Oxidized carbon nanotubes as sorbent for miniaturized solid-phase extraction of progestins from environmental water samp

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Oxidized carbon nanotubes as sorbent for miniaturized solid-phase extraction of progestins from environmental water samples prior to their determination by HPLC-UV Maite V. Aguinaga Martínez 1 & Natalia E. Llamas 1 & Francisco D. Ávila Orozco 1 & Claudia E. Domini 1 & Carolina C. Acebal 1 Received: 9 August 2019 / Accepted: 6 January 2020 # Springer-Verlag GmbH Austria, part of Springer Nature 2020

Abstract A solid-phase extraction method is presented for micro-extraction of three progestins (levonorgestrel, 19-norethisterone acetate and medroxyprogesterone acetate) from water samples. A mini-column was packed with 60 mg of oxidized multiwalled carbon nanotubes and coupled to a flow injection assembly. The extraction parameters, such as washing solution, eluent type, eluent volume, flow rate and sample volume, were optimized. Separation and determination were performed by HPLC with UV detection. The method has a good linear range (0.90–9.0 μg L−1), acceptable limits of detection (0.05–0.14 μg L−1) and low RSDs (0.8–4.6%). Attractive features of the method include low consumption of organic solvents and preconcentration factors of up to 100. The method was applied to analyze stream, underground and effluent water samples, and recoveries between 74 and 121% were obtained. Keywords Emerging contaminants . Hormones . Pharmaceuticals . Carbon-based sorbents . Nanoparticles . Sample preparation . Flow injection analysis . HPLC-UV

Introduction Emerging contaminants (ECs) are chemical substances, products and materials that are spread in the environment and are detected frequently in soils and surface, underground and drinking water [1]. These contaminants include pharmaceutical and personal care products, industrial and household products, and some endocrine disruptors, among others. Due to the high and continuous production of these substances and their massive consumption, their continuous introduction into the environment, mainly through industrial effluents and wastewater treatment plants, is unavoidable, [2]. As it was mentioned above, active pharmaceutical ingredients present in mass-use medications have been classified as ECs. Within this group are the synthetic steroid Electronic supplementary material The online version of this article (https://doi.org/10.1007/s00604-020-4116-z) contains supplementary material, which is available to authorized users. * Carolina C. Acebal [email protected] 1

INQUISUR, Departamento de Química, Universidad Nacional del Sur (UNS)-CONICET, Av. Alem 1253, 8000 Bahía Blanca, Argentina

hormones (SSH), such as estrogens and progestins, which are part of the contraceptive pills and are used in fertility treatments. The SSH, as well as some other ECs, can behave as endocrine disruptors and affect the hormonal balance of the organisms of many species, including human beings [3, 4]. Progestins can be classified as synthetic or natural. Within the first group are norethisterone, levonorgestrel and medroxyprogesterone, among others, and in the second, progesterone [5]. Sinc