Priority list of pharmaceutical active compounds in aquatic environments of Mexico considering their occurrence, environmental and human health risks.

Pharmaceutical active compounds (PhACs) are detected pollutants in aquatic environments worldwide at concentrations ranging from ng L-1 to µg L-1. Currently, PhAC monitoring is poorly realized in Mexico. This study proposes a priority list of PhACs in Mexican aquatic environments, considering their occurrence and environmental and human health risks. Ecological risks were assessed as Risk Quotients (RQ) values using the PhAC concentrations detected in surface water, obtaining high risks (RQ > 1) against aquatic organisms, especially of naproxen, ibuprofen, diclofenac, acetaminophen, 17ß-estradiol, carbamazepine, ketoprofen, caffeine. In contrast, potential human health risks (RQH) were assessed on the Mexican population using the concentrations quantified in groundwater, demonstrating potential risks (RQH > 0.2) on the population, particularly of DCF and CBZ. Thus, a priority list of PhACs can be used as a reference for environmental monitoring in Mexican water supplies as well as PhACs monitoring in countries of the Caribbean region and Central America.

Efficient removal of veterinary drugs from aqueous solutions using magnetically separable carbonaceous materials derived from cobalt and iron metal-organic frameworks.

Rapid synthesis of carbon-based magnetic materials derived from cobalt and iron metal-organic frameworks (MOFs), ZIF-67, and MIL-100(Fe), by microwave-assisted method, followed by carbonization under a N2 atmosphere is described in this study. The carbon-derived MOFs (CDMs) were evaluated for the removal of the emerging pollutants sulfadiazine (SDZ) and flumequine (FLU) used as veterinary drugs. The study aimed to link the adsorption behavior with their surface properties and elemental composition. C-ZIF-67 and C-MIL-100(Fe) showed hierarchical porous structures with specific surface areas of 295.6 and 163.4 m2 g-1, respectively. The Raman spectra of the CDMs show the characteristic D and G bands associated with defect-rich carbon and sp2 graphitic carbon, respectively. The CDMs exhibit cobalt species (Co3O4, CoO, and Co) in C-ZIF-67 and iron species (Fe2O3, Fe3O4, and Fe) in C-MIL-100 (Fe) which are related to the magnetic behavior of CDMs. C-ZIF-67 and C-MIL-100 (Fe) had saturation magnetization values of 22.9 and 53.7 emu g-1, respectively, allowing easy solid-liquid separation using a magnet. SDZ and FLU removal rates on CDMs follow pseudo-second-order kinetics, and adsorption isotherms fit the Langmuir model based on regression coefficient values. Adsorption thermodynamics calculations showed that the adsorption of SDZ and FLU by CDMs was a thermodynamically favorable process. Therefore, these properties of C-ZIF-67 and C-MIL-100 (Fe) and their regeneration ability facilitate their use as adsorbents for emerging pollutants.

Vachellia farnesiana Pods or a Polyphenolic Extract Derived from Them Exert Immunomodulatory, Metabolic, Renoprotective, and Prebiotic Effects in Mice Fed a High-Fat Diet.

Obesity causes systemic inflammation, hepatic and renal damage, as well as gut microbiota dysbiosis. Alternative vegetable sources rich in polyphenols are known to prevent or delay the progression of metabolic abnormalities during obesity. Vachellia farnesiana (VF) is a potent source of polyphenols with antioxidant and anti-inflammatory activities with potential anti-obesity effects. We performed an in vivo preventive or an interventional experimental study in mice and in vitro experiments with different cell types. In the preventive study, male C57BL/6 mice were fed with a Control diet, a high-fat diet, or a high-fat diet containing either 0.1% methyl gallate, 10% powdered VFP, or 0.5%, 1%, or 2% of a polyphenolic extract (PE) derived from VFP (Vachellia farnesiana pods) for 14 weeks. In the intervention study, two groups of mice were fed for 14 weeks with a high-fat diet and then one switched to a high-fat diet with 10% powdered VFP for ten additional weeks. In the in vitro studies, we evaluated the effect of a VFPE (Vachellia farnesiana polyphenolic extract) on glucose-stimulated insulin secretion in INS-1E cells or of naringenin or methyl gallate on mitochondrial activity in primary hepatocytes and C2C12 myotubes. VFP or a VFPE increased whole-body energy expenditure and mitochondrial activity in skeletal muscle; prevented insulin resistance, hepatic steatosis, and kidney damage; exerted immunomodulatory effects; and reshaped fecal gut microbiota composition in mice fed a high-fat diet. VFPE decreased insulin secretion in INS-1E cells, and its isolated compounds naringenin and methyl gallate increased mitochondrial activity in primary hepatocytes and C2C12 myotubes. In conclusion VFP or a VFPE prevented systemic inflammation, insulin resistance, and hepatic and renal damage in mice fed a high-fat diet associated with increased energy expenditure, improved mitochondrial function, and reduction in insulin secretion.

Ion-Imprinted Polymer Structurally Preorganized Using a Phenanthroline-Divinylbenzoate Complex with the Cu(II) Ion as Template and Some Adsorption Results.

The novel [Cuphen(VBA)2H2O] complex (phen: phenanthroline, VBA: vinylbenzoate) was prepared and used as a functional monomer to preorganize a new ion-imprinted polymer (IIP). By leaching the Cu(II) from the molecular imprinted polymer (MIP), [Cuphen(VBA)2H2O-co-EGDMA]n (EGDMA: ethylene glycol dimethacrylate), the IIP was obtained. A non-ion-imprinted polymer (NIIP) was also prepared. The crystal structure of the complex and some physicochemical, spectrophotometric techniques were also used for the MIP, IIP, and NIIP characterization. The results showed that the materials are nonsoluble in water and polar solvents, which are the main features of polymers. The surface area of the IIP is higher than the NIIP demonstrated by the blue methylene method. The SEM images show monoliths and particles smoothly packed together on spherical and prismatic-spherical surfaces in the morphology of MIP and IIP, respectively. Moreover, the MIP and IIP could be considered as mesoporous and microporous materials, shown by the size of the pores determined by the BET and BJH methods. Furthermore, the adsorption performance of the IIP was studied using copper(II) as a contaminant heavy metal. The maximum adsorption capacity of IIP was 287.45 mg/g at 1600 mg/L Cu2+ ions with 0.1 g of IIP at room temperature. The Freundlich model was found to best describe the equilibrium isotherm of the adsorption process. The competitive results indicate that the stability of the Cu-IIP complex is higher than the Ni-IIP complex with a selectivity coefficient of 1.61.

Iron metal-organic framework supported in a polymeric membrane for solid-phase extraction of anti-inflammatory drugs.

A solid-phase extraction methodology using a MIL-101(Fe)/PVDF membrane was proposed as a useful alternative for the simultaneous determination of naproxen, diclofenac, and ibuprofen, three anti-inflammatory drugs (NSAIDs), in wastewater samples by HPLC-CCD analysis. The MIL-101(Fe) was prepared by a rapid microwave-assisted method and supported in a polymeric PVDF membrane. The prepared material was characterized by X-ray diffraction (XRD), nitrogen adsorption-desorption, scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and Fourier-transform infrared spectroscopy (FT-IR). The factors that affect the extraction of the NSAIDs using the MIL-101(Fe)/PVDF membrane as the sample volume, the solution pH and the elution solvent were studied in detail. The selected conditions were 50 mL of sample solution at pH 3 and 5 mL of methanol: acetone (30:70, v v-1) acidified with formic acid at 2% as elution solvent. The analytical method was linear with determination coefficients (r2 ≥ 0.998) in the calibration ranges from 2 to 100 ng mL-1 for naproxen, 20-200 ng mL-1 for diclofenac, and 100-300 ng mL-1 for ibuprofen. The intra and inter-day precision (repeatability and reproducibility, respectively) of the method (RSD%, n = 5) were lower than 4.8% and 7.1%, respectively. The accuracy reported as recovery percentages ranged from 82 to 118%, and the limits of detection were between 1.8 and 32.3 ng mL-1. Moreover, MIL-101(Fe)/PVDF membrane exhibited improved adsorption efficiency compared to that of its analog MIL-101(Cr)/PVDF and the pristine PVDF membranes, obtaining in an easy and rapid (60 min) way a low-cost and low-toxic adsorbent with excellent stability, reusability, mechanic resistance, and simple operation which shows excellent performance.

Automated on-line monitoring of the TiO2-based photocatalytic degradation of dimethyl phthalate and diethyl phthalate.

A fully automated on-line system for monitoring the TiO2-based photocatalytic degradation of dimethyl phthalate (DMP) and diethyl phthalate (DEP) using sequential injection analysis (SIA) coupled to liquid chromatography (LC) with UV detection was proposed. The effects of the type of catalyst (sol-gel, Degussa P25 and Hombikat), the amount of catalyst (0.5, 1.0 and 1.5 g L-1), and the solution pH (4, 7 and 10) were evaluated through a three-level fractional factorial design (FFD) to verify the influence of the factors on the response variable (degradation efficiency, %). As a result of FFD evaluation, the main factor that influences the process is the type of catalyst. Degradation percentages close to 100% under UV-vis radiation were reached using the two commercial TiO2 materials, which present mixed phases (anatase/rutile), Degussa P25 (82%/18%) and Hombikat (76%/24%). 60% degradation was obtained using the laboratory-made pure anatase crystalline TiO2 phase. The pH and amount of catalyst showed minimum significant effect on the degradation efficiencies of DMP and DEP. Greater degradation efficiency was achieved using Degussa P25 at pH 10 with 1.5 g L-1 catalyst dosage. Under these conditions, complete degradation and 92% mineralization were achieved after 300 min of reaction. Additionally, a drastic decrease in the concentration of BOD5 and COD was observed, which results in significant enhancement of their biodegradability obtaining a BOD5/COD index of 0.66 after the photocatalytic treatment. The main intermediate products found were dimethyl 4-hydroxyphthalate, 4-hydroxy-diethyl phthalate, phthalic acid and phthalic anhydride indicating that the photocatalytic degradation pathway involved the hydrolysis reaction of the aliphatic chain and hydroxylation of the aromatic ring, obtaining products with lower toxicity than the initial molecules.

Salicylic acid degradation by advanced oxidation processes. Coupling of solar photoelectro-Fenton and solar heterogeneous photocatalysis.

A 3.0 L solar flow plant with a Pt/air-diffusion (anode/cathode) cell, a solar photoreactor and a photocatalytic photoreactor filled with TiO2-coated glass spheres has been utilized to couple solar photoelectro-Fenton (SPEF) and solar heterogeneous photocatalysis (SPC) for treating a 165mgL(-1) salicylic acid solution of pH 3.0. Organics were destroyed by OH radicals formed on the TiO2 photocatalyst and at the Pt anode during water oxidation and in the bulk from Fenton's reaction between added Fe(2+) and cathodically generated H2O2, along with the photolytic action of sunlight. Poor salicylic acid removal and mineralization were attained using SPC, anodic oxidation with electrogenerated H2O2 (AO-H2O2) and coupled AO-H2O2-SPC. The electro-Fenton process accelerated the substrate decay, but with low mineralization by the formation of byproducts that are hardly destroyed by OH. The mineralization was strongly increased by SPEF due to the photolysis of products by sunlight, being enhanced by coupled SPEF-SPC due to the additional oxidation by OH at the TiO2 surface. The effect of current density on the performance of both processes was examined. The most potent SPEF-SPC process at 150mAcm(-2) yielded 87% mineralization and 13% current efficiency after consuming 6.0AhL(-1). Maleic, fumaric and oxalic acids detected as final carboxylic acids were completely removed by SPEF and SPEF-SPC.

Persistent Organic Pollutants and Heavy Metal Concentrations in Soil from the Metropolitan Area of Monterrey, Nuevo Leon, Mexico.

The purpose of this study was to assess the levels of polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloroethane (DDT), dichlorodiphenyldichloroethane (DDE), and four heavy metals (arsenic, cadmium, and lead) in outdoor surface soils (50 samples) collected from the metropolitan area of Monterrey in Mexico. Total PBDEs levels ranged from 1.80 to 127 µg/kg, with mean total PBDEs level of 14.2 ± 21.5 µg/kg (geometric mean ± standard deviation). For PCBs, the mean total level in the studied soils was 23.5 ± 20.2 µg/kg (range 4.0-65.5 µg/kg). An important finding in our study was that all soil samples (100%) had detectable levels of the metabolite p,p'-DDE. Moreover, the mean total DDT level (∑p'p-DDT and p'p-DDE) was approximately 132 ± 175 µg/kg. The mean levels for arsenic, cadmium, and lead in soil were 5.30 ± 1.35 (range 1.55-7.85) mg/kg, 2.20 ± 1.20 (range 0.65-6.40) mg/kg, and 455 ± 204 (range 224-1230) mg/kg, respectively. Our study has several limitations, the most notable of which is the small sample of soils evaluated. However, this screening study provided concentration data for the occurrence of POPs and four heavy metals in soil from the metropolitan area of Monterrey, Nuevo Leon, Mexico, and taking into consideration that soil is an important pathway of exposure for people, a biomonitoring program for the surveillance of the general population in the metropolitan area of Monterrey, Nuevo Leon is deemed necessary.

Coupling of solar photoelectro-Fenton with a BDD anode and solar heterogeneous photocatalysis for the mineralization of the herbicide atrazine.

Here, the synergetic effect of coupling solar photoelectro-Fenton (SPEF) and solar heterogeneous photocatalysis (SPC) on the mineralization of 200mL of a 20mg L(-1) atrazine solution, prepared from the commercial herbicide Gesaprim, at pH 3.0 was studied. Uniform, homogeneous and adherent anatase-TiO2 films onto glass spheres of 5mm diameter were prepared by the sol-gel dip-coating method and used as catalyst for SPC. However, this procedure yielded a poor removal of the substrate because of the low oxidation ability of positive holes and OH formed at the catalyst surface to destroy it. Atrazine decay was improved using anodic oxidation (AO), electro-Fenton (EF), SPEF and coupled SPEF-SPC at 100mA. The electrolytic cell contained a boron-doped diamond (BDD) anode and H2O2 was generated at a BDD cathode fed with an air flow. The removal and mineralization of atrazine increased when more oxidizing agents were generated in the sequence AO

Performance of the photo-Fenton process in the degradation of a model azo dye mixture.

The degradation of a model mixture composed of Acid Yellow 36 (AY36) and Methyl Orange (MO) azo dyes was performed using the photo-Fenton process (PFP). The performance of this process conducted under artificial UV light (365 nm) was compared with the Fenton reaction. Some important operating parameters that affect the degradation of azo dyes, such as initial Fe(2+) and H(2)O(2) concentrations and the presence or absence of chloride ions, were investigated. Decolorisation of the dye mixture sample was achieved in 70 min with the photo-Fenton reaction, while the complete mineralization evaluated by TOC abatement was completed in 180 min. These results provide important knowledge for the treatment of wastewater containing azo dye mixtures by Fenton and photo-Fenton oxidation processes.