RESUMO
Chlorpyrifos (O, O-diethyl O-3,5,6-trichloropyridin-2-yl phosphorothioate) and carbaryl (1-naphthyl methylcarbamate) are often applied concurrently as insecticides in food production. The aim of this study was to research their migration behavior in a real environment. We researched the leaching of both pesticides by setting up field lysimeters on a farm with the typical soil used in fruit production today. In order to analyze the variables involved in this process, we performed complementary adsorption studies, we performed complementary adsorption studies using batches and undisturbed soil laboratory columns for both compounds. The results for pesticide transport through the lysimeters showed that less than 1% of chlorpyrifos was recovered in the leachates, while almost 17% was recovered for carbaryl. Having completed the experiment in undisturbed laboratory columns, soil analysis showed that chlorpyrifos mainly remained in the first 5 cm, while carbaryl moved down to the lower sections. These results can be explained in view of the sorption coefficient values (KD) obtained in horizons A and B for chlorpyrifos (393 and 184 L kg-1) and carbaryl (3.1 and 4.2 L kg-1), respectively. By integrating the results obtained in the different approaches, we were able to characterize the percolation modes of these pesticides in the soil matrix, thus contributing to the sustainable use of resources.
Assuntos
Carbaril/análise , Clorpirifos/análise , Poluentes do Solo/análise , Solo/química , Adsorção , Carbaril/química , Clorpirifos/química , Inseticidas/análise , Inseticidas/química , Poluentes do Solo/químicaRESUMO
Four-way data were obtained by recording the kinetic evolution of excitation-emission fluorescence matrices for samples containing the analytes carbaryl and 1-naphthol, two widely employed pesticides, in the concentration ranges 0-363 µg L(-1) and 0-512 µg L(-1), respectively. The reaction followed was the alkaline hydrolysis of carbaryl to produce 1-naphthol, a fact which introduced strong linear dependencies and multi-linearity losses in the analyzed system. Data processing was performed with unfolded partial least-squares combined with residual trilinearization (U-PLS/RTL) and also with a suitably initialized and restricted parallel factor model (PARAFAC), combined with calibration based on multi-linear regression. U-PLS/RTL is shown to be significantly simpler in its implementation and to provide similar figures of merit. The applied chemometric strategy is able to successfully determine the analytes in water samples containing uncalibrated interferences, such as other commonly employed agrochemicals and also a naturally occurring background signal.
Assuntos
Algoritmos , Carbaril/análise , Naftóis/análise , Praguicidas/análise , Espectrometria de Fluorescência , Água/química , Agroquímicos/análise , Agroquímicos/química , Calibragem , Carbaril/química , Hidrólise , Cinética , Análise dos Mínimos Quadrados , Modelos Lineares , Naftóis/química , Praguicidas/químicaRESUMO
An environmentally friendly analytical procedure with high sensitivity for determination of carbaryl pesticide in natural waters was developed. The flow system was designed with solenoid micro-pumps in order to improve mixing conditions and minimize reagent consumption as well as waste generation. A long pathlength (100 cm) flow cell based on a liquid core waveguide (LCW) was employed to increase the sensitivity in detection of the indophenol formed from the reaction between carbaryl and p-aminophenol (PAP). A clean-up step based on cloud-point extraction was explored to remove the interfering organic matter, avoiding the use of toxic organic solvents. A linear response was observed within the range 5-200 microg L(-1) and the detection limit, coefficient of variation and sampling rate were estimated as 1.7 microg L(-1) (99.7% confidence level), 0.7% (n=20) and 55 determinations per hour, respectively. The reagents consumption was 1.9 microg of PAP and 5.7 microg of potassium metaperiodate, with volume of 2.6 mL of effluent per determination. The proposed procedure was selective for the determination of carbaryl, without interference from other carbamate pesticides. Recoveries within 84% and 104% were estimated for carbaryl spiked to water samples and the results obtained were also in agreement with those found by a batch spectrophotometric procedure at the 95% confidence level. The waste of the analytical procedure was treated with potassium persulphate and ultraviolet irradiation, yielding a colorless residue and a decrease of 94% of total organic carbon. In addition, the residue after treatment was not toxic for Vibrio fischeri bacteria.
Assuntos
Carbaril/análise , Carbaril/química , Química Verde/métodos , Fotólise , Espectrofotometria/métodos , Gerenciamento de Resíduos/métodos , Aliivibrio fischeri/efeitos dos fármacos , Aminofenóis/química , Carbaril/isolamento & purificação , Carbaril/toxicidade , Fracionamento Químico , Química Verde/economia , Concentração de Íons de Hidrogênio , Hidrólise , Indicadores e Reagentes/química , Naftóis/química , Oxirredução , Espectrofotometria/economia , Fatores de Tempo , Gerenciamento de Resíduos/economiaRESUMO
The applicability of non-protected room temperature phosphorescence (NP-RTP) in real samples was demonstrated in the present work. In this methodology, only two reagents, potassium iodide and sodium sulfite, were used to obtain phosphorescent signals. Overlapping of the phosphorescence spectra was resolved by using first-derivative synchronous phosphorimetry. The synchronous first-derivative spectra of carbaryl and 1-naphthol in the mixture were completely separated by changing the synchronous wavelength interval; with 240 nm the first-derivative spectra of carbaryl were recorded, while with 200 nm those of 1-naphthol appeared. The intensities in the spectra were proportional to the concentration of carbaryl and 1-naphthol. The calibration graphs were linear up to at least 1.1 x 10(-5) mol L(-1) for carbaryl and 1.3 x 10(-5) mol L(-1) for 1-naphthol, and the correlation coefficients were 0.9971 and 0.9932, respectively. Carbaryl and 1-naphthol were successfully determined by the proposed method in a hydrolyzed sample of a commercial formulation.
Assuntos
Carbaril/análise , Inseticidas/análise , Medições Luminescentes/métodos , Naftóis/análise , Carbaril/química , Inseticidas/química , Medições Luminescentes/instrumentação , Naftóis/química , Oxigênio/química , Iodeto de Potássio/química , Análise Espectral , Sulfitos/química , Temperatura , Fatores de Tempo , Água/químicaRESUMO
This paper presents the results concerning the degradation of the pesticide carbaryl comparing two methods: electrochemical (EC) and photo-assisted electrochemical (PAEC). The experimental variables of applied current density, electrolyte flow-rate and initial carbaryl concentration were investigated. The results demonstrate that the electrochemical degradation of carbaryl was greatly enhanced when simultaneous UV light was applied. The greatest difference between the PAEC and EC method was apparent when lower current densities were applied. The extent of COD removal was much enhanced for the combined method, independent of the applied current density. It should be noted that the complete removal of carbaryl was achieved with out the need to add NaCl to the reaction mixture, avoiding the risk of chlorinated organic species formation.
Assuntos
Carbaril/química , Técnicas Eletroquímicas/métodos , Recuperação e Remediação Ambiental/métodos , Inibidores da Colinesterase , Descontaminação , Eletrodos , Poluentes Ambientais/química , Inseticidas , Processos Fotoquímicos , Raios UltravioletaRESUMO
This paper presents the study of a prospective electrochemical treatment system for the pesticide carbaryl. Three different dimensionally stable anodes were employed (Ti/Ru0.3 Ti0.7 O2, Ti/Ru0.3 Sn0.7 O2 and Ti/Ir0.3 Ti0.7 O2) and the effect of current density (10, 20, 40 and 60 mA cm(-2)) and supporting electrolyte (0.1 mol L(-1) NaCl and 0.033 mol L(-1) H2SO4) is discussed. All the electrodes present a low level of carbaryl and total organic carbon removal in H2SO4, even at highly positive potentials, indicating that the application of current is not, in itself, sufficient to promote effective oxidation of the pesticide and its products. However, in the presence of NaCl all the electrodes used present rapid diminishing of the carbaryl and total organic carbon content, thus suggesting enhanced activity. The results demonstrate the participation of partially oxidised Cl- species at the electrode surface, which act as an intermediate in the electron transfer between the pesticide molecule and the electrode. Thus, under such conditions, the feasibility of the electrochemical route for the treatment (total or partial) of waste that contains carbaryl is evident.