Quantitative profiling of perfluoroalkyl substances by ultrahigh-performance liquid chromatography and hybrid quadrupole time-of-flight mass spectrometry

Abstract

The accurate determination of perfluoroalkyl substances (PFSAs) in water, sediment, fish, meat, and human milk was achieved by ultrahigh-performance liquid chromatography-quadrupole time-of-flight mass spectrometry (UHPLC-QqTOF-MS) with an ABSciex Triple TOF®. A group of 21 PFSAs was selected as target to evaluate the quantitative possibilities. Full scan MS acquisition data allows quantification at relevant low levels (0.1-50 ng L(-1) in water, 0.05-2 ng g(-1) in sediments, 0.01-5 ng g(-1) in fish and meat, and 0.005-2 ng g(-1) in human milk depending on the compound). Automatic information dependent acquisition product ion mass spectrometry (IDA-MS/MS) confirms the identity even for those compounds that presented only one product ion. The preparation of a homemade database using the extracted ion chromatogram (XIC) Manager of the software based upon retention time, accurate mass, isotopic pattern, and MS/MS library searching achieves not only the successful identification of PFSAs but also of some pharmaceuticals, such as acetaminophen, ibuprofen, salicylic acid, and gemfibrozid. Mean recoveries and relative standard deviation (RSD) were 67-99% (9-16% RSD) for water, 62-103% (8-18% RSD) for sediment, 60-95% (8-17% RSD) for fish, 64-95% (8-15% RSD) for meat, and 63-95% (8-16%) for human milk. The quantitative data obtained for 60 samples by UHPLC-QqTOF-MS agree with those obtained by LC-MS/MS with a triple quadrupole (QqQ).

Applicability of mixed-mode chromatography for the simultaneous analysis of C1-C18 perfluoroalkylated substances

“…Although high resolution analyzers have been employed, such as quadrupole time-of-flight mass spectrometry (QTOF-MS), providing a high resolving power, selectivity and mass accuracy necessary for the discovery of novel PFAAs [15,16], the highest sensitivity is still provided by triple quadrupole mass spectrometers (QqQ) [17]. The main analytical challenge in ultrashort-and short-chain PFAAs analysis is chromatographic separation.…”

Simultaneous qualitative and quantitative analysis of fluoroalkyl sulfonates in riverine water by liquid chromatography coupled with Orbitrap high resolution mass spectrometry

“…Novel isopropyl-branched fluorinated substances were initially found in river water by selected suspect-ion monitoring strategy [19], and non-target polyfluorinated sulfonic acid were identified in firefighter serum samples by retrospective screening of the full-scan MS 1 spectrum with the aid of advanced statistical analysis [20,21]. Nevertheless, additional LC-MS/MS methods were applied thereafter to quantify the emerging pollutants due to the concern of poor sensitivity and linear dynamic range of HRMS for quantitative purpose.…”

Recent applications of CE‐ and HPLC‐MS in the analysis of human fluids

“…The continuous growth of the literature dedicated to breast milk (BM) analysis confirms the potential of this fluid to provide reliable information on human exposure to different compounds. A good number of reports focuses on the application of sophisticated LC‐MS/MS methods to detect/quantify highly fluorinated aliphatic compounds including perfluoroalkyl substances (PFASs) and brominated flame retardants (BFRs). These compounds are used in industrial applications ranging from textiles to paint and varnish and are associated with adverse health effects.…”