SPE-LC-MS/MS optimisation using response surface methodology for quantification of pharmaceuticals, pesticides and organic UV filters included in water protection guidelines.

The environmental concern about micropollutants (MPs) in aquatic environments has grown significantly in recent decades due to their widespread occurrence and potential risks to ecosystems and human health. Monitoring of MPs is crucial for understanding the status of aquatics systems, supporting risk assessments, developing elimination strategies, and informing regulatory decision-makers. However, due to the very low concentrations of MPs (usually ranging between ng L and μg L levels), their quantification requires highly sensitive and precise analytical methods.

Surface Wipe Sampling of Hazardous Medicinal Products: A European Interlaboratory Comparison Study.

Workplace monitoring of hazardous medicinal products (HMPs) using surface wipe sampling is becoming common practice in many European hospitals and pharmacies. However, no independent quality control is available to validate wiping procedures and analytical methods. This study aimed to conduct a Europe-wide interlaboratory comparison (ILC) program to independently and blindly assess laboratory performance and variability in HMP detection.

Tackling antineoplastic drugs' contamination in healthcare settings: New insights on surface cleaning approaches.

Effective decontamination of hospital surfaces is crucial to protect workers from antineoplastic drugs (ADs) since dermal absorption is the main exposure route to these hazardous medicinal products. Sampling after daily cleaning in oncologic settings from a tertiary hospital was initially performed and exhibited low contamination levels; however, cyclophosphamide was still found (up to 957 pg/cm) above the guidance value (100 pg/cm) in four locations, evidencing the need to properly assess and update the cleaning protocols. Then, cleaning efficiencies of six solutions and different protocols were evaluated (including, for the first time, four commercial cleaning solutions/disinfectants not designed specifically for AD removal) after deliberate contamination of three model surfaces with 13 pharmaceuticals: bicalutamide, capecitabine, cyclophosphamide, cyproterone, doxorubicin, etoposide, flutamide, ifosfamide, imatinib, megestrol, mycophenolate mofetil, paclitaxel, and prednisone.

Development and validation of a multicompound LLE-LC-MS/MS method for biomonitoring of hazardous medicinal products in urine of exposed workers.

Antineoplastic drugs are carcinogens, mutagens, or teratogenic substances, which can pose serious risks to professionals. Concerns about chronic exposure to these hazardous medicinal products (HMPs) have led to their prominence in the EU strategic framework on health and safety at work 2021-2027. To estimate and mitigate human exposure to HMPs, regular monitoring programs and, consequently, reliable, sensitive, multicomponent methods are crucial.

Occurrence of micropollutants in surface waters: Monitoring of Portuguese Lima and Douro River estuaries and interconnecting northwest coast.

This study monitored the occurrence of 34 MPs in 2 Portuguese estuaries and adjacent coastal area using solid-phase extraction and liquid chromatography-tandem mass spectrometry, covering: (i) an extensive monitoring study area; (ii) a multi-class group of organic MPs, including some outlined in European Union guidelines for water protection; (iii) a year-long monitoring campaign including different seasons; (iv) samples collected at both flood and ebb tide; and (v) samples taken from the water surface and bottom at each sampling point. Results showed that a specific group of compounds prevailed in the monitored areas, with concentrations depending on season, tide, and location. In general, the MPs found more frequently were isoproturon and perfluorooctanesulfonic acid, along with pharmaceuticals trimethoprim, acetaminophen, tramadol, diclofenac, and ketoprofen, which were mostly detected at higher concentrations.

Preliminary hazard assessment of a new nature-inspired antifouling (NIAF) agent.

A recently synthesized aminated 3,4-dioxygenated xanthone (Xantifoul2) was found to have promising antifouling (AF) effects against the settlement of the macrofouler Mytilus galloprovincialis larvae. Preliminary assessment indicated that Xantifoul2 has reduced ecotoxicological impacts: e.g.

Toxicity of butylone and its enantiomers to Daphnia magna and its degradation/toxicity potential using advanced oxidation technologies.

Butylone (BTL) is a chiral synthetic cathinone available as a racemate and reported as contaminant in wastewater effluents. However, there are no studies on its impact on ecosystems and possible enantioselectivity in ecotoxicity. This work aimed to evaluate: (i) the possible ecotoxicity of BTL as racemate or its isolated (R)- and (S)- enantiomers using Daphnia magna; and (ii) the efficiency of advanced oxidation technologies (AOTs) in the removal of BTL and reduction of toxic effects caused by wastewaters.

Spirulina-based carbon materials as adsorbents for drinking water taste and odor control: Removal efficiency and assessment of cyto-genotoxic effects.

The sensory quality of drinking water, and particularly its taste and odor (T&O) is a key determinant of consumer acceptability, as consumers evaluate water by their senses. Some of the conventional treatment processes to control compounds which impart unpleasant T&O have limitations because of their low efficiency and/or high costs. Therefore, there is a great need to develop an effective process for removing T&O compounds without secondary concerns.

Nanofiltration combined with ozone-based processes for the removal of antineoplastic drugs from wastewater effluents.

Over the past years, there has been an increasing concern about the occurrence of antineoplastic drugs in water bodies. The incomplete removal of these pharmaceuticals from wastewaters has been confirmed by several scientists, making it urgent to find a reliable technique or a combination of techniques capable to produce clean and safe water. In this work, the combination of nanofiltration and ozone (O)-based processes (NF + O, NF + O/HO and NF + O/HO/UVA) was studied aiming to produce clean water from wastewater treatment plant (WWTP) secondary effluents to be safely discharged into water bodies, reused in daily practices such as aquaculture activities or for recharging aquifers used as abstraction sources for drinking water production.

Per- and Poly-Fluoroalkyl Substances in Portuguese Rivers: Spatial-Temporal Monitoring.

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).

Antibiotics removal from aquaculture effluents by ozonation: chemical and toxicity descriptors.

Antibiotics are often applied in aquaculture to prevent fish diseases. These substances can cause disturbances on receiving waters, when not properly eliminated from the aquaculture effluents. In this work, ozone (O) was investigated as a possible oxidizing agent to remove fishery antibiotics from aquaculture effluents: florfenicol (FF), oxytetracycline (OTC), sulfadimethoxine (SDM), sulfamethoxazole (SMX), and trimethoprim (TMP).

Use of Chènevotte, a Valuable Co-Product of Industrial Hemp Fiber, as Adsorbent for Pollutant Removal. Part I: Chemical, Microscopic, Spectroscopic and Thermogravimetric Characterization of Raw and Modified Samples.

FINEAU (2021-2024) is a trans-disciplinary research project involving French, Serbian, Italian, Portuguese and Romanian colleagues, a French agricultural cooperative and two surface-treatment industries, intending to propose chènevotte, a co-product of the hemp industry, as an adsorbent for the removal of pollutants from polycontaminated wastewater. The first objective of FINEAU was to prepare and characterize chènevotte-based materials. In this study, the impact of water washing and treatments (KOH, NaCO and HPO) on the composition and structure of chènevotte (also called hemp shives) was evaluated using chemical analysis, X-ray diffraction (XRD) analysis, scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) spectroscopy, X-ray computed nanotomography (nano-CT), attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy, solid state NMR spectroscopy and thermogravimetric analysis.

Biosorbents from Plant Fibers of Hemp and Flax for Metal Removal: Comparison of Their Biosorption Properties.

Lignocellulosic fibers extracted from plants are considered an interesting raw material for environmentally friendly products with multiple applications. This work investigated the feasibility of using hemp- and flax-based materials in the form of felts as biosorbents for the removal of metals present in aqueous solutions. Biosorption of Al, Cd, Co, Cu, Mn, Ni and Zn from a single solution by the two lignocellulosic-based felts was examined using a batch mode.

Carbon xerogels combined with nanotubes as solid-phase extraction sorbent to determine metaflumizone and seven other surface and drinking water micropollutants.

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%).

Rethinking water treatment targets: Bacteria regrowth under unprovable conditions.

Ozonation is among the currently used technologies to remove chemical and biological contaminants from secondary treated urban wastewater (UWW). Despite its effectiveness on the abatement of organic micropollutants (OMPs) and disinfection, previous studies have shown that regrow of bacteria may occur upon storage of the ozonated UWW. This reactivation has been attributed to the high content of assimilable organic carbon after treatment.

UV-A activation of peroxymonosulfate for the removal of micropollutants from secondary treated wastewater.

The occurrence of micropollutants (MPs) in the aquatic environment poses a threat to the environment and to the human health. The application of sulfate radical-based advanced oxidation processes (SR-AOPs) to eliminate these contaminants has attracted attention in recent years. In this work, the simultaneous degradation of 20 multi-class MPs (classified into 5 main categories, namely antibiotics, beta-blockers, other pharmaceuticals, pesticides, and herbicides) was evaluated for the first time in secondary treated wastewater, by activating peroxymonosulfate (PMS) with UV-A radiation, without any pH adjustment or iron addition.

Solid-phase extraction cartridges with multi-walled carbon nanotubes and effect of the oxygen functionalities on the recovery efficiency of organic micropollutants.

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 HNO 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.

Toxicity Evaluation of TiO Nanoparticles on the 3D Skin Model: A Systematic Review.

Titanium dioxide nanoparticles (TiO NPs) are regularly used in sunscreens because of their photoprotective capacity. The advantage of using TiO on the nanometer scale is due to its transparency and better UV blocking efficiency. Due to the greater surface area/volume ratio, NPs become more (bio)-reactive giving rise to concerns about their potential toxicity.

Distribution of micropollutants in estuarine and sea water along the Portuguese coast.

This work provides the first spatial distribution report of micropollutants (MPs) in the entire Portuguese coast, comprising the ocean shore (sea water, SW) and whenever possible the nearest river discharging on it (estuarine water, EW). This surface water monitoring programme aimed to assess the spatial distribution of 37 MPs with a wide chemical nature, including some substances prioritized by the European Union Directive 39/2013/EU and contaminants of emerging concern targeted in the Watch List of Decisions 495/2015/EU and 840/2018/EU. The risk quotients were estimated in each sampling point for the detected MPs.

Quenchers in advanced oxidation technologies for analysis of micropollutants by liquid chromatography coupled to mass spectrometry: Sodium sulphite or catalase?

This work aimed to investigate the possible effect of 2 quenchers commonly used in HO-based advanced oxidation technologies (AOTs), i.e. catalase and sodium sulphite (NaSO), on the analytical signal of 3 detectors coupled to liquid chromatography (LC): tandem mass spectrometry (LC-MS/MS), fluorescence detection (LC-FD) and LC-diode array detection (LC-DAD).