Ibuprofen, Carbamazepine and β-Estradiol Determination Using Thin-Film Microextraction and Gas Chromatography-Mass Spectrometry

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 mu g 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 mu g L-1. The proposed method show similar analytical performance when compared to the determination of the analytes using stir bar sorptive extractionProject Fondecyt 1112123

Effects of applying biosolids to soils on the adsorption and bioavailability of 17α-ethinylestradiol and triclosan in wheat plants

Biosolids contain inorganic and organic contaminants, including pharmaceutical and personal care products (PPCPs) that have accounted for a series of emerging contaminants, such as triclosan (TCS) and the hormone 17 alpha-ethinylestradiol (EE2). The general aim of this study was to evaluate the effects of biosolid application on EE2 and TCS adsorption and bioavailability in soils through testing with wheat plants. For the bioavailability study, sand and two soils, Lampa and Lo Prado, were used. The sand and soils were treated using two biosolid application rates (0 and 90 mg ha(-1)), and the EE2 and TCS concentrations in the biosolids were determined as 0.54 +/- 0.06 and 8.31 +/- 0.19 mg kg(-1), respectively. The concentration observed in wheat plants indicated that EE2 and TCS are mainly concentrated in the roots rather than in the shoots. Furthermore, the bioavailability of the compounds in plants depends on the properties of the contaminants and the soil. Adsorption studies showed that increasing the soil organic matter content increases the adsorption of TCS and EE2 on these substrates and that both compounds follow the Freundlich adsorption model. The desorption procedure indicated that availability for both TCS and EE2 depended on the soil type because TCS and EE2 were small in the Lampa soil with and without biosolid application and TCS increased by nearly 50% in the Lo Prado soil. The Lo Prado soil had an acidic pH (5.9) and the Lampa soil had a neutral pH of 7.3, and the organic carbon content was smaller

Nonsteroidal anti-inflammatory drug determination in water samples by HPLC-DAD under isocratic conditions

Nonsteroidal anti-inflammatory drugs (NSAIDs) are a group of medications widely used by man to heal certain ailments. However, after consumption, they may be excreted in wastewaters with consequent environmental effects. NSAIDs are endocrine disruptors that can cause changes in animal physiology. The purpose of this study was to implement an analytical method that permits the determination of the presence of NSAIDs in water. Compound extraction was performed by solid-phase extraction (SPE) using an Oasis HLB cartridge. Analytes were analyzed by high-performance liquid chromatography with diode array detection (HPLC-DAD). The method was applied in water from the Maipo River and from a neighboring wastewater treatment plant in the Metropolitan Region of Pajaritos, Viña, Tuberia, Unión and Gansos sampling points in Chile. This method turned out to be adequate for the determination of NSAIDs in water samples with recovery percentages above 80%. Naproxen and ibuprofen were mostly detected

Determination of organic acids of low molecular weight and phosphate in soil by capillary electrophoresis

Capillary zone electrophoresis with indirect UV detection at 254 nm was found to be suitable for the determination of organic acids and phosphate in aqueous extracts of soil. The best support electrolyte solution was found to be 10mM p-hydroxybenzoic acid with 0.5mM tetradecyltrimethylammonium bromide to reverse electroosmotic flow. This methodology was tested with 9 analytes found in soils: acetate, citrate, formate, phosphate, lactate, oxalate, pyruvate, succinate, and tartrate. The results obtained show that the methodology is adequate for most of the analytes. The sensitivity to oxalate and citrate was low, and the high concentrations of major inorganic anions interfered with the detection of the former. The methodology was applied to the analysis of aqueous extracts of soil samples. Formate, phosphate, lactate, and acetate anions were detected in most of the samples

Caracterización de la materia orgánica disuelta presente en las aguas del Río Bío-Bío, VIII Región de Chile

The dissolved organic matter in rivers has different origin and its composition can vary both by natural conditions and the anthropic activity that takes place near rivers. This mobile fraction of the organic matter is composed of sub-fractions of different molecular weight and polarity, which confer different complexing capacity for the pollutants and thus a different impact on the environment. The aim of this study was to isolate and characterize the organic matter dissolved in a representative basin of a temperate zone in South America, such as Bio Bio River located in the VIII region of Chile. The material was characterized chemically and spectroscopically after fractionating by molecular weight and polarity. It is concluded that the dissolved organic matter of the Rucalhue sector has a terrestrial origin, with a high aromatic carbon content, in contrast with that from Laja and Concepcion, which has a greater anthropic impact. The dissolved organic matters from the sectors with high anthropic activity have larger molecular size and higher organic carbon content and conductivityNational Fund for Scientific and Technological Development (FONDECYT) 1111022

Pharmaceutical compounds determination in water samples: Comparison between solid phase extraction and STIR Bar sorptive extraction

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 n

Rapid Scanning of the Origin and Antioxidant Potential of Chilean Native Honey Through Infrared Spectroscopy and Chemometrics

Antioxidant compounds have the ability to trap free radicals; in honey, this capacity is related to the botanical origin of the sample, and therefore, there has been a growing interest in verifying the floral origin of beehive products and its relation with the polyphenolic compounds with potential antioxidant activity. A FTIR spectrum has been use to discriminate floral origin in Chilean monofloral samples and to predict their antioxidant capacity. Forty-nine honey samples from different geographical zones and botanical origin were classified according to melissopalynology analysis, and total phenolic and flavonoid contents were quantified by spectrophotometric methods. Discriminant analysis showed that Quillay (Quillaja saponaria), Corcolén (Azara petiolaris), and Tebo (Retanilla trinervia) honeys showed similarities related to their common geographical origin, while Ulmo (Eucryphia cordifolia) presents a differentiate behavior. The FTIR spectra were able to predict phenolic and flavonoid content, establishing the potential of spectroscopic tools for quality control in Chilean beehive industry

Determination of the bioavailable fraction of Cu and Zn in soils amended with biosolids as determined by diffusive gradients in thin films (DGT), BCR sequential extraction, and ryegrass plant

This study assessed the effect of biosolids applied at rates, 0, 30, 45, and 60 Mg ha(-1) on the chemical associations and bioavailability of Cu and Zn in soils from an important agricultural zone of the Metropolitan Region in Central Chile. Three methods were used to determine the bioavailability of Cu and Zn in soils: ryegrass (Lolium perenne) plants, diffusive gradients in thin films (DGT) technique, and Community Bureau of Reference (BCR) sequential extraction. The DGT effective concentration (C (E)) and sequential extract acid soluble fraction of the BCR extraction (most labile fraction of the soils, normally associated with bioavailability) were compared with total metal concentration in ryegrass plants as a means to compare the chemical and biological measures of bioavailability. Total Zn was higher in comparison to Cu for all treatments. Concentrations were within the limits set by the Chilean regulations for land-applied biosolids. Metals in the control soil were primarily found in the residual fraction of soils. Biosolids application generally decreased this fraction, with a subsequent increase observed mainly in the acid soluble fraction. The contents of Cu and Zn in ryegrass plants increased with increasing rates of biosolids. Comparison of the Cu and Zn content in ryegrass plants with C (E), showed a good correlation for Zn. However, the C (E) for soil Cu was only related to plant Cu for some of the soils studied. Correlation between Zn in ryegrass plants and the labile fraction of Zn as measured by the sequential extraction was excellent, with correlation coefficients > 0.9, while for Cu, correlation coefficients were lower

Compuestos bioactivos y propiedades antibacterianas de la miel monofloral de Ulmo

Monofloral Ulmo honey is a very appreciated product in the international market but more information is needed in order to support their health properties. Total phenolic and flavonoid contents, antioxidant capacity and antibacterial activity of monofloral Ulmo (Eucryphia cordifolia) honey samples were determined. The samples contained between 176 and 208 mg gallic acid eq (GAE)/100 g for total phenolic content (TPC) and 43-90 mg Quercetin eq/100 g for total flavonoid content (TFC). The antioxidant activity ranged between 91 and 152 mM eq Trolox/g and 28-49 mM eq Trolox/g for DPPH and ABTS assays, respectively. All phenolic extracts from honey samples inhibited Staphylococcus aureus, Streptococcus pyogenes, Pseudomonas aeruginosa and Escherichia coli by plate assays. The chromatographic profile showed that Ulmo honey contained the polyphenolic gallic, caffeic, and coumaric acids, the flavonoids pinocembrin, chrysin, quercetin, luteolin and apigenin, and abscisic acid.La miel monofloral de Ulmo es un producto muy apreciado en el mercado internacional, pero se necesita más información para respaldar sus propiedades saludables. Se determinaron los contenidos fenólicos y flavonoides totales, la capacidad antioxidante y la actividad antibacteriana de muestras de miel monofloral de Ulmo (Eucryphia cordifolia). Las muestras contenían entre 176 – 208 mg eq de ácido gálico (GAE)/100 g para el contenido fenólico total (TPC) y 43 – 90 mg eq de quercetina/100 g para el contenido total de flavonoides (TFC). La capacidad antioxidante osciló entre 91 – 152 mM eq Trolox/g y 28 – 49 mM eq Trolox/g, para los ensayos de DPPH y ABTS, respectivamente. Todos los extractos fenólicos de muestras de miel de ulmo inhibieron Staphylococcus aureus, Streptococcus pyogenes, Pseudomonas aeruginosa y Escherichia coli mediante ensayos en placa. El perfil cromatográfico mostró que la miel de ulmo contenía como compuestos bioactivos los ácidos, gálico, cafeico y cumárico, los flavonoides pinocembrina, crisina, quercetina, luteolina y apigenina, y ácido abscísico.projects FIC Regional Región del Libertador Bernardo O'Higgins: IDI 30126395-0. Interdisciplinario UC-VRI: 13-2014. FONDEQUIP: EQM 150102. Comisión Nacional de Investigación Científica y Tecnológica (CONICYT): 21110822. PAI-CONICYT Tesis de Doctorado en la Empresa: 781412002