RESUMO
The existing literature survey reports rare and conflicting studies on the effect of the preparation method of metal-based semiconductor photocatalysts on structural/morphological features, electronic properties, and kinetics regulating the photocatalytic H2 generation reaction. In this investigation, we compare the different copper/titania-based photocatalysts for H2 generation synthesized via distinct methods (i.e., photodeposition and impregnation). Our study aims to establish a stringent correlation between physicochemical/electronic properties and photocatalytic performances for H2 generation based on material characterization and kinetic modeling of the experimental outcomes. Estimating unknown kinetic parameters, such as charge recombination rate and quantum yield, suggests a mechanism regulating charge carrier lifetime depending on copper distribution on the TiO2 surface. We demonstrate that H2 generation photoefficiency recorded over impregnated CuxOy/TiO2 is related to an even distribution of Cu(0)/Cu(I) on TiO2, and the formation of an Ohmic junction concertedly extended charge carrier lifetime and separation. The outcomes of the kinetic analysis and the related modeling investigation underpin photocatalyst physicochemical and electronic properties. Overall, the present study lays the groundwork for the future design of metal-based semiconductor photocatalysts with high photoefficiencies for H2 evolution.
RESUMO
Silver is extensively used in electronics, industrial catalysis, and biomedical sector owing to its enhanced physicochemical properties. E-waste recycling may contribute significantly to enhance silver recovery in the view of a circular economy and limit the depletion of mineral sources. In this scenario, hydrometallurgical routes represent the most widely used techniques for silver extraction/recovery and require strong acidic solutions, high temperatures, and multiple operating units. An alternative sustainable route for silver recovery from leaching solutions used for silver extraction in industrial applications is herein proposed for the first time. The novel green process of silver recovery is based on the UV/vis light-driven photocatalytic deposition of pure metallic silver over low-cost and non-toxic ZnO photocatalyst. In the second step, ZnO is dissolved by slight acidification and pure metallic silver is easily recovered. Low environmental impact, mild operating conditions, and economic viability are among the major perks of the new silver recovery process developed. In the view of a full-scale implementation, several operating conditions of the recovery process (i.e., photocatalyst load, starting silver concentration, type of hole scavenger and irradiation) were thoroughly investigated. A mathematical model capable of describing the system behaviour under different operating conditions was also developed and allowed to estimate unknown kinetic parameters for the Ag-photodeposition process.
Assuntos
Óxido de Zinco , Óxido de Zinco/química , Prata/química , Cloretos , Catálise , Raios UltravioletaRESUMO
A great deal of interest is recorded among researchers in the identification of new catalytic systems that make possible the selective oxidation of organic species in the presence of non-toxic solvents, primarily water, through the use of inexpensive catalysts. The possibility to selectively oxidize benzyl alcohol to benzaldehyde is studied in the present work by using ferric ions as homogeneous catalysts and oxygen as an oxidant under UV-solar simulated radiation. Due to the possibility that Fe(III) aquo-complex photolysis could generate undesired reactive OH radicals with the consequent occurrence of side reactions, most of the runs are carried out at pH = 0.5 at which these events have a reduced incidence. The results indicate that benzyl alcohol can be partially converted into benzaldehyde with yield and selectivity values higher than 40% and 80% respectively for the conditions adopted, with a minor occurrence of benzoic acid formation. Reaction schemes to account for the experimental observations are provided.
RESUMO
Pd, Rh, Pt are employed in a wide range of applications, such as catalytic converters, fuel cells and electronic devices. In the last years, an increasing pressure on their market was recorded due to a growing demand and limited resources. Therefore, the recovery of these materials from wastes represents an interesting goal to be achieved. The most widely proposed techniques for recovering the palladium from wastes are leaching and ion exchange. Strong oxidizers, acids and high temperature (343-363 K) are used for leaching, leading problems for the environment and the safety. In this work the attention was focused on a system containing zero-valent palladium nanoparticles in which the leaching is performed in mild acidic conditions, by using chloride solutions containing cupric ions (NaCl/CuCl2). The process was studied at varying temperature, pH, chloride and cupric ion concentrations. Good results were obtained at pH 5.0 and temperatures between 288 K and 333 K. The process is more acceptable than the traditional ones from a safety point of view being characterized by less severe conditions (pH and temperatures). A shrinking spherical particles model was adopted to analyse the experimental data from which a development under a kinetic control was demonstrated.
RESUMO
The photodegradation process of methylisothiazolinone (MIT), benzisothiazolinone (BIT), and isoxazole (ISOX) in ultrapure water and synthetic wastewater by means of UV254 photolysis and by UV254/H2O2 advanced oxidation process were investigated in a microcapillary photoreactor designed for ultrafast photochemical transformation of microcontaminants. For the first time, we estimated key photo-kinetic parameters, i.e. quantum yields (35.4â¯mmol·ein-1 for MIT, and 13.5 and 55.8â¯mmol·ein-1 for BIT at pHâ¯=â¯4-6 and 8, respectively) and rate constants of the reaction of photo-generated OH radicals with MIT and BIT (2.09·109 and 5.9·109â¯Lâ¯mol-1·s-1 for MIT and BIT). The rate constants of the reaction of photo-generated OH radicals with ISOX in MilliQ water was also estimated (2.15·109â¯Lâ¯mol-1·s-1) and it was in good agreement with literature indications obtained in different aqueous matrices. The models were extended and validated to the case of simultaneous degradation of mixtures of these compounds and using synthetic wastewater as an aqueous matrix. High resolution-accurate mass spectrometry analysis enabled identification of the main intermediates (BIT200, B200, saccharin, BIT166) and enabled proposal of a novel degradation pathway for BIT under UV254/H2O2 treatment. This study demonstrates an ultrafast method to determine key photo-kinetic parameters of contaminants of emerging concern in water and wastewater, which are needed for design and validation of photochemical water treatment processes of municipal and industrial wastewaters.
Assuntos
Poluentes Químicos da Água , Purificação da Água , Peróxido de Hidrogênio , Isoxazóis , Oxirredução , Fotólise , Raios UltravioletaRESUMO
We assessed whether soil with high Cr contamination could be reclaimed by alkali, mineral, and organic acid-based ligands (OABLs) washing. We tested HNO3, H2SO4, HCl, NaOH, H2O2, lactic acid (LA), malic acid (MA), oxalic acid (OA), and citric acid (CA), together with EDTA, obtaining the highest efficiencies in presence of 1 M sulfuric acid (98%). Nonetheless we noted that using OABLs, we obtained a Cr(III) removal efficiency similar to the one obtained using mineral acids. Indeed 1 M of LA and MA and 0.8 M of OA allowed obtaining, respectively, 88%, 75%, and 67% removal percentage. The extraction process with OABLs was strongly dependent on intraparticle diffusion of Cr-LA, Cr-MA, and Cr-OA complexes. We also determined the apparent diffusion coefficients. Residual toxicity of treated soils was tested with the nematode, Caenorhabditis elegans. The OABL washing generally allowed getting a soil without Cr and with reduced toxicity. However, the washing process also removed other cations that acted as nutrients. Consequently, we conducted toxicity tests on enriched soil and found that the mortality index improved. In some cases (LA and MA), mortality was comparable to that observed with uncontaminated control samples. In contrast, when contaminated soils were washed with sulfuric acid, in all conditions, we observed significant ecotoxicity. Therefore, we concluded that only the OABL treatment provided a non-toxic soil that could be reused for anthropic activities.
Assuntos
Ácidos/química , Ácidos Carboxílicos/química , Cromo/isolamento & purificação , Recuperação e Remediação Ambiental/métodos , Solo/química , Agricultura , Animais , Caenorhabditis elegans , Testes de ToxicidadeRESUMO
The photoreduction of Cu(II) in presence of an organic species as sacrificial agent has been investigated by many research groups but some controversial results are reported in literature. In this work, the photoreduction process of Cu(II) in presence of formic acid is investigated aiming at clarifying the reaction mechanism and assess the reaction kinetics. The effect of operating conditions such as TiO(2) load, initial concentration of sacrificial agent, pH and ionic strength was studied. The results of the work are: (1) the system reactivity does not depend neither on pH (in the range 2.0-3.5) nor on ionic strength of the solution; (2) formic acid is adsorbed on TiO(2) surface; (3) the nature of anionic species can influence the Cu(II) photoreduction (e.g. the addition of sulphate or phosphates reduces the reaction rates); and (4) FA can be completely mineralized during this photoxidation process; for example, this is observed for a TiO(2) load of 0.1g/L after a reaction time of about 240 min. A simplified kinetic model is developed to describe the behavior of the system and validated by analysing the data collected during the experimental work.
Assuntos
Cobre/análise , Formiatos/análise , Titânio/análise , Reatores Biológicos , Concentração de Íons de Hidrogênio , Cinética , Oxirredução , Fotoquímica , Raios UltravioletaRESUMO
A pool of laboratory experiments is planned with the aim of evaluating the possibility to reduce the phytotoxicity of olive mill wastewater (OMW) with combined physico-chemical processes (centrifugation-ozonation, centrifugation-solar photolysis, centrifugation-solar modified photoFenton, centrifugation-solar modified photoFenton-ozonation). A moderate COD removal of an OMW is reached by using ozonation or solar modified photoFenton separately or solar modified photoFenton/O(3) combined process even for prolonged treatment times. The O(3)-treated OMWs are still toxic towards algal growth (Pseudokirchneriella subcapitata) and only for dilutions equal to or higher than 1:160 a stimulation of algal growth is observed. The sole ozonation does not reduce significantly the phytotoxicity of tested OMW measured through the GI calculation of Raphanus sativus L., Cucumis sativus L. and Lactuca sativa L. A marked reduction of OMW inhibition, higher than 50%, is evidenced for 1:8 dilution OMW samples ozonated for 2h. The long-term storage of OMW associated with solar irradiation without or with Fe(III) ions under continuous aeration is less efficient than ozonation, and the combined action of the two former treatments does not significantly contribute to enhance both COD removal and germination index. Better results are obtained on seed germination and root elongation of plantlets of the three selected species, which germinated on OMW-free solidified medium and were then transferred on a solidified culture medium containing O(3)-treated OMW diluted 1:2 and 1:4. The operating costs are estimated for the solar modified photoFenton-ozonation process.
Assuntos
Resíduos Industriais , Óleos de Plantas , Plantas/efeitos dos fármacos , Poluentes da Água/toxicidade , Ferro/química , Azeite de Oliva , Ozônio/química , Luz SolarRESUMO
The abatement of ferulic acid (FA), a polyphenolic constituent of olive mill wastewater, is studied in the pH range 5.0-7.0 by using hydrogen peroxide and an amorphous iron oxide as catalyst. The effect of pH, catalyst load, hydrogen peroxide and substrate starting concentrations is assessed during the investigation. A suitable reaction scheme is developed and used to build a mathematical model which satisfactorily describes the system's behavior. Kinetic constants for the proposed scheme as well as the total active site concentration of the catalyst in the studied pH range are estimated. The occurrence of internal mass-transfer limitation for the adopted granulometric fraction of the catalyst is demonstrated.
Assuntos
Ácidos Cumáricos/química , Compostos Férricos , Indústria Alimentícia , Peróxido de Hidrogênio , Resíduos Industriais , Ferro , Óleos de Plantas , Poluentes Químicos da Água/química , Azeite de Oliva , OxirreduçãoRESUMO
The concentration of antiretroviral drugs in wastewater treatment plants (WWTP) effluents and surface waters of many countries has increased significantly due to their widespread use for HIV treatment. In this study, the removal of stavudine and zidovudine under UV254 photolysis or UV254/H2O2 was investigated in a microcapillary film (MCF) photoreactor, using minimal water samples quantities. The UV254 quantum yield of zidovudine, (2.357⯱â¯0.0589)·10-2â¯molâ¯ein-1 (pH 4.0-8.0), was 28-fold higher that the yield of stavudine (8.34⯱â¯0.334)·10-4â¯molâ¯ein-1 (pH 6.0-8.0). The second-order rate constant kOH,iof reaction of hydroxyl radical with the antiretrovirals (UV254/H2O2 process) were determined by kinetics modeling: (9.98⯱â¯0.68)·108â¯M-1â¯s-1 (pH 4.0-8.0) for zidovudine and (2.03⯱â¯0.18)·109â¯M-1â¯s-1 (pH 6.0-8.0) for stavudine. A battery of ecotoxicological tests (i.e. inhibition growth, bioluminescence, mutagenic and genotoxic activity) using bacteria (Aliivibrio fischeri, Salmonella typhimurium), crustacean (Daphnia magna) and algae (Raphidocelis subcapitata) revealed a marked influence of the UV dose on the ecotoxicological activity. The UV254/H2O2 treatment process reduced the ecotoxicological risk associated to direct photolysis of the antiretrovirals aqueous solutions, but required significantly higher UV254 doses (≥2000 mJâ¯cm-2) in comparison to common water UV disinfection processes.
Assuntos
Antirretrovirais , Peróxido de Hidrogênio , Estavudina , Raios Ultravioleta , Poluentes Químicos da Água , Zidovudina , Aliivibrio fischeri/efeitos dos fármacos , Aliivibrio fischeri/crescimento & desenvolvimento , Animais , Antirretrovirais/química , Antirretrovirais/toxicidade , Daphnia/efeitos dos fármacos , Daphnia/fisiologia , Ecotoxicologia , Peróxido de Hidrogênio/química , Peróxido de Hidrogênio/efeitos da radiação , Cinética , Salmonella typhimurium/efeitos dos fármacos , Salmonella typhimurium/genética , Estavudina/química , Estavudina/toxicidade , Poluentes Químicos da Água/química , Poluentes Químicos da Água/toxicidade , Zidovudina/química , Zidovudina/toxicidadeRESUMO
Bezafibrate (BZF) is a lipid regulator largely used for the treatment of hyperlipidaemia. As a result of its wide use, unmetabolized BZF is released in the environment with potential toxic effects for aquatic living organisms. The results obtained in this work show that ozonation is an efficient method to degrade BZF: after 10 min of treatment (corresponding to a dose of 0.73 mmol L(-1) of ozone), the complete BZF abatement is achieved, starting from an initial concentration of 0.5 mmol L(-1). However, only a small part of the substrate is mineralized. Two different experimental approaches (absolute and competition method) are adopted to estimate the second-order kinetic constants for the ozone attack at pH=6.0, 7.0 and 8.0. A good agreement was observed between the two kinetic methods adopted. The identification of main intermediates, attempted by high-performance liquid chromatograph (HPLC)-MS technique, indicates that the oxidation of BZF develops through both the hydroxylation of the aromatic ring and the attack of ozone on the unchlorinated aromatic one. The assessment of by-products biodegradability and acute toxicity demonstrates that ozonation is a suitable technique to improve the biodegradability and reduce the toxicity of waters containing BZF.
Assuntos
Bezafibrato/química , Hipolipemiantes/química , Ozônio/química , Poluentes Químicos da Água/química , Aliivibrio fischeri/efeitos dos fármacos , Aliivibrio fischeri/metabolismo , Bezafibrato/toxicidade , Hipolipemiantes/toxicidade , Cinética , Medições Luminescentes , Eliminação de Resíduos Líquidos/métodos , Poluentes Químicos da Água/toxicidade , Purificação da Água/métodosRESUMO
The photochemical and ecotoxicological fate of acyclovir (ACY) through UV254 direct photolysis and in the presence of hydroxyl radicals (UV254/H2O2 process) were investigated in a microcapillary film (MCF) array photoreactor, which provided ultrarapid and accurate photochemical reaction kinetics. The UVC phototransformation of ACY was found to be unaffected by pH in the range from 4.5 to 8.0 and resembled an apparent autocatalytic reaction. The proposed mechanism included the formation of a photochemical intermediate (ÏACY = (1.62 ± 0.07)·10-3 mol ein-1) that further reacted with ACY to form by-products (k' = (5.64 ± 0.03)·10-3 M-1 s-1). The photolysis of ACY in the presence of hydrogen peroxide accelerated the removal of ACY as a result of formation of hydroxyl radicals. The kinetic constant for the reaction of OH radicals with ACY (kOH/ACY) determined with the kinetic modeling method was (1.23 ± 0.07)·109 M-1 s-1 and with the competition kinetics method was (2.30 ± 0.11)·109 M-1 s-1 with competition kinetics. The acute and chronic effects of the treated aqueous mixtures on different living organisms (Vibrio fischeri, Raphidocelis subcapitata, D. magna) revealed significantly lower toxicity for the samples treated with UV254/H2O2 in comparison to those collected during UV254 treatment. This result suggests that the addition of moderate quantity of hydrogen peroxide (30-150 mg L-1) might be a useful strategy to reduce the ecotoxicity of UV254 based sanitary engineered systems for water reclamation.
Assuntos
Aciclovir/química , Antivirais/química , Peróxido de Hidrogênio , Fotólise , Ecotoxicologia , Cinética , Oxirredução , Raios Ultravioleta , Água , Poluentes Químicos da ÁguaRESUMO
The photocatalytic removal of nitrate with simultaneous hydrogen generation was demonstrated using zero-valent nano-copper-modified titania (P25) as photocatalyst in the presence of UV-A-Vis radiation. Glycerol, a by-product in biodiesel production, was chosen as a hole scavenger. Under the adopted experimental conditions, a nitrate removal efficiency up to 100% and a simultaneous hydrogen production up to 14 µmol/L of H2 were achieved (catalyst load = 150 mg/L, initial concentration of nitrate = 50 mg/L, initial concentration of glycerol = 0.8 mol/L). The reaction rates were independent of the starting glycerol concentration. This process allows accomplishing nitrate removal, with the additional benefit of producing hydrogen under artificial UV-A radiation. A kinetic model was also developed and it may represent a benchmark for a detailed understanding of the process kinetics. A set of acute and chronic bioassays (Vibrio fischeri, Raphidocelis subcapitata, and Daphnia magna) was performed to evaluate the potential ecotoxicity of the nitrate/by-product mixture formed during the photocatalytic process. The ecotoxicological assessment indicated an ecotoxic effect of oxidation intermediates and by-products produced during the process.
Assuntos
Cobre/química , Hidrogênio/química , Nanopartículas Metálicas/química , Nitratos/isolamento & purificação , Titânio/química , Poluentes Químicos da Água/isolamento & purificação , Aliivibrio fischeri/efeitos dos fármacos , Animais , Catálise , Clorófitas/efeitos dos fármacos , Daphnia/efeitos dos fármacos , Ecotoxicologia , Glicerol/química , Cinética , Nitratos/química , Nitratos/farmacologia , Oxirredução , Tamanho da Partícula , Processos Fotoquímicos , Soluções , Raios Ultravioleta , Poluentes Químicos da Água/química , Poluentes Químicos da Água/farmacologiaRESUMO
Chlorinated hydrocarbons are widely used in chemical industries as solvents and intermediates for pesticides and dyes manufacture. Their presence was documented in rivers, groundwaters and seawaters. In this work, the oxidation of 1,2-dichlorobenzene in aqueous solutions by means of Fe(III) homogeneous photocatalysis under UV lamp and sunlight irradiations is studied. The results show that the best working conditions are found for pH=3.0 and initial [Fe(III)] concentration equal to 1.0x10(-4) molL(-1) although the investigated system can be utilized even at pH close to 4.0 but with slower abatement kinetics. Some dicholoroderivatives, such as 2,3-dichlorophenol, 3,4-dichlorophenol and 2-chlorophenol, are identified as oxidation intermediates. The values of the kinetic constant for the photochemical reoxidation of Fe(II) to Fe(III) are evaluated by a mathematical model in the range 1.58-3.78 Lmol(-1)s(-1) and 0.69-0.78 Lmol(-1)s(-1) for the systems irradiated by UV lamp and sunlight, respectively.
Assuntos
Clorobenzenos/isolamento & purificação , Ferro/química , Luz Solar , Raios Ultravioleta , Poluentes Químicos da Água/isolamento & purificação , Catálise , Clorobenzenos/química , Clorobenzenos/efeitos da radiação , Solventes/química , Solventes/isolamento & purificação , Solventes/efeitos da radiação , Poluentes Químicos da Água/química , Poluentes Químicos da Água/efeitos da radiação , Purificação da Água/métodosRESUMO
Antibiotic molecules have been reported among the xenobiotics present at trace levels in sewage treatment plant (STP) effluents and aquatic environment. Lincomycin, one of the most used in clinical practices whose presence in the STP effluents has been often documented, is submitted to an extensive investigation to assess its persistence in the environment and toxicity towards different algal strains. The possibility to remove the lincomycin from water by means of ozonation is demonstrated and a reduction of toxicity of ozonated solutions on S. leopoliensis, with respect to untreated solutions containing this compound, is obtained even just for 1h of treatment. Kinetic constants for the attack to lincomycin of ozone (from 1.53 x 10(5) M(-1)s(-1) at pH = 3.0 and 4.93 x 10(5) M(-1)s(-1) at pH = 6.7) and OH radicals (4.37 x 10(9) M(-1)s(-1) at pH = 5.5 and 4.59 x 10(9) M(-1)s(-1) at pH = 7.5) are also evaluated.
Assuntos
Antibacterianos/toxicidade , Lincomicina/toxicidade , Purificação da Água/métodos , Antibacterianos/química , Eucariotos , Cinética , Lincomicina/química , Oxidantes Fotoquímicos/química , Ozônio/química , Fotólise , Testes de Toxicidade , Eliminação de Resíduos LíquidosRESUMO
Kinetics of aerobic biodegradation have been investigated for twenty aromatic species using sludges collected from the aeration basin of municipal sewage treatment plants. The reproducibility of the results is tested with respect to the sludges period of collection and the wastewater treatment plant where they are taken. The comparison of kinetic constants, estimated for the investigated chemicals, allows to evaluate the reactivity effect of single groups (i.e., -OH, -CH3, -Cl, -NO2) into the aromatic structures. The search for easy structure-reactivity relationships is also attempted by means of contributing group methods.
Assuntos
Aerobiose , Hidrocarbonetos Aromáticos/análise , Esgotos/microbiologia , Poluentes Químicos da Água/análise , Purificação da Água/métodos , Biodegradação Ambiental , Hidrocarbonetos Aromáticos/química , Cinética , Relação Estrutura-AtividadeRESUMO
The cost of bio-oil refining from microalgal biomass can be significantly reduced by combining extraction and transesterification. The characterisation and optimisation of the combined steps have been carried out on strains of Stichococcus bacillaris, focusing on catalyst type and concentration, reaction time and temperature, methanol/biomass ratio, pre-mixing time and water content in the biomass. The bio-oil yield has been referenced as production of fatty acid methyl esters (FAMEs). The maximum yield (â¼17%) was achieved using dried biomass with alkaline catalyst at 60°C and methanol/biomass weight ratio of 79:1. Alkaline catalyst conditions gave faster reaction rates and higher bio-oil yields than acid catalyst. Yield was also strongly affected by water content in the biomass. A mechanistic interpretation has been proposed to elucidate the effect of the different operating conditions. However, the structural characteristics of the Chlorophyta cell wall can be very different, leading to different bio-oil yields when the same protocol is applied. Therefore, the optimised protocol of direct transesterification for Stichococcus bacillaris strains was tested on other Stichococcus strains and several other Chlorophyta species characterised by a different cell wall structure. It was clearly demonstrated that different results for bio-oil yield were obtained within the same microalgal species and much more within different microalgal genera.
Assuntos
Biocombustíveis , Clorófitas/metabolismo , Biocatálise , Biomassa , Biotecnologia , Parede Celular/metabolismo , Clorófitas/classificação , Clorófitas/crescimento & desenvolvimento , Esterificação , Concentração de Íons de Hidrogênio , Cinética , Metanol/metabolismo , Microalgas/classificação , Microalgas/crescimento & desenvolvimento , Microalgas/metabolismo , Especificidade da EspécieRESUMO
Objetivos: Comparar el tratamiento de pacientes con fracturas oblicuas o espiroideas largas de metacarpianos, mediante reducción abierta y fijación interna con tornillos interfragmentarios solos o placas y tornillos. Materiales y métodos: Se realizó un estudio retrospectivo comparativo entre 2 grupos de pacientes: uno con 24 pacientes tratados con tornillos interfragmentarios solos y otro con 17 pacientes tratados mediante osteosíntesis con placas y tornillos. En ambos, se utilizó un abordaje longitudinal dorsal, y se les indicó inmovilización posoperatoria con valva de yeso y rehabilitación con el mismo equipo de terapistas ocupacionales. Tras un seguimiento mínimo de 12 meses, se evaluaron los resultados con el puntaje DASH, la movilidad activa total, la distancia pulpejo-palma y la fuerza con dinamometría comparativa. Se consideró significativo un valor p <0,05. Resultados: El tiempo promedio de seguimiento fue de 24.5 meses (rango 12-43).No se hallaron diferencias estadísticamente significativas en el puntaje DASH, la movilidad activa total, la distancia pulpejo-palma y la fuerza. El tiempo hasta el reingreso laboral fue inferior en el grupo tratado con placas y tornillos, aunque se registraron dos casos de retiro de material, sumado, en uno de ellos, a adherencia tendinosa (tenólisis). Conclusiones: El tratamiento de pacientes con fracturas oblicuas o espiroideas largas de metacarpianos, mediante tornillos interfragmentarios solos o placas y tornillos logró resultados similares, se destaca el menor tiempo hasta la reincorporación laboral y la mayor cantidad de complicaciones con placas y tornillos. Nivel de Evidencia: III
Objective: To compare open reduction and internal fixation with interfragmentary screws and with plates and screws for the treatment of long oblique or spiral metacarpal fractures. Materials and methods: A comparative retrospective study was carried out between 2 groups of patients treated surgically. In the first group, 24 patients were treated with interfragmentary screws and in the second group, 17 patients were treated with plate and screw osteosynthesis. A dorsal longitudinal approach was used. Postoperatively, immobilization was performed using a plaster splint; both groups followed rehabilitation with same occupational therapist team. After a minimum follow-up of 12 months, they were evaluated with the DASH score, total active motion (TAM), pulp-to-palm distance, and comparative contralateral dynamometry. A p value < 0.05 was considered significant. Results: The average follow-up was 24.5 months (range 12-43 months). There were no statistically significant differences in DASH, TAM, pulp-to-palm distance, and strength. The group treated with plate and screw fixation returned to work earlier, although there were two cases of implant removal, in addition to tendon adherence (tenolysis) in one of them. Conclusions: The treatment of patients with long oblique or spiral metacarpal fractures with interfragmentary screws or plates and screws showed similar outcomes; the treatment with plate and screws allowed an earlier return to work but had a greater number of complications. Level of Evidence: III
Assuntos
Adulto , Pinos Ortopédicos , Parafusos Ósseos , Resultado do Tratamento , Ossos Metacarpais/cirurgia , Fraturas Ósseas , Traumatismos dos Dedos/cirurgia , Fixação Interna de FraturasRESUMO
A microcapillary film reactor (MCF) was adopted to evaluate and compare the removal efficiency of benzoylecgonine (BE), an emerging micropollutant deriving from illicit drug abuse (cocaine), in different aqueous matrices: milliQ water, synthetic and real wastewater and surface water. The removal processes investigated were the direct photolysis with UV radiation at 254 nm, and the advanced oxidation process (AOP) with the same UV radiation and hydrogen peroxide. As a result of the microfluidics approach developed through an innovative experimental apparatus, full conversion of BE was reached within a few seconds or minutes of residence time in the MCF depending on the process conditions adopted. The radiation dose was estimated to be approximately 5.5 J cm(-2). The innovative MCF reactor was found to be an effective tool for photochemical studies, especially when using highly priced, uncommon, or regulated substances. The removal efficiency was affected by the nature of the aqueous matrix, due to the presence of different xenobiotics and natural compounds that act primarily as HO(â¢) radical scavengers and secondly as inner UV254 filters. Moreover, nano-liquid chromatography (LC)-high resolution-mass spectrometry analysis was utilized to identify the main reaction transformation products, showing the formation of hydroxylated aromatics during the photochemical treatment.
Assuntos
Cocaína/análogos & derivados , Peróxido de Hidrogênio/química , Fotólise , Raios Ultravioleta , Cromatografia Líquida , Cocaína/análise , Cocaína/química , Cocaína/metabolismo , Água Doce/química , Espectrometria de Massas , Oxirredução , Eliminação de Resíduos Líquidos/métodos , Águas Residuárias/química , Poluentes Químicos da Água/análise , Poluentes Químicos da Água/química , Purificação da Água/métodosRESUMO
The presence of amoxicillin, a widely used antibiotic, has been documented in Sewage Treatment Plant (STP) effluents. As for other pharmaceuticals, ozonation is proposed as a process for its abatement from these effluents. The results of ozonation experiments on amoxicillin-containing aqueous solutions indicate that ozone attack is mainly directed towards the phenolic ring of the studied molecule leading to the formation of hydroxyderivative intermediates. No direct evidences of attack on sulfur atom with sulfoxide formation are found. A kinetic investigation is carried out allowing the assessment of the kinetics of direct ozone attack and that of OH radicals to amoxicillin.