CN112881553A - Extraction method of perfluoro and polyfluoro compounds - Google Patents
Extraction method of perfluoro and polyfluoro compounds Download PDFInfo
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Abstract
The invention provides a method for extracting perfluoro and polyfluoro compounds. The extraction method of the perfluoro-and polyfluoro-compounds comprises the following steps: (1) under an alkaline condition, leaching a target compound in an environmental solid sample by using an organic reagent, adjusting the pH value, and separating to obtain an extract liquid; (2) purifying the extract by using a SinCHERS column to finish the preparation of a sample detection solution; (3) and detecting and quantifying the target compound by using a high performance liquid chromatography-mass spectrometer. The extraction method provided by the invention can effectively improve the extraction efficiency of the perfluorinated and polyfluorinated compounds in solid samples such as soil, atmospheric particulates, sediments/sludge and the like, shorten the extraction time and reduce the extraction cost.
Description
Technical Field
The invention relates to the technical field of extraction methods, in particular to an extraction method of perfluoro and polyfluoro compounds.
Background
Perfluoro and polyfluoro compounds (PFAS) are a class of aliphatic compounds in which all (perfluoro) or part (polyfluoro) of the hydrogen atoms in the alkyl group are replaced by fluorine atoms in the molecular structure (Buck et al, 2011). PFAS has strong adsorption on solid materials (Gellrich et al, 2012), so that solid media such as soil/atmospheric particulates/sediment/sludge become important sinks for PFAS in the environment, and may become potential sources of such contaminants in other environmental media. In order to improve the extraction efficiency and rapidly analyze the occurrence level of PFAS in the environment and further discuss the risk evaluation and control measures thereof, the improvement of the extraction method of PFAS in the solid environment medium is urgently needed.
At present, the extraction method of PFAS in solid samples such as soil/atmospheric particulates/sediment/sludge and the like is mainly based on a limit extraction technology of solid phase extraction, and the basic flow comprises the following steps: 1) weighing a certain wet or dry weight of the solid sample into a centrifuge tube, and adding an isotopically labeled internal standard compound. 2) Adjusting the pH to alkaline to separate PFAS from the sample matrix by alkaline digestion (alkaline digestion), extracting PFAS from the sample one or more times using an organic solvent (such as methanol or acetonitrile, etc.), accelerating the partition equilibrium of contaminants between the sample matrix and the organic solvent using sonication and shaking techniques, adjusting the pH to neutral, and centrifuging to obtain the supernatant. 3) The resulting supernatant was concentrated by nitrogen-blowing. And if the pigment content of the concentrated solution is higher, removing the pigment by using an ENVI-CARB solid phase extraction column. 4) Redissolving the concentrated organic solvent into a certain volume of ultrapure water, and further purifying by using a solid phase extraction technology, wherein the solid phase extraction column usually adopts a WAX (Weak Anion-eX) solid phase extraction column, the extraction column is sequentially activated by using an ammonia-containing methanol solution, methanol and water before use, then an aqueous solution containing PFAS passes through the extraction column, and the PFAS is adsorbed in the extraction column. Eluting the extraction column with acetate buffer solution, drying the extraction column by vacuum pumping or freeze drying or shade drying, eluting with methanol and ammonia-containing methanol solution in sequence, or only methanol, and collecting eluate. 5) The eluate is concentrated to a small volume (such as 1mL) by nitrogen blowing or rotary evaporation, or is re-dissolved to a small volume (such as 1mL) by methanol or a mixed solution of methanol and ammonium acetate after being concentrated to dryness or nearly dryness. 6) And filtering the concentrated solution, and detecting and quantifying by using a liquid chromatography-mass spectrometer. The above procedures are presented in the papers published in the inventions of Tangli et al (2018), Bossi et al (2008), Higgins et al (2005), Wang et al (2013), Shi et al (2015), Wang et al (2016), Song et al (2018), Wang et al (2019), Zhou et al (2019) and Zhang et al (2020).
The prior art has the following disadvantages: 1) the tedious process of sonication, shaking, centrifugation, transfer, concentration, reconstitution, purification, drying, etc. is very time consuming. 2) The complicated extraction and purification steps lead to the use of more consumables such as organic reagents, ultrapure water, centrifuge tubes, solid-phase extraction columns, high-purity nitrogen and the like in the extraction process, and the cost is higher. 3) The complicated extraction and purification process increases the possibility of target pollutant loss, so that the recovery rate of the method is unstable.
Therefore, the development of a method for improving the extraction efficiency of perfluoro and polyfluoro compounds in solid samples such as soil, atmospheric particulates, sediments, sludge and the like, shortening the extraction time and reducing the extraction cost is a research focus in the field.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for extracting perfluoro-and polyfluoro-compounds. The extraction method can effectively improve the extraction efficiency of the perfluoro and polyfluoro compounds (PFAS) in solid samples such as soil, atmospheric particulates, sediments or sludge and the like, shorten the extraction time and reduce the extraction cost.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for extracting perfluoro-and polyfluoro-compounds, comprising the steps of:
(1) under an alkaline condition, leaching a target compound in an environmental solid sample by using an organic reagent, adjusting the pH value, and separating to obtain an extract liquid;
(2) purifying the extract by using a SinCHERS column to finish the preparation of a sample detection solution;
(3) and detecting and quantifying the target compound by using a high performance liquid chromatography-mass spectrometer.
The extraction method provided by the invention is the first application of the SinCHERS technology in the extraction of perfluoro and polyfluoro compounds in an environmental solid sample. Compared with the traditional sample pretreatment process, the method greatly shortens the time for extracting and purifying the pollutants in the sample, reduces the economic cost, and optimizes the extraction efficiency of certain long-chain perfluoro and polyfluoro compounds.
Preferably, in the step (1), an isotope-labeled compound is added into the environmental solid sample;
preferably, the mass ratio of the environmental solid sample to the isotopically labeled compound is (1-2): (2-10) ng, and may be, for example, 1g:2ng, 1g:4ng, 1g:6ng, 1g:8ng, 1g:10ng, 1.5g:2ng, 1.5g:4ng, 1.5g:6ng, 1.5g:8ng, 1.5g:10ng, 2g:2ng, 2g:3ng, 2g:5ng, 2g:7ng, 2g:9ng, 2g:10ng, etc.
Preferably, in step (1), the pH of the alkaline condition is 12.5-13.5, and may be, for example, 12.5, 12.6, 12.7, 12.8, 12.9, 13.0, 13.1, 13.2, 13.3, 13.4, 13.5, etc.
Preferably, in step (1), the organic reagent is selected from acetonitrile and/or methanol.
Preferably, in the step (1), the leaching with an organic reagent under alkaline conditions comprises the following specific steps: mixing an environmental solid sample and an isotope labeled compound, adding an alkali liquor and a first organic solvent, performing ultrasonic treatment after vortex, adding a second organic solvent, and oscillating.
Preferably, the mass-to-volume ratio of the environmental solid sample to the alkali solution is (1-2) g:1mL, and may be, for example, 1g:1mL, 1.2g:1mL, 1.4g:1mL, 1.6g:1mL, 1.8g:1mL, 2g:1mL, or the like.
Preferably, the concentration of the alkali solution is 0.1-1M (for example, it may be 0.1M, 0.2M, 0.4M, 0.6M, 0.8M, 1M, etc.), and the alkali solution is sodium hydroxide solution.
Preferably, the first organic solvent and the second organic solvent are both acetonitrile.
Preferably, the mass-to-volume ratio of the environmental solid sample to the first organic solvent is (1-2) g:4mL, and may be, for example, 1g:4mL, 1.2g:4mL, 1.4g:4mL, 1.6g:4mL, 1.8g:4mL, 2g:4mL, or the like.
Preferably, the vortex is performed by using a vortex apparatus, the rotation speed of the vortex is 800-1000rpm, such as 800rpm, 850rpm, 900rpm, 950rpm, 1000rpm and the like, and the time of the vortex is 5-10s, such as 5s, 6s, 7s, 8s, 9s, 10s and the like.
Preferably, the ultrasonic treatment is performed by using an ultrasonic cleaning machine, the frequency of the ultrasonic treatment is 45-55kHz, such as 45kHz, 46kHz, 48kHz, 50kHz, 52kHz, 55kHz, etc., and the time of the ultrasonic treatment is 30-40min, such as 30min, 32min, 34min, 36min, 38min, 40min, etc.
Preferably, the mass-to-volume ratio of the environmental solid sample to the second organic solvent is (1-2) g:16mL, and may be, for example, 1g:16mL, 1.2g:16mL, 1.4g:16mL, 1.6g:16mL, 1.8g:16mL, 2g:16mL, or the like.
Preferably, the oscillation is performed by using an oscillator, the rotation speed of the oscillation is 1900-2000rpm, such as 1900rpm, 1920rpm, 1940rpm, 1960rpm, 1980rpm, 2000rpm and the like, and the oscillation time is 30-40min, such as 30min, 32min, 34min, 36min, 38min, 40min and the like.
Preferably, in step (1), the pH is adjusted to 6.5-7.5, for example, 6.5, 6.8, 7.0, 7.2, 7.5, etc., preferably 7.
Preferably, in step (1), hydrochloric acid is used for adjusting the pH.
Preferably, the hydrochloric acid concentration is 1-3M, and may be, for example, 1M, 1.5M, 2M, 2.5M, 3M, or the like.
Preferably, the separation is a centrifugation at 4000-6000rpm (which may be 4000rpm, 4500rpm, 5000rpm, 5500rpm, 6000rpm, etc.), for a period of 4-6min (which may be 4min, 4.5min, 5min, 5.5min, 6min, etc.).
Preferably, in the step (2), the SinCHERS column is made of medical grade polypropylene.
Preferably, in the step (2), the SinCHERS column comprises: exhaust hole, reservoir, deflector, water-blocking gooseneck, sealing washer, porous filter element, purification filler, water-blocking filter element and filtrate funnel.
Air exhaust hole: in the using process, the organic extract liquid enters the liquid storage tank through the filler, and the air in the tank can be exhausted through the vent hole.
Liquid storage tank: storing the purified organic extract.
A guide plate: the SinCHERS column body is guided in the downward process in the centrifugal tube.
Water-blocking gooseneck: and a water-blocking filter disc is arranged in the purification device to ensure that the aqueous solution cannot contact the purification filler and the liquid storage tank.
Sealing rings: the medical-grade silica gel material is used for sealing between the SinCHERS column body and the centrifugal tube.
Porous filter disc: the porous polyethylene filter disc is used for fixing the purification filler.
Purifying and filling: adsorbing impurities dissolved in the organic extract, and purifying the extract. The type of the filler is selected and proportioned according to the conditions of target pollutants and impurities contained in the sample.
A water-blocking filter disc: the porous polyethylene filter is bonded with a strong hydrophobic water-blocking group, so that the organic extract can pass through but the aqueous solution cannot pass through.
A filtrate funnel: the upper organic extraction liquid in the centrifugal tube can be guided to pass through the purification filler and enter the liquid storage tank after purification.
Preferably, the purifying filler is selected from any one of anhydrous sulfate, graphitized carbon black or anion exchange filler or a combination of at least two thereof.
Preferably, the anhydrous sulfate is anhydrous magnesium sulfate and/or anhydrous sodium sulfate.
Preferably, the graphitized carbon black has an interlayer spacing of
Stone ofThe carbon black is inked.
Preferably, the anion exchange filler is an HLB anion exchange material.
Preferably, in the step (2), the step of purifying the extract by using the SinCHERS column to complete the preparation of the sample detection solution comprises the following specific operations: and (3) placing the SinCHERS column into a centrifugal tube filled with the extraction liquid, slowly pressing down the SinCHERS column to ensure that the extraction liquid enters a liquid storage tank of the SinCHERS column after being purified, pressing down the SinCHERS column until the column body of the SinCHERS column cannot descend, and finishing the purification.
Preferably, in the step (2), after the purification is finished, concentration, volume metering and filtration are carried out.
Preferably, the concentration is performed by nitrogen blowing.
Preferably, the constant volume adopts methanol or mixed solution of initial mobile phase proportion.
Preferably, the initial mobile phase is a mixture of ammonium acetate aqueous solution and acetonitrile (volume ratio 8:2), wherein the concentration of the ammonium acetate aqueous solution is 2-10mM, and may be, for example, 2mM, 3mM, 4mM, 5mM, 6mM, 7mM, 8mM, 9mM, 10mM, etc.
Preferably, the filtration is performed using a 0.2 μm GHP pin filter.
Preferably, in the step (3), in the hplc-ms, the chromatographic conditions are as follows: the mobile phase A component is ammonium acetate water solution, the B component is acetonitrile, and gradient elution is adopted.
Preferably, the gradient elution process is specifically: flow rate 0.3mL/min, 0min A fraction 80%, 14min A fraction 10%, 16min A fraction 10%, 16.01min A fraction 80%, 20min A fraction 80%, as follows:
preferably, in the hplc-ms, the mass spectrum conditions are as follows: the sample ionization mode is an electrospray ionization negative ion mode; the data acquisition mode is a multi-reaction detection scanning mode; the ion source temperature is 325 ℃ and 375 ℃ (for example, 325 ℃, 340 ℃, 360 ℃, 370 ℃, 375 ℃ and the like can be adopted); the carrier gas flow rate is 8-10L/min (for example, 8L/min, 8.5L/min, 9L/min, 9.5L/min, 10L/min, etc.); atomizer pressure 30-50psi (e.g., 30psi, 35psi, 38psi, 40psi, 45psi, 50psi, etc.); capillary voltage 3400-3600V (for example, 3400V, 3450V, 3500V, 3550V, 3600V, etc.); the Δ EMV voltage is 200-400V (e.g., 200V, 250V, 300V, 350V, 400V, etc.).
Preferably, in the hplc-ms, the mass spectrum conditions are as follows: the sample ionization mode is an electrospray ionization negative ion mode; the data acquisition mode is a multi-reaction detection scanning mode; the ion source temperature is 350 ℃; the carrier gas flow is 9L/min; atomizer pressure 40 psi; capillary voltage 3500V; the Δ EMV voltage was 400V.
The English and Chinese meanings for the abbreviation comparison table herein are shown in Table 1 below:
TABLE 1
Compared with the prior art, the invention has the following beneficial effects:
(1) the extraction method provided by the invention has the advantages that the extraction efficiency of the perfluorinated and polyfluorinated compounds in solid samples such as soil, atmospheric particulates, sediments/sludge and the like is effectively improved, the extraction time is shortened, and the extraction cost is reduced;
(2) the extraction method provided by the invention is the first application of the SinCHERS technology in the extraction of perfluoro and polyfluoro compounds in an environmental solid sample.
(3) The extraction method of the invention optimizes the recovery rate of some long-chain perfluoro and polyfluoro compounds.
Drawings
FIG. 1 is a schematic view of the external structure of the SinCHERS purification column of the present invention;
wherein, 1 is the exhaust hole, 2 is the reservoir, 3 is the deflector, 4 is the gooseneck that blocks water, 5 is the sealing washer.
FIG. 2 is a schematic view of the internal structure of the SinCHERS purification column of the present invention;
wherein 6 is a porous filter disc, 7 is a purification filler, 8 is a water-blocking filter disc, and 9 is a filter liquid funnel.
FIG. 3 is a schematic diagram of a sample preparation process based on the SinCHERS technique.
FIG. 4 is a chromatogram of 20 PFAS MRMs at a concentration of 100 ppb.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings. It should be understood by those skilled in the art that the specific embodiments are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
1. SinCHERS purification cartridge: the SinCHERS purifying column (called the SinCHERS column for short) is a product (Zhang, 2018) developed by Tianjin Anbang bonding (Anybond) science and technology limited company, and simplifies the traditional solid phase extraction sample purifying process into one step based on an optimized column structure and a using mode thereof. The external structure schematic diagram is shown in fig. 1, wherein 1 is an exhaust hole, 2 is a liquid storage tank, 3 is a guide plate, 4 is a water-blocking gooseneck, and 5 is a sealing ring. The schematic diagram of the internal structure is shown in fig. 2, wherein 6 is a porous filter disc, 7 is a purification filler, 8 is a water-blocking filter disc, and 9 is a filtrate funnel.
2. The main reagents and material sources are as follows: standard samples: PFAC-MXB (containing PFBA, PFPEA, PFHxA, PFHpA, PFOA, PFNA, PFDA, PFUdA, PFDoA, PFTrDA, PFTeDA, PFHxDA, PFODA, PFBS, PFHxS, PFOS, PFDS), HFPO-DA, 9Cl-PF3ONS, 11Cl-PF3OUdS, MPFAC-MXA (containing MPFBA, MPFHxA, MPFOA, MPFDA, MPFUdA, MPFDoA, MPFhXS, MPFOS), M3O-DA, Wellington laboratory, Canada; HPLC grade methanol, acetonitrile, Fisher, usa; analyzing pure sodium hydroxide, Meclin, Shanghai; hydrochloric acid; ammonium acetate (. gtoreq.98%), Sigma, USA; 0.2 μm ghp needle filter, PALL, usa; high purity nitrogen, seashore, beijing; Milli-Q ultrapure water, Millipore, usa; SinCHERS column, Anybond, Tianjin. Column, ACQUITY UPLC BEH C18 column (1.7 μm, 2.1X 100mm), Waters, USA.
3. Main equipment and instrument: agilent 1290 hplc/6460 triple quadrupole mass spectrometry system, Agilent, usa; electric auxiliary tools, Anybond, tianjin; an analytical balance; an ultrasonic cleaner; an oscillator; a centrifuge; a nitrogen blowing instrument.
Example 1
The embodiment provides a method for extracting perfluoro-and polyfluoro-compounds, which comprises the following steps:
(1) weighing 1g of solid sample into a 50 mL centrifuge tube, adding 5ng of isotope labeled compound for internal standard method quantification, adding 1mL of 0.5M sodium hydroxide solution and 4mL of acetonitrile, performing vortex mixing, performing ultrasonic treatment for 30min under a water bath condition, adding 16mL of acetonitrile, performing oscillation for 30min, fully transferring the component to be measured in the sample into organic extract, adding 250 mu L of 2M hydrochloric acid to adjust the pH value, performing vortex mixing, and performing 5000rmp centrifugation for 5 min;
(2) and (3) putting the SinCHERS column into a centrifuge tube, slowly pressing down to enable the supernatant to enter a liquid storage tank after purification, pressing down until the SinCHERS column cannot descend, finishing the purification process, taking out the purified liquid to the centrifuge tube, blowing and concentrating the purified liquid nitrogen to be nearly dry, fixing the volume to 0.5mL by using methanol, and finishing the sample preparation by passing through a 0.2 mu mGHP needle type filter.
Fig. 3 is a schematic diagram of a sample preparation process based on SinCHERS technology, and as shown in fig. 3, the sample preparation process of the present invention specifically includes: firstly, fully leaching a target compound in a solid sample by using an organic reagent under the alkaline pH condition, then adding an acid into a system to adjust the pH value of the system to be neutral, oscillating and centrifuging to ensure that the target compound is distributed and balanced in the system, so that the organic extraction liquid and other components are well layered. And (3) putting the SinCHERS column into a centrifuge tube, slowly pressing down, passing the organic extract through a purification filler for purification, entering a liquid storage tank, taking out liquid in the tank, concentrating, filtering and finishing sample preparation.
(4) And detecting and quantifying the target compound by using a high performance liquid chromatography-mass spectrometer.
Example 2
Analysis conditions of high performance liquid chromatography-mass spectrometer
Chromatographic conditions are as follows: the mobile phase A component is 10mM ammonium acetate water solution, the B component is acetonitrile, gradient elution is adopted, the flow rate is 0.3mL/min, the flow rate of 0min A component is 80%, the flow rate of 14min A component is 10%, the flow rate of 16min A component is 10%, and the flow rate of 16.01-20min A component is 80%; the column temperature of the chromatographic column is 40 ℃; the sample size was 5. mu.L.
Preferably the mass spectrometry conditions: the sample ionization mode is electrospray ionization (ESI) and negative ion mode; the data acquisition mode is a multi-reaction detection scanning mode (MRM); the ion source temperature is 350 ℃; the carrier gas flow is 9L/min; atomizer pressure 40 psi; capillary voltage 3500V; the Δ EMV voltage is 400V. The mass spectrum related parameters of 20 PFAS and 10 internal standards analyzed in the present invention are shown in table 2:
TABLE 2
Example 3
Standard curve and linear range
The standard substance mother liquor is prepared into a mixed standard solution taking methanol as a matrix, the mass concentration of the target compound is 0.01, 0.05, 0.1, 0.5, 1, 5, 10, 50 and 100ng/mL in sequence, and the mass concentration of the internal standard is 5 ng/mL. And sequentially injecting samples under optimized chromatographic and mass spectrum conditions, taking the concentration of the target compound as a horizontal coordinate and taking the relative concentration of the target compound and the internal standard as a vertical coordinate to obtain a standard curve, wherein the correlation coefficients are all more than 0.99.
The standard curves of 20 PFAS analyzed in the present invention were plotted using 9 points, and the standard curves and the correlation coefficients are specifically shown in table 3 below:
TABLE 3
| Target compound | Standard curve y | Coefficient of correlation R2 |
| PFBA | y＝0.973503×x+0.002975 | 0.99948374 |
| PFPeA | y＝0.648839×x+0.001978 | 0.99882159 |
| PFHxA | y＝0.987775×x+0.002726 | 0.99943135 |
| PFHpA | y＝0.733805×x+4.164726E-004 | 0.99954449 |
| PFOA | y＝0.820900×x+0.003527 | 0.99915578 |
| PFNA | y＝1.078512×x+0.001144 | 0.99968788 |
| PFDA | y＝0.813075×x+0.004311 | 0.99892783 |
| PFUdA | y＝0.960112×x+0.001778 | 0.99806305 |
| PFDoA | y＝0.877839×x+9.271068E-004 | 0.99971277 |
| PFTrDA | y＝0.795279×x+8.764125E-004 | 0.99866672 |
| PFTeDA | y＝0.372756×x+5.919902E-004 | 0.99899366 |
| PFHxDA | y＝0.384550×x+0.001586 | 0.99874425 |
| PFODA | y＝0.503981×x-0.001053 | 0.99924742 |
| PFBS | y＝2.174126×x+0.002864 | 0.99655284 |
| PFHxS | y＝2.681708×x+0.011187 | 0.99709442 |
| PFOS | y＝1.294013×x+0.009793 | 0.99573296 |
| PFDS | y＝0.961125×x-0.002001 | 0.99794131 |
| HFPO-DA | y＝1.180868×x+0.005533 | 0.99345773 |
| 9Cl-PF3ONS | y＝4.307754×x-6.738479E-004 | 0.99776625 |
| 11Cl-PF3OUdS | y＝3.085750×x-0.002417 | 0.9977711 |
Example 4
Method detection limit
According to the Method Detection Limit (MDL) determination method provided by the u.s.environmental protection agency, the detection limit of the PFAS method of the present invention can be calculated based on the detection result of the spiked sample by the following formula:
MDLS＝t(n-1，1-α＝0.99)SS
wherein, MDLs is the detection limit of the method based on the labeled sample, t(n-1,1-α＝0.99)The single tail t value, S, at a confidence level of 99%sSpecimen standard for repeated standard sample analysis resultsAnd (5) quasi deviation. Based on this method, the detection limits of the method for obtaining 20 target compounds are shown in table 4:
TABLE 4
| Target compound | MDL(ng/g dw) | Target compound | MDL(ng/g dw) |
| PFBA | 0.95 | PFTeDA | 1.03 |
| PFPeA | 0.75 | PFHxDA | 1.44 |
| PFHxA | 0.97 | PFODA | 1.07 |
| PFHpA | 0.70 | PFBS | 0.80 |
| PFOA | 0.48 | PFHxS | 1.27 |
| PFNA | 0.64 | PFOS | 0.58 |
| PFDA | 0.75 | PFDS | 0.46 |
| PFUdA | 0.62 | HFPO-DA | 2.31 |
| PFDoA | 1.06 | 9Cl-PF3ONS | 0.55 |
| PFTrDA | 0.95 | 11Cl-PF3OUdS | 0.68 |
Example 5
Process recovery of target compound
Taking soil of a rural grassland in Coheuman county, Twenty-Tung county, Henan province, Tibetan, Qinghai province, drying, homogenizing and grinding the soil to 100 meshes, taking the soil as a soil matrix, adding 10ng of each target compound, carrying out PFAS detection according to the steps in the example 1, and calculating the standard-adding recovery rate after deducting the background value. The process recoveries to obtain 20 PFAS are shown in table 5:
TABLE 5
Example 6
MRM chromatogram of target Compound
The MRM chromatograms of the 20 target compounds at a concentration of 100ppb are shown in fig. 4: as can be seen from FIG. 4, the method of the present invention can rapidly detect 20 perfluoro and polyfluoro compounds within 15 min.
The applicant states that the present invention is illustrated by the above examples of the extraction method of perfluoro and polyfluoro compounds, but the present invention is not limited to the above examples, i.e. it does not mean that the present invention must rely on the above examples to be carried out. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A method for extracting perfluoro-and polyfluoro-compounds, which is characterized by comprising the following steps:
(1) under an alkaline condition, leaching a target compound in an environmental solid sample by using an organic reagent, adjusting the pH value, and separating to obtain an extract liquid;
(2) purifying the extract by using a SinCHERS column to finish the preparation of a sample detection solution;
(3) and detecting and quantifying the target compound by using a high performance liquid chromatography-mass spectrometer.
2. The method for extracting perfluoro and polyfluoro compounds according to claim 1, wherein in step (1), an isotopically labeled compound is added to the environmental solid sample;
preferably, the mass ratio of the environmental solid sample to the isotopically labeled compound is (1-2) g (2-10) ng.
3. The extraction process of perfluoro and polyfluoro compounds according to claim 1 or 2, wherein in step (1), the pH of the alkaline condition is 12.5 to 13.5;
preferably, in step (1), the organic reagent is selected from acetonitrile and/or methanol.
4. The extraction method of perfluoro and polyfluoro compounds according to any of the claims 1 to 3, wherein the leaching with organic reagent under alkaline condition in the step (1) comprises the following specific steps: mixing an environmental solid sample and an isotope labeled compound, adding an alkali liquor and a first organic solvent, performing ultrasonic treatment after vortex, adding a second organic solvent, and oscillating.
5. The method for extracting perfluoro and polyfluoro compounds according to claim 4, wherein the mass-to-volume ratio of the environmental solid sample to the alkali solution is (1-2) g:1 mL;
preferably, the concentration of the alkali liquor is 0.1-1M, and the alkali liquor is a sodium hydroxide solution;
preferably, the first organic solvent and the second organic solvent are both acetonitrile;
preferably, the mass-to-volume ratio of the environmental solid sample to the first organic solvent is (1-2) g:4 mL;
preferably, the vortex is performed by a vortex instrument, the rotation speed of the vortex is 800-1000rpm, and the time of the vortex is 5-10 s;
preferably, the ultrasonic treatment is carried out by using an ultrasonic cleaning machine, the frequency of the ultrasonic treatment is 45-55kHz, and the time of the ultrasonic treatment is 30-40 min;
preferably, the mass-to-volume ratio of the environmental solid sample to the second organic solvent is (1-2) g:16 mL;
preferably, the oscillation is performed by using an oscillator, the rotation speed of the oscillation is 1900-2000rpm, and the oscillation time is 30-40 min.
6. The extraction process of perfluoro and polyfluoro compounds according to any of claims 1 to 5, wherein in step (1), the pH adjustment is to adjust the pH to 6.5 to 7.5, preferably to 7;
preferably, in the step (1), hydrochloric acid is used for adjusting the pH;
preferably, the hydrochloric acid concentration is 1-3M;
preferably, the separation is centrifugation, the rotation speed of the centrifugation is 4000-6000rpm, and the time of the centrifugation is 4-6 min.
7. The method for extracting perfluoro and polyfluoro compounds according to any one of claims 1 to 6, wherein in the step (2), the SinCHERS column is made of medical grade polypropylene;
preferably, in the step (2), the SinCHERS column comprises: the device comprises an exhaust hole, a liquid storage tank, a guide plate, a water-blocking gooseneck, a sealing ring, a porous filter disc, a purification filler, a water-blocking filter disc and a filtrate funnel;
preferably, the purifying filler is selected from any one of or a combination of at least two of anhydrous sulfate, graphitized carbon black or anion exchange filler, preferably the combination of anhydrous sulfate, graphitized carbon black and anion exchange filler.
8. The method for extracting perfluoro and polyfluoro compounds according to any one of claims 1 to 7, wherein the step (2) of purifying the extract by using a SinCHERS column to complete the preparation of the sample detection solution comprises the following specific operations: and (3) placing the SinCHERS column into a centrifugal tube filled with the extraction liquid, slowly pressing down the SinCHERS column to ensure that the extraction liquid enters a liquid storage tank of the SinCHERS column after being purified, pressing down the SinCHERS column until the column body of the SinCHERS column cannot descend, and finishing the purification.
9. The method for extracting perfluoro and polyfluoro compounds according to any one of claims 1 to 8, wherein in the step (2), the purification is completed and then concentration, constant volume and filtration are carried out;
preferably, the concentration is performed by nitrogen blowing;
preferably, the constant volume adopts methanol or a mixed solution with an initial mobile phase proportion;
preferably, the filtration is performed using a 0.2 μm GHP pin filter.
10. The extraction method of perfluoro and polyfluoro compounds according to any one of claims 1 to 9, wherein in the step (3), the conditions of chromatography in the hplc are as follows: the mobile phase A component is ammonium acetate water solution, the B component is acetonitrile, and gradient elution is adopted;
preferably, the gradient elution process is specifically: the flow rate is 0.3mL/min, the flow rate is 0min 80% of the A component, 14min 10% of the A component, 16min 10% of the A component, 16.01min 80% of the A component and 20min 80% of the A component;
preferably, in the hplc-ms, the mass spectrum conditions are as follows: the sample ionization mode is an electrospray ionization negative ion mode; the data acquisition mode is a multi-reaction detection scanning mode; the ion source temperature is 325-375 ℃; the carrier gas flow is 8-10L/min; atomizer pressure 30-50 psi; capillary voltage 3400-3600V; the Δ EMV voltage was 200-400V.
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| CN115025518B (en) * | 2022-05-11 | 2024-04-12 | 美罗医药科技有限公司 | Extraction separation column for liquid-liquid extraction, liquid-liquid extraction separation device, separation method and application |
| WO2024041610A1 (en) * | 2022-08-24 | 2024-02-29 | 中国科学院生态环境研究中心 | Method for determination of concentrations of per- and polyfluoroalkyl substances, and liquid chromatography-tandem mass spectrometry system |
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