Towards elevated perfluorooctanoic acid (PFOA) enrichment in water: Sequential liquid-liquid extraction pretreatment for ion chromatography detection.

The widespread detection of perfluorooctanoic acid (PFOA) in the environment has raised significant concerns. The standard PFOA analytical method relies on expensive solid-phase extraction (SPE) and liquid chromatography tandem mass spectrometry (LC-MS/MS) instruments, making routine use prohibitive. We herein proposed a cost-effective yet novel enrichment method for determining PFOA at ng L-1 level. This method entailed a two-step sample preparation process: firstly, PFOA was extracted and enriched using a forward-extraction under acidic conditions, followed by a backward-extraction and enrichment step utilizing alkaline water. The enriched samples were subsequently subjected to a common ion chromatography (IC). Results reveal that maintaining a forward-extraction pH below its pKa value (2.8) is essential, as protonated PFOA proves effective in enhancing the enrichment factor (EF). The challenge lied in driving PFOA from forward-extractant to aqueous backward-extractant due to the decreased hydrophobicity of deprotonated PFOA (log Kow2 = 1.0). In addition, we found that evaporating forward-extractant with alkaline backward-extractant (containing 5% methanol) reduced potential analytical uncertainties associated with PFOA evaporation and sorption. Under optimal conditions, the method achieved a detection limit of 9.2 ng L-1 and an impressive EF value of 719. Comparison with SPE-LC-MS/MS confirmed the proposed method as a promising alternative for PFOA determination. Although initially targeted for PFOA, the novel methodology is likely applicable to preconcentration of other poly-fluoroalkyl substances.

Fluorine-functionalized magnetic amino microporous organic network for enrichment of perfluoroalkyl substances.

Perfluoroalkyl substances (PFAS) are persistent organic pollutants that pose significant risks to human health and the environment. Efficient and selective enrichment of these compounds was crucial for their accurate detection and quantification in complex matrices. Herein, we report a novel magnetic solid-phase extraction (MSPE) method using fluorine-functionalized magnetic amino-microporous organic network (Fe3O4@MONNH2@F7) adsorbent for the efficient enrichment of PFAS from aqueous samples. The core-shell Fe3O4@MONNH2@F7 nanosphere was synthesized, featuring magnetic Fe3O4 nanoparticles as the core and a porous amino-functionalized MONs coating as the shell, which was further modified by fluorination. The synthesized adsorbent material exhibited high specific surface area, hydrophobicity, and abundant fluorine groups, facilitating efficient and selective adsorption of PFAS via electrostatic attraction, hydrophobic-hydrophobic interactions, fluorine-fluorine interactions, π-CF interactions and hydrogen bonding. Furthermore, the MSPE method coupled with ultra-high performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) allowed for the rapid, sensitive, and accurate determination of ultra-trace PFAS in real water samples, human serum, and human follicular fluid. Under optimal conditions, the established MSPE method demonstrated a linear range (2 to 2000 ng L-1), with a correlation coefficient exceeding 0.9977, low limits of detection ranging from 0.54 to 1.47 ng L-1, with a relative standard deviation (RSD) < 9.1%. Additionally, the method showed excellent performance in complex real samples (recovery ratio of 81.7 to 121.6 %). The adsorption mechanism was investigated through kinetic, isotherm, and molecular simulation studies, revealing that the introduction of fluorine groups enhanced the hydrophobic interaction and fluorine-fluorine attraction between the adsorbent and PFAS. This work provides a proof-of-concept strategy for designing adsorbent materials with high efficiency and selectivity by post-modification, which has great potential for the detection and analysis of PFAS in complex samples.

Ion exchange solid phase microextraction coupled to liquid chromatography/laminar flow tandem mass spectrometry for the determination of perfluoroalkyl substances in water samples.

Per- and polyfluoroalkyl substances (PFAS) are toxic and bioaccumulative compounds that are persistent in the environment due to their water and heat resistant properties. These compounds have been demonstrated to be ubiquitous in the environment, being found in water, soil, air and various biological matrices. The determination of PFAS at ultra-trace levels is thus critical to assess the extent of contamination in a particular matrix. In this work, solid phase microextraction (SPME) was evaluated as a pre-concentration technique to aid the quantitation of this class of pollutants below the EPA established advisory limits in drinking water at parts-per-trillion levels. Four model PFAS with varying physicochemical properties, namely hexafluoropropylene oxide dimer acid (GenX), perfluoro-1- butanesulfonate (PFBS), perfluoro-n-octanoic acid (PFOA) and perfluoro-1-octanesulfonate (PFOS) were studied as a proof of concept. Analysis was performed with the use of ultra-high pressure liquid chromatography-laminar flow tandem mass spectrometry (UHPLC-MS/MS). This study proposes the use of hydrophilic-lipophilic balance-weak anion-exchange/polyacrylonitrile (HLB-WAX/PAN) as a SPME coating, ideal for all model analytes. A sample volume of 1.5 mL was used for analysis, the optimized protocol including 20 min extraction, 20 min desorption and 6 min LC/MS analysis. This method achieved LOQs of 2.5 ng L- 1 (PFOS) and 1 ng L - 1 (GenX, PFBS and PFOA) with satisfactory precision and accuracy values evaluated over a period of 5 days.

Synthesis of magnetic chitosan biopolymeric spheres and their adsorption performances for PFOA and PFOS from aqueous environment.

Due to numerous applications and excellent environmental stability, long-chain perfluorinated chemicals (PFCs) are ubiquitous in water across the world and adversely affect the living organisms. Thus, this study focused on the mitigation of the most frequently used long-chain PFCs namely perfluorooctanoate (PFOA) and perfluorooctane sulfonate (PFOS) from water using reduced graphene oxide modified zinc ferrite immobilized chitosan beads (rGO-ZF@CB) as an adsorbent. The results from the adsorption isotherm and kinetic studies revealed that the adsorption data fitted well to the Langmuir and the pseudo-second-order models. According to the Langmuir isotherm, the rGO-ZF@CB possessed the maximum adsorption capacity of 16.07 mg/g for PFOA and 21.64 mg/g for PFOS. Both the electrostatic attractions and hydrophobic interactions have driven the removal of PFOA and PFOS by prepared rGO-ZF@CB. Eventually, the rGO-ZF@CB could be considered as an efficient adsorbent for the effective removal of PFOA and PFOS molecules from the aqueous environment.

PFAS Degradation in Ultrapure and Groundwater Using Non-Thermal Plasma.

Perfluoroalkyl substances (PFAS) represent one of the most recalcitrant class of compounds of emerging concern and their removal from water is a challenging goal. In this study, we investigated the removal efficiency of three selected PFAS from water, namely, perfluorooctanoic acid (PFOA), perfluorohexanoic acid (PFHxA) and pefluorooctanesulfonic acid (PFOS) using a custom-built non-thermal plasma generator. A modified full factorial design (with 2 levels, 3 variables and the central point in which both quadratic terms and interactions between couple of variables were considered) was used to investigate the effect of plasma discharge frequency, distance between the electrodes and water conductivity on treatment efficiency. Then, the plasma treatment running on optimized conditions was used to degrade PFAS at ppb level both individually and in mixture, in ultrapure and groundwater matrices. PFOS 1 ppb exhibited the best degradation reaching complete removal after 30 min of treatment in both water matrices (first order rate constant 0.107 min-1 in ultrapure water and 0.0633 min-1 in groundwater), while the degradation rate of PFOA and PFHxA was slower of around 65% and 83%, respectively. During plasma treatment, the production of reactive species in the liquid phase (hydroxyl radical, hydrogen peroxide) and in the gas phase (ozone, NOx) was investigated. Particular attention was dedicated to the nitrogen balance in solution where, following to NOx hydrolysis, total nitrogen (TN) was accumulated at the rate of up to 40 mgN L-1 h-1.

Comparison of extraction methods for per- and polyfluoroalkyl substances (PFAS) in human serum and placenta samples-insights into extractable organic fluorine (EOF).

Since the detection of per- and polyfluoroalkyl substances (PFAS) in humans and different environmental media in the last two decades, this substance group has attracted a lot of attention as well as increasing concerns. The fluorine mass balance approach, by comparing the levels of targeted PFAS after conversion to fluorine equivalents with those of extractable organic fluorine (EOF), showed the presence of unidentified organofluorine in different environmental samples. Out of the thousands of PFAS in existence, only a very small fraction is included in routine analysis. In recent years, liquid chromatography coupled with tandem-mass spectrometry (LC-MS/MS) has demonstrated the ability to analytically cover a wide spectrum of PFAS. In contrast, conventional extraction methods developed 10 to 15 years ago were only evaluated for a limited number of PFAS. The aim of the present study was to evaluate the advantages and disadvantages of three different extraction methods, adapted from the literatures without further optimization (ion-pair liquid-liquid extraction, solid-phase extraction (SPE), using hydrophilic-lipophilic (HLB) or weak anion exchange (WAX) sorbents), for human biomonitoring of 61 PFAS in serum and placental tissue samples. In addition, levels of EOF were compared among these extraction methods via spiked samples. Results showed that performance, in terms of recovery, differed between the extraction methods for different PFAS; different extraction methods resulted in different EOF concentrations indicating that the choice of extraction method is important for target PFAS and EOF analysis. Results of maternal serum samples, analyzed in two different laboratories using two different extraction methods, showed an accordance of 107.6% (± 21.3); the detected perfluoroalkyl acids (PFAAs) in maternal and cord serum samples were in the range of 0.076 to 2.9 ng/mL.Graphical abstract.

Analysis of per- and polyfluorinated alkyl substances in sub-sampled water matrices with online solid phase extraction/isotope dilution tandem mass spectrometry.

Sorption of PFASs onto surfaces of laboratory materials has been frequently reported. Due to the often complex and poorly understood nature of such sorption, workarounds have often included use of whole samples only, accompanied by sample vessel rinsing to desorb active surfaces. The resulting methods tend to require considerable sample preparation times and preclude typical activities such as aliquoting and dilution of water samples prior to extraction. This manuscript reports an approach for PFAS analysis which uses subsampling of water matrices from vessels including centrifuge tubes and autosampler vials, through the optimized use of solvent to reduce PFAS retention on subsampling vessels. Online solid phase extraction (SPE) using a weak anion exchange resin is then used to concentrate sample aliquots to improve sensitivity and allow for removal of matrix interferences. With the technique of ultra performance liquid chromatography (UPLC) coupled to isotope dilution tandem mass spectrometry, statistically based quantitation limits ranged from sub ng/L to single digit ng/L for carboxylate, sulfonate, and sulfonamide PFASs analytes from C4 to C12. Linear calibration ranges were from 0.25 to 4000 ng/L. Matrix effects relevant for drinking water treatment studies, such as cations, organic carbon, and competing PFAS compounds, were evaluated and found to not impact method performance within QC criteria consistent with study data quality objectives.

Robust Matrix Effect-Free Method for Simultaneous Determination of Legacy and Emerging Per- and Polyfluoroalkyl Substances in Crop and Soil Matrices.

Increasing use of emerging per- and polyfluoroalkyl substances (PFASs) has caused extensive concerns around the world. Effective detection methods to trace their pollution characteristics and environmental behaviors in complex soil-crop systems are urgently needed. In this study, a reliable and matrix effect (ME)-free method was developed for simultaneous determination of 14 legacy and emerging PFASs, including perfluorooctanoic acid, perfluorooctane sulfonate, 6 hydrogenous PFASs, 3 chlorinated PFASs, and 3 hexafluoropropylene oxide homologues, in 6 crop (the edible parts) and 5 soil matrices using ultrasonic extraction combined with solid-phase extraction and ultraperformance liquid chromatography-mass spectrometry (MS)/MS. The varieties of extractants and cleanup cartridges, the dosage of ammonia hydroxide, and the ME were studied to obtain an optimal pretreatment procedure. The developed method had high sensitivity and accuracy with satisfactory method detection limits (2.40-83.03 pg/g dry weight) and recoveries (72-117%) of all target analytes in matrices at five concentrations, that is, 0.1, 1, 10, 100, and 1000 ng/g. In addition, the ME of this method (0.82-1.15) was negligible for all PFASs, even considering 11 different matrices. The successful application of the ME-free method to simultaneously determine the legacy and emerging PFASs in crop and soil samples has demonstrated its excellent practicability for monitoring emerging PFASs in soil-crop systems.

Perfluorocarbons in Chemical Biology.

Perfluorocarbons, saturated carbon chains in which all the hydrogen atoms are replaced with fluorine, form a separate phase from both organic and aqueous solutions. Though perfluorinated compounds are not found in living systems, they can be used to modify biomolecules to confer orthogonal behavior within natural systems, such as improved stability, engineered assembly, and cell-permeability. Perfluorinated groups also provide handles for purification, mass spectrometry, and 19 F NMR studies in complex environments. Herein, we describe how the unique properties of perfluorocarbons have been employed to understand and manipulate biological systems.

A Highly Selective Extraction Approach for Per- and Polyfluoroalkyl Substances Based on Protein Affinity.

A selective extraction method with remarkable advantages (i.e., low cost, simplicity, and solvent savings) was developed for the detection of long-chain per- and polyfluoroalkyl substances (PFASs) based on their specific protein affinities. Bovine serum albumin (BSA) was selected to extract PFASs from aqueous samples, which were then desorbed using methanol. Finally, the PFASs were analyzed by high-performance liquid chromatography-tandem mass spectrometry. The optimal extraction conditions were as follows: sample volume, 10 mL; BSA concentration, 2 g/L; equilibration time, 5 min; pH, 3.4; salinity, 6% (w/v) NaCl; and water bath temperature, 80 °C. The protein affinity property was confirmed to be the major extraction mechanism, which significantly increased the selectivity for PFASs. The recoveries of this method for 15 legacy PFASs with CF2 ≥ 6 and three chlorinated polyfluoroether sulfonic acids in tap water, river water, and urine samples with three spiked levels were 73.3-122.3, 83.8-119.4, and 75.0-115.1%, respectively. The method limits of quantification in the three real matrix samples were 4.7-133.3 ng/L. Comparative experiments with conventional solid-phase extraction confirm that the developed approach can be a promising and alternative method for the extraction of PFASs from authentic aqueous samples. Moreover, the proposed method provides a new possibility for screening PFASs exhibiting high bioaccumulation and toxicity.

Biochar sorption of PFOS, PFOA, PFHxS and PFHxA in two soils with contrasting texture.

The ability to immobilise PFAS in soil may be an essential interim tool while technologies are developed for effective long-term treatment of PFAS contaminated soils. Serial sorption experiments were undertaken using a pine derived biochar produced at 750 °C (P750). All experiments were carried out either in individual mode (solution with one PFAS at 5 µg/L) or mix mode (solution with 5 µg/L of each: PFOS, PFOA, PFHxS and PFHxA), and carried out in 2:1 water to soil solutions. Soils had biochar added in the range 0-5% w/w. Kinetic data were fitted to the pseudo-second order model for both amended soils, with equilibrium times ranging 0.5-96 h for all congeners. PFOS sorption was 11.1 ± 4.5% in the loamy sand compared to 69.8 ± 4.9% in the sandy clay loam. While total sorption was higher in the unamended loamy sand than sandy clay loam for PFHxA, PFOA and PFOS, the effect of biochar amendment for each compound was found to be significantly higher in amended sandy clay loam than in amended loamy sand. Application of biochar reduced the desorbed PFAS fraction of all soils. Soil type and experimental mode played a significant role in influencing desorption. Overall, the relationship between sorbent and congener was demonstrated to be highly impacted by soil type, however the unique physiochemical properties of each PFAS congener greatly influenced its unique equilibrium, sorption and desorption behaviour for each amended soil and mode tested.

Investigating isomers/enantiomers of perfluorooctanoic acid in river water by gas chromatography-mass spectrometry with chiral derivatization.

Perfluorooctanoic acid (PFOA) in environmental media contains numerous isomers/enantiomers because of the PFOA manufacturing process and biological degradation of PFOA precursors. Few methods for analyzing PFOA enantiomers have been described. A simple derivatization method using (S)-1-phenethyl chloride that was developed to allow PFOA isomers/enantiomers to be separated by gas chromatography and analyzed by electron-capture negative ionization mass spectrometry is described here. PFOA standards were analyzed, and enantiomers of the chiral isomers perfluoro-3-methyl-heptanoic acid, perfluoro-4-methyl-heptanoic acid, and perfluoro-3,5-dimethyl-hexanoic acid were separated using an HP-5MS column. Linear PFOA and perfluoro-6-methyl-heptanoic acid were chromatographically separated from these enantiomers. The linear ranges (giving correlation coefficients r > 0.997) of the calibration curves for the isomers were 0.010-3.00 ng/mL. PFOA isomer/enantiomer concentrations in river water were determined using the method. The method separated the enantiomers of perfluoro-3-methyl-heptanoic acid and perfluoro-4-methyl-heptanoic acid, the isomers of perfluoro-6-methyl-heptanoic acid, and linear PFOA in river water. No significant differences were found between the PFOA enantiomer/isomer compositions of the sample and technical PFOA. Enantiomer ratios can provide information about the sources and transport of pollutant isomers/enantiomers in the environment. Enantiomeric separation requires effective separation techniques. Our method achieved chiral separation using a non-chiral GC column that is often used in general analytical laboratories. The method could be used to investigate the sources and fates of PFOA and the isomers/enantiomers of other potentially toxic persistent pollutants in the environment and the risks posed to humans.

Efficient removal of GenX (HFPO-DA) and other perfluorinated ether acids from drinking and recycled waters using anion exchange resins.

Carcinogenic GenX chemicals, heptafluoropropylene-oxide-dimer-acid (HFPO-DA), have been recently detected in surface, ground and recycled water sources worldwide. However, GenX removals under the influence of variable characteristics of the organic and inorganic compounds present in the natural water sources, have often been overlooked in scientific literature. This is critically important given that the ionic composition and characteristics of organic matter in natural waters are spatially and seasonally variable. A strongly basic anion exchange (IX) resin was used to remove GenX and two other perfluorinated ether acids (PFEAS) from natural surface and recycled water sources. Factors influencing the uptake behavior included the PFEAS concentrations, resin dosage, and background anion characteristics. The equivalent background compound was employed to evaluate the competitive uptake between natural organic matter (NOM), inorganic ions and PFEAS in natural water matrices. Experimental data were compared with different mathematical and physical models and it was depicted that approximately 4-6% of the initial NOM competed with PFEAS for active exchange sites. Further, IX was able to achieve complete PFEAS removal (Cfinal<10 ng/L) with simultaneous removal of>60% NOM and >80% inorganic ions. Results of this study indicate that IX exhibits great potential for PFEAS removal from natural drinking water sources.

Diatom-assisted biomicroreactor targeting the complete removal of perfluorinated compounds.

Persistent perfluorinated compounds (PFCs) have been recognized as a global environmental issue. Developing methods without leading to additional burden in nature will be essential for PFCs removal. Herein, we functionalized iron nanoparticles on living diatom (Dt) to efficiently enable the Fenton reaction and reactive oxygen species (ROS) production. Iron nanoparticles at the surface of living diatom act as promising catalytic agents to trigger OH radical generation from H2O2. Dt plays dual roles: i) as solid support for effective adsorption, and ii) it supplies oxygen and inherently produces ROS under stress conditions, which improves removal efficiency of PFCs. We also demonstrated its reusability by simple magnetic separation and 85% of decomposition efficiency could still be achieved. This newly developed diatom-assisted bioremediation strategy enables green and efficient PFC decomposition and shall be readily applicable to other persistent pollutants.

Guanidinocalix[5]arene for sensitive fluorescence detection and magnetic removal of perfluorinated pollutants.

Perfluorinated alkyl substances, such as perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA), are toxic materials that are known to globally contaminate water, air, and soil resources. Strategies for the simultaneous detection and removal of these compounds are desired to address this emerging health and environmental issue. Herein, we develop a type of guanidinocalix[5]arene that can selectively and strongly bind to PFOS and PFOA, which we use to demonstrate the sensitive and quantitative detection of these compounds in contaminated water through a fluorescent indicator displacement assay. Moreover, by co-assembling iron oxide nanoparticle with the amphiphilic guanidinocalix[5]arene, we are able to use simple magnetic absorption and filtration to efficiently remove PFOS and PFOA from contaminated water. This supramolecular approach that uses both molecular recognition and self-assembly of macrocyclic amphiphiles is promising for the detection and remediation of water pollution.

Novel chitosan-ethylene glycol hydrogel for the removal of aqueous perfluorooctanoic acid.

It is urgent to explore an effective removal method for perfluorooctanoic acid (PFOA) due to its recalcitrant nature. In this study, a novel chitosan-based hydrogel (CEGH) was prepared with a simple method using chitosan and ethylene glycol through a repeated freezing-thawing procedure. The adsorption of PFOA anions to CEGH agreed well to the Freundlich-Langmuir model with a maximum adsorption capacity as high as 1275.9 mg/g, which is higher than reported values of most adsorbents for PFOA. The adsorption was influenced by experimental conditions. Experimental results showed that the main removal mechanism was the ionic hydrogen bond interaction between carbonyl groups (COO-) of PFOA and protonated amine (NH+) of the CEGH adsorbent. Therefore, CEGH is a very attractive adsorbent that can be used to remove PFOA from water in the future.

Fluoro-functionalized paper-based solid-phase extraction for analysis of perfluorinated compounds by high-performance liquid chromatography coupled with electrospray ionization-tandem mass spectrometry.

Fluoro-functionalized paper was prepared and applied in solid phase extraction (SPE) for the analysis of trace-level perfluorinated compounds (PFCs). The proposed fluoro-functionalized paper-based solid-phase extraction (Fp-SPE) exhibits significant advantages for sample preparation, such as the biodegradability of paper-based adsorbent, simple manipulation and low cost. Owing to the fluorous affinity, the Fp-SPE technique with high sensitivity and high selectivity is more suitable for the selective enrichment of fluorine-containing molecules from the background of non-fluorinated organic compounds in a real water sample. Combined with high-performance liquid chromatography coupled with electrospray ionization-tandem mass spectrometry analysis (HPLC-MS/MS), the linear range of the PFCs, including perfluorobutyric acid (PFBA), perfluorooctanic acid (PFOA), perfluorooctane sulfonic acid (PFOS), and perfluorodecanoic acid (PFDA), was 0.20-5.0 ng/L with the limits of detection (LOD) ranging from 0.04-0.05 ng/L and the limits of quantification (LOQ) ranging from 0.15-0.20 ng/L. The method was then applied to the analysis of tap water, river water and waste water samples. The results of the actual sample analysis are consistent with that by reverse phase SPE (RP-SPE).

Bubble-Nucleation-Based Method for the Selective and Sensitive Electrochemical Detection of Surfactants.

We present the first bubble-nucleation-based electrochemical method for the selective and sensitive detection of surfactants. Our method takes advantage of the high surface activity of surfactant analyte to affect the electrochemical bubble nucleation and then transduces the change in nucleation condition to electrochemical signal for determining the surfactant concentration. Using this method, we demonstrate the quantitation of perfluorinated surfactants in water, a group of emerging environmental contaminants, with a remarkable limit of detection (LOD) down to 30 µg/L and a linear dynamic range of over 3 orders of magnitude. With the addition of a preconcentration step, we have achieved the LOD: 70 ng/L, the health advisory for perfluorooctanesulfonate (PFOS) and perfluorooctanoic acid (PFOA) in drinking water established by the U.S. Environmental Protection Agency. The experimental results are in quantitative agreement with our theoretical model derived from classical nucleation theory. Our method also exhibits an exceptional specificity for the surfactant analytes even in the presence of 1000-fold excess of nonsurfactant interference. This method has the potential to be further developed into a universal electrochemical detector for surfactant analysis because of its simplicity and the surface-activity-based detection mechanism.

Development and validation of an extraction method for the analysis of perfluoroalkyl substances (PFASs) in environmental and biotic matrices.

Although long chained PFASs have been phased-out in several countries, their persistence in the environment and bioaccumulative potential cause the environmental and biotic concentrations to remain high, highlighting the need to further monitor these pollutants. Currently several methods are used for the quantification of perfluoroalkyl substances (PFASs) in biological matrices including different ways to correct for recovery losses, each with its specific pros and contras. With this paper we aim to re-evaluate current methodologies and to create an updated new analytical guideline that is applicable for both abiotic and biotic matrices. The developed LC/MS/MS method was validated and shown to be specific, selective, linear, robust and sensitive. Reliable results could still be obtained 6 days after extraction. The recoveries varied, depending on the matrix, between 1% and 100%, but nevertheless, a high accuracy was obtained even at the lowest recoveries. A reduction of sample mass could significantly increase method recoveries and therefore it is highly recommended to take less matrix. We confirmed that using the ISTD closest in terms of functional group and carbon chain length is a suitable method for the quantification of PFASs that lack a corresponding ISTD. The newly described method was, depending on the matrix, similar in terms of sensitivity and reliability compared to a frequently used method and could be used simultaneously in future monitoring studies. Therefore, we recommend to select the purification method based on the target analytes as well as the sample matrix. CAPSULE: The newly described method was similar in terms of sensitivity and reliability compared to a frequently used method and a selection of purification methods should be based on the target analyte and sample matrix.

Identification and quantification of perfluorooctane sulfonamide isomers by liquid chromatography-tandem mass spectrometry.

Characterization of the isomers perfluorooctane sulfonamide (PFOSA), a key intermediate of the perfluorooctane sulfonate (PFOS) precursors, is a prerequisite to understand the contribution of precursors to PFOS in the environmental and biological matrices. However, the lack of commercial standards makes quantification of the PFOSA isomers in complex matrices a big challenge. For the first time, a liquid chromatography-tandem mass spectrometry (LC-MS/MS) method was established to identify and quantify PFOSA isomers. Improvement on chromatographic separation with selected reaction monitoring allowed full resolution of six monomethyl branched isomers of PFOSA. The isomers were identified and quantified using a series of characteristic fragment ions and the specific product ions of molecular anion m/z 498: m/z 78 (n-), m/z 169 (iso-), m/z 419 (1m-), m/z 164 (2m-), m/z 259 (3m-), m/z 269 (4m-) and m/z 219 (5m-PFOSA). With the aid of 19F nuclear magnetic resonance to define one technical product as standard, the developed method was used to quantify PFOSA isomers in other technical products and spiked fish blood samples. The results indicated that the developed method displayed strong application prospect for measuring trace level of PFOSA isomers in complex samples. The method detection limits for all isomers were in the range of 0.1-1 pg/g ww for blood samples.