CN109212055B - Gas chromatography-mass spectrometry combined method for determining four trace monohalogenated phenylacetic acids in drinking water - Google Patents
Gas chromatography-mass spectrometry combined method for determining four trace monohalogenated phenylacetic acids in drinking water Download PDFInfo
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- 235000020188 drinking water Nutrition 0.000 title claims abstract description 23
- 239000003651 drinking water Substances 0.000 title claims abstract description 23
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 title claims abstract description 14
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical class OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 title claims description 12
- 239000003463 adsorbent Substances 0.000 claims abstract description 45
- 150000001875 compounds Chemical class 0.000 claims abstract description 36
- 238000001212 derivatisation Methods 0.000 claims abstract description 34
- IUHXGZHKSYYDIL-UHFFFAOYSA-N 2-(2-iodophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC=C1I IUHXGZHKSYYDIL-UHFFFAOYSA-N 0.000 claims abstract description 13
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- IUJAAIZKRJJZGQ-UHFFFAOYSA-N 2-(2-chlorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC=C1Cl IUJAAIZKRJJZGQ-UHFFFAOYSA-N 0.000 claims description 12
- RPTRFSADOICSSK-UHFFFAOYSA-N 2-(2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC=C1F RPTRFSADOICSSK-UHFFFAOYSA-N 0.000 claims description 12
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- 238000001514 detection method Methods 0.000 abstract description 9
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- 238000010828 elution Methods 0.000 abstract 1
- IMACFCSSMIZSPP-UHFFFAOYSA-N phenacyl chloride Chemical compound ClCC(=O)C1=CC=CC=C1 IMACFCSSMIZSPP-UHFFFAOYSA-N 0.000 abstract 1
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- JGKPBAFQXDHRCH-UHFFFAOYSA-N diazomethane;hexane Chemical compound C=[N+]=[N-].CCCCCC JGKPBAFQXDHRCH-UHFFFAOYSA-N 0.000 description 3
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- -1 4-ethylbenzenesulfonate-magnesium-aluminum Chemical compound 0.000 description 2
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- IWYDHOAUDWTVEP-UHFFFAOYSA-N mandelic acid Chemical compound OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 description 2
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- ONDSBJMLAHVLMI-UHFFFAOYSA-N trimethylsilyldiazomethane Chemical compound C[Si](C)(C)[CH-][N+]#N ONDSBJMLAHVLMI-UHFFFAOYSA-N 0.000 description 2
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- UFYBTLOLWSABAU-UHFFFAOYSA-N (2-methylpyridin-4-yl)boronic acid Chemical compound CC1=CC(B(O)O)=CC=N1 UFYBTLOLWSABAU-UHFFFAOYSA-N 0.000 description 1
- WLJVXDMOQOGPHL-PPJXEINESA-N 2-phenylacetic acid Chemical class O[14C](=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-PPJXEINESA-N 0.000 description 1
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- PKHNTJMAHAGHIQ-UHFFFAOYSA-N ethylbenzene;sodium Chemical compound [Na].CCC1=CC=CC=C1 PKHNTJMAHAGHIQ-UHFFFAOYSA-N 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
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- 241000411851 herbal medicine Species 0.000 description 1
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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
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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
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
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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
- G01N2030/062—Preparation extracting sample from raw material
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Abstract
The invention relates to a trace harmful substance analysis and detection method, in particular to a gas chromatography-mass spectrometry combined method for determining trace 2-fluoroacetophenone, 2-chloroacetophenone, 4-bromophenylacetic acid and 2-iodophenylacetic acid in drinking water. The method comprises the steps of enriching a target compound in drinking water by using a novel adsorbent 4-ethyl benzene sulfonate-magnesium aluminum type hydrotalcite, dissolving the adsorbent by using an acid to realize complete elution of the target compound, efficiently extracting the compound by using a small amount of organic solvent, and rapidly analyzing and determining by using a gas chromatography-mass spectrometry combination method after methyl esterification and derivatization. The novel adsorbent adopted by the method realizes the rapid and efficient adsorption of the target object by adopting a dispersed solid phase extraction mode, so that a large amount of adsorption time can be saved; the complete desorption of the target can be realized by using the mode of dissolving the adsorbent by acid; the method has obvious advantages of safety, environmental protection and economic advantage by only being suitable for extracting a small amount of organic solvent.
Description
Technical Field
The invention relates to a method for analyzing and detecting harmful trace substances, in particular to a gas chromatography-mass spectrometry combined method for determining trace 2-fluorophenylacetic acid, 2-chlorophenylacetic acid, 4-bromophenylacetic acid and 2-iodophenylacetic acid in drinking water.
Background
The halogen-containing compound is an important source of environmental pollution, particularly water pollution, and 2-fluorophenylacetic acid, 2-chlorophenylacetic acid, 4-bromophenylacetic acid and 2-iodophenylacetic acid are common chemical products, have the characteristics of large polarity and water solubility, and can stably and durably exist in water, so that the halogen-containing compound becomes a source of harmful chemical substances for polluting drinking water.
At present, the detection method and the standard lack related to 2-fluorophenylacetic acid, 2-chlorophenylacetic acid, 4-bromophenylacetic acid and 2-iodophenylacetic acid, and the literature which can be referred to in the field of analysis and detection mainly is to apply high performance liquid chromatography to determine hydroxy-phenylacetic acid in Chinese herbal medicines and fermentation liquor, does not relate to the relevant research of pretreatment of analysis and test, and has little reference value for simultaneously determining four trace target compounds in water.
The inventor research team has conducted extensive research on Layered Double Hydroxide (LDHs) and modified materials thereof since 2011, prepared different intercalation anion modified LDHs and roasted product (LDO) materials thereof, and used the synthetic materials to develop application research on screening, investigation and optimization of adsorption enrichment performance of different target compounds.
In the previous research, the inventor uses various modified LDHs and corresponding LDO materials to perform selective tests on the adsorption performance of four monohalogenated phenylacetic acid compounds such as 2-fluorophenylacetic acid, 2-chlorophenylacetic acid, 4-bromophenylacetic acid, 2-iodophenylacetic acid and the like, and finds that the 4-ethylbenzenesulfonate-magnesium-aluminum type hydrotalcite adsorbent has good adsorption effect on four target substances in water. On the basis, the inventor further optimizes the performance and application method of the developed target compound in the adsorbent enriched water, and establishes a gas chromatography-mass spectrometry combined method for detecting four trace monohalophenylacetic acids in drinking water by using 4-ethyl benzene sulfonate-magnesium aluminum type hydrotalcite as an adsorbent.
The establishment of the method can provide a quick and efficient method for detecting trace 2-fluorophenylacetic acid, 2-chlorophenylacetic acid, 4-bromophenylacetic acid and 2-iodophenylacetic acid in drinking water, and plays an important role in monitoring water quality and guaranteeing health and safety of people for related departments.
Disclosure of Invention
In order to overcome the defects of detection method and lack of standard in the prior pretreatment of detecting the trace amount of monohalogenated phenylacetic acid in drinking water, the invention aims to provide a gas chromatography-mass spectrometry combined method which is based on the rapid adsorption of novel adsorbent dispersed solid phase extraction and is suitable for detecting the trace amount of monohalogenated phenylacetic acid in the drinking water.
The invention achieves the above object by the following technical means.
A gas chromatography-mass spectrometry combined method for measuring four trace monohalogenated phenylacetic acids in drinking water comprises the following steps:
adsorption of the compound of step 1: the drinking water sample is stored at 4 ℃ for standby, when in use, a proper amount of drinking water is added into a separating funnel, 0.20g of 4-ethyl benzene sulfonate-magnesium aluminum type hydrotalcite adsorbent is added into the separating funnel, and the adsorbent is oscillated for a certain time to adsorb a target compound in water;
analytical testing of the compound of step 4: adding a stop solution into a derivatization bottle to remove redundant derivatization agents, adding a proper amount of solid sodium bicarbonate and anhydrous sodium sulfate, carrying out vortex, absorbing an upper layer organic solution, filtering, and then carrying out analysis and test by using a gas chromatography-mass spectrometer according to the following conditions:
a) a chromatographic column: DB-5MS capillary column, 30m × 0.25mm, 0.25 μm thick; column flow rate: 1.00 mL/min.
b) Sample inlet temperature: 280 ℃; and (3) sample introduction mode: no shunt sampling; sample introduction amount: 2 μ L.
c) Temperature rising procedure: 60 deg.C (1 min hold), and heating to 210 deg.C (1 min hold) at a rate of 10 deg.C/min.
d) EI bombardment source: 70 ev; temperature of a chromatography-mass spectrometry connection port: 300 ℃; temperature of the quadrupole rods: 230 ℃; ion source temperature: at 150 ℃.
e) Carrier gas: high-purity helium (the purity is more than or equal to 99.999%).
f) Mass spectrum data acquisition mode: selected ion scan mode (SIM), solvent delay time: and 6 min.
g) The quantitative and qualitative ion of the compounds are given in the following table:
| serial number | Name of Compound | Quantitative ion | Qualitative ion |
| 1 | 2-fluorophenylacetic acid derivatives | 109.0 | 168.0，110.0 |
| 2 | 2-chlorophenylacetic acid derivatives | 125.0 | 149.0，184.0 |
| 3 | 4-bromophenylacetic acid derivatives | 168.9 | 227.9，170.9 |
| 4 | 2-iodophenylacetic acid derivatives | 149.0 | 216.9，121.0 |
Wherein,
the four monohalogenated phenylacetic acids in the step 1 are respectively 2-fluorophenylacetic acid, 2-chlorophenylacetic acid, 4-bromophenylacetic acid and 2-iodophenylacetic acid, the drinking water amount is 200mL, and the oscillation time is 15 min.
The hydrochloric acid solution in the step 2 is prepared from concentrated hydrochloric acid and water according to the volume ratio of 1:1, and the dosage is 1.00 mL.
2.0g of anhydrous sodium sulfate and 5mL of ethyl acetate as an organic extraction solvent are added in the step 3, the volume of an ethyl acetate solution for derivatization is 2.00mL, a derivatization reagent is 0.2mL of methanol and 0.1mL of trimethylsilyl diazomethane n-hexane solution with the concentration of 2moL/L, the water bath temperature is 30-50 ℃, and the derivatization time is 30 min.
The stop solution in the step 4 is the hydrochloric acid solution in the claim 3, the addition amount is 0.05mL, the addition amount of solid sodium bicarbonate is 0.1g, the addition amount of anhydrous sodium sulfate is 0.5g, the filter membrane is an organic phase filter membrane, and the pore diameter is 0.22 μm.
The method needs to be explained in the process of research and development: in the process of research and development of the method, the inventor researches and optimizes the use amount of the adsorbent, the selection of the extraction solvent, the selection and optimization of a target object derivatization method, the selection of chromatographic separation conditions and mass spectrum conditions, the selectivity and anti-interference of quantitative and qualitative ions and other factors according to the characteristics of the adsorbed target object, and provides a relatively excellent detection method on the basis.
Meanwhile, in consideration of quantitative accuracy of the target object, the method quantifies the target object by adopting the matrix correction curve on the premise that the isotope of the target object cannot be obtained so as to quantify the target object by an isotope internal standard method, so that systematic errors are eliminated as much as possible, and the quantitative accuracy is improved.
The invention has the advantages that:
(1) the novel adsorbent 4-ethyl benzene sulfonate-magnesium-aluminum type hydrotalcite adopted by the invention can quickly adsorb trace amount of monohalogenated phenylacetic acid in water in a dispersed solid phase extraction mode, so that the enrichment is efficient;
(2) according to the invention, by utilizing the characteristic that the 4-ethyl benzene sulfonate-magnesium aluminum type hydrotalcite adsorbent can be dissolved in acid, the adsorbent after adsorbing the target object is dissolved by using a hydrochloric acid solution, so that the target object can be completely desorbed from the adsorbent;
(3) the invention is only suitable for a small amount of organic solvent as the extraction solvent of the target object, and has the advantages of safety, environmental protection and economic advantage.
Drawings
FIG. 1 is a chromatogram of a matrix standard solution of monohalophenylacetic acid of an embodiment at a concentration of 200.0. mu.g/L, wherein 1 is 2-fluorophenylacetic acid, 2 is 2-chlorophenylacetic acid, 3 is 4-bromophenylacetic acid, and 4 is 2-iodophenylacetic acid.
Detailed Description
For further disclosure, but not limitation, the present invention is described in further detail below with reference to examples.
(1) The reagent medicines involved in the embodiments of the present invention are as follows:
2-fluorophenylacetic acid, 2-chlorophenylacetic acid, 4-bromophenylacetic acid and 2-iodophenylacetic acid, wherein the purity is more than or equal to 98.0%, and the Aladdin science and technology Limited company;
methanol, ethyl acetate, anhydrous sodium sulfate, sodium bicarbonate, analytically pure, group of Chinese medicines;
hydrochloric acid, super pure, group of national medicine; the water is first-grade water meeting the GB/T6682 specification.
Trimethylsilyldiazomethane solution, 2.0M in hexane, Alfa Aesar.
(2) The instruments involved in the examples of the present invention are as follows:
KH-75A type electric heating constant temperature air-blast drying oven, Kangheng instruments ltd, Guangzhou;
model 7890B-5977A gas chromatography-mass spectrometer with electron bombardment source (EI), Agilent technologies, Inc., USA.
(3) Analyzing and testing conditions by a gas chromatography-mass spectrometer:
a) a chromatographic column: DB-5MS capillary column, 30m × 0.25mm, 0.25 μm thick; column flow rate: 1.00 mL/min.
b) Sample inlet temperature: 280 ℃; and (3) sample introduction mode: no shunt sampling; sample introduction amount: 2 μ L.
c) Temperature rising procedure: 60 deg.C (1 min hold), and heating to 210 deg.C (1 min hold) at a rate of 10 deg.C/min.
d) EI bombardment source: 70 ev; temperature of a chromatography-mass spectrometry connection port: 300 ℃; temperature of the quadrupole rods: 230 ℃; ion source temperature: at 150 ℃.
e) Carrier gas: high-purity helium (the purity is more than or equal to 99.999%).
f) Mass spectrum data acquisition mode: selected ion scan mode (SIM), solvent delay time: and 6 min.
g) The quantitative and qualitative ion of the compounds are given in the following table:
| serial number | Name of Compound | Quantitative ion | Qualitative ion |
| 1 | 2-fluorophenylacetic acid derivatives | 109.0 | 168.0，110.0 |
| 2 | 2-chlorophenylacetic acid derivatives | 125.0 | 149.0，184.0 |
| 3 | 4-bromophenylacetic acid derivatives | 168.9 | 227.9，170.9 |
| 4 | 2-iodophenylacetic acid derivatives | 149.0 | 216.9，121.0 |
(4) Preparation of matrix calibration curve and determination of detection limit and quantitative limit
Accurately weighing the monohalogenated phenylacetic acid, dissolving with methanol to a constant volume, and preparing into a standard stock solution with the concentration of 1000mg/L, and storing at-4 ℃. When in use, the standard stock solution is gradually diluted by deionized water to prepare standard use solution with the concentration gradient of 10.0 mug/L, 20.0 mug/L, 40.0 mug/L, 100.0 mug/L and 200.0 mug/L.
Taking five 500mL separating funnels, adding 200mL deionized water into the separating funnels, respectively taking 5.00mL standard use solutions, preparing standard samples with series concentrations to prepare a matrix correction curve, then adding 0.20g of 4-ethyl benzene sulfonate-magnesium aluminum type hydrotalcite adsorbent into each funnel, and oscillating for 15min to adsorb the adsorbent; adding water in a separating funnel into a 50mL centrifuge tube with a plug, centrifuging at the rotating speed of 4500rpm for 3min to separate the solid adsorbent from the aqueous solution and discard the supernatant, combining all the lower-layer solid adsorbents into one centrifuge tube, adding 1.00mL of hydrochloric acid solution diluted by 1 time into the centrifuge tube, and realizing desorption of the adsorbed target after the solid adsorbent is dissolved; adding 2.0g of anhydrous sodium sulfate into the centrifuge tube, adding 5.0mL of ethyl acetate, whirling for 1min, centrifuging at the rotating speed of 4500rpm for 3min, taking the supernatant into a derivatization bottle, adding 0.2mL of methanol and 0.1mL of trimethylsilylated diazomethane n-hexane solution with the concentration of 2moL/L, sealing, uniformly mixing, standing in a water bath at 50 ℃ for derivatization for 30min, and finishing the methyl esterification derivatization process; adding 0.05mL of the above hydrochloric acid solution to the above derivatization bottle to remove excess trimethylsilylated diazomethane, then adding 0.1g of solid sodium bicarbonate and 0.5g of anhydrous sodium sulfate, vortexing to remove the remaining hydrochloric acid and water, and sucking the upper organic solution through an organic phase filter with a pore size of 0.22 μm, followed by analysis and testing by gas chromatography.
And (3) taking the concentration of the monohalogenated phenylacetic acid in the sample solution as an X axis, and taking the peak area of the chromatographic peak of the monohalogenated phenylacetic acid derivative on a gas chromatography-mass spectrometer as a Y axis to draw a matrix standard curve and use the matrix standard curve for external standard method quantification.
The triple value of the signal-to-noise ratio S/N is taken as the detection limit of the method (LOD, LOD is 3S/N), the ten times of the signal-to-noise ratio S/N is taken as the quantification limit of the method (LOQ, LOQ is 10S/N), and the detection limit and the quantification limit of each compound in water are calculated by combining the volume of the added matrix.
The relevant parameters of the matrix standard curve, LOD and LOQ are shown in Table 1.
TABLE 1 information on the matrix standard curves, detection limits and quantitation limits for four monohalophenylacetic acids
(5) Synthesis of 4-ethyl benzene sulfonate-magnesium-aluminum type hydrotalcite adsorbent
In order to enable those skilled in the art to repeatedly carry out the relevant experiments of the present invention, a method for synthesizing the key substance 4-ethylbenzenesulfonate-magnesium aluminum type hydrotalcite adsorbent used in the present invention is now provided, as follows:
the reagent and the drug related to the synthesis of the adsorbent are as follows:
4-ethyl benzene sulfonic acid sodium salt, analytically pure, group of Chinese medicine;
Mg6Al2(OH)16CO3·4H2o, analytical grade, Aldrich, usa.
② the apparatus related to the synthesis of the adsorbent is as follows:
an EXCEL type microwave digestion instrument, Shanghai Yao Instrument science and technology development Co., Ltd., digestion tank volume of 100 mL; microwave muffle furnace (sintering furnace), CEM corporation, usa; model VD53 vacuum drying cabinet, German Bindd technologies; HJ-5 multifunctional constant temperature stirrer, Kantai Ronghua Instrument manufacturing Co., Ltd; FS-12 type separatory funnel oscillator, New optical technology, Japan; 3K-15 type centrifuge, sigma technologies, germany; BF518945C-1 model box resistance furnace (muffle furnace), Saimer Feishell science, USA.
The concrete steps of synthesizing the adsorbent are as follows:
(a) roasting: mg of purchased Mg-Al type hydrotalcite6Al2(OH)16CO3·4H2O is placed in a muffle furnace toHeating the mixture to 500 ℃ at the heating rate of 5 ℃/min, and roasting the mixture for 6 hours to obtain a roasted product Mg6Al2O8(OH)2；
(b) Weighing: 12.493g of intercalator 4-ethyl benzene sodium sulfonate and 7.236g of roasted product Mg are weighed in a microwave digestion tank6Al2O8(OH)2。
(c) Microwave crystallization hydrothermal synthesis: boiling deionized water and keeping for 30min, then adding 100mL into the microwave digestion tank filled with the intercalation agent and the roasting product, sealing, placing the microwave digestion tank into a microwave digestion instrument, and carrying out microwave heating for 30min at 140 ℃ to complete synthesis;
(d) washing and drying: pouring out all solids and liquid in the microwave tank, heating and stirring with deionized water boiled for more than 30min to remove carbon dioxide, shaking, washing, centrifuging, vacuum drying at 90 deg.C for 12h, grinding, and storing.
Example 1
In this example 1, tap water was used as a sample matrix to perform a labeling recovery experiment to verify the feasibility of the method of the present invention, the tap water sample was taken from a laboratory of the integrated technical service center of the inspection and quarantine bureau of the Fuqing immigration, the tap water was collected after the tap was opened for 15min, and the tap water sample was treated according to the following steps:
1. adsorption of the compound:
adding 200mL of tap water into a 500mL separating funnel, adding 5.00mL of four compound standard solutions with the concentrations of 10.0 mu g/L, 20.0 mu g/L and 200.0 mu g/L respectively to prepare a three-level six-parallel standard sample, adding 0.20g of 4-ethyl benzene sulfonate-magnesium aluminum type hydrotalcite adsorbent respectively, and oscillating for 15min to adsorb the adsorbent;
2. desorption of the compound:
adding water in a separating funnel into a 50mL centrifuge tube with a plug, centrifuging at the rotating speed of 4500rpm for 3min to separate the solid adsorbent from the aqueous solution and discard the supernatant, combining all the lower-layer solid adsorbents into one centrifuge tube, adding 1.00mL of hydrochloric acid solution diluted by 1 time into the centrifuge tube, and realizing desorption of the adsorbed compound after the solid adsorbent is dissolved;
3. extraction and derivatization of compounds:
adding 2.0g of anhydrous sodium sulfate into the centrifuge tube, adding 5.00mL of ethyl acetate, whirling for 1min, centrifuging at the rotating speed of 4500rpm for 3min, taking the supernatant into a derivatization bottle, adding 0.2mL of methanol and 0.1mL of trimethylsilylated diazomethane n-hexane solution with the concentration of 2moL/L, sealing, uniformly mixing, standing in a water bath at 50 ℃ for derivatization for 30min, and finishing the methyl esterification derivatization process;
4. analysis and test:
to the above derivatization bottle was added 0.05mL of the above hydrochloric acid solution to remove excess trimethylsilylated diazomethane, followed by addition of 0.1g of solid sodium bicarbonate, 0.5g of anhydrous sodium sulfate, vortexing, and the upper organic solution was drawn up through an organic phase filter having a pore size of 0.22 μm and analyzed by gas chromatography.
The parameters relevant to the spiking recovery experiment of example 1 are shown in Table 2.
Table 2 experimental data on the addition concentration and recovery rate of the tap water sample (n ═ 6)
Example 2
In this example 2, a standard recovery experiment was performed using well water as a sample matrix to verify the feasibility of the method of the present invention, wherein the well water was produced by a well water source from yowey fishery limited, fu qing, and was treated according to the following steps:
1. adsorption of the compound:
adding 200mL of well water into a 500mL separating funnel, adding 5.00mL of four compound standard solutions with the concentrations of 10.0 mu g/L, 20.0 mu g/L and 200.0 mu g/L respectively to prepare a three-level six-parallel standard sample, adding 0.20g of 4-ethyl benzene sulfonate-magnesium aluminum type hydrotalcite adsorbent, and oscillating for 15min to adsorb the adsorbent;
2. desorption of the compound:
adding water in a separating funnel into a 50mL centrifuge tube with a plug, centrifuging at the rotating speed of 4500rpm for 3min to separate the solid adsorbent from the aqueous solution and discard the supernatant, combining all the lower-layer solid adsorbents into one centrifuge tube, adding 1.00mL of hydrochloric acid solution diluted by 1 time into the centrifuge tube, and realizing desorption of the adsorbed compound after the solid adsorbent is dissolved;
3. extraction and derivatization of compounds:
adding 2.0g of anhydrous sodium sulfate into the centrifuge tube, adding 5.00mL of ethyl acetate, whirling for 1min, centrifuging at the rotating speed of 4500rpm for 3min, separating 2.00mL of supernatant into a derivatization bottle, adding 0.2mL of methanol and 0.1mL of trimethylsilylated diazomethane n-hexane solution with the concentration of 2moL/L, sealing, uniformly mixing, standing in a water bath at 30 ℃ for derivatization for 30min, and finishing the methyl esterification derivatization process;
4. analysis and test:
to the above derivatization bottle was added 0.05mL of the above hydrochloric acid solution to remove excess trimethylsilylated diazomethane, followed by addition of 0.1g of solid sodium bicarbonate, 0.5g of anhydrous sodium sulfate, vortexing, and the upper organic solution was drawn up through an organic phase filter having a pore size of 0.22 μm and analyzed by gas chromatography.
The parameters relevant to the spiking recovery experiment of example 2 are shown in Table 3.
Table 3 experimental data on the addition concentration and recovery rate of the well water sample (n ═ 6)
The above-mentioned embodiments only express the embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the spirit of the invention, which falls within the scope of the invention, and therefore the scope of the patent of the invention shall be governed by the appended claims.
Claims (6)
1. A gas chromatography-mass spectrometry combined method for measuring four trace monohalogenated phenylacetic acids in drinking water is characterized by comprising the following steps:
(1) adsorption of the compound: the drinking water sample is stored at 4 ℃ for standby, when in use, a proper amount of drinking water is added into a separating funnel, 0.20g of 4-ethyl benzene sulfonate-magnesium aluminum type hydrotalcite adsorbent is added into the separating funnel, and the adsorbent is oscillated for a certain time to adsorb 2-fluorophenylacetic acid, 2-chlorophenylacetic acid, 4-bromophenylacetic acid and 2-iodophenylacetic acid in the water;
(2) desorption of the compound: transferring the mixture of the adsorbent and water in the separating funnel into a centrifuge tube with a plug for centrifugation, separating the solid adsorbent from the aqueous solution, discarding the supernatant, combining all the lower-layer solid adsorbents into one centrifuge tube, and adding a certain amount of hydrochloric acid solution into the centrifuge tube to dissolve the solid adsorbent so as to complete desorption of the adsorbed compound;
(3) extraction and derivatization of compounds: adding a certain amount of anhydrous sodium sulfate and an organic solvent into the centrifugal tube for extraction, performing vortex and centrifugation, taking supernatant liquid to a derivatization bottle, adding a derivatization reagent into the supernatant liquid, sealing, uniformly mixing, and placing the mixture in a constant-temperature water bath to finish the methyl esterification derivatization process;
(4) analytical testing of compounds: adding a stop solution into a derivatization bottle to remove redundant derivatization agents, adding a proper amount of solid sodium bicarbonate and anhydrous sodium sulfate, carrying out vortex, absorbing an upper layer organic solution, filtering, and then carrying out analysis and test by using a gas chromatography-mass spectrometer according to the following conditions:
a) a chromatographic column: DB-5MS capillary column, 30m × 0.25mm, 0.25 μm thick; column flow rate: 1.00 mL/min;
b) sample inlet temperature: 280 ℃; and (3) sample introduction mode: no shunt sampling; sample introduction amount: 2 mu L of the solution;
c) temperature rising procedure: keeping at 60 deg.C for 1min, heating to 210 deg.C at a speed of 10 deg.C/min, and keeping for 1 min;
d) EI bombardment source: 70 ev; temperature of a chromatography-mass spectrometry connection port: 300 ℃; temperature of the quadrupole rods: 230 ℃; ion source temperature: 150 ℃;
e) carrier gas: high-purity helium with the purity more than or equal to 99.999 percent;
f) mass spectrum data acquisition mode: selection of ion scan mode, solvent delay time: 6 min;
g) the quantitative and qualitative ion of the compounds are given in the following table:
。
2. The gas chromatography-mass spectrometry combination for measuring four trace monohalophenylacetic acids in drinking water as claimed in claim 1, wherein the drinking water amount in step (1) is 200mL, and the shaking time is 15 min.
3. The gas chromatography-mass spectrometry combination for determining four trace monohalophenylacetic acids in drinking water as claimed in claim 1, wherein the hydrochloric acid solution in step (2) is prepared from concentrated hydrochloric acid and water according to a volume ratio of 1:1, and the dosage is 1.00 mL.
4. The gas chromatography-mass spectrometry combination for measuring four trace monohalogenated phenylacetic acids in drinking water as claimed in claim 1, wherein the anhydrous sodium sulfate added in step (3) is 2.0g, the organic extraction solvent is 5.00mL of ethyl acetate, the volume of the ethyl acetate solution for derivatization is 2.00mL, the derivatization reagent is 0.2mL of methanol and 0.1mL of trimethylsilyl diazomethane n-hexane solution with the concentration of 2mol/L, the water bath temperature is 30 ℃ to 50 ℃, and the derivatization time is 30 min.
5. The gas chromatography-mass spectrometry combination for measuring four trace monohalophenylacetic acids in drinking water as claimed in claim 1, wherein the stop solution in step (4) is hydrochloric acid solution, the addition amount is 0.05mL, the addition amount of solid sodium bicarbonate is 0.1g, the addition amount of anhydrous sodium sulfate is 0.5g, the filter membrane for filtration is organic phase filter membrane, and the pore diameter is 0.22 μm.
6. The gas chromatography-mass spectrometry combination for the determination of four trace monohalophenylacetic acids in drinking water as claimed in claim 1, wherein the vortexing is vortexing for 1min to 2min and the centrifugation is performed at 4500rpm for 3 min.
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