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25 pages, 2119 KiB

Open AccessArticle

International Comparison, Risk Assessment, and Prioritisation of 26 Endocrine Disrupting Compounds in Three European River Catchments in the UK, Ireland, and Spain

by Helena Rapp-Wright, Sara Rodríguez-Mozaz, Diana Álvarez-Muñoz, Damià Barceló, Fiona Regan, Leon P. Barron and Blánaid White

Molecules 2023, 28(16), 5994; https://doi.org/10.3390/molecules28165994 - 10 Aug 2023

Viewed by 1306

Abstract

Endocrine-disrupting compounds (EDCs) constitute a wide variety of chemistries with diverse properties that may/can pose risks to both humans and the environment. Herein, a total of 26 compounds, including steroids, flame retardants, and plasticizers, were monitored in three major and heavily urbanized river [...] Read more.

Endocrine-disrupting compounds (EDCs) constitute a wide variety of chemistries with diverse properties that may/can pose risks to both humans and the environment. Herein, a total of 26 compounds, including steroids, flame retardants, and plasticizers, were monitored in three major and heavily urbanized river catchments: the R. Liffey (Ireland), the R. Thames (UK), and the R. Ter (Spain), by using a single solid-phase extraction liquid chromatography-mass spectrometry (SPE-LC-MS/MS) method. Occurrence and frequency rates were investigated across all locations over a 10-week period, with the highest concentration obtained for the flame retardant tris(2-chloroethyl) phosphate (TCEP) at 4767 ng∙L⁻¹ in the R. Thames in Central London. Geographical variations were observed between sites and were partially explained using principal component analysis (PCA) and hierarchical cluster analysis (HCA). In particular, discrimination between the R. Ter and the R. Thames was observed based on the presence and concentration of flame retardants, benzotriazole, and steroids. Environmental risk assessment (ERA) across sites showed that caffeine, a chemical marker, and bisphenol A (BPA), a plasticizer, were classified as high-risk for the R. Liffey and R. Thames, based on relative risk quotients (rRQs), and that caffeine was classified as high-risk for the R. Ter, based on RQs. The total risks at each location, namely ΣRQ_river, and ΣrRQ_river, were: 361, 455, and 723 for the rivers Liffey, Thames, and Ter, respectively. Caffeine, as expected, was ubiquitous in all 3 urban areas, though with the highest RQ observed in the R. Ter. High contributions of BPA were also observed across the three matrices. Therefore, these two compounds should be prioritized independently of location. This study represents a comprehensive EDC monitoring comparison between different European cities based on a single analytical method, which allowed for a geographically independent ERA prioritization to be performed. Full article

(This article belongs to the Special Issue Recent Progress in the Analysis and Detection of Pollutants of Emerging Concern in Environmental and Food Samples)

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9 pages, 2502 KiB

Open AccessArticle

Investigation of the Effects of Dioctyl Sulfosuccinate on the Photodegradation of Benzo[a]Pyrene in Aqueous Solutions under Various Wavelength Regimes

by Anthony M. Santana, Sadia Arif, Kristina Evteyeva, Fernando Barbosa, Jr. and Andres D. Campiglia

Molecules 2023, 28(15), 5797; https://doi.org/10.3390/molecules28155797 - 01 Aug 2023

Viewed by 705

Abstract

Due to the relatively high concentrations of polycyclic aromatic hydrocarbons (PAHs) in oil samples, oil spills in aquatic ecosystems release significant amounts of PAHs. Although remediation efforts often take place during or immediately after an oil spill incident, a portion of the released [...] Read more.

Due to the relatively high concentrations of polycyclic aromatic hydrocarbons (PAHs) in oil samples, oil spills in aquatic ecosystems release significant amounts of PAHs. Although remediation efforts often take place during or immediately after an oil spill incident, a portion of the released PAHs remains in the body of water. A natural phenomenon resulting from the direct exposure of PAHs to sunlight is photodegradation. This article investigates the effect of dioctyl sulfosuccinate (DOSS) on the photodegradation of benzo[a]pyrene (BaP), the most toxic PAH in the priority pollutants list of the US Environmental Protection Agency (EPA). DOSS is a surfactant typically used in the remediation of oil spills. Three lamps with maximum emission wavelengths at 350 nm, 419 nm, and 575 nm were individually and simultaneously used to irradiate aqueous solutions of BaP in the absence and the presence of DOSS. When irradiated with the 419 nm lamp or the 575 lamp, BaP showed no photodegradation. Upon irradiation with the 350 nm lamp and with the simultaneous use of the three lamps, the photodegradation of BaP followed first-order kinetics. Independent of the irradiation wavelength, the presence of DOSS increased the half-life of BaP in the aqueous solution. In the case of the 350 nm lamp, the rate constant of photodegradation in the absence and the presence of DOSS varied from (3.79 ± 0.97) × 10⁻³ min⁻¹ to (1.10 ± 0.13) × 10⁻³ min⁻¹, respectively. Under simultaneous irradiation with the lamps, the rate constant of photodegradation varied from (1.12 ± 0.35) × 10⁻³ min (no DOSS) to (3.30 ± 0.87) × 10⁻⁴ (with DOSS). Since the largest rate constants of photodegradation were observed in the absence of DOSS, the longer half-lives of BaP in the presence of surfactant were attributed to the incorporation of PAH molecules into the DOSS micelles. Full article

(This article belongs to the Special Issue Recent Progress in the Analysis and Detection of Pollutants of Emerging Concern in Environmental and Food Samples)

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14 pages, 2178 KiB

Open AccessArticle

Analysis of Silver Nanoparticles in Ground Beef by Single Particle Inductively Coupled Plasma Mass Spectrometry (SP-ICP-MS)

by Alexandre Chalifoux, Madjid Hadioui, Nesrine Amiri and Kevin J. Wilkinson

Molecules 2023, 28(11), 4442; https://doi.org/10.3390/molecules28114442 - 30 May 2023

Cited by 2 | Viewed by 1212

Abstract

The regulation and characterization of nanomaterials in foods are of great interest due to the potential risks associated with their exposure and the increasing number of applications where they are used within the food industry. One factor limiting the scientifically rigorous regulation of [...] Read more.

The regulation and characterization of nanomaterials in foods are of great interest due to the potential risks associated with their exposure and the increasing number of applications where they are used within the food industry. One factor limiting the scientifically rigorous regulation of nanoparticles in foods is the lack of standardized procedures for the extraction of nanoparticles (NPs) from complex matrices without alteration of their physico-chemical properties. To this end, we tested and optimized two sample preparation approaches (enzymatic- and alkaline-based hydrolyses) in order to extract 40 nm of Ag NP, following their equilibration with a fatty ground beef matrix. NPs were characterized using single particle inductively coupled plasma mass spectrometry (SP-ICP-MS). Fast sample processing times (<20 min) were achieved using ultrasonication to accelerate the matrix degradation. NP losses during the sample preparation were minimized by optimizing the choice of enzymes/chemicals, the use of surfactants, and the product concentration and sonication. The alkaline approach using TMAH (tetramethylammonium hydroxide) was found to have the highest recoveries (over 90%); however, processed samples were found to be less stable than the samples processed using an enzymatic digestion based upon pork pancreatin and lipase (≈60 % recovery). Low method detection limits (MDLs) of 4.8 × 10⁶ particles g⁻¹ with a size detection limit (SDL) of 10.9 nm were achieved for the enzymatic extraction whereas an MDL of 5.7 × 10⁷ particles g⁻¹ and an SDL of 10.5 nm were obtained for the alkaline hydrolysis. Full article

(This article belongs to the Special Issue Recent Progress in the Analysis and Detection of Pollutants of Emerging Concern in Environmental and Food Samples)

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17 pages, 1582 KiB

Open AccessArticle

Validation and Simultaneous Monitoring of 311 Pesticide Residues in Loamy Sand Agricultural Soils by LC-MS/MS and GC-MS/MS, Combined with QuEChERS-Based Extraction

by Petros Tsiantas, Eleftheria Bempelou, Maria Doula and Helen Karasali

Molecules 2023, 28(11), 4268; https://doi.org/10.3390/molecules28114268 - 23 May 2023

Cited by 4 | Viewed by 2078

Abstract

Soil can be contaminated by pesticide residues through agricultural practices, by direct application or through spray-drift in cultivations. The dissipation of those chemicals in the soil may pose risks to the environment and human health. A simple and sensitive multi-residue analytical method was [...] Read more.

Soil can be contaminated by pesticide residues through agricultural practices, by direct application or through spray-drift in cultivations. The dissipation of those chemicals in the soil may pose risks to the environment and human health. A simple and sensitive multi-residue analytical method was optimized and validated for the simultaneous determination of 311 active substances of pesticides in agricultural soils. The method involves sample preparation with QuEChERS-based extraction, and determination of the analytes with a combination of GC-MS/MS and LC-MS/MS techniques. Calibration plots were linear for both detectors over the range of five concentration levels, using matrix-matched calibration standards. The obtained recoveries from fortified-soil samples ranged from 70 to 119% and from 72.6 to 119% for GC-MS/MS and LC-MS/MS, respectively, while precision values were <20% in all cases. As regards the matrix effect (ME), signal suppression was observed in the liquid chromatography (LC)-amenable compounds, which was further estimated to be negligible. The gas chromatography (GC)-amenable compounds showed enhancement in the chromatographic response estimated as medium or strong ME. The calibrated limit of quantification (LOQ) value was 0.01 μg g⁻¹ dry weight for most of the analytes, while the corresponding calculated limit of determination (LOD) value was 0.003 μg g⁻¹ d.w. The proposed method was subsequently applied to agricultural soils from Greece, and positive determinations were obtained, among which were non-authorized compounds. The results indicate that the developed multi-residue method is fit for the purpose of analyzing low levels of pesticides in soil, according to EU requirements. Full article

(This article belongs to the Special Issue Recent Progress in the Analysis and Detection of Pollutants of Emerging Concern in Environmental and Food Samples)

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19 pages, 16038 KiB

Open AccessArticle

Intelligent Workflow and Software for Non-Target Analysis of Complex Samples Using a Mixture of Toxic Transformation Products of Unsymmetrical Dimethylhydrazine as an Example

by Anastasia Yu. Sholokhova, Dmitriy D. Matyushin, Oksana I. Grinevich, Svetlana A. Borovikova and Aleksey K. Buryak

Molecules 2023, 28(8), 3409; https://doi.org/10.3390/molecules28083409 - 12 Apr 2023

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Abstract

Unsymmetrical dimethylhydrazine (UDMH) is a widely used rocket propellant. Entering the environment or being stored in uncontrolled conditions, UDMH easily forms an enormous variety (at least many dozens) of transformation products. Environmental pollution by UDMH and its transformation products is a major problem [...] Read more.

Unsymmetrical dimethylhydrazine (UDMH) is a widely used rocket propellant. Entering the environment or being stored in uncontrolled conditions, UDMH easily forms an enormous variety (at least many dozens) of transformation products. Environmental pollution by UDMH and its transformation products is a major problem in many countries and across the Arctic region. Unfortunately, previous works often use only electron ionization mass spectrometry with a library search, or they consider only the molecular formula to propose the structures of new products. This is quite an unreliable approach. It was demonstrated that a newly proposed artificial intelligence-based workflow allows for the proposal of structures of UDMH transformation products with a greater degree of certainty. The presented free and open-source software with a convenient graphical user interface facilitates the non-target analysis of industrial samples. It has bundled machine learning models for the prediction of retention indices and mass spectra. A critical analysis of whether a combination of several methods of chromatography and mass spectrometry allows us to elucidate the structure of an unknown UDMH transformation product was provided. It was demonstrated that the use of gas chromatographic retention indices for two stationary phases (polar and non-polar) allows for the rejection of false candidates in many cases when only one retention index is not enough. The structures of five previously unknown UDMH transformation products were proposed, and four previously proposed structures were refined. Full article

(This article belongs to the Special Issue Recent Progress in the Analysis and Detection of Pollutants of Emerging Concern in Environmental and Food Samples)

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15 pages, 1718 KiB

Open AccessArticle

Quantitative Structure–Retention Relationship Analysis of Polycyclic Aromatic Compounds in Ultra-High Performance Chromatography

by Fabrizio Ruggieri, Alessandra Biancolillo, Angelo Antonio D’Archivio, Francesca Di Donato, Martina Foschi, Maria Anna Maggi and Claudia Quattrociocchi

Molecules 2023, 28(7), 3218; https://doi.org/10.3390/molecules28073218 - 04 Apr 2023

Cited by 1 | Viewed by 1345

Abstract

A comparative quantitative structure–retention relationship (QSRR) study was carried out to predict the retention time of polycyclic aromatic hydrocarbons (PAHs) using molecular descriptors. The molecular descriptors were generated by the software Dragon and employed to build QSRR models. The effect of chromatographic parameters, [...] Read more.

A comparative quantitative structure–retention relationship (QSRR) study was carried out to predict the retention time of polycyclic aromatic hydrocarbons (PAHs) using molecular descriptors. The molecular descriptors were generated by the software Dragon and employed to build QSRR models. The effect of chromatographic parameters, such as flow rate, temperature, and gradient time, was also considered. An artificial neural network (ANN) and Partial Least Squares Regression (PLS-R) were used to investigate the correlation between the retention time, taken as the response, and the predictors. Six descriptors were selected by the genetic algorithm for the development of the ANN model: the molecular weight (MW); ring descriptor types nCIR and nR10; radial distribution functions RDF090u and RDF030m; and the 3D-MoRSE descriptor Mor07u. The most significant descriptors in the PLS-R model were MW, RDF110u, Mor20u, Mor26u, and Mor30u; edge adjacency indice SM09_AEA (dm); 3D matrix-based descriptor SpPosA_RG; and the GETAWAY descriptor H7u. The built models were used to predict the retention of three analytes not included in the calibration set. Taking into account the statistical parameter RMSE for the prediction set (0.433 and 0.077 for the PLS-R and ANN models, respectively), the study confirmed that QSRR models, associated with chromatographic parameters, are better described by nonlinear methods. Full article

(This article belongs to the Special Issue Recent Progress in the Analysis and Detection of Pollutants of Emerging Concern in Environmental and Food Samples)

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15 pages, 1464 KiB

Open AccessArticle

Suspect Screening of Chemicals in Hospital Wastewaters Using Effect-Directed Analysis Approach as Prioritization Strategy

by Naroa Lopez-Herguedas, Leire Mijangos, Iker Alvarez-Mora, Belén González-Gaya, Teresa Uribe-Echeverria, Nestor Etxebarria, Olatz Zuloaga, Maitane Olivares and Ailette Prieto

Molecules 2023, 28(3), 1212; https://doi.org/10.3390/molecules28031212 - 26 Jan 2023

Viewed by 1919

Abstract

The increasing number of contaminants in the environment has pushed water monitoring programs to find out the most hazardous known and unknown chemicals in the environment. Sample treatment-simplification methods and non-target screening approaches can help researchers to not overlook potential chemicals present in [...] Read more.

The increasing number of contaminants in the environment has pushed water monitoring programs to find out the most hazardous known and unknown chemicals in the environment. Sample treatment-simplification methods and non-target screening approaches can help researchers to not overlook potential chemicals present in complex aqueous samples. In this work, an effect-directed analysis (EDA) protocol using the sea urchin embryo test (SET) as a toxicological in vivo bioassay was used as simplified strategy to identify potential unknown chemicals present in a very complex aqueous matrix such as hospital effluent. The SET bioassay was used for the first time here to evaluate potential toxic fractions in hospital effluent, which were obtained after a two-step fractionation using C₁₈ and aminopropyl chromatographic semi-preparative columns. The unknown compounds present in the toxic fractions were identified by means of liquid chromatography coupled to a Q Exactive Orbitrap high-resolution mass spectrometer (LC-HRMS) and using a suspect analysis approach. The results were complemented by gas chromatography-mass spectrometry analysis (GC-MS) in order to identify the widest range of chemical compounds present in the sample and the toxic fractions. Using EDA as sample treatment simplification method, the number of unknown chemicals (>446 features) detected in the raw sample was narrowed down to 94 potential toxic candidates identified in the significantly toxic fractions. Among them, the presence of 25 compounds was confirmed with available chemical standards including 14 pharmaceuticals, a personal care product, six pesticides and four industrial products. The observations found in this work emphasize the difficulties in identifying potential toxicity drivers in complex water samples, as in the case of hospital wastewater. Full article

(This article belongs to the Special Issue Recent Progress in the Analysis and Detection of Pollutants of Emerging Concern in Environmental and Food Samples)

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8 pages, 1107 KiB

Open AccessCommunication

Analysis of Engineered Nanoparticles in Seawater Using ICP-MS-Based Technology: From Negative to Positive Samples

by Olga V. Kuznetsova, Bernhard K. Keppler and Andrei R. Timerbaev

Molecules 2023, 28(3), 994; https://doi.org/10.3390/molecules28030994 - 19 Jan 2023

Cited by 3 | Viewed by 1683

Abstract

A growing global emission of engineered nanoparticles (ENPs) into the aquatic environment has become an emerging safety concern that requires methods capable of identifying the occurrence and possibly determining the amounts of ENPs. In this study, we employed sector-field inductively coupled mass spectrometry [...] Read more.

A growing global emission of engineered nanoparticles (ENPs) into the aquatic environment has become an emerging safety concern that requires methods capable of identifying the occurrence and possibly determining the amounts of ENPs. In this study, we employed sector-field inductively coupled mass spectrometry to assess the presence of ENPs in coastal seawater samples collected from the Black Sea in regions suffering different anthropogenic impacts. Ultrafiltration through commercial 3 kDa membrane filters was shown to be feasible to separate the ENPs from the bulk seawater, and the subsequent ultrasound-mediated acidic dissolution makes the metals constituting the ENPs amenable to analysis. This procedure allowed the ENPs bearing Cu, Zn, V, Mo, and Sn to be for the first time quantitated in seashore surface water, their concentration ranging from 0.1 to 1.0 μg L⁻¹ (as metal) and related to the presence of industry and/or urban stress. While these levels are decreased by natural dilution and possible sedimentation, the monitored ENPs remain measurable at a distance of 2 km from the coast. This can be attributed not only to local emission sources but also to some natural backgrounds. Full article

(This article belongs to the Special Issue Recent Progress in the Analysis and Detection of Pollutants of Emerging Concern in Environmental and Food Samples)

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13 pages, 1443 KiB

Open AccessArticle

Thermodynamic and Kinetic Investigation of the Adsorption and Desorption of Trimethoprim and Its Main Metabolites in Mediterranean Crop Soils

by Carmen Mejías, Juan Luis Santos, Julia Martín, Irene Aparicio and Esteban Alonso

Molecules 2023, 28(1), 437; https://doi.org/10.3390/molecules28010437 - 03 Jan 2023

Cited by 1 | Viewed by 1339

Abstract

The adsorption–desorption processes of organic pollutants into the soil are one of the main factors influencing their potential environmental risks and distribution in the environment. In the present work, the adsorption–desorption behavior of an antibiotic, trimethoprim (TMP), and two of its main metabolites, [...] Read more.

The adsorption–desorption processes of organic pollutants into the soil are one of the main factors influencing their potential environmental risks and distribution in the environment. In the present work, the adsorption–desorption behavior of an antibiotic, trimethoprim (TMP), and two of its main metabolites, 3-desmethyltrimethoprim (DM-TMP) and 4-hydroxytrimethoprim (OH-TMP), were assessed in three Mediterranean agricultural soils with different physicochemical characteristics. Results showed that the adsorption kinetic is performed in two steps: external sorption and intraparticle diffusion. The adsorptions of the studied compounds in soils were similar and fitted to the three models but were better fitted to a linear model. In the case of DM-TMP and OH-TMP, their adsorptions were positively correlated with the soil organic matter. In addition, desorption was higher in less organic matter soil (from 1.3 to 30.9%). Furthermore, the desorptions measured for the TMP metabolites were lower than those measured in the case of TMP (from 2.0 and 4.0% for OH-TMP and DM-TMP, respectively, to 9.0% for TMP). Full article

(This article belongs to the Special Issue Recent Progress in the Analysis and Detection of Pollutants of Emerging Concern in Environmental and Food Samples)

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11 pages, 964 KiB

Open AccessArticle

Comparison of Different Techniques for the Determination of Platinized Cytostatic Drugs in Urine Samples

by Marina Arenas, Julia Martín, Juan Luis Santos, Irene Aparicio, Omar Fernández-Sanfrancisco and Esteban Alonso

Molecules 2022, 27(23), 8139; https://doi.org/10.3390/molecules27238139 - 23 Nov 2022

Cited by 1 | Viewed by 1391

Abstract

Platinum-based cytostatic drugs are one of the most widely used cancer treatments. They are excreted via the urinary tract and can reach the environment through wastewater, posing a risk to human health due to their side effects. Four identification and quantification techniques, including [...] Read more.

Platinum-based cytostatic drugs are one of the most widely used cancer treatments. They are excreted via the urinary tract and can reach the environment through wastewater, posing a risk to human health due to their side effects. Four identification and quantification techniques, including liquid chromatography (LC) separation coupled to (i) a diode array ultraviolet (UV(DAD)) (ii), mass spectrometer in single ion monitoring mode (LC-MS) and (iii) multiple reaction monitoring mode (LC-MS/MS) and (iv) derivatization with diethyldithiocarbamate prior to LC-MS/MS analysis, have been optimized and compared for the multiresidue determination of main platinized cytostatic drugs (cisplatin, carboplatin, and oxaliplatin) in urine samples. Parameters that affect the efficiency of the chromatographic separation and analytical determination of different methods (column, mobile phase, wavelength, precursor ions, fragmentor, and product ions) were optimized. Analytical features, such as matrix effect, sensitivity, precision, selectivity, and linearity, were calculated. In terms of selectivity, the derivatization technique was discarded since it was only applicable to the platinated sum. A high dilution of the sample with LC-UV(DAD) was needed to reduce the matrix effect. Overall, the LC-MS/MS method presented the best analytical features (% RSD ≤ 12.8%, R² ≥ 0.991, or method-detection limits between 0.01–1 µg mL⁻¹). The selected method was applied to the quantification of platinized cytostatic drugs in hospital urine samples from oncologic patients. Full article

(This article belongs to the Special Issue Recent Progress in the Analysis and Detection of Pollutants of Emerging Concern in Environmental and Food Samples)

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11 pages, 2130 KiB

Open AccessArticle

The Ultratrace Determination of Fluoroquinolones in River Water Samples by an Online Solid-Phase Extraction Method Using a Molecularly Imprinted Polymer as a Selective Sorbent

by A. N. Baeza, Idoia Urriza-Arsuaga, F. Navarro-Villoslada and Javier L. Urraca

Molecules 2022, 27(23), 8120; https://doi.org/10.3390/molecules27238120 - 22 Nov 2022

Cited by 8 | Viewed by 1559

Abstract

Fluoroquinolones (FQs) are broad-spectrum antibiotics widely used to treat animal and human infections. The use of FQs in these activities has increased the presence of antibiotics in wastewater and food, triggering antimicrobial resistance, which has severe consequences for human health. The detection of [...] Read more.

Fluoroquinolones (FQs) are broad-spectrum antibiotics widely used to treat animal and human infections. The use of FQs in these activities has increased the presence of antibiotics in wastewater and food, triggering antimicrobial resistance, which has severe consequences for human health. The detection of antibiotics residues in water and food samples has attracted much attention. Herein, we report the development of a highly sensitive online solid-phase extraction methodology based on a selective molecularly imprinted polymer (MIP) and fluorescent detection (HPLC-FLD) for the determination of FQs in water at low ng L⁻¹ level concentration. Under the optimal conditions, good linearity was obtained ranging from 0.7 to 666 ng L⁻¹ for 7 FQs, achieving limits of detection (LOD) in the low ng L⁻¹ level and excellent precision. Recoveries ranged between 54 and 118% (RSD < 17%) for all the FQs tested. The method was applied to determining FQs in river water. These results demonstrated that the developed method is highly sensitive and selective. Full article

(This article belongs to the Special Issue Recent Progress in the Analysis and Detection of Pollutants of Emerging Concern in Environmental and Food Samples)

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12 pages, 1167 KiB

Open AccessArticle

Green and Efficient Determination of Fluoroquinolone Residues in Edible Green Fruits and Leafy Vegetables by Ultrasound-Assisted Extraction Followed by HPLC-MS/MS

by Francesca Merlo, Dario Centenaro, Federica Maraschi, Antonella Profumo and Andrea Speltini

Molecules 2022, 27(19), 6595; https://doi.org/10.3390/molecules27196595 - 05 Oct 2022

Cited by 7 | Viewed by 1336

Abstract

In this work, a simple, quick and efficient analytical method for determination of human and veterinary fluoroquinolone antimicrobial residues in lettuce, cucumber and spinach is developed. The procedure entails a 6 min ultrasound-assisted extraction (UAE, 3 × 2 min) in an alkaline (2% [...] Read more.

In this work, a simple, quick and efficient analytical method for determination of human and veterinary fluoroquinolone antimicrobial residues in lettuce, cucumber and spinach is developed. The procedure entails a 6 min ultrasound-assisted extraction (UAE, 3 × 2 min) in an alkaline (2% v/v NH₃) aqueous solution containing Mg²⁺ ions (3 × 6 mL), with no need for organic solvents. The extract is submitted to cleanup on the HLB™ cartridge and the fluoroquinolones are separated and quantified by HPLC-MS/MS in a 10 min chromatographic run, using a small amount of acetonitrile in the mobile phase. The method, entirely developed in real matrices, is validated according to the updated analytical guidelines and provided suitable recoveries in the range of 67–116% and precision (RSD ≤ 20%, n = 3) at different concentrations (15, 70 and 150 ng g⁻¹), with method quantification limits of 2–10 ng g⁻¹. Fluoroquinolones were detected and quantified at concentrations from few to hundreds of nanograms per gram in vegetables from supermarkets, demonstrating the applicability of the method for monitoring residues of these pharmaceuticals. Full article

(This article belongs to the Special Issue Recent Progress in the Analysis and Detection of Pollutants of Emerging Concern in Environmental and Food Samples)

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12 pages, 1257 KiB

Open AccessArticle

Utilization of a Novel Immunofluorescence Instrument Prototype for the Determination of the Herbicide Glyphosate

by Eszter Takács, Borbála Gémes, Fanni Szendrei, Csaba Keszei, Attila Barócsi, Sándor Lenk, László Domján, Mária Mörtl and András Székács

Molecules 2022, 27(19), 6514; https://doi.org/10.3390/molecules27196514 - 02 Oct 2022

Cited by 2 | Viewed by 1300

Abstract

An enzyme-linked fluorescent immunoassay (ELFIA) method has been developed for the quantitative analytical determination of the herbicide active ingredient glyphosate in environmental matrices (surface water, soil, and plant tissues). Glyphosate, as a ubiquitous agricultural pollutant, is a xenobiotic substance with exposure in aquatic [...] Read more.

An enzyme-linked fluorescent immunoassay (ELFIA) method has been developed for the quantitative analytical determination of the herbicide active ingredient glyphosate in environmental matrices (surface water, soil, and plant tissues). Glyphosate, as a ubiquitous agricultural pollutant, is a xenobiotic substance with exposure in aquatic and terrestrial ecosystems due its extremely high worldwide application rate. The immunoassay developed in Project Aquafluosense is part of a fluorescence-based instrumentation setup for the in situ determination of several characteristic water quality parameters. The 96-well microplate-based competitive immunoassay method applies fluorescence signal detection in the concentration range of 0–100 ng/mL glyphosate. Application of the fluorescent signal provides a limit of detection of 0.09 ng/mL, which is 2.5-fold lower than that obtained with a visual absorbance signal. Beside the improved limit of detection, determination by fluorescence provided a wider and steeper dynamic range for glyphosate detection. No matrix effect appeared for the undiluted surface water samples, while plant tissues and soil samples required dilution rates of 1:10 and 1:100, respectively. No cross-reaction was determined with the main metabolite of glyphosate, N-aminomethylphosphonic acid, and related compounds. Full article

(This article belongs to the Special Issue Recent Progress in the Analysis and Detection of Pollutants of Emerging Concern in Environmental and Food Samples)

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20 pages, 4429 KiB

Open AccessArticle

Simultaneous Prediction, Determination, and Extraction of Four Polycyclic Aromatic Hydrocarbons in the Environment Using a UCON–NaH₂PO₄ Aqueous Two-Phase Extraction System Combined with High-Performance Liquid Chromatography-Ultraviolet Detection

by He Chang, Yang Lu and Yantao Sun

Molecules 2022, 27(19), 6465; https://doi.org/10.3390/molecules27196465 - 30 Sep 2022

Cited by 1 | Viewed by 1422

Abstract

In this paper, a new aqueous two-phase extraction system(ATPES) consisting of UCON (poly(ethylene glycol-ran-propylene glycol) monobutyl ether)–NaH₂PO₄ was established, and four trace polycyclic aromatic hydrocarbons (PAHs: fluorene, anthracene, pyrene and phenanthrene) in water and soil were analyzed by high-performance liquid [...] Read more.

In this paper, a new aqueous two-phase extraction system(ATPES) consisting of UCON (poly(ethylene glycol-ran-propylene glycol) monobutyl ether)–NaH₂PO₄ was established, and four trace polycyclic aromatic hydrocarbons (PAHs: fluorene, anthracene, pyrene and phenanthrene) in water and soil were analyzed by high-performance liquid chromatography (HPLC)–ultraviolet detection. In the multi-factor experiment, the central composite design (CCD) was used to determine the optimum technological conditions. The final optimal conditions were as follows: the concentration of UCON was 0.45 g·mL⁻¹, the concentration of NaH₂PO₄ was 3.5 mol·L⁻¹, and the temperature was 30 °C. The recovery of the four targets was 98.91–99.84% with a relative standard deviation of 0.3–2.1%. Then UCON recycling and cyclic tests were designed in the experiment, and the results showed that the recovery of PAHs gradually increased in the three extractions because of the remaining PAHs in the salt phase of last extraction. The recovery of PAHs in the UCON recycling test was less than that in the extraction test due to the wastage of UCON. In addition, a two-phase aqueous extraction model was established based on the random forest (RF) model. The results obtained were compared with the experimental data, and the root mean square error (RMSE) was 0.0371–0.0514 and the correlation coefficient R² was 96.20–98.53%, proving that the model is robust and reliable. Full article

(This article belongs to the Special Issue Recent Progress in the Analysis and Detection of Pollutants of Emerging Concern in Environmental and Food Samples)

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13 pages, 2571 KiB

Open AccessArticle

Determination of Local Anesthetic Drugs in Human Plasma Using Magnetic Solid-Phase Extraction Coupled with High-Performance Liquid Chromatography

by Shan-Yan Liang, Fang Shi, Yong-Gang Zhao and Hong-Wei Wang

Molecules 2022, 27(17), 5509; https://doi.org/10.3390/molecules27175509 - 27 Aug 2022

Cited by 4 | Viewed by 1294

Abstract

In this work, magnetic tetraethylenepentamine (TEPA)-modified carboxyl–carbon nanotubes were synthesized, characterized, and used as adsorbents to conduct magnetic solid-phase extraction (MSPE) for the preconcentration of seven local anesthetic drugs (procaine, lidocaine, mepivacaine, oxybuprocaine, bupivacaine, tetracaine, and cinchocaine) from human plasma. The separation and [...] Read more.

In this work, magnetic tetraethylenepentamine (TEPA)-modified carboxyl–carbon nanotubes were synthesized, characterized, and used as adsorbents to conduct magnetic solid-phase extraction (MSPE) for the preconcentration of seven local anesthetic drugs (procaine, lidocaine, mepivacaine, oxybuprocaine, bupivacaine, tetracaine, and cinchocaine) from human plasma. The separation and determination of analytes were performed on high-performance liquid chromatography with UV detection. Several factors affected the extraction efficiency, such as the amount of adsorbents used, extraction time, sample pH, and optimization of elution conditions. Under optimal conditions, satisfactory linear relationships were obtained in the range of 0.02–5.00 mg/L, with the limits of detection (LOD) ranging from 0.003 mg/L to 0.008 mg/L. The recoveries of analytes for spiked human plasma were in the range of 82.0–108%. Moreover, the precision with intra-day and inter-day RSD values were obtained in the range of 1.5–7.7% and 1.5–8.3%. The results indicated that this method could determine the concentration of seven local anesthetic drugs in human plasma with high precision and repeatability and provide support for the clinical monitoring of the concentration of local anesthetic drugs in human plasma. Full article

(This article belongs to the Special Issue Recent Progress in the Analysis and Detection of Pollutants of Emerging Concern in Environmental and Food Samples)

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11 pages, 1007 KiB

Open AccessArticle

Octocrylene: From Sunscreens to the Degradation Pathway during Chlorination Processes: Formation of Byproducts and Their Ecotoxicity Assessment

by Antonio Medici, Lorenzo Saviano, Antonietta Siciliano, Giovanni Libralato, Marco Guida, Lucio Previtera, Giovanni Di Fabio and Armando Zarrelli

Molecules 2022, 27(16), 5286; https://doi.org/10.3390/molecules27165286 - 19 Aug 2022

Cited by 1 | Viewed by 2853

Abstract

Octocrylene is an organic sunscreen whose main action is to absorb UVB radiation and short UVA wavelengths; it is used in various cosmetic products in order to provide an adequate sun-protection factor or to protect the cosmetic formulations themselves from UV radiation. This [...] Read more.

Octocrylene is an organic sunscreen whose main action is to absorb UVB radiation and short UVA wavelengths; it is used in various cosmetic products in order to provide an adequate sun-protection factor or to protect the cosmetic formulations themselves from UV radiation. This filter is believed to be a possible endocrine disruptor and is also questioned due to its allergic and/or photoallergic potential. However, it continues to be widely used, and it has been found in various environments, not least those of swimming pools, where it is evidently released by consumers, to the point that it is now considered an emerging micropollutant. The present investigation presents the possible chemical fate of octocrylene in the typical chlorination conditions of wastewater or swimming pools. A total of 11 disinfection byproducts were identified, and 6 were identified for the first time, and separated by HPLC. These products were identified through careful mass spectrometry studies and 1D and 2D NMR experiments. A formation mechanism has been proposed that justifies the chemical structures of all of the compounds identified. The ecotoxicological assessment of octocrylene and their products was carried out by employing Phaeodactylum tricornutum, Brachionus plicatilis and Aliivibrio fischeri as bioindicators. The ecotoxicity results reveal that toxic byproducts might be generated during the oxidation process, increasing the potential risk to the marine environment. Full article

(This article belongs to the Special Issue Recent Progress in the Analysis and Detection of Pollutants of Emerging Concern in Environmental and Food Samples)

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17 pages, 3208 KiB

Open AccessArticle

USAEME-GC/MS Method for Easy and Sensitive Determination of Nine Bisphenol Analogues in Water and Wastewater

by Dariusz Kiejza, Urszula Kotowska, Weronika Polińska and Joanna Karpińska

Molecules 2022, 27(15), 4977; https://doi.org/10.3390/molecules27154977 - 05 Aug 2022

Cited by 5 | Viewed by 2052

Abstract

A new, simple and sensitive method for isolating nine compounds from the bisphenol group (analogues: A, B, C, E, F, G, Cl₂, Z, AP) based on one-step liquid–liquid microextraction with in situ acylation followed by gas chromatography-mass spectrometry was developed and [...] Read more.

A new, simple and sensitive method for isolating nine compounds from the bisphenol group (analogues: A, B, C, E, F, G, Cl₂, Z, AP) based on one-step liquid–liquid microextraction with in situ acylation followed by gas chromatography-mass spectrometry was developed and validated using influent and effluent wastewaters. The chemometric approach based on the Taguchi method was used to optimize the main conditions of simultaneous extraction and derivatization. The recoveries of the proposed procedure ranged from 85 to 122%, and the repeatability expressed by the coefficient of variation did not exceed 8%. The method’s limits of detection were in the range of 0.4–64 ng/L, and the method’s limits of quantification ranged from 1.3 to 194 ng/L. The developed method was used to determine the presence of the tested compounds in wastewater from a municipal wastewater treatment plant located in northeastern Poland. From this sample, eight analytes were detected. Concentrations of bisphenol A of 400 ng/L in influent and 100 ng/L in effluent were recorded, whereas other bisphenols reached 67 and 50 ng/L for influent and effluent, respectively. The removal efficiency of bisphenol analogues in the tested wastewater treatment plant ranged from 7 to approximately 88%. Full article

(This article belongs to the Special Issue Recent Progress in the Analysis and Detection of Pollutants of Emerging Concern in Environmental and Food Samples)

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Review

Jump to: Research

15 pages, 1981 KiB

Open AccessReview

Nanoscale Ion-Exchange Materials: From Analytical Chemistry to Industrial and Biomedical Applications

by Magdalena Matczuk, Lena Ruzik, Bernhard K. Keppler and Andrei R. Timerbaev

Molecules 2023, 28(18), 6490; https://doi.org/10.3390/molecules28186490 - 07 Sep 2023

Cited by 1 | Viewed by 827

Abstract

Nano-sized ion exchangers (NIEs) combine the properties of common bulk ion-exchange polymers with the unique advantages of downsizing into nanoparticulate matter. In particular, being by nature milti-charged ions exchangers, NIEs possess high reactivity and stability in suspensions. This brief review provides an introduction [...] Read more.

Nano-sized ion exchangers (NIEs) combine the properties of common bulk ion-exchange polymers with the unique advantages of downsizing into nanoparticulate matter. In particular, being by nature milti-charged ions exchangers, NIEs possess high reactivity and stability in suspensions. This brief review provides an introduction to the emerging landscape of various NIE materials and summarizes their actual and potential applications. Special attention is paid to the different methods of NIE fabrication and studying their ion-exchange behavior. Critically discussed are different examples of using NIEs in chemical analysis, e.g., as solid-phase extraction materials, ion chromatography separating phases, modifiers for capillary electrophoresis, etc., and in industry (fuel cells, catalysis, water softening). Also brought into focus is the potential of NIEs for controlled drug and contrast agent delivery. Full article

(This article belongs to the Special Issue Recent Progress in the Analysis and Detection of Pollutants of Emerging Concern in Environmental and Food Samples)

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19 pages, 784 KiB

Open AccessReview

Recent Trends in Multiclass Analysis of Emerging Endocrine Disrupting Contaminants (EDCs) in Drinking Water

by Abigail Lazofsky and Brian Buckley

Molecules 2022, 27(24), 8835; https://doi.org/10.3390/molecules27248835 - 13 Dec 2022

Cited by 5 | Viewed by 3683

Abstract

Ingestion of water is a major route of human exposure to environmental contaminants. There have been numerous studies exploring the different compounds present in drinking water, with recent attention drawn to a new class of emerging contaminants: endocrine-disrupting compounds (EDCs). EDCs encompass a [...] Read more.

Ingestion of water is a major route of human exposure to environmental contaminants. There have been numerous studies exploring the different compounds present in drinking water, with recent attention drawn to a new class of emerging contaminants: endocrine-disrupting compounds (EDCs). EDCs encompass a broad range of physio-chemically diverse compounds; from naturally occurring to manmade. Environmentally, EDCs are found as mixtures containing multiple classes at trace amounts. Human exposure to EDCs, even at low concentrations, is known to lead to adverse health effects. Therefore, the ability to evaluate EDC contamination with a high degree of sensitivity and accuracy is of the utmost importance. This review includes (i) discussion on the perceived and actual risks associated with EDC exposure (ii) regulatory actions that look to limit EDC contamination (iii) analytical methods, including sample preparation, instrumentation and bioassays that have been advanced and employed for multiclass EDC identification and quantitation. Full article

(This article belongs to the Special Issue Recent Progress in the Analysis and Detection of Pollutants of Emerging Concern in Environmental and Food Samples)

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48 pages, 904 KiB

Open AccessReview

An Overview of Analytical Methods to Determine Pharmaceutical Active Compounds in Aquatic Organisms

by María del Carmen Gómez-Regalado, Laura Martín-Pozo, Julia Martín, Juan Luis Santos, Irene Aparicio, Esteban Alonso and Alberto Zafra-Gómez

Molecules 2022, 27(21), 7569; https://doi.org/10.3390/molecules27217569 - 04 Nov 2022

Cited by 1 | Viewed by 1814

Abstract

There is increasing scientific evidence that some pharmaceuticals are present in the marine ecosystems at concentrations that may cause adverse effects on the organisms that inhabit them. At present, there is still very little scientific literature on the (bio)accumulation of these compounds in [...] Read more.

There is increasing scientific evidence that some pharmaceuticals are present in the marine ecosystems at concentrations that may cause adverse effects on the organisms that inhabit them. At present, there is still very little scientific literature on the (bio)accumulation of these compounds in different species, let alone on the relationship between the presence of these compounds and the adverse effects they produce. However, attempts have been made to optimize and validate analytical methods for the determination of residues of pharmaceuticals in marine biota by studying the stages of sample treatment, sample clean-up and subsequent analysis. The proposed bibliographic review includes a summary of the most commonly techniques, and its analytical features, proposed to determine pharmaceutical compounds in aquatic organisms at different levels of the trophic chain in the last 10 years. Full article

(This article belongs to the Special Issue Recent Progress in the Analysis and Detection of Pollutants of Emerging Concern in Environmental and Food Samples)

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20 pages, 4733 KiB

Open AccessReview

Lab-in-Syringe, a Useful Technique for the Analysis and Detection of Pollutants of Emerging Concern in Environmental and Food Samples

by Víctor Cerdà, Sergio L. C. Ferreira and Piyawan Phansi

Molecules 2022, 27(21), 7279; https://doi.org/10.3390/molecules27217279 - 26 Oct 2022

Cited by 3 | Viewed by 1549

Abstract

Lab-in-syringe is a new approach for the integration of various analytical extraction steps inside a syringe. Fully automated dispersive liquid–liquid microextraction is carried out in-syringe using a very simple instrumental setup. Dispersion is achieved by aspiration of the organic phase and then the [...] Read more.

Lab-in-syringe is a new approach for the integration of various analytical extraction steps inside a syringe. Fully automated dispersive liquid–liquid microextraction is carried out in-syringe using a very simple instrumental setup. Dispersion is achieved by aspiration of the organic phase and then the watery phase into the syringe as rapidly as possible. After aggregation of the solvent droplets, the organic phase is pushed towards the detector allowing a highly sensitive spectrophotometric or fluorimetric detection. This technique is very useful not only for the preconcentration of analyte, but also for the elimination of their interferences. In this work, its application is described using solvents that are lighter and denser than water. The magnetically assisted variant and its coupling to different instruments has been also described with the aim of increasing the resolution of complex samples, especially useful for the determination of emerging contaminants. Full article

(This article belongs to the Special Issue Recent Progress in the Analysis and Detection of Pollutants of Emerging Concern in Environmental and Food Samples)

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