RESUMO Os neonicotinóides são uma geração relativamente nova de inseticidas que tem sido utilizado para o controle de pragas, como pulgões, cigarrinhas e moscas brancas. Este artigo apresenta pela primeira vez a determinação de resíduos de quatro inseticidas neonicotinóides (acetamiprida, tiametoxam, tiaclopride e imidaclopride) em méis chilenos empregando para extração o método QuEChERS seguido de UHPLC-MS/MS. Foram encontrados limites de detecção e quantificação aceitáveis para todos os analitos variando de 0,34 a 1,43 μg kg-1 e de 0,30 a 4,76 μg kg-1, respectivamente. A extração usando o método QuEChERS proporcionou uma recuperação maior que 79% e a precisão do método não excedeu um coeficiente de variação de 20%. Esses dados estão de acordo com os critérios internacionais que recomendam limites gerais de recuperação de 70 - 120%. Das 16 amostras de mel analisadas foram detectados pesticidas neonicotinoides em três delas. Essas três amostras foram coletadas na mesma área geográfica (Rengo), a qual se caracteriza pela produção de grãos e frutas. A análise da origem botânica desses méis mostrou a ausência de grãos de pólen de espécies cultivadas nesta zona, porém mostrou uma presença majoritária de grãos de pólen de ervas daninhas, como Medicago sativa, Galega officinalis e Brassica rapa, as quais podem estar associadas a estes cultivos. Embora os níveis de resíduos neonicotinoides encontrados neste estudo são baixos, os resultados confirmam a ocorrência atual de uma transferência destes inseticidas ao mel das de abelhas expostas.

ABSTRACT Neonicotinoids are a relatively new generation of insecticides that have been used for control of pests such as aphids, leafhoppers and whiteflies. This paper presents for the first time a determination of residues of four neonicotinoid insecticides (acetamiprid, thiamethoxam, thiacloprid and imidacloprid) in Chilean honey using QuEChERS extraction and UHPLC-MS/MS analysis. The limits of detection and quantification found for all analytes ranging from 0.34 to 1.43 μg kg-1 and from 0.30 to 4.76 μg kg-1, respectively. The extraction using QuEChERS method provided recoveries over 79% and the precision showed coefficient of variation lower than 20%. These data are in agreement with the international criteria that recommend general recovery limits of 70 - 120%. Of the 16 samples analyzed, in three honey samples neonicotinoids pesticides were detected. These three samples were collected from the same geographical area (Rengo). Fruit and grain production characterize the province of Rengo. The analysis of the botanical origin of these honeys showed the absence of pollen grains of crops and the majority presence of pollen grains of weeds such as Medicago sativa, Galega officinalis and Brassica rapa, which could be associated with crops. Although the residue levels found were low, the results also confirm the actual occurrence of a transfer of neonicotinoid insecticides from exposed honeybees into honey.

Abstract The differences between entire quillay honeys and their separated phenolic extracts in terms of phenolic content, flavonoid content and scavenging activity assessed through an Oxygen Radicals Absorbance Capacity (ORAC) assay were determined. The separated phenolic extracts of honey were obtained using Amberlite XAD-2, which is the procedure most used in analytical methods, biological assays and functional food development. The results showed that phenolic and flavonoid contents and antioxidant activity were higher in entire honeys than in their separated phenolic extracts. The recovery of phenolic acids and flavonoids was variable and depended upon the method employed. The application of polyvinylpolypyrrolidone (PVPP), a water insoluble synthetic polymer, in the separated extracts indicated an important influence of non-phenolic reducing compounds in the polyphenolic content measured by the Folin-Ciocalteu method. This showed the elution with methanol of these compounds together with phenolic compounds using an Amberlite XAD-2 column. The antioxidant capacity assessed through ORAC-FL and ORAC-PGR was less influenced by the interference of non-phenolic compounds than by that of total phenolic and flavonoid contents.

Resumen Se estudió la diferencia entre miel de quillay entera y sus extractos fenólicos en función del contenido de compuestos fenólicos totales, flavonoides y de la actividad antioxidante mediante el ensayo de la Capacidad de Absorción de Radicales de Oxígeno (ORAC). Los extractos fenólicos se obtuvieron utilizando columna de Amberlite XAD-2, procedimiento muy empleado en estudios analíticos, biológicos y en el desarrollo de alimentos funcionales. Los resultados demostraran que el contenido de fenoles totales, flavonoides y la capacidad antioxidante son mayores en las mieles enteras que en sus extractos fenólicos separados. Sin embargo, la recuperación de ácidos fenólicos y flavonoides es variable y depende de la metodología empleada. La aplicación de polivinilpolipirrolidona (PVPP), un polímero sintético insoluble en agua, en los extractos separados indicó una importante influencia de compuestos reductores no fenólicos en la medida de fenoles totales determinada por el método de Folin-Ciocalteu. Esto demuestra que utilizando columna Amberlite XAD-2 compuestos no-fenólicos son eluídos con metanol conjuntamente los fenoles. La capacidad antioxidante medida por ORAC es menos influenciada por la contribución de compuestos no fenólicos que los valores de fenoles totales obtenidos por el método FC.

ABSTRACT A variety of organic compounds and their metabolites used in pharmaceutical and personal care products (PPCP´s) are continuously introduced into the environment by domestic or industrial wastewater. Solid phase extraction (polymeric dinivylbenzene cartridge) and stir bar sorptive extraction (polydimethylsiloxane phase) methodologies were optimized for the determination of some selected PPCP´s in aqueous matrices. Carbamazepine, β estradiol, 3-(4-methylbenzylidene)champhor, benzophenone-1 and ibuprofen were extracted from aqueous samples and methanol was used as conditioning/eluting solvent. The variables involved in the extraction of the analytes in the original sample were studied, pH between 3 and 6 and sample volume between 50 and 500 mL were considered. Three concentration levels were extracted at the optimal conditions of pH 5 and 500 mL of sample volume with a recovery up to 89%. The determination was performed in a GC-MS, and a derivatization step using BSTFA+TMCS (99:1) was needed previous to the injection. Real samples from Maipo River and Villarrica Lake were analyzed with the optimized method, and concentrations below the detection limit were detected.

ABSTRACT Nonsteroidal anti-inflammatory drugs are widely used by humans as therapeutic agents to treat or prevent illnesses. Once ingested, part of them is excreted and enters the wastewater treatment plants generating biosolids that they may be used as fertilizing complements. The purpose of this study was to investigate the mobility of nonsteroidal anti-inflammatory drugs (ketoprofen, naproxen, diclofenac and ibuprofen) in soils and soils amended with biosolid. Studies of NSAIDs adsorption on two different soils were carried through batch equilibrium at room temperature. The mobility of NSAIDs in soils was studied through the use of leaching columns incorporating in the top section soil enriched with NSAIDs with and without biosolid. Ketoprofen, naproxen and ibuprofen were determined in the leaching columns. Anti-inflammatory mobility in the soil profile depends on the specific characteristics of each system soil-biosolid. In both soils there was little mobility of anti-inflammatory in the soil profile. In Linderos soil were found in greater quantity of Ibuprofen, naproxen and diclofenac that in Lonquén soil.

Peumus boldus is an endemic Chilean tree whose edible fruit lack a history of scientific research. The aim of this study was to determine its nutritional composition (moisture, ash, crude fiber, proteins, carbohydrates and lipids) and polyphenolic content (total phenolic content, HPLC-DAD, HPLC-MS/MS analysis) at different stages of development. The results show that the fruit decreased in ash, crude fiber and total phenolic content throughout its development, while its carbohydrate and protein content increased. An increase in phenolic molecules such as catechin and epicatechin was also observed. This is the first report on the nutritional composition and phenolic content of Peumus boldus Mol. fruits.

Peumus boldus es un árbol endémico de Chile cuyos frutos comestibles no han sido investigados científicamente. El objetivo de este estudio fue determinar su composición nutricional (humedad, cenizas, fibra cruda, proteínas, carbohidratos y lípidos) y su contenido polifenólico (contenido de fenoles totales, análisis HPLC-DAD, HPLC-MS / MS) en diferentes etapas de desarrollo. Los resultados mostraron que los frutos disminuyeron en cenizas, fibra cruda y el contenido fenólico total a lo largo de su desarrollo; mientras que su contenido de carbohidratos y proteínas aumentó. También se observó un incremento en algunos flavonoides tales como catequina y epicatequina. Este es el primer informe de la composición nutricional y contenido fenólico de los frutos de Peumus boldus Mol.

The use of thin-film microextraction for the extraction of selected pharmaceutical compounds followed by gas chromatography-mass spectrometry detection was evaluated. A segment of polysiloxanes polymer sheet was used as low cost, single use, disposable extraction phase, while Milli-Q water spiked at 20 µg L−1 with the analytes was used for the optimization assays. The controlling parameters for the extraction were optimized via experimental design and it was found that an extraction time of 3 h using a sample volume of 1000 mL at pH 4 with the addition of 20% methanol and 20% sodium chloride provided the greatest extraction efficiency. Recoveries between 67.1 and 85.0% were achieved, with a repeteability lower than 20% (expressed as coefficient of variation) and limit of detection ranged from 0.41 and 0.92 µg L−1. The proposed method show similar analytical performance when compared to the determination of the analytes using stir bar sorptive extraction.