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Carbamazepine is a widely used antiepileptic drug to control and treat a variety of disorders that is frequently detected in surface water, and in municipal and urban wastewater. This recalcitrant pollutant could be removed by alternative advanced oxidation technology such as heterogeneous photocatalysis. Ce-modified ZnO and Pd-modified TiO2 were synthesized by a microwave-assisted sol-gel method. According to the characterizations (Raman spectroscopy, UV-Vis diffuse reflectance spectroscopy, scanning electron microscopy, and X-ray photoelectron spectroscopy), a mixture of oxides was determined in both materials: CeO2/ZnO and PdO/TiO2. Photocatalytic degradation of carbamazepine in pure water under visible light (3 h) was assayed. The degradation percentage obtained with each catalyst was 80%, 53%, 20%, and 9% for ZnO, Ce-modified ZnO, TiO2, and Pd-modified TiO2, respectively. The leaching of Zn as a possible source of water contamination was tested, finding the lowest value for Ce-modified ZnO by adjusting the initial pH up to neutrality. Later, an environmentally relevant concentration of carbamazepine (228 µg L-1) was assayed, using local surface water (pH = 8.3). Despite the presence of other compounds in the real water matrix, after 5 h of photocatalysis, a 56% of degradation of the pharmaceutical and low leaching of Zn were achieved. The use of Ce-modified ZnO activated by visible light is a promising strategy for the abatement of pharmaceutical active compounds.

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The growing appearance of antibiotic-resistant strains of microorganisms originated from the widespread use and ubiquitous presence of such drugs is a major concern in the world. The development of methodologies able to detect such substances at low concentration in real water samples is mandatory to overcome this problem. Europium(III) is known to form complexes with tetracycline (TC) with photoluminescent characteristics useful for TC determination. In the present work, we synthesized for the first time carbon nanoparticles (CN) showing delayed photoluminescence using a Europium(III) doping synthesis. The new material (PCNEu) was characterized both morphologically and spectroscopically, showing an analytical photoluminescent signal in presence of TC, arising from the 5D0→7F2 transition of europium, one hundred times higher than that of the europium salt alone in presence of the antibiotic. This enhancement is a consequence of the amplifying effect exerted by nanoparticle structure itself, leading to an efficient synergistic "antenna effect" in the system PCNEu - TC. The analytical signal is affected both by pH and the nature of the buffer used, and it allows the detection of tetracycline in waters with a limit of detection of 2.18 nM and recoveries between 90 and 110%. The analytical performance of the developed methodology enables having lower limits of detection than other luminescent and chemiluminescent reported methodologies.

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This article presents the use of generalized additive model for location scale and shape (GAMLSS) in the qualitative and quantitative analysis of the relationships between environmental parameters and cyanotoxins in the tropical reservoirs of Colombia. The physicochemical parameters were evaluated on each of the cyanotoxins detected with levels high by ultra-high-performance liquid chromatography coupled to triple quadrupole mass spectrometry. The models showed a relation between cyanotoxins and the nutrients as soluble total Kjeldahl nitrogen (NTK), soluble phosphorus (soluble P), total phosphorus (total P), and nitrates (NO3-), among other nutrients that are necessary for the growth of organisms that produce toxins. This model confirms that the NTK and soluble P variables favor an increase in the concentration of MC-LR and MC-YR cyanotoxins in the Abreo Malpaso reservoir. The variables NO3- and dissolved O2 contribute to a higher concentration of MC-LR, MC-YR, and MC-ADRR cyanotoxins in the Peñol reservoir. Finally, the variable total P favors the increase in the concentration of MC-LR cyanotoxin and the variable dissolved O2 favors the increase in the concentration of cyanotoxin [D-Asp3, (E)-Dhb7] -MC-RR in the Playas reservoir.

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Contamination of natural water (NW) by emerging contaminants has been widely pointed out as one of the main challenges to ensure high-quality drinking water. Thus, the effectiveness of a solar-driven free chlorine advanced oxidation process simultaneously investigating the elimination of six organic microcontaminants (OMCs) and three bacteria from NW at a pilot-scale was evaluated in this study. Firstly, the solar/free chlorine process was studied at lab-scale using a solar simulator to evaluate the effect of free chlorine concentration (0.5-10 mg L-1) on OMC degradation and generation of toxic oxyanions (e.g., ClO3- ions). Thus, the best free chlorine concentration observed was applied for the simultaneous removal of OMCs and pathogens under natural solar light at pilot scale. At lab-scale, the solar/free chlorine (2.5 mg L-1) process achieved 80% of total degradation in 5 min (1.4 kJ L-1 of accumulative UV energy) with an oxidant consumption of 0.3 mg L-1 and without ClO3- generation. Similar results were attained under natural solar irradiation at a pilot-scale. For all bacteria strains, the legally required detection limit (DL = 1 CFU 100 mL-1) for reclaimed water reuse was attained in a short contact time. Still, more importantly, the solar/free chlorine (2.5 mg L-1) process effectively avoided the possible bacterial regrowth in the post-treated sample after six days. Finally, the combination of free chlorine with solar irradiation provided a simple and energy-efficient process for OMC and bacteria removal in NW at a pilot-scale.

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This study investigated for the first time the efficiency of an advanced oxidation process (AOP) zero valent iron/hydrogen peroxide (ZVI/H2O2) employing iron nails for the removal of Natural Organic Matter (NOM) from natural water of Regent's Park lake, London, UK. The low cost of nails and their easy separation from the water after the treatment make this AOP attractive for water utilities in low- and middle-income countries. The process was investigated as a pre-oxidation step for drinking water treatment. Results showed that UV254 removal in the natural water was lower than that of simulated water containing commercial humic acid (HA), indicating a matrix effect. Statistical analysis confirmed the maximum removal of dissolved organic carbon (DOC) in natural water depends on the initial pH (best at 4.5) and H2O2 dosage (best at 100% excess of stoichiometric dosage). DOC and UV254 removals under this operational condition were 51% and 89%, respectively. Molecular weight (MW) and specific UV absorbance (SUVA254) were significantly reduced to 74% and 78%, respectively. Formation of Chloroform THM in natural water sample after the ZVI/H2O2 process (initial pH 4.5) was below the limit for drinking water, and 48% less than the THM formation in the same water not subjected to pre-oxidation. Characterization of oxidation products on the iron-nail-ZVI surface after the ZVI/H2O2 treatment by SEM, XRD, and XPS identified the formation of magnetite and lepidocrocite. Results suggest that the investigated ZVI/H2O2 process is a promising technology for removing NOM and reducing THM formation during drinking water treatment.

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This study focused on the detection and quantification of eight cyanotoxins in water samples in three reservoirs located in the eastern department of Antioquia, Colombia. The reservoirs are a source of water supply and hydroelectricity, and also generate economic activities in fishing and recreation. Between May 2015 and October 2016, 8 samplings were carried out at times of high temperatures, which ranged from 20 to 29 °C. This period was selected because of a significant or strong El Niño phenomenon, according to the World Meteorological Organization. For the study, 270 integrated samples were taken from the photic zone (PZ) and the surface of the reservoirs, at each of the three sampling points. The samples were analyzed by the analytical technique of ultra-high-performance liquid chromatography coupled to triple quadrupole mass spectrometry (UHPLC MS/MS). The quantification performed for six microcystins (MCs), a nodularin (NOD) and a cylindrospermopsin (CYN), showed positive results well above 1 µg L-1. In the water of the Abreo Malpaso and Peñol reservoirs, microcystin-LR (MC-LR), microcystin-YR (MC-YR) and [D-Asp3,(E)-Dhb7]- microcystin-RR toxins were detected at levels of considerable concentration, especially between May and September 2015, when there was no rainfall in this region. In the Playas reservoir, positive results for [D-Asp3,(E)-Dhb7]-MC-RR were detected from May to November 2015, with the highest concentrations being reached in dry season. The temperatures reached and the changes in climatic conditions witnessed during the monitoring period of this study were important factors in the production of cyanotoxins. This was evidenced in this work by the high concentrations of detected cyanotoxins and their absence in periods of rain, as happened from the second quarter of 2016 until the end of the study in October. This is the first study of the detection and quantification of cyanotoxins in tropical reservoirs of northeastern Colombia using the UHPLC MS/MS analytical technique, which allowed the toxins to be unequivocally detected and confirmed. A method was developed and validated, proving to be sensitive, reproducible and accurate. For each of the toxins (microcystin-LR (MC-LR), microcystin-RR (MC-RR), microcystin-YR (MC-YR), [D-Asp3,(E)-Dhb7]- microcystin-RR, microcystin-LW (MC-LW), microcystin-LF (MC-LF), nodularin (NOD) and cylindrospermopsina (CYN)) the correlation coefficients (R2) were in a range between 0.9907 and 0.9999. Verification of the accuracy of the method was performed through a calibration curve in solvent. The recovery percentages of the accuracy and precision tests of the method for low level, medium level and high level were in a range between 64% and 115% for all the cyanotoxins. The validation of the cyanotoxin method shows that it is possible to detect them individually in natural water with a quantification limit (LOQ) of approximately 0.05 µg L-1.

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The polished silver solid amalgam electrode (p-AgSAE) combined with square wave voltammetry (SWV) was used in the development of an analytical procedure to Methomyl determination in natural water samples. The experimental and voltammetric parameters were optimized and the use of cationic surfactant cetyltrimethyl ammonium bromide promoted a considerable change in the kinetic and mechanism of the Methomyl reaction. Was observed the presence one-single reduction peak, related to a totally irreversible two-electrons transfer, followed by chemical reaction involving two protons. Analytical parameters (linearity range, analytical curve equations, correlation coefficient, detection and quantification limits, recovery efficiency, and relative standard deviation for intraday and interday experiments) were evaluated indicating that the proposed voltammetric procedure is suitable for determination of Methomyl. The application of the proposed procedure in natural water analysis indicated high robustness with only simple filtration, without pre-concentration steps, good stability and suitable sensitivity to determination of Methomyl in natural water samples.

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Foram feitos estudos comparativos entre 4 métodos para determinação de nitrato em amostras de águas naturais, colhidas em 10 poços na cidade de Aso Paulo. Procurou-se destacar os problemas operacionais e os possíveis interferentes para cada método. Com base nos resultados obtidos, foi sugerido o método do ácido fenoldissufônico como o mais apropriado para o uso em análises de rotina de amostras de água (AU).

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