Collaborative analysis and detection methods of PFASs and CUPs in water and their applications

Abstract

The present invention discloses a collaborative analysis and detection method for PFASs and CUPs in water bodies and its application. The detection method of the present invention comprises the following steps: activating solid phase extraction columns and connecting them in series, adding a recovery indicator to a water sample, loading the water sample onto a solid phase extraction column, eluting the solid phase extraction column with methanol and 1% ammonia methanol, respectively, to collect 32 CUPs and 29 PFASs, combining the eluates and concentrating them to 0.5 mL. After passing through a 0.22 μm filter membrane, an internal standard is added, and the target compound is determined by LC-MS / MS. This method can simultaneously enrich 29 PFASs and 32 CUPs in water bodies, and has the characteristics of short processing time, high detection accuracy and good reproducibility.

Description

Technical Field

[0001] The present invention belongs to the field of environmental analysis, and mainly relates to a collaborative analysis and detection method and application of PFASs and CUPs in water. Background Art

[0002] Per- and polyfluoroalkyl substances (PFASs) are a class of emerging persistent organic pollutants (POPs) in which all or part of the hydrogen atoms on their carbon chains are replaced by fluorine atoms. PFASs possess properties such as high stability, high surface activity, and high chemical inertness, making them widely used as additives and surfactants in industry and finished product manufacturing. Currently, there is a wide variety of pesticides (CUPs), primarily including organophosphorus pesticides, carbamate pesticides, and neonicotinoid pesticides. CUPs are widely used in agricultural production and daily life. Studies have shown that PFASs and CUPs have multiple toxic effects, including reproductive and developmental toxicity, endocrine disruption, and neurotoxicity. PFASs and CUPs have been detected in various media, including water, soil, the atmosphere, and biological samples. Water is a significant reservoir of PFASs and CUPs in the environment. Currently, there is a lack of collaborative analytical and detection methods for PFASs and CUPs in water. Therefore, the present invention provides a collaborative analytical and detection method for PFASs and CUPs in water. Summary of the Invention

[0003] The purpose of the present invention is to overcome the shortcomings of the existing technology and provide a collaborative analysis and detection method for PFASs and CUPs in water bodies to improve the analysis and detection efficiency of PFASs and CUPs in water samples.

[0004] Another object of the present invention is to provide an application of the above-mentioned collaborative analysis and detection method for PFASs and CUPs in water.

[0005] The purpose of the present invention is achieved through the following technical solutions:

[0006] The specific steps of the collaborative analysis and detection method for PFASs and CUPs in water are as follows:

[0007] (1) Activate WAX ​​solid phase extraction column and HLB solid phase extraction column;

[0008] (2) Connect the column tube, WAX and HLB solid phase extraction columns in order from top to bottom;

[0009] (3) Filter samples;

[0010] (4) Add the sample to the column tube and pass it through the WAX ​​and HLB solid phase extraction columns in sequence for adsorption;

[0011] (5) After adsorption is complete, the WAX ​​and HLB solid phase extraction columns are eluted, and the eluate is collected and concentrated;

[0012] (6) The concentrated eluate was filtered, an internal standard was added, and PFASs and CUPs were detected using liquid chromatography-mass spectrometry (LC-MS / MS).

[0013] The HLB solid phase extraction column described in step (1) is an Oasis HLB column (60 mg / 3 mL, Waters).

[0014] The WAX ​​solid phase extraction column described in step (1) is an Oasis WAX cartridge (60 mg / 3 mL, Waters).

[0015] The activated HLB solid phase extraction column in step (1) is activated by sequentially adding 10 mL of ethyl acetate, 10 mL of methanol and 5 mL of ultrapure water into the HLB solid phase extraction column.

[0016] The activation of the WAX ​​solid phase extraction column in step (1) is performed by sequentially adding 4 mL of methanol containing 1% ammonia water, 4 mL of methanol, and 4 mL of ammonium acetate buffer solution with a pH of 4 to the WAX ​​solid phase extraction column for activation.

[0017] The sample described in step (3) is a liquid sample; preferably a water sample.

[0018] The filtration in step (3) is performed through a 0.45 μm filter membrane.

[0019] A recovery indicator is also added to the sample described in step (3); preferably, the added PFASs recovery indicator is at least one of M3-PFBA, M3-PFBS, M-PFHxA, M-PFHxS, M-PFOA, M2-8:2FTCA, M-PFOS, D3-MeFOSA, and MPFUnDA, and the CUPs recovery indicator is at least one of D5-Atrazine, D4-Thiamethoxam, D3-Clothianidin, and D3-Acetamiprid; more preferably, the spiked amounts of PFASs and CUPs recoveries are 10 ng and 25 ng, respectively.

[0020] The sample flow rate in step (4) is controlled at 3-10 mL / min, preferably 5 mL / min.

[0021] The elution in step (5) is to sequentially elute the WAX ​​and HLB columns with 4 mL of methanol and 4 mL of methanol containing 1% ammonia water.

[0022] The eluate collected in step (5) is collected using a 15 mL polypropylene (PP) centrifuge tube.

[0023] The concentration in step (5) is performed by concentrating the solution to 0.5 mL using a gentle nitrogen stream in a water bath at 35-45° C.; preferably, the solution is concentrated to 0.5 mL using a gentle nitrogen stream in a water bath at 38° C.

[0024] The filtration in step (6) is performed using a 0.22 μm organic filter membrane.

[0025] The internal standard described in step (6) is a PFASs internal standard and / or a CUPs internal standard, the PFASs internal standard is at least one of MPFBA, M8PFOA, M7PFUnDA, M3PFHxS, and M8PFOS, and the CUPs internal standard is at least one of D10-Chlorpyrifos, D14-Trifluralin, D3-Dinotefuran, and D4-Imidacloprid; preferably, the added amount of the PFASs internal standard is 10 ng each, and the added amount of the CUPs internal standard is 25 ng each.

[0026] The liquid chromatography-mass spectrometry detection of PFASs and CUPs in step (6) is to use a Thermo Scientific Vanquish LC-MS / MS to detect PFASs and CUPs in the concentrate.

[0027] The above-mentioned liquid chromatography conditions for detecting PFASs are:

[0028] A ZORBAX Extend-C18 column was used to separate different PFASs based on two elution procedures;

[0029] Elution procedure 1:

[0030] The PFASs analyzed included 4:2monoPAP, PFBA, 6:2monoPAP, PFPeA,

[0031] 4:2FTSA, PFBS, PFPeS, PFHpA, ADONA, 6:2FTSA, PFOA, PFHpS, 8:2FTUCA, PFNA, 8:2FTS, PFDA, 6:2Cl-PFESA, PFUnDA, PFDS, PFDoDA, 8:2Cl-PFESA, 6:6PFPiA, PFTrDA, 6:2diPAP, 6:8PFPiA, 8:2diPAP;

[0032] Mobile phase A: 2 mM ammonium acetate aqueous solution, pH = 10.25;

[0033] Mobile phase B: 5 mM 1-MP ACN:MeOH solution (volume ratio = 1:1);

[0034] The column temperature was 35°C, the flow rate was 0.25 mL / min, the gradient curve was 5, the injection volume was 2 μL, and the total run time was 18 min;

[0035] The specific gradient elution program is as follows: from 0 to 1.1 minutes, the volume percentage of mobile phase B is 10%; from 1.1 to 2.0 minutes, the volume percentage of mobile phase B is increased to 45%; from 2.0 to 8.0 minutes, the volume percentage of mobile phase B is increased to 90% and maintained for 6.9 minutes, and within 0.1 minutes, the volume percentage of mobile phase B is reduced to 10% and maintained for 3 minutes;

[0036] Elution procedure 2:

[0037] The PFASs analyzed included PFHxS, PFHxA, and PFOS;

[0038] Mobile phase A: 2 mM ammonium acetate in water;

[0039] Mobile phase B: methanol solution containing 2 mM ammonium acetate;

[0040] The column temperature was 35°C, the flow rate was 0.30 mL / min, the gradient curve was 5, the injection volume was 2 μL, and the total run time was 12 min;

[0041] The specific gradient elution program is: from 0 to 1.0 min, the volume percentage of mobile phase B increases from 10% to 100% and is maintained for 1 min; from 2.0 to 8.0 min, the volume percentage of mobile phase B decreases from 100% to 10%; and then is maintained for 12.0 min.

[0042] The above-mentioned mass spectrometry conditions for detecting PFASs are:

[0043] Quantitative analysis was performed using electrospray ionization in selected reaction monitoring mode with the following mass spectrometry parameters: spray voltage of 2500 V, sheath gas and auxiliary gas flows of 40 and 10 Arb, respectively; ion transfer tube temperature of 400°C, and heater temperature of 350°C. Qualitative and quantitative analysis was performed using X-Calibur software. Qualitative analysis was based on ion pair information and retention time, while quantitative analysis was performed using the internal standard method and a multipoint calibration standard curve.

[0044] The above-mentioned liquid chromatography conditions for detecting CUPs are:

[0045] Acclaim chromatographic column TM RSLC 120C18 2.2μm Column temperature 40°C;

[0046] Mobile phase A: ultrapure water containing 0.2% formic acid;

[0047] Mobile phase B: methanol containing 2 mM ammonium formate;

[0048] The column temperature was 40°C, the gradient curve was 5, the injection volume was 2 μL, and the total run time was 23 min;

[0049] The specific gradient elution program is: from 0 to 0.5 min, the mobile phase flow rate is maintained at 0.3 mL / min, and the percentage of mobile phase B is 0%; from 0.5 to 1.0 min, the percentage of mobile phase B is increased to 50%; from 1.0 to 19.0 min, the percentage of mobile phase B is increased to 100% and maintained for 0.1 min, from 19.1 to 20.4 min, the mobile phase flow rate is maintained at 0.4 mL / min, and the percentage of mobile phase B is 100%; from 20.4 to 20.5 min, the mobile phase flow rate is maintained at 0.3 mL / min, and the percentage of mobile phase B is reduced to 2%; from 20.5 to 23.0 min, the percentage of mobile phase B is reduced to 0%.

[0050] The above-mentioned conditions for detecting mass spectra in CUPs are:

[0051] CUPs were quantitatively analyzed using electrospray ionization and selected reaction detection mode. The mass spectrometry parameters were as follows: sheath gas and auxiliary gas flow rates were 40 and 8 Arb, respectively, and the spray voltage was 3500 V. The ion transfer tube temperature was 300°C, and the heater temperature was 350°C. Qualitative and quantitative analysis was performed using X-Calibur. Qualitative analysis was based on ion pair information and retention time, while quantitative analysis was performed using the internal standard method and a multi-point calibration standard curve.

[0052] The PFASs include at least one of 4:2monoPAP, PFBA, 6:2monoPAP, PFPeA, 4:2FTSA, PFBS, PFPeS, PFHpA, ADONA, 6:2FTSA, PFOA, PFHpS, 8:2FTUCA, PFNA, 8:2FTS, PFDA, 6:2Cl-PFESA, PFUnDA, PFDS, PFDoDA, 8:2Cl-PFESA, 6:6PFPiA, PFTrDA, 6:2diPAP, 6:8PFPiA, 8:2diPAP, PFHxS, PFHxA, and PFOS.

[0053] The CUPs include desethylatrazine (CIAT), prometon, bromacil, carbaryl, ametryn, atrazine, diuron, azoxystrobin, trifluralin, boscalid, pronamide, metolachlor, desulfinylfipronil, fipronil, dinoterufan, thiacloprid-amide, thiamethoxam, flonicamid, cloth At least one of ianidin-desmethyl, clothianidin-desmethyl(TZNG), nitenpyram, imidacloprid, thiacloprid, clothianidin, imidaclothiz, n-desmethyl-thiamethoxam, dicama, acetamiprid, acetamiprid-n-desmethyl, dimethoate, sulfoxaflor, and imidacloprid-olefin.

[0054] The application of the above-mentioned collaborative analysis and detection method of PFASs and CUPs in water in the detection of water pollutants.

[0055] The present invention has the following advantages and effects compared to the prior art:

[0056] 1. This invention achieves the simultaneous enrichment of PFASs and CUPs in water by connecting WAX and HLB solid-phase extraction columns in series, simplifying sample pretreatment and significantly shortening enrichment time. Application of this invention to the analysis of PFASs and CUPs in water yielded recoveries ranging from 80% to 120% for all recovery indicators.

[0057] 2. Provides a method for simultaneously enriching, purifying, and concentrating 61 organic pollutants in water, including 29 PFASs and 32 CUPs. This method simplifies the coordinated extraction of PFASs and CUPs from water, saving time for sample analysis and cleanup. It also provides a targeted instrumental detection method for these compounds, boasting high recovery rates for target compounds and excellent reproducibility. BRIEF DESCRIPTION OF THE DRAWINGS

[0058] Figure 1 This is a schematic diagram of the solid phase extraction cartridge connection.

[0059] Figure 2 This is a graph showing the recovery rates of PFASs and CUPs in the examples.

[0060] Figure 3 This is a graph showing the recovery rates of PFASs in Comparative Example 1 and Comparative Example 2.

[0061] Figure 4 This is a graph showing the recovery rates of PFASs in Comparative Examples 3 and 4.

[0062] Figure 5 This is a graph showing the recovery rates of PFASs in Comparative Examples 5 and 6.

[0063] Figure 6 This is a graph showing the recovery rates of CUPs in Comparative Examples 1 and 2.

[0064] Figure 7 This is a graph showing the recovery rates of CUPs in Comparative Examples 3 and 4.

[0065] Figure 8 This is a graph showing the recovery rates of CUPs in Comparative Examples 5 and 6. DETAILED DESCRIPTION

[0066] The present invention will be further described below by way of specific embodiments, but the embodiments of the present invention are not limited to the following embodiments.

[0067] Example 1

[0068] (1) An HLB solid-phase extraction column (Oasis HLB cartridge, 60 mg / 3 mL, Waters) was activated with 10 mL of ethyl acetate, 10 mL of methanol, and 5 mL of ultrapure water, followed by activation of a WAX solid-phase extraction column (Oasis WAX cartridge, 60 mg / 3 mL, Waters) with 4 mL of methanol containing 1% ammonia, 4 mL of methanol, and 4 mL of ammonium acetate buffer solution at pH 4.

[0069] (2) Connect the activated column in step (1) to the 60 mL column tube. The order of connection from top to bottom is 60 mL column tube, WAX column and HLB column.

[0070] (3) To 1 L of water sample (filtered through a 0.45 μm glass fiber filter), 10 ng each of M3-PFBA, M3-PFBS, M-PFHxA, M-PFHxS, M-PFOA, M2-8:2FTCA, M-PFOS, D3-MeFOSA, MPFUnDA and 25 ng each of D5-atrazine, D4-thiamethoxam, D3-clothianidin, and D3-acetamiprid recovery indicator were added in sequence.

[0071] (4) The spiked water sample in step (3) was loaded into the column tube described in step (2) at a flow rate of 5 mL / min.

[0072] (5) After the water sample is adsorbed, the small column in step (4) is vacuum dried for 1 min, and then the small column in step (4) is eluted with 4 mL of methanol and 4 mL of methanol containing 1% ammonia water, respectively, with the flow rate controlled at 3 seconds / drop. At the same time, the eluate is collected in a 15 mL PP centrifuge tube and the collected eluate is concentrated to 0.5 mL at 38°C using a gentle nitrogen flow.

[0073] (6) The concentrated solution obtained in step (5) was filtered through a 0.22 μm organic filter membrane, and 10 ng of each of MPFBA, M8PFOA, M7PFUnDA, M3PFHxS, and M8PFOS and 25 ng of each of D3-dinotefuran and D4-imidacloprid internal standard compounds were added, and then the target PFASs and CUPs were detected using LC-MS / MS.

[0074] PFASs tested include 4:2monoPAP, PFBA, 6:2monoPAP, PFPeA, 4:2FTSA, PFBS, PFPeS, PFHpA, ADONA, 6:2FTSA, PFOA, PFHpS, 8:2FTUCA, PFNA, 8:2F TS, PFDA, 6:2Cl-PFESA, PFUnDA, PFDS, PFDoDA, 8:2Cl-PFESA, 6:6PFPiA, PFTrDA, 6:2diPAP, 6:8PFPiA, 8:2diPAP, PFHxS, PFHxA, PFOS;

[0075] CUPs include CIAT, prometon, bromacil, carbaryl, ametryn, atrazine, diuron, azoxystrobin, trifluralin, boscalid, pronamide, metolachlor, desulfinyllfipronil, fipronil, dinoterufan, thiacloprid-amide, thiamethoxam, flonicamid, clothianidin-desmethyl, TZNG, nitenpyram, imidacloprid, thiacloprid, clothianidin, imidaclothiz, n-desmethyl-thiamethoxam, dicama, acetamiprid, acetamiprid-n-desmethyl, dimethoate, sulfoxaflor, imidacloprid-olefin.

[0076] In step (6), Thermo Scientific Vanquish LC-MS / MS was used to detect PFASs and CUPs in the concentrate. A ZORBAX Extend-C18 column (3×150 mm, 3.5 μm, Agilent Technologies, USA) was used to separate different PFASs based on two elution procedures. Elution procedure 1: The mobile phases were 2 mM ammonium acetate aqueous solution (A) at pH = 10.25 and 5 mM 1-MP ACN:MeOH (v:v, 1:1) solution (B), column temperature 35°C, injection volume 2 μL, and total run time 18 min. The PFASs analyzed included: 4:2monoPAP, PFBA, 6:2monoPAP, PFPeA,

[0077] 4:2FTSA, PFBS, PFPeS, PFHpA, ADONA, 6:2FTSA, PFOA, PFHpS,

[0078] 8:2FTUCA, PFNA, 8:2FTS, PFDA, 6:2Cl-PFESA, PFUnDA, PFDS, PFDoDA, 8:2Cl-PFESA, 6:6PFPiA, PFTrDA, 6:2diPAP, 6:8PFPiA, 8:2diPAP. The specific gradient elution program is:

[0079] Table 1 Liquid phase elution procedure of PFASs in group 1

[0080]

[0081] Elution procedure 2: The mobile phases were 2 mM ammonium acetate in water (A) and 2 mM ammonium acetate in methanol (B), respectively. The column temperature was 35°C, the injection volume was 2 μL, and the total run time was 12 min. The PFASs analyzed included: PFHxS, PFHxA, and PFOS. The specific gradient elution procedure was:

[0082] Table 2 Liquid phase elution procedures for PFASs in the second group

[0083]

[0084]

[0085] PFASs were quantitatively analyzed using electrospray ionization in selected reaction monitoring mode. Mass spectrometry parameters were as follows: spray voltage 2500 V, sheath gas and auxiliary gas flows of 40 and 10 Arb, respectively. Ion transfer tube temperature was 400°C, and heater temperature was 350°C. Qualitative and quantitative analysis was performed using an X-Calibur. Ion pair information and retention time were used for qualitative analysis, while internal standard analysis and multipoint calibration were used for quantitative analysis. CAS and ion pair information for the 29 PFASs are shown in Table 3.

[0086] Table 3 CAS number and ion pair information of PFASs

[0087]

[0088]

[0089] PFASs standards were purchased from Wellington Laboratories Inc., Canada, and CUPs standards were purchased from Shanghai Anpu Cuishi Standard Technology Co., Ltd.

[0090] The parameters of the CUPs high-performance liquid chromatography are as follows: the chromatographic column is Acclaim TM RSLC 120C18 2.2μm (2.1×100 mm); column temperature 40°C; mobile phases were ultrapure water containing 0.2% formic acid (A) and methanol containing 2 mM ammonium formate (B). The liquid phase gradient elution program was:

[0091] Table 4 CUPs liquid phase elution program

[0092]

[0093] CUPs were quantitatively analyzed using electrospray ionization in selected reaction detection mode. Mass spectrometry parameters were as follows: sheath gas and auxiliary gas flows of 40 and 8 Arb, respectively, and a spray voltage of 3500 V. The ion transfer tube temperature was 300°C, and the heater temperature was 350°C. Qualitative and quantitative analysis was performed using an X-Calibur. Ion pair information and retention time were used for qualitative analysis, while internal standard analysis and multipoint calibration were used for quantitative analysis. CAS and ion pair information for the 32 CUPs are shown in Table 5.

[0094] Table 5 CAS number and ion pair information of CUPs

[0095]

[0096] The linear equation and correlation coefficient (r) of the standard curve in the detection and analysis of PFASs and CUPs 2 ), linear range (ng / L) and limit of quantification (ng / L) are shown in Table 6.

[0097] Table 6 Linear range, linear equation, correlation coefficient and quantification limit of PFASs and CUPs

[0098]

[0099]

[0100] Comparative Example 1:

[0101] The experimental procedures were consistent with those in Example 1, except that in step (5), 7 mL of methanol and 7 mL of 1% ammonia in methanol were used to elute the cartridge. After sample enrichment and concentration, the target PFASs and CUPs were detected using LC-MS / MS, consistent with the example.

[0102] Comparative Example 2:

[0103] The experimental procedures were consistent with those in Example 1, except that in step (5), 7 mL of methanol and 7 mL of 2% ammonia in methanol were used to elute the cartridge. After sample enrichment and concentration, the target PFASs and CUPs were detected using LC-MS / MS, consistent with the example.

[0104] Comparative Example 3:

[0105] The experimental procedures were consistent with those in Example 1, except that in step (5), 7 mL of methanol and 7 mL of 3% ammonia in methanol were used to elute the cartridge. After sample enrichment and concentration, the target PFASs and CUPs were detected using LC-MS / MS, consistent with the example.

[0106] Comparative Example 4:

[0107] The experimental procedures were consistent with those in Example 1, except that only 7 mL of 1% ammonia methanol was used to elute the cartridge in step (5). After sample enrichment and concentration, the target PFASs and CUPs were detected using LC-MS / MS, consistent with the example.

[0108] Comparative Example 5:

[0109] The experimental procedures were consistent with those in Example 1, except that only a WAX solid-phase extraction column was used for purification. In step (1), only the WAX ​​solid-phase extraction column was activated, omitting the assembly step (2). In step (4), the water sample was loaded onto the WAX ​​solid-phase extraction column. After sample enrichment and concentration, the target PFASs and CUPs were detected using LC-MS / MS, consistent with the example.

[0110] Comparative Example 6:

[0111] The experimental procedures were consistent with those in Example 1, except that only an HLB solid-phase extraction column was used for purification. In step (1), only the HLB solid-phase extraction column was activated, omitting the assembly step (2). In step (4), the water sample was loaded onto the HLB solid-phase extraction column. After sample enrichment and concentration, the target PFASs and CUPs were detected using LC-MS / MS, consistent with the example.

[0112] The spiked amount (ng), average recovery rate and relative standard deviation (RSD) of each target compound in the examples and comparative examples are shown in Tables 7 to 8. Figures 2 to 8 shown.

[0113] Table 7 The spiked amount (ng), average recovery rate and relative standard deviation (RSD) of each target compound in Examples and Comparative Examples 1 to 3

[0114]

[0115]

[0116] Table 8: The spiked amount (ng), average recovery rate and relative standard deviation (RSD) of each target compound in Examples and Comparative Examples 4 to 6

[0117]

[0118]

[0119]

[0120] Analysis of the experimental results of this embodiment and comparative example:

[0121] The average recoveries of the target PFASs and CUPs ranged from 60% to 120%. The average recovery of the recovery indicator ranged from 80% to 120%, demonstrating the high recovery and good reproducibility of this method. The average recoveries of the target compounds and the recovery indicator are shown in Table 7.

[0122] Using the experimental methods in Comparative Examples 1, 2, 3, 4, 5 and 6, the average recoveries of the target PFASs were 40% to 120%, 55% to 130%, 50% to 120%, 50% to 130%, 60% to 160% and 0% to 130%, respectively; the average recoveries of the target CUPs were 50% to 165%, 60% to 120%, 50% to

[0123] The average recovery rates of PFASs recovery rate indicators were 75% to 100%, 70% to 100%, 70% to 100%, 50% to 90%, 90% to 120%, respectively.

[0124] 140% and 3% to 130%; the average recovery rates of CUPs recovery indicators were 110% to 130%,

[0125] The average recovery rates and relative standard deviations of the target compounds in Comparative Examples 1, 2, 3, 4, 5 and 6 are shown in Tables 7 and 8.

[0126] Compared with the examples, the relative standard deviations of 6:2diPAP, 6:8PFPiA, and 8:2diPAP in Comparative Examples 1, 2, 3, and 4 were large, the reproducibility was low, and the recovery rate of CIAT was low; the recovery rate of dicama in Comparative Example 1 was too high (165%); the recovery rate of Comparative Example 2 fluctuated widely, as manifested in that the recovery rate of PFBA was too low (57%), while the recovery rate of 4:2monoPAP was too high (130%); the recovery rate of 4:2monoPAP in PFASs in Comparative Example 5 exceeded 150%, and the recoveries of pronamide and metolachlor in CUPs were low; the recovery rate of 6:2monoPAP in Comparative Example 6 was 0, and 4:2monoPAP, PFBA, PFPeA, and M3PFBA(SS) also showed very low recovery levels, with recoveries of 30%, 17%, 28%, and 3%, respectively.

[0127] From the above results, it can be concluded that this experimental method can be used for the coordinated analysis and detection of PFASs and CUPs in water bodies, with high recovery rate of target compounds and good reproducibility.

[0128] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be considered as equivalent replacement methods and are included in the scope of protection of the present invention.

Claims

1. A collaborative analysis and detection method for PFASs and CUPs in water, characterized by The specific steps are as follows: (1) Activation of WAX solid phase extraction columns and HLB solid phase extraction columns; (2) Connect the column tube, WAX and HLB solid phase extraction columns in order from top to bottom; (3) Filter samples; (4) Add the sample to the column tube and pass it through the WAX ​​and HLB solid phase extraction columns in sequence for adsorption; (5) After adsorption is completed, the WAX ​​and HLB solid phase extraction columns are eluted, and the eluate is collected and concentrated; (6) Filter and concentrate the eluate, add internal standard, and then use liquid chromatography-mass spectrometry to detect PFASs and CUPs; The HLB solid phase extraction column in step (1) is an Oasis HLB column; The WAX ​​solid phase extraction column in step (1) is an Oasis WAX column; The activated HLB solid phase extraction column in step (1) is activated by sequentially adding 10 mL of ethyl acetate, 10 mL of methanol and 5 mL of ultrapure water to the HLB solid phase extraction column; The activation of the WAX ​​solid phase extraction column in step (1) is performed by sequentially adding 4 mL of methanol containing 1% ammonia water, 4 mL of methanol, and 4 mL of ammonium acetate buffer solution with a pH of 4 to the WAX ​​solid phase extraction column for activation; The elution in step (5) is to sequentially elute the WAX ​​column and the HLB column with 4 mL of methanol and 4 mL of methanol containing 1% ammonia water; The PFASs include at least one of 4:2monoPAP, PFBA, 6:2monoPAP, PFPeA, 4:2FTSA, PFBS, PFPeS, PFHpA, ADONA, 6:2FTSA, PFOA, PFHpS, 8:2FTUCA, PFNA, 8:2FTS, PFDA, 6:2Cl-PFESA, PFUnDA, PFDS, PFDoDA, 8:2Cl-PFESA, 6:6PFPiA, PFTrDA, 6:2diPAP, 6:8PFPiA, 8:2diPAP, PFHxS, PFHxA, and PFOS; The CUPs include desethylatrazine, prometon, bromacil, carbaryl, ametryn, atrazine, diuron, azoxystrobin, trifluralin, boscalid, pronamide, metolachlor, desulfinylfipronil, fipronil, dinoterufan, thiacloprid-amide, thiamethoxam, flon At least one of icamid, clothianidin-desmethyl, nitenpyram, imidacloprid, thiacloprid, clothianidin, imidaclothiz, n-desmethyl-thiamethoxam, dicama, acetamiprid, acetamiprid-n-desmethyl, dimethoate, sulfoxaflor, and imidacloprid-olefin.

2. The collaborative analysis and detection method according to claim 1, characterized in that: The sample described in step (3) is a liquid sample; The filtration in step (3) is performed through a 0.45 μm filter membrane; The sample in step (3) is further added with a recovery indicator, wherein the recovery indicator includes a PFASs recovery indicator and / or a CUPs recovery indicator; The PFASs recovery rate indicator is at least one of M3-PFBA, M3-PFBS, M-PFHxA, M-PFHxS, M-PFOA, M2-8:2FTCA, M-PFOS, D3-MeFOSA, and MPFUnDA; The CUPs recovery rate indicator is at least one of D5-Atrazine, D4-Thiamethoxam, D3-Clothianidin, and D3-Acetamiprid.

3. The collaborative analysis and detection method according to claim 1, wherein: The sample flow rate described in step (4) is controlled at 3 to 10 mL / min; The eluate collected in step (5) is collected using a 15 mL polypropylene centrifuge tube; The concentration in step (5) is to concentrate the solution to 0.5 mL using a gentle nitrogen stream in a water bath at 35-45°C; The filtration in step (6) is performed using a 0.22 μm organic filter membrane.

4. The collaborative analysis and detection method according to claim 1, wherein: The internal standard in step (6) is a PFASs internal standard and / or a CUPs internal standard; The PFASs internal standard is at least one of MPFBA, M8PFOA, M7PFUnDA, M3PFHxS, and M8PFOS; The CUPs internal standard is at least one of D10-Chlorpyrifos, D14-Trifluralin, D3-Dinotefuran, and D4-Imidacloprid.

5. The collaborative analysis and detection method according to claim 1, characterized in that: The liquid chromatography-mass spectrometry method for detecting PFASs and CUPs in step (6) is to use a Thermo Scientific Vanquish LC-MS / MS to detect PFASs and CUPs in the concentrate; The conditions for liquid chromatography detection of PFASs are: A ZORBAX Extend-C18 column was used to separate different PFASs based on two elution procedures; Elution procedure 1: The PFASs analyzed include 4:2monoPAP, PFBA, 6:2monoPAP, PFPeA, 4:2FTSA, PFBS, PFPeS, PFHpA, ADONA, 6:2FTSA, PFOA, PFHpS, 8:2FTUCA, PFNA, 8:2FTS, PFDA, 6:2Cl-PFESA, PFUnDA, PFDS, PFDoDA, 8:2Cl-PFESA, 6:6PFPiA, PFTrDA, 6:2diPAP, 6:8PFPiA, 8:2diPAP; Mobile phase A: 2 mM ammonium acetate aqueous solution at pH 10.25; Mobile phase B: 5 mM 1-MP ACN:MeOH solution (volume ratio = 1:1); The column temperature was 35 °C, the flow rate was 0.25 mL / min, the gradient curve was 5, the injection volume was 2 μL, and the total run time was 18 min; The specific gradient elution program was as follows: 0-1.1 min, the volume percentage of mobile phase B was 10%; 1.1-2.0 min, the volume percentage of mobile phase B increased from 10% to 45%; From 2.0 to 8.0 min, the volume percentage of mobile phase B increased from 45% to 90% and maintained for 6.9 min, and then decreased from 90% to 10% within 0.1 min and maintained for 3 min; Elution procedure 2: The PFASs analyzed included PFHxS, PFHxA, and PFOS; Mobile phase A: 2 mM ammonium acetate in water; Mobile phase B: methanol solution containing 2 mM ammonium acetate; The column temperature was 35 °C, the flow rate was 0.30 mL / min, the gradient curve was 5, the injection volume was 2 μL, and the total run time was 12 min; The specific gradient elution program was as follows: from 0 to 1.0 min, the volume percentage of mobile phase B increased from 10% to 100% and was maintained for 1 min; from 2.0 to 8.0 min, the volume percentage of mobile phase B decreased from 100% to 10% and was then maintained for 12 min; The conditions for detecting mass spectrometry in PFASs are: Quantitative analysis was performed using electrospray ionization in selected reaction monitoring mode. The mass spectrometry parameters were as follows: spray voltage 2500 V, sheath gas and auxiliary gas flows of 40 and 10 Arb, respectively; ion transfer tube temperature 400°C, and heater temperature 350°C. Qualitative and quantitative analysis was performed using X-Calibur software. Ion pair information and retention time were used for qualitative analysis, while internal standard analysis and multipoint calibration were used for quantitative analysis. The conditions for detecting liquid chromatography in CUPs are: Acclaim chromatographic column TM RSLC 120 C18 2.2 μm 120Å, column temperature 40 °C; Mobile phase A: ultrapure water containing 0.2% formic acid; Mobile phase B: methanol containing 2 mM ammonium formate; The column temperature was 40 °C, the gradient curve was 5, the injection volume was 2 μL, and the total run time was 23 min; The specific liquid phase gradient elution program was: 0-0.5 min, the mobile phase flow rate was maintained at 0.3 mL / min, and the percentage of mobile phase B was 0%; From 0.5 to 1.0 min, the percentage of mobile phase B increased from 0% to 50%; from 1.0 to 19.0 min, the percentage of mobile phase B increased from 50% to 100% and maintained for 0.1 min; from 19.1 to 20.4 min, the mobile phase flow rate was maintained at 0.4 mL / min, and the percentage of mobile phase B was 100%; from 20.4 to 20.5 min, the mobile phase flow rate was maintained at 0.3 mL / min, and the percentage of mobile phase B decreased from 100% to 2%; from 20.5 to 23.0 min, the percentage of mobile phase B decreased from 2% to 0%; The conditions for detecting mass spectrometry in CUPs are: CUPs were quantitatively analyzed using electrospray ionization in selected reaction detection mode. The mass spectrometry parameters were as follows: sheath gas and auxiliary gas flows of 40 and 8 Arb, respectively, spray voltage of 3500 V, ion transfer tube temperature of 300°C, and heater temperature of 350°C. Qualitative and quantitative analysis was performed using X-Calibur software. Qualitative analysis was based on ion pair information and retention time, while quantitative analysis was performed using an internal standard method and a multipoint calibration standard curve.

6. Use of the collaborative analysis and detection method for PFASs and CUPs in water as described in any one of claims 1 to 5 in the detection of water pollutants.

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