CN110579557B - HPLC analysis detection method for simultaneously detecting 12 monocyclic aromatic hydrocarbons in water - Google Patents
HPLC analysis detection method for simultaneously detecting 12 monocyclic aromatic hydrocarbons in water Download PDFInfo
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- -1 monocyclic aromatic hydrocarbons Chemical class 0.000 title claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000001514 detection method Methods 0.000 title claims abstract description 31
- 238000004128 high performance liquid chromatography Methods 0.000 title claims abstract description 26
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 23
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 claims abstract description 22
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 22
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims abstract description 14
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000004458 analytical method Methods 0.000 claims abstract description 13
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims abstract description 10
- RMBFBMJGBANMMK-UHFFFAOYSA-N 2,4-dinitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O RMBFBMJGBANMMK-UHFFFAOYSA-N 0.000 claims abstract description 10
- XTRDKALNCIHHNI-UHFFFAOYSA-N 2,6-dinitrotoluene Chemical compound CC1=C([N+]([O-])=O)C=CC=C1[N+]([O-])=O XTRDKALNCIHHNI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 8
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 claims abstract description 7
- CKAPSXZOOQJIBF-UHFFFAOYSA-N hexachlorobenzene Chemical compound ClC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl CKAPSXZOOQJIBF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 238000002347 injection Methods 0.000 claims abstract description 3
- 239000007924 injection Substances 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- 239000012086 standard solution Substances 0.000 claims description 19
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 15
- 238000010828 elution Methods 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- PBCJIPOGFJYBJE-UHFFFAOYSA-N acetonitrile;hydrate Chemical compound O.CC#N PBCJIPOGFJYBJE-UHFFFAOYSA-N 0.000 claims description 7
- 239000013558 reference substance Substances 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229920000742 Cotton Polymers 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- YTJSFYQNRXLOIC-UHFFFAOYSA-N octadecylsilane Chemical compound CCCCCCCCCCCCCCCCCC[SiH3] YTJSFYQNRXLOIC-UHFFFAOYSA-N 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 238000002390 rotary evaporation Methods 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- FKHIFSZMMVMEQY-UHFFFAOYSA-N talc Chemical compound [Mg+2].[O-][Si]([O-])=O FKHIFSZMMVMEQY-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000000622 liquid--liquid extraction Methods 0.000 claims description 3
- 238000000638 solvent extraction Methods 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 2
- 238000012544 monitoring process Methods 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- 238000002386 leaching Methods 0.000 abstract 1
- 239000012088 reference solution Substances 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 8
- 125000002950 monocyclic group Chemical group 0.000 description 4
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 229940117389 dichlorobenzene Drugs 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- CWRYPZZKDGJXCA-UHFFFAOYSA-N acenaphthene Chemical compound C1=CC(CC2)=C3C2=CC=CC3=C1 CWRYPZZKDGJXCA-UHFFFAOYSA-N 0.000 description 2
- 239000012491 analyte Substances 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
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- 238000011002 quantification Methods 0.000 description 2
- 206010028400 Mutagenic effect Diseases 0.000 description 1
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000243 mutagenic effect Toxicity 0.000 description 1
- 230000003505 mutagenic effect Effects 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000012284 sample analysis method Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000956 solid--liquid extraction Methods 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 231100000378 teratogenic Toxicity 0.000 description 1
- 230000003390 teratogenic effect Effects 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
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- 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
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
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Abstract
The invention provides an HPLC analysis detection method for simultaneously detecting 12 monocyclic aromatic hydrocarbons in water, belonging to the technical field of high performance liquid chromatography analysis. The method comprises the steps of firstly preparing reference solutions of 12 monocyclic aromatic hydrocarbons, namely chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, hexachlorobenzene, 1,2, 4-trichlorobenzene, benzene, toluene, ethylbenzene, nitrobenzene, 2, 4-dinitrotoluene and 2, 6-dinitrotoluene, then extracting an actual water sample for later use, and finally detecting the content of the 12 monocyclic aromatic hydrocarbons by adopting a liquid chromatography-diode array detector (HPLC-PDA). The method optimizes the leacheate, gradient leaching conditions, detection wavelength, sample injection amount and the like, finally establishes a proper analysis method, can achieve better separation of all substances, has the remarkable advantages of good reproducibility, high accuracy and high precision, lays a good foundation for simultaneous online monitoring of the monocyclic aromatic hydrocarbon in the water, and can effectively save detection cost and time.
Description
Technical Field
The invention relates to the technical field of high performance liquid chromatography analysis, in particular to an HPLC analysis detection method for simultaneously detecting 12 monocyclic aromatic hydrocarbons in water.
Background
At present, most countries around the world have single-ring aromatic compounds listed as one of the important pollutants for environmental monitoring. The U.S. environmental protection agency blacklists the prioritized organic pollutants for 12 single ring aromatic hydrocarbons as early as 1976. Compared with other monocyclic aromatic hydrocarbons, the 12 monocyclic aromatic hydrocarbons have wider distribution in the environment, higher concentration, easier contact with human beings, stronger carcinogenic, teratogenic and mutagenic effects and great harm to human health.
The research of Chinese researchers on monocyclic aromatic hydrocarbons in water mainly aims at preferentially monitoring pollutants of 12 monocyclic aromatic hydrocarbons confirmed by US EPA, and the analysis method mainly comprises gas chromatography, high performance liquid chromatography, gas chromatography-mass spectrometry and the like. The gas chromatography has high resolution and low detection limit, but because the monocyclic aromatic hydrocarbon has the characteristics of semi-volatility and non-volatility, the analysis by adopting the gas chromatography and the gas chromatography-mass spectrometry has the problems of higher sample analysis temperature and unsatisfactory component separation, while the high-performance liquid chromatograph adopts a fluorescence detector, although the high sensitivity is realized, because acenaphthene has no fluorescence effect, 12 monocyclic aromatic hydrocarbons cannot be simultaneously detected, and certain defects exist.
Disclosure of Invention
The invention aims to provide an HPLC analysis detection method for simultaneously detecting 12 monocyclic aromatic hydrocarbons in water.
The method comprises the following steps:
(1) dissolving 12 monocyclic aromatic standard substances with one of methanol or acetonitrile, and respectively preparing into 200 μ g/mL solution-1The solution of (1) is used as a standard solution of 12 monocyclic aromatic hydrocarbon reference substances for standby;
(2) performing liquid-liquid extraction on an actual water sample by using n-hexane for three times, activating Florisil by using n-hexane, filling a column by using a wet method, padding a layer of absorbent cotton soaked in dichloromethane and dried at the lower end of the column to slow down the flow rate to 2-3mL/min, allowing the sample to pass through the column, drying, then pouring prepared 60mL, 80mL and 100mL of leacheate, wherein the leacheate is petroleum ether/dichloromethane with the volume ratio of 9:1, respectively collecting three leacheate solutions, performing rotary evaporation and concentration, fixing the volume to 1mL, and filtering by using a 0.22 mu m PVDF filter membrane to a sample bottle for later use;
(3) respectively taking 12 kinds of monocyclic aromatic reference substance standard solutions prepared in the step (1), preparing a standard solution with gradient concentration, analyzing by using a high performance liquid chromatography, and drawing a standard curve of 12 kinds of monocyclic aromatic by taking the concentration as a horizontal coordinate and a peak area as a vertical coordinate according to a liquid chromatogram obtained by analysis;
(4) and (3) detecting the solution processed in the step (2) under the same high performance liquid chromatography condition in the step (3), and calculating the content of 12 monocyclic aromatic hydrocarbons in the actual water sample in the step (2) according to the standard curve in the step (3).
Wherein the monocyclic aromatic hydrocarbon in 12 is chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, hexachlorobenzene, 1,2, 4-trichlorobenzene, benzene, toluene, ethylbenzene, nitrobenzene, 2, 4-dinitrotoluene and 2, 6-dinitrotoluene.
The analysis condition range of the high performance liquid chromatography in the step (3) is as follows: octadecylsilane chemically bonded silica is used as a filler for the chromatographic column; the column temperature is 20-30 ℃; the volume ratio of acetonitrile to water in the mobile phase is (20-70): (30-80), gradient elution is carried out in the mobile phase; the detection wavelength range is 190-250 nm; the sample injection amount is 1-20 mu L; the flow rate is 0.3-1.5 mL/min.
The invention uses common octadecylsilane chemically bonded silica as column packing, and uses acetonitrile-water system as mobile phase to perform gradient elution relative to chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, hexachlorobenzene, 1,2, 4-trichlorobenzene, benzene, toluene, ethylbenzene, nitrobenzene, 2, 4-dinitrotoluene and 2, 6-dinitrotoluene, the 12 single-ring aromatic hydrocarbons have larger polarity difference and more isomers, such as three o-m-p-chlorobenzene in dichlorobenzene, 2, 4-dinitrotoluene in nitrobenzene and 2, 6-dinitrotoluene in nitrobenzene are difficult isomers to separate. Scientific research finally confirms that the analysis conditions of the high performance liquid chromatography in the step (3) are as follows: column C18, 5 μm, 250 × 4.6mm i.d.; column temperature: 20-30 ℃; the mobile phase composition is an acetonitrile-water system; gradient elution; detection wavelength: 210 nm; sample introduction amount: 10 mu L of the solution; flow rate: 0.8 mL/min.
Wherein, the gradient elution procedure is as follows:
the technical scheme of the invention has the following beneficial effects:
1. the invention utilizes high performance liquid chromatography, and cooperates with a diode array detector to simultaneously detect and analyze p-chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, hexachlorobenzene, 1,2, 4-trichlorobenzene, benzene, toluene, ethylbenzene, nitrobenzene, 2, 4-dinitrotoluene and 2, 6-dinitrotoluene, and because a plurality of isomers exist in monocyclic aromatic hydrocarbon in 12: three kinds of o-m-chlorobenzene in dichlorobenzene, 2, 4-dinitrotoluene in nitrobenzene and 2, 6-dinitrotoluene are difficult to separate isomers, so that the separation of various substances and the determination of target substances are difficult to realize. None of the chromatographic conditions disclosed so far enables simultaneous determination of 12 single ring aromatics in the present invention.
2. In the detection method, the separation degree of 12 monocyclic aromatic hydrocarbons is good, the base line is stable, the method has the remarkable advantages of good reproducibility, high accuracy and high precision, lays a good foundation for the simultaneous online monitoring of the monocyclic aromatic hydrocarbons in water, and can effectively save the detection cost and time.
Drawings
FIG. 1 is a chromatogram of a standard solution of 12 kinds of monocyclic aromatic hydrocarbons involved in the HPLC analysis and detection method for simultaneously detecting 12 kinds of monocyclic aromatic hydrocarbons in water according to the present invention;
FIG. 2 is a chromatogram for detecting 12 kinds of monocyclic aromatic hydrocarbons in an actual water sample;
FIG. 3 is a comparison graph of chromatographic peaks of 12 kinds of monocyclic aromatic hydrocarbons detected in an actual water sample and chromatographic peaks of a standard substance.
Wherein: 1-nitrobenzene; 2-toluene; 3-2, 6-dinitrotoluene; 4-2, 4-dinitrotoluene; 5-chlorobenzene; 6-1, 2, 4-trichlorobenzene; 7-o-dichlorobenzene; 8-m-dichlorobenzene; 9-p-dichlorobenzene; 10-ethylbenzene; 11-benzene; 12-hexachlorobenzene.
Detailed Description
In order to make the technical problems, technical solutions and advantages of the present invention more apparent, the following detailed description is given with reference to the accompanying drawings and specific embodiments.
The invention provides an HPLC analysis detection method for simultaneously detecting 12 monocyclic aromatic hydrocarbons in water.
The method comprises the following steps:
(1) dissolving 12 monocyclic aromatic standard substances with one of methanol or acetonitrile, and respectively preparing into 200 μ g/mL solution-1The solution of (1) is used as a standard solution of 12 monocyclic aromatic hydrocarbon reference substances for standby;
(2) performing liquid-liquid extraction on an actual water sample by using n-hexane for three times, activating Florisil by using n-hexane, filling a column by using a wet method, padding a layer of absorbent cotton soaked in dichloromethane and dried at the lower end of the column to slow down the flow rate to 2-3mL/min, allowing the sample to pass through the column, drying, then pouring prepared 60mL, 80mL and 100mL of leacheate, wherein the leacheate is petroleum ether/dichloromethane with the volume ratio of 9:1, respectively collecting three leacheate solutions, performing rotary evaporation and concentration, fixing the volume to 1mL, and filtering by using a 0.22 mu m PVDF filter membrane to a sample bottle for later use;
(3) respectively taking 12 kinds of monocyclic aromatic reference substance standard solutions prepared in the step (1), preparing a standard solution with gradient concentration, analyzing by using a high performance liquid chromatography, and drawing a standard curve of 12 kinds of monocyclic aromatic by taking the concentration as a horizontal coordinate and a peak area as a vertical coordinate according to a liquid chromatogram obtained by analysis;
(4) and (3) detecting the solution processed in the step (2) under the same high performance liquid chromatography condition in the step (3), and calculating the content of 12 monocyclic aromatic hydrocarbons in the actual water sample in the step (2) according to the standard curve in the step (3).
Wherein the monocyclic aromatic hydrocarbon in 12 is chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, hexachlorobenzene, 1,2, 4-trichlorobenzene, benzene, toluene, ethylbenzene, nitrobenzene, 2, 4-dinitrotoluene and 2, 6-dinitrotoluene.
The invention uses common octadecylsilane chemically bonded silica as column packing, and uses acetonitrile-water system as mobile phase to perform gradient elution relative to chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, hexachlorobenzene, 1,2, 4-trichlorobenzene, benzene, toluene, ethylbenzene, nitrobenzene, 2, 4-dinitrotoluene and 2, 6-dinitrotoluene, the 12 single-ring aromatic hydrocarbons have larger polarity difference and more isomers, such as three o-m-p-chlorobenzene in dichlorobenzene, 2, 4-dinitrotoluene in nitrobenzene and 2, 6-dinitrotoluene in nitrobenzene are difficult isomers to separate. Scientific research finally confirms that the analysis conditions of the high performance liquid chromatography in the step (3) are as follows: column C18, 5 μm, 250 × 4.6mm i.d.; column temperature: 20-30 ℃; the mobile phase composition is an acetonitrile-water system; gradient elution; detection wavelength: 210 nm; sample introduction amount: 10 mu L of the solution; flow rate: 0.8 mL/min.
The following description is given with reference to specific examples.
First, a standard solution was prepared.
1. Preparation of Standard solutions
Respectively dissolving 12 monocyclic aromatic standard substances in acetonitrile, and respectively preparing into 200 μ g/mL solution-1Preparing 12 kinds of monocyclic aromatic hydrocarbon reference substance standard solution for standby;
2. chromatographic conditions
Column C18, 5 μm, 250 × 4.6mm (i.d.); column temperature: 20-30 ℃; the mobile phase composition is acetonitrile-water system gradient elution; detection wavelength: 210 nm; sample introduction amount: 10 mu L of the solution; flow rate: 0.8mL/min, and the gradient elution procedure is shown in Table 1.
TABLE 1 gradient elution procedure
3. Preparation and linear relationship of standard solution
12 types of monocyclic aromatic standard solutions with the concentrations of 0.5. mu.g/mL, 1. mu.g/mL, 2. mu.g/mL, 4. mu.g/mL, 6. mu.g/mL, 10. mu.g/mL, 14. mu.g/mL, 50. mu.g/m, 100. mu.g/mL and 200. mu.g/mL are prepared respectively, high performance liquid phase detection is carried out, and the chromatogram obtained by the detection is shown in FIG. 1. And (4) carrying out parallel measurement for three times, and taking an average value to obtain a linear equation. The linear equations and linear ranges for the 12 monocyclic aromatics are shown in table 2.
TABLE 212 linear equations and Linear ranges for monocyclic aromatics
From table 2, it can be seen that, in a certain concentration range, 12 monocyclic aromatic hydrocarbons exhibit a good linear relationship, and the linear correlation coefficient is not lower than 0.9996.
4. Detection limit and quantification limit
Adding a small amount of monocyclic aromatic standard solution into 1L of ultrapure water, pretreating according to an optimized treatment method, carrying out high performance liquid chromatography, taking the mass concentration of an analyte corresponding to 3 times of a noise signal of a high performance liquid chromatography instrument as a method detection limit, and taking the mass concentration of the analyte corresponding to 10 times of the noise signal of the instrument as a method quantitative limit. And actually preparing a sample with the calculated detection limit concentration to verify whether the signal response generated during the sample measurement meets the requirement that the instrument signal is 3 times of the noise, and if the signal response is obviously lower or higher than 3 times, increasing or reducing the addition of the monocyclic aromatic standard solution by the sample to enable the instrument signal to be 3 times of the noise, thereby obtaining the method detection limit and the quantitative limit.
The detection and quantification limits for the 12 monocyclic aromatics are shown in table 3.
Detection and quantitation limits for 312 monocyclic aromatics in Table
The actual water sample analysis and detection method comprises the following steps:
1. treatment of real water samples
500mL of actual water sample is taken and extracted by 50mL of n-hexane for three times. Activating a certain amount of Florisil with n-hexane, filling the column with wet method, wherein the column height is 20cm, and placing a layer of absorbent cotton soaked in dichloromethane and dried at the lower end of the column to slow down the flow rate to 2-3 mL/min. After the sample passes through the column and is dried, 60mL, 80mL and 100mL of prepared leacheate (petroleum ether/dichloromethane, 9:1) are poured in, three times of leacheate are collected respectively, the three times of leacheate is concentrated by rotary evaporation, the volume is fixed to 1mL, and the three times of leacheate is filtered to a sample bottle by a PVDF filter membrane (0.22 mu m) for chromatographic analysis.
2. Chromatographic conditions
Column C18, 5 μm, 250 × 4.6mm (i.d.); column temperature: 20-30 ℃; the mobile phase composition is acetonitrile-water system gradient elution; detection wavelength: 210 nm; sample introduction amount: 10 mu L of the solution; flow rate: 0.8mL/min, and the gradient elution procedure is shown in Table 1.
3. Determination of monocyclic aromatic hydrocarbons in actual water sample
The peak area of the monocyclic aromatic hydrocarbon is obtained according to the chromatogram of the actual water sample (as shown in fig. 2), and then the contents of various monocyclic aromatic hydrocarbons in the water sample are calculated according to the linear equation, as shown in table 4.
TABLE 4 content of monocyclic aromatic hydrocarbons in actual water sample
4. Accuracy and precision of the method
The external standard method for the experiment quantifies the accuracy (standard recovery rate) and precision of 12 monocyclic aromatic hydrocarbons by peak area respectively.
50 mu L of 12 monocyclic aromatic hydrocarbon standard solutions with the concentration of 200 mu g/mL are added into 500mL of actual water sample and fully mixed. Processing according to a pretreatment mode of solid-liquid extraction, simultaneously processing 7 samples, simultaneously preparing two standard solutions of monocyclic aromatic hydrocarbon with the concentration of 10 mu g/mL as confirmation, carrying out high performance liquid detection, measuring the peak area of the standard sample, taking the ratio of the peak area of the standard sample to the average value of the peak areas of the two confirmation standard samples as the recovery rate of the standard sample, and calculating the relative standard deviation. The results are shown in tables 5 and 6.
Method accuracy of tabulated 512 monocyclic aromatic spiked samples
The method accuracy of each component of the monocyclic aromatic standard adding sample, namely the average standard adding recovery rate is 86.87-102.6%.
Precision of the monocyclic aromatic spiked samples in Table 612
The precision of the method for adding each component of the standard sample of the monocyclic aromatic hydrocarbon is 1.902% -5.011%.
The comparison graph of the chromatographic peaks of 12 monocyclic aromatic hydrocarbons detected in the actual water sample and the chromatographic peaks of the standard substance is shown in fig. 3.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (2)
1. An HPLC analysis detection method for simultaneously detecting 12 monocyclic aromatic hydrocarbons in water is characterized in that: the method comprises the following steps:
(1) dissolving 12 monocyclic aromatic standard substances with one of methanol or acetonitrile, and respectively preparing into 200 μ g/mL solution-1The solution of (1) is used as a standard solution of 12 monocyclic aromatic hydrocarbon reference substances for standby;
(2) performing liquid-liquid extraction on an actual water sample by using n-hexane for three times, activating Florisil by using n-hexane, filling a column by using a wet method, padding a layer of absorbent cotton soaked in dichloromethane and dried at the lower end of the column to slow down the flow rate to 2-3mL/min, allowing the sample to pass through the column, drying, then pouring prepared 60mL, 80mL and 100mL of leacheate, wherein the leacheate is petroleum ether/dichloromethane with the volume ratio of 9:1, respectively collecting three leacheate solutions, performing rotary evaporation and concentration, fixing the volume to 1mL, and filtering by using a 0.22 mu m PVDF filter membrane to a sample bottle for later use;
(3) respectively taking 12 kinds of monocyclic aromatic reference substance standard solutions prepared in the step (1), preparing a standard solution with gradient concentration, analyzing by using a high performance liquid chromatography, and drawing a standard curve of 12 kinds of monocyclic aromatic by taking the concentration as a horizontal coordinate and a peak area as a vertical coordinate according to a liquid chromatogram obtained by analysis;
(4) detecting the solution processed in the step (2) under the same high performance liquid chromatography condition in the step (3), and calculating the content of 12 monocyclic aromatic hydrocarbons in the actual water sample in the step (2) according to the standard curve in the step (3);
the monocyclic aromatic hydrocarbon in 12 is chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, hexachlorobenzene, 1,2, 4-trichlorobenzene, benzene, toluene, ethylbenzene, nitrobenzene, 2, 4-dinitrotoluene and 2, 6-dinitrotoluene;
the analysis condition range of the high performance liquid chromatography in the step (3) is as follows: octadecylsilane chemically bonded silica is used as a filler for the chromatographic column; the column temperature is 20-30 ℃; the volume ratio of acetonitrile to water in the mobile phase is (20-70): (30-80), gradient elution is carried out in the mobile phase; the detection wavelength range is 190-250 nm; the sample injection amount is 1-20 mu L; the flow rate is 0.3-1.5 mL/min;
the gradient elution procedure was as follows:
2. the HPLC analytical detection method for simultaneously detecting 12 monocyclic aromatic hydrocarbons in water according to claim 1, wherein: the preferable high performance liquid chromatography conditions in the step (3) are as follows: column C18, 5 μm, 250 × 4.6mm i.d.; column temperature: 20-30 ℃; the mobile phase composition is an acetonitrile-water system; gradient elution; detection wavelength: 210 nm; sample introduction amount: 10 mu L of the solution; flow rate: 0.8 mL/min.
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