RESUMEN

In this work, the photo-, electro-, and photo-electro-oxidation of chloramphenicol was investigated. The photo-experiments were carried out with different irradiation sources (an ultraviolet and a simulated solar source) using self-doped titanium nanotubes (SDTNT), a very promising and innovative material that deserves further investigations in the degradation of different pollutants. The photo-electrooxidation (j = 15 mA cm-2) under simulated solar irradiation presented the best efficiency, with ca. 100% degradation and kinetic constant of k = 0.04427 min-1. The FTIR analysis demonstrated a structural modification of the standard molecule occurred for all conditions used, suggesting a modification in functional groups responsible for the biological activity. Furthermore, the TOC analysis showed a significant mineralization of the pollutant (66% from the initial concentration). In addition, both photo-electrooxidation approaches have demonstrated a positive value of S, where the simulated solar irradiation reached the highest value S = 0.6960. The experimental results pointed out evidence that the methodology employed herein for chloramphenicol degradation is greatly interesting and the photo-electrooxidation under simulated solar irradiation is a promising approach for this purpose.

Asunto(s)

RESUMEN

Coastal environments, such as those in the Santa Catarina State (SC, Brazil), are considered the primary receptors of anthropogenic pollutants. In this study, our objective was to evaluate the levels of emerging contaminants (ECs) and persistent organic pollutants (POPs) in indigenous Crassostrea gasar oysters from different regions of SC coast in the summer season (March 2022). Field collections were conducted in the São Francisco do Sul, Itajaí, Florianópolis and Laguna coastal zones. We analyzed the bioaccumulation levels of 75 compounds, including antibiotics (AB), endocrine disruptors (ED), non-steroidal anti-inflammatory drugs (NSAIDs), polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and pesticides. Furthermore, we assessed biomarker responses related to biotransformation, antioxidant defense, heat shock protection and oxidative damage in oysters' gills. Prevalence of ECs was observed in the central and southern regions, while the highest concentrations of POPs were detected in the central-northern regions of SC. Oysters exhibited an induction in biotransformation systems (cyp2au1 and cyp356a1, sult and GST activity) and antioxidant enzymes activities (SOD, CAT and GPx). Higher susceptibility to lipid peroxidation was observed in the animals from Florianópolis compared to other regions. Correlation analyses indicated possible associations between contaminants and environmental variables in the biomarker responses, serving as a warning related to climate change. Our results highlight the influence of anthropogenic activities on SC, serving as baseline of ECs and POPs levels in the coastal areas of Santa Catarina, indicating more critical zones for extensive monitoring, aiming to conserve coastal regions.

Asunto(s)

RESUMEN

Non-steroidal anti-inflammatory drugs (NSAIDs) act as antipyretics, analgesics and anti-inflammatories. Among them, diclofenac and ibuprofen are the most consumed drugs worldwide. During the COVID-19 pandemic, some NSAIDs, such as dipyrone and paracetamol, have been used to alleviate the symptoms of the disease, causing an increase in the concentrations of these drugs in water. However, due to the low concentration of these compounds in drinking water and groundwater, few studies have been carried out on the subject, especially in Brazil. Thus, this study aimed to evaluate the contamination of the surface water, groundwater, and water treated with diclofenac, dipyrone, ibuprofen, and paracetamol at 3 cities (Orocó, Santa Maria da Boa Vista and Petrolândia) in the Brazilian semiarid region, in addition to analyzing the removal of these drugs by conventional water treatment (coagulation, flocculation, sedimentation, filtration and disinfection) in stations to each city. All drugs analyzed were detected in surface and treated waters. In groundwater, only dipyrone was not found. Dipyrone was seen in surface water with a maximum concentration of 1858.02 µg.L-1, followed by ibuprofen (785.28 µg.L-1), diclofenac (759.06 µg.L-1) and paracetamol (533.64 µg.L-1). The high concentrations derive from the increased consumption of these substances during the COVID-19 pandemic. During the conventional water treatment, the maximum removal of diclofenac, dipyrone, ibuprofen and paracetamol was 22.42%; 3.00%; 32.74%; and 1.58%, respectively, which confirms the inefficiency of this treatment in removing drugs. The variation in removal rate of the analyzed drugs is due to the difference in the hydrophobicity of the compounds.

RESUMEN

Pharmaceutical compounds are designed to elicit a biological reaction in specific organisms. However, they may also elicit a biological response in non-specific organisms when exposed to ambient quantities. Therefore, the potential human health hazards and environmental effects associated with pharmaceutically active compounds presented in aquatic environments are being studied by researchers all over the world. Owing to their broad-spectrum occurrence in various environmental matrices, direct or indirect environmental hazardous impacts, and human-health related consequences, several pharmaceutically active compounds have been categorized as emerging contaminants (ECs) of top concern. ECs are often recalcitrant and resistant to abate from water matrices. In this review, we have examined the classification, occurrence, and environmental hazards of pharmaceutically active compounds. Moreover, because of their toxicity and the inefficiency of wastewater treatment plants to remove pharmaceutical pollutants, novel wastewater remediation technologies are urgently required. Thus, we have also analyzed the recent advances in microbes-assisted bioremediation as a suitable, cost-effective, and eco-friendly alternative for the decontamination of pharmaceutical pollutants. Finally, the most important factors to reach optimal bioremediation are discussed.

Asunto(s)

RESUMEN

Compiling and reporting data related to the presence of pharmaceuticals and pesticides are crucial means of assessing the risk those chemicals pose to human health and environment. Data sets from different sources were combined using a data fusion approach to produce a spatial and temporal variation of contaminants presents in water from Lake Guaíba (29°55'-30°24' S; 51°01'-51°20' W). Lake Guaíba is a 496 km2 water body situated in the geological depression of Rio Grande do Sul State, Brazil; that is fed by several rivers from the metropolitan area, the 5th largest metro area in Brazil, with approximately 5 million inhabitants. Analytical methodology to quantify pharmaceuticals and pesticides by LC-QTOF-MS and GC-MS/MS was validated for 41 pharmaceutical and 62 pesticides. Furthermore, 27 chemical elements were analyzed by ICP-MS, and physical chemical parameters were determined using established methodologies. All validation parameters were in accordance with the National Institute of Metrology, Standardization, and Industrial Quality. Thirty-five water samples were analyzed from January to August 2019, and 15 pharmaceuticals and 25 pesticides were present in concentrations ranging from 6.00 ng L-1 to 580.00 ng L-1. Twenty-seven elements were analyzed during the same period, and 18 were present in concentrations ranging from 0.2 µg L-1 to 7060 µg L-1. Samples were tagged according to the points and months of collection to identify temporal and spatial patterns. The main findings show that the compounds are distributed throughout the studied area without an apparent regular pattern, suggesting that events in a specific point affect the entire ecosystem. Conversely, temporal variations were well defined, as samples were grouped according to the climatic conditions of the months of collection. Considering the calculated quotient risks, atrazine, cyproconazole, diuron, and simazine showed the highest risk levels for algae; acetaminophen, diclofenac, and ibuprofen showed the highest risk levels for aquatics invertebrates.

Asunto(s)

RESUMEN

An automated method was developed using on-line solid-phase extraction (SPE) as a sample preparation step, coupled to liquid chromatography-tandem mass spectrometry (LC-MS/MS), for determination of pharmaceutical compounds in wastewater samples at nanograms per liter to micrograms per liter concentration levels. This method is suitable for use in routine analysis, especially in environmental applications, avoiding cross-contamination and requiring minimal sample handling. Results can be obtained rapidly, with a chromatographic run time of only 24 min (including sample preparation and chromatographic analysis). Using a 50 µL injection volume, the method was validated according to international guidelines, considering parameters included in terms of method detection (MDL) and quantification limit (MQL), linearity, inter-day and intra-day precisions, and matrix effects. Assessment of chromatographic efficiency considered peak resolution and asymmetry, and carryover was evaluated to ensure analytical reliability and the ability to reuse the SPE cartridge. The intra- and inter-day precisions were lower than 10 and 17%, respectively. The MDL values ranged from 1×10-6 to 1 µg L-1, while the MQL values were from 0.001 to 3 µg L-1. Matrix effects were minimized by isotope dilution calibration. Application of the method to 20 wastewater samples showed that caffeine was the most frequently detected compound, with the highest concentration of 715 µg L-1, while other pharmaceutical compounds were detected in fewer samples and at lower concentrations (up to 8.51 µg L-1).

Asunto(s)

RESUMEN

Conventional sewage treatment systems are generally not designed to remove micropollutants, requiring the development of new technologies, such as the combination of biological processes with advanced oxidative processes. The configuration of an anaerobic expanded granular sludge bed (EGSB) reactor stands out for its use of granular biomass and high sludge bed expansion. Ozonation is an advanced oxidative process that stands out as one of the most promising technologies for the degradation of micropollutants. Thus, the present work aimed to evaluate the removal of drugs through the application of ozonation as a polishing process for the effluent of an EGSB reactor that was fed with synthetic sewage. Ozonation was shown to be efficient in the degradation of these compounds, reaching removals above 90%. It was found that the degradation profile of each drug varied according to its chemical structure since some drugs are more susceptible to oxidation than others and since the concentrations of pharmaceuticals are also related to their removal. Moreover, the assessment of risks to the environment and human health confirmed the need to assess the best scenario for risk reduction considering all drugs, since even with almost complete removal of some compounds, the effluents still showed toxicity. Thus, the high removal efficiencies found for the evaluated micropollutants showed that this technique has the potential to be used to improve the quality of biological reactor effluents or even to be combined in effluent reuse systems.

Asunto(s)

RESUMEN

Among all emerging contaminants, pharmaceutical compounds as tetracycline (TC) can cause potential environmental impact in water quality. In this work, the removal of TC drug on activated carbon from aqueous solution was studied and the best operating parameters were obtained. In addition, a real aqueous matrix was enriched with TC and the optimized conditions were applied to study the adsorption process efficiency. For this, the influence of pH, contact time between phases and dosage of adsorbent solid was evaluated. The investigation of kinetics, equilibrium and thermodynamic was also performed. The adsorbent material was characterized by SEM analysis and N2 adsorption/desorption isotherms to confirm its properties. Batch experiments showed that the most suitable experimental conditions for adsorption in aqueous solution were: pH 4.0, contact time 90 min and dosage of adsorbent solid 30 g.L-1. Under these conditions, it was possible to obtain 92.7% of TC removal with predominance of a spontaneous, favorable and endothermic chemisorption process. Adsorption experiments with real aqueous matrix provided 99.4% TC removal. These results show the potential of adsorption as a wastewater treatment applied to remove emerging pollutants as TC from real aqueous contaminated water.

Asunto(s)

RESUMEN

Pharmaceutical active compounds (PhACs) are environmentally ubiquitous around the world, and the countries of Latin America (LATAM) are not the exception; however there is still little knowledge of the magnitude and conditions of their occurrence in LATAM and of the environmental consequences of their presence. The present work reviews 79 documents published from 2007 to 2019 on the occurrence, concentrations, and sources of PhACs and hormones in surface water (SW), wastewater (WW), and treated wastewater (TWW) in LATAM and on the circumstances of their release to the environment. Research efforts are reported in only ten countries and confirm the presence of 159 PhACs, mainly analgesics and anti-inflammatories, although extraordinarily high concentrations of carbamazepine (830 µg/L) and ethinylestradiol (6.8 µg/L) were found in Ecuador and Brazil, respectively. The analysis of maximum concentrations and the ecotoxicological risk assessment corroborate that (1) these values exceed the environmental concentrations found in other parts of the world, (2) the environmental risk posed by these concentrations is remarkably high, and (3) there is no statistically significant difference between the maximum concentrations found in WW and those found in TWW. The main source of PhACs in LATAM's aquatic environment is WW; hence, these countries should direct substantial efforts to develop efficient and cost-effective treatment technologies and plan and apply WW management strategies and regulations. This analysis presents the current states of occurrence, concentrations, and sources of PhACs in the aquatic environment of LATAM and outlines the magnitude of the environmental problem in that part of the world.

Asunto(s)

RESUMEN

This study presents the extraction of antibiotic amoxicillin (AMX) from aqueous solution employing activated carbons (AC) from olive biomass (OB). Two AC were prepared using ZnCl2 (activator agent), and a conventional muffle furnace (ACF) or microwave oven (ACMW). The structure, morphology, and textural properties from both AC were analyzed by scanning electron microscope (SEM), pH of point-zero-charge (pHPZC), infrared spectroscopy (FTIR), and N2 adsorption/desorption isotherms. AC with mesoporous structures rich in oxygenated groups and high specific area (as high as 1742 m2 g-1) were helpful for the efficient and fast adsorption of AMX. The Avrami kinetic nonlinear equation showed the best fitting for the empirical data when related to the pseudo-1st and pseudo-2nd order. The isothermal experimental data followed the Liu nonlinear model, displaying at 25 °C the maximum sorption capacity of 237.02 and 166.96 mg g-1 for the ACF and ACMW, respectively. An adsorption test with synthetic hospital effluent was carried out to evaluate the possibility of applying both adsorbents in wastewater purification. The purification efficiency was up to 94.4% and 91.96% for ACF and ACMW, respectively. Therefore, the AC obtained from OB (containing a mixture of seed, pulp, and olive peel) has a high potential for application in removing emerging contaminants from the wastewater.

Asunto(s)

RESUMEN

Establishing scientifically the macro-location of a micropollutants monitoring network in tropical Andean rivers is a complex process, because information gathering is restricted by high-cost of analysis and limited availability of analytical techniques, which lead to inadequate sampling strategies that hinder the representativeness of samples. Thus, this work proposes a methodology for determining the number of representative sampling sections in a micropollutant monitoring network to characterise the ecological risk in tropical Andean torrential rivers. The proposed methodology consists of four stages: identification of the potential sampling units by Spline interpolation; calculation of the number of representative sections for a stratified sampling with an acceptable level of confidence and error; spatial allocation of the potential sampling units into sections by hierarchical cluster analysis; and representation of the spatial distribution of the sampling sections through a geographic information system (GIS). The proposed methodology is dynamic, and therefore, it can be revisited as more data are obtained in the subsequent years; it has the possibility of being applied to other inter-Andean valley rivers that interact with the tropical Andean sloppy mountains and serves as a tool for decision making by environmental authorities regarding the optimisation of the existing monitoring networks in terms of micropollutants to promote sustainable management of water resources. The proposed methodology is applied in the Upper Cauca River Basin (UCRB), which is located in southwest Colombia, South America.

Asunto(s)

RESUMEN

This study investigates the mineralization efficiency, i.e. removal of total organic carbon (TOC) in hospital wastewater by direct ozonation, ozonation with UV radiation (O3/UV), homogeneous catalytic ozonation (O3/Fe2+) and homogeneous photocatalytic ozonation (O3/Fe2+/UV). The influence of pH and reaction time was evaluated. For the best process, toxicity and degradation efficiency of the selected pharmaceutical compounds (PhCs) were determined. The results showed that the PhCs detected in the hospital wastewater were completely degraded when the mineralization efficiency reached 54.7% for O3/UV with 120 minutes of reaction time using a rate of 1.57 g O3 h-1. This process also achieved a higher chemical oxygen demand removal efficiency (64.05%), an increased aromaticity reduction efficiency (81%) and a toxicity reduction.

Asunto(s)

RESUMEN

The biodegradation of fluoxetine, mefenamic acid, and metoprolol using ammonium-nitrite-oxidizing consortium, nitrite-oxidizing consortium, and heterotrophic biomass was evaluated in batch tests applying different retention times. The ammonium-nitrite-oxidizing consortium presented the highest biodegradation percentages for mefenamic acid and metoprolol, of 85 and 64% respectively. This consortium was also capable to biodegrade 79% of fluoxetine. The heterotrophic consortium showed the highest ability to biodegrade fluoxetine reaching 85%, and it also had a high potential for biodegrading mefenamic acid and metoprolol, of 66 and 58% respectively. The nitrite-oxidizing consortium presented the lowest biodegradation of the three pharmaceuticals, of less than 48%. The determination of the selected pharmaceuticals in the dissolved phase and in the biomass indicated that biodegradation was the major removal mechanism of the three compounds. Based on the obtained results, the biodegradation kinetics was adjusted to pseudo-first-order for the three pharmaceuticals. The values of k biol for fluoxetine, mefenamic acid, and metoprolol determined with the three consortiums indicated that ammonium-nitrite-oxidizing and heterotrophic biomass allow a partial biodegradation of the compounds, while no substantial biodegradation can be expected using nitrite-oxidizing consortium. Metoprolol was the less biodegradable compound. The sorption of fluoxetine and mefenamic acid onto biomass had a significant contribution for their removal (6-14%). The lowest sorption coefficients were obtained for metoprolol indicating that the sorption onto biomass is poor (3-4%), and the contribution of this process to the global removal can be neglected.

Asunto(s)

RESUMEN

This work has assessed the seasonal changes and the dynamics in the concentration of six pharmaceutical compounds during photolysis as a tertiary treatment of sewage previously treated by an anaerobic/aerobic system comprising a UASB (Upflow Anaerobic Sludge Blanket) reactor and a trickling filter (TF). The target compounds were four antibiotics (ciprofloxacin (CPF), clindamycin (CLM), sulfamethoxazole (SMX), and trimetoprim), one ß-blocker (atenolol), and one anti-inflammatory (diclofenac (DCF)). Six hydraulic retention times (HRTs) were evaluated (5, 10, 20, 40, 80, and 160 min) with the intent of varying the ultraviolet C (UVC) radiation doses applied to the effluent from biological treatment containing the target contaminants. The concentrations of pharmaceutical compounds in the effluent of the UASB/TF system were in agreement with the concentration levels reported in the literature. Aside from DCF, the seasonality seems to be a preponderant characteristic regarding the pharmaceutical concentration found in the effluent of biological treatment systems. The radiation dose of 117 mJ cm-2 seemed to be most suited for the photolysis application to tertiary treatment of domestic effluents. It was observed that lower UVC doses led to deconjugation of pharmaceuticals, which can result in increased concentrations of target pollutants in the photoreactor effluent.

Asunto(s)

RESUMEN

Hospital wastewater contains a great variety of pharmaceutical compounds (PhCs), mainly due to excretion by patients. These PhCs, called emerging pollutants, are not fully eliminated in treatment plants, and are consequently detected in various environmental matrices, contributing to bacterial resistance and adverse environmental impacts on water resources. This study explores a consumption-based approach to predict the contribution of PhCs to a Brazilian hospital's wastewater. This approach identifies the consumption of major pharmaceutical classes in the studied hospital. Overall, this approach demonstrates a unique opportunity to screen PhCs used in hospitals and identify priority pollutants in hospital wastewater.

Asunto(s)

RESUMEN

Lab-scale photolysis, biodegradation and transport experiments were carried out for naproxen, carbamazepine and triclosan in soil, wastewater and surface water from a region where untreated wastewater is used for agricultural irrigation. Results showed that both photolysis and biodegradation occurred for the three emerging pollutants in the tested matrices as follows: triclosan>naproxen>carbamazepine. The highest photolysis rate for the three pollutants was obtained in experiments using surface water, while biodegradation rates were higher in wastewater and soil than in surface water. Carbamazepine showed to be recalcitrant to biodegradation both in soil and water; although photolysis occurred at a higher level than biodegradation, this compound was poorly degraded by natural processes. Transport experiments showed that naproxen was the most mobile compound through the first 30cm of the soil profile; conversely, the mobility of carbamazepine and triclosan through the soil was delayed. Biodegradation of target pollutants occurred within soil columns during transport experiments. Triclosan was not detected either in leachates or the soil in columns, suggesting its complete biodegradation. Data of these experiments can be used to develop more reliable fate-on-the-field and environmental risk assessment studies.

Asunto(s)

RESUMEN

Cyclohexylamine reacts with 5-chloro-3-methyl-1-(pyridin-2-yl)-1H-pyrazole-4-carbaldehyde to give 5-cyclohexylamino-3-methyl-1-(pyridin-2-yl)-1H-pyrazole-4-carbaldehyde, C16H20N4O, (I), formed by nucleophilic substitution, but with 5-chloro-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde the product is (Z)-4-[(cyclohexylamino)methylidene]-3-methyl-1-phenyl-1H-pyrazol-5(4H)-one, C17H21N3O, (II), formed by condensation followed by hydrolysis. Compound (II) crystallizes with Z' = 2, and in one of the two independent molecular types the cyclohexylamine unit is disordered over two sets of atomic sites having occupancies of 0.65 (3) and 0.35 (3). The vinylogous amide portion in each compound shows evidence of electronic polarization, such that in each the O atom carries a partial negative charge and the N atom of the cyclohexylamine portion carries a partial positive charge. The molecules of (I) contain an intramolecular N-H...N hydrogen bond, and they are linked by C-H...O hydrogen bonds to form sheets. Each of the two independent molecules of (II) contains an intramolecular N-H...O hydrogen bond and each molecular type forms a centrosymmetric dimer containing one R2(2)(4) ring and two inversion-related S(6) rings.

Asunto(s)

RESUMEN

The molecular structures of (E)-1-(4-{[1-(4-fluorophenyl)-3,5-dimethyl-1H-pyrazol-4-yl]diazenyl}phenyl)ethanone, C19H17FN4O, (III), and (E)-1-(4-chlorophenyl)-3,5-dimethyl-4-[2-(2-nitrophenyl)diazenyl]-1H-pyrazole, C17H14ClN5O2, (IV), prepared by reaction of the corresponding ß-diketohydrazones with substituted arylhydrazines in acid media, are nonplanar, with the planes of the lateral phenyl rings forming dihedral angles with that of the central pyrazole ring varying from 2.71 (7) to 45.22 (7)°. The crystal structures are supported by C-H...O, C-H...π and π-π weak intermolecular interactions together with some unusual trifurcated C-Cl...Cl-C contacts, which are discussed in detail.

RESUMEN

The title substituted pyrazole derivatives, C17H15N5O3 and C18H15F3N4O, share most of their molecular features, in particular the hydrazinylidene (-HN-N=) rather than the diazene (-N=N-) tautomeric form, and differ only in the substituents (NO2 and CF3) on one of the outer phenyl rings. The molecular units are basically planar, with the rotation of the phenyl rings being hindered by the presence of two intramolecular hydrogen bonds having the keto O atom as acceptor. In both structures, the packing is governed by weak C-H...O, C-H...π and π-π interactions. The subtle way in which minor structural differences lead to rather different supramolecular structures is analysed.

Asunto(s)