Al/Cu-PILC as a Photo-Fenton Catalyst: Paracetamol Mineralization.

Pillared clays have shown to effectively catalyze the photo-Fenton process without the necessity of acidic conditions, which is a very attractive feature from the perspective of environmentally friendly processes, especially when high natural abundance of chemical elements are incorporated. In this work, the catalytic activity of Al/Cu interlayered pillared clays for the degradation and mineralization of paracetamol through a photo-Fenton-like process was investigated. Al/Cu-pillared clays were prepared by adding ane Al/Cu pillaring solution to a bentonite suspension. X-ray diffraction (XRD) confirmed the enlargement of the interlayer space of the clay provoked by the pillaring process and Al and Cu species in the prepared samples were verified by atomic absorption spectroscopy (AAS). The specific surface area of pure bentonite was 2-fold increased after the Al/Cu pillaring process. A synthetic paracetamol solution with an initial concentration of 100 ppm was prepared for the assessment of the activity of the prepared materials. Different catalyst concentrations were tested (0.2, 0.5, 0.75, and 1 g L-1) and the complete removal of paracetamol was achieved in all cases, but the highest mineralization rate (69.8 mg total organic carbon (TOC) gcat -1 h-1) corresponds to the catalyst loading of 0.5 g L-1. An ultraviolet-C (UVC) light source was employed, and no adjustment of the pH to acidic conditions was needed to achieve these results. Liquid chromatography coupled to mass spectroscopy (LC-MS) was employed to identify the reaction intermediates of paracetamol degradation. A proposed pathway for the oxidation of paracetamol molecule is presented. The effect of Cu content in the pillared clay and the stability and reusability of the catalyst were also assessed. The kinetic constants of paracetamol removal were 0.2318 and 0.0698 min-1, under photo-Fenton and UV + H2O2 processes, respectively.

New material for arsenic (V) removal based on chitosan supported onto modified polypropylene membrane.

This paper presents a new material easily synthesized and with low cost, with the possibility of remove arsenic and the potential capability for the remediate water bodies. In this work, the efficiency in removing arsenic of the chitosan, supported onto modified polypropylene membrane, was studied using an aqueous As(V) solution of 0.4 mg/L, achieving a removal efficiency of 75%, which corresponds to an adsorption capacity of 0.031 mg/g. The As(V) adsorption depends on pH and the degree of chitosan grafting on the polypropylene membrane. A pseudo-second-order equation describes the adsorption of the membrane, classifying it as a chemisorption process. The chitosan supported on the membrane was characterized by the analysis of wettability, FT-IR-ATR, SEM-EDS, XRD powder, and surface charge. The As ions coordinate to the chitosan polar groups, allowing their removal from the aqueous solution.

Biodiesel Production from Waste Cooking Oil Catalyzed by a Bifunctional Catalyst.

The objective of this study was to prepare bifunctional catalysts based on iron and CaO and test them in the biodiesel production using waste cooking oil (WCO) as feedstock. Two iron precursors were studied, Fe2O3 and Fe(NO3)3·9H2O. The identified crystalline phases were Ca2Fe2O5 and CaFeO3. Surface morphology and textural properties (distribution of active species, specific surface area, size, and pore volume) were also analyzed. Additionally, thermal stability was studied and 800 °C was established as the optimum calcination temperature. The density of both acidic and basic sites was higher with the catalyst prepared with Fe2O3 than with that prepared with Fe(NO3)3·9H2O. The latter, however, leads to reach equilibrium in half of the time than with the former. This was ascribed to the ratio of acidic to basic sites, which is higher with the catalyst prepared with the precursor salt. This ratio not only affects the overall cost of the process by affecting the time at which equilibrium is reached but also by dictating the methanol/oil molar ratio at which the equilibrium is reached sooner. The prepared bifunctional catalyst allowed us to produce biodiesel with 90% of methyl ester content at atmospheric pressure, reaction temperature of 60 °C, reaction time of 2 h, with 12:1 M ratio of methanol/WCO, 10 wt % of Fe over CaO, and a catalyst loading of 5 wt %. This catalyst can be used at least 3 times. The so-obtained biodiesel met the European norm EN-14214 regarding viscosity and density.

Ibuprofen at environmentally relevant concentrations alters embryonic development, induces teratogenesis and oxidative stress in Cyprinus carpio.

Ibuprofen (IBU) is a non-steroidal anti-inflammatory (NSAIDs) that is used in various conditions. The prescriptions and the global consumption of this drug are very high and its annual production oscillates in millions of tons, this generates that the IBU is present in many waterbodies because it is discharged through the municipal, hospital and industrial effluents. For the above, the purpose of this work was to determine if IBU at environmentally relevant concentrations was capable of inducing alterations to embryonic development, teratogenic effects and oxidative stress in oocytes and embryos of Cyprinus carpio. Oocytes of common carp were exposed to IBU concentrations between 1.5 and 11.5 µg L-1 (environmentally relevant). LC50 and EC50 of malformations were determined to calculate the teratogenic index (TI). Also, main alterations to embryonic development and teratogenic effects were evaluated. Oxidative stress was evaluated by determining biomarkers of cellular oxidation and antioxidation using the same concentrations at 72 and 96 hpf in embryos of Cyprinus carpio. The results showed a LC50 of 4.17 µg L-1, EC50 of 1.39 µg L-1 and TI of 3.0. The main embryonic development disorders and teratogenic effects were delayed hatching, hypopigmentation, pericardial edema, yolk deformation, and developmental delay. Biomarkers of cellular oxidation and antioxidants were increased with respect to the control in a concentration-dependent manner. The results of the study allow us to conclude that IBU at environmentally relevant concentrations is capable of inducing embryotoxicity and teratogenicity in a fish of commercial interest like Cyprinus carpio.

The Influence of Drying Temperatures on the Metabolic Profiles and Antioxidant Activity of Manilkara zapota Leaves.

In the present study, the leaves of Manilkara zapota (L.) P. Royen (Sapotaceae), an evergreen tree recognized for its medicinal properties in Southern Mexico, were used as a model to study the effect of different drying temperatures on its metabolic profile and therefore, its antioxidant potential. For this purpose, a methanol extraction of leaves dried at room temperature (25 °C) or by heat convection (50, 75 and 100 °C) were compared in terms of drying efficiency, yield of extraction, total phenol content, 1H-NMR metabolic profile, and DPPH antioxidant activity. The drying curves enabled the fact to be uncovered that drying efficiency improves with increase of temperature, as does the level of total phenols and antioxidant activity. A metabolomics approach using principal component analysis (PCA) and orthogonal projections to latent structures discriminant analysis (OPLS-DA) of the corresponding 1H-NMR profiles allowed the impact of the drying temperature on their metabolic profile to be documented and also, caffeic acid and epicatechin as main secondary metabolites contributing to the antioxidant activity of M. zapota to be identified.

Biological hazard evaluation of a pharmaceutical effluent before and after a photo-Fenton treatment.

The aim of this study was to evaluate the biological hazard of a pharmaceutical effluent before and after treatment. For the former, the determined 96h-LC50 value was 1.2%. The photo-Fenton treatment catalyzed with an iron-pillared clay reduced this parameter by 341.7%. Statistically significant increases with respect to the control group (P<0.05) were observed at 12, 24, 48 and 72h in HPC (50.2, 30.4, 66.9 and 43.3%), LPX (22, 83.2, 62.7 and 59.5%) and PCC (14.6, 23.6, 24.4 and 25.6%) and antioxidant enzymes SOD (29.4, 38.5, 32.7 and 49.5%) and CAT (48.4, 50.3, 38.8 and 46.1%) in Hyalella azteca before treatment. Also increases in damage index were observed before treatment of 53.1, 59.9, 66.6 and 72.1% at 12, 24, 48 and 72h, respectively. After treatment the same biomarkers of oxidative stress decreased with respect to before treatment being to HPC (29.3, 22.5, 41.6 and 31.7%); LPX (14.2, 43.1, 30.7 and 35.5%); PCC (12.6, 21.3, 24.2 and 23.9%); SOD (39.2, 33.9, 49.5 and 37.9%) and CAT (28.6, 35.8, 33.7 and 31.7) at 12, 24, 48 and 72h, respectively (P<0.05). The damage index were decreased at 12, 24, 48 and 72h in 48.9, 57.8, 67.3 and 72.1%, respectively. In conclusion, the obtained results demonstrate the need of performing bioassays in order to characterize an effluent before discharge and not base such a decision only upon current normativity. In addition, it was also concluded that the heterogeneous photo-Fenton process decreases the presence of PCT, oxidative stress, genotoxic damage and LC50 in Hyalella azteca.

Oxidative stress induced in Hyalella azteca by an effluent from a NSAID-manufacturing plant in Mexico.

Production in the pharmaceutical industry has increased and along with it, the amount of wastewater of various characteristics and contaminant concentrations. The main chemicals in these effluents are solvents, detergents, disinfectants-such as sodium hypochlorite (NaClO)-and pharmaceutical products, all of which are potentially ecotoxic. Therefore, this study aimed to evaluate the oxidative stress induced in the amphipod Hyalella azteca by the effluent from a nonsteroidal anti-inflammatory drug (NSAID)-manufacturing plant. The median lethal concentration (72 h-LC50) was determined and H. azteca were exposed to the lowest observed adverse effect level (0.0732 %) for 12, 24, 48 and 72 h, and biomarkers of oxidative stress were evaluated [hydroperoxide content (HPC), lipid peroxidation (LPX), protein carbonyl content (PCC), and the activity of the superoxidant enzymes superoxide dismutase (SOD), catalase (CAT) and glutathione peroxidase (GPx)]. Statistically significant increases with respect to the control group (P < 0.05) were observed in HPC, LPX and PCC in H. azteca at all exposure times. Antioxidant enzymes activity SOD, CAT and GPx activity also increased significantly (P < 0.05) with respect to the control group. In conclusion, the industrial effluent analyzed in the present study contains NSAIDs and NaClO, and induces oxidative stress in H. azteca.