Simultaneous determination of substituted diphenylamine antioxidants and benzotriazole ultra violet stabilizers in blood plasma and fish homogenates by ultra high performance liquid chromatography-electrospray tandem mass spectrometry.

Analytical methods were developed for the determination of eight substituted diphenylamines (SDPAs) and six benzotriazole UV stabilizers (BZT-UVs) in blood plasma and fish homogenate matrices. Liquid-liquid extraction by methyl tert-butyl ether and denaturation by KOH following silica gel packed column clean-up was employed for blood plasma preparation. For the fish homogenate samples, ultrasonic assisted solvent extraction combined with automated gel permeation chromatography and silica gel packed column clean-up was used. The target compounds were determined by optimized ultra performance liquid chromatography-tandem mass spectrometry in positive electrospray ionization mode. The method limits of quantification (MLOQs) of the 14 analytes ranged from 0.002 to 1.5ngg(-1) and 0.001 to 2.3ngg(-1) (wet weight, w.w.) for blood plasma and fish homogenate, respectively. The total recoveries of the target compounds varied from 61% to 100% (mean 77±9%). Eleven targets including monobutyl- (C4), dibutyl- (C4C4), monooctyl- (C8), monobutyl monooctyl- (C4C8), dioctyl-(C8C8), monononyl- (C9), dinonly-(C9C9) and 4,4'-bis(α,α-dimethylbenzyl)-(diAMS) DPAs, as well as 2-(2H-Benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol (UV234), 2,4-di-tert-butyl-6-(5-chloro-2H-benzotriazol-2-yl) phenol (UV327) and 2-(2H-Benzotriazol-2-yl)-4,6-di-tert-pentylphenol (UV328) were identified in the environmental biota samples, with concentrations in the range of <MLOQ-934pgg(-1), <MLOQ-4.2×10(3)pgg(-1) and <MLOQ-3.9×10(3)pgg(-1)w.w. for bottle nose dolphin (Tursiops truncatus) plasma, northern pike (Esox lucius) plasma and white sucker (Catostomus commersonii) homogenate, respectively. This is the first report of an analytical method development for SDPAs in biotic matrices and BZT-UVs in blood plasma samples.

Lu Z ，Peart TE ，Cook CJ ，De Silva AO ... -  《-》

Substituted diphenylamine antioxidants and benzotriazole UV stabilizers in blood plasma of fish, turtles, birds and dolphins from North America.

Substituted diphenylamine antioxidants (SDPAs) and benzotriazole UV stabilizers (BZT-UVs) are additives used in industrial and commercial applications to prevent degradation by oxidation and are contaminants of emerging environmental concern. Little is known about the fate of these contaminants in wildlife, particularly in reptiles, birds and marine mammals. Nine SDPAs and six BZT-UVs were measured in blood plasma of seven fish species, snapping turtles (Chelydra serpentina), double-crested cormorants (Phalacrocorax auritus), and bottlenose dolphins (Tursiops truncatus) from various locations in North America. Plasma SDPAs were more frequently (90-100%) detected and with higher concentrations (median: 25-270 pg g-1, wet weight (ww)) in organisms from urban areas than rural locations (median: <method limits of quantification -136 pg g-1). The concentrations of most SDPAs generally followed the order of fish ≥ snapping turtles > double-crested cormorants > bottlenose dolphins. Of the three quantifiable BZT-UVs, 2-(2H-benzotriazol-2-yl)-4,6-di-tert-pentylphenol (UV328) showed higher detection frequency in most species of fish, bird and turtle (range of 0-67%), indicating the widespread distribution of UV328 in the aquatic environment of lower Great Lakes region.

Lu Z ，De Silva AO ，Zhou W ，Tetreault GR ，de Solla SR ，Fair PA ，Houde M ，Bossart G ，Muir DCG ... -  《-》

Occurrence and fate of substituted diphenylamine antioxidants and benzotriazole UV stabilizers in various Canadian wastewater treatment processes.

Substituted diphenylamine antioxidants (SDPAs) and benzotriazole UV stabilizers (BZT-UVs) are additives used in industrial and consumer products to prevent degradation or color change of materials, but their environmental fate and disposition are not well characterized. In this study, SDPAs and BZT-UVs were analyzed in 68 liquid and 39 solid samples collected from 9 wastewater treatment plants (WWTPs) in Canada to investigate the occurrence and fate of these contaminants. The median concentrations of ΣSDPAs and ΣBZT-UVs was 483 and 76.2 ng L-1 in influent, 28.4 and 4.84 ng L-1 in effluent, and 2750 and 457 ng g-1 in biosolids (dry weight), respectively. Dinonyl-diphenylamine (C9C9) was the predominant congener of SDPAs in all matrices (>40%). For target BZT-UVs, the major components were 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol (UV234) and 2-(2H-benzotriazol-2-yl)-4,6-di-tert-pentylphenol (UV328). SDPAs and BZT-UVs were effectively removed (>90%) from the liquid stream in most WWTPs mainly through sludge sorption and separation, but biotransformation, UV treatment and filtration may also contribute to removal of some contaminants in advanced treatment plants. In contrast, the removal efficiency of target contaminants using chemically assisted primary treatment was low, likely due to the short hydraulic retention time of this site. Our results suggest that wastewater effluent is a vector of SDPAs and BZT-UVs to the aquatic environment. The results also highlight the high concentrations of SDPAs and BZT-UVs associated with the solid stream in WWTPs, which could affect the beneficial use of biosolids (e.g., compost or land applications).

Lu Z ，Smyth SA ，Peart TE ，De Silva AO ... -  《-》

Distribution and trophodynamics of substituted diphenylamine antioxidants and benzotriazole UV stabilizers in a freshwater ecosystem and the adjacent riparian environment.

Lu Z ，De Silva AO ，Spencer C ，Tetreault GR ，de Solla SR ，Muir DCG ... -  《-》

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

Robust 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 clean-up 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.

Liu R ，Ruan T ，Song S ，Lin Y ，Jiang G ... -  《-》