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.

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.

Fármacos anti-inflamatórios não-esteroidais (NSAIDs) são um grupo de medicamentos largamente utilizados para combater certas doenças. No entanto, após o consumo, podem ser excretados em águas residuais com consequente efeito ambiental. NSAIDs são disruptores endócrinos que podem causar alterações na fisiologia animal. O objetivo deste estudo foi desenvolver um método de análise que permita a determinação da presença de NSAIDs em água. A extração do composto foi realizada por extração em fase sólida (SPE), usando um cartucho Oasis HLB. Os analitos foram analisados por cromatografia líquida de alta eficiência com detecção por arranjo de diodos (HPLC-DAD). O método foi aplicado em águas do Rio Maipo e de uma estação de tratamento de águas residuais vizinha à Região Metropolitana dos pontos de amostragem Pajaritos, Viña, Tuberia, Unión e Gansos no Chile. Este método mostrou-se adequado na determinação dos NSAIDs em amostras de água com percentagens de recuperação acima de 80%. Naproxeno e ibuprofeno foram detectados principalmente em amostras de água do Rio Maipo, com concentrações variando entre 0,33 e 0,83 µg L-1.

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 in the Maipo River water samples, with concentrations ranging from 0.33 to 0.83 µg L-1.

O efeito da aplicação de biossólido na distribuição e extração de Cr, Cu, Ni, Pb e Zn foi avaliado em solos Molisol de uma importante zona destinada à agricultura no Chile central. Massas de 15 e 30 Mg ha-1 de biossólidos foram adicionadas aos solos e os mesmos foram incubados por 60 dias sob condições controladas de umidade e temperatura. Quatro biossólidos domésticos foram obtidos em uma das plantas de tratamento de águas residuárias de Santiago. As extrações sequenciais a partir de amostras de biossólido e solo foram efetuadas de acordo com o procedimento recomendado pelo BCR, que se baseia em quatro extrações para obter uma fração solúvel em ácido (trocável, carbonatos), uma fração reduzível (óxidos de ferro/manganês), uma fração oxidável (matéria orgânica e sulfetos) e uma fração residual. Os metais traço foram determinados por espectrometria de absorção atômica com chama e espectrometria de massa acoplada ao plasma indutivo. Dentre os metais determinados em biossólidos, Zn apresentou a concentração mais alta. A quantidade de metais traço determinada em alguns biossólidos, exceto para Ni, foi abaixo dos limites permitidos pela legislação Chilena para biossólidos. Em geral, desconsiderando-se a fração residual, os metais foram encontrados predominantemente nas frações reduzíveis e oxidáveis. Um planejamento multifatorial foi empregado para avaliar os efeitos da quantidade de biossólido aplicada, do tipo de biossólido e do tempo de incubação. A incorporação do biossólido à razão de 30 Mg ha-1 produziu um aumento na disponibilidade de Zn e Ni em todos os solos e de Cu na maioria deles. Por outro lado, Cr e Pb não variaram significativamente. Em geral, os fatores incubação e tipo de biossólido não apresentaram efeitos pronunciados quando comparados com as condições iniciais.

The effect of biosolid application on the distribution and extractability of Cr, Cu, Ni, Pb, and Zn was assessed in Mollisol soils from an important agricultural zone in central Chile. These were amended with biosolids at the amounts of 15 and 30 Mg ha-1 and incubated for 60 days under controlled conditions of moisture and temperature. Four domestic biosolids were obtained from the monofill at one of the Santiago wastewater treatment plants. Biosolid and soil sequential extraction was performed according to the procedure recommended by BCR, which considers four extractions to obtain an acid-soluble fraction (exchangeable, carbonates), a reducible fraction (iron/manganese oxides), an oxidizable fraction (organic matter and sulfides) and the residual one. Trace metals were determined by flame atomic absorption spectrometry and inductively coupled plasma mass spectrometry. Among the metals determined in biosolids, Zn had the highest concentration. Total trace metal contents found, except for Ni in some biosolids, was below the limits allowed by the Chilean regulation for biosolids. In general, without considering the residual fraction, the metals were found predominantly as reducible and oxidizable fractions. A multifactorial design was applied to assess the effects of biosolid application amounts, biosolid type and incubation time. Biosolid incorporation at the amount of 30 Mg ha-1 produced an increase in Zn and Ni availability in all soils and Cu in most of them, while Cr, and Pb showed no significant variations. In general, the factors incubation and type of biosolid did not show remarkable effects compared with initial conditions.