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.

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.

Sulfonamides degradation assisted by UV, UV/H2O2 and UV/K2S2O8: Efficiency, mechanism and byproducts cytotoxicity.

The objective of this study was to analyze the effectiveness of UVC, UVC/H2O2 and UVC/K2S2O8 on the degradation of SAs. Rate constant values increased in the order SMZ < SDZ < SML and showed the higher photodegradation of sulfonamides with a penta-heterocycle. Quantum yields were 1.72 × 10-5 mol E-1, 3.02 × 10-5 mol E-1, and 6.32 × 10-5 mol E-1 for SMZ, SDZ and SML, respectively, at 60 min of treatment. R254 values show that the dose habitually utilized for water disinfection is inadequate to remove this type of antibiotic. The initial sulfonamide concentration has a major impact on the degradation rate. The degradation rates were higher at pH 12 for SMZ and SML. SMZ and SML photodegradation kλ values are higher in tap versus distilled water. The presence of radical promoters generates a greater increase in the degradation rate, UVC/K2S2O8 cost less energy, a mechanism was proposed, and the degradation by-products are less toxic than the original product.

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.

Halide removal from waters by silver nanoparticles and hydrogen peroxide.

The objective of this study was to remove halides from waters by silver nanoparticles (AgNPs) and hydrogen peroxide (H2O2). The experimental parameters were optimized and the mechanism involved was also determined. The AgNP/H2O2 process proved efficacious for bromide and chloride removal from water through the selective precipitation of AgCl and AgBr on the AgNP surface. The optimal AgNP and H2O2 concentrations to be added to the solution were determined for the halide concentrations under study. The removal of Cl- and Br- anions was more effective at basic pH, reaching values of up to 100% for both ions. The formation of OH, O2-, radicals was detected during the oxidation of Ag(0) into Ag(I), determining the reaction mechanism as a function of solution pH. Moreover, the results obtained show that: i) the efficacy of the oxidation of Ag(0) into Ag(I) is higher at pH11, ii) AgNPs can be generated by the O2- radical formation, and iii) the presence of NaCl and dissolved organic matter (tannic acid [TAN]) on the solution matrix reduces the efficacy of bromide removal from the medium due to: i) precipitation of AgCl on the AgNP surface, and ii) the radical scavenger capacity of TAN. AgNPs exhausted can be regenerated by using UV or solar light, and toxicity test results show that AgNPs inhibit luminescence of Vibrio fischeri bacteria.

Strategies to evaluate biodegradability: application to chlorinated herbicides.

The biodegradability of nitrochlorinated (diuron and atrazine) and chlorophenoxy herbicides (2,4-D and MCPA) has been studied through several bioassays using different testing times and biomass/substrate ratios. A fast biodegradability test using unacclimated activated sludge yielded no biodegradation of the herbicides in 24 h. The inherent biodegradability test gave degradation percentages of around 20-30% for the nitrochlorinated herbicides and almost complete removal of the chlorophenoxy compounds. Long-term biodegradability assays were performed using sequencing batch reactor (SBR) and sequencing batch membrane bioreactor (SB-MBR). Fixed concentrations of each herbicide below the corresponding EC50 value for activated sludge were used (30 mg L(-1) for diuron and atrazine and 50 mg L(-1) for 2,4-D and MCPA). No signs of herbicide degradation appeared before 35 days in the case of diuron and atrazine and 21 days for 2,4-D, whereas MCPA was partially degraded since the early stages. Around 25-36% degradation of the nitrochlorinated herbicides and 53-77% of the chlorophenoxy ones was achieved after 180 and 135 days, respectively, in SBR, whereas complete disappearance of 2,4-D was reached after 80 days in SB-MBR.

Coupling Fenton and biological oxidation for the removal of nitrochlorinated herbicides from water.

The combination of Fenton and biological oxidation for the removal of the nitrochlorinated herbicides alachlor, atrazine and diuron in aqueous solution has been studied. The H2O2 dose was varied from 20 to 100% of the stoichiometric amount related to the initial chemical oxygen demand (COD). The effluents from Fenton oxidation were analyzed for ecotoxicity, biodegradability, total organic carbon (TOC), COD and intermediate byproducts. The chemical step resulted in a significant improvement of the biodegradability in spite of its negligible or even slightly negative effect on the ecotoxicity. Working at 60% of the stoichiometric H2O2 dose allowed obtaining highly biodegradable effluents in the cases of alachlor and atrazine. That dose was even lower (40% of the stoichiometric) for diuron. The subsequent biological treatment was carried out in a sequencing batch reactor (SBR) and the combined Fenton-biological treatment allowed up to around 80% of COD reduction.

Identification of by-products and toxicity assessment in aqueous-phase hydrodechlorination of diuron with palladium on activated carbon catalysts.

The hydrodechlorination (HDC) of diuron in aqueous phase with hydrogen using two different activated carbon-supported Pd catalysts was studied. A commercial activated carbon and one prepared by chemical activation of grape seeds with phosphoric acid (GS) were evaluated as supports, being the catalysts tested in a wide range of temperature (30-100 °C) and space-time (78-311 kgcat h mol(-1)). Diuron conversion was above 70% under all the conditions tested. The Pd catalyst supported on GS showed the highest activity in terms of diuron conversion within the temperature range studied, allowing nearly complete conversion above 50 °C. However, a gradual loss of activity with time was observed for this catalyst. A complete route of hydrogenation of diuron was elucidated. Two reaction routes one leading to fenuron and another to aniline were identified. As the temperature and space-time were increased, the formation of fenuron (via monuron) was found to be favored. The toxicity of the reaction products was evaluated, being the route to fenuron and monuron, the one giving rise to a significant decrease of ecotoxicity.

Comparison of experimental methods for determination of toxicity and biodegradability of xenobiotic compounds.

Different methods for determining the toxicity and biodegradability of hazardous compounds evaluating their susceptibility to biological treatment were studied. Several compounds including chlorophenols and herbicides have been evaluated. Toxicity was analyzed in terms of EC50 and by a simple respirometric procedure based on the OECD Method 209 and by the Microtox® bioassay. The values of EC50 obtained from respirometry were in all the cases higher than those from the Microtox® test. The respirometric inhibition values of chlorophenols were related well with the number of chlorine atoms and their position in the aromatic ring. In general, herbicides showed lower inhibition, being alachlor the less toxic from this criterion. For determination of biodegradability an easier and faster alternative to the OECD Method 301, with a higher biomass to substrate ratio is proposed. When this test was negative, the Zahn-Wellens one was performed in order to evaluate the inherent biodegradability. In the fast test of biodegradability, 4-chlorocatechol and 4-chlorophenol showed a complete biodegradation by an unacclimated sludge upon 48 h. These results together with their low respirometric inhibition, allow concluding that these compounds could be conveniently removed in a WWTP. Alachlor, 2,4-dichlorophenol, 2,4,6-trichlorophenol and MCPA showed a partial biodegradation upon 28 days by the Zahn-Wellens inherent biodegradability test.

[Use of a blood recuperating device. Total knee arthroplasty]. / Empleo del recuperador de sangre. Artroplastia total de rodilla.

The authors evaluate the adoption of a protocol to recuperate blood from drainage during surgery for knee prosthesis. They carried out a prospective study on 19 patients diagnosed with knee arthrosis and who underwent surgery for Total Knee Arthroplasty from September 2006 through June 2007. The medical instrument used was Bellovac, produced by Astral Tech. In the Post anesthesia Reanimation Unit, four patients received a homologous transfusion (27.50%). Prior to the adoption of this protocol, the rate of transfusion was 37%. Hemoglobin during preoperative procedures was not a risk factor for a homologous transfusion. This is associated with the volume drained and reinserted. Patients who received a transfusion had drained 450 cc or more. The study did not record any complication due to the use of the recuperating device. The use of this device made it possible to decrease homologous blood transfusions.

[Proptosis as the first sign of recurrent scirrhous breast carcinoma]. / Proptosis como primera manifestación de recidiva de cáncer escirro de mama.

OBJECTIVE: To inform clinicians of a metastatic orbital neoplasm that frequently masquerades as an orbital inflammatory syndrome. CASE REPORT: The case of a 61-year-old woman, diagnosed and treated seven years ago for a scirrhous breast carcinoma is presented. She complained of blurred vision and proptosis of the left eye and these symptoms were the first manifestation of tumor relapse. DISCUSSION: When orbital inflammation is detected in an adult female patient, a full medical history must be obtained and physical examination performed, as orbital metastases have been reported to be the initial manifestation of malignancy in 30 to 50% of cases.

Proptosis como primera manifestación de recidiva de cáncer escirro de mama / Proptosis as the first signo of recurrent scirrhous breast carcinoma

Objetivo: Informar a los clínicos que las metástasis orbitarias son con frecuencia catalogadas de síndromes inflamatorios.Caso clínico: Se presenta el caso de una mujer de 61 años diagnosticada y tratada siete años antes de un carcinoma escirro de mama. La paciente aquejaba visión borrosa y proptosis en su ojo izquierdo como primera manifestación de la recidiva tumoral.Discusión: Cuando se diagnostica una inflamación orbitaria en una paciente mujer adulta, se debe realizar una meticulosa historia clínica, debido a que las metástasis orbitarias han sido descritas como manifestación inicial de malignidad en el 30 a 50% de los casos

Objective: To inform clinicians of a metastatic orbital neoplasm that frequently masquerades as an orbital inflammatory syndrome. Case report: The case of a 61-year-old woman, diagnosed and treated seven years ago for a scirrhous breast carcinoma is presented. She complained of blurred vision and proptosis of the left eye and these symptoms were the first manifestation of tumor relapse. Discussion: When orbital inflammation is detected in an adult female patient, a full medical history must be obtained and physical examination performed, as orbital metastases have been reported to be the initial manifestation of malignancy in 30 to 50% of cases

[Primary orbital mucocele: exophthalmos and optic atrophy]. / Mucocele orbitario primario: proptosis y atrofia óptica.

OBJECTIVE: Primary intraorbital mucoceles arising from the optic canal are extremely rare. We describe a patient with compressive optic neuropathy caused by an intraorbital mucocele. CLINICAL CASE: A 51-year-old woman presented with proptosis and reduced vision. Magnetic resonance imaging showed a mass compressing the optic nerve. There was no direct connection between any paranasal sinus and the mass cavity, as assessed in imaging studies and intraoperatively confirmed. The pathological diagnosis after the operation indicated a mucocele. DISCUSSION: Considering the absence of air pockets in the orbit, the mucocele might have originated from ectopic mucinous tissue that appeared during the development of the optic canal.

Mucocele orbitario primario: proptosis y atrofia óptica / Primary orbital mucocele: exophthalmos and optic atrophy

Objetivo: Los mucoceles orbitarios primarios que crecen desde el canal óptico son extremadamente raros. Describimos una paciente con neuropatía óptica compresiva secundaria a un mucocele intraorbitario.Caso clínico: Una mujer de 51 años presentó proptosis y disminución de visión. La Resonancia Magnética Nuclear mostró una masa que comprimía el nervio óptico. No había comunicación entre los senos paranasales y la masa orbitaria, como se confirmó en los estudios de imagen y posteriormente en el intraoperatorio. El estudio anatomopatológico confirmó un mucocele.Discusión: Considerando la ausencia de neumatización de la órbita, el mucocele debe originarse de tejido mucinoso ectópico que aparece durante el desarrollo del canal óptico

Objective: Primary intraorbital mucoceles arising from the optic canal are extremely rare. We describe a patient with compressive optic neuropathy caused by an intraorbital mucocele. Clinical case: A 51-year-old woman presented with proptosis and reduced vision. Magnetic resonance imaging showed a mass compressing the optic nerve. There was no direct connection between any paranasal sinus and the mass cavity, as assessed in imaging studies and intraoperatively confirmed. The pathological diagnosis after the operation indicated a mucocele. Discussion: Considering the absence of air pockets in the orbit, the mucocele might have originated from ectopic mucinous tissue that appeared during the development of the optic canal