthropogenic activities.

2016Journal article

Restricted access