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In this experimental study, the use of acrylic acid, and 1-vinylimidazole as monomers for the synthesis of one polymer (PVI) and one copolymer (PVI- co -PAA) was examined using trimethylolpropane trimethacrylate as the cross-linking agent. The synthesized polymeric materials were characterized using Fourier transform infrared spectroscopy (FTIR), BET analysis, Thermogravimetric analysis (TGA) and scanning electron microscopy (SEM) and were evaluated towards their adsorption efficiency for the removal of two non-steroidal anti-inflammatory drugs, ibuprofen (IBU) and diclofenac (DCF), from single-component aqueous solutions. Parameters like pH, contact time, initial concentration of the drug and temperature were examined for their possible effect to the process. Acidic conditions appear to favor the uptake of the studied compounds. Moreover, the adsorption equilibrium data were fitted to Langmuir and Freundlich models calculating the maximum adsorption capacity, while Langmuir model exhibited a better fit indicating monolayer coverage of the pharmaceuticals onto the surface of synthesized derivatives. Furthermore, increase of temperature from 25 to 65 ℃ caused an enhancement of the adsorption ability, for both polymeric materials. while thermodynamic analysis revealed the spontaneous and endothermic nature of the process. [Display omitted] • PVI and PVI- co -PAA polymers were synthesized. • Characterization was conducted with FTIR, TGA, BET and SEM analysis. • Acid pH appears to favor the process. • Equilibrium data exhibited better fitting to Langmuir model. • Thermodynamic analysis showed the spontaneous and endothermic nature of the process. [ABSTRACT FROM AUTHOR]

• Electrodeposited Ni on a Ti substrate assists efficient deposition of a uniform Ir film by galvanic replacement. • Anodization of Ir(Ni)/Ti samples results in IrOx/Ir(Ni)/Ti anodes with a 2 A mgIr−1 mass-specific current for OER, at η=300 mV. • Combination of Ti support stability and IrOx-Ni high electrocatalytic activity for OER leads to promising candidates for industrial oxygen evolving anodes. IrO 2 -Ni-modified Ti electrodes have been prepared by a Ni-mediated galvanic replacement method. A smooth Ni film has been electrodeposited on the Ti substrate from a Watts bath and its surface layers spontaneously exchanged with metallic Ir upon treatment with an Ir(IV) solution. Anodization of the resulting Ir(Ni)/Ti electrodes by means of continuous potential cycling in acid solutions resulted in the formation of porous IrO 2 coatings showing typical Ir oxide/hydroxide surface electrochemistry. SEM pictures revealed that the thus prepared IrO 2 /Ir(Ni)/Ti electrodes consisted of continuous films with a nodular morphology (as confirmed by AFM). The composition of the coatings was estimated by EDS and XPS spectroscopy while the Ir mass loading was determined by ICP-MS following etching in acid. These electrodes have been tested as oxygen evolution reaction (OER) anodes by slow potential sweep voltammetry and were proven comparable or better than state-of-the-art thin thermal film and nanoparticulate IrNiO x -based electrodes (exhibiting ca 2 A mg Ir −1 at η=300 mV). The recently established enhancement of IrO 2 OER activity by Ni, combined with the widespread use of Ti as a stable electrode substrate, make IrO 2 /Ir(Ni)/Ti attractive candidates for Dimensionally Stable Electrodes (DSAs). [ABSTRACT FROM AUTHOR]

[Display omitted] • Innovative combination of FT-IR, Py-GC–MS and LC–Orbitrap MS/MS to reveal the varnishes' origin. • FT-IR proved similarity between the obtained spectra and those corresponding to natural resins. • Py-GC–MS evidenced the fatty acids profile in drying oils and dammarane skeleton among others. • Drying/essential oils, mastic and dammar were reliably identified by Orbitrap MS/MS. • Successful application of the proposed workflow to restore an original artwork. This study deals with the investigation of old varnishes from six paintings belonging to the collection of the "Teloglion Foundation of Arts", Aristotle University of Thessaloniki in Greece employing three complementary analytical techniques. The purpose of this research was to identify the origin of the protective layers of the varnishes with the ultimate goal of their safe removal during their treatment. To identify the components of the varnishes, sampling was carried out in both a mechanical and chemical way from selected areas of all the works of art. The samples were firstly studied with Fourier-Transform Infrared Spectroscopy (FT-IR), secondly with Pyrolysis-Gas Chromatography/Mass Spectrometry (Py-GC–MS), and finally with Liquid Chromatography–Orbitrap High-Resolution Mass Spectrometry (LC–Orbitrap HRMS). The application of these methods led not only to the verification of the compounds of the varnishes, but also to the presence of specific fatty acids included in the drying oils, as well as diterpene and triterpene resins. FT-IR spectra were very similar to those corresponding to natural resins, while Py-GC–MS evidenced the fatty acids profile in drying oils as well as the presence of dammarane skeleton among others. The main findings from LC–Orbitrap MS/MS included drying and essential oils, mastic, and dammar. Based on the obtained results, a solubility study of varnishes was also performed. The appropriate mixture of solvents for the coating varnishes removal was investigated with the aid of the Teas solubility triangle and the most suitable solvent mixture for the proper restoration was proposed. A conservation effort for one painting was carried out successfully, confirming the applicability of the method. [ABSTRACT FROM AUTHOR]

• Simultaneous analysis of 135 PPCPs, 17 illicit drugs, 11 PFAs and 9 OPFRs • Comprehensive sample pretreatment optimization employing response surface modeling • Q-Orbitrap in full-scan and data dependent MS2 acquisition used for quantitation • Method performance meth the requirements of the established guidelines • Successful application of the method to influent and effluent wastewaters Multi-residue analysis is highly desirable for water quality control. To this end, a comprehensive workflow for the quantitative analysis of 172 anthropogenic organic compounds belonging to emerging contaminants (pharmaceuticals and personal care products, illicit drugs, organophosphate flame retardants and perfluoroalkyl substances) has been developed for application to wastewater and tap water, based on solid phase extraction (SPE) and Orbitrap high resolution mass spectrometry (HRMS). Due to the large number of analytes with various physicochemical characteristics that should be efficiently extracted, the response surface methodology (RSM) employing a central composite design (CCD) and desirability function (DF) approach was exploited to optimize the sample preparation process, instead of the conventional single-factor analysis. The factors included in the design of experiments (DoE) were sample pH, eluent solvents composition and volume. Statistical analysis (ANOVA) proved the adequacy of the proposed model (2- factor interaction) as p-value < 0.05 followed by different diagnostic tests confirmed the good fitting. The best values to acquire DF close to 1 were pH 3.5, methanol/ethyl acetate ratio 87:13 and eluent volume 6 mL. The streamlined method was validated in terms of accuracy, linearity, method limits, reproducibility, and matrix effect. The proposed workflow combines sensitivity and robustness, with recoveries over 70%, method quantification limits <1 ng/L, and relative standard deviations <20% for most of the compounds. Slight matrix effect (ME) was observed for most of PPCPs, IDs and PFAs, in contrast with most of the OPFRs, for which strong ME was calculated. Method applicability was tested over wastewater collected from a municipal wastewater treatment plant in Thessaloniki (Greece), revealing the presence of 69 and 40 compounds in influents and effluents, respectively, at varying concentrations. [ABSTRACT FROM AUTHOR]

In the present study the effects of sublethal concentrations of polystyrene microplastics (PS-MPs) on zebrafish were evaluated at multiple levels, related to fish activity and oxidative stress, metabolic changes and contraction parameters in the heart tissue. Zebrafish were fed for 21 days food enriched with PS-MPs (particle sizes 3–12 µm) and a battery of stress indices like DNA damage, lipid peroxidation, autophagy, ubiquitin levels, caspases activation, metabolite adjustments, frequency and force of ventricular contraction were measured in fish heart, parallel to fish swimming velocity. In particular, exposure to PS-MPs caused significant decrease in heart function and swimming competence, while enhanced levels of oxidative stress indices and metabolic adjustments were observed in the heart of challenged species. Among stress indices, DNA damage was more vulnerable to the effect of PS-MPs. Our results provide evidence on the multiplicity of the PS-MPs effects on cellular function, physiology and metabolic pathways and heart rate of adult fish and subsequent effects on fish activity and fish fitness thus enlightening MPs characterization as a potent environmental pollutant. [Display omitted] • Polystyrene microplastics (PS-MPs) effects were evaluated on zebrafish heart. • PS-MPs decrease significantly heart frequency of ventricular contraction. • PS-MPs decrease significantly swimming velocity. • PS-MPs caused increased levels of oxidative stress indices and metabolic adjustments. [ABSTRACT FROM AUTHOR]

This study focused on the Analytical Quality by Design (AQbD) optimization of the chromatographic separation and mass spectrometric detection of a wide group of structurally heterogeneous model pharmaceutical compounds (PhCs) and transformation products (TPs), chosen to cover the challenging issues of the co-presence of compounds characterized by (i) a wide range of physicochemical properties, (ii) the same mass transitions, and (iii) different ionisation modes. Italian consumption of PhCs were also considered as election criteria of target analytes. Octadecyl and pentafluorophenyl stationary phases, acetonitrile/methanol ratios and acidity of the eluents, column temperature, initial organic phase percentage, and elution gradient were investigated by AQbD, aiming at optimizing critical resolutions, sensitivities, and analysis time. Statistically significant models were obtained in most cases with fitting and cross-validation coefficients in the ranges of 0.681-0.998 and 0.514-0.967, respectively. After optimization, the analysis of target analytes was performed in a single chromatographic run, adopting a mixed acquisition mode based on scheduled acquisition windows comprising both single polarity and continuous polarity switching. For most investigated analytes the method provided detection limits in the sub-ng/L to low ng/L range, meeting for macrolides the sensitivity requested by the "Watch List" 2018/840/EU. The optimized method was applied to the direct injection analysis of PhCs and TPs in four wastewater treatment plant (WWTP) effluents and surface water (SW) samples collected in the receiving water bodies. Absolute values of matrix effect were found to be far higher than 20% for most target analytes in most samples. Seventeen PhCs and two TPs were quantified in at least one sample, at the wide concentration range of about 1-3200 ng/L. The most occurring PhCs in both WWTP effluents and SWs were levofloxacin (202-1239 and 100-830 ng/L), furosemide (865-3234 and 230-880 ng/L), ketoprofen (295-1104 and 270-490 ng/L), and ibuprofen (886-3232 and 690-1440 ng/L). [ABSTRACT FROM AUTHOR]

Considering that the extensive biomedical, pharmaceutics, cosmetic and other industrial applications of biomaterials (BMs) is of great concern nowadays, regarding their environmental risk, the present study aimed to investigate the effects of four BMs, poly(ε-caprolactone) (PCL), poly(butylene succinate) (PBSu), chitosan (CS) and modified chitosan (succinic acid grafted chitosan) (CS-Suc) in the form of microplastics (particle sizes less than 1 mm) on biochemical parameters of snails Cornu aspersum hemocytes. Due to the absence of knowledge about the environmentally relevant concentrations of BMs, snails were initially treated through their food with a wide range of nominal concentrations of each BM to define the half maximal effective concentration (NRRT 50), according to the destabilization degree of hemocytes' lysosomal membranes (by mean of neutral red retention time/NRRT assay). Thereafter, snails were treated with each BM, at concentrations lower than the estimated NRRT 50 values in all cases, for periods up to 15 days. After the end of the exposure period, a battery of stress indices were measured in hemocytes of challenged snails. According to the results, all parameters tested in BMs-treated snails statistically differed from those measured in BMs-free snails, thus indicating the pro-oxidant potential of BMs, as well as their ability to affect animals' physiology. The most considerable effect in most cases seems to be caused by modified chitosan and PCL, while chitosan appears to be the least toxic. A common response mechanism of snails' blood cells against the 4 BMs used in the present study was shown. After exposure to each of the studied BMs a significant augmentation in protein carbonyls, MDA equivalents and DNA damage, while a significant reduction in NRRT values was determined in the snails hemocytes, in relation to the unexposed animals. From the biochemical parameters examined, MDA equivalents and DNA damage seem to be more susceptible than the other parameters studied, to respond to BMs effect, with MDA to react with more sensitivity to PCL and CS, while DNA damage to CS-Suc and PBSu. Our results could suggest the simultaneous use of the latter biomarkers in biomonitoring studies of terrestrial ecosystems against the specific BMs. [Display omitted] • The effect of several biomaterials in microplastics form on snails has been studied for first time. • Their effect on biochemical parameters of snails Cornu aspersum hemocytes was evaluated. • Biomaterials caused significant alterations in all measured parameters (DNA damage, lysosomal membrane stability, etc). • Modified chitosan and PCL caused the most considerable effect. [ABSTRACT FROM AUTHOR]

The goal of this work was the application of a synthesized cross-linked and grafted zwitterionic chitosan derivative to the removal of a mixture of five anti-inflammatory compounds from aqueous matrix. This floating polymer supported nanocomposite material consisting of bio-based chitosan (CS) and was synthesized by free radical polymerization, using acrylic monomer [2-(Methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide (MEDSP) as grafting agent. The composition and morphology of new CS-MEDSP material was characterized before and after adsorption, by using different procedures, for instance Fourier Transform Infrared spectroscopy (FTIR), X-ray powder diffraction (XRD) and Scanning electron microscopy (SEM). As model pollutants a mixture of pharmaceuticals from the group of anti-inflammatories was employed: diclofenac, ibuprofen, ketoprofen, paracetamol and salicylic acid (equal concentrations). An adsorption assessment was performed at different pH values concluding that pH = 4 was the optimum value. By testing different isotherm equations, the equilibrium data for the adsorption of the target compounds were evaluated. For the detection of compounds, an LC-MS system was utilized, in both ionization modes. Accordingly, results indicated a high adsorption/desorption ability of tested material being suitable for disposal of the certain remedies from aqueous systems. [Display omitted] [ABSTRACT FROM AUTHOR]

The present study comprehensively investigates the phototransformation and ecotoxicity of a mixture of twelve pharmaceutically active compounds (PhACs) susceptible to photolysis. Namely, three antibiotics (ciprofloxacin, levofloxacin, moxifloxacin), three antidepressants (bupropion, duloxetine, olanzapine), three anti-inflammatory drugs (diclofenac, ketoprofen, nimesulide), two beta-blockers (propranolol, timolol) and the antihistamine ranitidine were treated under simulated solar irradiation in ultra-pure and river water. A total of 166 different transformation products (TPs) were identified by ultra-high performance liquid chromatography coupled with Orbitrap high resolution mass spectrometry (UHPLC–Orbitrap HRMS), revealing the formation of twelve novel TPs and forty-nine not previously described in photolytic studies. The kinetic profiles of the major TPs resulting from a series of chemical reactions involving hydroxylation, cleavage and oxidation, dehalogenation, decarboxylation, dealkylation and photo substitution have been investigated and the transformation pathways have been suggested. Additionally, an in vitro approach to the toxicity assessment of daphnids was contrasted with ecotoxicity data based on the Ecological Structure Activity Relationships (ECOSAR) software comprising the in silico tool to determine the adverse effects of the whole mixture of photolabile parent compounds and TPs. The results demonstrated that photolysis of the target mixture leads to a decrease of the observed toxicity. Unlabelled Image • Photo fate of a multi-component mixture of 12 PhACs • Identification of 166 transformation products by HRMS • In silico toxicity prediction of parent compounds and TPs using ECOSAR • In vitro toxicity assessment using D. magna [ABSTRACT FROM AUTHOR]

• Gallic acid (GA)/Cu(II)/PMS effectively degraded TBBPA at pH 4.3 − 9.0. • Cu(III) was the dominant oxidant responsible for TBBPA degradation. • GA acted as electron donor to accelerate Cu redox cycling for PMS activation. • TBBPA degraded via electron abstraction, debromination and ring-opening pathways. • Cu(II) and NOM present in water can activate PMS to degrade TBBPA effectively. Copper ion (Cu(II)) in water or wastewater has been reported to trigger peroxymonosulfate (PMS) oxidation of organic contaminants (OCs). However, this process can only work in alkaline condition, which limits its potential application. In this study, we found that the introduction of natural polyphenols in the Cu(II)/PMS process can significantly promote the degradation of tetrabromobisphenol A (TBBPA), one of the most widely used brominated flame retardants, in the pH range of 4.3−9.0. With gallic acid (GA) as a representative natural polyphenol, the degradation of TBBPA by GA/Cu(II)/PMS process reached 84.6% in 10 min at initial pH of 4.3 (without pH adjustment), which was 2.2 times higher than that by Cu(II)/PMS process. Multiple reactive oxidants, including Cu(III), hydroxyl radical (HO•) and singlet oxygen, were generated in this process among which Cu(III) and HO• contributed to TBBPA degradation with Cu(III) playing the dominant role. GA accelerated the reduction of Cu(II) to Cu(I) due to the strong chelation and electron-donating capacity of ortho-hydroxyl groups in GA, and then Cu(I) was quickly oxidized by PMS to Cu(III) which can be further acid-catalyzed to produce HO•. TBBPA transformation mainly proceeded through electron abstraction, oxidative debromination and ring-opening reaction pathways. The feasibility of in-situ utilizing natural organic matter (NOM, enriched with polyphenol moieties) to accelerate the degradation of TBBPA by Cu(II)/PMS process in surface water and wastewater was confirmed. The findings of this study indicate that the coupling of NOM and Cu(II), which are present in contaminated water or wastewater, can potentially improve PMS oxidation of OCs in a wide range of pH. Image, graphical abstract [ABSTRACT FROM AUTHOR]

The photocatalytic activity of two bio-based polymer photocatalysts [poly(ethylene terephthalate)-TiO 2 (PET-TiO 2) and poly(L-lactic acid)-graphene oxide-TiO 2 (PLLA-GO-TiO 2)] towards Tamoxifen (TAM), Cyclophosphamide (CP), Cytarabine (CYT) and 5-Fluorouracil (5-FLU) removal was explored and compared. The highest photocatalytic activity for the degradation of the cytostatic drugs was accomplished by PET-TiO 2. Among the contaminants, TAM was the most easily removed, requiring 90 min for complete elimination, while CP showed the highest resistance to photocatalysis, not being completely removed after 6 h. Liquid chromatography coupled with high-resolution mass spectrometry analysis was employed for the identification of several transformation products (TPs) and potential pathways were proposed. A total of seventy (70) TPs including thirty-four (34) novel ones detected in AOPs were identified. The ecotoxicity of the mixture of the cytostatic drugs and TPs formed during the photocatalytic treatment was evaluated using Daphnia magna assay and was associated with the occurrence of specific TPs during the treatment process. The follow-up ECOSAR (Ecological Structure Activity Relationship) analysis further elucidated that only minor chemical transformations, such as the hydroxylation or the oxidative opening of an aromatic ring system, could hamper the adverse effects of cytostatic drugs in aquatic species. Such a comparative study on the mixture toxicity of cytostatics and their TPs is presented for the first time. Unlabelled Image • Effective photocatalytic degradation of a mixture of four cytostatic drugs • Increased efficiency of the nanocomposite PET/TiO 2 film compared to PLLA/GO/TiO 2 • Identification of 70 transformation products of cytostatics by Q-Orbitrap HRMS • Increased toxicity at the end of treatment via bioassay (D. magna) • In silico toxicity prediction of all transformation products by ECOSAR [ABSTRACT FROM AUTHOR]

Unlabelled Image • Global review on the occurrence of antivirals in WWTPs, groundwater, surface and drinking water. • The determination of antivirals should be incorporated to multi-class analytical methods. • Occurrence of antiviral drugs in influents and effluents varies significantly worldwide. • More surveys are required to assess the chemical status in groundwater and drinking water. • Urgent need for risk assessment and toxicity studies against non-target organisms. The environmental release of antiviral drugs is of considerable concern due to potential ecosystem alterations and the development of antiviral resistance. As a result, interest on their occurrence and fate in natural and engineered systems has grown substantially in recent years. The main scope of this review is to fill the void of information on the knowledge on the worldwide occurrence of antiviral drugs in wastewaters and natural waters and correlate their levels with their environmental fate. According to the conducted literature survey, few monitoring data exists for several European countries, such as Germany, France, and the UK. Lesser data are available for Asia, where approximately 80% of the studies focus on Japan. Several articles study the occurrence of mostly antiretroantivirals in sub-Saharan African countries, while there is a lack of data for other developing regions of the world, including the rest of Africa, South America, and the biggest part of Asia. An importantly smaller number of studies exists for North America, while no studies exist for Oceania. The against innfluenza drug oseltamivir along with its active carboxy metabolite is found to be the most studied antiviral drug. The distribution of antiviral drugs across all geographic regions varies from low ng L−1 to high μg L−1 levels, in some cases, even in surface waters. This overarching review reveals that monitoring of antiviral drugs is necessary, and some of those compounds may require toxicological attention, in the light of either spatial and temporal high concentration or potential antiviral resistance. Based on the information provided herein, the need for a better understanding of the water quality hazards posed by antiviral drugs existence in wastewater outputs and freshwater ecosystems is demosntrated. Finally, the future challenges concerning the occurrence, fate, and potential ecotoxicological risk to organisms posed by antiviral drug residues are discussed. [ABSTRACT FROM AUTHOR]

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

The limited knowledge on the stability, removal, and the fate of bisphenol A analogues in the aqueous environment led us to assess the removal by hydrolysis, adsorption, biological treatment and UV photolysis of eighteen common bisphenol compounds (BPs). Hydrolysis of BPs does not occur. The main factor affecting their stability in wastewater samples is storage time, and safe storage conditions were found to be −20 °C or 4 °C for up to four weeks. The results also revealed no significant reduction in the levels of BPs standards when stored in either methanol or ultrapure water. BPE was found to be the most stable, followed by BPF isomers, BPS and BPF, while BP26DM was the least stable and BPM, BPPH, BPP, BPBP and BPFL were quickly adsorbed. For most BPs, the removal efficiency of biological treatment was >85%, and there was no difference between the suspended activated sludge and moving bed bioreactors. Different adsorption affinities of the BPs to biomass were observed and reflect the differences in their K ow. In terms of degradability, direct UV photolysis in water produced three groups of BPs: (A) highly removable (RE > 94%), (B) moderately removable (RE 50–80%) and (C) poorly removable (RE 25–45%). In nearly all cases degradation followed pseudo-first-order kinetics. Image 1 • Hydrolysis of BPs does not occur. • BPs stability in the matrix is ranked as followed: MeOH > ultrapure water > WW. • BPs are efficiently removed by biological treatment. • UV photolysis achieved high REs of BPs after 4 h of irradiation. • New insights into a better understanding of BPs environmental behaviour. [ABSTRACT FROM AUTHOR]

Technological advancements in liquid chromatography (LC) electrospray ionization (ESI) high-resolution mass spectrometry (HRMS) have made it an increasingly popular analytical technique in non-targeted analysis (NTA) of environmental and biological samples. One critical limitation of current methods in NTA is the lack of available analytical standards for many of the compounds detected in biological and environmental samples. Computational approaches can provide estimates of concentrations by modeling the relative response factor of a compound (RRF) expressed as the peak area of a given peak divided by its concentration. In this paper, we explore the application of molecular dynamics (MD) in the development of a computational workflow for predicting RRF. We obtained measurements of RRF for 48 compounds with LC - quadrupole time-of-flight (QTOF) MS and calculated their RRF. We used the CGenFF force field to generate the topologies and GROMACS to conduct the (MD) simulations. We calculated the Lennard-Jones and Coulomb interactions between the analytes and all other molecules in the ESI droplet, which were then sampled to construct a multilinear regression model for predicting RRF using Monte Carlo simulations. The best performing model showed a coefficient of determination ( R ) of 0.82 and a mean absolute error (MAE) of 0.13 log units. This performance is comparable to other predictive models including machine learning models. While there is a need for further evaluation of diverse chemical structures, our approach showed promise in predictions of RRF.2 ) of 0.82 and a mean absolute error (MAE) of 0.13 log units. This performance is comparable to other predictive models including machine learning models. While there is a need for further evaluation of diverse chemical structures, our approach showed promise in predictions of RRF., Competing Interests: The authors declare that they have no competing interests to report., (This journal is © The Royal Society of Chemistry.)

In this study, the adsorption of a mixture of high-consumed drugs onto virgin and aged PET microplastics has been studied for the time ever. The target mixture comprised two anti-inflammatory drugs, diclofenac and ketoprofen, one anti-hypertensive, valsartan, and four common antibiotics, indomethacin, trimethoprim, isoniazid, and metronidazole. Two types of PET MPs (virgin and UV-aged) were used in the experimental procedure. Kinetic studies were conducted, and adsorption isotherms were obtained revealing the possible interactions that take place between adsorbents and adsorbates. Among the studied pharmaceuticals, diclofenac presents the highest uptake due to its hydrophobic nature, while aging appears to induce the adsorption of the drugs in MPs. Factors like pH or the environmental matrix were also evaluated. The results revealed that sorption is pH-dependent, while more complicated matrices like wastewater or seawater exhibit lower uptake than distilled water due to the natural organic matter present or the increased salinity, respectively. Finally, desorption studies were also conducted in three different aqueous solutions examining the pH effect. The desorption of the compounds was higher for diclofenac, followed by valsartan, and ketoprofen. The desorption percentages of antibiotics were quite low., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

In the present study a novel, cost-effective, environmentally friendly, and efficient analytical method was developed to analyze fungicide residues in water and wine. The method relies on the application of a newly developed sorbent nanomaterial named Nano-Cs-NAT, synthesized by modifying chitosan, a naturally occurring, low-cost polysaccharide, through grafting with two acrylic monomers and a cross-linker. Nano-Cs-NAT was introduced as analytical sorbent for Dispersive Micro Solid Phase Extraction (D-μ-SPE) before Liquid Chromatography-Orbitrap High-Resolution Mass Spectrometry (LC-Orbitrap HRMS) analysis of twelve fungicides commonly used in viticulture (among the others, triazoles, strobilurines and N -substituted imidazoles). Characterization of the sorbent was conducted, confirming the successful acrylation of chitosan. A multivariate approach was employed to optimize D-μ-SPE extraction parameters. The material was found to be highly effective in simultaneously purifying and concentrating the target analytes, enhancing overall analytical efficiency and sensitivity. The Nano-Cs-NAT-D-μ-SPE-LC-Orbitrap-HRMS method was thoroughly validated, exhibiting good recoveries (72-104%), reproducibility (average RSD ≤ 6%) and repeatability (average RSD ≤ 7%). It also achieved low limits of detection (LOD) in river water (average LOD of 0.04 μg L -1 ) and wine (average LOD of 0.72 μg kg -1 ), highlighting its potential for routine fungicide residue analysis. This developed method addresses environmental and food safety concerns by providing an efficient solution for detecting fungicide residues in waters and wine.

Non-targeted analysis (NTA) has made critical contributions in the fields of environmental chemistry and environmental health. One critical bottleneck is the lack of available analytical standards for most chemicals in the environment. Our study aims to explore a novel approach that integrates measurements of equilibrium partition ratios between organic solvents and water ( K ) to predictions of molecular structures. These properties can be used as a fingerprint, which with the help of a machine learning algorithm can be converted into a series of functional groups (RDKit fragments), which can be used to search chemical databases. We conducted partitioning experiments using a chemical mixture containing 185 chemicals in 10 different organic solvents and water. Both a liquid chromatography quadrupole time-of-flight mass spectrometer (LC-QTOF MS) and a LC-Orbitrap MS were used to assess the feasibility of the experimental method and the accuracy of the algorithm at predicting the correct functional groups. The two methods showed differences in log SW with the QTOF method showing a mean absolute error (MAE) of 0.22 and the Orbitrap method 0.33. The differences also culminated into errors in the predictions of RDKit fragments with the MAE for the QTOF method being 0.23 and for the Orbitrap method being 0.31. Our approach presents a new angle in structure elucidation for NTA and showed promise in assisting with compound identification.K SW with the QTOF method showing a mean absolute error (MAE) of 0.22 and the Orbitrap method 0.33. The differences also culminated into errors in the predictions of RDKit fragments with the MAE for the QTOF method being 0.23 and for the Orbitrap method being 0.31. Our approach presents a new angle in structure elucidation for NTA and showed promise in assisting with compound identification.

Over the past three decades, environmental concerns about the water pollution have been raised on societal and industrial levels. The presence of pollutants stemming from cosmetic products has been documented in wastewater streams outflowing from industrial as well as wastewater treatment plants. To this end, a series of consistent measures should be taken to prevent emerging contaminants of water resources. This need has driven the development of technologies, in an attempt to mitigate their impact on the environment. This work offers a thorough review of existing knowledge on cosmetic wastewater treatment approaches, including, coagulation, dissolved air flotation, adsorption, activated sludge, biodegradation, constructed wetlands, and advanced oxidation processes. Various studies have already documented the appearance of cosmetics in samples retrieved from wastewater treatment plants (WWTPs), which have definitely promoted our comprehension of the path of cosmetics within the treatment cycle; however, there are still multiple blanks to our knowledge. All treatments have, without exception, their own limitations, not only cost-wise, but also in terms of being feasible, effective, practical, reliable, and environmentally friendly., (© 2022. The Author(s).)