Detection, Fate and Removal of Contaminants of Emerging Concern in Aqueous Environment

A special issue of Separations (ISSN 2297-8739).

Deadline for manuscript submissions: closed (31 January 2021) | Viewed by 23087

Special Issue Editor

Laboratory of Analytical Chemistry, Department of Chemistry, University of Ioannina, 45110 Ioannina Greece
Interests: sample preparation; microextraction methodologies; gas-chromatography; high performance liquid-chromatography; mass spectrometry; method development and validation; chemometrics; emerging contaminants

Special Issue Information

Dear Colleagues,

A vast array of chemicals is released into the environment from industrial and household products and applications. Some of these chemicals have been classified as contaminants of emerging concern (CECs), and most of them have not been regulated or commonly monitored in the environment. At the same time their fate, behavior and ecotoxicological effects and have not been fully evaluated for the risks they might pose to the environment. In some cases, their release to the environment has likely occurred for a long time (pharmaceuticals, hormones, sunscreens, UV filters, disinfection by-products, etc.), but may not have been recognized as CECs until new detection methods were developed.

The aim of this Special Issue is to cover the developments in the determination of CECs as well as their fate and removal from aqueous environment.

Dr. Vasilios Sakkas
Guest Editor

Manuscript Submission Information

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Keywords

  • organic contaminants of emerging concern
  • extraction
  • determination
  • analysis
  • occurrence
  • gas chromatography
  • liquid chromatography
  • mass spectrometry

Published Papers (6 papers)

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Research

23 pages, 5523 KiB  
Article
Enhanced Photocatalytic Activity of CuWO4 Doped TiO2 Photocatalyst Towards Carbamazepine Removal under UV Irradiation
by Chukwuka Bethel Anucha, Ilknur Altin, Emin Bacaksız, Tayfur Kucukomeroglu, Masho Hilawie Belay and Vassilis N. Stathopoulos
Separations 2021, 8(3), 25; https://doi.org/10.3390/separations8030025 - 26 Feb 2021
Cited by 27 | Viewed by 4117
Abstract
Abatement of contaminants of emerging concerns (CECs) in water sources has been widely studied employing TiO2 based heterogeneous photocatalysis. However, low quantum energy yield among other limitations of titania has led to its modification with other semiconductor materials for improved photocatalytic activity. [...] Read more.
Abatement of contaminants of emerging concerns (CECs) in water sources has been widely studied employing TiO2 based heterogeneous photocatalysis. However, low quantum energy yield among other limitations of titania has led to its modification with other semiconductor materials for improved photocatalytic activity. In this work, a 0.05 wt.% CuWO4 over TiO2 was prepared as a powder composite. Each component part synthesized via the sol-gel method for TiO2, and CuWO4 by co-precipitation assisted hydrothermal method from precursor salts, underwent gentle mechanical agitation. Homogenization of the nanopowder precursors was performed by zirconia ball milling for 2 h. The final material was obtained after annealing at 500 °C for 3.5 h. Structural and morphological characterization of the synthesized material has been achieved employing X-ray diffraction (XRD), Fourier transform infra-red (FTIR) spectroscopy, Brunauer–Emmett–Teller (BET) N2 adsorption–desorption analysis, Scanning electron microscopy-coupled Energy dispersive X-ray spectroscopy (SEM-EDS), Transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and UV-Vis diffuse reflectance spectroscopy (UV-vis DRS) for optical characterization. The 0.05 wt.% CuWO4-TiO2 catalyst was investigated for its photocatalytic activity over carbamazepine (CBZ), achieving a degradation of almost 100% after 2 h irradiation. A comparison with pure TiO2 prepared under those same conditions was made. The effect of pH, chemical scavengers, H2O2 as well as contaminant ion effects (anions, cations), and humic acid (HA) was investigated, and their related influences on the photocatalyst efficiency towards CBZ degradation highlighted accordingly. Full article
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21 pages, 3726 KiB  
Article
Immobilized TiO2/ZnO Sensitized Copper (II) Phthalocyanine Heterostructure for the Degradation of Ibuprofen under UV Irradiation
by Chukwuka BethelAnucha, IIknur Altin, Emin Bacaksiz, Ismail Degirmencioglu, Tayfur Kucukomeroglu, Salih Yılmaz and Vassilis N. Stathopoulos
Separations 2021, 8(3), 24; https://doi.org/10.3390/separations8030024 - 26 Feb 2021
Cited by 17 | Viewed by 3601
Abstract
Photocatalytic coatings of TiO2/ZnO/CuPc were developed on stainless steel substrates by subsequent sol gel dip coating for TiO2, spray pyrolysis for ZnO, and spin coating for copper (ii) phthalocyanine (CuPc) deposition. The latter compound was successfully prepared using a [...] Read more.
Photocatalytic coatings of TiO2/ZnO/CuPc were developed on stainless steel substrates by subsequent sol gel dip coating for TiO2, spray pyrolysis for ZnO, and spin coating for copper (ii) phthalocyanine (CuPc) deposition. The latter compound was successfully prepared using a Schiff-based process. The materials and coatings developed were characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy with attached energy dispersive spectroscopy (SEM-EDS), UV-Vis spectroscopy, room temperature photoluminescence (RTPL) spectroscopy, H1-nuclear magnetic resonance (1H-NMR) spectroscopy, C13-nuclear magnetic resonance (13C-NMR) spectroscopy, and matrix-assisted laser desorption/ionization-time of flight (MALDI-TOF) mass spectrometry (MS). The as-deposited TiO2/ZnO/CuPc on stainless steel retained in pristine state the structural and morphological/spectroscopic characteristics of its respective components. Estimated energy band gap values were 3.22 eV, 3.19 eV, 3.19 eV for TiO2, ZnO, TiO2/ZnO respectively and 1.60 eV, 2.44 eV, and 2.92 eV for CuPc. The photocatalytic efficiency of the fabricated TiO2/ZnO/CuPc coatings was tested toward ibuprofen (IBF). After 4 h irradiation under 365 nm UV, an increased degradation of about 80% was achieved over an initial 5 mg/L ibuprofen (IBF). This was much higher compared to about 42% and 18% IBF degradation by TiO2/ZnO and TiO2 thin film, respectively. In all cases, the stability of the best-performing photocatalyst was investigated showing a small decline to 77% of IBF degradation after the 5th cycle run. The effect of pH, reactive oxygen species (ROS) probe, shed light on a possible catalytic mechanism that was suggested. Full article
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20 pages, 5990 KiB  
Article
Synthesis and Characterization of B/NaF and Silicon Phthalocyanine-Modified TiO2 and an Evaluation of Their Photocatalytic Removal of Carbamazepine
by Chukwuka B. Anucha, IIknur Altin, Debora Fabbri, Ismail Degirmencioglu, Paola Calza, Giuliana Magnacca, Vassilis N. Stathopoulos and Emin Bacaksiz
Separations 2020, 7(4), 71; https://doi.org/10.3390/separations7040071 - 10 Dec 2020
Cited by 11 | Viewed by 2274
Abstract
This study investigated the synthesis of two different types of photocatalysts, namely, boron/sodium fluoride co-doped titanium dioxide (B/NaF-TiO2), and its analogue, a dye-sensitized form of silicon-based axial methoxy substituted phthalocyanine (B/NaF-TiO2SiPc). Structural and morphological characterizations were performed via X-ray [...] Read more.
This study investigated the synthesis of two different types of photocatalysts, namely, boron/sodium fluoride co-doped titanium dioxide (B/NaF-TiO2), and its analogue, a dye-sensitized form of silicon-based axial methoxy substituted phthalocyanine (B/NaF-TiO2SiPc). Structural and morphological characterizations were performed via X-ray diffraction (XRD); Fourier transform infra-red (FTIR); N2 adsorption–desorption at 77 K by Brunauer–Emmett–Teller (BET) and Barrett, Joyner, and Halenda (BJH) methods; transmission electron microscopy (TEM); X-ray photoelectron spectroscopy (XPS); and UV–visible absorption spectroscopy. The estimated crystallite size of pure TiO2 and pure B/NaF-TiO2 was 24 nm, and that of B/NaF-TiO2SiPc was 29 nm, whereas particle sizes determined by TEM were 25, 28, and 31 nm for pure TiO2, B/NaF-TiO2 and B/NaF-TiO2SiPc respectively. No significant differences between B/NaF-TiO2 and B/NaF-TiO2SiPc were observed for surface area by (BET) analysis (13 m2/g) or total pore volume by the BJH application model (0.05 cm3/g). Energy band gap values obtained for B/NaF-TiO2 and B/NaF-TiO2SiPc were 3.10 and 2.90 eV respectively, lower than pure TiO2 (3.17 eV). The photocatalytic activity of the synthesized materials was tested using carbamazepine (CBZ) as the model substrate. Carbamazepine removal after 4 h of irradiation was almost 100% for B/NaF-TiO2 and 70% for B/NaF-TiO2SiPc; however, the substrate mineralization proceeded slower, suggesting the presence of organic intermediates after the complete disappearance of the pollutant. Full article
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19 pages, 1682 KiB  
Article
Exploring the Efficiency of UHPLC-Orbitrap MS for the Determination of 20 Pharmaceuticals and Acesulfame K in Hospital and Urban Wastewaters with the Aid of FPSE
by Maria Kalaboka, Christoforos Chrimatopoulos, Cristina Jiménez-Holgado, Vasiliki Boti, Vasilios Sakkas and Triantafyllos Albanis
Separations 2020, 7(3), 46; https://doi.org/10.3390/separations7030046 - 04 Sep 2020
Cited by 8 | Viewed by 3381
Abstract
Aside from the classical residues of persistent organic pollutants (POPs), the occurrence of emerging contaminants (ECs) in the environment has become a subject of increasing concern due to their harmful impact on the aquatic environment. Wastewater treatment plant (WWTP) effluents are major sources [...] Read more.
Aside from the classical residues of persistent organic pollutants (POPs), the occurrence of emerging contaminants (ECs) in the environment has become a subject of increasing concern due to their harmful impact on the aquatic environment. Wastewater treatment plant (WWTP) effluents are major sources of environmental pollution. Therefore, data concerning their existence is required. In this study, twenty compounds representative of different drug groups considered ECs and belonging to antibiotics, antipsychotics, anti-inflammatory drugs plus acesulfame K were selected to be accurately detected and quantified with UHPLC–LTQ-Orbitrap MS in hospital and urban WWTP effluents. Chromatographic parameters (column efficiency, mobile phase, etc.), as well as mass spectrometry conditions concerning ionization mode and Orbitrap analysis (ESI options, mass resolving power, AGC target, tube lens, injection time), were evaluated. Moreover, a novel fabric phase sorptive extraction (FPSE) method based on fiber glass coated with PEG300 was employed as sample preparation process. Experimental parameters affecting extraction and desorption steps such as sample pH, extraction time, ionic strength, elution time and solvent have been optimized. The optimized methodology was validated providing excellent linearity (R2 > 0.99), and low detection and quantification limits up to 3.1 and 9.3 ng/L, for carbamazepine, respectively. Relative recoveries ranged from 81.1% to 114.0%, while a medium matrix effect for most of the target compounds occurred. Applying the above analytical method in effluents of WWTPs from NW Greece, nine compounds were quantified with concentrations that varied from 55.4 to 728.4 ng/L. Full article
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14 pages, 1892 KiB  
Article
Investigating the Utility of Fabric Phase Sorptive Extraction and HPLC-UV-Vis/DAD to Determine Antidepressant Drugs in Environmental Aqueous Samples
by Cristina Jiménez-Holgado, Christoforos Chrimatopoulos, Vassilis Stathopoulos and Vasilios Sakkas
Separations 2020, 7(3), 39; https://doi.org/10.3390/separations7030039 - 08 Jul 2020
Cited by 15 | Viewed by 4342
Abstract
Depression is considered to be one of the most prevalent mental disorders in humans. Antidepressant drugs are released in large concentrations and cause adverse effects on the environment and/or human health. Fabric Phase Sorptive Extraction (FPSE), a contemporary solid sorbent-handling technique, is a [...] Read more.
Depression is considered to be one of the most prevalent mental disorders in humans. Antidepressant drugs are released in large concentrations and cause adverse effects on the environment and/or human health. Fabric Phase Sorptive Extraction (FPSE), a contemporary solid sorbent-handling technique, is a quick, sensitive, and simple analytical process. This paper describes a micro-extraction FPSE procedure coupled with High-Performance Liquid-Chromatography–Photodiode Array Detection (FPSE-HPLC–DAD) for the simultaneous extraction and analysis of five antidepressants, namely citalopram, clozapine, mirtazapine, bupropion and sertraline. Three fabric media (Whatman Cellulose filter, Whatman Microfiber Glass filter and Polylactic acid disks) and two different sol–gel sorbents (polyethylene glycol (PEG 300), alongside poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (PEG-PPG-PEG 5.800)) were tested. The best FPSE device was observed to be the microfiber glass filter coated with PEG 300 sol–gel sorbent. In addition, the parameters that affect the efficiency of the process (FPSE media and sorbents, sample pH, extraction time, elution time, etc.) were optimized. The proposed methodology displays a linear range with absolute recovery values higher than 60%, RSD% of less than 13% and LOQs in the range between 1.9–10.7 μg·L−1. Finally, the method was applied in hospital and urban effluents and lake water samples, but none of the analytes were detected. Full article
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18 pages, 4965 KiB  
Article
Perfluoroalkyl Substance Assessment in Turin Metropolitan Area and Correlation with Potential Sources of Pollution According to the Water Safety Plan Risk Management Approach
by Rita Binetti, Paola Calza, Giovanni Costantino, Stefania Morgillo and Dimitra Papagiannaki
Separations 2019, 6(1), 17; https://doi.org/10.3390/separations6010017 - 19 Mar 2019
Cited by 7 | Viewed by 4669
Abstract
Per and polyfluoroalkyl substances (PFASs) are a huge class of Contaminants of Emerging Concern, well-known to be persistent, bioaccumulative and toxic. They have been detected in different environmental matrices, in wildlife and even in humans, with drinking water being considered as the main [...] Read more.
Per and polyfluoroalkyl substances (PFASs) are a huge class of Contaminants of Emerging Concern, well-known to be persistent, bioaccumulative and toxic. They have been detected in different environmental matrices, in wildlife and even in humans, with drinking water being considered as the main exposure route. Therefore, the present study focused on the estimation of PFAS in the Metropolitan Area of Turin, where SMAT (Società Metropolitana Acque Torino S.p.A.) is in charge of the management of the water cycle and the development of a tool for supporting “smart” water quality monitoring programs to address emerging pollutants’ assessments using multivariate spatial and statistical analysis tools. A new “green” analytical method was developed and validated in order to determine 16 different PFAS in drinking water with a direct injection to the Ultra High Performance Liquid Chromatography tandem Mass Spectrometry (UHPLC-MS/MS) system and without any pretreatment step. The validation of this analytical method resulted in really low Quantification Limits (5 ng L−1), in satisfying recoveries (70%–102%) and in a good linearity (R2 = 0.99) for every compound. Among the results, only 4 compounds and only 6% of the samples showed a pollution level higher than the limits of and Quantification (LOQ). Finally, the correlation study between the assessment findings and the industrial sites which serve as potential sources of pollution in the monitored area was carried out. Full article
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