Automated, High-Throughput Analysis of Tire-Derived p-Phenylenediamine Quinones (PPDQs) in Water by Online Membrane Sampling Coupled to MS/MS

The tire-derived contaminant N-(1,3-dimethylbutyl)-N & PRIME;-phenyl-p-phenylenediamine quinone (6-PPDQ) was recently identified as a potent toxin to coho salmon (Oncorhynchus kisutch). Studies investigating 6-PPDQ have employed solid-phase extraction (SPE) or liquid-liquid extraction (LLE) with liquid chromatography-mass spectrometry (LC-MS), providing excellent sensitivity and selectivity. However, cleanup and pre-enrichment steps (SPE/LLE) followed by chromatographic separation can be time- and cost-intensive, limiting sample throughput. The ubiquitous distribution of 6-PPDQ necessitates numerous measurements to identify hotspots for targeted mitigation. We recently developed condensed phase membrane introduction mass spectrometry (CP-MIMS) for rapid 6-PPDQ analysis (2.5 min/sample), with a simple workflow and low limit of detection (8 ng/L). Here, we describe improved quantitation using isotopically labeled internal standards and inclusion of a suite of PPDQ analogues. A low-cost autosampler and data processing software were developed from a three-dimensional (3D) printer and Matlab to fully realize the high-throughput capabilities of CP-MIMS. Cross-validation with a commercial LC-MS method for 10 surface waters provides excellent agreement (slope: 1.01; R-2 = 0.992). We employ this analytical approach to probe fundamental questions regarding sample stability and sorption of 6-PPDQ under lab-controlled conditions. Further, the results for 192 surface water samples provide the first spatiotemporal characterization of PPDQs on Vancouver Island and the lower mainland of British Columbia.