Abstract A new low-cost material is presented for the first time, aiming to study the sorption process for the stir-bar sorptive extraction (SBSE) technique. The bars were made using a composition of a commercial epoxy resin and montmorillonite, under different compositions and a final ratio of 70% (epoxy) and 30% (montmorillonite) was employed, providing the best mechanical and chemical resistance. A PTFE support was developed to hold the bars permitting the magnetic stirring, without turbulent behavior even under long times of stirring at 1000 rpm. The bars were employed to study the sorption of the herbicide atrazine (ATZ), and the best extraction conditions were: sample volume 20.0 mL, pH 6.0, extraction time of 15 min, room temperature, stirring speed of 100 rpm, and 10.0% (w v-1) NaCl. This preliminary evaluation suggests that the modified bars could be employed for ATZ sorption, affording close to 71% of ATZ removal, and presented robust characteristics to be used at least 80 times.

This work evaluated the photocatalytic activity of suspended TiO2, and TiO2-coated glass Raschig rings with respect to degradation of estrogens estrone (E1), 17β-estradiol (E2), and 17α-ethinylestradiol (EE2) in aqueous solutions and wastewater effluent samples. Gas chromatography/tandem mass spectrometry (GC-MS/MS) studies were carried out to identify degradation products for EE2. TiO2 suspensions allowed degradation rates higher than 90% for all studied estrogens in 30 min for an artificial (ultraviolet A) UVA-assisted process and aqueous solution. Immobilized TiO2 showed less favorable degradation kinetics, requiring ca. 60 min to achieve almost complete estrogen degradation. Some derivatized degradation products were identified for the first time by GC-MS/MS applying ultraviolet C (UVC) photolysis and TiO2/UVA photocatalysis. A degradation route was suggested for EE2 in UVC photolysis and TiO2/UVA processes. In the degradation of pretreated sewage samples, the immobilized TiO2 was more efficient than free TiO2, allowing ca. 85% removal of E2 and EE2 in 60 min.

Resumo Este trabalho teve como objetivo determinar duas drogas psicotrópicas mais dispensadas pelos Centros de Atenção Psicossocial (CAPS) nas águas de um rio urbano (sub-bacia do rio Belém, Curitiba - PR, Brasil). Foi desenvolvido e validado um método analítico SPE seguido de HPLC-DAD. Os cartuchos Strata-X® foram utilizados para extrair carbamezepina (CZ) e diazepam (DZ) das águas e as condições de SPE foram otimizadas por um planejamento fatorial 23. O método validado foi específico para compostos alvo. Os coeficientes de correlação foram superiores a 0,9998, a recuperação entre 85,8 e 98,4% e a precisão abaixo de 6,60% (RSD, n = 3). Este método foi aplicado com sucesso para analisar amostras de rios e pontos críticos de poluição foram reconhecidos. A CZ e DZ foram encontradas em concentrações variando de 0,670 a 0,856 μg L-1 e de LOQ a 0,763 μg L-1, respectivamente, confirmam que o consumo de drogas está diretamente relacionado à poluição do rio na região estudada.

Abstract This work sought to determine the two psychotropic drugs most commonly released by Psychosocial Care Centers (CAPS) into urban river waters (Belém sub-basin, Curitiba, PR, Brazil). A simple analytical method using SPE followed by a HPLC-DAD was developed and validated. Strata-X® cartridges were used to extract (carbamazepine) CZ and diazepam (DZ) from water and SPE conditions were optimized by 23 factorial design. The validated method was specific for target compounds; correlation coefficients were above 0.9998, recovery between 85.8 and 98.4% and precision below 6.60% (RSD, n=3). This method was successfully applied to analyze river samples and pollution hotspots were identified. The CZ and DZ concentrations found ranged from 0.670 to 0.856 µg L-1 and from LOQ to 0.763 µg L-1, respectively, and confirmed that drug consumption is directly related to river pollution in the studied region.

A sensitive high-performance liquid chromatography-fluorescence detection method (HPLC-FLD) was developed and validated for 17β-estradiol (E2) and 17α-ethinylestradiol (EE2) determination in wastewater samples. Sample preparation was performed by solid-phase extraction (SPE) on Hypersep C18 cartridges. Conditioning and elution solvents and sample volume were investigated by a 23 factorial design for both analytes. The pre-concentration factor was 2500 times, allowing to quantify 5.0 ng L-1 for both hormones. The SPE-HPLC-FLD method was successfully applied to detect and quantify trace amount of target compounds in raw and treated wastewater samples. E2 was found below limit of quantification in influent and effluent samples. Nevertheless, the recoveries of E2 in standard addition experiments were between 41 and 72%, with relative standard deviations between 4 and 16%. An important matrix effect was observed in the determination of EE2, with fluorescence signal suppression.