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

Joseph Monaghan; Angelina Jaeger; Joshua K Jai; Haley Tomlin; Jamieson Atkinson; Tanya M Brown; Chris G Gill; Erik T Krogh

doi:10.1021/acsestwater.3c00275

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

ACS ES T Water. 2023 Sep 12;3(10):3293-3304. doi: 10.1021/acsestwater.3c00275. eCollection 2023 Oct 13.

Authors

Joseph Monaghan^{1

2}, Angelina Jaeger¹, Joshua K Jai¹, Haley Tomlin³, Jamieson Atkinson³, Tanya M Brown^{4

5}, Chris G Gill^{1

2

6

7}, Erik T Krogh^{1

2}

Affiliations

¹ Applied Environmental Research Laboratories, Chemistry, Vancouver Island University, 900 Fifth Street, Nanaimo, British Columbia, Canada V9R 5S5.
² Department of Chemistry, University of Victoria, P.O. Box 3055, 3800 Finnerty Road, Victoria, British Columbia, Canada V8P 5C2.
³ British Columbia Conservation Foundation, 1885 Boxwood Road #105, Nanaimo, British Columbia, Canada V9S 5X9.
⁴ Pacific Science Enterprise Centre, Fisheries and Oceans Canada, 4160 Marine Drive, West Vancouver, British Columbia, Canada V7V 1H2.
⁵ School of Resources and Environmental Management, Simon Fraser University, 8888 University Drive West, Burnaby, British Columbia, Canada V5A 1S6.
⁶ Department of Chemistry, Simon Fraser University, Burnaby, British Columbia, Canada V5A 1S6.
⁷ Department of Environmental and Occupational Health Sciences, University of Washington, 1959 NE Pacific Street, Seattle, Washington 98195-1618, United States.

PMID: 38455156
PMCID: PMC10916759 (available on 2024-09-12)
DOI: 10.1021/acsestwater.3c00275

Abstract

The tire-derived contaminant N-(1,3-dimethylbutyl)-N'-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; R² = 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.