Quantitative analysis of phosphoric acid esters in aqueous samples by isotope dilution stir-bar sorptive extraction combined with direct analysis in real time (DART)-Orbitrap mass spectrometry

由 ty10086 提交于 周四, 08/26/2021 - 13:31
文章英文标题
Quantitative analysis of phosphoric acid esters in aqueous samples by isotope dilution stir-bar sorptive extraction combined with direct analysis in real time (DART)-Orbitrap mass spectrometry
正文
Abstract(#br)A novel hyphenated technique, namely the combination of stir bar sorptive extraction (SBSE) with isotope dilution direct analysis in real time (DART) Orbitrap™ mass spectrometry (OT-MS) is presented for the extraction of phosphoric acid alkyl esters (tri- (TnBP), di- (HDBP), and mono-butyl phosphate (H2MBP)) from aqueous samples. First, SBSE of phosphate esters was performed using a Twister™ coated with 24\u003cce:hsp sp=\"0.25\"/\u003eμL of polydimethylsiloxane (PDMS) as the extracting phase. SBSE was optimized for extraction pH, phase ratio (PDMS volume/aqueous phase volume), stirring speed, extraction time and temperature. Then, coupling of SBSE to DART/Orbitrap-MS was achieved by placing the Twister™ in the middle of an open-ended glass tube between the DART and the Orbitrap™. The DART mass spectrometric response of phosphate esters was probed using commercially available and synthesized alkyl phosphate ester standards. The positive ion full scan spectra of alkyl phosphate triesters (TnBP) was characterized by the product of self-protonation [M\u003cce:hsp sp=\"0.25\"/\u003e+\u003cce:hsp sp=\"0.25\"/\u003eH] + and, during collision-induced dissociation (CID), the major fragmentation ions corresponded to consecutive loss of alkyl chains. Negative ionization gave abundant [M\u003cce:hsp sp=\"0.25\"/\u003e−\u003cce:hsp sp=\"0.25\"/\u003eH] − ions for both HDnBP and H2MnBP. Twisters™ coated with PDMS successfully extracted phosphate acid esters (tri-, di- and mono-esters) granted that the analytes are present in the aqueous solution in the neutral form. SBSE/DART/Orbitrap-MS results show a good linearity between the concentrations and relative peak areas for the analytes in the concentration range studied (0.1–750\u003cce:hsp sp=\"0.25\"/\u003eng\u003cce:hsp sp=\"0.25\"/\u003emL −1 ). Reproducibility of this SBSE/DART/Orbitrap-MS method was evaluated in terms of %RSD by extracting a sample of water fortified with the analytes. The %RSDs for TnBP, HDnBP and H 2 MnBP were 4, 3 and 3% ( n \u003cce:hsp sp=\"0.25\"/\u003e=\u003cce:hsp sp=\"0.25\"/\u003e5) using the respective perdeuterated internal standards. Matrix effects were investigated by matrix matched calibration standards using underground water samples (UWS) and river water samples (RWS). Matrix effects were effectively compensated by the addition of the perdeuterated internal standards. The application of this new SBSE/DART/Orbitrap-MS method should be very valuable for on-site sampling/monitoring, limiting the transport of large volumes of water samples from the sampling site to the laboratory.
文章内容（英文）
Abstract(#br)A novel hyphenated technique, namely the combination of stir bar sorptive extraction (SBSE) with isotope dilution direct analysis in real time (DART) Orbitrap™ mass spectrometry (OT-MS) is presented for the extraction of phosphoric acid alkyl esters (tri- (TnBP), di- (HDBP), and mono-butyl phosphate (H2MBP)) from aqueous samples. First, SBSE of phosphate esters was performed using a Twister™ coated with 24\u003cce:hsp sp=\"0.25\"/\u003eμL of polydimethylsiloxane (PDMS) as the extracting phase. SBSE was optimized for extraction pH, phase ratio (PDMS volume/aqueous phase volume), stirring speed, extraction time and temperature. Then, coupling of SBSE to DART/Orbitrap-MS was achieved by placing the Twister™ in the middle of an open-ended glass tube between the DART and the Orbitrap™. The DART mass spectrometric response of phosphate esters was probed using commercially available and synthesized alkyl phosphate ester standards. The positive ion full scan spectra of alkyl phosphate triesters (TnBP) was characterized by the product of self-protonation [M\u003cce:hsp sp=\"0.25\"/\u003e+\u003cce:hsp sp=\"0.25\"/\u003eH] + and, during collision-induced dissociation (CID), the major fragmentation ions corresponded to consecutive loss of alkyl chains. Negative ionization gave abundant [M\u003cce:hsp sp=\"0.25\"/\u003e−\u003cce:hsp sp=\"0.25\"/\u003eH] − ions for both HDnBP and H2MnBP. Twisters™ coated with PDMS successfully extracted phosphate acid esters (tri-, di- and mono-esters) granted that the analytes are present in the aqueous solution in the neutral form. SBSE/DART/Orbitrap-MS results show a good linearity between the concentrations and relative peak areas for the analytes in the concentration range studied (0.1–750\u003cce:hsp sp=\"0.25\"/\u003eng\u003cce:hsp sp=\"0.25\"/\u003emL −1 ). Reproducibility of this SBSE/DART/Orbitrap-MS method was evaluated in terms of %RSD by extracting a sample of water fortified with the analytes. The %RSDs for TnBP, HDnBP and H 2 MnBP were 4, 3 and 3% ( n \u003cce:hsp sp=\"0.25\"/\u003e=\u003cce:hsp sp=\"0.25\"/\u003e5) using the respective perdeuterated internal standards. Matrix effects were investigated by matrix matched calibration standards using underground water samples (UWS) and river water samples (RWS). Matrix effects were effectively compensated by the addition of the perdeuterated internal standards. The application of this new SBSE/DART/Orbitrap-MS method should be very valuable for on-site sampling/monitoring, limiting the transport of large volumes of water samples from the sampling site to the laboratory.
来源出处
Journal|[J]Analytica Chimica ActaVolume 869, 2015. PP 1-10
DOI
https://doi.org/10.1016/j.aca.2015.01.010

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