Determination of synthetic phenolic antioxidants and relative metabolites in sewage treatment plant and recipient river by high performance liquid chromatography–electrospray tandem mass spectrometry

Abstract

a b s t r a c tRobust analytical methods were developed for the determination of eight emerging synthetic phenolic antioxidants (SPAs) and three metabolites in sewage sludge, effluent and river water matrices. Accelerated solvent extraction was employed for the extraction of the target analytes from sludge, dichloromethane/hexane = 3:1 (extraction solvent) and 90• C (extraction temperature) were used after optimization. Silica gel packed column was chosen for the subsequent cleanup procedure for sludge extract. For the water sample analysis, liquid-liquid extraction combined with silica gel clean-up was used. The targets were determined by optimized high performance liquid chromatography-tandem mass spectrometry method in negative electrospray ionization mode. The method quantification limits of the 11 analytes ranged from 0.1 to 23 ng/L, 0.1 to 20 ng/L and 0.1 to 15 ng/g for sewage effluent, river water and sludge matrices, respectively. The total recoveries of the pretreatment varied from 63 to 106%, with relative standard deviations less than 17% for the three matrices at different spiking levels. Nine targets including 2,6-di-tert-butyl-4-methylphenol (BHT), 3,5-di-tert-butyl-4-hydroxybenzaldehyde (BHT-CHO), 2,6-di-tert-butyl-1,4-benzoquinone (BHT-Q), 2,6-di-tert-butyl-4-hydroxy-4-methyl-2,5-cyclohexadienone (BHT-quinol), 3-tert-butyl-4-hydroxyanisole (BHA), 4-tert-octylphenol (4-tOP), 2,2 -methylenebis(6-tert-butyl-4-methylphenol) (AO 2246), 4,4 -butylidenebis(2-(1,1-dimethylethyl)-5-methyl-phenol) (AO 44B25) and 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene (AO 330) were identified in the collected samples, with concentrations ranging 1.1-2325 ng/g and 0.4-2510 ng/L for sludge and water matrices, respectively. Sewage effluent was considered as a possible contamination source of certain SPA homologues and relative metabolites to the recipient aquatic systems.

Fast and Sensitive LC-MS Detection of Bisphenol A and Butylhydroxyanisole in WWTP Sewage Sludge

“…Due to their relatively high hydrophobicity (log Kow = 3.32 and 3.50 respectively), BPA and BHA strongly interact with organic molecules and as a result are predominantly found in sewage sludge produced in wastewater treatment plants [18]. Because of this, both Bisphenol A and Butylhydroxyanisole are frequently detected in sewage sludge (0.1-3.2 × 10 7 µg/kg BPA [19] and 5-10 ng/g BHA [20]). In recent years, an increasing number of studies were reported on the BPA levels in the environment and its possible biological effects [21], both BPA and BHA being considered omnipresent in the environmental compartments over the last decades [22,23].…”

Potential emerging chemical risks in the food chain associated with substances registered under REACH

“…The substance is primarily used as an antioxidant and stabilizer in rubber and a variety of (co)polymers. It was detected in the effluent and the sludge from a STP in China 53 and in groundwater in Slovenia. 54 DBMC was also detected in childcare articles 55 as well as some food packaging materials, [55][56][57][58][59] while data on the occurrence in food are lacking.…”

Low‐density‐solvent‐based air‐assisted liquid–liquid microextraction followed by gas chromatography with flame ionization detection for the determination of synthetic phenolic antioxidants in milk samples

“…Different studies have revealed that these synthetic components could enter in the human body through the intake of foods, pharmaceutical products, etc. These additives could have harmful effects on human health . Therefore, their use is subject to regulations which define the permitted percentage of these compounds as well as their concentration limits .…”