Monaghan Joseph, Jaeger Angelina, Agua Alon R, Stanton Ryan S, Pirrung Michael, Gill Chris G, Krogh Erik T
Applied Environmental Research Laboratories, Chemistry, Vancouver Island University, 900 Fifth Street, Nanaimo, British Columbia, Canada V9R 5S5.
Department of Chemistry, University of Victoria, P.O. Box 3055, Victoria, British Columbia, Canada V8P 5C2.
Environ Sci Technol Lett. 2021 Oct 20;8(12):1051-1056. doi: 10.1021/acs.estlett.1c00794. eCollection 2021 Dec 14.
The oxidative transformation product of a common tire preservative, identified as -(1,3-dimethylbutyl)-'-phenyl--phenylenediamine quinone (6-PPDQ), has recently been found to contribute to "urban runoff mortality syndrome" in Coho salmon at nanogram per liter levels. Given the number of fish-bearing streams with multiple stormwater inputs, large-scale campaigns to identify 6-PPDQ sources and evaluate mitigation strategies will require sensitive, high-throughput analytical methods. We report the development and optimization of a direct sampling tandem mass spectrometry method for semiquantitative 6-PPDQ determinations using a thin polydimethylsiloxane membrane immersion probe. The method requires no sample cleanup steps or chromatographic separations, even in complex, heterogeneous samples. Quantitation is achieved by the method of standard additions, with a detection limit of 8 ng/L and a duty cycle of 15 min/sample. High-throughput screening provides semiquantitative concentrations with similar sensitivity and a full analytical duty cycle of 2.5 min/sample. Preliminary data and performance metrics are reported for 6-PPDQ present in representative environmental and stormwater samples. The method is readily adapted for real-time process monitoring, demonstrated by following the dissolution of 6-PPDQ from tire fragments and subsequent removal in response to added sorbents.
一种常见轮胎防腐剂的氧化转化产物，被鉴定为 -（1,3 - 二甲基丁基）- '- 苯基 - - 苯二胺醌（6 - PPDQ），最近发现其在纳克每升水平时会导致银大麻哈鱼出现“城市径流死亡综合征”。鉴于有多个雨水输入的含鱼溪流数量众多，开展大规模活动以确定6 - PPDQ来源并评估缓解策略将需要灵敏、高通量的分析方法。我们报告了一种使用薄聚二甲基硅氧烷膜浸入探头进行6 - PPDQ半定量测定的直接采样串联质谱方法的开发与优化。该方法即使在复杂的异质样品中也无需样品净化步骤或色谱分离。通过标准加入法进行定量，检测限为8 ng/L，每个样品的分析周期为15分钟。高通量筛选可提供具有相似灵敏度的半定量浓度，且每个样品的完整分析周期为2.5分钟。报告了代表性环境和雨水样品中6 - PPDQ的初步数据和性能指标。该方法易于适用于实时过程监测，通过跟踪6 - PPDQ从轮胎碎片中的溶解以及随后因添加吸附剂而去除得以证明。
