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Fluvial sediment analysis and water quality assessment are useful to identify anthropic and natural sources of pollution in rivers. Currently, there is a lack of information about water quality in the Pixquiac basin (Veracruz state, Mexico), and this scarcity of data prevents authorities to take adequate measures to protect water resources. The basin is a crucial territory for Xalapa, the capital city of Veracruz state, as it gets 39% of its drinkable water from it. This research analyzed 10 physicochemical parameters and 12 metal concentrations in various rivers and sources during two seasons. Dissolved metals presented average concentrations (µg/L): Al (456.25) > Fe (199.4) > Mn (16.86) > Ba (13.8) > Zn (7.6) > Cu (1.03) > Pb (0.27) > As (0.12) > Ni (0.118) (Cd, Cr and Hg undetectable). Metals in sediment recorded average concentrations (ppm): Fe (38575) > Al (38425) > Mn (460) > Ba (206.2) > Zn (65.1) > Cr (29.8) > Ni (20.9) > Cu (16.4) > Pb (4.8) > As (2.1) (Cd and Hg undetectable). During the rainy season, Water Quality Index (WAWQI) classified stations P17 and P18's water as "unsuitable for drinking" with values of 110.4 and 117.6. Enrichment factor (EF) recorded a "moderate enrichment" of Pb in sediment in P24. Pollution was mainly explained by wastewater discharges in rivers but also because of erosion and rainfall events. Statistical analysis presented strong relationships between trace and major metals which could explain a common natural origin for metals in water and sediment: rock lixiviation.
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Agua Potable , Monitoreo del Ambiente , Sedimentos Geológicos , Contaminantes Químicos del Agua , Calidad del Agua , Abastecimiento de Agua , México , Contaminantes Químicos del Agua/análisis , Monitoreo del Ambiente/métodos , Sedimentos Geológicos/química , Agua Potable/química , Ríos/química , Metales Pesados/análisis , Metales/análisisRESUMEN
In this study, UiO-67 (Zr)/g-C3N4 composites (U67N) were synthesized at wt.% ratios of 05:95, 15:85, and 30:70 using the solvothermal method at 80 °C for 24 h followed by calcination at 350 °C. The composites were characterized using UV-Vis diffuse reflectance spectroscopy, Fourier-transform infrared spectroscopy, photoluminescence spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction, scanning electron microscopy-energy-dispersive X-ray spectroscopy, transmission electron microscopy, and nitrogen physisorption analysis. In addition, thermal stability analysis of UiO-67 was conducted using thermogravimetric analysis. The photocatalytic performance of the composites was assessed during the degradation and mineralization of a mixture of methylparaben (MeP) and propylparaben (PrP) under simulated sunlight. The adsorption process of U67N 15:85 was characterized through kinetic studies and adsorption capacity experiments, which were modeled using pseudo-first-order and pseudo-second-order kinetics and Langmuir and Freundlich isotherms, respectively. The influence of pH levels 3, 5, and 7 on the photocatalytic degradation of the mixture was investigated, revealing enhanced degradation and mineralization at pH 3. The U67N composite exhibited dual capability in removing contaminants through adsorption and photocatalytic processes. Among the prepared composites, U67N 15:85 demonstrated the highest photocatalytic activity, achieving removal efficiencies of 96.8% for MeP, 92.5% for PrP, and 45.7% for total organic carbon in 300 kJ/m2 accumulated energy (3 h of reaction time). The detoxification of the effluent was confirmed through acute toxicity evaluation using the Vibrio fischeri method. The oxidation mechanism of the heterojunction formed between UiO-67 (Zr) and g-C3N4 was proposed based on PL analysis, photoelectrochemistry studies (including photocurrent response, Nyquist, and Mott-Schottky analyses), and scavenger assays.
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Parabenos , Contaminantes Químicos del Agua , Parabenos/química , Adsorción , Contaminantes Químicos del Agua/química , Estructuras Metalorgánicas/química , Catálisis , CinéticaRESUMEN
The quality of life and human survival is dependent on sustainable development and sanitation of water bodies in an environment. The present research focuses on cyclicity data of more than 750,000 records of parameters associated with the water quality from a rural-urban river monitoring stations in real-time from River Atoyac in Central Mexico. The events detected in the instrumental records correlated with 2528 laboratory and instrumental determinations. The 64 polluting compounds were grouped into inorganic compounds (metals and metalloids) and organic compounds (pesticides, herbicides, hydrocarbons). Metal associated compounds were grouped along mechanical, pharmaceutical and textile industries which associates itself with the entry of polluting components. The cyclicity of the events was detected through Discrete Fourier Transformation time series analysis identifying the predominant events in each station. These highlight the events at 23-26 h corresponding to a circadian pattern of the metabolism of the city. Likewise, pollution signals were detected at 3.3, 5.5, and 12-14 h, associated with discharges from economic activities. Multivariate statistical techniques were used to identify the circadian extremes of a regionalized cycle of polluting compounds in each of the stations. The results of this research allow pollution prevention using a mathematical analysis of time series of different quality parameters collected at monitoring stations in real-time as a tool for predicting polluting events. The DFT analysis makes it possible to prevent polluting events in different bodies of water, allowing to support the development of public policies based on the supervision and control of pollution.
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Monitoreo del Ambiente , Contaminantes Químicos del Agua , Humanos , Monitoreo del Ambiente/métodos , Ríos , Análisis de Fourier , México , Calidad de Vida , Contaminantes Químicos del Agua/análisisRESUMEN
Introduction: A high percentage of patients with non-severe (17.9%) and severe (2.9%) atypical pneumonia do not display pulmonary tomographic findings upon hospital admission; furthermore, lesion associated with COVI-19 are peripherally distributed in a multifocal ground-glass pattern, as well as displaying an irregular consolidation pattern, with a posterior or lower lobe predilection. The main objective of this study was to identify the pulmonary radiological patterns in patients diagnosed with SARS-CoV-2 pneumonia, the factors associated with the need for mechanical ventilation, as well as their survival rates at 30 days. Methods: We report the pulmonary tomographic findings of 490 consecutive patients with severe and critical pneumonia due to SARS-CoV-2. The patients were classified according to the tomography and demographic findings, sepsis severity prognostic scales, Charlson comorbidity index (CCI), the Sequential Organ Failure Assessment (SOFA), and the Acute Physiology and Chronic Health Evaluation (APACHE IV). The Kaplan-Meier method was used to calculate survival distributions. Results: 89.80% of patients had ground-glass opacities, 81.63% radiologic consolidation sign, 42.45% vascular thickening pattern, 37.55% lymphadenopathies, 14.90% pleural effusion, and 2.65% pulmonary thrombosis; meanwhile, 91.02% had bilateral lesions, 85.51% had peripheral lesions, and 75.92% had basal lobe lesions. APACHE IV (HR, 1.191, 95% CI [1.126, 1.260]), SOFA (HR, 5.178, 95%CI [3.103, 8.641]), and CCI (HR, 0.673, 95%CI [0.510, 0.889]), as well as the pulmonary damage severity index (HR, 1.282, 95%CI [1.151, 1.428]), predict the need for invasive mechanical ventilation. Only moderate ARDS patients with mild and severe lung disease showed different 30-day mortality distributions (χ2 = 7.00, p = 0.008). Discussion: Although the survival distributions did not vary significantly, an overwhelming majority of patients (i.e., 84.35%) with a higher pulmonary damage severity index (i.e., 23>) died within 30 days of hospital admission, while only 25.91% with moderate lung damage and 2.42% with mild lung damage.
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The results of the successful implementation of a treatment based on the injection of ozone (O3) and oxygen (O2) into a contaminated body of water are reported for the first time. Three decontaminating units (SCAVENGER™), which have the capacity to inject up to 120 g O3/h and 250 Kg O2/h in the form of microbubbles (90 ± 10 µm in diameter), were placed in the contaminated Valsequillo reservoir, Central Mexico. In order to evaluate the efficacy of the treatment, 20 physicochemical parameters, 18 organic compounds, 66 inorganic compounds and 11 biological indicators were measured before, during and after the treatment; all of them in several representative sites of the east side of the Valsequillo reservoir. After 5 months of operating the SCAVENGER™ units in the eastern part of the reservoir, the concentration of Dissolved Oxygen (DO) increased 68%. Likewise, the chemical reducing conditions of the reservoir reflected by the low oxidation-reduction potential (ORP; -237 ± 75 mV) became quasi-oxidant (10 ± 58 mV). The treatment was efficient in water disinfection, presenting an 80% reduction in Fecal Coliforms (FC). Some heavy metals also showed a decrease in their concentration, being as follows: Al (65%), Cr (35%), Pb (46%), Zn (60%), Mn (20%), Mo (40%), Fe (32%), As (58%) and Co (26%). Due to the selective reactivity of ozone towards aliphatic and aromatic unsaturated compounds, several organic compounds reduced in their concentration by up to two orders of magnitude. Based on the above, it is evident that the treatment with ozone and oxygen was effective in substantially improving the quality of water in the east side of the Valsequillo reservoir.
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River Atoyac is considered to be one of the most polluted rivers in Mexico due to the discharges of untreated or partially treated wastewater from industrial and municipal activities. In order to improve the river water quality, it is obligatory to identify the possible contaminant sources for upholding a well-balanced ecosystem. Henceforth, the present study incorporates the application of a continuous real-time monitoring system to identify the provenance of pollutants of the river mainly from anomaly events. Four monitoring stations were installed all along the River Atoyac in the State of Puebla, Central Mexico. The real-time monitoring systems have an ability to measure various water quality parameters for every 15 minutes such as Temperature (T), pH, Conductivity (EC), turbidity (TURB), Dissolved Oxygen (DO), Oxidation Reduction Potential (ORP) and Spectral Absorption Coefficient (SAC). In total, eight water samples of anomaly events (i.e.) 2 per monitoring station during rainy (August-September) and winter seasons (November-December), that were detected using the parameters previously mentioned were procured and also analyzed in the laboratory for evaluating almost 54 physicochemical, inorganic and organic characteristics. Statistical results of factorial analysis explained that 30% of the total variance corresponded to textile effluents, 23% related to discharges produced by automobile and petrochemical industries, and 18% of the total variance defined the agricultural activities. Additionally, indices like Overall Index Pollution, Heavy Metal Evaluation Index, Screening Quick Reference Table and Molecular ratios of hydrocarbons for PAH sources was also calculated to estimate the grade of pollution and associated ecotoxicological risks. The present study also enlightens the fact that the assessed results will definitely provide valuable information for the management of river water quality by developing stringent public policies by governmental agencies for the sustainable conservation of Atoyac River.
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The development of a new method to determine the presence of the organoarsenic additives p-arsanilic acid (ASA), roxarsone (ROX) and nitarsone (NIT) in livestock feeds by high performance liquid chromatography coupled to ultraviolet oxidation hydride generation atomic fluorescence spectrometry (HPLC-UV/HG-AFS) after microwave assisted extraction (MAE) was proposed. Chromatographic separation was achieved on a C18 column with 2% acetic acid/methanol (96:4, v/v) as the mobile phase. The limits of detection (LODs) were 0.13, 0.09 and 0.08mgL-1, and the limits of quantification (LOQs) were 0.44, 0.30 and 0.28mgL-1. The relative standard deviations (RSDs) for ASA, ROX and NIT determined from five measurements of the mixed calibration standard were 3.3, 5.3, and 5.4%, respectively. MAE extraction of phenylated arsenic compounds using 1.5M H3PO4 at 120°C for 45min allowed for maximum recoveries (%) of total arsenic (As) and organoarsenic species, with no degradation of these compounds. The extraction of total As was approximately 97%, and the As species recoveries were between 95.2 and 97.0%. The results of the analysis were validated using mass balance by comparing the sum of extracted As with the total concentration of As in the corresponding samples. The method was successfully applied to determine the presence of these compounds in feed samples. ASA was the only As species detected in chicken feed samples, with a concentration between 0.72 and 12.91mgkg-1.
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Alimentación Animal , Ganado , Animales , Arsénico , Cromatografía Líquida de Alta Presión , Análisis de los Alimentos , Microondas , Espectrometría de FluorescenciaRESUMEN
In this study, the photocatalytic removal of an emerging contaminant, diclofenac (DCF) sodium, was performed using the nitrogen-doped WO3/TiO2-coupled oxide catalyst (WO3/TiO2-N). The catalyst synthesis was accomplished by a sol-gel method using tetrabutyl orthotitanate (C16H36O4Ti), ammonium p-tungstate [(NH4)10H2W12O42·4H2O] and ammonium nitrate (NH4NO3) as the nitrogen source. For comparison, TiO2 and WO3/TiO2 were also prepared under similar conditions. Analysis by X-ray diffraction (XRD), N2 adsorption-desorption, scanning electron microscopy (SEM), transmission electron microscopy (TEM), diffuse reflectance UV-Vis spectroscopy (DRS) and X-ray photoelectron spectroscopy (XPS) were conducted to characterize the synthesized materials. The photocatalytic efficiency of the semiconductors was determined in a batch reactor irradiated with simulated solar light. Residual and mineralized DCF were quantified by high-performance liquid chromatography, total organic carbon analysis and ion exchange chromatography. The results indicated that the tungsten atoms were dispersed on the surface of TiO2 as WO3. The partial substitution of oxygen by nitrogen atoms into the lattice of TiO2 was an important factor to improve the photocatalytic efficiency of WO3/TiO2. Therefore, the best photocatalytic activity was obtained with the WO3/TiO2-N0.18 catalyst, reaching 100% DCF transformation at 250 kJ m-2 and complete mineralization at 400 kJ m-2 of solar-accumulated energy.
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Diclofenaco/química , Nitrógeno/química , Titanio/química , Adsorción , Catálisis , Microscopía Electrónica de Rastreo , Microscopía Electrónica de Transmisión , Óxidos , Procesos Fotoquímicos , Espectroscopía de Fotoelectrones , Tungsteno , Difracción de Rayos XRESUMEN
Photocatalytic degradation of 4-chloro-2-methylphenoxyacetic acid (MCPA) in aqueous solution using Cr(III)-doped TiO2 under UV and visible light was investigated. The semiconductor material was synthesized by a microwave-assisted sol-gel method with Cr(III) doping contents of 0.02, 0.04, and 0.06 wt%. The catalyst was characterized using X-ray powder diffraction (XRD), scanning electron microscopy (SEM), nitrogen physisorption, UV-Vis diffuse reflectance spectroscopy (DRS), and atomic absorption spectroscopy (AAS). The photocatalytic activity for the photodegradation of MCPA was followed by reversed-phase high-performance liquid chromatography (HPLC) and total organic carbon (TOC) analysis. The intermediates formed during degradation were identified using gas chromatography-mass spectrometry (GC-MS). Chloride ion evolution was measured by ion chromatography. Characterization results showed that Cr(III)-doped TiO2 materials possessed a small crystalline size, high surface area, and mesoporous structure. UV-Vis DRS showed enhanced absorption in the visible region as a function of the Cr(III) concentration. The Cr(III)-doped TiO2 catalyst with 0.04 wt% of Cr(III) was more active than bare TiO2 for the degradation of MCPA under both UV and visible light. The intermediates identified during MCPA degradation were 4-chloro-2-methylphenol (CMP), 2-(4-hydroxy-2-methylphenoxy) acetic acid (HMPA), and 2-hydroxybuta-1,3-diene-1,4-diyl-bis (oxy)dimethanol (HBDM); the formation of these intermediates depended on the radiation source.
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Microondas , Titanio/química , Catálisis , CresolesRESUMEN
The leaching of antimony (Sb) from polyethylene terephthalate (PET) bottling material was assessed in twelve brands of bottled water purchased in Mexican supermarkets by atomic fluorescence spectrometry with a hydride generation system (HG-AFS). Dowex® 1X8-100 ion-exchange resin was used to preconcentrate trace amounts of Sb in water samples. Migration experiments from the PET bottle material were performed in water according to the following storage conditions: 1) temperature (25 and 75°C), 2) pH (3 and 7) and 3) exposure time (5 and 15days), using ultrapure water as a simulant for liquid foods. The test conditions were studied by a 2(3) factorial experimental design. The Sb concentration measured in the PET packaging materials varied between 73.0 and 111.3mg/kg. The Sb concentration (0.28-2.30µg/L) in all of the PET bottled drinking water samples examined at the initial stage of the study was below the maximum contaminant level of 5µg/L prescribed by European Union (EU) regulations. The parameters studied (pH, temperature, and storage time) significantly affected the release of Sb, with temperature having the highest positive significant effect within the studied experimental domain. The highest Sb concentration leached from PET containers was in water samples at pH7 stored at 75°C for a period of 5days. The extent of Sb leaching from the PET ingredients for different brands of drinking water can differ by as much as one order of magnitude in experiments conducted under the worst-case conditions. The chronic daily intake (CDI) caused by the release of Sb in one brand exceeded the Environmental Protection Agency (USEPA) regulated CDI value of 400ng/kg/day, with values of 514.3 and 566.2ng/kg/day for adults and children. Thus, the appropriate selection of the polymer used for the production of PET bottles seems to ensure low Sb levels in water samples.
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Antimonio/análisis , Agua Potable/química , Contaminación de Alimentos/análisis , Tereftalatos Polietilenos/química , Contaminantes Químicos del Agua/análisis , Antimonio/química , Embalaje de Alimentos , Temperatura , Contaminantes Químicos del Agua/química , Calidad del AguaRESUMEN
In this work, nitrogen-doped ZnO material was synthesized by the sol-gel method using zinc acetate as the precursor and urea as the nitrogen source (15, 20, 25 and 30% wt.). For comparative purposes, bare ZnO was also prepared. The influence of N doping on structural, morphological, optical and photocatalytic properties was investigated. The synthesized catalysts were characterized by XRD, SEM-EDS, diffuse reflectance UV-Vis spectroscopy, BET and XPS analysis. The photocatalytic activity of N-doped ZnO catalysts was evaluated during the degradation of a mixture of herbicides (2,4-D and picloram) under visible radiation ≥400 nm. The photo-absorption wavelength range of the N-doped ZnO samples was shifted to longer wavelength compared to those of the unmodified ZnO. Among different amounts of dopant agent, the 30% N-doped ZnO material showed higher visible-light activity compared with pure ZnO. Several degradation by-products were identified by using HPLC and ESI-MS/MS. The enhancement of visible photocatalytic activity of the N-doped ZnO semiconductor could be mainly due to their capability in reducing the electron-hole pair recombination.
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Ácido 2,4-Diclorofenoxiacético/química , Herbicidas/química , Nitrógeno/química , Procesos Fotoquímicos , Picloram/química , Óxido de Zinc/química , Óxido de Zinc/síntesis química , Catálisis , Técnicas de Química SintéticaRESUMEN
In this study, a multisyringe chromatography system (MSC) using a C18 monolithic column was proposed for the on-line monitoring of the photocatalytic degradation of isoniazid (INH, 10 mg L(-1)) and pyrazinamide (PYRA, 5mgL(-1)) mixtures in aqueous solution using a small sample volume (200 µL) with an on-line filtration device in a fully automated approach. During the photocatalytic oxidation using TiO2 or ZnO semiconductor materials, total organic carbon (TOC) and the formed intermediates were analyzed off-line using ion chromatography, ion exclusion HPLC, and ESI-MS/MS. The results showed that TiO2 exhibits a better photocatalytic activity than ZnO under UV irradiation (365 nm) for the degradation of INH and PYRA mixtures, generating 97% and 92% degradation, respectively. The optimal oxidation conditions were identified as pH 7 and 1.0 g L(-1) of TiO2 as catalyst. The mineralization of the initial organic compounds was confirmed by the regular decrease in TOC, which indicated 63% mineralization, and the quantitative release of nitrate and nitrite ions, which represent 33% of the nitrogen in these compounds. The major intermediates of INH degradation included isonicotinamide, isonicotinic acid, and pyridine, while the ESI-MS/MS analysis of PYRA aqueous solution after photocatalytic treatment showed the formation of pyrazin-2-ylmethanol, pyrazin-2-ol, and pyrazine. Three low-molecular weight compounds, acetamide, acetic acid and formic acid, were detected during INH and PYRA decomposition. PYRA was more resistant to photocatalytic degradation due to the presence of the pyrazine ring, which provides greater stability against OH attack.
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Antituberculosos/aislamiento & purificación , Monitoreo del Ambiente/métodos , Isoniazida/aislamiento & purificación , Pirazinamida/aislamiento & purificación , Contaminantes Químicos del Agua/aislamiento & purificación , Purificación del Agua/métodos , Antituberculosos/análisis , Antituberculosos/efectos de la radiación , Catálisis , Cromatografía Líquida de Alta Presión , Monitoreo del Ambiente/instrumentación , Diseño de Equipo , Isoniazida/análisis , Isoniazida/efectos de la radiación , Oxidación-Reducción , Procesos Fotoquímicos , Pirazinamida/análisis , Pirazinamida/efectos de la radiación , Espectrometría de Masa por Ionización de Electrospray , Espectrometría de Masas en Tándem , Titanio/química , Rayos Ultravioleta , Contaminantes Químicos del Agua/análisis , Contaminantes Químicos del Agua/efectos de la radiación , Purificación del Agua/instrumentación , Óxido de Zinc/químicaRESUMEN
The presence of arsenic (As) in agricultural food products is a matter of concern because it can cause adverse health effects at low concentrations. Agricultural-product intake constitutes a principal source for As exposure in humans. In this study, the contribution of the chemical-soil parameters in As accumulation and translocation in the maize crop from a mining area of San Luis Potosi was evaluated. The total arsenic concentration and arsenic speciation were determined by HG-AFS and IC-HG-AFS, respectively. The data analysis was conducted by cluster analysis (CA) and principal component analysis (PCA). The soil pH presented a negative correlation with the accumulated As in each maize plant part, and parameters such as iron (Fe) and manganese (Mn) presented a higher correlation with the As translocation in maize. Thus, the metabolic stress in maize may induce organic acid exudation leading a higher As bioavailability. A high As inorganic/organic ratio in edible maize plant tissues suggests a substantial risk of poisoning by this metalloid. Careful attention to the chemical changes in the rhizosphere of the agricultural zones that can affect As transfer through the food chain could reduce the As-intoxication risk of maize consumers.
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Arsénico/análisis , Monitoreo del Ambiente , Contaminantes del Suelo/análisis , Zea mays/química , Agricultura , México , Minería , Suelo/químicaRESUMEN
Arsenic (As) is a metalloid that may represent a serious environmental threat, due to its wide abundance and the high toxicity particularly of its inorganic forms. The use of arsenic-contaminated groundwater for irrigation purposes in crop fields elevates the arsenic concentration in topsoil and its phytoavailability for crops. The transfer of arsenic through the crops-soil-water system is one of the more important pathways of human exposure. According to the Food and Agriculture Organization of the United Nations, maize (Zea mays L.) is the most cultivated cereal in the world. This cereal constitutes a staple food for humans in the most of the developing countries in Latin America, Africa, and Asia. Thus, this review summarizes the existing literature concerning the conditions involved in agricultural soil that leads to As influx into maize crops and the uptake mechanisms, metabolism and phytotoxicity of As in corn plants. Additionally, the studies of the As accumulation in raw corn grain and corn food are summarized, and the As biotransfer into the human diet is highlighted. Due to high As levels found in editable plant part for livestock and humans, the As uptake by corn crop through water-soil-maize system may represent an important pathway of As exposure in countries with high maize consumption.
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Arsénico/metabolismo , Contaminantes del Suelo/metabolismo , Zea mays/metabolismo , Agricultura , Productos Agrícolas/metabolismo , Contaminación de Alimentos/estadística & datos numéricos , Suelo/químicaRESUMEN
In this work, the potential of a membrane optode coupled to a multisyringe flow injection system (MSFIA) was assessed for determining the Cr(VI) concentration in paint samples. The detection is based on the color obtained from the reaction of Cr(VI) with 1,5-diphenylcarbazide in the presence of sulfuric acid (H(2)SO(4)). The redox product was immobilized on a poly(styrene-divinylbenzene) (SDB-XC) membrane optode. The analyte in the sample was then directly quantified at the surface of the disk by measuring the intensity of reflected incident light using a bifurcated optical fiber at 540 nm. Experimental parameters (concentration of reagents, sample volume, flow rate of sample solutions, eluent concentration, and effect of diverse ions) were studied in detail. The overall time required for the complete procedure was 4 min and only required 0.2 mL of the sample volume. The dynamic working response of Cr(VI) was found within the concentration range of 2.4-1000 µg L(-1) with a limit of detection (LOD) of 0.7 µg L(-1), while the relative standard deviation (RSD) for 400 µg L(-1) Cr(VI) was lower than 2% (n=6). This developed method was used to determine Cr(VI) concentrations in the paint samples, for which an alkaline extraction procedure was proposed. The extraction procedure was based on the use of a 7.5% Na(2)CO(3)/5% NaOH solution at 90 °C for 30 min. Under optimal conditions, the recoveries ranged from 99% to 101%. The complete method was validated using a certified reference material (ERA-QC540, soil sample) and by comparing the results with those obtained using atomic absorption spectrometry (AAS).
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Simultaneous determination of three herbicides (dicamba, 2,4-D, and atrazine) has been achieved by on-line solid-phase extraction (SPE) coupled to multisyringe chromatography (MSC) with UV detection. The preconcentration conditions were optimized; a preconcentration flow rate of 0.5 mL min(-1) and elution at 0.8 mL min(-1) were the optimum conditions. A C(18) (8 mm i.d.) membrane extraction disk conditioned with 0.3 mol L(-1) HCl in 0.5% MeOH was used. A 3-mL sample was preconcentrated, then eluted with 0.43 mL 40:60 water-MeOH. A C(18) monolithic column (25 mm × 4.6 mm) was used for chromatographic separation. Separation of the three compounds was achieved in 10 min by use of 0.01% aqueous acetic acid-MeOH (60:40) as mobile phase at a flow rate of 0.8 mL min(-1). The limits of detection (LOD) were 13, 57, and 22 µg L(-1) for dicamba, 2,4-D, and atrazine, respectively. The sampling frequency was three analyses per hour, and each analysis consumed only 7.3 mL solvent. The method was applied to spiked water samples, and recovery between 85 and 112% was obtained. Recovery was significantly better than in the conventional HPLC-UV method. These results indicated the reliability and accuracy of this flow-based method. This is the first time this family of herbicides has been simultaneously analyzed by on-line SPE-MSC using a monolithic column.
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Ácido 2,4-Diclorofenoxiacético/aislamiento & purificación , Atrazina/aislamiento & purificación , Dicamba/aislamiento & purificación , Herbicidas/aislamiento & purificación , Extracción en Fase Sólida/instrumentación , Contaminantes Químicos del Agua/aislamiento & purificación , Ácido 2,4-Diclorofenoxiacético/análisis , Atrazina/análisis , Cromatografía Líquida de Alta Presión/instrumentación , Dicamba/análisis , Agua Potable/análisis , Diseño de Equipo , Herbicidas/análisis , Límite de Detección , Contaminantes Químicos del Agua/análisisRESUMEN
The photocatalytic reduction of Cr(VI) from agricultural soil leachates irrigated with Cr(VI)-containing waste hydroponic solution was evaluated in this work. For this purpose, zinc oxide was used as a catalyst under UV irradiation (lambda = 365 nm). The reduction of Cr(VI) was preliminarily evaluated on synthetic solutions with a concentration of 15 mg L(-1) to optimize the catalyst loading and the solution pH and to determine the effect of organic matter. Greater removal of Cr(VI) was observed at pH 7, and the optimum catalyst loading was found to be 2 g L(-1), which achieved an 84% Cr(VI) reduction in 6 h. The influence of dissolved organic matter on the reduction of Cr(VI) was evaluated through the addition of different concentrations of humic acid (HA) to the chromium solution. The removal of Cr(VI) was continuously enhanced as the HA concentration gradually increased from 0 to 14 mg L(-1). The percentage of hexavalent chromium reduction from soil leachates was in the range of 13-99%, and the rate constant was significantly enhanced by the presence of organic compounds in the soil pore water. Thus, a marked synergistic effect between the photocatalytic reduction of Cr(VI) and the organic matter in soil (e.g. humic substances) was observed in real samples and was similar to that observed in the Cr(VI) synthetic solution that contained HA.
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Agricultura , Cromo/química , Contaminantes del Suelo/química , Rayos Ultravioleta , Óxido de Zinc/química , Catálisis , Concentración de Iones de Hidrógeno , Oxidación-Reducción , Procesos Fotoquímicos , Aguas ResidualesRESUMEN
In this paper, a novel automatic approach for the speciation of inorganic mercury (Hg(2+)), methylmercury (MeHg(+)) and ethylmercury (EtHg(+)) using multisyringe chromatography (MSC) coupled to cold-vapor atomic fluorescence spectrometry (CV/AFS) was developed. For the first time, the separation of mercury species was accomplished on a RP C18 monolithic column using a multi-isocratic elution program. The elution protocol involved the use of 0.005% 2-mercapthoethanol in 240 mM ammonium acetate (pH 6)-acetonitrile (99:1, v/v), followed by 0.005% 2-mercapthoethanol in 240 mM ammonium acetate (pH 6)-acetonitrile (90:10, v/v). The eluted mercury species were then oxidized under post-column UV radiation and reduced using tin(II) chloride in an acidic medium. Subsequently, the generated mercury metal were separated from the reaction mixture and further atomized in the flame atomizer and detected by AFS. Under the optimized experimental conditions, the limits of detection (3σ) were found to be 0.03, 0.11 and 0.09 µg L(-1) for MeHg(+), Hg(2+) and EtHg(+), respectively. The relative standard deviation (RSD, n=6) of the peak height for 3, 6 and 3 µg L(-1) of MeHg(+), Hg(2+) and EtHg(+) (as Hg) ranged from 2.4 to 4.0%. Compared with the conventional HPLC-CV/AFS hyphenated systems, the proposed MSC-CV/AFS system permitted a higher sampling frequency and low instrumental and operational costs. The developed method was validated by the determination of a certified reference material DORM-2 (dogfish muscle), and was further applied for the determination of mercury species environmental and biological samples.
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This work shows preliminary results on the electrochemical oxidation process (EOP) using boron-doped diamond (BDD) electrode for acidic yellow 36 oxidation, a common azo dye used in textile industry. The study is centred in the synergetic effect of ferrous ions and hydroxyl free radicals for improving discoloration of azo dye. The assays were carried out in a typical glass cell under potentiostatic conditions. On experimental conditions, the EOP was able to partially remove the dye from the reaction mixture. The reaction rate increased significantly by addition of Fe(2+) (1mM as ferrous sulphate) to the system and by (assumed) generation of ferrate ion [Fe(VI)] over BDD electrode. Ferrate is considered as a highly oxidizing reagent capable of removing the colorant from the reaction mixture, in synergistic action with the hydroxyl radicals produced on the BDD surface. Further increases in the Fe(2+) concentration lead to depletion of the reaction rate probably due to the hydroxyl radical scavenging effect of Fe(2+) excess in the system.