Geospatial Assessment of Trace-Level Benzophenone-3 in a Fish-Bearing River Using Direct Mass Spectrometry

Abstract

Benzophenone-3 (2-hydroxy-4-methoxybenzophenone) is present in many sunscreens/cosmetics due to its UV-filtering properties and has consequently been observed in recreational waters. There are growing concerns about endocrine disruption in aquatic organisms and broader impacts in freshwater and marine systems. Therefore, there is value in cost-effective, sensitive techniques that allow for high-density, spatiotemporal data to protect environmental health and inform public policy. Condensed-phase membrane introduction mass spectrometry coupled with liquid electron ionization with in situ chemical ionization (CP-MIMS-LEI/CI) is a novel direct tandem MS technique that fulfills these criteria and was applied for the direct measurement of benzophenone-3 in environmental water samples without any sample preparation. We report results that are sensitive (20 ng/L detection limit), reproducible (11% interday variability), and comparable to those of liquid chromatography tandem mass spectrometry (LC–MS/MS) for environmental samples (n = 4; 12–24% different). CP-MIMS-LEI/CI was applied to samples (n = 33) from the Cowichan River and Cowichan Lake (British Columbia, Canada), an important fish-bearing system significant to First Nations culture, salmonid production, and recreation. The quantitative analysis afforded by CP-MIMS-LEI/CI enabled geospatial benzophenone-3 analysis, identifying elevated concentrations (>180 ng/L) associated with local recreational activity. LC–MS/MS measurements for samples from two locations suggest a correlation between the number of swimmers and benzophenone-3 concentrations (R 2 = 0.88 and 0.94).

Aqueous-phase photochemical oxidation of water-soluble brown carbon aerosols arising from solid biomass fuel burning

“…and multifunctional internal standards (e.g., gemfibrozil) in complex sample matrices (e.g., waste water) and found bias to be within ± 15%. Additionally, several studies [60][61][62] have used single-functional compounds as an internal standard to identify a range of compounds in complex sample matrices during direct flow-injection MS analysis.…”

Water Analysis: Emerging Contaminants and Current Issues

“…Vandergrift et al developed a new direct mass spectrometry method for trace level determination of BP-3 in surface waters. 193 This method used condensed-phase membrane introduction mass spectrometry (MIMS) coupled to liquid electron ionization with in situ chemical ionization and enabled the direct measurement of BP-3 without any sample preparation. LODs of 20 ng/L were achieved, with 11% interday variability.…”

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

“…The acceptor phase composition, ion source, and MS parameters can be optimized for a specific analyte class. This approach has been implemented for polycyclic aromatic hydrocarbons, 22−24 phthalates, 23 UV filters, 25 and naphthenic acids. 22,26,27 CP-MIMS provides continuous, real-time data allowing dynamic processes such as organic synthesis 28 or sorption/desorption phenomena 27 to be studied directly.…”

“…The acceptor phase composition, ion source, and MS parameters can be optimized for a specific analyte class. This approach has been implemented for polycyclic aromatic hydrocarbons, − phthalates, UV filters, and naphthenic acids. ,, CP-MIMS provides continuous, real-time data allowing dynamic processes such as organic synthesis or sorption/desorption phenomena to be studied directly. We have previously reported a preliminary CP-MIMS method using tandem MS for analysis of 6-PPDQ exhibiting environmentally relevant detection limits (8 ng/L) and a short analytical duty cycle (2.5 min/sample) …”