Assessing the adsorption of a diverse range of pharmaceuticals to virgin and aged poly (ethylene terephthalate) microplastics in different environmental matrices.

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.

Unravelling psychoactive substances and their metabolites and transformation products: High-Resolution Mass Spectrometry approaches for comprehensive target and suspect screening in wastewater.

Untangling the consumption rates of psychiatric drugs and their metabolites/ transformation products-(TPs) through wastewater gains attention lately. However, the potential environmental impact caused by their release remains ambiguous. As it follows, the monitoring of this class of pharmaceuticals as well as the evaluation of their potential toxicity is a matter of high concern. In the light of the above, here, wastewater samples, were collected in a 1-year and a half sampling campaign (2020-2021) and were further subjected to solid phase extraction. A Q Exactive Focus Orbitrap mass analyzer was employed for the analysis of the samples. For the data curation, except of the monitoring of targets, a comprehensive suspect screening workflow was developed and slightly optimized based on a lab made HRMS database for the investigation of legally or illegally prescribed psychiatric drugs and their relevant metabolites/TPs in influents and effluents. Carbamazepine and amisulpride were quantified at the highest mean concentrations 243 and 225 ng/L respectively, in influents. In effluents, the highest mean concentrations were calculated for carbamazepine (180 ng/L) and venlafaxine (117 ng/L). The implementation of suspect screening approach enhanced the comprehensiveness of analysis by detecting 29 compounds not included in the target list. O-Desmethylvenlafaxine was the predominant metabolite in influents presenting a mean concentration equal to 87 ng/L while the same pattern was also noticed in effluents where the mean concentration was up to 91 ng/L. From the group of suspect compounds for which no analytical standards were available, the predominant compounds with detection frequency 100 % were norephedrine and codeine in influents while in effluents, oxazepam was detected in 81 % of the analyzed samples. Finally, in silico and mathematical tools were employed for the assessment of the risk posed to environmental systems. Most of the detected compounds present high risk in all trophic levels.

Exploring patterns of antibiotics during and after COVID-19 pandemic in wastewaters of northern Greece: Potential adverse effects on aquatic environment.

Antibiotics, recognized as Emerging Contaminants (ECs), have raised concerns due to their pervasive presence in wastewater treatment plants (WWTPs) and subsequent release into aquatic environments, posing potential ecological risks and contributing to the development of antibiotic-resistant genes. The COVID-19 pandemic prompted an unprecedented surge in antibiotic consumption, necessitating a comprehensive assessment of its impact on antibiotic levels in wastewater. In this light, a four-year monitoring study (2020-2023) was conducted in a WWTP located in the Northern Greece (Thessaloniki), employing High-Resolution Mass Spectrometry (HRMS) technology to monitor twenty antibiotics, during distinct phases pre-, during, and post-COVID-19. Our findings revealed that macrolides and fluoroquinolones were among the most often detected categories during the sampling period. Among the compounds detected, azithromycin and clarithromycin showed the most significant increases during the pandemic, doubling their average concentrations. This establishes a clear correlation between the rise in their concentrations and the incidence of COVID-19 cases. A general downward trend after 2021 was attributed to the new restrictions posed in Greece during this year, regarding the liberal prescription of antibiotics. Seasonal variation revealed a minute augmentation of antibiotics' use during the months that infections are increased. Additionally, the study highlights the ecological risks associated with elevated antibiotic presence and emphasizes the need for continued monitoring and regulatory measures to mitigate potential ecological repercussions. These findings contribute to our understanding of the complex interplay between antibiotic consumption, environmental presence, and the COVID-19 pandemic's impact on antibiotic pollution in WWTPs.

Photo-assisted transformation of furosemide: Exploring transformation pathways, structure database and suspect and non-target workflows for comprehensive screening of unknown transformation products in wastewaters and landfill leachates.

In recent years, transformation products-(TPs) of pharmaceuticals in the environment have received considerable attention. In this context, here, a customized overview of transformation of Furosemide-(FRS) in aqueous matrices treated by photo-oxidation is provided as a proof of concept. Hence, the primary goal of the study was to display an integrated strategy by combining the target (parent-molecule) and suspect screening-(SS) approaches (TPs) in order to build an in-house High-Resolution mass spectrometry (HRMS) database able to provide reference information (chromatographic/spectral) for environmental investigations in complex matrices (wastewaters/landfill leachates). Data analysis was performed by optimizing a SS workflow. Additional confirmation for the proposed structural elucidation was provided by correlating retention time to the proposed structure employing three prediction models. This approach was applied for the tentative identification of 35 TPs of FRS, 28 of which are reported herein for the first time. Finally, SS and non-target analysis (NTA) have been successfully applied for retrospective screening of FRS and its TPs in real samples. The findings demonstrated that SS allows the proper identification of TPs of FRS in complex matrices proving its outstanding importance compared to NTA. In total, six TPs were identified by SS with potential ecotoxicological implications for two of them according to in silico risk assessment.

Does climbazole instigate a threat in the environment as persistent, mobile and toxic compound? Unveiling the occurrence and potential ecological risks of its phototransformation products in the water cycle.

Persistent, mobile, and toxic chemicals (PMT), such as the antimycotic climbazole-(CBZ), proliferate in water cycle and imperil drinking water quality, sparking off research about their environmental fate. Unlike the parent compound, its transformation products-(TPs) are scarcely investigated, much less as PMTs. To this end, phototransformation of CBZ was investigated. A novel suspect-screening workflow was developed and optimized by cross-comparing the results of the identified photo-TPs against literature data to create an enhanced HRMS-database for environmental investigations of CBZ/TPs in the water cycle. In total, 24 TPs were identified, 14 of which are reported for the first time. Isomerism, dechlorination, hydroxylation, and cleavage of the ether or C-N bond are suggested as the main transformation routes. A screening of CBZ/TPs was conducted in wastewater, leachates, surface, and groundwater, revealing a maximum concentration of 464.8 ng/L in groundwater. In silico and in vitro methods were used for toxicity assessment, indicating toxicity for CBZ and some TPs. Seemingly, CBZ is rightly considered as PMT, and a higher potential to occur in surface or groundwater than non-PM chemicals appears. Likewise, the occurrence of TPs due to PMT properties or emission patterns was evaluated.

AOP-Based Transformation of Abacavir in Different Environments: Evolution Profile of Descyclopropyl-Abacavir and In Silico Toxicity Assessment of the Main Transformation Products.

This study explores the photocatalytic transformation of the antiviral drug abacavir employing different advanced oxidation processes (AOPs) such as UV/TiO2, UV/MOF/H2O2, UV/MOF/S2O82-, UV/Fe2+/H2O2, and UV/Fe2+/S2O82-. All processes appear to be effective in eliminating abacavir within a few minutes, while the evolution profile of the basic transformation product, descyclopropyl-abacavir (TP-247) was also monitored. Moreover, the implementation of the most efficient technologies towards the removal of abacavir in different matrices such as wastewater effluent and leachate was also assessed, revealing that the organic matter present or the inorganic constituents can retard the whole process. Four major transformation products were detected, and their time-evolution profiles were recorded in all studied matrices, revealing that different transformation pathways dominate in each matrix. Finally, the prediction of the toxicity of the major TPs employing ECOSAR software was conducted and showed that only hydroxylation can play a detoxification role in the treated solution.

Do poly(lactic acid) microplastics instigate a threat? A perception for their dynamic towards environmental pollution and toxicity.

Fears concerning microplastics (MPs) environmental fate and persistence are progressively expanding on a global basis, with the emphasis given to manufacturing bioplastics for substituting petro-derived plastics extensively growing. Among them, poly(lactic acid) (PLA) holds a pioneering role towards the replacement of conventional polymeric materials, owing to its multifunctional properties, enclosing superior mechanical properties, low cost, renewability, great biocompatibility, transparency, and thermoplasticity launching many fields of application. Due to the wide applicability of PLA in several sectors of everyday life, its waste to be released into the environment is expected to follow a growing tendency during the upcoming years. Even though PLA is a biodegradable polyester, it actually degrades under specific composting environments, including a rich oxygen environment with high temperatures (58-80 °C), high humidity (>60% moisture) as well as the presence of micro-organisms (thermophilic bacteria). Additionally, in various studies it has been implied that PLA displays slower degradation performance when found in blends with other conventional polymers, underlining the unspecified effects on PLA degradation profile, keeping thus the information about PLA degradation from a blur standpoint. Therefore, a deepened understanding of the fate and dynamic effects of PLA MPs is of primary importance. Nevertheless, the current examination of the effects of PLA MPs in terms of sorption capacities and toxicity is so far limited and broadly unexplored since the current scientific emphasis has been merely centered on the conventional MPs' behavior. In this light, the present review provides an inclusive overview of the ongoing research of poly(lactic acid) in the framework of microplastics' pollution, while the future trends and missing points in this context are highlighted.

Overarching issues on relevant pesticide transformation products in the aquatic environment: A review.

The intensification of agricultural production during the last decades has forced the rapid increase in the use of pesticides that finally end up in the aquatic environment. Albeit well-documented, pesticides continue to raise researchers' attention, because of their potential adverse impacts on the environment and, inevitably, humans. Once entering the aquatic bodies, pesticides undergo biotic and abiotic processes, resulting in transformation products (TPs) that sometimes are even more toxic than the parent compounds. A substantial shift of the scientific interest in the TPs of pesticides has been observed since their environmental fate, occurrence and toxicity is still in its formative stage. In an ongoing effort to expand the existing knowledge on the topic, several interesting works have been performed mostly in European countries, such as France, Germany, Italy, Switzerland, Greece, and Spain that counts the highest number of relevant publications. Pesticide TPs have been also studied to a lesser extent in Asia, North and South America. To this end, the main objective of this review is to delineate the global occurrence, fate, toxicity as well as the analytical challenges related to pesticide TPs in surface, ground, and wastewaters, with the view to contribute to a better understanding of the environmental problems related with TPs formation. The concentration levels of the TPs, ranging from the low ng/L to high µg/L scale and distributed worldwide. Ultimately, an attempt to predict the acute and chronic toxicity of TPs has been carried out with the aid of an in-silico approach based on ECOSAR, revealing increased chronic toxicity for the majority of the identified TPs, despite the change they underwent, while a small portion of them presented serious acute toxicity values.

Assessment of a wide array of organic micropollutants of emerging concern in wastewater treatment plants in Greece: Occurrence, removals, mass loading and potential risks.

Exploring the contamination profile of multi-class emerging contaminants (ECs) in wastewater is highly desirable. To this end, the occurrence, removal, mass loading and risks associated with a large panel of pharmaceuticals and personal care products, illicit drugs, perfluorinated compounds and organophosphate flame retardants in two wastewater treatment plants (WWTPs) in the region of Thessaloniki (Greece) after a survey is illustrated. Influent and effluent wastewaters were submitted to solid phase extraction on Oasis HLB cartridges, followed by ultra-high-performance liquid chromatography Orbitrap high-resolution mass spectrometry (UHPLC-Orbitrap MS). Influent concentrations in both WWTPs were notably higher than effluent, with caffeine, acetaminophen, irbesartan and valsartan being the most ubiquitous compounds, exhibiting elevated concentrations. Average effluent concentrations ranged from below the method quantification limits (80% in both WWTPs, allowing the correlation between logKow and removals. Interesting trends for the illicit drugs were revealed by means of mass loading estimation, as in the case of benzoylecgonine (71.6 mg/day/1000 inhabitants). Ecotoxicological risk assessment was evaluated for both single components and mixture, using three approaches: risk quotient (RQ), risk quotient considering frequency (RQf) and toxic units (TU). Irbesartan and telmisartan posed a high risk in all trophic levels, while fish was the most sensitive taxa for diclofenac. This work aspires to intensify the surveillance programs for the receiving water bodies, as well as to motivate the investigation of toxicity to non-target organisms.

Microplastics in the environment: Sampling, pretreatment, analysis and occurrence based on current and newly-exploited chromatographic approaches.

The omnipresent character of microplastics (MPs) in environmental matrices, organisms and products has recently posed the need of their qualitative as well as quantitative analysis imperative, in order to provide data about their abundance and specification of polymer types in several substrates. In this framework, current and emerging approaches based on the chromatographic separation are of increased relevance in the field of MPs analysis and possess a large number of merits, since most of them are applicable in various complex matrices, sensitive and ideal for the detection of small-sized particles, whereas the common absence of any special pre-treatment step before analysis should also be highlighted. Αnalytical pyrolysis coupled with gas chromatography mass spectrometry (GC-MS) has recently gained ground as a powerful means to deliver information on MPs composition and degradation after their release into environment. Several instrumentations and trends in the area of analytical pyrolysis are thoroughly described within this review, while newly-exploited chromatographic methods in the field of MPs analysis, including Liquid Chromatography (LC) and Gel Permeation Chromatography (GPC) in this line are also investigated. The present review fills the gap of standardization concerning sampling, pre-treatment and chromatographic approaches and gathers all the available methodologies applied inside this area in accordance with the studied substrate, with the most examined environmental matrices being the solid one. After investigating the various works, some development options arise and it appears that chromatographic approaches should focus on improved extraction processes in terms of MPs isolation, since it is a crucial part in plastic items monitoring and is commonly depended on the polymer type and matrix. Special attention is given on the potential of chromatographic techniques for microplastics identification as well as quantification by confirming the current research status and knowledge gaps and highlighting some of the recent trends in this field.

Sample preparation optimization by central composite design for multi class determination of 172 emerging contaminants in wastewaters and tap water using liquid chromatography high-resolution mass spectrometry.

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.

Exploring the phototransformation and assessing the in vitro and in silico toxicity of a mixture of pharmaceuticals susceptible to photolysis.

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.

New insights into transformation pathways of a mixture of cytostatic drugs using Polyester-TiO2 films: Identification of intermediates and toxicity assessment.

The photocatalytic activity of two bio-based polymer photocatalysts [poly(ethylene terephthalate)-TiO2 (PET-TiO2) and poly(L-lactic acid)-graphene oxide-TiO2 (PLLA-GO-TiO2)] 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-TiO2. 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.

Antiviral drugs in aquatic environment and wastewater treatment plants: A review on occurrence, fate, removal and ecotoxicity.

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.

Removal of antibiotics in aqueous media by using new synthesized bio-based poly(ethylene terephthalate)-TiO2 photocatalysts.

Recently the synthesis and application of bio-based composite materials, which contain polymeric and inorganic units such as TiO2, has gained much attention in the field of water/wastewater treatment, due to their better (and more practical) performance parameters. In the present study, recycled poly(ethylene terephthalate) (PET) has been used and evaluated as supporting polymer for Aeroxide P25 TiO2 immobilization. PET-TiO2 composite films were synthesized at different TiO2 content (10%, 30% and 47% TiO2) and characterized with different techniques such as X-ray Powder Diffraction (XRD), Thermogravimetric analysis (TGA), Differential scanning calorimetry (DSC), Scanning electron microscopy (SEM), etc. The photocatalytic activity of the new (synthesized) bio-based TiO2 composite films was investigated under simulated solar irradiation for the degradation of a mixture of antibiotic pharmaceuticals (Isoniazid, Metronizadole, Sulfadiazine, Sulfamethoxazole, Trimethoprim, Norfloxacin, Moxifloxacin and Lincomycin). The immobilization of TiO2 was successful in all cases and by increasing the photocatalyst concentration results in higher photocatalytic efficiencies. The new composite films were tested two times to assess their reusability, which found to be better for PET-10%-TiO2 composite films; therefore the latter has been used for further investigation thus exhibiting good stability even after five cycles. The results showed that PET-10%-TiO2 was efficient in degrading the antibiotic mixture in water and in wastewater matrix.

Occurrence and removal of transformation products of PPCPs and illicit drugs in wastewaters: a review.

Pharmaceuticals and personal care products (PPCPs) along with illicit drugs (IDs) are newly recognized classes of environmental pollutants and are receiving considerable attention because of their environmental impacts: frequent occurrence, persistence and risk to aquatic life and humans. However, relatively little information is often available with regard to their possible biotic and abiotic transformation products (TPs). This lack of knowledge has resulted in a substantial amount of ongoing effort to develop methods and approaches that would assess their occurrence, degradability potential elimination mechanisms and efficiencies in sewage treatment plants as well as environmental and human health risks. In this article, an extensive literature survey was performed in order to present the current stage of knowledge and progress made in the occurrence of TPs of PPCPs and IDs in raw and treated wastewaters. Apart from the TPs resulting from structural transformations of the parent compound in the aquatic environment or in technological treatment facilities (e.g. sewage and drinking water treatment plants), free metabolites and drug conjugates formed during human metabolism have also been included in this review as they are also released into the aquatic environment through wastewaters. Their concentration levels were reported in influents and effluents of WWTPs, hospital effluents and their removals in the treatment plants were discussed. Finally, information on the toxicity of TPs has been compiled when available.

Synthesis of stable aromatic and heteroaromatic sulfonyl-amidoximes and evaluation of their antioxidant and lipid peroxidation activity.

We describe herein the synthesis of stable aromatic and heteroaromatic sulfonyl-amidoximes, from the reaction of amidoximes with the corresponding sulfonyl chlorides, in low to excellent yields. Evaluation of their antioxidant activity has shown that 17 out of 28 compounds highly compete DMSO for hydroxyl radicals, while five of them inhibit lipid peroxidation. Combining the reducing and anti-lipid peroxidation ability it seems that compounds 13 and 31 could be used as lead molecules.