Salt-induced matrix effects on PFAS quantification in online SPE-LC-MS/MS analysis
Aleum Lee1, Soo Min Song1,2, Hee Sun Moon3,4
1Groundwater Environment Research Center, Geo-Environment Research Division, Korea Institute of Geoscience and Mineral Resources (KIGAM), Daejeon, 34132, Korea.
Residual inorganic ions in water significantly impact perfluoroalkyl substances (PFAS) quantification using online SPE-LC-MS/MS. Salt addition improves detection limits for short-chain PFAS but complicates accurate measurement due to incomplete internal standard correction.
Area of Science:
- Environmental Chemistry
- Analytical Chemistry
- Mass Spectrometry
Background:
- Residual inorganic ions in automated online solid-phase extraction (SPE) can interfere with electrospray ionization.
- This interference can lead to biased quantification of perfluoroalkyl substances (PFAS) in environmental water samples.
- Accurate PFAS analysis is crucial for environmental monitoring and risk assessment.
Purpose of the Study:
- To evaluate the influence of modest salt concentrations (NaCl and CaCl2) on PFAS analytical response.
- To assess the effectiveness of isotope dilution for correcting salt-dependent matrix effects in online SPE-LC-MS/MS.
- To understand how salt concentration affects the quantification of various PFAS chain lengths.
Main Methods:
- Utilized an automated online SPE-LC-MS/MS system operating in negative ESI-MRM mode.
- Introduced controlled concentrations of NaCl and CaCl2 (10-30 mg/L) into the sample matrix.
- Analyzed perfluorobutanoic acid (PFBA) and a suite of other PFAS compounds, including isotopically labeled internal standards.
Main Results:
- Salt addition improved detection limits for PFBA, making it detectable and quantifiable.
- Isotope dilution provided incomplete compensation for salt-induced response changes, particularly for short-chain PFAS.
- Matrix effects ranged widely (-74% to +1005%), with short-chain PFAS showing significant enhancement (up to tenfold for PFPeA) and longer-chain PFAS showing weaker or negative effects.
- NaCl amplified chain length-dependent contrast more than CaCl2, leading to divergent responses for C8-C9 compounds.
Conclusions:
- Environmentally relevant salt concentrations substantially alter PFAS response patterns in automated online SPE-LC-MS/MS.
- Ionic composition of water matrices must be considered during method validation and data interpretation for PFAS quantification.
- Internal standardization offers incomplete correction for salt-dependent matrix effects, especially for short-chain PFAS.
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