Application of Gas Chromatography to Determination of Total Organic Fluorine after Defluorination of Perfluorooctanoic Acid as a Model Compound

Koc, Mariusz; Donten, Magdalena A.; Musijowski, Jacek; Guo, Xinghua; Fauland, Alexander; Lankmayr, Ernst; Trojanowicz, Marek

doi:10.5562/cca1798

Cited by 9 publications

(4 citation statements)

References 18 publications

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“…11a shows example chromatograms recorded for triphenylsilyl fluoride (TPSiF). In determinations of PFOA with GC/MS, the MDL value was evaluated as 43 ng · L −1 [99]. Similarly to results of works reported above for CIC method, in examined natural water samples the obtained TOF values indicate the presence of larger amounts of perfluoroalkyl substances, than sum of 8 most commonly occurring PFASs determined with LC/MS (Fig.…”

Section: Determination Of Total Organic Fluorine (Tof)mentioning

confidence: 72%

“…As the application of ion-chromatography in determination of fluoride in hydrolyzate was unsuccessful [97], the use of other modes of chromatography for determination of fluoride required a derivatization to fluorosilane derivative [97, 98]. The obtained derivative can be determined both by RP-HPLC with UV detection [97], as well as GC with FID or MS detection [99]. For PFOA the MDL value for whole procedure with preconcentration and HPLC determination was evaluated as 20 ng · L −1 [97], and Fig.…”

Section: Determination Of Total Organic Fluorine (Tof)mentioning

confidence: 99%

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Recent developments in methods for analysis of perfluorinated persistent pollutants

Trojanowicz

Koc

2013

Microchim Acta

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Perfluoroalkyl substances (PFASs) are proliferated into the environment on a global scale and present in the organisms of animals and humans even in remote locations. Persistent organic pollutants of that kind therefore have stimulated substantial improvement in analytical methods. The aim of this review is to present recent achievements in PFASs determination in various matrices with different methods and its comparison to measurements of Total Organic Fluorine (TOF). Analytical methods used for PFASs determinations are dominated by chromatography, mostly in combination with mass spectrometric detection. However, HPLC may be also hyphenated with conductivity or fluorimetric detection, and gas chromatography may be combined with flame ionization or electron capture detection. The presence of a large number of PFASs species in environmental and biological samples necessitates parallel attempts to develop a total PFASs index that reflects the total content of PFASs in various matrices. Increasing attention is currently paid to the determination of branched isomers of PFASs, and their determination in food.FigureThe aim of this review is to present recent achievements in perfluoroalkyl substances (PFASs) determination in various matrices with different methods and its comparison to measurements of Total Organic Fluorine (TOF). Increasing attention is currently paid to the determination of branched isomers of PFASs, and their determination in food.

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Section: Determination Of Total Organic Fluorine (Tof)mentioning

confidence: 72%

Section: Determination Of Total Organic Fluorine (Tof)mentioning

confidence: 99%

Recent developments in methods for analysis of perfluorinated persistent pollutants

Trojanowicz

Koc

2013

Microchim Acta

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“…From the literature, it is known that fluorine atoms have an attraction to silicone groups. For example, the derivatization of free fluorine ions by triphenylsilanol (TPSiOH) to triphenylfluorosilane (TPSiF) can be performed (under strong acidic conditions) 17 . In the mass spectrum of TPSiF, the molecular ion ( m / z 278) is observed, while the fragment ion at m / z 201 corresponds to the loss of one aromatic ring (M − 77), m / z 181 corresponds to the loss of neutral HF from m / z 201, and an ion m / z 154 is observed.…”

Section: Resultsmentioning

confidence: 99%

Electron ionization induced fragmentation of fluorinated derivatives of bisphenols

Caban

Stepnowski

2020

Rapid Comm Mass Spectrometry

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Rationale Fluorinated derivatization agents allow for the identification and quantification of emerging pollutants with high sensitivity, yet details of their potential applications using electron ionization are lacking. The fluorine atom itself does not effectively participate in electron ionization. Furthermore, limited information exists regarding the effect of fluorine during electron ionization‐induced fragmentation. To fill this gap, this report presents the fragmentation pathways of the fluorinated derivatives of ten bisphenol analogues as exemplary emerging pollutants. Methods The bisphenols were derivatized by the acetylation reagent trifluoroacetic anhydride and a new silylation reagent, namely dimethyl(3,3,3‐trifluoropropyl)silyldiethylamine (DIMETRIS; previously applied for the analysis of selected pharmaceuticals in environmental samples), and analyzed using GC/MS (electron ionization, 70 eV). Deuterated bisphenol A was added to the group of analytes to confirm the proposed fragmentation pathways. Results The specific chemical structure of bisphenols gives the possibility of several resonance hybrids of C‐centered radicals. This, in turn, results in several fragmentation pathways, unique for each resonance hybrid. Sequential losses of radicals and neutral fragments were observed in both types of derivative, with final stable carbenium ions. McLafferty‐type rearrangements were observed between the native structure of the analytes and the introduced substituents. The gamma‐shift of F onto Si in the Si(CH2)2CF3 substituent is proposed to explain the loss of the fragment with a mass of 78 u. Conclusions Both types of derivatization reagent used were found to be applicable, although the use of DIMETRIS was limited for high‐mass bisphenols. The introduction of fluorine by derivatization brings benefits for the qualitative and quantitative analysis of bisphenol‐type compounds using GC/MS because of the presence of characteristic ions in the mass spectra.

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“…Following the adsorption process, the mixture was filtered using a syringe filter with a pore size of 2.0 µm. The amount of PFOA that remained in the mixture was quantified with gas chromatography-flame ionization detection (GC-FID), which was modified from Koc et al [26]. Helium was used as the carrier gas, flowing at a rate of 30 mL/min, whereas the column flow was 5.0 mL/min.…”

Section: Pfoa Determinationmentioning

confidence: 99%

Investigation of Kinetic, Equilibrium, and Thermodynamic Modeling of Perfluorooctanoic Acid (PFOA) Adsorption in the Presence of Natural Organic Matter (NOM) by Dielectric Barrier Discharge Plasma-Modified Granular Activated Carbon (GAC)

Sahara,

Wongsawaeng,

Ngaosuwan

et al. 2024

Water

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Perfluorooctanoic acid (PFOA) contamination in water sources poses significant environmental and health concerns. The kinetic, equilibrium, and thermodynamic features of PFOA adsorption in the existence of natural organic matter (NOM) were thoroughly investigated in this work using granular activated carbon (GAC) modified by dielectric barrier discharge (DBD) plasma. The impacts of DBD plasma parameters on the adsorption process were systematically examined. The results demonstrated that GAC modified by DBD plasma exhibited enhanced adsorption performance for PFOA, even in the presence of NOM. The optimal condition for plasma-treated GAC was achieved with 20 min of plasma treatment time and 100 W of plasma power, resulting in 92% PFOA removal efficiency in deionized water (DIW) and 97% removal efficiency in Chao Phraya River water (CPRW). A kinetic investigation using the pseudo-first-order model (PFOM), the pseudo-second-order model (PSOM), and the Elovich model (EM) indicated that plasma treatment time and NOM presence influenced the adsorption capacity and rate constants of PFOA with the PSOM having emerged as the most fitting kinetic model. The Langmuir isotherm model indicates monolayer adsorption of PFOA on plasma-treated GAC, with higher maximum adsorption capacity while NOM is present. The Redlich–Peterson and Sips isotherm models indicated varying adsorption capacity and heterogeneity in the adsorption system. The Sips model was determined as the most fitting isotherm model. Furthermore, the favorable and spontaneous character of PFOA adsorption onto plasma-treated GAC was validated by thermodynamic analysis, with endothermic heat absorption during the process. Overall, this comprehensive investigation provides valuable insights into the adsorption characteristics of PFOA in the existence of NOM using GAC modified by DBD plasma.

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Application of Gas Chromatography to Determination of Total Organic Fluorine after Defluorination of Perfluorooctanoic Acid as a Model Compound

Cited by 9 publications

References 18 publications

Recent developments in methods for analysis of perfluorinated persistent pollutants

Recent developments in methods for analysis of perfluorinated persistent pollutants

Electron ionization induced fragmentation of fluorinated derivatives of bisphenols

Investigation of Kinetic, Equilibrium, and Thermodynamic Modeling of Perfluorooctanoic Acid (PFOA) Adsorption in the Presence of Natural Organic Matter (NOM) by Dielectric Barrier Discharge Plasma-Modified Granular Activated Carbon (GAC)

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