Sand as a solid support in ultrasound-assisted MSPD: A simple, green and low-cost method for multiresidue pesticide determination in fruits and vegetables.

Sand was studied as a solid support in ultrasound-assisted matrix solid-phase dispersion (UA-MSPD) for the extraction of different pesticide classes, including organophosphates, carbamates, triazoles and pyrethroids from fruits and vegetables, with determination by GC-MS and LC-MS/MS. The performance of sand was compared with that of different types of classic solid supports and alternative natural materials from renewable sources. The best results were obtained using 0.5 g sample, 1 g sand as a solid support, 20 mg activated charcoal and 5 mL ethyl acetate as elution solvent. Recoveries ranged from 55 to 140% with an RSD ≤ 20%. LOQs varied from 0.005 to 0.5 mg kg-1 for all analytes. Thiamethoxam, captan, chlorpyrifos, dimethoate and pyrimethanil were found in strawberry samples at concentrations from 0.01 to 0.06 mg kg-1. Acephate and tebuconazole were found in a tomato sample at concentrations of 0.45 and 0.30 mg kg-1, respectively. The method developed was efficient, simple, cheap, robust, and environmentally friendly.

Optimization of a laccase-mediator system with natural redox-mediating compounds for pesticide removal.

This study proposed the optimization of a laccase-mediator system to reduce pesticide levels (bentazone, carbofuran, diuron, clomazone, tebuconazole, and pyraclostrobin) on aqueous medium. Firstly, the mediator concentration of 1 mM was established (average removal of 36%). After that, seven redox-mediating compounds, namely, 2,20-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt, caffeic acid, chlorogenic acid, p-coumaric acid, ferulic acid, gallic acid, protocatechuic acid, and vanillin, were compared regarding their removal efficiency. The highest removal (77%) was achieved with the laccase-vanillin system. After this screening, the optimization was carried out by a 22 full factorial design. Variables under study were the enzyme (laccase) activity and vanillin concentration. Maximum removal (53-85%) was achieved with 0.95 U/mL laccase and 1.8 mM vanillin. Pesticide removal in reaction media was fitted to the first-order kinetics equation with an average half-time life of 2.2 h. This is the first study of the use of this natural compound as a mediator in the degradation of the pesticides under investigation. The results of this study contribute, with alternative methods, to decrease pesticide levels since they are highly persistent in aqueous samples and, as a result, mitigate the environmental impact.

Sample as solid support in MSPD: A new possibility for determination of pharmaceuticals, personal care and degradation products in sewage sludge.

A method based on matrix-solid phase dispersion (MSPD), focused on the principles of green analytical chemistry, aimed at the use of alternative solid supports and less toxic solvents, was developed for the simultaneous determination of 19 pharmaceuticals, 4 personal care products (PPCPs) and 4 degradation products in sewage sludge samples. Higher recoveries were achieved when 2 g sample was macerated for 5 min in a glass mortar, transferred to a centrifuge tube, and 1 min vortex agitation with 5 mL methanol. The performance of the method was evaluated through linearity, recovery, precision (intra-day), method detection and quantification limits (MDL and MQL) and matrix effect. The calibration curves prepared in methanol and in the matrix extract showed a correlation coefficient ranging from 0.98 to 0.99. MQL values ranged from 1.25 to 1250 ng g-1. Recoveries between 50 and 120% were reached with RSDs lower than 20% for most compounds. The method presented low and medium matrix effects for most analytes. This method was successfully applied to real samples and of the 27 compounds determined, amitriptyline, carbamazepine, diclofenac, haloperidol, ketoconazole, miconazole, albendazole, mebendazole, thiabendazole, triclosan and triclocarban were detected in concentrations between 2.5 and 5400 ng g-1.

Environmentally friendly procedure based on VA-MSPD for the determination of booster biocides in fish tissue.

Booster biocides have been widely applied to ships and other submerged structures. These compounds can be released into the marine environment as the result of vessel hull leaching and may remain in different environmental compartments. This study aimed at introducing an environmentally friendly procedure for the extraction of irgarol and diuron from fish samples by vortex-assisted matrix solid phase dispersion (VA-MSPD) with detection by liquid chromatography tandem mass spectrometry. Different types of solid supports and solvents were evaluated. The best results were found when 0.5g mussel shell, 0.5g sodium sulfate and 5mL ethanol were used. Analytical recoveries ranged from 81 to 110%, with RSD below 10%, whereas the matrix effect was between -17 and 1% (for all samples under study). LOQ values of irgarol and diuron were 5 and 50ngg-1, respectively. The method under investigation proved to be a promising alternative to controlling contamination of fish by booster biocides, with low consumption of biodegradable reagents.

Characterization and application of the enzyme peroxidase to the degradation of the mycotoxin DON.

Deoxynivalenol (DON), one of the main mycotoxins found in food matrices, has high level of toxicity. This study aimed to characterize the peroxidase enzyme extracted from rice bran to be applied to the biodegradation of DON in order to evaluate the potential peroxidase (PO) from rice bran (RB) has to degrade DON in optimal conditions. Purification and recovery factors of PO extracted from RB and purified by three-phase partitioning were 5.7% and 50%, respectively. PO had the highest level of activity in the phosphate buffer 5 mM pH 5.5 in both crude and purified forms, whose reaction temperatures were 25°C and 10°C. At the end of production, purification and characterization steps, specific activities of the bran were 115.79 U mg-1 and 4363 U g-1. Reduction in the mycotoxin DON in optimal conditions determined for PO from RB was 20.3%, a promising result when the aim is to adequate mycotoxicological levels to foods.

Dispersive liquid-liquid microextraction based on solidification of floating organic droplet for the determination of triazine and triazoles in mineral water samples.

A simple, rapid, and sensitive method for the determination of atrazine, simazine, cyproconazole, tebuconazole, and epoxiconazole in mineral water employing the dispersive liquid-liquid microextraction with solidification of a floating organic drop with determination by liquid chromatography tandem mass spectrometry has been developed. A mixed solution of 250 µL 1-dodecanol and 1250 µL methanol was injected rapidly into 10 mL aqueous solution (pH 7.0) with 2% w/v NaCl. After centrifugation for 5 min at 2000 rpm, the organic solvent droplets floated on the surface of the aqueous solution and the floating solvent solidified. The method limits of detection were between 3.75 and 37.5 ng/L and limits of quantification were between 12.5 and 125 ng/L. The recoveries ranged from 70 to 118% for repeatability and between 76 and 95% for intermediate precision with a relative standard deviation from 2 to 18% for all compounds. Low matrix effect was observed. The proposed method can be successfully applied in routine analysis for determination of pesticide residues in mineral water samples, allowing for monitoring of triazine and triazoles at levels below the regulatory limits set by international and national legislations.

Evaluation of alternative sorbents for dispersive solid-phase extraction clean-up in the QuEChERS method for the determination of pesticide residues in rice by liquid chromatography with tandem mass spectrometry.

Many compounds are used for pest control during the production and storage of rice, making it necessary to employ multiclass methods for pesticide residues determination. For this purpose, QuEChERS-based methods are very efficient, fast and accurate, and improvements in the clean-up step are important, especially for complex matrices, like cereals. In this work, different sorbents such as chitosan, florisil(®) , alumina, diatomaceous earth, graphitized carbon black, besides the commonly used primary secondary amine and octadecylsilane, were evaluated for dispersive solid-phase extraction clean-up in acetate-buffered QuEChERS method for the determination of residues of 20 representative pesticides and one metabolite in rice by liquid chromatography coupled to tandem mass spectrometry. The sorbent C18 presented the best results, however, chitosan showed similar results, and the best performance among the unconventional sorbents evaluated. The method limit of quantification, attending accuracy (70-120% recovery) and precision (RSD ≤20%) criteria, ranged from 5 to 20 µg/kg. Results showed that chitosan is an effective alternative to reduce analysis costs, maintaining the method reliability and accuracy.

Biochemical responses over time in common carp Cyprinus carpio (Teleostei, Cyprinidae) during fed supplementation with α-lipoic acid.

The current study aimed to evaluate the influence of lipoic acid (LA) supplementation (439.84±6.71 mg LA/kg feed) on antioxidants responses throughout the time in intestine, liver and muscle of juvenile common carp Cyprinus carpio. Two experimental groups were fed during four weeks with a diet with or without LA. Glutathione-S-transferase (GST) activity, glutathione (GSH) content, antioxidant capacity against peroxyl radicals (ACAP) and lipid peroxidation (TBARS) were evaluated in these organs. Also, a technique to measure protein disulfide bonds and sulfhydryl groups was optimized for intestine samples. GST activity was significantly higher (p<0.05) in intestine after two weeks of supplementation. GSH content was also significantly higher (p<0.05) in intestine, liver and muscle of fish fed with LA after two and three weeks, respectively. Total capacity antioxidant against peroxyl radicals was significantly increased (p<0.05) in the muscle of animals fed with LA after the fourth week. Concentration of disulfide bonds was higher in the intestine of fish fed with LA but this group also showed higher concentration of sulfhydryl groups (p<0.05). It is concluded that supplementation with LA is a safe strategy to induce antioxidant responses and improves the antioxidant status in different organs of common carp. Two week of supplementation are required to induce antioxidant responses in intestine and liver and three week for muscle.

Study of vortex-assisted MSPD and LC-MS/MS using alternative solid supports for pharmaceutical extraction from marketed fish.

A procedure based on vortex-assisted matrix solid-phase dispersion (MSPD) for the extraction of 15 pharmaceuticals from fish samples with determination by liquid chromatography-tandem mass spectrometry (LC-MS/MS) was validated. Florisil, C18, diatomaceous earth, chitin, and chitosan were evaluated as solid supports. Best results were obtained with 0.5 g of diatomaceous earth, 0.5 g of sodium sulfate, and 5 mL of methanol. Analytical recoveries ranged from 58 to 128 % with relative standard deviation (RSD) lower than 15 %. Limit of quantification (LOQ) values for the 15 compounds ranged from 5 to 1000 ng g(-1). The method under investigation has shown to be a simple and fast extraction tool with minimum instrumentation and low amount of reagent, resulting in method low cost. Besides, alternative materials, such as chitin and chitosan, which were applied to the dispersion step for the first time, were found to be interesting alternatives.

Evaluation of the QuEChERS method for the extraction of pharmaceuticals and personal care products from drinking-water treatment sludge with determination by UPLC-ESI-MS/MS.

A modified version of the QuEChERS method has been evaluated for the determination of 21 pharmaceuticals and 6 personal care products (PPCPs) in drinking-water sludge samples by employing ultra high liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The performance of the method was evaluated through linearity, recovery, precision (intra-day), method detection and quantification limits (MDL and MQL) and matrix effect. The calibration curves prepared in acetonitrile and in the matrix extract showed a correlation coefficient ranging from 0.98 to 0.99. MQLs values were on the ng g(-1) order of magnitude for most compounds. Recoveries between 50% and 93% were reached with RSDs lower than 10% for most compounds. Matrix effect was almost absent with values lower than 16% for 93% of the compounds. By coupling a quick and simple extraction called QuEChERS with the UPLC-MS/MS analysis, a method that is both selective and sensitive was obtained. This methodology was successfully applied to real samples and caffeine and benzophenone-3 were detected in ng g(-1) levels.

New sorbent in the dispersive solid phase extraction step of quick, easy, cheap, effective, rugged, and safe for the extraction of organic contaminants in drinking water treatment sludge.

Recent studies have shown a decrease in the concentration of pesticides, pharmaceuticals and personal care products (PCPs) in water after treatment. A possible explanation for this phenomenon is that these compounds may adhere to the sludge; however, investigation of these compounds in drinking water treatment sludge has been scarce. The sludge generated by drinking water treatment plants during flocculation and decantation steps should get some special attention not only because it has been classified as non-inert waste but also because it is a very complex matrix, consisting essentially of inorganic (sand, argil and silt) and organic (humic substances) compounds. In the first step of this study, three QuEChERS methods were used, and then compared, for the extraction of pesticides (atrazine, simazine, clomazone and tebuconazole), pharmaceuticals (amitriptyline, caffeine, diclofenac and ibuprofen) and PCPs (methylparaben, propylparaben, triclocarban and bisphenol A) from drinking water treatment sludge. Afterwards, the study of different sorbents in the dispersive solid phase extraction (d-SPE) step was evaluated. Finally, a new QuEChERS method employing chitin, obtained from shrimp shell waste, was performed in the d-SPE step. After having been optimized, the method showed limits of quantification (LOQ) between 1 and 50 µg kg(-1) and the analytical curves showed r values higher than 0.98, when liquid chromatography tandem mass spectrometry was employed. Recoveries ranged between 50 and 120% with RSD≤15%. The matrix effect was evaluated and compensated with matrix-matched calibration. The method was applied to drinking water treatment sludge samples and methylparaben and tebuconazole were found in concentration

Environmentally friendly system for the degradation of multipesticide residues in aqueous media by the Fenton's reaction.

A Fenton oxidation system employing zero-valent iron (whose source was swarf, a residue of metallurgical industries, in powder form) and hydrogen peroxide for the treatment of an aqueous solution with six pesticides was developed, and the effect of the iron metal content, pH, and hydrogen peroxide concentration was evaluated. The characterization of the aqueous solution resulted in: pH 5.6, 105 mg L(-1) of dissolved organic carbon, and 44.6 NTU turbidity. In addition, the characterization of the swarf by FAAS and ICP-MS showed 98.43 ± 7.40 % of zero-valent iron. The removal was strongly affected by the content of iron metal, pH, and hydrogen peroxide concentration. The best degradation conditions were 2.0 g swarf, pH 2.0, and 5 mmol L(-1) H2O2. At the end of the treatment, the pesticide degradation ranged from 60 to 100%, leading to 55% mineralization. Besides, all hydrogen peroxide was consumed and the determination of total dissolved iron resulted in 2 mg L(-1). Thus, the advantages of this system are rapid degradation (up to 20 min), high-degradation rates, simple handling, and low cost.

Assessment of modified matrix solid-phase dispersion as sample preparation for the determination of CH3Hg+ and Hg2+ in fish.

This paper reports, for the first time, the development of an analytical method employing modified matrix solid-phase dispersion (MSPD) for the extraction of CH3Hg(+) and Hg(2+) species from fish samples. Separation and determination of mercury species were performed by gas chromatography coupled to mass spectrometry (GC/MS). Important MSPD parameters, such as sample mass, type and mass of solid support, concentration of extraction solution (HCl and NaCl), and stirring time, were investigated by the response surface methodology. The derivatization step and the separation of mercury species were also evaluated for the determination by GC/MS. Quantitative recoveries were obtained with 0.2 g of fish sample, 0.5 g of SiO2 as the solid support, 0.5 mol L(-1) NaCl and 4.2 mol L(-1) HCl as the extraction solution, and 1 min stirring time. The MSPD method showed to be suitable for the extraction and determination of mercury species in certified reference materials of dogfish liver (DOLT-3) and dogfish muscle (DORM-2). It had good agreement (about 99%) with the certified values, and the relative standard deviation was lower than 9.5%. The limits of detection were 0.06 and 0.12 µg g(-1), for CH3Hg(+) and Hg(2+), respectively. A matrix effect was observed, and the quantification was carried out by the matrix-matched calibration. The method was applied to tuna fish ( Thunnus thynnus ), angel shark ( Squatina squatina ), and guitarfish ( Rhinobatos percellens ) samples. The results of the mercury speciation by MPSD and GC/MS were compared to the total mercury concentration determined by flow injection cold vapor generation inductively coupled plasma mass spectrometry, after microwave-assisted digestion. Agreement ranged from 102% to 105%.

Simultaneous determination of pesticides and 5-hydroxymethylfurfural in honey by the modified QuEChERS method and liquid chromatography coupled to tandem mass spectrometry.

Nowadays, bee products are being produced in an environment polluted by different sources of contamination, such as pesticides, which can be transported by honey bees to the hive and incorporated into honey. In addition, the increasing consumption of honey has demanded efficient quality control for this product. In this study, the determination of the pesticides fipronil, imidacloprid, thiamethoxam, dimethoate, carbendazin, tebuconazole, amitraz, τ-fluvalinate and 5-hydroxymethylfurfural (HMF) which are used as indicators of honey quality, was carried out simultaneously. For the sample preparation, the optimized QuEChERS method was used and the determinations were done by LC-APCI-MS/MS. The LOQs of the method ranged between 0.005 and 1.0 mg kg(-1). For the recovery calculations and method evaluation a working curve was drawn. All the analytical curves showed r values higher than 0.99. The recoveries ranged between 70% and 112%, with RSD lower than 20% for all compounds. The matrix effect was evaluated, and most of the compounds showed signal enrichment. The applicability of the method for honey from different flowers was verified, and the method showed robustness and recoveries in the range 70-120% established for all compounds in samples belonging to different blossoms. HMF was detected in all samples, with concentrations ranging between 4.6 and 51.7 mg kg(-1); it was below the maximum concentration allowed by the legislation.

Evaluation of a modified QuEChERS extraction of multiple classes of pesticides from a rice paddy soil by LC-APCI-MS/MS.

A new method for the determination of clomazone, fipronil, tebuconazole, propiconazole, and azoxystrobin in samples of rice paddy soil is presented. The extraction of the pesticides from soil samples was performed by using a modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) method. Some extraction conditions such as salt addition, sample acidification, use of buffer, and cleanup step were evaluated. The optimized method dealt with a single extraction of the compounds under study with acidified acetonitrile, followed by the addition of MgSO(4) and NaCl prior to the final determination by liquid chromatography-atmospheric chemical pressure ionization-tandem mass spectrometry. Validation studies were carried out in soil samples. Recoveries of the spiked samples ranged between 70.3 and 120% with relative standard deviation lower than 18.2%. The limits of quantification were between 10 and 50 µg kg(-1). The method was applied to the analysis of real samples of soils where rice is cultivated.

Toxicity mechanisms of onion (Allium cepa) extracts and compounds in multidrug resistant erythroleukemic cell line.

Onion (Allium cepa) is being studied as a potential anticancer agent, but little is known regarding its effect in multidrug resistance (MDR) cells. In this work, the cytotoxicity of crude onion extract (OE) and fractioned extract (aqueous, methanolic and ethyl acetate), as well as some onion compounds (quercetin and propyl disulfide) were evaluated in Lucena MDR human erythroleukemic and its K562 parental cell line. The capacity of OE to induce apoptosis and/or necrosis in these cells, the possible participation of oxidative stress and DNA damage were also assessed. Similar sensitivities were obtained for both tumoral cells, however only OE caused significant effects in the cells. In K562 cells, a significant increase of apoptosis was verified while the Lucena cells experienced a significant increase of necrosis. An antioxidant capacity was verified for OE discarding oxidative damage. However, OE provoked similar significant DNA damage in both cell lines. Thus, the OE capacity to overcome the MDR phenotype suggests anti-MDR action of OE.

Toxicity mechanisms of onion (Allium cepa) extracts and compounds in multidrug resistant erythroleukemic cell line

Onion (Allium cepa) is being studied as a potential anticancer agent, but little is known regarding its effect in multidrug resistance (MDR) cells. In this work, the cytotoxicity of crude onion extract (OE) and fractioned extract (aqueous, methanolic and ethyl acetate), as well as some onion compounds (quercetin and propyl disulfide) were evaluated in Lucena MDR human erythroleukemic and its K562 parental cell line. The capacity of OE to induce apoptosis and/or necrosis in these cells, the possible participation of oxidative stress and DNA damage were also assessed. Similar sensitivities were obtained for both tumoral cells, however only OE caused significant effects in the cells. In K562 cells, a significant increase of apoptosis was verified while the Lucena cells experienced a significant increase of necrosis. An antioxidant capacity was verified for OE discarding oxidative damage. However, OE provoked similar significant DNA damage in both cell lines. Thus, the OE capacity to overcome the MDR phenotype suggests anti-MDR action of OE.