CN109212051B - Gas chromatography-mass spectrometry combined method for determining nine trace amounts of halogenated nicotinic acid in drinking water - Google Patents
Gas chromatography-mass spectrometry combined method for determining nine trace amounts of halogenated nicotinic acid in drinking water Download PDFInfo
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- 238000004458 analytical method Methods 0.000 claims abstract description 9
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- 238000001179 sorption measurement Methods 0.000 claims abstract description 8
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- GCRNGPNGNJSZCC-UHFFFAOYSA-N tert-butyl 3-amino-3a,4,6,6a-tetrahydro-1h-pyrrolo[3,4-c]pyrazole-5-carboxylate Chemical compound N1N=C(N)C2CN(C(=O)OC(C)(C)C)CC21 GCRNGPNGNJSZCC-UHFFFAOYSA-N 0.000 claims abstract description 5
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- 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
- G01N30/08—Preparation using an enricher
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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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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-fluoroisonicotinic acid, 5-fluoronicotinic acid, 2-chloro-5-fluoronicotinic acid, 2-chloroisonicotinic acid, 5-chloronicotinic acid, 3-bromoisonicotinic acid, 5-bromonicotinic acid, 2, 6-dichloro-5-fluoronicotinic acid and 5-bromo-6-chloronicotinic acid in drinking water. The method comprises the steps of taking a novel p-toluenesulfonate-magnesium-aluminum type hydrotalcite roasted product as an adsorbent to enrich a target compound in drinking water, dissolving the adsorbent with an acid to realize complete elution of the target compound, carrying out high-efficiency extraction on the compound with a small amount of organic solvent, selecting and optimizing a derivatization method, and carrying out rapid analysis and determination by a gas chromatography-mass spectrometry combined method. 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, the complete desorption of the target object can be realized by applying an acid-soluble adsorbent, and the method has the obvious advantages of safety, environmental protection and economic advantages only by 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 measuring trace 2-fluoroisonicotinic acid, 5-fluoronicotinic acid, 2-chloro-5-fluoronicotinic acid, 2-chloroisonicotinic acid, 5-chloronicotinic acid, 3-bromoisonicotinic acid, 5-bromonicotinic acid, 2, 6-dichloro-5-fluoronicotinic acid and 5-bromo-6-chloronicotinic acid in drinking water.
Background
2-fluoroisonicotinic acid, 5-fluoronicotinic acid, 2-chloro-5-fluoronicotinic acid, 2-chloroisonicotinic acid, 5-chloronicotinic acid, 3-bromoisonicotinic acid, 5-bromonicotinic acid, 2, 6-dichloro-5-fluoronicotinic acid and 5-bromo-6-chloronicotinic acid are nine common halogen-containing chemical products, have the characteristics of large polarity and easy dissolution in water, and can stably and durably exist in water, thereby becoming a source of harmful chemical substances polluting drinking water. These halogen-containing compounds can enter human body through drinking water, thus bringing harm to the health safety of people.
Currently, the detection of the nicotinic acid in the food is mainly the national standard GB/T5009.89-2003 for the determination of the nicotinic acid in the food, wherein the determination is mainly carried out by using a microbial culture-fermentation-product titration identification mode. The standard is not mentioned in the nine halogen-containing nicotinic acids in the invention, and the inventor searches the literature and finds that no relevant literature reports the detection methods of the substances at present. Therefore, the detection of trace amount of halogenated nicotinic acid compounds in the polluted drinking water is in a state of lacking of methods and standards, so that people can pay attention to the harm of the compounds to the health of human bodies but suffer from no effective detection monitoring method.
Layered Double Hydroxide (LDHs) is a typical Layered material with a supramolecular intercalation structure, and is mainly composed of positively charged laminates formed by combining Hydroxides of divalent and trivalent metals and negatively charged anions intercalated between the laminates. Two notable features of this material are: space adjustability between the laminate layers and replaceability of the intercalated anions. Based on the method, people can modify the LDHs material according to the difficulty of replaceability of intercalation anions of the LDHs material and the adjustability of the distance between the layers, and then select different types of intercalation anions according to the requirements of practical application to modify the material to obtain a functional material with novel application.
Meanwhile, the modified material is roasted at the temperature of 450-500 ℃, anions inserted between the laminated plates can be effectively removed, and only a cavity-shaped laminated plate structure with an adjusted interval is left, so that a roasted product (LDO) is obtained. The gaps between the laminates are adjusted after the materials are modified, so that the selectivity of different targets entering the laminates is shown. Generally in the field of LDHs and their corresponding LDOs for use as adsorbents, some LDHs exhibit higher adsorption performance than their corresponding LDHs due to their more hollow void structures.
The inventor carries out adsorption experiments on nine halogenated nicotinic acid compounds in water by applying a roasted product (STS-MgAl-LDO) of the p-toluenesulfonate-magnesium-aluminum type hydrotalcite in earlier researches, and the result shows that the adsorbent for the roasted product of the p-toluenesulfonate-magnesium-aluminum type hydrotalcite has a good adsorption effect on a target object. 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 nine kinds of trace halogenated nicotinic acid in drinking water by taking a p-toluenesulfonate-magnesium aluminum type hydrotalcite roasted product as an adsorbent.
Disclosure of Invention
Under the circumstance that the drinking water is polluted by halogenated nicotinic acid compounds and no good trace residue monitoring technology exists, the invention aims to overcome the defects that the existing detection method for nine kinds of trace halogenated nicotinic acid in the drinking water is lack and the monitoring technology for the trace residues of the substances in the drinking water is weak, and provides a gas chromatography-mass spectrometry combined method which is based on a novel adsorbent, can be quickly adsorbed in a dispersed solid phase extraction mode and is suitable for detecting the nine kinds of trace halogenated nicotinic 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 nine trace amounts of halogenated nicotinic acid in drinking water comprises the following steps:
adsorption of the compound of step 1: sampling drinking water, storing at 4 ℃, adding 0.20g of p-toluenesulfonate-magnesium-aluminum type hydrotalcite roasted product adsorbent into a separating funnel filled with a water sample when in use, and oscillating for a certain time to enable the adsorbent to adsorb a target compound in the water;
analytical testing of the compound of step 4: placing the derivative bottle in a refrigerator below-10 ℃ for cooling for 10min to 15min, adding 0.5mL of saturated sodium chloride aqueous solution and 0.5g of sodium bicarbonate powder into the derivative bottle, carrying out vortex, adding 1.0g of anhydrous sodium sulfate into the derivative bottle, carrying out vortex and centrifugation, completely taking an organic solution, blowing the organic solution to the vicinity of dry nitrogen at 40 ℃, carrying out volume determination by acetone, then passing through an organic phase filter membrane, and carrying out analysis and test by a gas chromatography-mass spectrometry method 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: 250 ℃; and (3) sample introduction mode: no shunt sampling; sample introduction amount: 2 μ L.
c) Temperature rising procedure: 60 deg.C (keeping 1min), heating to 120 deg.C at 10 deg.C/min (keeping 1min), heating to 140 deg.C at 10 deg.C/min (keeping 5min), and running at 250 deg.C (keeping 3 min).
d) EI bombardment source: 70 ev; temperature of a chromatography-mass spectrometry connection port: 280 ℃; 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-fluoroisonicotinic acid derivatives | 124.1 | 155.1，137.1 |
| 2 | 5-fluoronicotinic acid derivatives | 124.1 | 155.1，137.1 |
| 3 | 2-chloro-5-fluoronicotinic acid derivatives | 158.0 | 189.0，130.0 |
| 4 | 2-chloroisonicotinic acid derivatives | 140.0 | 171.0，112.0 |
| 5 | 5-chloronicotinic acid derivatives | 140.0 | 171.0，112.0 |
| 6 | 3-bromoisonicotinic acid derivatives | 184.0 | 215.0，156.0 |
| 7 | 5-Bromonicotinic acid derivatives | 184.0 | 215.0，156.0 |
| 8 | 2, 6-dichloro-5-fluoronicotinic acid derivatives | 192.0 | 194.0，223.0 |
| 9 | 5-bromo-6-chloronicotinic acid derivatives | 219.9 | 250.9，191.9 |
Wherein,
the drinking water amount in the step 1 is 200mL, and the oscillation time is 15 min.
The hydrochloric acid solution A in the step 2 is prepared from concentrated hydrochloric acid and water according to the volume ratio of 1:1, and the dosage is 2.00 mL.
The anhydrous sodium sulfate added in the step 3 is 2.0g, the organic extraction solvent is prepared from ethyl acetate and methyl tert-butyl ether according to the volume ratio of 1:1, the dosage of the extraction solvent is 5.00mL, and the dosage of 2mol/L HCl-methanol solution is 1.00 mL.
The volume of the acetone for constant volume in the step 4 is 5.00mL, the filter membrane is an organic phase filter membrane, and the aperture is 0.22 mu m
The vortex described in the above step is vortex for 1min, and the centrifugation is run at 4500rpm for 3 min.
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 variety and the dosage of the adsorbent, the selection and the proportion of an extraction solvent, the selection and the optimization of various derivatization methods of a target object, the selection and the optimization of chromatographic separation conditions, the selection and the optimization of mass spectrum conditions, the selectivity and the anti-interference performance of quantitative and qualitative ions and other factors, 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 adopted by the invention can quickly adsorb nine trace halogenated nicotinic acids in water by adopting a dispersed solid-phase extraction mode on a toluene sulfonate-magnesium aluminum type hydrotalcite roasted product, so that the enrichment is efficient;
(2) according to the invention, by utilizing the characteristic that the p-toluenesulfonate-magnesium-aluminum type hydrotalcite calcined product 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 nine kinds of halogenated nicotinic acids in the embodiment at a concentration of 500.0. mu.g/L, wherein 1 is 2-fluoroisonicotinic acid, 2 is 5-fluoronicotinic acid, 3 is 2-chloro-5-fluoronicotinic acid, 4 is 2-chloroisonicotinic acid, 5 is 5-chloronicotinic acid, 6 is 3-bromoisonicotinic acid, 7 is 5-bromonicotinic acid, 8 is 2, 6-dichloro-5-fluoronicotinic acid, and 9 is 5-bromo-6-chloronicotinic acid. Wherein, the peak-appearing time interval of the 3-bromoisonicotinic acid and the 5-bromonicotinic acid is short, so that the 3-bromoisonicotinic acid and the 5-bromonicotinic acid are in an overlapped state in a total chromatogram, but the ion extraction function of GC-MS is not applied to influence the quantification.
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:
nine kinds of compound solid standard substances such as 5-fluoronicotinic acid, 5-chloronicotinic acid, 5-bromonicotinic acid and the like, the purity is more than or equal to 98.0 percent, and the Shanghai Michelle chemical technology company Limited;
methanol, ethyl acetate, methyl tert-butyl ether, acetone, sodium chloride, 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.
(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: 250 ℃; and (3) sample introduction mode: no shunt sampling; sample introduction amount: 2 μ L.
c) Temperature rising procedure: 60 deg.C (keeping 1min), heating to 120 deg.C at 10 deg.C/min (keeping 1min), heating to 140 deg.C at 10 deg.C/min (keeping 5min), and running at 250 deg.C (keeping 3 min).
d) EI bombardment source: 70 ev; temperature of a chromatography-mass spectrometry connection port: 280 ℃; 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:
(4) preparation of matrix calibration curve and determination of detection limit and quantitative limit
Accurately weighing the target substance, dissolving with methanol to constant volume, and making into standard stock solution with concentration of 1000mg/L, and storing at-4 deg.C. 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 of the standard use solution, mixing to prepare a matrix calibration curve sample with a series of concentrations, then adding 0.20g of p-toluenesulfonate-magnesium aluminum type hydrotalcite calcination product adsorbent into each funnel, and oscillating for 15min to enable the adsorbent to adsorb; 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 a mixed solution of ethyl acetate and methyl tert-butyl ether (volume ratio is 1:1), whirling for 1min, centrifuging at the rotating speed of 4500rpm for 3min, taking supernatant into a derivatization bottle, adding 1.00mL of a proper amount of 2mol/L HCl-methanol solution, sealing, whirling, uniformly mixing, and placing in a water bath at 60 ℃ for 30min to finish the derivatization process; placing the derivative bottle in a refrigerator below-10 ℃ for cooling for 10min, adding 0.5mL of saturated sodium chloride aqueous solution and 0.5g of sodium bicarbonate powder into the derivative bottle, swirling, adding 1.0g of anhydrous sodium sulfate into the derivative bottle, swirling, centrifuging, completely taking the organic solution, blowing the organic solution to the near dry state at 40 ℃ by nitrogen, metering the volume by 5.00mL of acetone, passing through an organic phase filter membrane with the aperture of 0.22 mu m, and performing analysis and test by using a gas chromatography-mass spectrometry combined method.
And (3) taking the concentration of the target in the sample solution as an X axis, and taking the chromatographic peak area of the 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 curve, detection limit and quantification limit of nine trace halogenated nicotinic acids
(5) Synthesis of p-methyl benzene sulfonate-magnesium-aluminum type hydrotalcite calcined product 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 p-toluenesulfonate-magnesium aluminum type hydrotalcite calcined product adsorbent, which is a key substance 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:
sodium p-toluenesulfonate, analytically pure, pharmaceutical group;
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) first roasting: mg of purchased Mg-Al type hydrotalcite6Al2(OH)16CO3·4H2Placing O in a muffle furnace, heating at a heating rate of 5 ℃/min to 500 ℃, and roasting for 6h to obtain a roasted product Mg6Al2O8(OH)2；
(b) Weighing: 13.509g of intercalation agent sodium p-toluenesulfonate and 7.236g of roasting 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 the deionized water which is boiled for more than 30min and is removed of carbon dioxide, oscillating, washing and centrifuging, and taking out white solid substances to obtain the methyl benzene sulfonate-magnesium aluminum type hydrotalcite;
(e) and (3) second roasting: and (d) placing the product obtained in the step (d) in a muffle furnace, heating to 500 ℃ at a heating rate of 5 ℃/min, roasting for 6h, grinding and storing to obtain a roasted product of the methyl benzene sulfonate-magnesium aluminum type hydrotalcite, namely the adsorbent applied to the method development.
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, wherein the tap water sample was taken from a laboratory of the integrated technical service center of the inspection and quarantine bureau for export and import of Fuqing, and when sampling, the tap water was opened for 5min, and a large beaker was used to take a water sample, and then the sample was stored at 4 ℃ for further use. When in use, the preparation method comprises the following steps:
1. adsorption of the compound:
adding 200mL of tap water into a 500mL separating funnel, adding 5.00mL of nine 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 three-level six-parallel labeled positive samples, adding 0.20g of p-toluenesulfonate-magnesium aluminum type hydrotalcite calcined product adsorbent into the positive samples 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 5.0mL of a mixed solution of ethyl acetate and methyl tert-butyl ether (volume ratio is 1:1), whirling for 1min, centrifuging at the rotating speed of 4500rpm for 3min, taking supernatant into a derivatization bottle, adding 1.00mL of a proper amount of 2mol/L HCl-methanol solution, sealing, whirling, uniformly mixing, and placing in a water bath at 60 ℃ for 30min to finish the derivatization process;
4. analysis and test:
placing the derivative bottle in a refrigerator below-10 ℃ for cooling for 10min, adding 0.5mL of saturated sodium chloride aqueous solution and 0.5g of sodium bicarbonate powder into the derivative bottle, swirling, adding 1.0g of anhydrous sodium sulfate into the derivative bottle, swirling, centrifuging, completely taking the organic solution, blowing the organic solution to the near dry state at 40 ℃ by nitrogen, metering the volume by 5.00mL of acetone, passing through an organic phase filter membrane with the aperture of 0.22 mu m, and performing analysis and test by using a gas chromatography-mass spectrometry combined method.
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 addition recovery experiment is performed by using well water as a sample matrix to verify the feasibility of the method, wherein the well water sample is well water for production of Longxiang aquatic food products, ltd, located in Fuqing, and is 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 nine 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 three-level six-parallel labeled positive samples, adding 0.20g of p-toluenesulfonate-magnesium aluminum type hydrotalcite roasted product adsorbent into the positive samples 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 5.0mL of a mixed solution of ethyl acetate and methyl tert-butyl ether (volume ratio is 1:1), whirling for 1min, centrifuging at the rotating speed of 4500rpm for 3min, taking supernatant into a derivatization bottle, adding 1.00mL of a proper amount of 2mol/L HCl-methanol solution, sealing, whirling, uniformly mixing, and placing in a water bath at 60 ℃ for 30min to finish the derivatization process;
4. analysis and test:
placing the derivative bottle in a refrigerator below-10 ℃ for cooling for 10min, adding 0.5mL of saturated sodium chloride aqueous solution and 0.5g of sodium bicarbonate powder into the derivative bottle, swirling, adding 1.0g of anhydrous sodium sulfate into the derivative bottle, swirling, centrifuging, completely taking the organic solution, blowing the organic solution to the near dry state at 40 ℃ by nitrogen, metering the volume by 5.00mL of acetone, passing through an organic phase filter membrane with the aperture of 0.22 mu m, and performing analysis and test by using a gas chromatography-mass spectrometry combined method.
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 nine trace amounts of halogenated nicotinic acid in drinking water is characterized by comprising the following steps:
(1) adsorption of the compound: sampling drinking water, storing at 4 deg.C, adding 0.20g p-toluenesulfonate-magnesium aluminum type hydrotalcite calcined product adsorbent into a separating funnel filled with water sample, and oscillating for a certain time to make the adsorbent adsorb 2-fluoroisonicotinic acid, 5-fluoronicotinic acid, 2-chloro-5-fluoronicotinic acid, 2-chloroisonicotinic acid, 5-chloronicotinic acid, 3-bromoisonicotinic acid, 5-bromonicotinic acid, 2, 6-dichloro-5-fluoronicotinic acid and 5-bromo-6-chloronicotinic acid in 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 A into the centrifuge tube to dissolve the solid adsorbent, thereby completing 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 to a derivatization bottle, adding a proper amount of 2mol/L HCl-methanol solution into the derivatization bottle, sealing, performing vortex mixing, and placing the mixture in a water bath at 60 ℃ for 30min to complete the derivatization process;
(4) analytical testing of compounds: placing the derivative bottle in a refrigerator below-10 ℃ for cooling for 10min to 15min, adding 0.5mL of saturated sodium chloride aqueous solution and 0.5g of sodium bicarbonate powder into the derivative bottle, carrying out vortex, adding 2.0g of anhydrous sodium sulfate into the derivative bottle, carrying out vortex and centrifugation, completely taking an organic solution, blowing the organic solution to the vicinity of dry nitrogen at 40 ℃, carrying out volume determination by acetone, passing through an organic phase filter membrane, and carrying out analysis and test by a gas chromatography-mass spectrometry method 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: 250 ℃; 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 120 deg.C at a speed of 10 deg.C/min for 1min, heating to 140 deg.C at a speed of 10 deg.C/min for 5min, and then operating at 250 deg.C for 3 min;
d) EI bombardment source: 70 ev; temperature of a chromatography-mass spectrometry connection port: 280 ℃; 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 nine trace amounts of halogenated nicotinic acid in drinking water as claimed in claim 1, wherein the drinking water sample amount in step (1) is 200mL, and the oscillation time is 15 min.
3. The gas chromatography-mass spectrometry combination for measuring nine trace amounts of halogenated nicotinic acid in drinking water as claimed in claim 1, wherein the hydrochloric acid solution A in step (2) is prepared by 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 method for measuring nine trace amounts of halogenated nicotinic acid 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 prepared from ethyl acetate and methyl tert-butyl ether according to the volume ratio of 1:1, the amount of the extraction solvent is 5.00mL, the amount of 2mol/L HCl-methanol solution is 1.00mL, and the volume of acetone for constant volume is 5.00 mL.
5. The gas chromatography-mass spectrometry combination for measuring nine trace amounts of halogenated nicotinic acids in drinking water as claimed in claim 1, wherein the volume of acetone used for volume determination in step (4) is 5.00mL, and the filter membrane for filtration is an organic phase filter membrane with a pore size of 0.22 μm.
6. The gas chromatography-mass spectrometry combination for the determination of nine traces of halonicotinic acid in drinking water as claimed in claim 1, wherein the vortexing is vortexing for 1min and the centrifugation is performed at 4500rpm for 3 min.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101812016A (en) * | 2009-02-23 | 2010-08-25 | 浙江海翔药业股份有限公司 | Method for preparing 6-methylnicotinic acid etoricoxib intermediate and ester thereof |
| CN103265479A (en) * | 2013-06-14 | 2013-08-28 | 南开大学 | Synthetic method of 6-chloromethyl niacin tert-butyl ester |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101812016A (en) * | 2009-02-23 | 2010-08-25 | 浙江海翔药业股份有限公司 | Method for preparing 6-methylnicotinic acid etoricoxib intermediate and ester thereof |
| CN103265479A (en) * | 2013-06-14 | 2013-08-28 | 南开大学 | Synthetic method of 6-chloromethyl niacin tert-butyl ester |
Non-Patent Citations (5)
| Title |
|---|
| 5-卤代烟酸与5-卤代烟酸乙酯的分离及HPLC测定研究;周雪枫;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20061215(第12期);第E014-427页 * |
| Application of Dissolvable Layered Double Hydroxides As Sorbent in Dispersive Solid-Phase Extraction and Extraction by Co-Precipitation for the Determination of Aromatic Acid Anions;Sheng Tang 等;《Analytical Chemistry》;20130716;第85卷;第7426-7433页 * |
| 对甲苯磺酸根插层Mg3Al- LDHS的制备及其对水中六种苯氧羧酸类除草剂的吸附性能;丁立平 等;《化学工程师》;20180625(第06期);第8页第1.1、1.4.1节 * |
| 柱前衍生-固相萃取/气相色谱法测定油菜、土壤中二氯吡啶酸;吴祥为 等;《分析试验室》;20091231;第28卷(第12期);第35-36页第1.2、1.3、1.5节 * |
| 硅烷化衍生-气相色谱-质谱联用法测定烟酸;庄付磊 等;《理化检验-化学分册》;20101231;第46卷(第5期);第506-508页 * |
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