Method for the Analysis of Volatile and Non-Volatile Per- and Polyfluoroalkyl Compounds in Water Samples

Abstract

To provide an analysis method of a volatile or nonvolatile per- and poly-fluoroalkyl compound in a water sample, which enable the simultaneous quantitative analysis of a volatile or nonvolatile per- and poly-fluoroalkyl compound in a water sample.SOLUTION: An analysis method includes: a circulation process in which a water sample is sealed in a container, a column filled with a solid-phase adsorbent is immersed in the water sample and a liquid feed pump is connected to one side, the water sample is sucked through the column by the liquid feed pump and the water sample passing through the column is returned to the container and the water sample is thus circulated; a collection process in which the circulation process is repeated multiple times and a volatile or nonvolatile per- and poly-fluoroalkyl compound in the water sample is adsorbed by a solid-phase adsorbent; and an analysis process in which the column after the collection process is taken out of the container and the volatile or nonvolatile per- and poly-fluoroalkyl compound adsorbed by the solid-phase adsorbent is extracted and measured by an organic solvent.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a method for the quantitative analysis of volatile and non-volatile per- and polyfluoroalkyl compounds contained in a water sample. [Background technology]

[0002] Per- and polyfluoroalkyl compounds are fluorine-substituted aliphatic compounds that have high thermal stability, high chemical stability, and high surface modification activity. Taking advantage of these properties, per- and polyfluoroalkyl compounds are widely used in industrial and chemical applications such as surface treatment agents, packaging materials, and liquid fire extinguishing agents.

[0003] Some per- and polyfluoroalkyl compounds are very stable chemical substances and are difficult to decompose under natural conditions after being released into the environment. For this reason, in recent years, per- and polyfluoroalkyl compounds have been recognized as persistent organic pollutants (POPs), and the production and use of perfluorooctane sulfonate (PFOS) (IUPAC name: 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-1-sulfonic acid) has been restricted since 2010 under the Stockholm Convention on Persistent Organic Pollutants (POPs Convention).

[0004] Perfluoroalkyl compounds have a completely fluorinated linear alkyl group and are substances represented by the chemical formula (i). Examples include perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) (IUPAC name: 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoic acid).

[0005]

number

[0006] Polyfluoroalkyl compounds are compounds in which some of the hydrogen atoms in an alkyl group have been replaced with fluorine, and are represented by the chemical formula (ii). For example, there is fluorotelomer alcohol (FTOH).

[0007]

number

[0008] Thus, since per- and polyfluoroalkyl compounds continue to remain in nature (in water, soil, and air), the establishment of a quantitative test method for per- and polyfluoroalkyl compounds is being considered. The objective of the study of a quantitative test method is to develop a collector with high adsorption and desorption performance for per- and polyfluoroalkyl compounds and a test method using the collector. Water or air, which is a sample containing trace amounts of per- and polyfluoroalkyl compounds, is brought into contact with the collector to collect the per- and polyfluoroalkyl compounds, and the compounds adsorbed by the collector are desorbed in an extract by an extraction process and concentrated. After concentration, quantitative measurement is performed using an apparatus such as LC-MS / MS or GC-MS / MS, making it possible to measure the concentration of per- and polyfluoroalkyl compounds contained in the sample.

[0009] As an existing adsorption material, for example, an organic fluorine compound adsorbent made of cyclodextrin polymer has been proposed (Patent Document 1). This adsorbent is specialized for adsorption only and cannot desorb the compounds, so it is not suitable for use as an adsorption material used in quantitative measurement. In addition, cyclodextrin polymer is in powder or fine particle form, which makes it difficult to handle and has high resistance when passing liquid or air, resulting in problems such as the risk of fine powder leaking to the secondary side.

[0010] In addition, per- and polyfluoroalkyl compounds remain in the environment in various forms with a wide range of physicochemical properties, and existing adsorbents do not have sufficient collection performance, making it difficult to accurately quantitatively measure them.

[0011] Among these per- and polyfluoroalkyl compounds, the solid-phase extraction method is mainly used as an analysis method for ionic per- and polyfluoroalkyl compounds such as PFOS and PFOA. For non-volatile compounds that are easily water-soluble such as ionic per- and polyfluoroalkyl compounds, analysis by the solid-phase extraction method is considered to be effective. However, analysis by the solid-phase extraction method for volatile per- and polyfluoroalkyl compounds such as FTOH is considered to be difficult.

[0012] As a method for measuring per- and polyfluoroalkyl compounds in water, a method for collecting nonvolatile per- and polyfluoroalkyl compounds is shown in ISO21675. According to this method, a water sample containing nonvolatile per- and polyfluoroalkyl compounds is passed through a solid-phase column filled with a solid-phase adsorbent made of a weak anion exchange material, and the nonvolatile per- and polyfluoroalkyl compounds are collected by the solid-phase adsorbent in the solid-phase column, and the compounds adsorbed by the solid-phase adsorbent are desorbed in the extract by an extraction process and concentrated. After concentration, the concentration of nonvolatile per- and polyfluoroalkyl compounds contained in the sample is measured by quantitative measurement using LC-MS / MS. However, due to the nature of volatile per- and polyfluoroalkyl compounds, it is difficult to collect them using a solid-phase column.

[0013] Therefore, the applicant conducted further research to enable simultaneous quantitative analysis of volatile and non-volatile per- and polyfluoroalkyl compounds contained in water samples, and discovered that the method enables the effective collection of volatile and non-volatile per- and polyfluoroalkyl compounds in water samples, greatly contributing to highly accurate quantitative measurement. [Prior art documents] [Patent documents]

[0014] [Patent Document 1] JP 2012-101159 A Summary of the Invention [Problem to be solved by the invention]

[0015] The present invention has been made in consideration of the above points, and in particular provides a method for quantitatively analyzing volatile or non-volatile per- and polyfluoroalkyl compounds in a water sample, which enables simultaneous quantitative analysis of volatile or non-volatile per- and polyfluoroalkyl compounds. [Means for solving the problem]

[0016] That is, the first invention relates to an analytical method for quantitatively analyzing volatile or nonvolatile per- and polyfluoroalkyl compounds in a water sample, which comprises a circulation step in which the water sample is sealed in a container, a column filled with a solid-phase adsorbent is immersed in the water sample and a liquid delivery pump is connected to one side, the water sample is sucked through the column by the liquid delivery pump, and the water sample that has passed through the column is returned to the container to circulate the water sample, a collection step in which the circulation step is repeated multiple times to adsorb the volatile or nonvolatile per- and polyfluoroalkyl compounds in the water sample by the solid-phase adsorbent, and an analysis step in which the column that has been subjected to the collection step is removed from the container, and the volatile or nonvolatile per- and polyfluoroalkyl compounds adsorbed by the solid-phase adsorbent are extracted with an organic solvent and measured.

[0017] A second aspect of the present invention relates to a method for analyzing volatile or non-volatile per- and polyfluoroalkyl compounds in a water sample according to the first aspect of the present invention, wherein the solid phase adsorbent is an activated carbon adsorbent.

[0018] The third invention relates to a method for analyzing volatile or non-volatile per- and polyfluoroalkyl compounds in a water sample according to the first or second invention, wherein the column is a syringe-type or disk-type solid-phase column. Effect of the Invention

[0019] According to the first invention, the method for analyzing volatile or non-volatile per- and polyfluoroalkyl compounds in a water sample is a quantitative analysis method for analyzing volatile or non-volatile per- and polyfluoroalkyl compounds in a water sample, in which a water sample is sealed in a container, a column filled with a solid-phase adsorbent is immersed in the water sample and a liquid pump is connected to one side, the water sample is sucked through the column by the liquid pump, and the water sample that has passed through the column is returned to the container to circulate the water sample. The circulation process is repeated multiple times to adsorb the volatile or non-volatile per- and polyfluoroalkyl compounds in the water sample by the solid-phase adsorbent, and the column that has undergone the collection process is removed from the container, and the volatile or non-volatile per- and polyfluoroalkyl compounds adsorbed by the solid-phase adsorbent are extracted with an organic solvent and measured. This makes it possible to simultaneously quantitatively measure volatile or non-volatile per- and polyfluoroalkyl compounds in a water sample, which has not been established at present, and the compounds can be efficiently collected, thereby improving the accuracy of quantitative analysis.

[0020] According to the second invention, the method for analyzing volatile or non-volatile per- and polyfluoroalkyl compounds in water samples is the same as in the first invention, except that the solid phase adsorbent is an activated carbon adsorbent, so that per- and polyfluoroalkyl compounds can be efficiently captured in a desorbable manner, thereby improving the accuracy of quantitative analysis of the compounds.

[0021] According to the third invention, the method for analyzing volatile or non-volatile per- and polyfluoroalkyl compounds in water samples, in the first or second invention, the column shape is a syringe-type or disk-type solid phase column, which makes it possible to increase the collection efficiency of per- and polyfluoroalkyl compounds while providing good handleability. [Brief description of the drawings]

[0022] [Figure 1]FIG. 1 is a schematic diagram of a collection device used in the method of analyzing per- and polyfluoroalkyl compounds in a water sample of the present invention. [Diagram 2] FIG. 1 is a schematic diagram showing a disk-type solid phase column. [Diagram 3] FIG. 3 is a partial cross-sectional view of the disk-type solid phase column of FIG. 2. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0023] The activated carbon used as a solid-phase adsorbent in the quantitative analysis method for volatile or non-volatile per- and polyfluoroalkyl compounds of the present invention is an activated carbon that adsorbs per- and polyfluoroalkyl compounds present in a water sample in a releasable manner.

[0024] The measurement accuracy of the analytical method is highly dependent on the adsorption performance of the activated carbon used as the solid-phase adsorbent for per- and polyfluoroalkyl compounds, and therefore the activated carbon used in the analytical method of the present invention is required to have good adsorption performance for the compounds.

[0025] The activated carbon is preferably housed in a disk-type solid phase column 10 as shown in Figures 2 and 3. By housing an activated carbon filter section 20 in the solid phase column, analysis can be performed immediately after removing the solid phase column. The activated carbon filter section 20 is easy to handle if it is formed into, for example, a felt filter section 21 as shown in Figure 3. In addition, since it is easy to attach and detach, it is easy to replace, can be used continuously, and is easy to handle.

[0026] The activated carbon is made of fibrous activated carbon or granular activated carbon. The fibrous activated carbon is obtained by carbonizing and activating suitable fibers, and examples of such activated carbon include phenol resin-based, acrylic resin-based, cellulose-based, and coal pitch-based activated carbon. The fiber length and cross-sectional diameter are suitable.

[0027] The raw materials for granular activated carbon include wood (scrap wood, thinned wood, sawdust), coffee bean residue, rice husks, coconut shells, bark, and fruit. These naturally derived raw materials are more likely to develop pores when carbonized and activated. In addition, since it is a secondary use of waste, it can be procured at low cost. Other raw materials that can be used include tires, petroleum pitch, burned synthetic resins such as urethane resin and phenolic resin, and even coal.

[0028] The activated carbon raw material is heated and carbonized at a temperature range of 200°C to 600°C as necessary to form micropores. The activated carbon raw material is then exposed to steam and carbon dioxide gas at a temperature range of 600°C to 1200°C for activation. As a result, activated carbon with various types of developed pores is produced. Other activation methods include activation with zinc chloride. Sequential washing is also performed.

[0029] The physical properties of the activated carbon thus produced determine the adsorption performance of the adsorbed substance. The adsorption performance of the activated carbon that adsorbs per- and polyfluoroalkyl compounds, which are the target adsorbed substances of the present invention, is determined by the specific surface area, which is an index showing the amount of pores formed in the activated carbon. In this specification, the specific surface area of ​​each prototype is measured by the BET method (Brunauer, Emmett and Teller method). The higher the adsorption and desorption performance of the activated carbon as a solid-phase adsorbent, the more accurate the quantitative analysis of per- and polyfluoroalkyl compounds in water samples.

[0030] Activated carbon is also defined by the pore size. In the case of an adsorbent such as activated carbon, there are micropores, mesopores, and macropores. The adsorption target and performance of activated carbon change depending on which range of pores is developed more. The activated carbon desired in the present invention is one that effectively and releasably adsorbs molecules of per- and polyfluoroalkyl compounds.

[0031] The adsorption capacity of activated carbon that adsorbs per- and polyfluoroalkyl compounds in a desorbable manner is as follows: 2 / g or more. By forming a certain number of pores in the activated carbon, the adsorption performance of the compound is ensured.

[0032] The analytical method for per- and polyfluoroalkyl compounds in water samples in the present invention is an analytical method that applies the in situ adsorption method. The in situ adsorption method is a concept in which a collection device such as a sampler is placed in the medium to be analyzed and is held by a collection material such as an adsorbent. The in situ adsorption method is characterized in that, in order to reduce the risk of contamination, concentration changes, and chemical substance deterioration during sampling of environmental water (river water, lake water, seawater), transportation to a laboratory, etc., collection on a solid-phase adsorbent and extraction work as necessary are performed at the sampling site, and reliable collection by a solid-phase adsorbent is required. In the in situ adsorption method, the target substance is collected by a one-pass or circulation method, and a method that efficiently collects the target substance is selected. Regardless of the collection method, the collection operation is performed in units of several hours to achieve the required sensitivity and adsorption amount.

[0033] In the solid-phase extraction method, the liquid is usually passed through the solid-phase adsorbent at a speed of 1 drop / second, and if the speed is increased beyond this, the collection performance of the solid-phase adsorbent may decrease. On the other hand, if the liquid passing speed is slower than this, the time required for passing the liquid becomes significantly longer when the measurement target is a water sample of several hundred milliliters to several liters, which is not preferable.

[0034] In the analysis method of the present invention, as shown in the schematic diagram of the collection device 1 used in the analysis method of the present invention shown in FIG. 1, the water sample W is placed in a container C and sealed, a column S filled with activated carbon, which is a solid-phase adsorbent A, is immersed in the container C, the water sample W is sucked from one side of the immersed column S by a liquid delivery pump P to pass the water sample W through the column S, and the passed water sample W is returned to the sealed container C. This operation is repeated to pass the water sample W through the column S many times. The liquid moves in the direction of the arrow in the figure. This is a method in which the per- and polyfluoroalkyl compounds, which are the measurement targets adsorbed to the solid-phase adsorbent, are desorbed from the solid-phase adsorbent by a solvent and measured and analyzed. It is preferable to adjust the amount of gas phase in the container C as small as possible. The symbol T in the figure indicates a tube that connects the column S and the liquid delivery pump P and is connected to return the water sample W from the liquid delivery pump P to the container C.

[0035] In the analysis method of the present invention, the water sample containing the per- and polyfluoroalkyl compounds to be measured is sealed, so there is little concern about distribution to the gas phase, and volatile or non-volatile per- and polyfluoroalkyl compounds can be comprehensively analyzed at the same time. The water sample is preferably circulated at a flow rate of about 2 to 20 ml / min for 10 to 30 hours. If the flow rate is too small, the number of circulations of the water sample per hour may decrease, which may result in poor adsorption efficiency of the target substance, and if the flow rate is too large, the contact time between the water sample and the solid phase adsorbent may be shortened. In addition, if the circulation time is too short, the water sample may not be able to contact the solid phase adsorbent sufficiently, and the per- and polyfluoroalkyl compounds may not be completely adsorbed by the solid phase adsorbent and may remain, so it is necessary to perform the circulation operation for a certain period of time or more. Although the circulation time depends on the flow rate and the temperature of the water sample, it is considered that it is best to perform the circulation operation for about 20 hours.

[0036] In conventional solid-phase extraction, the average surface velocity is 100 h -1The time required for adsorption is considered to be insufficient when activated carbon is used as the solid-phase adsorbent, because the contact time with the solid-phase adsorbent is short. For this reason, in consideration of the suppression of distribution of volatile per- and polyfluoroalkyl compounds from water samples to the gas phase and the securing of sufficient contact time with the solid-phase adsorbent, it was decided to study the application of an in situ adsorption method to capture and analyze volatile or non-volatile per- and polyfluoroalkyl compounds.

[0037] Examples of per- and polyfluoroalkyl compounds present in water samples include FTOH, PFOS, and PFOA, as mentioned above.

[0038] The per- and polyfluoroalkyl compounds are adsorbed by a solid-phase adsorbent, which may be a polymer-based adsorbent in addition to the activated carbon described above.

[0039] Polymer-based adsorbents, such as styrene-divinylbenzene copolymers, are reverse-phase solid-phase adsorbents that are primarily used to separate hydrophobic components from polar solvents. They have a porous structure similar to activated carbon, and adsorb hydrophobic components primarily through intermolecular forces (van der Waals forces).

[0040] The per- and polyfluoroalkyl compounds adsorbed by the solid-phase adsorbent are extracted and measured with an organic solvent, such as dichloromethane, ethyl acetate, methanol, or a mixture thereof. EXAMPLES

[0041] Quantitative determination of per- and polyfluoroalkyl compounds in water samples Next, the inventors carried out analytical experiments using the solid phase adsorbents described below for the purpose of quantitatively measuring volatile or non-volatile per- and polyfluoroalkyl compounds in water samples by the analytical method of the present invention.

[0042] [Solid phase adsorbent] The inventors used the following activated carbon as a solid phase adsorbent for adsorbing per- and polyfluoroalkyl compounds.

[0043] <Activated carbon> 90 mg of fibrous activated carbon "GAIAC (registered trademark)" (manufactured by Futamura Chemical Co., Ltd.) was packed into a PP disk-type solid phase column. The physical properties of the activated carbon are as follows: Surface oxide amount: 0.48 (meq / g) BET specific surface area: 1474(m 2 / g) Average pore diameter: 1.64 (nm)

[0044] [Analysis of per- and polyfluoroalkyl compounds in water samples] The per- and polyfluoroalkyl compounds examined this time were non-volatile perfluoroalkyls PFBS (IUPAC name: 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonic acid), PFHxS (IUPAC name: 1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane-1-sulfonic acid), PFHpS (IUPAC name: 1,1,2,2,3,3,4,4,5,5,6,7,7,7-pentadecafluoroheptane-1-sulfonic acid), PFOS, and PFDS (IUPAC name: UPAC name: 1,1,2,2,3,3,4,4,5,5,6,7,7,8,8,9,9,10,10,10-heneicosafluorodecane-1-sulfonic acid), PFBA (IUPAC name: 2,2,3,3,4,4,4-heptafluorobutanoic acid), PFPeA (IUPAC name: 2,2,3,3,4,4,5,5,5-nonafluoropentanoic acid), PFHxA (IUPAC name: 2,2,3,3,4,4,5,5,6,6,6-undecafluorohexanoic acid), PFHpA (IUPAC name: 2,2,3,3,4 , 4,5,5,6,6,7,7,7-tridecafluorooctanoic acid), PFOA, PFNA (IUPAC name: 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluorononanoic acid), PFDA (IUPAC name: 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-nonadecafluorodecanoic acid), and the volatile polyfluoroalkyl 4:2FTOH (IUPAC name: 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexafluoropropane). FTOH (IUPAC name: 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-1-octanol), 6:2FTOH (IUPAC name: 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro-1-decanol), and 10:2FTOH (IUPAC name: 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heneicosafluoro-1-dodecanol).

[0045] PFBS, PFHxS, PFHpS, PFOS, and PFDS are compounds with 4 to 10 carbon atoms and have the following chemical formula (iii). PFBA, PFPeA, PFHxA, PFHpA, PFOA, PFNA, and PFDA are compounds with 3 to 9 carbon atoms and have the following chemical formula (iv).

[0046]

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[0047]

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[0048] 100μl of a standard solution in which non-volatile per- and polyfluoroalkyl compounds were diluted to 10ng / ml (10ppb) with methanol, and 200μl of a standard solution in which volatile per- and polyfluoroalkyl compounds were diluted to 100ng / ml (100ppb) with methanol were added to PP bottles containing 500ml each of ultrapure water and commercially available mineral water, to prepare water samples. All standard reagents used were manufactured by Wellington Laboratories Japan Co., Ltd. The one using ultrapure water is Test Example 1, and the one using mineral water is Test Example 2.

[0049] Two of the above-mentioned disk-type solid phase columns were connected in series, and a Tygon tube with an inner diameter of 2.15 mm and an outer diameter of 4.2 mm was connected to the outlet side. The tube was connected to a cassette tube pump (manufactured by AS ONE Corporation) to form a collection device. Two holes with a diameter of 4.2 mm were provided in the lid of the container in which the water sample was sealed, and the tube was passed through to ensure sealing during the circulation process. The inlet side (primary side) of the solid phase column was located at the bottom side of the container, and the outlet side (secondary side) was located at the top of the container. When the water sample that had passed through the column returned to the container, the tip of the tube was positioned so that it would drip onto the water surface from the top side of the container.

[0050] The circulation step or collection step was carried out by circulating the solution at a flow rate of 11 ml / min for 18 hours. After the collection step, the disk-type solid phase column was removed from the vessel and dehydrated by suction using an aspirator for about 15 seconds.

[0051] The disk-type solid phase column after dehydration was connected to a manifold, and 1 ml of methanol, 4 ml of ethyl acetate, and 6 ml of dichloromethane were passed through at a rate of 1 drop / second, respectively, to collect extract 1. Furthermore, 4 ml of methanol was passed through the disk-type solid phase column after the extraction operation again at a rate of 1 drop / second, to collect extract 2. Note that the disk-type solid phase columns connected in series were each subjected to an extraction operation individually. Extract 1 was centrifuged at 3000 rpm for 3 minutes to separate it into an organic solvent layer and an aqueous layer, and the aqueous layer was removed using a paper wiper.

[0052] Extract Solution 1 and Extract Solution 2 were set to about 25°C and concentrated to a constant volume of 1 ml using a nitrogen blowing concentrator to obtain Concentrated Solution 1 of Extract Solution 1 and Concentrated Solution 2 of Extract Solution 2. When the aqueous layer separated again due to a temperature drop caused by the heat of vaporization, the aqueous layer was removed using a paper wiper.

[0053] 0.5 ml of concentrated solution 1 of extract 1 was taken, 2 ml of methanol was added, the temperature was set to about 25° C., and the solution was concentrated to a constant volume of 0.5 ml using a nitrogen blowing concentrator to obtain concentrated solution 3 of extract 1.

[0054] Volatile per- and polyfluoroalkyl compounds were quantitatively measured in MRM mode using GC-MS / MS ("GCMS-TQ8050", Shimadzu Corporation) for concentrated solutions 1 and 2, and the analysis results were confirmed. In addition, non-volatile perfluoroalkyl compounds were measured using LC-MS / MS ("Triple Quad 4500", ABSCIEX) for concentrated solutions 2 and 3.

[0055] <Comparative Example> As a comparative example, an analytical experiment was carried out by solid-phase extraction using the same solid-phase adsorbent and disk-type solid-phase column.

[0056] Each standard substance was diluted with methanol to 100ng / ml (100ppb), and 100μl of the standard solution was added to 100ml of ultrapure water to prepare a 100ng / l (100ppt) water sample. As a pre-wash for the solid-phase adsorbent, 15ml of a mixed solvent mainly composed of dichloromethane and ethyl acetate was passed through at a rate of 1 drop / second, followed by 5ml of methanol and 15ml of ultrapure water in the same order.

[0057] 100 ml of the prepared water sample was passed through the solid phase column at a rate of 1 drop / second, and then 5 ml of ultrapure water was added to the container in which the water sample was prepared and passed through to wash out the target components remaining in the container. After passing the liquid through the solid phase column, the water in the column was removed by centrifugation (3500 rpm, 30 minutes).

[0058] After centrifugation, 4 ml of methanol solution was added to the container to wash out the target substance remaining on the inner wall, and the extract A was collected by passing the dehydrated disk-type solid-phase column at a rate of 1 drop / second. In addition, extract B was collected by passing 15 ml of a mixed solvent mainly composed of dichloromethane and ethyl acetate in the same manner. The collected extract A and extract B were concentrated to 1 ml using a nitrogen blowing concentrator. After concentration, 50 mg of sodium sulfate (Na2SO4) was added to extract A to remove the water that had been mixed in. Quantitative measurement of extract A and extract B was performed in MRM mode using GC-MS / MS ("GCMS-TQ8050", manufactured by Shimadzu Corporation) to confirm the analysis results.

[0059] Tables 1 and 2 show the recovery rates (%) for each target substance in the analytical experiments of Test Example 1, Test Example 2, and Comparative Example 1. For the non-volatile target substances, PFBS, PFHxS, PFHpS, PFOS, PFDS, PFBA, PFPeA, PFHxA, PFHpA, PFOA, PFNA, and PFDA were used as native standard reagents, and PFBA, PFHxS, PFHpS, PFOS, PFDS, PFBA, PFPeA, PFHxA, PFHpA, PFOA, PFNA, and PFDA were used as surrogate standard reagents. 13 C3-PFBS, 13 C3-PFHxS, 13 C8-PFOS, 13 C4-PFBA,13 C5-PFPeA, 13 C5-PFHxA, 13 C4-PFHpA, 13 C8-PFOA, 13 C5-PFNA, 13 The results of using C6-PFDA are shown in Table 1. Volatile target substances were 4:2FTOH, 6:2FTOH, 8:2FTOH, and 10:2FTOH as native standard reagents, and d4-4:2FTOH and d2- as surrogate standard reagents. 13 C2-6: 2FTOH, d2- 13 C2-8: 2FTOH, d2- 13 The results using C2-10:2FTOH are shown in Table 2. In the table, "-" indicates that the experiment was not conducted.

[0060] [Table 1]

[0061] [Table 2]

[0062] [Results and Discussion] Test Examples 1 and 2 relating to the analytical method of the present invention showed better recovery rates of non-volatile per- and polyfluoroalkyl compounds in water samples than the comparative example of the solid phase extraction method, and also showed high recovery rates for volatile per- and polyfluoroalkyl compounds. It was shown that the analytical method of the present invention is excellent as an analytical method for simultaneously quantitatively measuring volatile and non-volatile per- and polyfluoroalkyl compounds in water samples.

[0063] In the comparative example, the recovery rate of all volatile per- and polyfluoroalkyl compounds was 50% or less, indicating that sufficient recovery rates were not obtained. In contrast, in Test Example 1 and Test Example 2, which used the same solid-phase adsorbent, the recovery rate of all target substances was 50% or more, indicating that the target substances could be recovered satisfactorily.

[0064] It is understood that the solid-phase extraction method in the comparative example is not suitable for simultaneous quantitative analysis of volatile or non-volatile per- and polyfluoroalkyl compounds, because there is a possibility that volatile per- and polyfluoroalkyl compounds are distributed into the gas phase, and because a single pass at a rate of 1 drop / second does not provide sufficient contact between the solid-phase adsorbent and the water sample, and it is considered that the time required for adsorption of the target substances is not secured.

[0065] In contrast, in the analytical method of the present invention, the water sample is repeatedly brought into contact with a solid-phase adsorbent in a sealed container to adsorb the target substances, thereby suppressing the distribution of volatile per- and polyfluoroalkyl compounds into the gas phase while ensuring the time necessary for adsorption of the target substances through circulation trials.It is therefore understood that this makes it possible to comprehensively capture volatile and non-volatile per- and polyfluoroalkyl compounds all at once, making simultaneous quantitative analysis possible. [Industrial Applicability]

[0066] The method for analyzing volatile or non-volatile per- and polyfluoroalkyl compounds in water samples of the present invention makes it possible to simultaneously quantitatively measure all volatile or non-volatile per- and polyfluoroalkyl compounds present in water samples, which was previously considered difficult to do. [Explanation of symbols]

[0067] 1 Collection device 10 Disk-type solid phase column 11 Intake opening 12 Main body 20 Activated carbon filter section 21 Felt filter part A Solid phase adsorbent C container P Liquid delivery pump S Column T-Tube W Water sample

Claims

1. 1. A method for quantitatively analyzing volatile and non-volatile per- and polyfluoroalkyl compounds in a water sample, comprising: The water sample is sealed in a container, A column packed with a solid-phase adsorbent is immersed in the water sample and a liquid delivery pump is connected to one side of the column; The water sample is drawn through the column by the liquid delivery pump, a circulation step in which the water sample that has passed through the column is returned to the container to circulate the water sample; a collection step in which the circulation step is repeated multiple times to adsorb the volatile or non-volatile per- and polyfluoroalkyl compounds in the water sample by the solid phase adsorbent; The column that has been subjected to the collection step is removed from the container, and an analysis step in which the volatile or non-volatile per- and polyfluoroalkyl compounds adsorbed by the solid-phase adsorbent are extracted with an organic solvent and measured. A method for analyzing volatile or non-volatile per- and polyfluoroalkyl compounds in a water sample, comprising:

2. 2. The method for analyzing volatile or non-volatile per- and polyfluoroalkyl compounds in a water sample according to claim 1, wherein said solid phase adsorbent is an activated carbon adsorbent.

3. 3. The method for analyzing volatile or non-volatile per- and polyfluoroalkyl compounds according to claim 1 or 2, wherein the column is a syringe-type or disk-type solid-phase column.

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