Acetylcholinesterase Biosensor Based on Functionalized Renewable Carbon Platform for Detection of Carbaryl in Food.

Enzymatic electrochemical biosensors play an important role in the agri-food sector due to the need to develop sustainable, low-cost, and easy-to-use analytical devices. Such biosensors can be used to monitor pathogens, endocrine disruptors, and pesticides, such as carbaryl, widely used in many crops. The use of renewable carbon (RC) sources, provided from biomass pyrolysis has been often applied in the fabrication of such sensors. This material is a great candidate for biosensor fabrication due to the presence of surface functional groups, porosity, and moderate surface area. This work describes the functionalization of RC material through an acid treatment with a sulfonitric solution HNO3/H2SO4 (1:3) and the resulting material was characterized by scanning electron microscopy. The obtained RC functionalized (RCF) and the acetylcholinesterase enzyme (AChE) were applied in the construction of the electrochemical biosensor on glassy carbon (GC) electrode and used to detect carbaryl in apple samples. The GC/RCF/AChE biosensor was able to detect the carbaryl pesticide from 5.0 to 30.0 nmol L-1, displaying a LOD of 4.5 nmol L-1. The detection of carbaryl in apple samples presented recoveries between 102.5 to 118.6% through the standard addition method. The proposed biosensor is a promising renewable tool for food safety.

Combined microfiltration and adsorption process applied to public water supply treatment: water quality influence on pesticides removal.

Granular activated carbon (GAC) fixed bed adsorption technology was applied to remove carbamates carbaryl, methomyl and carbofuran from public water supply. In order to minimize the effect of clogging and to evaluate adsorbent saturation for carbamates, the microfiltration (MF) was previously used to adsorb and the backwash procedure of the GAC bed was carried out. The determination and quantification of the carbamates were performed by analytical technique in high performance liquid chromatography with post-column derivatization and fluorescence detector. The MF of the water previously adsorbed in the GAC fixed bed allowed the greater removal of 100% of the carbamates pesticides with an initial concentration of 25 µg L-1 during the first 48 h of operation. The saturation of the GAC fixed bed occurred in 240 h, due to the partial removal of the natural organic matter by the MF, consequently the competition for adsorptive sites of the GAC was smaller. The backwashing procedure contributed to the partial recovery of the performance of the hydraulic filtration and allowed to identify the saturation of the adsorption column, since the sealing phenomenon preceded the saturation. Finally, the use of public water supply was considered a relevant and positive aspect, since it allowed the identification of the performance of this technology in the removal of carbamates pesticides considering the presence of substances inherent to the public water supply.

Performance of the fixed-bed of granular activated carbon for the removal of pesticides from water supply.

The application of a fixed bed adsorption column of granular activated carbon (FBAC-GAC), in the removal of carbaryl, methomyl and carbofuran at a concentration of 25 µg L-1 for each carbamate, from the public water supply was investigated. For the determination of the presence of pesticides in the water supply, the analytical technique of high-performance liquid chromatography with post-column derivatization was used. Under conditions of constant diffusivity, the FBAC-GAC was saturated after 196 h of operation on a pilot scale. The exhaust rate of the granular activated carbon (GAC) in the FBAC-GAC until the point of saturation was 0.02 kg GAC m-3 of treated water. By comparing a rapid small-scale column test and FBAC-GAC, it was confirmed that the predominant intraparticle diffusivity in the adsorption column was constant diffusivity. Based on the results obtained on a pilot scale, it was possible to estimate the values to be applied in the FBAC-GAC (full scale) to remove the pesticides, which are particle size with an average diameter of 1.5 mm GAC; relationship between the internal diameter of the column and the average diameter of GAC ≥50 in order to avoid preferential flow near the adsorption column wall; surface application rate 240 m3 m-2 d-1 and an empty bed contact time of 3 min. ABBREVIATIONS: BV: bed volume; CD: constant diffusivity; EBCT: empty bed contact time; FBAC-GAC: fixed bed adsorption column of granular activated carbon; GAC: granular activated carbon; MPV: maximum permitted values; NOM: natural organic matter; PD: proportional diffusivity; pHPCZ: pH of the zero charge point; SAR: surface application rate; RSSCT: rapid small-scale column test; WTCS: water treated conventional system.

An integrated approach for assessing the migration behavior of chlorpyrifos and carbaryl in the unsaturated soil zone.

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.

Tradescantia as a biomonitor for pesticide genotoxicity evaluation of iprodione, carbaryl, dimethoate and 4,4'-DDE.

There is a current tendency to develop and apply environmentally friendly techniques that meet the requirements of green analytical chemistry as an alternative to conventional analytical methods. For toxicity evaluation, these alternatives may be found in bioassays such as Tradescantia. This technique, developed in the 1980s, is highly sensitive to evaluate environmental mutagens, simple and cheap. In this paper, the sensibility of both the Tradescantia micronucleus bioassay (Trad-MCN) and the Tradescantia stamen hair bioassay (Trad-SH) were studied for carbaryl, dimethoate and iprodione, common agricultural and domestic pesticides that are currently used in Chile, which have never been tested with such bioassays. Biomonitor exposures were performed by capillary absorption for each individual pesticide over a wide range of concentrations, from maximum residue limits (trace levels) up to the application dose in agricultural fields. In addition, the organochloride 4,4'-DDE was included but only in the concentration range from 0.01mgL-1 to 1mgL-1, mimicking residue concentrations since it is not a commercial product but, rather, the main breakdown product of the persistent organochloride pesticide 4,4-DDT, whose use was discontinued in Chile in the 1980s. The Trad-MCN bioassay revealed a significant increase in micronucleus frequency at the early tetrads of meiotic pollen mother cells of the biomonitor Tradescantia pallida var. purpurea, induced by 4,4'-DDE (for 1mgL-1), dimethoate (for 40mgL-1, 200mgL-1, 400mg/L-1) and carbaryl (for 889mgL-1). Iprodione did not generate any significant change at the tested concentration. Meanwhile, the Trad-SH bioassay was carried out by analysis of the phenotype variations of the stamen hair cells of the Tradescantia clone KU-20 for the same pesticides and doses. This bioassay was not sufficiently sensitive for toxicity evaluation of most of the pesticides tested, with exception of dimethoate in low doses (2 and 5mg/L-1).

Carbaryl degradation by bacterial isolates from a soil ecosystem of the Gaza Strip

Abstract Carbaryl is an important and widely used insecticide that pollutes soil and water systems. Bacteria from the local soil ecosystem of the Gaza Strip capable of utilizing carbaryl as the sole source of carbon and nitrogen were isolated and identified as belonging to Bacillus, Morganella, Pseudomonas, Aeromonas and Corynebacterium genera. Carbaryl biodegradation by Bacillus, Morganella and Corynebacterium isolates was analyzed in minimal liquid media supplemented with carbaryl as the only source of carbon and nitrogen. Bacillus and Morganella exhibited 94.6% and 87.3% carbaryl degradation, respectively, while Corynebacterium showed only moderate carbaryl degradation at 48.8%. These results indicate that bacterial isolates from a local soil ecosystem in the Gaza Strip are able to degrade carbaryl and can be used to decrease the risk of environmental contamination by this insecticide.(AU)

Carbaryl degradation by bacterial isolates from a soil ecosystem of the Gaza Strip

Abstract Carbaryl is an important and widely used insecticide that pollutes soil and water systems. Bacteria from the local soil ecosystem of the Gaza Strip capable of utilizing carbaryl as the sole source of carbon and nitrogen were isolated and identified as belonging to Bacillus, Morganella, Pseudomonas, Aeromonas and Corynebacterium genera. Carbaryl biodegradation by Bacillus, Morganella and Corynebacterium isolates was analyzed in minimal liquid media supplemented with carbaryl as the only source of carbon and nitrogen. Bacillus and Morganella exhibited 94.6% and 87.3% carbaryl degradation, respectively, while Corynebacterium showed only moderate carbaryl degradation at 48.8%. These results indicate that bacterial isolates from a local soil ecosystem in the Gaza Strip are able to degrade carbaryl and can be used to decrease the risk of environmental contamination by this insecticide.

Avaliação de melanócitos humanos expostos ao inseticida carbaril e à radiação solar em cultura / Evaluation of cultured human melanocytes exposed to carbaryl insecticide and solar radiation

O carbaril (metilcarbamato de naftila), um inseticida de amplo espectro, foi recentemente associado ao desenvolvimento de melanoma cutâneo em estudo epidemiológico de coorte com trabalhadores agrícolas norte-americanos, expostos também à radiação solar, o principal fator etiológico para o desenvolvimento de tumores cutâneos. Apesar de abrangente e bem planejado, aquele estudo epidemiológico não é suficiente para caracterizar a contribuição direta do inseticida e da radiação solar na melanomagênese. Diversos estudos têm explorado o efeito sinérgico de determinadas substâncias químicas à radiação UV, potencializando seus efeitos deletérios sobre a pele, e possivelmente contribuindo para o desenvolvimento de tumores. A hipótese deste trabalho é de que a exposição ao carbaril associada à radiação solar possa estimular a transformação de melanócitos. Esse estudo visou caracterizar melanócitos humanos após exposição individual ou combinada ao carbaril (100uM) e à radiação solar (375 mJ/ cm2). Em ensaio de microarray, o carbaril, mas não a radiação solar, induziu uma importante resposta a estresse oxidativo, evidenciada pelo aumento da expressão de genes antioxidantes, como o Hemeoxigenase-1 (HMOX1), e pela diminuição da expressão do gene MiTF, regulador da atividade melanocítica; os resultados foram confirmados por qRT-PCR. Além disso, tanto o carbaril quanto a radiação solar induziram respostas que sugerem dano ao DNA e alteração de ciclo celular. A expressão dos genes nestas categorias, como p21 e BRCA1/2, foi notavelmente mais intensa no grupo de tratamento combinado e de fato, ensaios por citometria de fluxo demonstraram parada de ciclo celular na fase S, redução do número de células em apoptose e indução mais rápida de lesões do tipo CPD neste grupo experimental. Nossos dados sugerem que o carbaril é genotóxico para melanócitos humanos, especialmente quando associado à radiação solar

Carbaryl (1-naphthyl-methylcarbamate), a broad spectrum insecticide, has recently been associated with the development of cutaneous melanoma in an epidemiological cohort study with U.S. farm workers also exposed to ultraviolet radiation, which is known to be the main etiologic factor for skin carcinogenesis. Although comprehensive and well designed, the epidemiological study is not sufficient to characterize the direct contribution of the insecticide and solar radiation in melanomagenesis. Several studies have explored the synergistic effect of certain chemicals with UV radiation, increasing its deleterious effects on the skin, possibly contributing to tumor development. We hypothesized that Carbaryl exposure associated with UV solar radiation may induce melanocyte transformation. This study aims to characterize human melanocytes after individual or combined exposure to Carbaryl (100uM) and solar radiation (375 mJ/ cm2). In a microarray analysis, Carbaryl, but not solar radiation, induced an important oxidative stress response, evidenced by the upregulation of antioxidant genes, such as Hemeoxygenase-1 (HMOX1), and downregulation of MiTF, the main regulator of melanocytic activity; results were confirmed by qRT-PCR. Moreover, both Carbaryl and solar UV induced a gene response that suggests DNA damage and cell cycle alteration. The expression of genes in these categories, such as p21 and BRCA1/2, was notably more intense in the combined treatment group in an additive manner and in fact, flow cytometry assays demonstrated cell cycle arrest in S phase, reduced apoptosis induction and faster induction of CPD lesions in this experimental group. Our data suggests that carbaryl is genotoxic to human melanocytes, especially when associated with solar radiation

Evaluación de riesgo por plaguicidas sobre aguas superficiales de la región norpatagónica argentina / Assessing pesticide hazards on surface water from the northern patagonian region argentina

Aunque el manejo integrado de plagas se aplica en forma creciente en la Región Norpatagónica, todavía una amplia gama de plaguicidas es utilizada con el fin de controlar apropiadamente las principales plagas agrícolas. Otros agroquímicos también son aplicados en las actividades industriales asociadas. El objetivo del presente trabajo es evaluar el impacto potencial causado por estos plaguicidas sobre los organismos acuáticos y para ello se utilizan datos bibliográficos de toxicidad aguda y resultados analíticos locales. Se utilizó un procedimiento escalonado, permitiendo la selección de aquellos xenobióticos ambientales que justificarían un estudio de ecotoxicidad posterior. Los residuos máximos de metil azinfos (S-(3,4-dihydro-4-oxobenzo[d]-[1,2,3]-triazin-3-ylmethyl)O,O-dimethyl phosphordithioate), indican la probabilidad de efectos agudos en el 37% de las especies estudiadas en el río, principalmente peces y zooplancton. Este valor se incrementa en los drenajes hasta un 42%. En el caso del carbaril (1-napthylmethylcarbamate) los residuos encontrados en drenajes afectarían al 14% de las especies estudiadas, mientras que en el río el impacto es despreciable.(AU)

Although the Integrated Pest Management (IPM) is increasingly being applied in the Northern Patagonia Region, different pesticides are still used in order to properly control agricultural pests. Other agrochemicals are also applied in the agriculture associated activities like conservation and packaging industries. The potential impact caused by these pesticides on aquatic organisms is assessed in the present study by means of acute toxicity data available in the literature and local analytical results. A tiered procedure was used allowing the selection of those environmental xenobiotics that need further ecotoxicity studies. The observed maximum residues of azinphos-methyl, (S-(3,4-dihydro-4-oxobenzo[d]-[1,2,3]-triazin-3-ylmethyl) O,O-dimethyl phosphordithioate), indicate the probability of acute effects in 37 % of the studied species in the river, mainly fish and zooplankton.This value increased in drainage channels samples up to 42 %. Additionally, carbaryl (1-napthylmethylcarbamate) residues foundin drainage channels affect 14 % of the studied species, while in the river samples the impact was negligible.(AU)

Evaluación de riesgo por plaguicidas sobre aguas superficiales de la región norpatagónica argentina / Assessing pesticide hazards on surface water from the northern patagonian region argentina

Aunque el manejo integrado de plagas se aplica en forma creciente en la Región Norpatagónica, todavía una amplia gama de plaguicidas es utilizada con el fin de controlar apropiadamente las principales plagas agrícolas. Otros agroquímicos también son aplicados en las actividades industriales asociadas. El objetivo del presente trabajo es evaluar el impacto potencial causado por estos plaguicidas sobre los organismos acuáticos y para ello se utilizan datos bibliográficos de toxicidad aguda y resultados analíticos locales. Se utilizó un procedimiento escalonado, permitiendo la selección de aquellos xenobióticos ambientales que justificarían un estudio de ecotoxicidad posterior. Los residuos máximos de metil azinfos (S-(3,4-dihydro-4-oxobenzo[d]-[1,2,3]-triazin-3-ylmethyl)O,O-dimethyl phosphordithioate), indican la probabilidad de efectos agudos en el 37% de las especies estudiadas en el río, principalmente peces y zooplancton. Este valor se incrementa en los drenajes hasta un 42%. En el caso del carbaril (1-napthylmethylcarbamate) los residuos encontrados en drenajes afectarían al 14% de las especies estudiadas, mientras que en el río el impacto es despreciable.

Although the Integrated Pest Management (IPM) is increasingly being applied in the Northern Patagonia Region, different pesticides are still used in order to properly control agricultural pests. Other agrochemicals are also applied in the agriculture associated activities like conservation and packaging industries. The potential impact caused by these pesticides on aquatic organisms is assessed in the present study by means of acute toxicity data available in the literature and local analytical results. A tiered procedure was used allowing the selection of those environmental xenobiotics that need further ecotoxicity studies. The observed maximum residues of azinphos-methyl, (S-(3,4-dihydro-4-oxobenzo[d]-[1,2,3]-triazin-3-ylmethyl) O,O-dimethyl phosphordithioate), indicate the probability of acute effects in 37 % of the studied species in the river, mainly fish and zooplankton.This value increased in drainage channels samples up to 42 %. Additionally, carbaryl (1-napthylmethylcarbamate) residues foundin drainage channels affect 14 % of the studied species, while in the river samples the impact was negligible.