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 ... -  《-》

Substituted Diphenylamine Antioxidants and Benzotriazole UV Stabilizers in Aquatic Organisms in the Great Lakes of North America: Terrestrial Exposure and Biodilution.

Lu Z ，De Silva AO ，McGoldrick DJ ，Zhou W ，Peart TE ，Cook C ，Tetreault GR ，Martin PA ，de Solla SR ... -  《-》

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 ... -  《-》

Occurrence of substituted diphenylamine antioxidants and benzotriazole UV stabilizers in Arctic seabirds and seals.

Substituted diphenylamine antioxidants (SDPAs) and benzotriazole UV stabilizers (BZT-UVs) are contaminants of emerging environmental concern. However, little is known about the occurrence of these contaminants in the Arctic. In this study, we investigated the levels of 11 SDPAs and 6 BZT-UVs in livers and eggs of two seabird species, the black-legged kittiwake (Rissa tridactyla) and northern fulmar (Fulmarus glacialis), as well as the liver of ringed seals (Pusa hispida) from Canadian high- and sub-Arctic sites. The concentrations of ΣSDPAs in seabird livers (median 336 pg g-1, wet weight (ww)) were significantly higher than the eggs (median 24 pg g-1, ww) and the seal livers (median 38 pg g-1, ww), suggesting liver was a primary tissue of SDPA accumulation in seabirds and that seabirds were at greater risk of exposure to SDPAs than marine mammals in the Arctic. The predominant SDPA was monostyryl octyl-diphenylamine and this compound was detected in every seabird and seal sample, indicating the widespread distribution of this contaminant in Arctic food webs. Unlike SDPAs, the detection rate and concentrations of BZT-UVs in seals were higher than in seabirds. The compound 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol (UV329) or its isomer 2-(2H-benzotriazol-2-yl)-4-(tert-butyl)-6-(sec-butyl) phenol (UV350) was the predominant BZT-UVs in seals, with the concentrations of ΣBZT-UVs between <method quantification limits and 1.66 × 104 pg g-1 (ww) (median: 2.36 × 103 pg g-1, ww). This is the first report of the different distribution patterns of SDPAs and BZT-UVs in wildlife from Canadian Arctic sites.

Lu Z ，De Silva AO ，Provencher JF ，Mallory ML ，Kirk JL ，Houde M ，Stewart C ，Braune BM ，Avery-Gomm S ，Muir DCG ... -  《-》

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 ... -  《-》