TY - JOUR
AU - Zongbao, Chen,
AB - Abstract In this work, a new method was developed for perfluorinated compounds (PFCs) analysis in water samples based on decyl-perfluorinated magnetic mesoporous nanocomposites microspheres-assisted extraction and microwave-assisted derivatization followed by gas chromatography–mass spectrometry analysis. The decyl-perfluorinated magnetic mesoporous nanocomposites have several advantages such as fast separation ability, good dispersibility in water sample and high selective preconcentration of PFCs. Various parameters, including eluting solvent and volume, the amounts of absorbents, extraction time and elution time, the microwave-assisted derivatization conditions were optimized. Validation studies showed that this method has good linearity (r2 > 0.9970), satisfactory precision (RSD < 7.8%) and high recovery (93–107%). The limits of detection were found to be 0.055–0.086 μg/L and the limits of quantification be 0.18–0.28 μg/L, respectively. The results indicated that the proposed method has advantages of convenience, good sensitivity and high efficiency. The method has been applied successfully to analyze perfluorinated organic acids in real water samples. Introduction Perfluorinated compounds (PFCs) are a large group of organic compounds that are characterized by a fully or partially fluorinated hydrophobic and lipophobic carbon chain attached to one or more different hydrophilic functional groups (1). PFCs have been widely used in textile, carpet, paper and leather treatment and as performance chemicals in products such as fire-fighting foams, floor polishes, shampoos, paints and inks. Furthermore, PFCs are also used in industrial applications as surfactants, emulsifiers, wetting agents, additives and coatings (2). PFCs break down very slowly in the environment and have been recognized as emerging pollutants of global relevance. Two major PFCs, perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS), have been added as new persistent organic pollutants (POPs) by the Stockholm Convention in 2009 (3). These chemicals have frequently been detected in environmental samples and often occur at high concentrations. Recently, more and more evidence showed that PFCs existed in surface waters, wildlife, human and wastewaters (4, 5). These pollutants can produce composite toxicity and have possibility to cause liver toxicity, nerves and embryo toxicity, reproductive and genetic toxicity, as well as carcinogenicity in experimental animals (6). The determination of PFCs present in environmental samples is becoming an urgent task due to their toxic or carcinogenic characteristics (4). Due to the complexity of environmental matrixes and the low concentration level of PFCs existing in the environmental samples, extraction and preconcentration of FPCs are essential before chromatographic separation. Many pretreatment methods have been developed for the analysis of trace amounts of various chemicals over the past decades, the most commonly applied sample preparation methods for the analysis of trace amounts of various chemicals are based on solid-phase extraction (SPE) (7–14). Recently, a new mode of SPE termed as magnetic solid-phase extraction (MSPE) has been developed. It has several advantages in comparison with traditional SPE. The separation process can be performed directly in crude samples containing suspended solid materials without the need of additional centrifugation or filtration, which makes the separation easier and faster. Therefore, MSPE has found wide applications in sample pretreatment (15–27) and preconcentration of perfluorinated compounds (4, 28–31). In MSPE, the adsorbent material is a key factor. The current research in MSPE is oriented on the development of novel adsorbents with high adsorption capacity, good selectivity and good dispersibility in aqueous matrix. The application proposed an interior pore-walls decyl-perfluorinated functionalized magnetic mesoporous microspheres (F17-Fe3O4@mSiO2) to separate and enrich PFC. The fluorous functionalized interior pore-walls contributed to the high selective preconcentration of PFCs due to fluorous affinity; and abundant silanol groups on the exterior surface of microspheres contributed to the good dispersibility in water samples. The materials have the anti-interference ability to macromolecular proteins due to size exclusion, and high magnetic achieves rapid separation. Because of these advantages, the new material is considered particularly suitable for the selective rapid separation and enrichment of PFCs in complicated matrix. Liquid chromatography–mass spectrometry (LC–MS) and Liquid chromatography–tandem mass spectrometry (LC–MS-MS) are the most widely used techniques for trace analysis of PFCs (32–39). But LC–MS is problematic due to background contamination arising from fluoropolymers in the equipment. LC–MS-MS is expensive, many laboratories do not have this equipment and would prefer readily available GC techniques (40). In this work, decyl-perfluorinated magnetic mesoporous nanocomposites were synthesized, and the as-made nanocomposites were successfully applied as an effective adsorbent for the preconcentration of PFCs in environmental water samples prior to microwave-assisted derivatization gas chromatography–mass spectrometry. Experimention conditions and the method validations were studied. Experimental Reagents and materials Bis[trimethylsilyl]trifluoroacetamide were purchased from Sigma (St. Louis, MO, USA), which contains 1% trimethylchlorosilane (BSTFA–TMCS 99:1). PFOA, perfluorononanoic acid (PFNA), perfluorododecanoic acid (PFDoA) were obtained from Alfa Aesar (Ward Hill, MA); FeCl3·6H2O, tetraethylorthosilicate (TEOS), ethylene glycolethanol, cetyltrimethylammonium bromide (CTAB), ammonium formate and ammonium acetate were all bought from J&K Chemical Corporation (Beijing, China). All the other chemicals were of analytical grade, and were purchased from Shanghai Chemical Reagent Co. (Shanghai, China). PFCs stock standards were prepared in acetonitrile, with 100 mg/L concentration for each compound, and were kept at −4°C. Working standard solutions were prepared by dilution of an appropriate amount of the above stock solution in acetonitrile. The deionized water used was MilliQ grade (Millipore, Bedford, MA, USA). Lake water samples were gathered from the Po Yang Lake, Shangrao, China. GC–MS analysis An HP 6890 GC system, combined to an HPMD5973 quadrupole mass spectrometer coupled with an electron impact ion source was employed in these experimental researches. The extracted compounds were separated on an HP-5MS capillary column (30 m × 0.25 mm × 0.25 μm). A 1-μL of the sample was injected in splitless mode. The control program of the oven temperature is set as follows. The initial temperature is set at 50°C, and held for 2 min, followed by increasing at 10°C/min to 110°C, then, raising again with a rate of 25°C/min to 280°C and keeping at 280°C for 5 min. The injection temperature was 250°C. The carrier gas is helium (99.999%) with the flow rate of 1 mL/min. The quadrupole temperature, transfer line temperature and MS ion source temperature were 150°C, 280°C and 230°C, respectively. The ionizing energy is set at 70 eV. The quantitative analysis was carried out in SIM mode. Synthesis and characterization of F17-Fe3O4@mSiO2 The magnetic Fe3O4 microspheres were synthesized through solvothermal reaction as described in our previous work (41). In detail, 1.35 g of Iron (III) chloride hexahydrate (FeCl3·6H2O) was first dissolved in 75 mL ethylene glycol under magnetic stirring at room temperature. Next, 3.6 g of anhydrous sodium acetate was added and dissolved in the same solution. The obtained mixed solution was stirred for 0.5 h and then transferred into a sealed vessel and heated at 200°C for 16 h, and then cooled overnight at room temperature subsequently. The product was obtained by separating with magnet and washing with water repeatedly, and then dried in vacuum box at 50°C to gain the black powder. The F17–Fe3O4@mSiO2 microspheres were synthesized through a surfactant involved sol–gel process. First, 75 mL of deionized water was prepared in a 1,000-mL three-necked round-bottomed flask. Then, 75-mg magnetic Fe3O4 and 750 mg of CTAB were added into the flask and sonicated for 30 min. Afterwards, 675 mL of NaOH solution (1 mM) was added into the flask and further sonicated for 5 min to form a stable dispersion. The mixture solution was heated at 60°C for 30 min. After that, 3.75 mL of TEOS/ethanol (v/v, 1:4) solution was added drop by drop under vigorous stirring, followed by heating at 60°C for 30 min with stirring. Subsequently, 225 μL of TEOS/1 H, 1H, 2H, 2HPDTES (2:1, v/v) mixed solution was injected into the dispersion, and the dispersion was further heated at 60°C for 16 h. The product was collected by magnetic separation and refluxed in ethanol at 60°C to remove the CTAB templates. Finally, the F17–Fe3O4@mSiO2 composites were dried in vacuum box at 50°C. Transmission electron microscopy (TEM) images were taken on a JEOL 2011 microscope (Japan) with the high voltage at 200 kV. Scanning electronic microscope (SEM) images were recorded on a Philips XL30 electron microscope (Netherlands) operating at 20 kV. Fourier transform infrared spectra (FT-IR) were collected on Nicolet Fourier spectrophotometer using KBr pellets (USA). MSPE procedure and derivatization MSPE procedure for the extraction of PFCs was as follows: First, 40 mL of aqueous solution containing PFCs with a concentration of 20 μg/L was added in a vial of 50 mL with PTFE-silicone septum. Then 20 mg of F17–Fe3O4@mSiO2 were added in the vial to extract the analytes, and the mixture was vortexed for 20 min. Next, a magnetic bar was placed beside the vial to grasp the F17–Fe3O4@mSiO2 which had already extracted the analytes. Subsequently, the residual solution was removed from the vial with the sorbent remained in the vial. Again, 0.6 mL fresh acetonitrile was added and then the mixture was ultrasonicated for 15 min to desorb and re-dissolve the analytes. The eluate was then evaporated to dryness under a stream of nitrogen, and then 50 μL 20% (V:V) BSTFA–TMCS (99:1)/acetonitrile was added into the screw vial. The residue was reacted with the BSTFA–TMCS under microwave irradiation with microwave power of 300 W and an irradiation time of 8 min. Following derivatization, 1 μL of the obtained solution was injected into GC–MS system for analysis. Validation of the method The linearity plot about the mass spectrometry signal versus the concentration of perfluorinated was obtained by analyzing of the PFCs over the dynamic range (0.2–200 μg/L) using three replicates per point. The method precision was studied by six repeated analyses of PFCs in water by MSPE under the optimum conditions. The relative standard deviation (RSD) was calculated on the basis of the obtained peak areas. Recovery was also investigated by adding 50 μL of standard stock solution (20 μg/mL) to 40 mL aqueous samples containing known amounts of PFCs. Triplicate measurements were performed by MSPE–GC–MS. LOD and LOQ were calculated using the following equation: LOD = 3 × SD/m and LOD = 10 × SD/m, where SD is the standard deviation of the lowest concentration and m is the slope of the calibration curve (42). Results Characterization of the F17–Fe3O4@mSiO2 composites The morphologies of F17–Fe3O4@mSiO2 composites were characterized by SEM (Figure 1a) and TEM (Figure 1b). From the SEM image of the F17–Fe3O4@mSiO2 composites, it was observed that the diameter of magnetic particles was near 250 nm. The TEM images suggested that the porous silica shells were coated on the Fe3O4 and the coating layer was about 40 nm. The F17–Fe3O4@mSiO2 microspheres have a great dispersibility in aqueous solution, indicating the numerous silanol groups on the exterior surface of the microspheres, as well as the inner modification of the hydrophobic decyl-perfluorinated groups. The FT-IR spectrum of F17–Fe3O4@mSiO2 is shown in Figure 2. The peak 590 cm−1 is attributed to the Fe–O–Fe stretching vibration of Fe3O4. The peaks at 1,074 and 1,654 cm−1 were assigned to Si–O–Si and O–Si–C vibration, respectively. The peaks of 2,854 and 2,925 cm−1 originate from C–H stretching of CH2 in the PDTES. And the peak at 1,208 cm−1 comes from C–F vibration. This FT-IR spectrum shows that the F17 groups have been successfully modified in the synthesized microsphere. Figure 3a is the optical photograph of the aqueous dispersions of F17–Fe3O4@mSiO2 microspheres, which indicates a good dispersibility in aqueous solution, indicating the numerous silanol groups on the exterior surface of the microspheres, as well as the inner modification of the hydrophobic decyl-perfluorinated groups. Figure 3b is the optical photograph of the aqueous dispersions of F17–Fe3O4@mSiO2 microspheres after the magnet has been placed for 1 mim, which shows separation is very fast. Figure 1. View largeDownload slide SEM (a) and TEM (b) images of F17–Fe3O4@mSiO2 composites. Figure 1. View largeDownload slide SEM (a) and TEM (b) images of F17–Fe3O4@mSiO2 composites. Figure 2. View largeDownload slide FT-IR spectra of Fe3O4 and F17–Fe3O4@mSiO2 microspheres. Figure 2. View largeDownload slide FT-IR spectra of Fe3O4 and F17–Fe3O4@mSiO2 microspheres. Figure 3. View largeDownload slide (a) aqueous dispersions of F17–Fe3O4@mSiO2 microspheres (b) aqueous of F17–Fe3O4@mSiO2 microspheres after the magnet was placed for 1 min. Figure 3. View largeDownload slide (a) aqueous dispersions of F17–Fe3O4@mSiO2 microspheres (b) aqueous of F17–Fe3O4@mSiO2 microspheres after the magnet was placed for 1 min. Optimization of extraction conditions In order to obtain the maximal extraction efficiency, several important parameters, such as type and volume of elution solvent, amounts of the F17–Fe3O4@mSiO2, adsorption time and elution time, were studied and optimized. Analytes in aqueous matrix were extracted, derivatization and injected into the GC–MS for analysis. Type and volume of elution solvent selection The selection of the eluting solvent is quite important for the extraction of analytes by the F17–Fe3O4@mSiO2 composites. In this study, methanol, acetonitrile, ethanol were selected as the eluting solvents, and then they obtained eluting efficiencies were compared. The results are shown in Figure 4. As seen from Figure 4, acetonitrile had the highest efficiency. Thus, acetonitrile was selected as the optimized eluting solvent in the following work. The volume of elution solvent is also taken as an important parameter to obtain reliable and reproducible analytical results. In this work, to get the influence to the extraction efficiency, 0.4 mL, 0.6 mL, 0.8 mL and 1.0 mL acetonitrile were selected. The results showed that the maximum extraction efficiency of these analytes was obtained when the elution volume reached to 0.6 mL. Figure 4. View largeDownload slide The optimization of eluting solvent. Figure 4. View largeDownload slide The optimization of eluting solvent. Amounts of the F17–Fe3O4@mSiO2 composites selection The adsorbent amount can effect significantly on extraction efficiency. In this work, the different amounts of the F17–Fe3O4@mSiO2 composites (5 mg, 10 mg, 15 mg, 20 mg and 30 mg) were used for the extraction of the analytes. According to the results shown in Figure 5, more analytes were extracted with the amount of the F17–Fe3O4@mSiO2 composites increasing. When the amount reached 20 mg, the curves turned out to be flat, and there was no distinct improvement to extraction efficiency. So, we selected 20 mg the F17–Fe3O4@mSiO2 composites as the optimal amount. Figure 5. View largeDownload slide The effect of amount of F17–Fe3O4@mSiO2 microspheres. Figure 5. View largeDownload slide The effect of amount of F17–Fe3O4@mSiO2 microspheres. Effect of extraction time and elution time Extraction time is also a key parameter which will act on the efficiency. In this work, different extraction time (5 min, 10 min, 15 min, 20 min and 30 min) was selected for the test. As is shown in Figure 6, the extraction efficiency increased with the extraction time increasing from 5 min to 20 min and then kept almost constant after 20 min. Therefore, the extraction time of 20 min was chose as the optimal extraction time. At extraction time 20 min, different eluting time (5 min, 10 min, 15 min, 20 min and 25 min) was also investigated. The results showed that 15 min was enough to achieve to the maximum extraction efficiency of all the analytes. So in the real operation, the elution time of 15 min was selected. Figure 6. View largeDownload slide The effect of different extraction time. Figure 6. View largeDownload slide The effect of different extraction time. Optimization of the microwave-assisted derivatization conditions The effects of microwave power and irradiation time were investigated in the study. A volume of 50 μL of the PFCs standard solution with the concentration of 50 μg/L was injected into a 2-mL screw vial, and evaporated to dryness under a stream of nitrogen, and then mixed with another 50-μL BSTFA-acetonitrile (1:4) solution in the same screw vial. The residue was reacted with the BSTFA under microwave irradiation circumstance with changing microwave power (200 W, 300 W, 400 W and 500 W) and sustaining times (4 min, 6 min, 8 min and 10 min). The results showed that the best derivatization efficiency was obtained at a microwave power of 300 W and an irradiation time of 8 min. Following derivatization, 1.0 μL products were injected into the GC–MS and analyzed with three replicate measurements. Validations of the method Under the optimal experimental conditions, the linearity, precision, the limit of detection, the limit of quantification and the recovery of the proposed method were tested carefully. The linear ranges and correlation coefficients (r2) obtained for each PFCs are given in Table I. As seen from Table I, the corresponding values (r2) were 0.997–0.999. Precision of the method varied from 5.1 to 7.8%. The LOD values were calculated on the basis of triple times of S/N ratio and the values of the analytes fall in the range of 0.055–0.086 μg/L. In the case of S/N being 10, the LOQ values of analytes were 0.18–0.28 μg/L. Table I. The Validation Data of MSPE–GC–MS Procedure Compounds Calibration equations R2 Linear range μg/L RSD (%) (n = 5) LOD μg/L LOQ μg/L Relative recovery % PFOA y = 3956x + 65550 0.999 0.2–200 5.1 0.086 0.28 93 PHNA y = 10599x + 3981 0.998 0.2–200 7.8 0.064 0.21 102 PFDoA y = 12338x − 17292 0.997 0.2–200 7.3 0.055 0.18 107 Compounds Calibration equations R2 Linear range μg/L RSD (%) (n = 5) LOD μg/L LOQ μg/L Relative recovery % PFOA y = 3956x + 65550 0.999 0.2–200 5.1 0.086 0.28 93 PHNA y = 10599x + 3981 0.998 0.2–200 7.8 0.064 0.21 102 PFDoA y = 12338x − 17292 0.997 0.2–200 7.3 0.055 0.18 107 Table I. The Validation Data of MSPE–GC–MS Procedure Compounds Calibration equations R2 Linear range μg/L RSD (%) (n = 5) LOD μg/L LOQ μg/L Relative recovery % PFOA y = 3956x + 65550 0.999 0.2–200 5.1 0.086 0.28 93 PHNA y = 10599x + 3981 0.998 0.2–200 7.8 0.064 0.21 102 PFDoA y = 12338x − 17292 0.997 0.2–200 7.3 0.055 0.18 107 Compounds Calibration equations R2 Linear range μg/L RSD (%) (n = 5) LOD μg/L LOQ μg/L Relative recovery % PFOA y = 3956x + 65550 0.999 0.2–200 5.1 0.086 0.28 93 PHNA y = 10599x + 3981 0.998 0.2–200 7.8 0.064 0.21 102 PFDoA y = 12338x − 17292 0.997 0.2–200 7.3 0.055 0.18 107 Quantitative analysis of PFCs in water sample Furthermore, the proposed method was applied to the analysis of real samples of the lake water spiked with perfluorinated standards (10 μg/L concentration of each compound). The water samples were collected in December 2016 at 5 cm below the lake surface. The water samples were filtered through a 0.45 mm membrane filter prior to analysis. The GC–MS chromatograms of the spiked real sample are given in Figure 7. The relative recovery (RR) was obtained as the following equation: RR = (Cfounded − Creal)/Cadded × 100%, where Cfounded, Creal and Cadded represent apart the concentrations of the analyte after addition of known amount of standard in the real sample, the concentration of the analyte in real sample and the concentration of known amount of standard which was spiked into the real sample. The recoveries of the spiked water sample for PFOA, PFNA and PFDoA were 93, 102 and 107%, respectively. The results showed that the method is precise and sensitive enough for the detection of PFCs and can be applied in practical samples. Figure 7. View largeDownload slide The GC–MS chromatograms of the spiked-lake water by the proposed method. Figure 7. View largeDownload slide The GC–MS chromatograms of the spiked-lake water by the proposed method. Discussion As seen from Table I, the correlation coefficient value of more than 0.997 shows that the method has fine linearity. The precision ranged from 5.1% to 7.8%, the LOQ fall into 0.18–0.28 μg/L, and the recovery value of more than 93% show that the method has an acceptable precision, high recovery, and low detection limits. So, the proposed method was reliable and perhaps promising. Comparison of other analytical methods In the previous work (4, 5, 30–32, 36) many methods have been successfully developed for the analysis of PFCs. For easy comparison, these involved extraction time, linear ranges, LOD, RSD and recovery in the previous analysis methods and our approach are listed in Table II. The extraction time of the proposed method is similar to that of two MSPE techniques (4, 31) but shorter than that of two SPE techniques (5, 32). This shows that this proposed method in this article is relatively rapid. The LODs values of the proposed method are close to that of the four previous methods (30–32, 36), which indicates the sensitivity of this proposed method for the detection of PFCs is at least at the same high level as that of the previous announced methods. The RSD values of this method are lower than that of three of the previous methods (5, 30, 36), showing that the proposed method has good repeatability. The RR values of the proposed method are better than that of most of the previous methods (4, 5, 30, 32, 36, 43), These results further demonstrated that the proposed method is a more promising tool for the detection of PFCs, at analysis speed, sensitivity and repeatability. Table II. Comparison of the Proposed Method with Other Methods for Determination of Perfluorinated Compounds in Liquid Samples Extraction method Determination method Sample Extraction time (min) Adsorbent LR ng/L LODs ng/L RSDs % Recovery % Ref. μ-SPE LC–MS-MS Water 30 CTAB-MCM-41 1–50 0.02–0.08 1.9–10.5 64.7–127 5 d-SPE UHPLC–MS-MS Honey 35 ENV 1,000–20,000 16–40 2.7–4.9 40–87 32 SPE UPLC–ESI-MS Water 15 MWCNTs 500–10,000 3–6 4–7 71–102 43 MSPE UHPLC–MS-MS Water 12 Fe3O4@SiO2@FBC 0.25–25 0.01–0.06 4.1 89.3–111.3 4 MSPE LC–MS-MS Serum 8 Fe3O4@mSiO2-F17 200–1000,000 20–50 2.6–14.2 83.1–92.4 30 MSPE UHPLC–MS Water 10 F17–Fe3O4@mSiO2 50–500,00 8–125 2.6–7.6 93.4–105.7 31 SPE UHPLC–MS-MS Milk 20 C18 – 3–200 3–19 80–117 36 MSPE GC–MS Water 20 F17–Fe3O4@mSiO2 200–200,000 55–86 5.1–7.8 93–107 This method Extraction method Determination method Sample Extraction time (min) Adsorbent LR ng/L LODs ng/L RSDs % Recovery % Ref. μ-SPE LC–MS-MS Water 30 CTAB-MCM-41 1–50 0.02–0.08 1.9–10.5 64.7–127 5 d-SPE UHPLC–MS-MS Honey 35 ENV 1,000–20,000 16–40 2.7–4.9 40–87 32 SPE UPLC–ESI-MS Water 15 MWCNTs 500–10,000 3–6 4–7 71–102 43 MSPE UHPLC–MS-MS Water 12 Fe3O4@SiO2@FBC 0.25–25 0.01–0.06 4.1 89.3–111.3 4 MSPE LC–MS-MS Serum 8 Fe3O4@mSiO2-F17 200–1000,000 20–50 2.6–14.2 83.1–92.4 30 MSPE UHPLC–MS Water 10 F17–Fe3O4@mSiO2 50–500,00 8–125 2.6–7.6 93.4–105.7 31 SPE UHPLC–MS-MS Milk 20 C18 – 3–200 3–19 80–117 36 MSPE GC–MS Water 20 F17–Fe3O4@mSiO2 200–200,000 55–86 5.1–7.8 93–107 This method EVN: styrene-diviylbenzene. MWCNTs: multiwalled carbon nanotubes. Fe3O4@SiO2@FBC MNPs: 3-fluorobenzoyl chloride functionalized magnetic nanoparticles. Table II. Comparison of the Proposed Method with Other Methods for Determination of Perfluorinated Compounds in Liquid Samples Extraction method Determination method Sample Extraction time (min) Adsorbent LR ng/L LODs ng/L RSDs % Recovery % Ref. μ-SPE LC–MS-MS Water 30 CTAB-MCM-41 1–50 0.02–0.08 1.9–10.5 64.7–127 5 d-SPE UHPLC–MS-MS Honey 35 ENV 1,000–20,000 16–40 2.7–4.9 40–87 32 SPE UPLC–ESI-MS Water 15 MWCNTs 500–10,000 3–6 4–7 71–102 43 MSPE UHPLC–MS-MS Water 12 Fe3O4@SiO2@FBC 0.25–25 0.01–0.06 4.1 89.3–111.3 4 MSPE LC–MS-MS Serum 8 Fe3O4@mSiO2-F17 200–1000,000 20–50 2.6–14.2 83.1–92.4 30 MSPE UHPLC–MS Water 10 F17–Fe3O4@mSiO2 50–500,00 8–125 2.6–7.6 93.4–105.7 31 SPE UHPLC–MS-MS Milk 20 C18 – 3–200 3–19 80–117 36 MSPE GC–MS Water 20 F17–Fe3O4@mSiO2 200–200,000 55–86 5.1–7.8 93–107 This method Extraction method Determination method Sample Extraction time (min) Adsorbent LR ng/L LODs ng/L RSDs % Recovery % Ref. μ-SPE LC–MS-MS Water 30 CTAB-MCM-41 1–50 0.02–0.08 1.9–10.5 64.7–127 5 d-SPE UHPLC–MS-MS Honey 35 ENV 1,000–20,000 16–40 2.7–4.9 40–87 32 SPE UPLC–ESI-MS Water 15 MWCNTs 500–10,000 3–6 4–7 71–102 43 MSPE UHPLC–MS-MS Water 12 Fe3O4@SiO2@FBC 0.25–25 0.01–0.06 4.1 89.3–111.3 4 MSPE LC–MS-MS Serum 8 Fe3O4@mSiO2-F17 200–1000,000 20–50 2.6–14.2 83.1–92.4 30 MSPE UHPLC–MS Water 10 F17–Fe3O4@mSiO2 50–500,00 8–125 2.6–7.6 93.4–105.7 31 SPE UHPLC–MS-MS Milk 20 C18 – 3–200 3–19 80–117 36 MSPE GC–MS Water 20 F17–Fe3O4@mSiO2 200–200,000 55–86 5.1–7.8 93–107 This method EVN: styrene-diviylbenzene. MWCNTs: multiwalled carbon nanotubes. Fe3O4@SiO2@FBC MNPs: 3-fluorobenzoyl chloride functionalized magnetic nanoparticles. Conclusions In this work, F17–Fe3O4@mSiO2 composites were synthesized via a simple one-pot sol–gel coating reaction. The composites used as the adsorbents for PFCs analysis have several advantages, including fast separation ability, good dispersibility in aqueous samples and high selective preconcentration of perfluorinated compounds. Under optimized conditions, a rapid and sensitive method for the determination of PFCs was established by MSPE and microwave-assisted derivatization followed by GC–MS detection. Finally, the proposed method was successfully applied for the analysis of PFCs from environmental water samples. Due to the high specificity of the fluorous–fluorous interaction between the fluorous microspheres and PFCs, the F17–Fe3O4@mSiO2 microspheres adsorbents could prevent the extraction of targeted analytes from being interfered by other components in the complicated matrix. It is a potential tool for the assessments of PFCs exposure in more complicated matrix such as urine and blood serum due to the virtue of the high specificity of fluorous affinity. Funding The project was sponsored by the Natural Science Foundation of Jiangxi Province, China (20142BAB203012). References 1 Zabaleta , I. , Bizkarguenaga , E. , Iparragirre , A. , Navarro , P. , Prieto , A. , Fernández , L.A. , et al. . ; Focused ultrasound solid–liquid extraction for the determination of perfluorinated compounds in fish, vegetables and amended soil ; Journal of Chromatography A , ( 2014 ); 1331 : 27 – 37 . Google Scholar Crossref Search ADS PubMed 2 Zabaleta , I. , Bizkarguenaga , E. , Prieto , A. , Ortiz-Zarragoitia , M. , Fernández , L.A. , Zuloaga , O. ; Simultaneous determination of perfluorinated compounds and their potential precursors in mussel tissue and fish muscle tissue and liver samples by liquid chromatography–electrospray-tandem massspectrometry ; Journal of Chromatography. A , ( 2015 ); 1387 : 13 – 23 . Google Scholar Crossref Search ADS PubMed 3 Wu , Y.N. , Wang , Y.X. , Li , J.G. , Zhao , Y.F. , Guo , F.F. , Liu , J.Y. , et al. . ; Perfluorinated compounds in seafood from coastal areas in China ; Environment International , ( 2012 ); 42 : 64 – 71 . Google Scholar Crossref Search ADS 4 Yan , Z.H. , Cai , Y. , Zhu , G.H. , Yuan , J.B. , Tu , L.D. , Chen , C.Y. , et al. . ; Synthesis of 3-fluorobenzoyl chloride functionalized magnetic sorbent for highly efficient enrichment of perfluorinated compounds from river water samples ; Journal of Chromatography A , ( 2013 ); 1321 : 21 – 29 . Google Scholar Crossref Search ADS PubMed 5 Lashgari , M. , Basheer , C. , Lee , H.K. ; Application of surfactant-templated ordered mesoporous material as sorbent in micro-solid phase extraction followed by liquid chromatography–triple quadrupole mass spectrometry for determination of perfluorinated carboxylic acids in aqueous media ; Talanta , ( 2015 ); 141 : 200 – 206 . Google Scholar Crossref Search ADS PubMed 6 Fang , X.M. , Wang , J.S. , Dai , J.Y. ; The progressin environmental distributions and toxicological effects of perfluoroalkyl acids ; Advances in Earth Science , ( 2010 ); 25 : 543 – 551 . 7 Arabi , M. , Ghaedi , M. , Abbas Ostovan , A. ; Development of a lower toxic approach based on green synthesis of water-compatible molecularly imprinted nanoparticles for the extraction of hydrochlorothiazide from human urine ; ACS Sustainable Chemistry & Engineering , ( 2017 ); 5 : 3775 – 3785 . Google Scholar Crossref Search ADS 8 Dastkhoon , M. , Ghaedi , M. , Asfaram , A. , Arabi , M. , Ostovan , A. , Goudarzi , A. ; Cu@SnS/SnO2 nanoparticles as novel sorbent for dispersive micro solid phase extraction of atorvastatin in human plasma and urine samples by high-performance liquid chromatography with UV detection: application of central composite design (CCD) ; Ultrasonics Sonochemistry , ( 2017 ); 38 : 463 – 472 . Google Scholar Crossref Search ADS PubMed 9 Ostovan , A. , Ghaedi , M. , Arabi , M. , Arash Asfaram , A. ; Hollow porous molecularly imprinted polymer for highly selective clean-up followed by influential preconcentration of ultra-traceglibenclamide from bio-fluid ; Journal of Chromatography A , ( 2017 ); 1520 : 65 – 74 . Google Scholar Crossref Search ADS PubMed 10 Arabi , M. , Ostovan , A. , Ghaedi , M. , Purkait , M.K. ; Novel strategy for synthesis of magnetic dummy molecularly imprinted nanoparticles based on functionalized silica as an efficient sorbent for the determination of acrylamide in potato chips: optimization by experimental design methodology ; Talanta , ( 2016 ); 154 : 526 – 532 . Google Scholar Crossref Search ADS PubMed 11 Arabi , M. , Ghaedi , M. , Ostovan , A. ; Development of dummy molecularly imprinted based on functionalized silica nanoparticles for determination of acrylamide in processed food by matrix solid phase dispersion ; Food Chemistry , ( 2016 ); 210 : 78 – 84 . Google Scholar Crossref Search ADS PubMed 12 Arabi , M. , Ghaedi , M. , Abbas Ostovan , A. ; Water compatible molecularly imprinted nanoparticles as a restricted access material for extraction of hippuric acid, a biological indicator of toluene exposure, from human urine ; Microchimica Acta , ( 2017 ); 184 : 879 – 887 . Google Scholar Crossref Search ADS 13 Arabi , M. , Ghaedi , M. , Ostovan , A. ; Synthesis and application of in-situ molecularly imprinted silicamonolithic in pipette-tip solid-phase microextraction for these preparation and determination of gallic acid in orange juice samples ; Journal of Chromatography B , ( 2017 ); 1048 : 102 – 110 . Google Scholar Crossref Search ADS 14 Dastkhoon , M. , Mehrorang Ghaedi , M. , Asfaram , A. , Arabi , M. , Ostovan , A. , Alireza Goudarzi , A. ; Cu@SnS/SnO2 nanoparticles as novel sorbent for dispersive micro solid phase extraction of atorvastatin in human plasma and urine samples by high-performance liquid chromatography with UV detection: Application of central composite design (CCD) ; Ultrasonics Sonochemistry , ( 2017 ); 36 : 42 – 49 . Google Scholar Crossref Search ADS PubMed 15 Khan , M. , Yilmaz , E. , Sevinc , B. , Sahmetlioglu , E. , Shah , J. , Jan , M.R. , et al. . ; Preparation and characterization of magnetic allylamine modified graphene oxide-poly(vinyl acetate-co-divinylbenzene) nanocomposite for vortex assisted magnetic solid phase extraction of some metal ions ; Talanta , ( 2016 ); 146 : 130 – 137 . Google Scholar Crossref Search ADS PubMed 16 Xu , M. , Liu , M.H. , Sun , M.R. , Chen , K. , Cao , X.J. , Hu , Y.M. ; Magnetic solid-phase extraction of phthalate esters (PAEs) in apparel textile by core–shell structured Fe3O4@silica@triblock-copolymer magnetic microspheres ; Talanta , ( 2016 ); 150 : 125 – 134 . Google Scholar Crossref Search ADS PubMed 17 Cai , Y. , Yan , Z.H. , Wang , L.J. , NguyenVan , M.N. , Cai , Q.Y. ; Magnetic solid phase extraction and static headspace gas chromatography–mass spectrometry method for the analysis of polycyclic aromatic hydrocarbons ; Journal of Chromatography A , ( 2016 ); 1429 : 97 – 106 . Google Scholar Crossref Search ADS PubMed 18 Wang , X.Y. , Song , G.X. , Deng , C.H. ; Development of magnetic graphene @hydrophilic polydopamine for the enrichment and analysis of phthalates in environmental water samples ; Talanta , ( 2015 ); 132 : 753 – 759 . Google Scholar Crossref Search ADS PubMed 19 Sun , N.R. , Zhang , X.M. , Deng , C.H. ; Designed synthesis of MOF-derived magnetic nanoporous carbon materials for selective enrichment of glycans for glycomics analysis ; Nanoscale , ( 2015 ); 7 : 6487 – 6491 . Google Scholar Crossref Search ADS PubMed 20 Pan , S.D. , Zhou , L.X. , Zhao , Y.G. , Chen , X.H. , Shen , H.Y. , Cai , M.Q. , et al. . ; Amine-functional magnetic polymer modified graphene oxide as magnetic solid-phase extraction materials combined with liquid chromatography–tandem mass spectrometry for chlorophenols analysis in environmental water ; Journal of Chromatography A , ( 2014 ); 1362 : 34 – 42 . Google Scholar Crossref Search ADS PubMed 21 Ye , Q. , Liu , L.H. , Chen , Z.B. , Hong , L.M. ; Analysis of phthalate acid esters in environmental water by magnetic graphene solid phase extraction coupled with gas chromatography–mass spectrometry ; Journal of Chromatography A , ( 2014 ); 1329 : 24 – 29 . Google Scholar Crossref Search ADS PubMed 22 Ye , Q. , Liu , L.H. , Chen , Z.B. , Hong , L.M. ; Analysis of chlorophenols in environmental water using polydopamine-coated magnetic graphene as an extraction material coupled with high-performance liquid chromatography ; Journal of Separation Science , ( 2016 ); 39 : 1684 – 1690 . Google Scholar Crossref Search ADS PubMed 23 Ye , Q. , Chen , Z.B. , Liu , L.H. , Hong , L.M. ; Determination of bisphenols in environmental water samples using polydopamine-coated magnetic Fe3O4 as a magnetic solid-phase extraction material coupled with high-performance liquid chromatography ; Analytical Methods , ( 2016 ); 8 : 3391 – 3396 . Google Scholar Crossref Search ADS 24 Dong , Y.L. , Guo , D.Q. , Cui , H. , Li , X.J. , He , Y.J. ; Magnetic solid phase extraction of glyphosate and aminomethylphosphonic acid in river water using Ti4+-immobilized Fe3O4 nanoparticles by capillary electrophoresis ; Analytical Methods , ( 2015 ); 7 : 5862 – 5868 . Google Scholar Crossref Search ADS 25 Tao , Y. , Jiang , Y.H. , Lia , W.D. , Cai , B.C. ; Rapid magnetic solid-phase extraction combined with ultra-high performance liquid chromatography and quadrupole-time-of-flight mass spectrometry for analysis of thrombin binders from a crude extract and injection of Erigeron breviscapus ; RSC Advanced , ( 2016 ); 6 : 34782 – 34790 . Google Scholar Crossref Search ADS 26 Aliyari , E. , Alvand , M. , Shemirani , F. ; Modified surface-active ionic liquid-coated magnetic graphene oxide as a new magnetic solid phase extraction sorbent for preconcentration of trace nickel ; RSC Advances , ( 2016 ); 6 : 64193 – 64202 . Google Scholar Crossref Search ADS 27 Wu , C.L. , Zhu , G.F. , Fan , J. , Wang , J.J. ; Preparation of neutral red functionalized Fe3O4 @SiO2 and its application to the magnetic solid phase extraction of trace Hg(II) from environmental water samples ; RSC Advances , ( 2016 ); 6 : 86428 – 86435 . Google Scholar Crossref Search ADS 28 Yan , Z.H. , Zhu , G.H. , Cai , Y. , Yuan , J.B. , Yao , S.Z. ; Preparation of fluorine functionalized magnetic nanoparticles for fast extraction and analysis of perfluorinated compounds from traditional Chinese medicine samples ; Analytical Methods , ( 2015 ); 7 : 9054 – 9063 . Google Scholar Crossref Search ADS 29 Liang , X.T. , Zou , Y. , Liu , S.Q. , Chen , C.Y. , Hu , J.P. , Yao , S.Z. ; Facile and robust dual interaction modification of hexadecyldimethyl amine magnetic nanoparticles for the ultrasensitive analysis of perfluorinated compounds in environmental water ; Journal of Separation Science , ( 2015 ); 38 : 1394 – 1401 . Google Scholar Crossref Search ADS PubMed 30 Liu , X.D. , Yu , Y.J. , Li , Y. , Zhang , H.Y. , Ling , J. , Sun , X.N. , et al. . ; Fluorocarbon-bonded magnetic mesoporous microspheres for the analysis of perfluorinated compounds in human serum by high-performance liquid chromatography coupled to tandem mass spectrometry ; Analytica Chimica Acta , ( 2014 ); 844 : 35 – 43 . Google Scholar Crossref Search ADS PubMed 31 Yang , L. , Yu , W.J. , Yan , X.M. , Deng , C.H. ; Decyl-perfluorinated magnetic mesoporous microspheres for extraction and analysis perfluorinated compounds in water using ultrahigh-performance liquid chromatography–mass spectrometry ; Journal of Separation Science , ( 2012 ); 35 : 2629 – 2636 . Google Scholar Crossref Search ADS PubMed 32 Surm , M. , Wiczkowski , W. , Cieślik , E. , Zieliński , H. ; Method development for the determination of PFOA and PFOS in honey based on the dispersive Solid Phase Extraction (d-SPE) with micro-UHPLC–MS/MS system ; Microchemical Journal , ( 2015 ); 121 : 150 – 156 . Google Scholar Crossref Search ADS 33 Scott Boone , J. , Guan , B. , Vigo , C. , Boone , T. , Byrne , C. , Ferrario , J. ; A method for the analysis of perfluorinated compounds in environmental and drinking waters and the determination of their lowest concentration minimal reporting levels ; Journal of Chromatography A , ( 2014 ); 1345 : 68 – 77 . Google Scholar Crossref Search ADS PubMed 34 He , J.L. , Peng , T. , Xie , J. , Dai , H.H. , Chen , D.D. , Yue , Z.F. , et al. . ; Determination of 20 perfluorinated compounds in animal liver by HPLC–MS/MS ; Chinese Journal of Analytical Chemistry , ( 2015 ); 43 : 40 – 48 . Google Scholar Crossref Search ADS 35 Stahl , T. , Hofmann , A. , Cöllen , M. , Falk , S. , Brunn , H. ; Analysis of selected perfluoroalkyl substances (PFASs) in beer to evaluate the effect of beer consumption on human PFAS exposure: a pilot study ; European Food Research and Technology , ( 2014 ); 238 : 443 – 449 . Google Scholar Crossref Search ADS 36 Lankova , D. , Lacina , O. , Pulkrabova , J. , Hajslova , J. ; The determination of perfluoroalkyl substances, brominated flame retardants and their metabolites in human breast milk and infant formula ; Talanta , ( 2013 ); 117 : 318 – 325 . Google Scholar Crossref Search ADS PubMed 37 Capriotti , A.L. , Cavaliere , C. , Cavazzini , A. , Foglia , P. , Laganà , A. , Piovesana , S. , et al. . ; High performance liquid chromatography tandem mass spectrometry determination of perfluorinated acids in cow milk ; Journal of Chromatography A , ( 2013 ); 1319 : 72 – 79 . Google Scholar Crossref Search ADS PubMed 38 Garcí-Valcárcel , A.I. , Tadeo , J.L. ; Fast ultrasound-assisted extraction combined with LC–MS/MS of perfluorinated compounds in manure ; Journal of Separation Science , ( 2013 ); 36 : 2507 – 2513 . Google Scholar Crossref Search ADS PubMed 39 Taniyasu , S. , Kannan , K. , Wu , Q. , Kwok , KY. , Yeung , L.W.Y. , Lam , P.K.S. , et al. . ; Inter-laboratory trials for analysis of perfluorooctanesulfonate and perfluorooctanoate in water samples: performance and recommendations ; Analytica Chimica Acta , ( 2013 ); 770 : 111 – 120 . Google Scholar Crossref Search ADS PubMed 40 Dufkova , V. , Cabala , R. , Maradova , D. , Sticha , M. ; A fast derivatization procedure for gas chromatographic analysis of perfluorinated organic acids ; Journal of Chromatography A , ( 2009 ); 1216 : 8659 – 8664 . Google Scholar Crossref Search ADS PubMed 41 Ye , Q. ; Rapid analysis of the essential oil components of dried zanthoxylum bungeanum maxim by Fe2O3 magnetic microspheres assisted microwave distillation and simultaneous headspace single-drop microextraction followed by gas chromatography–mass spectrometry ; Journal of Separation Science , ( 2013 ); 36 : 2028 – 2034 . Google Scholar Crossref Search ADS PubMed 42 Currie , L.A. ; Detection and quantification limits: origins and historical overview ; Analytica Chimica Acta , ( 2009 ); 391 : 127 – 134 . Google Scholar Crossref Search ADS 43 Speltini , A. , Mattia Maiocchi , M. , Cucca , L. , Daniele Merli , D. , Profumo , A. ; Solid-phase extraction of PFOA and PFOS from surface waters on functionalized multiwalled carbon nanotubes followed by UPLC–ESI-MS ; Analytical and Bioanalytical Chemistry , ( 2014 ); 406 : 3657 – 3665 . Google Scholar Crossref Search ADS PubMed © The Author(s) 2018. Published by Oxford University Press. 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TI - Analysis of Perfluorinated Compounds in Environmental Water Using Decyl-perfluorinated Magnetic Mesoporous Microspheres as Magnetic Solid-Phase Extraction Materials and Microwave-Assisted Derivatization Followed by Gas Chromatography–mass Spectrometry
JF - Journal of Chromatographic Science
DO - 10.1093/chromsci/bmy073
DA - 2018-11-01
UR - https://www.deepdyve.com/lp/oxford-university-press/analysis-of-perfluorinated-compounds-in-environmental-water-using-1HJrdYZjAa
SP - 955
VL - 56
IS - 10
DP - DeepDyve
ER -