Profile and Different Approaches for Size Characterization of Microplastics in Drinking Water from the Lisbon Water Supply System.

Microplastics (MPs) contribute to the overall pollution of water sources, affecting not only aquatic ecosystems but also water for human consumption (WHC). Currently, there needs to be a global consensus on safe levels of microplastics in WHC, which will allow regulatory efforts and risk assessments to be carried out. Therefore, this study aims to characterize MP particles in WHC of the Lisbon water supply system (LWSS) and compare two approaches to quantify these particles (length and width of the particles, and the area equivalent diameter (AED) of the particles). The quantification of MP particles was made via micro-FTIR (Fourier Transform Infrared Spectroscopy) on transmission mode after water filtration on 5 µm silicon filters. Thirty-eight WHC samples from the LWSS showed MPs up to 836 MPs/L, with an average value of 196 MPs/L. The most representative polymer was polyethylene (PE, 77.2%). The other eight polymers were also quantified. The length and width of MPs ranged between 84 µm and 41 µm, respectively. The AED of MPs ranged between 24 µm and 405 µm. The MP dimensions of both approaches can differ significantly.

Understanding the bioaccumulation of pharmaceutical active compounds by clams Ruditapes decussatus exposed to a UWWTP discharge.

Twenty-four pharmaceutical active compounds (PhACs) were evaluated in the soft tissues of clams Ruditappes decussatus exposed along a 1.5-km dispersal gradient of the treated effluent from an urban wastewater treatment plant discharging in Ria Formosa, and compared with those in the marine waters and discharged effluents. The clams were exposed for 1 month, in June-July 2016, 2017 and 2018. PhACs were quantified by high performance liquid chromatography coupled to tandem mass spectrometry after the quick, easy, cheap, effective, rugged and safe (QuEChERS) method (clams) or solid-phase extraction (water samples). The most representative PhACs in the effluents and receiving waters (regardless of the tidal dilution effect) were diclofenac, carbamazepine and caffeine (on average ≤ 2 µg/L) and only caffeine exhibited significant inter-annual differences, with higher values in 2017. In turn, the most bioaccumulated PhACs in clams were caffeine (0.54-27 ng/g wet weight, significantly higher in 2016) and acetaminophen (0.37-3.7 ng/g wet weight, significant lower in 2016). A multivariate principal component analysis showed (i) PhAC bioaccumulation primarily depended on biotic factors (clams length and weight), (ii) PhAC physicochemical properties Log Kow, pKa and water solubility interplaying with water abiotic variables were more relevant for explaining data variability in water than the physical dilution/tidal mixing, (iii) this process, reflected by the salinity gradient, had a tertiary role in data variation, responsible for spatial discrimination of marine waters. This study provides a better understanding of PhACs bioaccumulation by clams Ruditapes decussatus in real environmental conditions, under the influence of urban treated effluent dispersal in Ria Formosa coastal lagoon, a major producer of bivalves, ultimately disentangling key factors of PhAC bioaccumulation.

Chlorination and oxidation of sulfonamides by free chlorine: Identification and behaviour of reaction products by UPLC-MS/MS.

Sulfonamides (SAs) are one class of the most widely used antibiotics around the world and have been frequently detected in municipal wastewater and surface water in recent years. Their transformation in waste water treatment plants (WWTP) and in water treatment plants (WTP), as well as, their fate and transport in the aquatic environment are of concern. The reaction of six sulfonamides (sulfamethoxazole, sulfapyridine, sulfamethazine, sulfamerazine, sulfathiazole and sulfadiazine) with free chlorine was investigated at a laboratory scale in order to identify the main chlorination by-products. A previously validated method, liquid chromatography/mass spectrometry, was used to analyse SAs and their chlorination by-products. At room temperature, pH 6-7, reaction times of up to 2 h and an initial concentration of 2 mg/L of free chlorine, the majority of SAs suffered degradation of around 65%, with the exception of sulfamethoxazole and sulfathiazole (20%). The main reaction of SAs with free chlorine occurred in the first minute.

Validation of an FT-IR microscopy method for the monitorization of microplastics in water for human consumption in Portugal: Lisbon case study.

The growing anthropogenic contamination of natural water by microplastics (MPs) confirms the urgent need to preserve this precious resource. MPs are part of the group of contaminants of emerging concern, and the occurrence studies in surface water and water for human consumption (WHC) are mandatory for environmental and human health risk assessment. This study aims to optimize and validate a Fourier transform infrared spectroscopy method coupled with optical microscopy (micro-FTIR) in transmission mode to monitor MPs in WHC. Water sample (250 mL; without sample pre-treatment) was filtered through 5 µm silicon filters. The infrared spectra identification was performed by OMNIC mathematical correlation, using various spectra libraries for polymers (including the in-house IR spectra library), a background reading on a clean silicon filter, and an aperture of 100 µm × 100 µm. The validated method showed good accuracy, with an average recovery for representative polymers of 91%, a relative standard deviation of 13%, and a reporting limit (RL) of 44 MPs/L. Sixty WHC samples from the Lisbon water supply system showed MPs ranging from 0 (< RL) to 934 MPs/L, with an average value of 309 MPs/L. The most representative polymers were polyethylene (PE, 76.8%), polyethylene terephthalate (PET, 6.9%), polypropylene (PP, 6%), polystyrene (PS, 4%), and polyamide (PA,4%). In terms of size, the microplastic particles had an average length and width of 76 µm and 39 µm, respectively.

Physicochemical, Nutritional, and Medicinal Properties of Opuntia ficus-indica (L.) Mill. and Its Main Agro-Industrial Use: A Review.

The cactus, Opuntia ficus-indica (L.) Mill. (OFI) belongs to the Cactaceae family, which contains about 130 genera and nearly 1600 species. This review aims to evaluate this plant from several perspectives, namely, botanic, physicochemical, nutritional, and medicinal properties, as well as agro-industrial use. The botanical aspects and morphological characteristics of OFI enable genetic variability, ecological adaptation, and broad geographic distribution. Due to its physicochemical and nutritional composition, it has several medicinal properties appropriate (or suitable) for several industries, such as pharmaceutical, food, and cosmetics. Its fruit, the prickly pear (PP), has potential agro-industrial expansion through the application of different conservation and transformation methods, making it possible to obtain a variety of products. The PP is a source of several nutrients and is an effective system to produce varied foods, which have several advantages from a nutritional, sensory, economic, and shelf-life point of view.

Water quality and adverse health effects on the hemodialysis patients: An overview.

Hemodialysis is considered a treatment of choice for patients with renal failure worldwide, allowing the replacement of some kidney functions by diffusion and ultrafiltration processes. Over 4 million people require some form of renal replacement therapy, with hemodialysis being the most common. During the procedure, contaminants in the water and the resulting dialysate may pass into the patient's blood and lead to toxicity. Thus, the quality of the associated dialysis solutions is a critical issue. Accordingly, the discussion of the importance of a dialysis water delivery system controlled by current standards and recommendations, with efficient monitoring methods, disinfection systems, and chemical and microbiological analysis, is crucial for improving the health outcomes of these patients. The importance of treatment, monitoring, and regulation is emphasized by presenting several case studies concerning the contamination of hemodialysis water and the adverse effects on the respective patients.

Functionalisation of Electrospun Cellulose Acetate Membranes with PEDOT and PPy for Electronic Controlled Drug Release.

Controlled drug release via electrical stimulation from drug-impregnated fibres was studied using electrospun cellulose acetate (CA) membranes and encapsulated ibuprofen (IBU). This research outlines the influence of polypyrrole (PPy) and poly(3,4-ethylenedioxythiophene) (PEDOT)-functionalised CA membranes and their suitability for dermal electronic-controlled drug release. Micro Raman analysis confirmed polymer functionalisation of CA membranes and drug incorporation. Scanning electron microscopy (SEM) images evidenced the presence of PPy and PEDOT coatings. The kinetic of drug release was analysed, and the passive and active release was compared. In the proposed systems, the drug release is controlled by very low electrical potentials. A potential of -0.3 V applied to membranes showed the ibuprofen retention, and a positive potential of +0.3 V, +0.5 V, or +0.8 V, depending on the conductive polymer and membrane configuration, enhanced the drug release. A small adhesive patch was constructed to validate this system for cutaneous application and verified an "ON/OFF" ibuprofen release pattern from membranes.

Single Mutations in Cytochrome P450 Oxidoreductase Can Alter the Specificity of Human Cytochrome P450 1A2-Mediated Caffeine Metabolism.

A unique cytochrome P450 (CYP) oxidoreductase (CPR) sustains activities of human microsomal CYPs. Its function requires toggling between a closed conformation enabling electron transfers from NADPH to FAD and then FMN cofactors and open conformations forming complexes and transferring electrons to CYPs. We previously demonstrated that distinct features of the hinge region linking the FAD and FMN domain (FD) modulate conformer poses and their interactions with CYPs. Specific FD residues contribute in a CYP isoform-dependent manner to the recognition and electron transfer mechanisms that are additionally modulated by the structure of CYP-bound substrate. To obtain insights into the underlying mechanisms, we analyzed how hinge region and FD mutations influence CYP1A2-mediated caffeine metabolism. Activities, metabolite profiles, regiospecificity and coupling efficiencies were evaluated in regard to the structural features and molecular dynamics of complexes bearing alternate substrate poses at the CYP active site. Studies reveal that FD variants not only modulate CYP activities but surprisingly the regiospecificity of reactions. Computational approaches evidenced that the considered mutations are generally in close contact with residues at the FD-CYP interface, exhibiting induced fits during complexation and modified dynamics depending on caffeine presence and orientation. It was concluded that dynamic coupling between FD mutations, the complex interface and CYP active site exist consistently with the observed regiospecific alterations.

Different approaches for estimation of the expanded uncertainty of an analytical method developed for determining pharmaceutical active compounds in wastewater using solid-phase extraction and a liquid chromatography coupled with tandem mass spectrometry method.

Although the evaluation of the uncertainty of an analytical method is a mandatory step in the method's validation, its applicability to the monitoring of trace compounds in complex samples is not simple, nor is it part of the routine of most laboratories, namely those dedicated to research. This manuscript focuses on the full validation of an analytical procedure for determining trace concentrations of twenty-four pharmaceutical active compounds (PhACs) in wastewaters using solid-phase extraction (SPE) and ultra-high performance liquid chromatography coupled with tandem mass spectrometry (UHPLC-MS/MS). The method optimization was performed on different wastewater matrices, namely influents and final effluents from two distinct wastewater treatment plants (WWTPs). Matrix effects and extraction efficiency (absolute recovery) of the developed method were determined. Validation was performed to obtain the method's linearity/working range, precision, trueness, method detection limits (MDLs) and method quantification limits (MQLs). The expanded uncertainty of the data obtained was estimated according to the requirements of international procedures dedicated to the expression of uncertainty. Different approaches for the estimation of uncertainty were applied. The validated method was used in the analysis of target PhACs in wastewater samples collected at two WWTPs. The obtained results facilitated the introduction of a validated method for routine measurement of PhACs in wastewater samples and allowed method accreditation by the competent national authority.

Biomarker Responses of the Clam Ruditapes decussatus Exposed to a Complex Mixture of Environmental Stressors under the Influence of an Urban Wastewater-Treatment Plant.

To evaluate the potential impact of an urban wastewater-treatment plant on Ria Formosa coastal lagoon, a sentinel species, the clam Ruditapes decussatus, was exposed along a gradient of the effluent's dispersal for 1 mo. Three exposure sites were selected to study the responses of 3 biomarkers: electron transport system, acetylcholinesterase, and lipid peroxidation. As complementary data, morphometric measurements, condition index, and lipid and protein content were considered together with in situ physicochemical characterization of the sites (temperature, salinity, pH, and dissolved oxygen). Electron transport system activity levels were between 35.7 and 50.5 nmol O2 /min g protein, acetylcholinesterase activity levels ranged from 2.6 to 3.8 nmol/min g protein, and lipid peroxidation ranged from 174.7 to 246.4 nmol malondialdehyde/g protein. The exposure sites shaped the response not only of biomarkers but also of "health" parameters (protein, lipids, and condition index). Lipid peroxidation was the most responsive biomarker also associated with electron transport system, especially at the closest site to the urban wastewater-treatment plant. Because of the presence of complex mixtures of contaminants in urban effluents, biomarker responses can provide valuable information in environmental assessment. However, it is vital to identify all biological and ecological factors induced by the natural life cycle of clams. Abiotic factors can mask or overlap the response of biomarkers and should be considered in a multibiomarker approach. Environ Toxicol Chem 2021;40:272-283. © 2020 SETAC.

Optimization and in-house validation of the TDA-AAS method for mercury control in water and wastewater treatment plant sludges.

The thermal decomposition, amalgamation, and atomic absorption spectrometry (TDA-AAS) method was validated for mercury (Hg) determination in sludge samples. A linear range was obtained from 30 to 200 ng. The TDA-AAS method provides a limit of quantification (LOQ) well below the legal maximum admitted concentration of Hg in sludge samples, which makes it suitable to measure its concentrations at the imposed legal limits, and for monitoring studies of Hg trace levels in sludge samples. Repeatability and within-laboratory reproducibility of the method were good with relative standard deviations lower than 6%. Expanded uncertainty, estimated using a top-down approach with the data obtained from accuracy and precision studies, was 18% for a coverage factor k = 2. Mercury concentration in sludge samples from water treatment plants was below the LOQ (0.33 mg Hg per kg dw) and in wastewater treatment plants was well below the legal limit for their reuse in agriculture (16 mg Hg per kg dw).

Experimental and statistical validation of SPME-GC-MS analysis of phenol and chlorophenols in raw and treated water.

A procedure based on solid-phase microextraction (SPME) and gas chromatography coupled with mass spectrometry (GC-MS) was developed and validated in order to analyse 10 phenols in water samples. The optimised conditions were obtained using polyacrylate fibre (PA), 20ml of sample volume, 10% NaCl, pH 4.0 and direct extraction at 35 degrees C and 1000rpm, for 40min. The linear range and quantification limits for these compounds by SPME-GC-MS were defined. An evaluation of the main uncertainty sources of this method is included, which allows expanded uncertainties in the 9.4-35% range for the majority of the compounds. The main source of uncertainty is associated with matrix effects. The validated method is suitable for monitoring the production and distribution of potable water and was used, in field trials, for the analysis of samples from main intakes of water (surface or underground) and from water supply system of a large area (Lisbon and neighbour municipalities).

Chemical and biochemical characterization and in vivo safety evaluation of pharmaceuticals in drinking water.

The water constituents that are currently subject to legal control are only a small fraction of the vast number of chemical substances and microorganisms that may occur in both the environment and water resources. The main objective of the present study was to study the health impact resulting from exposure to a mixture of pharmaceuticals that have been detected in tap water at low doses. Analyses of atenolol, caffeine, erythromycin, carbamazepine, and their metabolites in blood, urine, feces, fat tissue, liver, and kidney after exposure to a mixture of these pharmaceuticals in treated drinking water were performed. The effects of this exposure were assessed in rats by measuring biochemical markers of organ injury or dysfunction. Simultaneously, the selected pharmaceuticals were also quantified in both physiological fluids and organ homogenates by liquid chromatography-tandem mass spectrometry (performed in multiple reaction monitoring mode and full scan mode). Following exposure of rats to a concentration of a pharmaceutical which was 10 times higher than the concentration known to be present in tap water, trace levels of some pharmaceuticals and their metabolites were detected in biological samples. This exposure did, however, not lead to significant organ injury or dysfunction. Thus, the authors report an experimental model that can be used to characterize the safety profile of pharmaceuticals in treated drinking water using a multiorgan toxicity approach. Environ Toxicol Chem 2016;35:2674-2682. © 2016 SETAC.

Occurrence of pharmaceuticals in a water supply system and related human health risk assessment.

A monitoring study of 31 pharmaceuticals along Lisbon's drinking water supply system was implemented, which comprised the analysis of 250 samples including raw water (surface water and groundwater), and drinking water. Of the 31 pharmaceutical compounds, only sixteen were quantified in the analyzed samples, with levels ranging from 0.005 to 46 ng/L in raw water samples and 0.09-46 ng/L in drinking water samples. The human health risk assessment performed showed that appreciable risks to the consumer's health arising from exposure to trace levels of pharmaceuticals in drinking water are extremely unlikely, as RQs values were all below 0.001. Also, pharmaceuticals were selected as indicators to be used as a tool to control the quality of raw water and the treatment efficiency in the drinking water treatment plants.

Chemical composition of green tea (Camellia sinensis) infusions commercialized in Portugal.

To evaluate the potential benefits and risks associated with tea consumption it is important to identify the constituents of this beverage. Levels of some minerals, caffeine and catechins in green tea samples commercialized in Portugal were evaluated. Potassium is the metal present in larger amount (92-151 mg/l). The content of sodium, calcium, fluoride, aluminium, manganese and iron were 35-69, 1.9-3.5, 0.80-2.0, 1.0-2.2, 0.52-1.9, 0.020-0.128 mg/l, respectively. Chromium and selenium were not detected. The resulting data showed considerable variability in catechins content. The levels of epigallocatechin gallate (EGCG) ranged from 117 to 442 mg/l, epicatechin 3-gallate (EGC) from 203 to 471 mg/l, epigallocatechin (ECG) from 16.9 to 150 mg/l, epicatechin (EC) from 25 to 81 mg/l and catechin (C) from 9.03 to 115 mg/l. Caffeine contents in the green tea infusions studied were between 141-338 mg/l. Green tea infusions provide significant amounts of catechins and could be an important source of some minerals.

Analysis of BTEX and other substituted benzenes in water using headspace SPME-GC-FID: method validation.

The analysis of BTEX and other substituted benzenes in water samples using solid phase microextraction (SPME) and quantification by gas chromatography with flame ionization detection (GC-FID) was validated. The best analytical conditions were obtained using PDMS/DVB/CAR fibre using headspace extraction (HS-SPME) at 50 [degree]C for 20 min without stirring. The linear range for each compound by HS-SPME with GC/FID was defined. The detection limits for these compounds obtained with PDMS/DVB/CAR fibre and GC/FID were: benzene (15 ng L(-1)), toluene (160 ng L(-1)), monochlorobenzene (54 ng L(-1)), ethylbenzene (32 ng L(-1)), m-xylene (56 ng L(-1)), p-xylene (69 ng L(-1)), styrene (35 ng L(-1)), o-xylene (42 ng L(-1)), m-dichlorobenzene (180 ng L(-1)), p-dichlorobenzene (230 ng L(-1)), o-dichlorobenzene (250 ng L(-1)) and trichlorobenzene (260 ng L(-1)). This headspace SPME-GC-FID method was compared with a previously validated method of analysis using closed-loop-stripping analysis (CLSA). The headspace SPME-GC-FID method is suitable for monitoring the production and distribution of potable water and was used, in field trials, for the analysis of samples from main intakes of water (surface or underground) and from the water supply system of a large area (Lisbon and neighbouring municipalities).