RESUMO
In the present study, two agro-industrial wastes, sugarcane bagasse, and peanut shell were employed as support of magnetite nanoparticles for the synthesis of magnetic bio-composites: magnetic sugarcane bagasse (MBO) and magnetic peanut shell (MPSo). The presence of magnetite was verified by Raman spectroscopy. Magnetic nanoparticles shape and size distribution were studied by TEM, while composites morphologies were observed by SEM. Structural characteristics of the pesticides and their possible chemical adsorption on composites were analyzed by FTIR. The removal was carried out by a batch adsorption process, and UV-VIS technique was used for pesticide concentration estimation. Elovich model described better all systems pointing out to a chemical adsorption process occurring. Experimental data isotherms of carbofuran and iprodione can be best explained by more than one mathematical model, but Sip was the ordinary equation in all systems. Maximum adsorption capacities of 175 and 89.3 mg/g for carbofuran, and 119 and 2.76 mg/g for iprodione, were obtained for MBo and MPSo, respectively.
Assuntos
Aminoimidazol Carboxamida/análogos & derivados , Arachis/química , Carbofurano , Hidantoínas/química , Praguicidas , Saccharum , Poluentes Químicos da Água , Adsorção , Aminoimidazol Carboxamida/química , Carbofurano/química , Celulose , Fenômenos MagnéticosRESUMO
Carbofuran is an anticholinesterase carbamate commonly used as an insecticide, nematicide and acaricide in agricultural practice throughout the world. However, data on its sorption in temperate soils from Europe is limited. Laboratory studies were conducted to determine the adsorption of carbofuran on three distinct Austrian soils using batch experiments and radiometric techniques. Carbofuran adsorption capacity of the soils was found to be low in the three soils tested and showed to be related to the soils clay and organic carbon contents. The pesticide presented linear adsorption isotherms in all of the three soils. Due to the low sorption of carbofuran in the soils tested and to its high water solubility, there is a risk of migration to water bodies through run off and consequent negative effects on aquatic organisms and soil biota.
Assuntos
Carbofurano/química , Modelos Químicos , Poluentes do Solo/química , Adsorção , Agricultura , Áustria , Carbamatos , Carbofurano/análise , Radioisótopos de Carbono/análise , Inibidores da Colinesterase , Argila , Inseticidas/análise , Praguicidas , Solo/química , Poluentes do Solo/análiseRESUMO
Antibiotic-containing wastewaters produced in agricultural activities may depress the pesticide-degrading capacity of biomixtures contained in biopurification systems. This work aimed to assay the effect of oxytetracycline (OTC) on the removal of carbofuran (CFN) in an optimized biomixture, and to determine the capacity of the system to dissipate OTC. During co-application of CFN+OTC, CFN removal and its accelerated degradation were not negatively affected. Similarly, different doses of OTC (10-500mgkg-1) did not significantly affect CFN mineralization, and the process even exhibited a hormetic-like effect. Moreover, the biomixture was able to remove OTC with a half-life of 34.0 d. DGGE-cluster analyses indicated that fungal and bacterial communities remained relatively stable during OTC application and CFN+OTC co-application, with similarities of over 70% (bacteria) and 80% (fungi). Overall, these findings support the potential use of this matrix to discard OTC-containing wastewater in this system originally intended for CFN removal.
Assuntos
Carbofurano/química , Oxitetraciclina/química , Praguicidas/análise , Águas Residuárias/análise , Biodegradação Ambiental , Carbofurano/metabolismo , Fazendas , Oxitetraciclina/metabolismoRESUMO
In order to contribute to the increase of the body of knowledge on the sensitivity of tropical indigenous species to pesticides, acute and chronic toxicity tests were conducted with the neotropical cladoceran Ceriodaphnia silvestrii. Tests were carried out with the active ingredients diuron and carbofuran and one of their commercial formulations, the Diuron Nortox® 500 SC and the Furadan® 350 SC, respectively. For carbofuran, the active ingredient was more toxic than the commercial product, whereas for diuron, the commercial product appeared more toxic. In addition, hormetic effects on fertility were recorded for intermediate diuron concentrations. Acute and chronic toxicity data indicated that C. silvestrii was among the most sensitive invertebrate species for both test compounds. Based on concentrations measured in Brazilian water bodies, these compounds represent ecological risks for causing direct and indirect toxic effects on C. silvestrii and other aquatic organisms. Our results support previous claims on the advantages of using native species to better tune ecological risk assessment of chemicals in tropical ecosystems.
Assuntos
Carbofurano/química , Cladocera/efeitos dos fármacos , Diurona/química , Praguicidas/química , Animais , Brasil , Cladocera/química , Ecologia , Ecossistema , Praguicidas/farmacologiaRESUMO
Carbofuran is a toxic carbamate pesticide, and its use has increased in recent years. While marketing information indicates stability in different chemical media, carbofuran exhibits relative photolability. The aim of this research was to decompose carbofuran and to identify the photoproducts achieved when two different doped titania photocatalysts were employed under UV irradiation. The iron-doped TiO2 materials were obtained (a) via a hydrothermal method and (b) by an ultrasound-assisted sol-gel method. The precursors were TiOSO4â xH2O and Fe3(NO3)·9H2O. X-ray studies confirmed that the anatase phase of the iron-doped TiO2 resulted from the two preparation methods. The photocatalytic performance of the prepared materials was monitored by LC/ESI-QTOF-MS, enabling the identification of photoproducts: oxo-carbamates, hydroxylated benzofuranes, a carboxamide, and one amine. By using the iron-doped TiO2 materials, 2,2-dimethyl-2,3-dihydrobenzofuran-3,7-diol was the most abundant photoproduct, and N,2,2-trimethyl-2,3-dihydrobenzofuran-7-amine was the only compound that had not been previously reported in the photolysis and photocatalysis of carbofuran. The product 3-hydroxy carbofuran, a cholinesterase inhibitor, was quantified and was found to be transformed into compounds that lack this inhibitive property.
Assuntos
Carbofurano/química , Ferro/química , Titânio/química , Carbofurano/análogos & derivados , Catálise , Colinesterases , Fotólise , Raios UltravioletaRESUMO
The aim of this work was to determine the efficiency of a straw/compost/soil biomixture for pesticide depuration during its aging and continuous use, for a period of over a year, based on its capacity to remove carbofuran (CFN), while simultaneously monitoring the variations in microbial community structure. Successive CFN spikings were applied in the biomixture at 6-week intervals, and the removal efficiency was determined 48 h post-application. Initially, only a discrete degradation performance was observed (9.9%), but one CFN application was sufficient to induce efficient elimination (>88.5%) of the pesticide at subsequent influxes for a period of over 6 months. A statistically significant reduction on CFN removal efficiency after this time was detected, reaching levels similar to the fresh-prepared biomixture (14.8%) at the end of the experiment. Simultaneous DGGE analyses showed only modest changes on microbial community patterns through time for both, bacteria and fungi. The clustering of genetic fingerprints in chronological groups corresponding to significantly different CFN degradation efficiencies indicates that biomixture aging changes not only the composition of microbial communities, but also their suitability to engage in pesticide degradation. Periodic substitution of straw/compost/soil biomixture in biopurification systems or regular provision of easily-degradable organic substrates should be considered to maintain an adequate depuration capacity on this system.
Assuntos
Biodegradação Ambiental , Carbofurano/química , Microbiologia do Solo , Solo/química , Aldicarb/análise , Bactérias/metabolismo , Carbamatos/análise , DNA/análise , Eletroforese , Recuperação e Remediação Ambiental , Fungos/metabolismo , Metomil/análise , Resíduos de Praguicidas/análise , Praguicidas/análise , RNA Ribossômico 16S/análise , Poluentes do Solo/análiseRESUMO
Pesticide biopurification systems contain a biologically active matrix (biomixture) responsible for the accelerated elimination of pesticides in wastewaters derived from pest control in crop fields. Biomixtures have been typically prepared using the volumetric composition 50:25:25 (lignocellulosic substrate/humic component/soil); nonetheless, formal composition optimization has not been performed so far. Carbofuran is an insecticide/nematicide of high toxicity widely employed in developing countries. Therefore, the composition of a highly efficient biomixture (composed of coconut fiber, compost, and soil, FCS) for the removal of carbofuran was optimized by means of a central composite design and response surface methodology. The volumetric content of soil and the ratio coconut fiber/compost were used as the design variables. The performance of the biomixture was assayed by considering the elimination of carbofuran, the mineralization of (14)C-carbofuran, and the residual toxicity of the matrix, as response variables. Based on the models, the optimal volumetric composition of the FCS biomixture consists of 45:13:42 (coconut fiber/compost/soil), which resulted in minimal residual toxicity and â¼99% carbofuran elimination after 3 days. This optimized biomixture considerably differs from the standard 50:25:25 composition, which remarks the importance of assessing the performance of newly developed biomixtures during the design of biopurification systems.
Assuntos
Carbofurano/isolamento & purificação , Praguicidas/isolamento & purificação , Poluentes do Solo/isolamento & purificação , Biodegradação Ambiental , Carbofurano/química , Cocos/química , Modelos Químicos , Praguicidas/química , Solo/química , Poluentes do Solo/química , Águas Residuárias/químicaRESUMO
A biomixture constitutes the active core of the on-farm biopurification systems, employed for the detoxification of pesticide-containing wastewaters. As biomixtures should be prepared considering the available local materials, the present work aimed to evaluate the performance of ten different biomixtures elaborated with by-products from local farming, in the degradation of the insecticide/nematicide carbofuran (CFN), in order to identify suitable autochthonous biomixtures to be used in the tropics. Five different lignocellulosic materials mixed with either compost or peat and soil were employed in the preparation of the biomixtures. The comprehensive evaluation of the biomixtures included removal of the parent compound, formation of transformation products, mineralization of radiolabeled CFN, and determination of the residual toxicity of the process. Detoxification capacity of the matrices was high, and compost-based biomixtures showed better performance than peat-based biomixtures. CFN removal over 98.5% was achieved within 16 days (eight out of ten biomixtures), with half-lives below 5 days in most of the cases. 3-Hydroxycarbofuran and 3-ketocarbofuran were found as transformation products at very low concentrations suggesting their further degradation. Mineralization of CFN was also achieved after 64 days (2.9 to 15.1%); several biomixtures presented higher mineralization than the soil itself. Acute toxicity determinations with Daphnia magna revealed a marked detoxification in the matrices at the end of the process; low residual toxicity was observed only in two of the peat-based biomixtures. Overall best efficiency was achieved with the biomixture composed of coconut fiber-compost-soil; however, results suggest that in the case of unavailability of coconut fiber, other biomixtures may be employed with similar performance.
Assuntos
Carbofurano/análogos & derivados , Praguicidas/química , Poluentes Químicos da Água/química , Adaptação Fisiológica , Agricultura , Biodegradação Ambiental , Carbofurano/análise , Carbofurano/química , Meia-Vida , Praguicidas/análise , Solo/química , Microbiologia do Solo , Clima Tropical , Águas Residuárias/química , Poluentes Químicos da Água/análise , Purificação da ÁguaRESUMO
In this work, a biosensor was constructed by physical adsorption of the isolated endophytic fungus Eupenicillium shearii FREI-39 esterase on halloysite, using graphite powder, multi-walled carbon nanotubes and mineral oil for the determination of carbofuran pesticide by inhibition of the esterase using square-wave voltammetry (SWV). Specific esterase activities were determined each 2 days over a period of 15 days of growth in four different inoculation media. The highest specific activity was found on 6th day, with 33.08 U on PDA broth. The best performance of the proposed biosensor was obtained using 0.5 U esterase activity. The carbofuran concentration response was linear in the range from 5.0 to 100.0 µg L(-1) (r=0.9986) with detection and quantification limits of 1.69 µg L(-1) and 5.13 µg L(-1), respectively. A recovery study of carbofuran in spiked water samples showed values ranging from 103.8±6.7% to 106.7±9.7%. The biosensor showed good repeatability and reproducibility and remained stable for a period of 20 weeks. The determination of carbofuran in spiked water samples using the proposed biosensor was satisfactory when compared to the chromatographic reference method. The results showed no significant difference at the 95% confidence level with t-test statistics. The application of enzymes from endophytic fungi in constructing biosensors broadens the biotechnological importance of these microorganisms.
Assuntos
Técnicas Biossensoriais/métodos , Carbofurano/isolamento & purificação , Esterases/química , Praguicidas/isolamento & purificação , Carbofurano/química , Enzimas Imobilizadas/química , Eupenicillium/química , Eupenicillium/enzimologia , Nanotubos de Carbono/química , Praguicidas/químicaRESUMO
The degradation of the pesticide carbofuran (CBF) using solar photo-Fenton treatment, at both the laboratory and the pilot scale, was evaluated. At the laboratory scale, in a suntest reactor, the Fe(2+) concentration and H(2)O(2) concentration were evaluated and optimized using the surface response methodology and the Pareto diagram. Under optimal conditions experiments were performed to evaluate the evolution of the substrate removal, oxidation, subsequent mineralization, toxicity and the formation of chloride ions during the treatment. The analysis and evolution of five CBF by-products as well as several control and reactivity tests at the density functional theory level were used to depict a general scheme of the main degradation pathway of CBF via the photo-Fenton system. Finally, at the pilot scale, a sample of the commercial CBF product Furadan was eliminated after 420 min by the photo-Fenton system using direct sunlight. Under these conditions, after 900 min 89% of toxicity (1/E(50) on Vibrio fischeri bacteria), 97% of chemical oxygen demand, and 90% of dissolved organic carbon were removed.
Assuntos
Carbofurano/química , Praguicidas/química , Luz Solar , Análise da Demanda Biológica de OxigênioRESUMO
In this work the TiO(2) solar-photocatalytical degradation of the pesticide carbofuran (CBF) in water, at lab and pilot scale, was studied. At lab scale the evaluation of CBF concentration (14-282 µmol L(-1)) showed that the system followed a Langmuir-Hinshelwood kinetics type. TiO(2) concentration (0.05-2 g L(-1)) and initial pH (3-9) were also evaluated and optimized using the surface response methodology and the Pareto diagram. In the range of variables studied, initial pH 7.60 and 1.43 g L(-1) of TiO(2) favoured the efficiency of the process. Under optimal conditions the evolution of substrate, chemical oxygen demand, dissolved organic carbon, toxicity and organics by-products were evaluated. In the pilot scale tests, using direct sunlight, 55 mg L(-1) of CBF in a commercial formulation was eliminated after 420 min; while after 900 min of treatment 80% of toxicity (1/E(50) on Vibrium Fischeri), 80% of chemical oxygen demand and 60% of dissolved organic carbon were removed. The analysis and evolution of five CBF by-products, as well the evaluation of the treatment in the presence of isopropanol or using acetonitrile as a solvent suggest that the degradation is mainly carried out by OH radical attack. Finally, a schema depicting the main degradation pathway is proposed.