Magnetic rubber@ Magnesium Aluminum layered double hydroxide as nanostructured sorbent; application in determination of estrogenic hormones and bisphenol A

Emerging contaminants are defined as any chemical, microbial or radiological uncontrolled substances. Pharmaceuticals, personal care products, endocrine disruptors compounds (EDCs), agrochemicals and perchlorates are examples of emerging contaminants [1]. In recent years, there has been widespread debate about human exposure to emerging contaminants in the scientific community [2]. Recognition of emerging contaminants that have been observed in water resources in recent years is necessary [3], [4], [5], [6], [7], [8], [9]. There are two types of endocrine disrupting compounds: compounds of natural or synthetic origin. Bio originated steroid hormones such as Estrone (E1), 17-β-estradiol (E2) are among the compounds of natural origin. Estrogens are 18-carbon compounds with a cyclopentane-perhydro-phenanthrene structure [10]. Estrogens are known as female hormones, which play important role in their growth and reproduction system. Also, small amounts of them are found in males [11]. In the recent decades, estrogens as high-consumption drugs have been produced and consumed in large quantities in the medicine, veterinary medicine and living stock farming. So, their excretion through urine, feces and blood are known as a key environmental pollution of water resources and cause serious ecological problems [12]. Unlike Steroid hormones, bisphenol A (BPA) which are used in the production of polycarbonate plastics and epoxy resins, is among the endocrine disrupting compounds of synthetic origin [13]. Due to high risks of trace concentrations estrogenic hormones and BPA to growth, reproduction, brain function, immune system of living things including human and animals health and as well as the effect on the environmental safety, they must be monitored and controlled [14]. The most preferred analytical method for determination of hormones and BPA is liquid chromatographic methods [15], [16], [17], [18], [19], [20], [21]. Gas chromatography is also can be used but derivatization step makes it, time consuming with low recovery [22]. Magnetic solid phase extraction (MSPE) is one of the most practical extraction methods which was introduced by Safarikova et al [23]. MSPE has advantages such as efficient and simple separation using magnetic field, high preconcentration factors, good recoveries, easy and cheap preparation, reduced solvent use and high adsorption capacity [24]. Layered double hydroxides (LDHs) are important two-dimensional layered materials. LDHs are classified as synthetic brucite like clays with formula of [M2+1-xM3+x.x(OH)2]An−x/n .mH2O]. Synthesis of LDHs with variable functionalities according to the need can be performed due to tunable composition of them. On the other hand, large surface area, high exchange capacity for anions and thermal stability introduces LDHs as excellent candidate to use as sorbents in solid phase extraction and microextraction [25], [26], [27], [28]. In this work, in order to integrate advantages of MSPE as an efficient extraction technique and LDHs as high-performance sorbent, synthesis of magnetic sorbent based on Rubber-Fe3O4@SiO2@Mg-Al LDH was studied. The proposed sorbent showed porous, crystalline and nanosized structure with superior paramagnetic properties. Application of the prepared sorbent was studied in extraction of estrogenic hormones (E1 and E2) and BPA from aqueous samples including tap water, bottled drinking water and municipal sewage water prior to their liquid chromatographic determination.

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