Search

Abstract Carbon xerogels (CXs) were synthesized by polycondensation of resorcinol and formaldehyde, followed by thermal annealing, and subjected to hydrothermal oxidation. Solid-phase extraction (SPE) cartridges were filled with CXs and tested for extraction of metaflumizone and other seven environmental micropollutants (acetamiprid, atrazine, isoproturon, methiocarb, carbamazepine, diclofenac, and perfluorooctanesulfonic acid) before chromatographic analysis. The recoveries obtained with the pristine CX were low for most analytes, except for metaflumizone (69 ± 5%). Moreover, it was concluded that the adsorption/desorption process of the micropollutants performed better on CXs with a less acidic surface (i.e., pristine CX). Thus, cartridges were prepared with pristine CX and multi-walled carbon nanotubes (MWCNTs) in a multi-layer configuration. This reusable cartridge was able to simultaneously extract the eight micropollutants and was used to validate an analytical methodology based on SPE followed by ultra-high performance liquid chromatography-tandem mass spectrometry. A widespread occurrence of 6/8 target compounds was observed in surface water collected in rivers supplying three drinking water treatment plants and in the resulting drinking water at the endpoint of each distribution system. Therefore, the first study employing CXs and MWCNTs as sorbent in multi-layer SPE cartridges is herein reported as a proof of concept for determination of multi-class water micropollutants.

Abstract Pristine and functionalized multi-walled carbon nanotubes (MWCNTs) were investigated as adsorbent materials inside solid-phase extraction (SPE) cartridges for extraction and preconcentration of 8 EU-relevant organic micropollutants (with different pKa and polarity) before chromatographic analysis of surface water. The recoveries obtained were > 60% for 5/8 target pollutants (acetamiprid, atrazine, carbamazepine, diclofenac, and isoproturon) using a low amount of this reusable adsorbent (50 mg) and an eco-friendly solvent (ethanol) for both conditioning and elution steps. The introduction of oxygenated surface groups in the carbon nanotubes by using a controlled HNO3 hydrothermal oxidation method, considerably improved the recoveries obtained for PFOS (perfluorooctanesulfonic acid) and methiocarb, which was ascribed to the hydrogen bond adsorption mechanism, but decreased those observed for the pesticide acetamiprid and for two pharmaceuticals (carbamazepine and diclofenac), suggesting π–π dispersive interactions. Moreover, a good correlation was found between the recovery obtained for methiocarb and the amount of oxygenated surface groups on functionalized MWCNTs, which was mainly attributed to the increase of phenols and carbonyl and quinone groups. Thus, the HNO3 hydrothermal oxidation method can be used to finely tune the surface chemistry (and texture) of MWCNTs according to the specific micropollutants to be extracted and quantified in real water samples.

Eighteen per-and polyfluoroalkyl substances (PFASs) were investigated in surface waters of four river basins in Portugal (Ave, Leça, Antuã, and Cértima) during the dry and wet seasons. All sampling sites showed contamination in at least one of the seasons. In the dry season, perfluorooctanoate acid (PFOA) and perfluoro-octane sulfonate (PFOS), were the most frequent PFASs, while during the wet season these were PFOA and perfluobutane-sulfonic acid (PFBS). Compounds detected at higher concentrations were PFOS (22.6 ng L−1) and perfluoro-butanoic acid (PFBA) (22.6 ng L−1) in the dry and wet seasons, respectively. Moreover, the prospective environmental risks of PFASs, detected at higher concentrations, were evaluated based on the Risk Quotient (RQ) classification, which comprises acute and chronic toxicity. The results show that the RQ values of eight out of the nine PFASs were below 0.01, indicating low risk to organisms at different trophic levels in the four rivers in both seasons, wet and dry. Nevertheless, in the specific case of perfluoro-tetradecanoic acid (PFTeA), the RQ values calculated exceeded 1 for fish (96 h) and daphnids (48 h), indicating a high risk for these organisms. Furthermore, the RQ values were higher than 0.1, indicating a medium risk for fish, daphnids and green algae (96 h).

Population in cities is growing worldwide, which puts the systems that offer basic services to citizens under pressure. Among these systems, the Municipal Solid Waste Management System (MSWMS) is also affected. Waste collection and transportation is the first task in an MSWMS, carried out traditionally in most cases. This approach leads to inefficient resource and time expense since routes are prescheduled or defined upon drivers’ choices. The waste collection is recognized as an NP-hard problem that can be modeled as a Capacitated Waste Collection Problem (CWCP). Despite the good quality of works currently available in the literature, the execution time of algorithms is often forgotten, and faster algorithms are required to increase the feasibility of the solutions found. In this paper, we show the performance of the open-source Google OR-Tools to solve the CWCP in Bragança, Portugal (inland city). The three metaheuristics available in this tool were able to reduce significantly the cost associated with waste collection in less than 2 s of execution time. The result obtained in this work proves the applicability of the OR-Tools to be explored for waste collection problems considering bigger systems. Furthermore, the fast response can be useful for developing new platforms for dynamic vehicle routing problems that represent scenarios closer to the real one. We anticipate the proven efficacy of OR-Tools to solve CWCP as the starting point of developments toward applying optimization algorithms to solve real and dynamic problems.

Abstract Graphyne (GY) and graphdiyne (GDY) have been employed in photocatalysis since 2012, presenting intriguing electronic and optical properties, such as high electron mobility and intrinsic bandgap due to their high π‐conjugated structures. Authors are reporting the enhanced photocatalytic efficiency of these carbon allotropes when combined with different metal oxides or other carbon materials. However, the synthesis of graphyne‐family members (GFMs) is still very recent, and not much is known about the true potential of these photocatalytic materials. In this review article, the implications of different synthesis routes on the structural features and photocatalytic properties of these materials are elucidated. The application of GFMs in the nicotinamide adenine dinucleotide (NADH) regeneration, hydrogen and oxygen evolution, and carbon dioxide reduction is discussed, as well as in the degradation of pollutants and bacteria inactivation in water and wastewater treatment.

Cytostatics are drugs used in cancer treatment, which pose serious risks to healthcare workers. Dermal absorption via surface contamination is the key exposure route; thus, rapid, reliable, and validated analytical methods for multicomponent detection are crucial to identify the exposure risk. A surface-wipe-sampling technique compatible with hospitals’ safety requirements (gauze, 1 mL isopropanol) and a fast and simple extraction method (1 mL acetonitrile, 20 min ultrasonic bath, evaporation, reconstitution in 200 µL acetonitrile), coupled with liquid chromatography–tandem mass spectrometry analysis, were developed. It allowed identification and quantification of 13 cytostatics on surfaces: cyclophosphamide, doxorubicin, etoposide, ifosfamide, paclitaxel, bicalutamide, capecitabine, cyproterone, flutamide, imatinib, megestrol, mycophenolate mofetil, prednisone. Good linearity, sensitivity, and precision were achieved (R2 > 0.997, IDLs < 4.0 pg/cm2, average CV 16%, respectively). Accuracy for four model surfaces (melamine-coated wood, phenolic compact, steel 304, steel 316) was acceptable (80 ± 12%), except for capecitabine and doxorubicin. Global uncertainty is below 35% for concentrations above 100 pg/cm2 (except for capecitabine and doxorubicin)—a guidance value for relevant contamination. Method application in a Portuguese university hospital (28 samples) identified the presence of seven cytostatics, at concentrations below 100 pg/cm2, except for three samples. The widespread presence of cyclophosphamide evinces the necessity to review implemented procedures.

A high-performance liquid chromatography (HPLC) method capable to detect 4-nitrophenol (4-NP) in aqueous solutions with concentration in the range 0.0495-118.8 mg L-1 was developed and validated under the typical criteria for in -house pre-validations. Accordingly, linearity was demonstrated through the Fisher’s exact probability test. Accuracy and precision were then assessed in three concentrationlevels over the linear range. The reproducibility of the catalytic wet peroxide oxidation (CWPO) of 4-NP was evaluated together with the analytical error of 4-NP determination in independent experiments. In this case, the sum of both contributions to error never reached 3%.Two multi-component HPLC methods were also developed for the determination of possible aromatic intermediates (hydroquinone, 1,4-benzoquinone, catechol, 4-nitrocatechol and phenol) and carboxylic acids (oxalic, formic, malic, malonic, acetic and maleic acids) resulting from the 4-NP degradation. The combination of these analytical methods already led to the proposal of an oxidation/mineralization mechanism for the CWPO of 4-NP.

The amount of applications associated with microfluidic devices is increasing since the introduction of Lab-on-a-chip devices in the 1990s, especially regarding biomedical and clinical fields. However, in order for this technology to leave the fundamental research and become a day-life technology (e.g., as point-of-care testing), it needs to be disposable and reasonably less expensive. Polymers, due to their several advantages, such as easier microfabrication and low-cost, fill these needs. Several methods are reported regarding microfabrication and, thus, the main aim of the present work is to provide an overview of the most relevant microfabrication techniques found in literature employing polymers, clarifying also the main advantages and disadvantages of each technique and especially considering their cost and time-consumption. Moreover, a future outlook of low-cost microfabrication techniques and standard methods is provided.

A simple tailor-made protocol to synthesize graphene-based magnetic nanoparticles (GbMNPs) for nanomedicine is herein reported. Different GbMNPs with very distinctive physicochemical and toxicological properties were synthesized by adjusting the number of carbon precursors in the coating of superparamagnetic iron oxide nanoparticles. In vitro tests show the ability to use these GbMNPs as intelligent and on-demand drug nanocarrier systems for drug delivery, exhibiting the following features: good colloidal stability, good loading capacity of the chemotherapeutic drug doxorubicin, high pH-controlled release of the encapsulated drug (targeting tumour acidic pH conditions), superparamagnetic behaviour and biocompatibility. Due to their combined properties (i.e., physicochemical, magnetic, and biocompatibility), GbMNPs show high potentiality to be combined with other biomedical techniques, such as magnetic hyperthermia, which can represent an enhancement in the treatment of cancer.