Hydrothermal synthesis of a photocatalyst based on Byrsonima crassifolia and TiO2 for degradation of crystal violet by UV and visible radiation.

This work presents a one-step synthesis methodology for preparing a hydrochar (HC) doped with TiO2 (HC-TiO2) for its application on the degradation of crystal violet (CV) using UV and visible radiation. Byrsonima crassifolia stones were used as precursors along with TiO2 particles. The HC-TiO2 sample was synthesized at 210 °C for 9 h using autogenous pressure. The photocatalyst was characterized to evaluate the TiO2 dispersion, specific surface area, graphitization degree, and band-gap value. Finally, the degradation of CV was investigated by varying the operating conditions of the system, the reuse of the catalyst, and the degradation mechanism. The physicochemical characterization of the HC-TiO2 composite showed good dispersion of TiO2 in the carbonaceous particle. The presence of TiO2 on the hydrochar surface yields a bandgap value of 1.17 eV, enhancing photocatalyst activation with visible radiation. The degradation results evidenced a synergistic effect with both types of radiation due to the hybridized π electrons in the sp2-hybridized structures in the HC surface. The degradation percentages were on average 20% higher using UV radiation than visible radiation under the following conditions: [CV] = 20 mg/L, 1 g/L of photocatalyst load, and pH = 7.0. The reusability experiments demonstrated the feasibility of reusing the HC-TiO2 material up to 5 times with a similar photodegradation percentage. Finally, the results indicated that the HC-TiO2 composite could be considered an efficient material for the photocatalytic treatment of water contaminated with CV.

An efficient removal approach for degradation of metformin from aqueous solutions with sulfate radicals.

Metformin consumption for diabetes treatment is increasing, leading to its presence in wastewater treatment plants where conventional methods cannot remove it. Therefore, this work aims to analyze the performance of advanced oxidation processes using sulfate radicals in the degradation of metformin from water. Experiments were performed in a photoreactor provided with a low-pressure Hg lamp, using K2S2O8 as oxidant and varying the initial metformin concentration (CA0), oxidant concentration (Cox), temperature (T), and pH in a response surface experimental design. The degradation percentages ranged from 26.1 to 87.3%, while the mineralization percentages varied between 15.1 and 64%. Analysis of variance (ANOVA) showed that the output variables were more significantly affected by CA0, Cox, and T. Besides, a reduction of CA0 and an increase of Cox up to 5000 µM maximizes the metformin degradation since the generation of radicals and their interaction with metformin molecules are favored. For the greatest degradation percentage, the first order apparent rate constant achieved was 0.084 min-1. Furthermore, while in acidic pH, temperature benefits metformin degradation, an opposite behavior is obtained in a basic medium because of recombination and inhibition reactions. Moreover, three degradation pathways were suggested based on the six products detected by HPLC-MS: N-cyanoguanidine m/z = 85; N,N-dimethylurea m/z = 89; N,N-dimethyl-cyanamide m/z = 71 N,N-dimethyl-formamide m/z = 74; glicolonitrilo m/z = 58; and guanidine m/z = 60. Finally, it was shown that in general the toxicity of the degradation byproducts was lower than the toxicity of metformin toward Chlamydomonas reinhardtii.

Electrocatalytic activity of calcined manganese ferrite solid nanospheres in the oxygen reduction reaction.

In this study, we synthesized MnFe2O4 solid nanospheres (MSN) calcined at different temperatures (200-500 °C) and MSN-based materials mixed with carbon black, for their use as electrocatalysts in the oxygen reduction reaction (ORR) in alkaline medium (0.1 M KOH). It was demonstrated that the calcination temperature of MSN material determined its chemical surface composition and microstructure and it had an important effect on the electrocatalytic properties for ORR, which in turn was reflected in the performance of MSN/CB-based electrocatalysts. The study revealed that the presence of Mn species plays a key role in the ORR activity. Among tested, MSN200/CB and MSN350/CB exhibited the best electrochemical performances together with outstanding stability.

Oxidation of sulfonamides by ferrate(VI): Reaction kinetics, transformation byproducts and toxicity assesment.

This study was aimed at the degradation of sulfonamides (SNs) via oxidation with Fe(VI). The reaction kinetics, identification of degradation byproducts and their toxicity were investigated. The pH solution and Fe(VI) loading had significant effects on the degradation of the sulfonamides. The maximum degradation rate occurred at pH 3.0 with a 6:1 ratio Fe(VI): sulfonamide, obtaining 100% degradation of 15 mg L-1 SN within 5 min. Although Fe(VI) also showed an appreciable reactivity towards SNs (kapp = 9.85-19.63 × 102 M-1 s-1) at pH 7. The influence of solution pH on the values of kapp can be explained considering the specific reaction between Fe(VI) and SNs. Degradation rates are also influenced by the presence of inorganic ions in different water matrixes. For this reason, ions present in groundwater enhanced the SNs degradation through a synergistic effect among carbonates, sulfates and Fe(VI). Degradation byproducts identified, through UPLC analysis, allowed us to proposed three degradation pathways depending on pH. At acid pH there is a cleavage of C-S and S-N bonds. At neutral pH nitroso and nitro-derivates are formed. At basic pH hydroxylation is the main reaction. The cytotoxicity assay of HEK-293 and J774 cell lines exposed to Fe(VI) indicated that transformation byproducts had a lower toxicity than SNs as baseline products. Accordingly, this research suggests that Fe(VI) can act as a chemical oxidant to remove SNs antibiotics and it can be used to treat antibiotic pollution in wastewater.

Degradation of the diuretic hydrochlorothiazide by UV/Solar radiation assisted oxidation processes.

The objective of this study was to analyse the effectiveness of advanced oxidation processes (AOPs) with Solar and UV radiation (UV/H2O2, UV/K2S2O8) for the degradation of hydrochlorothiazide (HCTZ), a widely used diuretic drug, in aqueous solution focusing on the influence of four experimental parameters: initial concentration of HCTZ, solution pH, nature of the water matrix, and initial concentration of radicals. The obtained results showed that using both kinds of direct photolysis (UV and Solar), the percentage of degraded HCTZ was low, but there was a decrease in the degradation rate favored by the increase of the initial concentration of this pollutant. In addition, the degradation rates were higher at acid pHs. With regard to the nature of water, the degradation rate varied in the order: ultrapure > superficial > tap water. This is due to the presence of organic and inorganic matter (bicarbonates, nitrates, and chlorides) in surface and tap water, that react with the radicals generated, which reduces the availability of radical species, generating competitive kinetics. The presence of radical-promoter species increased the degradation rate of the pollutant, reaching a degradation of 100% of HCTZ after 20 min of treatment. The results obtained point out that the degradation rate was higher in the presence of HO radicals. This behavior was attributed to the higher oxidation power of HO versus radicals. The determination of the degradation by-products led to structures very similar to the parent compound. For example, the corresponding hydroxylated dechlorinated derivative of HCTZ was found in all the systems used. The cytotoxicity test showed that these byproducts have a lower toxicity than the original product. Finally, the economic viability study confirmed that the UV/K2S2O8 system has the lowest cost.

Halide removal from water using silver doped magnetic-microparticles.

This study proposes the use of new materials based on core-shell structure magnetic microparticles with Ag0 (Ag(0)-MPs) on their surface to remove bromides and chlorides from waters intended for human consumption. Hydrogen peroxide was used as oxidizing agent, Ag(0)-MPs is thereby oxidized to Ag (I)-MPs, which, when in contact with Cl- and Br- ions, form the corresponding silver halide (AgCl and AgBr) on the surface of Ag-MPs. The concentration of Cl- and Br- ions was followed by using ion selective electrodes (ISEs). Silver microparticles were characterized by high-resolution scanning electron microscopy and X-ray photoelectron spectroscopy, while the presence of AgCl and AgBr on Ag-MPs was determined by microanalysis. We analyzed the influence of operational variables, including: hydrogen peroxide concentration in Ag-MP system, medium pH, influence of Cl- ions on Br- ion removal, and influence of tannic acid as surrogate of organic matter in the medium. Regarding the influence of pH, Br-and Cl- removal was constant within the pH range studied (3.5-7), being more effective for Br- than for Cl- ions. Accordingly, this research states that the system Ag-MPs/H2O2 can remove up to 67.01% of Br- ions and 56.92% of Cl- ions from water (pH = 7, [Ag-MPs]0 = 100 mg L-1, [H2O2]0 = 0.2 mM); it is reusable, regenerated by radiation and can be easily removed by applying a magnetically assisted chemical separation process.

Photocatalytic oxidation of diuron using nickel organic xerogel under simulated solar irradiation.

In this study, a nickel organic xerogel (X-Ni) was used as semiconductor photocatalyst for the degradation of the herbicide diuron (DRN) in aqueous solution. The main objective of this work was to analyze and compare the effectiveness of solar irradiation to remove DRN from water both by direct photolysis and photocatalytic degradation. We examined the influence of the initial concentration of the herbicide, the solution pH, the presence of different ions in the medium, the chemical composition of the water, and the presence of a photocatalyst, after 240 min of irradiation. Direct photolysis achieved a low percentage of DRN degradation but was favored: i) by a reduction in the initial concentration of the herbicide (from 35.6% to 79.0% for 0.150 × 10-3 mol/L and 0.021 × 10-3 mol/L of DRN, respectively) and ii) at solution pHs at which diuron is positively charged (78.6% for pH 2 and 50.4% for pH 7), as suggested by DFT calculations carried out for DRN and its protonated form (DRN-H+). The corresponding mono-demethylated DRN derivative, 1-(3,4-dichlorophenyl)-3-methylurea (DCPU), was identified as a DRN degradation byproduct. In addition, the presence of certain anions in the medium significantly affected the overall degradation process by direct photolysis, due to the additional generation of HO radicals. We highlight that the presence of X-Ni considerably improved the photodegradation process under solar irradiation. The photocatalytic degradation rate constant was directly proportional to the xerogel concentration, because an increase in catalyst dose produced an increase in surface active sites for the photodegradation of DRN, enhancing the overall efficiency of the process. Thus, when 4167 mg/g of X-Ni was added, the DRN removal rate was 3-fold higher and both percentage of degradation and mineralization increased 88.5% with respect to the results obtained by direct photolysis.

Lanthanum-doped silica xerogels for the removal of fluorides from waters.

The objective of this study was to determine the influence of different operational variables on fluoride (F-) removal from waters using lanthanum (La)-doped silica xerogels and the mechanisms involved in this process. Accordingly, four xerogels were synthesized, one acting as blank (X-B), two doped with LaCl3 and dried at different temperatures (X-LaCl and X-LaCl-M), and a fourth doped with La2O3 (X-LaO). The results show that fluorides are only removed when La-doped xerogels are utilized. In addition, X-LaCl yielded the highest adsorption capacity, removing 28.44% of the initial fluoride concentration at a solution pH of 7. Chemical characterization of materials confirmed that fluoride removal from waters is due to the precipitation of LaF3 on the surface of La-doped xerogels. The presence of dissolved organic matter on the aqueous solution also reduce the removal capacity of La xerogels. Finally, analysis of the influence of solution pH revealed that the adsorption capacity of all xerogels was highest at a solution pH of 7.

Nitroimidazoles adsorption on activated carbon cloth from aqueous solution.

The objective of this study was to analyze the equilibrium and adsorption kinetics of nitroimidazoles on activated carbon cloth (ACC), determining the main interactions responsible for the adsorption process and the diffusion mechanism of these compounds on this material. The influence of the different operational variables, such as ionic strength, pH, temperature, and type of water (ultrapure, surface, and waste), was also studied. The results obtained show that the ACC has a high capacity to adsorb nitroimidazoles in aqueous solution. Electrostatic interactions play an important role at pH<3, which favors the repulsive forces between dimetridazole or metronidazole and the ACC surface. The formation of hydrogen bonds and dispersive interactions play the predominant role at higher pH values. Modifications of the ACC with NH3, K2S2O8, and O3 demonstrated that its surface chemistry plays a predominant role in nitroimidazole adsorption on this material. The adsorption capacity of ACC is considerably high in surface waters and reduced in urban wastewater, due to the levels of alkalinity and dissolved organic matter present in the different types of water. Finally, the results of applying kinetic models revealed that the global adsorption rate of dimetridazole and metronidazole is controlled by intraparticle diffusion.

Adsorption mechanisms of metal cations from water on an oxidized carbon surface.

Adsorption of Cr(III), Mn(II), Cu(II) and Zn(II) on an oxidized activated carbon cloth was studied. Its surface chemistry was characterized by potentiometric titration. This technique revealed the amount of surface oxygen functionalities and their acidity constant distribution. The acidity constant range involved in the metal cation adsorption was obtained from this distribution. Metal cation adsorption increased with higher adsorption temperature due to the increase in the negative surface charge of the oxidized activated carbon. Adsorption was by proton exchange and the number, amount and strength of the surface acid groups involved could be obtained. The proton exchange was by an inner-sphere or outer-sphere surface metal complex formation mechanism. In the case of divalent cation adsorption, the increase in temperature changed the adsorption mechanism from outer-sphere to inner-sphere. However, the adsorption mechanism of Cr(III) was outer-sphere and independent of temperature. Adsorption capacity augmented with the increase in the charge-to-size ratio of the hexa-aquo cations. In addition, the adsorption capacity of divalent cations increased with the rise in stability of the surface metal complex formed.

Batch and column adsorption of herbicide fluroxypyr on different types of activated carbons from water with varied degrees of hardness and alkalinity.

There has been little research into the effects of the water hardness and alkalinity of surface waters on the adsorption of herbicides on activated carbons. The aim of this study was to determine the influence of these water characteristics on fluroxypyr adsorption on different activated carbons. At low fluroxypyr surface concentrations, the amount adsorbed from distilled water was related to the surface hydrophobicity. Surface area of carbons covered by fluroxypyr molecules ranged from 60 to 65%. Variations in fluroxypyr solubility with water hardness and alkalinity showed a salting-in effect. Calcium, magnesium and bicarbonate ions were adsorbed to a varied extent on the activated carbons. The presence of fluroxypyr in solution decreased their adsorption due to a competition effect. K(F) from the Freundlich equation linearly increased with water hardness due to salt-screened electrostatic repulsions between charged fluroxypyr molecules. The amount adsorbed from distilled water was largest at high fluroxypyr solution concentrations, because there was no competition between inorganic ions and fluroxypyr molecules. The column breakthrough volume and the amount adsorbed at breakthrough were smaller in tap versus distilled water. Carbon consumption was lower with activated carbon cloth than with the use of granular activated carbon.

Adsorption and thermal desorption of the herbicide fluroxypyr on activated carbon fibers and cloth at different pH values.

Adsorption of fluroxypyr was studied at pH values between 2 and 10 and at temperatures of 298 and 313 K. Adsorption capacity decreased when the solution pH increased. This was explained by changes in fluroxypyr solubility and in dispersive and electrostatic adsorbent-adsorbate interactions with the increase in pH. The highest adsorption was found at pH 2, when the solubility was the lowest and only dispersive interactions operated. An increase in temperature produced a decrease in adsorption capacity. Thermal desorption of fluroxypyr up to 1073 K left a residue on the carbon surface, which increased with higher adsorption pH. Differential thermogravimetry (DTG) profiles showed two desorption peaks at pH values of 2 and 4 and only one peak at pH values of 7 and 10. The appearance of one or two peaks may be related to the type of adsorbate-adsorbent interactions established during adsorption. The predominance of electrostatic interactions favours the strongly bound or chemisorbed fluroxypyr. One important conclusion is that the highest amounts of fluroxypyr are adsorbed and thermally desorbed when there are only non-electrostatic interactions between fluroxypyr molecules and carbon surface. Activation desorption energy and pre-exponential factor were obtained from the shift in temperature of desorption peaks with higher heating rate.

Kinetics of diuron and amitrole adsorption from aqueous solution on activated carbons.

A study was conducted on the adsorption kinetics of diuron and amitrole from aqueous solutions on activated carbons of different particle sizes and on an activated carbon fiber. Different kinetic models were applied to the experimental results obtained. A pseudo-second-order rate equation fitted the adsorption kinetics data better than a pseudo-first-order rate equation. Amitrole showed faster adsorption kinetics compared with diuron because of the smaller size of the former herbicide, despite its lower driving force for adsorption. Both reaction rate constants increased when the particle size decreased. The activated carbon fiber and the activated carbon of smallest particle size (0.03 mm) showed similar adsorption kinetics. The intraparticle diffusion rate constant increased with higher initial concentration of herbicides in solution and with lower particle size of the adsorbent. This is because the rise in initial concentration increased the amount adsorbed at equilibrium, and the reduction in particle size increased the number of collisions between adsorbate and adsorbent particles. Demineralization of the activated carbon with particle size of 0.5mm had practically no effect on the adsorption kinetics.

Removal of diuron and amitrole from water under static and dynamic conditions using activated carbons in form of fibers, cloth, and grains.

This study investigated the removal of the herbicides diuron and amitrole from water under static and dynamic conditions using different activated carbons in the form of fibers, cloth, and grains. In all cases, there was much greater adsorption of diuron than of amitrole due to the lower solubility, greater hydrophobicity, and larger dipolar moment of the former. The activated carbon cloth was the best adsorbent for diuron under dynamic conditions because it had the largest mesopore volume, water-accessible pore volume, and surface area. However, the best adsorbent for amitrole under dynamic conditions was the granular activated carbon due to its higher surface basicity. Comparisons using the best adsorbent for each herbicide showed that diuron was removed by the activated carbon more efficiently compared with amitrole under both dynamic and static conditions.

Effect of surface chemistry, solution pH, and ionic strength on the removal of herbicides diuron and amitrole from water by an activated carbon fiber.

A study was conducted on the effects of carbon surface chemistry, solution pH, and ionic strength on the removal of diuron and amitrole from aqueous solutions by adsorption on an as-received and oxidized activated carbon fiber. Results obtained were explained by the surface characteristics of the adsorbents and the characteristics of the herbicide molecules. Under the experimental conditions used, diuron uptake was much higher than that of amitrole, despite its larger molecular dimensions, due to the lesser water solubility, greater hydrophobicity, and larger dipolar moment of diuron compared with amitrole. Uptake variations associated with differences in carbon surface oxidation, solution pH, and ionic strength were explained by corresponding changes in electrostatic, hydrophobic, and van der Waals interactions.

Cadmium ion adsorption on different carbon adsorbents from aqueous solutions. Effect of surface chemistry, pore texture, ionic strength, and dissolved natural organic matter.

Adsorption of Cd(II) species at pH = 5 was studied on three carbon adsorbents: granular activated carbon, activated carbon fiber, and activated carbon cloth. As-received and oxidized adsorbents were used. Cd(II) adsorption greatly increased after oxidation due to the introduction of carboxyl groups. The use of a buffer solution to control the pH introduced some changes in the surface chemistry of carbons through the adsorption of one of the compounds used, biphthalate anions. The increase in ionic strength reduced Cd(II) uptake on both as-received and oxidized carbons due to a screening of the electrostatic attractions between the Cd(II) positive species and the negative surface charge, which in the case of as-received carbons derived from the biphthalate anions adsorbed and in the oxidized ones from the carboxyl groups. Tannic acid was used as a model compound for natural organic matter. Its adsorption was greatly reduced after oxidation, and most of the carbon adsorbents preadsorbed with tannic acid showed an increase in Cd(II) uptake. In the case of competitive adsorption between Cd(II) species and tannic acid molecules, there was a decrease in Cd(II) uptake on the as-received carbon whereas the contrary occurred with the oxidized carbons. These results illustrate the great importance of carbon surface chemistry in this competitive adsorption process. Finally, under all experimental conditions used, when the adsorption capacity of carbons was compared under the same conditions it increased in the following order: granular activated carbon < activated carbon fiber < activated carbon cloth.