Determination of six non-ionic PFAS in consumer products

Abstract

This application provides a method for determining six types of non-ionic PFAS in consumer products, specifically: pre-treating the analyte; specifically, adding a first volume of a first reagent to each gram of the analyte, ultrasonically extracting for a first time at a first temperature, adding the first reagent when evaporating to a remaining second volume at a second temperature, adding a liquid, fixing the liquid to a third volume, filtering to obtain a sample test solution; sampling the sample test solution to obtain an on-machine test solution; and performing qualitative and quantitative analysis on the on-machine test solution by gas chromatography-mass spectrometry. By pre-treating the analyte and then determining it with a gas chromatography-mass spectrometry instrument, the content of the six non-ionic PFAS in the analyte can be determined, the use of such substances can be standardized, and risks can be avoided for social production.

Description

Technical Field

[0001] The present application relates to the field of analytical chemistry technology, and in particular to a method for determining six non-ionic PFAS in consumer products. Background Art

[0002] PFAS (Per and Polyfluoroalkyl Substances) are a large class of fluorinated organic compounds with strong water- and oil-repellent properties. They are commonly used in waterproof coatings, non-stick coatings, and antifouling agents for various materials. PFAS substances are mostly stable and difficult to decompose naturally in the natural environment. They are widely detected in water and soil. Furthermore, most of these substances are highly toxic and carcinogenic. Therefore, they have received widespread attention from governments around the world. Multiple regulations have been introduced to regulate PFAS substances, including perfluorooctane sulfonic acid and perfluorooctanoic acid, and various related methods have been introduced to measure these two substances.

[0003] On August 5, 2021, the European Union issued Directive (EU) 2021 / 1297, which added C9-C14 perfluorocarboxylic acids, their salts, and related compounds to its control scope. C9-C14 perfluorocarboxylic acids and their salts have similar properties to perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA), making their determination relatively straightforward. However, their related compounds, particularly non-ionic compounds, have structures significantly different from those of PFOS and PFOA, and there is currently no reliable method for determining their content. Summary of the Invention

[0004] In view of the above problems, the present application is proposed to provide a method for determining six non-ionic PFAS in consumer products that overcomes the above problems or at least partially solves the above problems, including:

[0005] The method for determining six non-ionic PFAS in consumer products includes the following steps:

[0006] Pre-treating the analyte; specifically, adding a first volume of a first reagent per gram of the analyte, ultrasonically extracting at a first temperature for a first time, adding the first reagent when evaporation to a second volume at a second temperature, adding a liquid to adjust the volume of the liquid to a third volume, and filtering to obtain a sample solution;

[0007] Sampling the sample test solution to obtain the test solution for the machine;

[0008] The test solution is subjected to qualitative and quantitative analysis by gas chromatography-mass spectrometry.

[0009] Furthermore, the first volume is 10-20 mL.

[0010] Furthermore, the first reagent is tert-butyl methyl ether.

[0011] Furthermore, the first temperature is 30-50°C.

[0012] Furthermore, the first duration is 50-80 minutes.

[0013] Furthermore, the second temperature is 30-40°C.

[0014] Furthermore, the second volume is the 1-2 mL.

[0015] Furthermore, the third volume is 5 mL.

[0016] Furthermore, the analyte is a solid fragment with a total weight not exceeding 5 g.

[0017] Furthermore, the heating curve of the gas chromatography-mass spectrometer is as follows: starting temperature 40°C, holding for 1 minute, increasing to 100°C at 15°C / min, then increasing to 250°C at 25°C / min, and holding for 1 minute.

[0018] This application has the following advantages:

[0019] In the embodiments of the present application, the gap in the prior art of not determining the content of non-ionic PFAS is filled. The present application provides a method for determining six non-ionic PFAS in consumer products, specifically: pre-treating the analyte; specifically, adding a first volume of a first reagent to each gram of the analyte, ultrasonically extracting for a first time at a first temperature, adding the first reagent when evaporating to a remaining second volume at a second temperature, adding a liquid to adjust the liquid to a third volume, filtering to obtain a sample test solution; sampling the sample test solution to obtain an on-machine test solution; and performing qualitative and quantitative analysis on the on-machine test solution by gas chromatography-mass spectrometry. By pre-treating the analyte and then measuring it with gas chromatography-mass spectrometry, the contents of six non-ionic PFAS in the analyte, including 1-perfluorodecylethanol (10:2FTOH), 1-perfluorodecylethyl acrylate (10:2FTA), 1-perfluorodecylethyl methacrylate (10:2FTMA), 1-iodo-1H,1H,2H,2H-perfluorododecane (10:2FTI), 1-perfluorododecylethanol (10:2FTOH) and 1-iodo-1H,1H,2H,2H-perfluorotetradecane (12:2FTI), can be determined, so as to standardize the use of such substances and avoid risks for social production. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] In order to more clearly illustrate the technical solution of the present application, the following is a brief introduction to the drawings required for the description of the present application. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without any creative work.

[0021] Figure 1 This is a flowchart of the steps of the method for determining six non-ionic PFAS in consumer products provided in one embodiment of the present application;

[0022] Figure 2 This is a chromatogram of 1-perfluorodecylethanol (10:2FTOH) provided in one embodiment of the present application;

[0023] Figure 3 This is a chromatogram of 1-perfluorodecyl ethyl acrylate (10:2FTA) provided in one embodiment of the present application;

[0024] Figure 4 This is a chromatogram of 1-perfluorodecylethyl methacrylate (10:2FTMA) provided in one embodiment of the present application;

[0025] Figure 5 This is a chromatogram of 1-iodo-1H,1H,2H,2H-perfluorododecane (10:2FTI) provided in one embodiment of the present application;

[0026] Figure 6 This is a chromatogram of 1-perfluorododecylethanol (12:2FTOH) provided in one embodiment of the present application;

[0027] Figure 7 This is a chromatogram of 1-iodo-1H,1H,2H,2H-perfluorotetradecane (12:2FTI) provided in one embodiment of the present application. DETAILED DESCRIPTION

[0028] To make the objectives, features, and advantages of this application more readily apparent, the present application is further described below in conjunction with the accompanying drawings and specific embodiments. It is apparent that the embodiments described are only a portion of the embodiments of this application, not all of them. All other embodiments derived by persons of ordinary skill in the art based on the embodiments in this application without inventive effort are also within the scope of protection of this application.

[0029] By analyzing the existing technology, the inventors found that after a certain pretreatment of the analyte, by studying the instrument parameters and improving the instrument method, the content of six non-ionic PFAS in consumer products can be determined using a gas chromatography-mass spectrometer.

[0030] Reference Figure 1, shows the determination method of six non-ionic PFAS in consumer products provided by one embodiment of the present application:

[0031] The method comprises:

[0032] S110, pre-treating the analyte; specifically, adding a first volume of a first reagent per gram of the analyte, ultrasonically extracting at a first temperature for a first time, adding the first reagent after evaporation to a second volume at a second temperature, adding a liquid to adjust the volume of the liquid to a third volume, and filtering to obtain a sample solution;

[0033] S120, sampling the sample test solution to obtain an on-machine test solution;

[0034] S130, performing qualitative and quantitative analysis on the test solution using a gas chromatography-mass spectrometer.

[0035] In the embodiments of the present application, the gap in the prior art of not determining the content of non-ionic PFAS is filled. The present application provides a method for determining six non-ionic PFAS in consumer products, specifically: pre-treating the analyte; specifically, adding a first volume of a first reagent to each gram of the analyte, ultrasonically extracting for a first time at a first temperature, adding the first reagent when evaporating to a remaining second volume at a second temperature, adding a liquid to adjust the liquid to a third volume, filtering to obtain a sample test solution; sampling the sample test solution to obtain an on-machine test solution; and performing qualitative and quantitative analysis on the on-machine test solution by gas chromatography-mass spectrometry. By pre-treating the analyte and then measuring it with gas chromatography-mass spectrometry, the contents of six non-ionic PFAS in the analyte, including 1-perfluorodecylethanol (10:2FTOH), 1-perfluorodecylethyl acrylate (10:2FTA), 1-perfluorodecylethyl methacrylate (10:2FTMA), 1-iodo-1H,1H,2H,2H-perfluorododecane (10:2FTI), 1-perfluorododecylethanol (10:2FTOH) and 1-iodo-1H,1H,2H,2H-perfluorotetradecane (12:2FTI), can be determined, so as to standardize the use of such substances and avoid risks for social production.

[0036] Below, the determination method of six non-ionic PFAS in consumer products in this exemplary embodiment will be further described.

[0037] As described in step S110, the object to be tested is pretreated; specifically, a first volume of a first reagent is added to each gram of the object to be tested, ultrasonic extraction is performed at a first temperature for a first time, and when the first reagent is evaporated to a remaining second volume at a second temperature, a liquid is added to adjust the volume of the liquid to a third volume, and the sample solution is obtained by filtration.

[0038] In one embodiment of the present invention, the following description can be combined to further illustrate the specific process of step S110 of "pre-treating the object to be tested; specifically, adding a first volume of a first reagent per gram of the object to be tested, ultrasonically extracting at a first temperature for a first time, adding the first reagent when evaporating to a remaining second volume at a second temperature, adding liquid to adjust the volume of the liquid to a third volume, and filtering to obtain a sample test solution."

[0039] As described in the following steps, the first volume is 10-20 mL;

[0040] As described in the following steps, the first reagent is tert-butyl methyl ether;

[0041] As described in the following steps, the first temperature is 30-50°C;

[0042] As described in the following steps, the first duration is 50-80 minutes;

[0043] As described in the following steps, the second temperature is 30-40°C;

[0044] As described in the following steps, the second volume is 1-2 mL;

[0045] As described in the following steps, the analyte is a solid fragment weighing no more than 5g. The analyte is a small amount of target substance extracted from a target object for testing. This method provides an effective way to obtain various data from the target object without affecting its primary properties. The amount of analyte extracted must be sufficient for 3-5 tests. The sampling area for the analyte must be selected randomly, without subjectivity.

[0046] In one specific implementation, the sample is chopped, 2 g of the homogenized sample is weighed into a 50 mL test tube, 20-40 mL of tert-butyl methyl ether is added, ultrasonic extraction is performed at 40°C for 60 min, the solution is removed, the test tube and the sample residue are rinsed with 10 mL of tert-butyl methyl ether, and the solution is combined into a round-bottom flask. Rotary evaporation is performed at 35°C and 300 mbar until the remaining solution in the flask is about 1 mL. The remaining liquid is then transferred to a 5 mL volumetric flask, the flask is rinsed with a small amount of tert-butyl methyl ether and combined into the volumetric flask, and finally the volume is adjusted with tert-butyl methyl ether.

[0047] As described in step S120, the sample test solution is sampled to obtain the test solution for the machine.

[0048] It should be noted that for routine sampling operations, 1 mL of sample solution is generally taken.

[0049] As described in step S130, the test solution is subjected to qualitative and quantitative analysis by gas chromatography-mass spectrometry.

[0050] The instrument parameters are:

[0051] Instrument: Gas chromatography-mass spectrometry (GC-MS);

[0052] Chromatographic column: DB-624;

[0053] Heating curve: starting temperature 40℃, hold for 1 min, increase to 100℃ at 15℃ / min, then increase to 250℃ at 25℃ / min, hold for 1 min;

[0054] Inlet temperature: 250°C;

[0055] Injection volume: 1 μL;

[0056] Shunt mode: pulse without shunt;

[0057] Data analysis: The external standard method was used for quantitative calculation, and the quantitative and qualitative ions are shown in Table 1:

[0058]

[0059]

[0060] Table 1

[0061] Main technical parameters:

[0062] Linear range (mg / L): 0.02, 0.05, 0.1; correlation coefficient R 2 Greater than 0.995.

[0063] like Figure 2 Shown is the chromatogram of 1-perfluorodecylethanol (10:2FTOH);

[0064] like Figure 3 Shown is the chromatogram of 1-perfluorodecylethyl acrylate (10:2FTA);

[0065] like Figure 4 Shown is the chromatogram of 1-perfluorodecylethyl methacrylate (10:2FTMA);

[0066] like Figure 5 Shown is the chromatogram of 1-iodo-1H,1H,2H,2H-perfluorododecane (10:2FTI);

[0067] like Figure 6 Shown is the chromatogram of 1-perfluorododecylethanol (12:2FTOH);

[0068] like Figure 7 Shown is the chromatogram of 1-iodo-1H,1H,2H,2H-perfluorotetradecane (12:2FTI).

[0069] In one specific implementation, a coating sample is tested.

[0070] Cut the sample into pieces and weigh 2 g into a test tube. Add 100 μL of a 10 mg / L mixed standard stock solution of six substances, add 20-40 mL of tert-butyl methyl ether, and perform ultrasonic extraction at 40°C for 60 min. Take out the solution, rinse the test tube and sample residue with 10 mL of tert-butyl methyl ether, and combine the solution into a round-bottom flask. Rotate and evaporate at 35°C and 300 mbar until the remaining solution in the flask is about 1 mL. Then transfer the remaining liquid to a 5 mL volumetric flask, rinse the flask with a small amount of tert-butyl methyl ether and combine it into the volumetric flask. Finally, make up to volume with tert-butyl methyl ether and filter it onto the machine.

[0071] The spiked recoveries are shown in Table 2:

[0072] name Recovery rate 10:2FTOH 102％ 10:2FTA 104％ 10:2 FTMA 99％ 10:2FTI 108％ 12:2FTI 112％ 12:2FTOH 110％

[0073] Table 2

[0074] Linearity and minimum detection limit:

[0075] Linear range (mg / L): 0.02, 0.05, 0.1; correlation coefficient R 2 =0.995

[0076] Minimum detection limit: 50mg / kg.

[0077] Although preferred embodiments of the present invention have been described, those skilled in the art may make additional changes and modifications to these embodiments once they become aware of the basic inventive concepts. Therefore, the appended claims are intended to be interpreted as including the preferred embodiments and all changes and modifications that fall within the scope of the embodiments of the present invention.

[0078] Finally, it should be noted that, in this document, relational terms such as first and second, etc., are used only to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the terms "comprises," "comprising," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or terminal device that includes a series of elements includes not only those elements, but also other elements not explicitly listed, or elements inherent to such process, method, article, or terminal device. In the absence of further limitations, an element defined by the phrase "comprising a ..." does not exclude the presence of additional identical elements in the process, method, article, or terminal device that includes the element.

[0079] The above is a detailed introduction to the determination method of six non-ionic PFAS in consumer products provided by this application. Specific examples are used herein to illustrate the principles and implementation methods of this application. The description of the above embodiments is only used to help understand the method of this application and its core ideas. At the same time, for those skilled in the art, according to the ideas of this application, there will be changes in the specific implementation methods and application scopes. In summary, the content of this specification should not be understood as limiting this application.

Claims

1. A method for determining six non-ionic PFAS in consumer products, characterized in that: The assay components are 1-perfluorodecylethanol (10:2FTOH), 1-perfluorodecylethyl acrylate (10:2FTA), 1-perfluorodecylethyl methacrylate (10:2FTMA), 1-iodo-1H,1H,2H,2H-perfluorododecane (10:2FTI), 1-perfluorododecylethanol (10:2FTOH) and 1-iodo-1H,1H,2H,2H-perfluorotetradecane (12:2FTI), and include the following steps: Pre-treating the analyte; specifically, adding 10-20 ml of tert-butyl methyl ether per gram of the analyte, ultrasonically extracting at 30-50° C. for a first time, evaporating at a second temperature until 1-2 ml remains, adding tert-butyl methyl ether to adjust the volume to 5 ml, and filtering to obtain a sample test solution; Sampling the sample test solution to obtain the test solution for the machine; The test solution was subjected to qualitative and quantitative analysis by gas chromatography-mass spectrometry; the instrument parameters were as follows: chromatographic column: DB-624; heating curve: starting temperature 40°C, maintained for 1 min, increased to 100°C at 15°C / min, then increased to 250°C at 25°C / min, maintained for 1 min; injection port temperature: 250°C; injection volume: 1 μL; split mode: pulsed without splitting.

2. The measuring method according to claim 1, wherein The first duration is 50-80 minutes.

3. The measuring method according to claim 1, wherein The second temperature is 30-40°C.

4. The measuring method according to claim 1, wherein The object to be tested is a solid fragment with a total amount not greater than 5 g.

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