Papers by Evroula Hapeshi

Water Research, Nov 1, 2012
This work investigated the application of a solar driven advanced oxidation process (solar photo-... more This work investigated the application of a solar driven advanced oxidation process (solar photo-Fenton), for the degradation of antibiotics at low concentration level (mg L À1) in secondary treated domestic effluents at a pilot-scale. The examined antibiotics were ofloxacin (OFX) and trimethoprim (TMP). A compound parabolic collector (CPC) pilot plant was used for the photocatalytic experiments. The process was mainly evaluated by a fast and reliable analytical method based on a UPLC-MS/MS system. Solar photo-Fenton process using low iron and hydrogen peroxide doses ([Fe 2þ ] 0 ¼ 5 mg L À1 ; [H 2 O 2 ] 0 ¼ 75 mg L À1) was proved to be an efficient method for the elimination of these compounds with relatively high degradation rates. The photocatalytic degradation of OFX and TMP with the solar photo-Fenton process followed apparent first-order kinetics. A modification of the first-order kinetic expression was proposed and has been successfully used to explain the degradation kinetics of the compounds during the solar photo-Fenton treatment. The results demonstrated the capacity of the applied advanced process to reduce the initial wastewater toxicity against the examined plant species (Sorghum saccharatum, Lepidium sativum, Sinapis alba) and the water flea Daphnia magna. The phytotoxicity of the treated samples, expressed as root growth inhibition, was higher compared to that observed on the inhibition of seed germination. Enterococci, including those resistant to OFX and TMP, were completely eliminated at the end of the treatment. The total cost of the full scale unit for the treatment of 150 m 3 day À1 of secondary wastewater effluent was found to be 0.85 V m À3 .

Journal of Chromatography B, May 1, 2003
ABSTRACT A rapid, accurate and sensitive method has been developed and validated for the quantita... more ABSTRACT A rapid, accurate and sensitive method has been developed and validated for the quantitative simultaneous determination of four cephalosporins, cephalexin and cefadroxil (first-generation), cefaclor (second-generation) and cefataxim (third-generation), in pharmaceuticals as well as in human blood serum and urine. A Spherisorb ODS-2 250 x 4-mm, 5-microm analytical column was used with an eluting system consisting of a mixture of acetate buffer (pH 4.0)-CH(3)OH 78-22% (v/v) at a flow-rate 1.2 ml/min. Detection was performed with a variable wavelength UV-Vis detector at 265 nm resulting in limit of detection of 0.2 ng for cefadroxil and cephalexin, but only 0.1 ng for cefotaxime and cefaclor per 20-microl injection. Hydrochlorothiazide (HCT) (6-chloro-3,4-dihydro-7 sulfanyl-2H-1,2,4-benzothiadiazine-1-1-dioxide) was used as internal standard at a concentration of 2 ng/microl. A rectilinear relationship was observed up to 8, 5, 12 and 35 ng/microl for cefadroxil, cefotaxime, cefaclor, cephalexin, respectively. Analysis time was less than 7 min. The statistical evaluation of the method was examined by means of within-day repeatability (n=8) and day-to-day precision (n=9) and was found to be satisfactory with high accuracy and precision. The method was applied to the determination of the cephalosporins in commercial pharmaceuticals and in biological fluids: human blood serum after solid-phase extraction and urine simply after filtration and dilution. Recovery of analytes in spiked samples was in the range from 76.3 to 112.0%, over the range of 1-8 ng/microl.
Nanomaterials, Jun 25, 2023
This article is an open access article distributed under the terms and conditions of the Creative... more This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY

Separations
In recent years, the scientific community has turned its attention to the further study and appli... more In recent years, the scientific community has turned its attention to the further study and application of green chemistry as well as to sustainable development in reducing the consumption of raw materials, solvents, and energy. The application of green chemistry aims to ensure the protection of the environment and to also, consequently, improve the quality of human life. It offers several benefits, both socially and economically. In the last few decades, new alternative non-conventional green extraction methodologies have been developed for the purposes of the extraction of active ingredient compounds from various raw products. The main objective of this literature review is to present the current knowledge and future perspectives regarding the green extraction of tea species in respect of the isolation of safe active biomolecules, which can be used as commercially available products—both as dietary supplements and pharmaceutical formulations. More specifically, in this literature ...

Nanomaterials
Mono-doped (Mo-TiO2 and W-TiO2) and co-doped TiO2 (Co-Mo-TiO2, Co-W-TiO2, Cu-Mo-TiO2, Cu-W-TiO2, ... more Mono-doped (Mo-TiO2 and W-TiO2) and co-doped TiO2 (Co-Mo-TiO2, Co-W-TiO2, Cu-Mo-TiO2, Cu-W-TiO2, Zn-Mo-TiO2, and Zn-W-TiO2) catalysts were synthesized by simple impregnation methods and tested for the photocatalytic degradation of 4-tert-butylphenol in water under UV (365 nm) light irradiation. The catalysts were characterized with various analytical methods. X-ray diffraction (XRD), Raman, Diffuse reflectance (DR) spectroscopies, Scanning electron microscopy (SEM), Transmission electron microscopy (TEM), and Energy dispersive spectroscopy (EDS) were applied to investigate the structure, optical properties, morphology, and elemental composition of the prepared catalysts. The XRD patterns revealed the presence of peaks corresponding to the WO3 in W-TiO2, Co-W-TiO2, Cu-W-TiO2, and Zn-W-TiO2. The co-doping of Cu and Mo to the TiO2 lattice was evidenced by the shift of XRD planes towards higher 2θ values, confirming the lattice distortion. Elemental mapping images confirmed the successf...

Journal of Separation Science
Analysis of vancomycin and teicoplanin in biological fluids is vital since they are used in the t... more Analysis of vancomycin and teicoplanin in biological fluids is vital since they are used in the treatment of hospital infections. For the determination of both glycopeptides in urine, a sensitive and accurate analytical method using high‐performance liquid chromatography coupled with photodiode array and mass spectrometry was developed and validated. This research work is the first attempt to develop a chromatographic method for the determination of two glycopeptides with structural similarities. Moreover, the used non‐invasive sampling method is an advantage of this research effort, especially when the blood sampling is difficult. Urine was treated with acetonitrile and 5% trichloroacetic acid, followed by solid‐phase extraction. The chromatographic separation was established at a C18 column (4.6 × 150 mm, 5 μm), using a gradient method and an electrospray ionization source in a positive mode. The linearity of the method was R2≥ 0.9900. The precision was estimated with a maximum co...
Members and partners of the Sewage analyses CORe group Europe - (SCORE) measured five illicit dru... more Members and partners of the Sewage analyses CORe group Europe - (SCORE) measured five illicit drug residues in wastewater 2011-2017 (every year one week). The data set covers in total 143 wastewater treatment plants in 120 cities from 37 countries, which were monitored at least once.
Chemical Engineering Journal, 2017
h i g h l i g h t s An integrated pilot-scale MBR with solar Fenton system was examined. The inte... more h i g h l i g h t s An integrated pilot-scale MBR with solar Fenton system was examined. The integrated process revealed a high removal efficiency of antibiotics. Selected antibiotic-tolerant bacteria were efficiently removed. The total DNA content in the examined samples was removed by more than 97%. The antibiotic resistance genes sul1 and ermB were not completely removed.

Water Research, 2015
This study evaluates the feasibility of UV-C-driven advanced oxidation process induced by sulfate... more This study evaluates the feasibility of UV-C-driven advanced oxidation process induced by sulfate radicals ðSO 4 À Þ in degrading erythromycin (ERY) in secondary treated wastewater. The results revealed that 10 mg L À1 of sodium persulfate (SPS) can result in rapid and complete antibiotic degradation within 90 min of irradiation, while ERY decay exhibited a pseudo-first-order kinetics pattern under the different experimental conditions applied. ERY degradation rate was strongly affected by the chemical composition of the aqueous matrix and it decreased in the order of: ultrapure water (k app ¼ 0.55 min À1) > bottled water (k app ¼ 0.26 min À1) > humic acid solution (k app ¼ 0.05 min À1) > wastewater effluents (k app ¼ 0.03 min À1). Inherent pH conditions (i.e. pH 8) yielded an increased ERY degradation rate, compared to that observed at pH 3 and 5. The contribution of hydroxyl and sulfate radicals (HO and SO 4 À) on ERY degradation was found to be ca. 37% and 63%, respectively. Seven transformation products (TPs) were tentatively elucidated during ERY oxidation, with the 14-membered lactone ring of the ERY molecule being intact in all cases. The observed phytotoxicity against the tested plant species can potentially be attributed to the dissolved effluent organic matter (dE f OM) present in wastewater effluents and its associated-oxidation products and not to the TPs generated from the oxidation of ERY. This study evidences the potential use of the UV-C/SPS process in producing a final treated effluent with lower phytotoxicity (<10%) compared to the untreated wastewater. Finally, under the optimum experimental conditions, the UV-C/SPS process resulted in total inactivation of ERY-resistant Escherichia coli within 90 min.

CLEAN – Soil, Air, Water, 2015
Two multi‐residue methods based on off‐line solid phase extraction followed by LC‐MS/MS have been... more Two multi‐residue methods based on off‐line solid phase extraction followed by LC‐MS/MS have been applied in samples collected from three sewage treatment plants for the identification and quantification of licit and illicit drugs. The occurrence of the drugs in wastewater appears to be influenced by both the operational parameters of each plant and their consumption in the area served by the corresponding plant. Generally, the present study demonstrated that both licit and illicit drugs were found in the effluent wastewater of all urban wastewater treatment plants; a fact suggesting that they are bioresistance. These compounds were determined in relatively high concentrations (licit drugs: below limit of detection (BLD) to 5520 ng/L and illicit drugs: BLD to 5815 ng/L) in all effluent wastewater samples monitored in this study. The major groups of licit drugs detected in the effluents were antibiotics, β‐blockers, analgesics, and non‐steroidal‐anti‐inflammatory drugs suggesting tha...

Quorum sensing (QS) is a form of intra- and inter-species communication system which is employed ... more Quorum sensing (QS) is a form of intra- and inter-species communication system which is employed by bacteria to regulate their collective behavior in a cell population-dependent manner. QS has been implicated in the virulence of several pathogenic bacteria. This work aimed to investigate the anti-quorum sensing (anti-QS) potential of ethanolic extracts of eight aromatic plants of Cyprus namely, Origanum vulgare subsp. hirtum, Rosmarinus officinalis, Salvia officinalis, Lavendula spp., Calendula officinalis, Melissa officinalis, Sideritis cypria, and Aloysia citriodora. We initially assess the effects of the extracts on autoinducer 2 (AI-2) signaling activity, using Vibrio harveyi BB170 as a reported strain. We subsequently assess the effect of the ethanolic extracts on QS-related processes including biofilm formation and swarming and swimming motilities of Escherichia coli MG1655. Of the tested ethanolic extracts those of Origanum vulgare subsp. hirtum, Rosmarinus officinalis, and S...
Chemical Engineering Journal, 2017

Environmental Science and Pollution Research, 2017
Veterinary antibiotics could enter the environment after the application of manure or farm wastew... more Veterinary antibiotics could enter the environment after the application of manure or farm wastewater on soil as fertilizer. In this study, a UPLC-MS/MS analytical method was developed and validated for the simultaneous determination of enrofloxacin (ENR) and ciprofloxacin (CIP) at environmental relevant concentrations in piggery wastewater, piggery wastewater solids, agricultural soil and ground water with good performance characteristics. The method recovery for ENR and CIP was 94.2 and 89.9% in the filtered piggery wastewater, 81.3 and 82% in the wastewater solid material, 78.1 and 76.8% in the soil and 95.6 and 97.3% in the ground water. The Limit of Detection (LOD) and Limit of Quantification (LOQ) for ENR were 21 and 64 ng L −1 and for CIP was 18 and 54 ng L −1 , respectively. The method was implemented to monitor ENR and CIP in the wastewater of a piggery facility in Cyprus which applied anaerobic treatment before the final disposal of the reclaimed water. The highest antibiotic concentrations were measured in the wastewater samples collected from the nursery, where ENR is continuously used, with average concentration 31.4 μg L −1 for ENR and 16.0 μg L −1 for CIP. After the anaerobic digester, the two antibiotics were found only on the solid matter of the treated wastewater with an average concentration of 1.7 μg kg −1 for ENR and 1.0 μg kg −1 for CIP. The antibiotics adsorption at pH = 7 on clay soil, quartz sand and on solid matter isolated from the piggery wastewater was found to be higher than 95% for all solid materials. The concentration of the antibiotics in soil samples taken from a field where reclaimed piggery wastewater was applied for 10 years and in samples of groundwater from a nearby well was found for all samples below the LOD.
Water Research, 2017
Corrigendum to: "Long-term wastewater irrigation of vegetables in real agricultural systems: Conc... more Corrigendum to: "Long-term wastewater irrigation of vegetables in real agricultural systems: Concentration of pharmaceuticals in soil, uptake and bioaccumulation in tomato fruits and human health risk assessment." [Water Res. 109 (2017) 24e34]

Water Research, 2017
Wastewater (WW) reuse for vegetable crops irrigation is regularly applied worldwide. Such a pract... more Wastewater (WW) reuse for vegetable crops irrigation is regularly applied worldwide. Such a practice has been found to allow the uptake of pharmaceutical active compounds (PhACs) by plants and their subsequent entrance to the food web, representing an important alternative pathway for the exposure of humans to PhACs, with potential health implications. Herein we report the impacts of the long-term (three consecutive years) WW irrigation of a tomato crop with two differently treated effluents under real agricultural conditions, on (1) the soil concentration of selected PhACs (i.e. diclofenac, DCF; sulfamethoxazole, SMX; trimethoprim, TMP), (2) the bioaccumulation of these PhACs in tomato fruits, and (3) the human risks associated with the consumption of WW-irrigated fruits. Results revealed that the concentration of the studied PhACs in both the soil and tomato fruits varied depending on the qualitative characteristics of the treated effluent applied and the duration of WW irrigation. The PhAC with the highest soil concentration throughout the studied period was SMX (0.98 mg kg À1), followed by TMP (0.62 mg kg À1) and DCF (0.35 mg kg À1). DCF was not found in tomato fruits harvested from WW-irrigated plants during the first year of the study. However, DCF displayed the highest fruit concentration (11.63 mg kg À1) throughout the study (as a result of prolonged WW irrigation), followed by SMX (5.26 mg kg À1) and TMP (3.40 mg kg À1). The calculated fruit bioconcentration factors (BCF F) were extremely high for DCF in the 2nd (108) and 3rd year (132) of the experimental period, with the respective values for SMX (0.5e5.4) and TMP (0.2e6.4) being significantly lower. The estimated threshold of toxicity concern (TTC) and hazard quotients (HQ) values revealed that the consumption of fruits harvested from tomato plants irrigated for long period with the WW applied for irrigation under field conditions in this study represent a de minimis risk to human health. However, more studies need to be performed in order to obtain more solid information on the safety of WW reuse for irrigation.

Agricultural Water Management, 2016
Water scarcity renders wastewater (WW) reuse for irrigation an increasingly common practice world... more Water scarcity renders wastewater (WW) reuse for irrigation an increasingly common practice worldwide. Comprehensive guidelines and criteria have been established to secure the safety of WW irrigation, especially for food crops or crops that are eaten raw. The aim of this short-term study was to assess the impacts of strawberry crop irrigation with tertiary treated wastewater (WW) using common irrigation techniques (Drip, sprinkler, drip under plastic mulch), as compared to potable water (PW) irrigation, on strawberry fruits' quality and safety, and on crops' productivity. The impacts on fruits' weight and marketability, as well as on fruits' taste (soluble solids, titratable acidity and soluble solids/titratable acidity ratio), antioxidant capacity (ascorbic acid concentration, FRAP, total phenolics and total anthocyanin content), heavy metal content (Cu, Zn, Mn, Co, Ni) and microbial contamination (total coliform, E. coli, Salmonella spp., Listeria spp), were evaluated. The results revealed that WW irrigation did not significantly affect the fruits' marketability, taste and antioxidant capacity, as well as the heavy metal content, in comparison to controlled irrigation, regardless of the irrigation technique applied. Fruits heavy metal content was found to be below the maximum permissible levels (MPLs) set for fruit safety, whereas no microbiological contamination (total coliform, E. coli, Salmonella spp., Listeria spp.) of fruits was found in all irrigation water treatments. Overall, the results obtained with regard to the parameters examined highlight the potential for the reuse of the advanced tertiary treated effluent of good quality as a valid alternative for the irrigation of strawberry crops, even with sprinklers. However, further long-term studies are needed in order for such a practice to be regulated.

Catalysis Today, 2015
The extensive use of estrogens and their release, through various pathways, into the environment,... more The extensive use of estrogens and their release, through various pathways, into the environment, constitutes an emerging environmental problem that poses serious threats onto public health. In this work the efficiency of UVC/H 2 O 2 and solar/Fe 2+ treatment to degrade 17␣-ethynylestradiol (EE2) in environmentally relevant concentrations of 100 g/L in secondary-treated wastewater matrices was investigated. Also, photolytic treatment was performed under different irradiation sources, namely UVC, UVA and simulated solar light. The effect of H 2 O 2 (0-20 mg/L) and Fe 2+ (0-15 mg/L) concentration was investigated and, at optimal operating parameters, EE2 removal was 100% after 15 min of UVC/H 2 O 2 treatment, while EE2 removal reached 86% after 60 min of solar/Fe 2+ treatment. In addition, the effect of water matrix and pH was studied. Total organic carbon (TOC) and yeast estrogen screening (YES) measurements showed the formation of stable intermediate products during EE2 treatment and an attempt to elucidate the reaction pathways and mechanisms through the identification of transformation products (TPs) by means of UPLC-MS/MS was made. Several TPs, including quinone methide and 1,2-quinone derivatives, were identified and competing pathways were suggested, in which hydroxylation, alkylation, dealkylation, demethylation and dehydroxylation, amongst others were described as major transformation mechanisms.

Environmental Science and Pollution Research, 2013
The capability of a moving bed biofilm reactor (MBBR) to remove the iodinated contrast media (ICM... more The capability of a moving bed biofilm reactor (MBBR) to remove the iodinated contrast media (ICM) iohexol (IOX) and diatrizoate (DTZ) from municipal wastewater was studied. A selected number of clones of microorganisms present in the biofilm were identified. Biotransformation products were tentatively identified and the toxicity of the treated effluent was assessed. Microbial samples were DNAsequenced and subjected to phylogenetic analysis in order to confirm the identity of the microorganisms present and determine the microbial diversity. The analysis demonstrated that the wastewater was populated by a bacterial consortium related to different members of Proteobacteria, Firmicutes, and Nitrisporae. The optimum removal values of the ICM achieved were 79 % for IOX and 73 % for DTZ, whereas 13 biotransformation products for IOX and 14 for DTZ were identified. Their determination was performed using ultra-performance liquid chromatography-tandem mass spectrometry. The toxicity of the treated effluent tested to Daphnia magna showed no statistical difference compared to that without the addition of the two ICM. The MBBR was proven to be a technology able to remove a significant percentage of the two ICM from urban wastewater without the formation of toxic biodegradation products. A large number of biotransformation products was found to be formed. Even though the amount of clones sequenced in this study does not reveal the entire bacterial diversity present, it provides an indication of the predominating phylotypes inhabiting the study site.
Journal of Separation Science

Nanomaterials, 2022
Biochar from spent malt rootlets was employed as the template to synthesize hybrid biochar-ceria ... more Biochar from spent malt rootlets was employed as the template to synthesize hybrid biochar-ceria materials through a wet impregnation method. The materials were tested for the activation of persulfate (SPS) and subsequent degradation of sulfamethoxazole (SMX), a representative antibiotic, in various matrices. Different calcination temperatures in the range 300–500 °C were employed and the resulting materials were characterized by means of N2 adsorption and potentiometric mass titration as well as TGA, XRD, SEM, FTIR, DRS, and Raman spectroscopy. Calcination temperature affects the biochar content and the physicochemical properties of the hybrid materials, which were tested for the degradation of 500 μg L−1 SMX with SPS (in the range 200–500 mg L−1) in various matrices including ultrapure water (UPW), bottled water, wastewater, and UPW spiked with bicarbonate, chloride, or humic acid. Materials calcined at 300–350 °C, with a surface area of ca. 120 m2 g−1, were the most active, yield...
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Papers by Evroula Hapeshi