CN113820421A - Method for measuring 6 phenolic compounds in water - Google Patents
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- CN113820421A CN113820421A CN202111117416.8A CN202111117416A CN113820421A CN 113820421 A CN113820421 A CN 113820421A CN 202111117416 A CN202111117416 A CN 202111117416A CN 113820421 A CN113820421 A CN 113820421A
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- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical class OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/08—Preparation using an enricher
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/28—Control of physical parameters of the fluid carrier
- G01N30/34—Control of physical parameters of the fluid carrier of fluid composition, e.g. gradient
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- G01N2030/042—Standards
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Abstract
The invention discloses a method for measuring 6 phenolic compounds in water, which comprises the following steps: collecting and storing a sample; and (3) enriching and purifying the sample by using a solid phase extraction column, then injecting the sample, and separating and detecting the phenolic compound by using high performance liquid chromatography-tandem mass spectrometry. And (4) performing qualitative determination according to retention time and characteristic ions, and performing quantitative determination by an internal standard method. The method can directly measure the phenolic compounds, is simple and quick, and solves the problems of complicated steps and long time consumption of a derivatization-gas chromatography mass spectrometry method; the method has high sensitivity and qualitative and quantitative capability, solves the problems of poor qualitative capability of liquid chromatography and low sensitivity of direct sample introduction/high performance liquid chromatography-tandem mass spectrometry, is suitable for preferentially controlling the determination of 6 phenolic compounds in water, and has high use value.
Description
Technical Field
The invention relates to the technical field of phenolic compound determination, in particular to a method for determining 6 phenolic compounds in water.
Background
The phenolic compound is a toxic and harmful industrial pollutant, has carcinogenicity, teratogenicity and mutagenicity, and is widely present in water. Mainly from petroleum, oil refining, coking, gas washing, synthetic resin, chemical engineering, pesticide degradation, wood preservation, synthetic fiber, paper making and the like. Phenolic substances can be accumulated in food, acute poisoning can occur when the phenolic substances are absorbed by a human body to exceed a certain amount, and if the water polluted by phenols is drunk for a long time, rash, dizziness, anemia and various nervous system symptoms can be caused, so that the organic pollutants have great harm to the health of the human body, and are important organic pollutants for detection in the field of environmental monitoring. At present, 6 items in the blacklist of the organic pollutants for preferential control in China are phenolic compounds, including phenol, 3-cresol, 2, 4-dichlorophenol, 2,4, 6-trichlorophenol, pentachlorophenol and 4-nitrophenol.
The phenolic compounds are generally analyzed by gas chromatography, gas chromatography-mass spectrometry, liquid chromatography-mass spectrometry, etc. The phenolic compound has strong polarity, poor peak pattern in gas chromatography and low sensitivity, and generally requires derivatization, but the derivatization method has complicated steps and consumes time. The high performance liquid chromatography can directly measure the phenolic compounds without derivatization reaction, but the qualitative capability of the liquid chromatography is poor. The analysis method for simultaneously measuring nitrophenols and chlorophenols in water by direct injection/high performance liquid chromatography-tandem mass spectrometry has been reported in documents, but the direct injection method for measuring phenol and 3-cresol has lower sensitivity than nitrophenols and chlorophenols, and the liquid chromatography-mass spectrometry combined method for measuring phenol and 3-cresol in water has few reports. The method adopts solid phase extraction to enrich and purify the sample, and simultaneously analyzes phenol, 3-cresol, 2, 4-dichlorophenol, 2,4, 6-trichlorophenol, pentachlorophenol and 4-nitrophenol in water by using a high performance liquid chromatography-tandem mass spectrometry method, is sensitive, accurate, simple and rapid, and has high use value in detection of phenolic compounds in water.
Disclosure of Invention
In order to overcome the defects in the prior art and establish a high-sensitivity, accurate and rapid analysis method for simultaneously measuring 6 phenolic compounds preferentially controlled in water, the invention firstly provides a method for detecting the phenolic compounds in water by adopting solid phase extraction-high performance liquid chromatography-tandem mass spectrometry, and has high use value.
In order to achieve the purpose, the invention provides the following technical scheme:
a method for assaying 6 phenolic compounds in water, comprising the steps of:
s1, collecting and storing samples
Collecting a sample in a 1L brown pre-cleaned glass sample bottle, and collecting a positive sample and a negative sample; the collected sample is timely attached with a sampling information label and quickly transferred to refrigeration equipment at about 4 ℃ for storage; the sample is sent to a laboratory for detection as soon as possible, the sample extraction time is not more than 7 days, and the sample extraction liquid detection time is not more than 40 days;
s2 sample preparation
Filtering a water sample by using a solvent filter and selecting a filter membrane; fixing the solid phase extraction column on a solid phase extraction device, and sequentially activating with 10mL of methanol and 10mL of pure water to ensure that the column head of the small column is infiltrated; measuring 100mL of filtered sample, adjusting the pH value to 2 by using hydrochloric acid, and passing the sample through a small column at a flow rate of not more than 10 mL/min; then leaching the small column by using 10mL of pure water; then blowing by nitrogen or drying the small column by a vacuum pump of a solid phase extraction device for 10min to remove residual moisture in the small column; then eluting the small column by 15mL of acetonitrile containing 1% acetic acid, and receiving the eluent into a collecting pipe; concentrating the eluate to about 0.5mL by a concentration device, and diluting to 1.0mL by pure water; adding 10.0 mu L of internal standard use solution, uniformly mixing, placing in a brown sample injection bottle, and detecting; preparing a blank sample of a laboratory by using pure water instead of the sample according to the same steps as the preparation of the sample;
s3, analysis conditions of instrument
Liquid chromatography conditions: mobile phase A: pure water, mobile phase B: methanol, gradient elution procedure is shown in table 2; flow rate: 0.3 mL/min; column temperature: 30 ℃; sample introduction volume: 20 mu L of the solution;
TABLE 2 gradient elution procedure
Mass spectrum conditions: atmospheric pressure chemical ionization source (APCI), negative ion mode ionization; needle Current (NC)3 mA; the ion source temperature is 550 ℃; collision gas (CAD)48 KPa; curtain gas (CUR)276 KPa; atomizing gas (GS1)276 KPa; multiple reaction monitoring mode (MRM), quantitative analysis of ion pairs see table 3; analyzing 6 phenols according to analysis conditions to obtain a liquid chromatogram-triple quadrupole tandem mass spectrogram;
TABLE 3 triple quadrupole tandem Mass Spectrometry parameters for targets
Table 3 MS/MS parameters of target compounds
Note 1: the strip is quantitative daughter ion of the secondary mass spectrum, and the other strip is qualitative daughter ion;
s4, Standard series of formulations and sample assays
Transferring a proper amount of phenolic compound mixed standard use solution, diluting with acetonitrile-water mixed solution to prepare standard series solution with at least 5 concentration points, wherein the mass concentration of phenol and 4-nitrophenol in the standard solution is respectively 10.0 mu g/L, 50.0 mu g/L, 100 mu g/L, 200 mu g/L, 500 mu g/L and 1000 mu g/L, the mass concentration of 2, 4-dichlorophenol is respectively 2.00 mu g/L, 10.0 mu g/L, 20.0 mu g/L, 40.0 mu g/L, 100 mu g/L and 200 mu g/L, the mass concentration of 3-cresol, 2,4, 6-trichlorophenol and pentachlorophenol is respectively 1.00 mu g/L, 5.00 mu g/L, 10.0 mu g/L, 20.0 mu g/L, 50.0 mu g/L and 100 mu g/L, transferring 1.0mL of standard series solution into a brown sample injection bottle, adding 10.0 μ L of internal standard solution, and mixing uniformly to be tested;
analyzing according to instrument conditions, sequentially injecting samples into the standard series of solutions from low concentration to high concentration, taking the ratio of the concentration of a target component in the standard series of solutions to the concentration of an internal standard substance as a horizontal coordinate, and taking the ratio of the corresponding peak area to the peak area of the internal standard substance as a vertical coordinate, and establishing a standard curve linear regression equation; taking a sample to be tested and determining according to the same instrument analysis conditions as the calibration curve;
s5, qualitative analysis
Detecting the parent ions and the daughter ions according to the determination in the table 3, wherein the absolute value of the relative deviation between the retention time of the target in the sample and the retention time of the target in the standard sample is less than 2.5%; comparing the qualitative and quantitative relative abundance of the target substance to be detected (Ksam, formula 1) with the qualitative and quantitative relative abundance of the corresponding target substance (Kstd, formula 2) in the standard solution with the approximate concentration, and determining that the target substance exists in the sample if the obtained deviation is within the maximum allowable deviation range specified in Table 4;
Ksam＝A2/A1×100……………………………………(1)
in the formula:
ksam-the relative abundance of a certain set of stator ions in a sample,%;
A2-peak area (or peak height) of a second mass spectrometric daughter ion of a certain component in the sample;
A1-determining the peak area (or peak height) of a quantum ion in a second mass spectrum of a certain component in the sample;
Kstd＝Astd2/Astd1×100…………………………………(2)
in the formula:
kstd-the relative abundance of a certain set of stator ions in the standard sample,%;
Astd2-peak area (or peak height) of a second mass spectrometric determinant ion of a certain component in a standard sample;
Astd1determining the peak area (or peak height) of quantum ions by using a certain component secondary mass spectrum in the standard sample;
TABLE 4 maximum permissible deviation of relative ion abundance in qualitative confirmation
| Kstd/％ | KsamAllowable deviation/%) |
| Kstd>50 | ±20 |
| 20<Kstd≤50 | ±25 |
| 10<Kstd≤20 | ±30 |
| Kstd≤10 | ±50 |
S6, quantitative analysis
Carrying out quantitative analysis by a standard curve method; for components with wide linear range, a regression curve method can be adopted, and for samples with concentration close to the detection limit, standard single-point correction close to the detection limit concentration is adopted;
s7, calculating the result
The mass concentration of phenolic compounds in the sample (. mu.g/L) was calculated according to formula (3):
ρi＝ρ1i×V1×D/V (3)
in the formula:
ρi-the mass concentration of the i-th phenolic compound in the sample, μ g/L;
ρ1i-mass concentration of the i-th phenolic compound in the sample from the standard curve,. mu.g/L;
V1-sample volume, mL;
v is the sample volume, mL;
d is dilution multiple.
In step S1, if residual chlorine is present in the water, 80mg of sodium thiosulfate per liter of water is added to remove the chlorine.
The filter membrane is as follows: 0.22 μm or 0.45 μm teflon filter.
The methanol (CH)3OH): liquid chromatography stage; acetonitrile (CH)3CN): liquid chromatography stage; acetic acid (CH)3COOH): purifying by liquid chromatography; hydrochloric acid: rho (HCl) ═ 1.19g/mL, premium grade purity.
The acetonitrile-water mixed solution: mixing acetonitrile and pure water according to the volume ratio of 1: 1.
The standard stock solution of the phenolic compound: rho is 1000 mg/L; preparing with standard substance with purity of more than 99.0%, dissolving with methanol, freezing below-10 deg.C, and storing in dark place.
The phenolic compound mixed standard use solution: rho is 1.00 mg/L-10.0 mg/L; sucking a proper amount of standard stock solution of the phenolic compound, diluting the stock solution with methanol to prepare a mixed standard use solution with the concentration of phenol and 4-nitrophenol being 10.0mg/L, the concentration of 2, 4-dichlorophenol being 2.00mg/L, and the concentration of 3-cresol, 2,4, 6-trichlorophenol and pentachlorophenol being 1.00mg/L, freezing the mixed standard use solution at the temperature of below 10 ℃ below zero, keeping the mixed standard use solution away from light and storing the mixed standard use solution for 1 month.
The internal standard stock solution: rho is 1000 mg/L; the internal standard substance is 4-nitrophenol-d4The preparation method comprises preparing with standard substance with purity of more than 99.0%, dissolving with methanol, freezing below-10 deg.C, and storing in dark place.
The internal standard use solution: rho is 1.00 mg/L; diluting the stock solution with methanol as required, freezing below-10 deg.C, and storing in dark place.
The invention has the technical effects and advantages that:
1. the method can directly measure the phenolic compounds, is simple and quick, and solves the problems of complicated steps and long time consumption of a derivatization-gas chromatography mass spectrometry method; the method has high sensitivity and qualitative and quantitative capability, solves the problems of poor qualitative capability of liquid chromatography and low sensitivity of direct sample introduction/high performance liquid chromatography-tandem mass spectrometry, is suitable for preferentially controlling the determination of 6 phenolic compounds in water, and has high use value.
2. The method adopts solid phase extraction to enrich and purify the sample, and simultaneously analyzes phenol, 3-cresol, 2, 4-dichlorophenol, 2,4, 6-trichlorophenol, pentachlorophenol and 4-nitrophenol in water by using a high performance liquid chromatography-tandem mass spectrometry method, is sensitive, accurate, simple and rapid, and has high use value in detection of phenolic compounds in water.
Drawings
FIG. 1 is a total ion flow chromatogram of a phenolic compound and an internal standard.
In the figure: 1: phenol; 2: 4-nitrophenol-d 4; 3: 4-nitrophenol; 4: 3-cresol; 5: 2, 4-dichlorophenol; 6: 2,4, 6-trichlorophenol; 7: pentachlorophenol.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example one
1.1 reagents and materials
1.1.1 pure Water: meets the first-grade water specified in GB/T6682.
1.1.2 methanol (CH)3OH): and (5) purifying by liquid chromatography.
1.1.3 acetonitrile (CH)3CN): liquid chromatography stage.
1.1.4 acetic acid (CH)3COOH): and (5) purifying by liquid chromatography.
1.1.5 hydrochloric acid: rho (HCl) ═ 1.19g/mL, premium grade purity.
1.1.6 sodium thiosulfate (Na)2S2O3·5H2O)。
1.1.7 acetonitrile-water mixed solution: 1+1.
Acetonitrile (1.1.3) and pure water (1.1.1) were mixed in a volume ratio of 1: 1.
1.1.8 standard stock solutions of phenolic compounds: rho is 1000 mg/L.
Can be prepared from standard substance with purity of more than 99.0%, dissolved in methanol (1.1.2), and stored at-10 deg.C in dark place. The certified standard solution can also be purchased directly and stored according to the product specification of the manufacturer.
1.1.9 phenolic compound mix standard use solutions: rho is 1.00 mg/L-10.0 mg/L.
Sucking a proper amount of standard stock solution (1.1.9) of the phenolic compound, diluting with methanol (1.1.2) to prepare a mixed standard use solution with the concentration of phenol and 4-nitrophenol of 10.0mg/L, the concentration of 2, 4-dichlorophenol of 2.00mg/L, and the concentration of 3-cresol, 2,4, 6-trichlorophenol and pentachlorophenol of 1.00mg/L, freezing below-10 ℃, keeping out of the sun, and storing for 1 month.
1.1.10 stock solutions: rho is 1000 mg/L.
The internal standard substance is 4-nitrophenol-d4The preparation method comprises preparing standard substance with purity of more than 99.0%, dissolving with methanol (1.1.2), freezing below-10 deg.C, and storing in dark place. The certified standard solution can also be purchased directly and stored according to the product specification of the manufacturer.
1.1.11 internal standard use solution: rho is 1.00 mg/L.
The stock solution (5.18) was diluted with methanol (1.1.2) as needed, frozen below-10 ℃ and stored away from light.
1.1.12 solid phase extraction column: polystyrene-divinylbenzene-vinylpyrrolidone (6mL, 500mg) or other equivalent extraction column.
1.1.13 Filter Membrane: 0.22 μm or 0.45 μm teflon filter.
1.1.14 Nitrogen: the purity is more than or equal to 99.99 percent.
1.2 instruments and devices
1.2.1 liquid chromatography-triple quadrupole mass spectrometer: is provided with an atmospheric pressure chemical ionization source (APCI), and has the functions of gradient elution and multi-reaction monitoring.
1.2.2 chromatographic column: c with filler particle size of 2.6 μm, column length of 100mm and inner diameter of 3.0mm18Reversed phase liquid chromatography or other chromatography columns with similar performance.
1.2.3 concentration plant: a rotary evaporator or other equivalent performance device.
1.2.4 solid phase extraction device: the flow rate can be adjusted automatically or manually (with a vacuum pump).
1.2.5 sample bottles: 1L ground or brown glass bottle with polytetrafluoroethylene inner liner bottle cap.
1.2.6 microsyringe or pipette: 10. mu.L, 50. mu.L, 100. mu.L, 500. mu.L, 1.0 mL.
1.2.7 general laboratory instruments and equipment.
The measurement method is as follows:
s1, collecting and storing samples
Samples should be taken in 1L brown pre-washed glass sample bottles (1.2.5), one bottle each of which is typically taken as a positive. If residual chlorine is present in the water, 80mg of sodium thiosulfate (1.1.8) per liter of water are added to remove the chlorine. The collected sample should be timely attached with a sampling information label and quickly transferred to a refrigeration device at about 4 ℃ for storage. The sample should be sent to the laboratory for detection as soon as possible, the sample extraction time is not more than 7 days, and the sample extraction liquid detection time is not more than 40 days.
S2 sample preparation
The water sample was filtered using a solvent filter selection filter (1.1.13). The solid phase extraction column (1.1.12) is fixed on a solid phase extraction device (1.2.4) and activated by 10mL of methanol (1.1.2) and 10mL of pure water (1.1.1) in sequence to ensure the column head of the small column to be infiltrated. 100mL of filtered sample was measured, adjusted to pH 2 with hydrochloric acid (1.1.7) and passed through the column at a flow rate no greater than 10 mL/min. The sample volume can be reduced appropriately according to the actual situation. The column was then rinsed with 10mL of pure water (1.1.1). The column was then dried for 10min with a nitrogen purge (1.1.15) or vacuum pump of the solid phase extraction apparatus to remove residual moisture from the column. The column was then eluted with 15mL of acetonitrile (1.1.3) containing 1% acetic acid (1.1.4) and the eluate was received in a collection tube. The eluate was concentrated to about 0.5mL by a concentration device (1.2.3), and the volume was adjusted to 1.0mL with pure water (1.1.1). 10.0 μ L of the internal standard solution (1.1.11) was added, mixed well and placed in a brown sample bottle for testing. Preparation of a laboratory blank was carried out in the same procedure as the preparation of the sample, with pure water (1.1.1) instead of the sample.
S3, analysis conditions of instrument
Liquid chromatography conditions: mobile phase A: pure water (1.1.1), mobile phase B: methanol (1.1.2), gradient elution procedure see table 2; flow rate: 0.3 mL/min; column temperature: 30 ℃; sample introduction volume: 20 μ L.
TABLE 2 gradient elution procedure
Mass spectrum conditions: atmospheric pressure chemical ionization source (APCI), negative ion mode ionization; needle Current (NC)3 mA; the ion source temperature is 550 ℃; collision gas (CAD)48 KPa; curtain gas (CUR)276 KPa; atomizing gas (GS1)276 KPa; multiple reaction monitoring mode (MRM), quantitative analysis of ion pairs is shown in table 3. The liquid chromatography-triple quadrupole tandem mass spectrum obtained by analyzing 6 phenols according to the analysis conditions is shown in FIG. 1.
TABLE 3 triple quadrupole tandem Mass Spectrometry parameters for targets
Table 3 MS/MS parameters of target compounds
Note 1: the band is the quantifier ion of the secondary mass spectrum, and the other is the quantifier ion.
S4, Standard series of formulations and sample assays
Transferring an appropriate amount of the phenolic compound mixed standard use solution (1.1.10), diluting with acetonitrile-water mixed solution (1.1.7), preparing standard series solution with at least 5 concentration points, wherein the mass concentration of phenol and 4-nitrophenol in the standard solution is respectively 10.0 μ g/L, 50.0 μ g/L, 100 μ g/L, 200 μ g/L, 500 μ g/L and 1000 μ g/L, the mass concentration of 2, 4-dichlorophenol is respectively 2.00 μ g/L, 10.0 μ g/L, 20.0 μ g/L, 40.0 μ g/L, 100 μ g/L and 200 μ g/L, the mass concentration of 3-cresol, 2,4, 6-trichlorophenol and pentachlorophenol is respectively 1.00 μ g/L, 5.00 μ g/L, 10.0 μ g/L, 20.0 μ g/L, 50.0 μ g/L and 100 μ g/L, transferring 1.0mL of the standard series solution into a brown sample introduction bottle, adding 10.0 μ L of the internal standard use solution (1.1.12), and uniformly mixing for testing.
Analyzing according to instrument conditions, sequentially injecting samples into the standard series of solutions from low concentration to high concentration, taking the ratio of the concentration of the target component in the standard series of solutions to the concentration of the internal standard substance as a horizontal coordinate, and taking the ratio of the corresponding peak area to the peak area of the internal standard substance as a vertical coordinate, and establishing a standard curve linear regression equation. And (4) taking a sample to be tested and determining according to the same instrument analysis conditions as the calibration curve drawing.
S5, qualitative analysis
Detecting the parent ions and the daughter ions according to the determination in the table 3, wherein the absolute value of the relative deviation between the retention time of the target in the sample and the retention time of the target in the standard sample is less than 2.5%; and comparing the qualitative and quantitative relative abundance of the target substance to be detected (Ksam, formula 1) with the qualitative and quantitative relative abundance of the corresponding target substance in the standard solution with the approximate concentration (Kstd, formula 2), and determining that the target substance exists in the sample if the obtained deviation is within the maximum allowable deviation range specified in Table 4.
Ksam＝A2/A1×100……………………………………(1)
In the formula:
ksam-the relative abundance of a certain set of stator ions in a sample,%;
A2-peak area (or peak height) of a second mass spectrometric daughter ion of a certain component in the sample;
A1-determining the peak area (or peak height) of the quantum ion by the second mass spectrum of a certain component in the sample.
Kstd＝Astd2/Astd1×100…………………………………(2)
In the formula:
kstd-the relative abundance of a certain set of stator ions in the standard sample,%;
Astd2-peak area (or peak height) of a second mass spectrometric determinant ion of a certain component in a standard sample;
Astd1secondary mass spectrometry of a certain component in the standard sample determines the peak area (or peak height) of the quantum ion.
TABLE 4 maximum permissible deviation of relative ion abundance in qualitative confirmation
S6, quantitative analysis
Quantitative analysis was performed by standard curve method. Regression curves can be used for components with wide linear range, and standard single-point calibration close to detection limit concentration is preferably used for samples with concentration close to detection limit.
S7, calculating the result
The mass concentration of phenolic compounds in the sample (. mu.g/L) was calculated according to formula (3):
ρi＝ρ1i×V1×D/V (3)
in the formula:
ρi-the mass concentration of the i-th phenolic compound in the sample, μ g/L;
ρ1i-mass concentration of the i-th phenolic compound in the sample from the standard curve,. mu.g/L;
V1-sample volume, mL;
v is the sample volume, mL;
d is dilution multiple.
Example two
And (3) enriching and purifying the sample by using a solid phase extraction column, then injecting the sample, and separating and detecting the phenolic compound by using high performance liquid chromatography-tandem mass spectrometry. And (4) performing qualitative determination according to retention time and characteristic ions, and performing quantitative determination by an internal standard method.
When the sampling volume is 100mL (enrichment is 100 times) and the injection volume is 20 mu L, the method detection limit of 6 phenolic compounds is 0.005 mu g/L-0.05 mu g/L, and the method quantitative limit is 0.02 mu g/L-0.2 mu g/L, which is shown in Table 1.
TABLE 1 detection and lower determination limits of the methods
| Serial number | Compound (I) | Detection limit (μ g/L) | Method quantitative limit (mu g/L) |
| 1 | Phenol and its preparation | 0.05 | 0.2 |
| 2 | 4-nitrophenols | 0.05 | 0.2 |
| 3 | 3-cresols | 0.005 | 0.02 |
| 4 | 2, 4-dichlorophenol | 0.01 | 0.04 |
| 5 | 2,4, 6-trichlorophenol | 0.005 | 0.02 |
| 6 | Pentachlorophenol | 0.005 | 0.02 |
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that are within the spirit and principle of the present invention are intended to be included in the scope of the present invention.
Claims (9)
1. A method for measuring 6 phenolic compounds in water is characterized by comprising the following steps:
s1, collecting and storing samples
Collecting a sample in a 1L brown pre-cleaned glass sample bottle, and collecting a positive sample and a negative sample; the collected sample is timely attached with a sampling information label and quickly transferred to refrigeration equipment at about 4 ℃ for storage; the sample is sent to a laboratory for detection as soon as possible, the sample extraction time is not more than 7 days, and the sample extraction liquid detection time is not more than 40 days;
s2 sample preparation
Filtering a water sample by using a solvent filter and selecting a filter membrane; fixing the solid phase extraction column on a solid phase extraction device, and sequentially activating with 10mL of methanol and 10mL of pure water to ensure that the column head of the small column is infiltrated; measuring 100mL of filtered sample, adjusting the pH value to 2 by using hydrochloric acid, and passing the sample through a small column at a flow rate of not more than 10 mL/min; then leaching the small column by using 10mL of pure water; then blowing by nitrogen or drying the small column by a vacuum pump of a solid phase extraction device for 10min to remove residual moisture in the small column; then eluting the small column by 15mL of acetonitrile containing 1% acetic acid, and receiving the eluent into a collecting pipe; concentrating the eluate to about 0.5mL by a concentration device, and diluting to 1.0mL by pure water; adding 10.0 mu L of internal standard use solution, uniformly mixing, placing in a brown sample injection bottle, and detecting; preparing a blank sample of a laboratory by using pure water instead of the sample according to the same steps as the preparation of the sample;
s3, analysis conditions of instrument
Liquid chromatography conditions: mobile phase A: pure water, mobile phase B: methanol, gradient elution procedure is shown in table 2; flow rate: 0.3 mL/min; column temperature: 30 ℃; sample introduction volume: 20 mu L of the solution;
TABLE 2 gradient elution procedure
Mass spectrum conditions: atmospheric pressure chemical ionization source (APCI), negative ion mode ionization; needle Current (NC)3 mA; the ion source temperature is 550 ℃; collision gas (CAD)48 KPa; curtain gas (CUR)276 KPa; atomizing gas (GS1)276 KPa; multiple reaction monitoring mode (MRM), quantitative analysis of ion pairs see table 3; analyzing 6 phenols according to analysis conditions to obtain a liquid chromatogram-triple quadrupole tandem mass spectrogram;
TABLE 3 triple quadrupole tandem Mass Spectrometry parameters for targets
Table 3 MS/MS parameters of target compounds
Note 1: the strip is quantitative daughter ion of the secondary mass spectrum, and the other strip is qualitative daughter ion;
s4, Standard series of formulations and sample assays
Transferring a proper amount of phenolic compound mixed standard use solution, diluting with acetonitrile-water mixed solution to prepare standard series solution with at least 5 concentration points, wherein the mass concentration of phenol and 4-nitrophenol in the standard solution is respectively 10.0 mu g/L, 50.0 mu g/L, 100 mu g/L, 200 mu g/L, 500 mu g/L and 1000 mu g/L, the mass concentration of 2, 4-dichlorophenol is respectively 2.00 mu g/L, 10.0 mu g/L, 20.0 mu g/L, 40.0 mu g/L, 100 mu g/L and 200 mu g/L, the mass concentration of 3-cresol, 2,4, 6-trichlorophenol and pentachlorophenol is respectively 1.00 mu g/L, 5.00 mu g/L, 10.0 mu g/L, 20.0 mu g/L, 50.0 mu g/L and 100 mu g/L, transferring 1.0mL of standard series solution into a brown sample injection bottle, adding 10.0 μ L of internal standard solution, and mixing uniformly to be tested;
analyzing according to instrument conditions, sequentially injecting samples into the standard series of solutions from low concentration to high concentration, taking the ratio of the concentration of a target component in the standard series of solutions to the concentration of an internal standard substance as a horizontal coordinate, and taking the ratio of the corresponding peak area to the peak area of the internal standard substance as a vertical coordinate, and establishing a standard curve linear regression equation; taking a sample to be tested and determining according to the same instrument analysis conditions as the calibration curve;
s5, qualitative analysis
Detecting the parent ions and the daughter ions according to the determination in the table 3, wherein the absolute value of the relative deviation between the retention time of the target in the sample and the retention time of the target in the standard sample is less than 2.5%; comparing the qualitative and quantitative relative abundance of the target substance to be detected (Ksam, formula 1) with the qualitative and quantitative relative abundance of the corresponding target substance (Kstd, formula 2) in the standard solution with the approximate concentration, and determining that the target substance exists in the sample if the obtained deviation is within the maximum allowable deviation range specified in Table 4;
Ksam＝A2/A1×100……………………………………(1)
in the formula:
ksam-the relative abundance of a certain set of stator ions in a sample,%;
A2-peak area (or peak height) of a second mass spectrometric daughter ion of a certain component in the sample;
A1-determining the peak area (or peak height) of a quantum ion in a second mass spectrum of a certain component in the sample;
Kstd＝Astd2/Astd1×100…………………………………(2)
in the formula:
kstd-the relative abundance of a certain set of stator ions in the standard sample,%;
Astd2-peak area (or peak height) of a second mass spectrometric determinant ion of a certain component in a standard sample;
Astd1determining the peak area (or peak height) of quantum ions by using a certain component secondary mass spectrum in the standard sample;
TABLE 4 maximum permissible deviation of relative ion abundance in qualitative confirmation
S6, quantitative analysis
Carrying out quantitative analysis by a standard curve method; for components with wide linear range, a regression curve method can be adopted, and for samples with concentration close to the detection limit, standard single-point correction close to the detection limit concentration is adopted;
s7, calculating the result
The mass concentration of phenolic compounds in the sample (. mu.g/L) was calculated according to formula (3):
ρi＝ρ1i×V1×D/V (3)
in the formula:
ρi-the mass concentration of the i-th phenolic compound in the sample, μ g/L;
ρ1i-mass concentration of the i-th phenolic compound in the sample from the standard curve,. mu.g/L;
V1-sample volume, mL;
v is the sample volume, mL;
d is dilution multiple.
2. The method of claim 1, wherein the method comprises the steps of: in step S1, if residual chlorine is present in the water, 80mg of sodium thiosulfate per liter of water is added to remove the chlorine.
3. The method of claim 1, wherein the method comprises the steps of: the filter membrane is as follows: 0.22 μm or 0.45 μm teflon filter.
4. The method of claim 1, wherein the method comprises the steps of: the methanol (CH)3OH): liquid chromatography stage; acetonitrile (CH)3CN): liquid chromatography stage; acetic acid (CH)3COOH): purifying by liquid chromatography; hydrochloric acid: rho (HCl) ═ 1.19g/mL, premium grade purity.
5. The method of claim 1, wherein the method comprises the steps of: the acetonitrile-water mixed solution: mixing acetonitrile and pure water according to the volume ratio of 1: 1.
6. The method of claim 1, wherein the method comprises the steps of: the standard stock solution of the phenolic compound: rho is 1000 mg/L; preparing with standard substance with purity of more than 99.0%, dissolving with methanol, freezing below-10 deg.C, and storing in dark place.
7. The method of claim 1, wherein the method comprises the steps of: the phenolic compound mixed standard use solution: rho is 1.00 mg/L-10.0 mg/L; sucking a proper amount of standard stock solution of the phenolic compound, diluting the stock solution with methanol to prepare a mixed standard use solution with the concentration of phenol and 4-nitrophenol being 10.0mg/L, the concentration of 2, 4-dichlorophenol being 2.00mg/L, and the concentration of 3-cresol, 2,4, 6-trichlorophenol and pentachlorophenol being 1.00mg/L, freezing the mixed standard use solution at the temperature of below 10 ℃ below zero, keeping the mixed standard use solution away from light and storing the mixed standard use solution for 1 month.
8. The method of claim 1, wherein the method comprises the steps of: the internal standard stock solution: rho is 1000 mg/L; the internal standard substance is 4-nitrophenol-d4The preparation method comprises preparing with standard substance with purity of more than 99.0%, dissolving with methanol, freezing below-10 deg.C, and storing in dark place.
9. The method of claim 1, wherein the method comprises the steps of: the internal standard use solution: rho is 1.00 mg/L; diluting the stock solution with methanol as required, freezing below-10 deg.C, and storing in dark place.
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