Headspace solid-phase microextraction followed by gas chromatography tandem mass spectrometry for the sensitive determination of benzotriazole UV stabilizers in water samples

Abstract

A sensitive procedure for the determination of five ultraviolet (UV) absorbers, belonging to the benzotriazole class, in environmental water samples is proposed. Analytes were first extracted and concentrated from the matrix and then selectively determined by gas chromatography in combination with tandem mass spectrometry detection. The high lipophilic character of some of the investigated species resulted in a strong trend to remain sorbed on solid surfaces, even after addition of considerable percentages of methanol (up to 30%) to water. Thus, minimizing sample handling during the enrichment step is mandatory in order to obtain acceptable accuracy and precision. Solid-phase microextraction (SPME), as sample preparation approach, fulfilled the above requirement and provided acceptable figures of merit for the determination of target species in environmental water samples, including raw wastewater. Optimization of SPME conditions showed that the combination of headspace extraction, with a sample temperature of 100 degrees C and addition of 15 mg of NaCl per milliliter of sample rendered the best compromise in terms of extraction efficiency for all species. Considering a sampling time of 30 min with a poly(dimethylsiloxane)-divinylbenzene-coated SPME fiber, limits of quantification below 2 ng l(-1) and relative standard deviations between 5% and 12% were achieved. Three of the five species included in this research were determined in raw wastewater with a maximum concentration of 57 ng l(-1) for the Tinuvin 326 UV absorber.

Acute toxicity of benzotriazole ultraviolet stabilizers on freshwater crustacean (Daphnia pulex)

“…Recent study (Carpinteiro et al, 2010) reported that concentrations of UV-P, -326, and -328, in raw wastewater samples ranged from 5 ± 2 to 16 ± 1, from 3.5 ± 0.5 to 57 ± 9, and from 1.0 ± 0.1 to 19 ± 2 ng/l, respectively. The results of the above survey show that, BUVSs residues exist in very low concentrations; which were mostly below detection limits and the detected levels in the Nakata et al, (2009).…”

“…BUVSs enter aquatic environments either directly, via wash-off from skin and clothes during water recreational activities, or indirectly, via discharges of sewage and swimming pool waters. As a result, BUVSs have been detected in environmental and biological matrices such as water, soil, sediment and organisms (Nakata et al, 2009;Carpinteiro et al, 2010). Furthermore, Nakata et al (2009) reported that UV-320, -326, -327, and -328 were accumulated in birds, fish and many invertebrates, as well as in sediments.…”

On-line solid-phase extraction coupled to ultra-performance liquid chromatography with tandem mass spectrometry detection for the determination of benzotriazole UV stabilizers in coastal marine and wastewater samples

“…Relevant concentrations of some of these seven BUVSs have been found in different marine organisms like fish [25] lugworms, oysters, clams, crabs, ducks, sharks [15], and even in birds and mammals [24,26]. The presence of some BUVSs has also been reported in sediments samples [15,27,28], sewage sludges [29], wastewater [28,30], and surface waters [28].…”

“…It has been reported that the most lipophilic compounds can be lost during the sample pretreatment due to adsorption on the glass flask [30]. Therefore, a 10 % (v/v) of methanol was added to avoid this loss.…”

Benzotriazole ultraviolet stabilizers alter the expression of the thyroid hormone pathway in zebrafish (Danio rerio) embryos

“…Due to their high production volume and wide application, BUVSs have been frequently detected in various environmental matrices such as municipal waste water, sewage sludge, sediment, soil, and indoor dust (Lai et al, 2014;Ramos et al, 2016;Wang et al, 2013a). Most BUVSs are detected in aquatic environments at mean concentrations ranging from 2.3 to 544.9 ng/L (Carpinteiro et al, 2010(Carpinteiro et al, , 2012García-Guerra et al, 2016;Kameda et al, 2011;Liu et al, 2011;Montesdeoca-Esponda et al, 2012;Song et al, 2014). Among these BUVSs, UV-326, UV-327, and UV-328 appear to be the most frequently detected compounds in environmental samples (Cantwell et al, 2015;Kameda et al, 2011;Langford et al, 2015;Liu et al, 2011;Nakata et al, 2009;Ruan et al, 2012;Song et al, 2014;Wick et al, 2016;Zhang et al, 2011).…”