CN109212057B - Gas chromatography-mass spectrometry combined method for measuring five trace plant growth regulators in water source water - Google Patents
Gas chromatography-mass spectrometry combined method for measuring five trace plant growth regulators in water source water Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 44
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 title claims abstract description 17
- 239000005648 plant growth regulator Substances 0.000 title claims description 15
- 239000003463 adsorbent Substances 0.000 claims abstract description 49
- 150000001875 compounds Chemical class 0.000 claims abstract description 35
- 238000001212 derivatisation Methods 0.000 claims abstract description 32
- JLIDBLDQVAYHNE-YKALOCIXSA-N (+)-Abscisic acid Chemical compound OC(=O)/C=C(/C)\C=C\[C@@]1(O)C(C)=CC(=O)CC1(C)C JLIDBLDQVAYHNE-YKALOCIXSA-N 0.000 claims abstract description 20
- OJOBTAOGJIWAGB-UHFFFAOYSA-N acetosyringone Chemical compound COC1=CC(C(C)=O)=CC(OC)=C1O OJOBTAOGJIWAGB-UHFFFAOYSA-N 0.000 claims abstract description 20
- TXCGAZHTZHNUAI-UHFFFAOYSA-N clofibric acid Chemical compound OC(=O)C(C)(C)OC1=CC=C(Cl)C=C1 TXCGAZHTZHNUAI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001179 sorption measurement Methods 0.000 claims abstract description 15
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 14
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 14
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 14
- 239000003315 2-(4-chlorophenoxy)-2-methylpropanoic acid Substances 0.000 claims abstract description 13
- 229950008441 clofibric acid Drugs 0.000 claims abstract description 13
- -1 dodecyl benzene sulfonate-magnesium aluminum Chemical compound 0.000 claims abstract description 13
- ZMZGFLUUZLELNE-UHFFFAOYSA-N 2,3,5-triiodobenzoic acid Chemical compound OC(=O)C1=CC(I)=CC(I)=C1I ZMZGFLUUZLELNE-UHFFFAOYSA-N 0.000 claims abstract description 12
- FCRACOPGPMPSHN-UHFFFAOYSA-N desoxyabscisic acid Natural products OC(=O)C=C(C)C=CC1C(C)=CC(=O)CC1(C)C FCRACOPGPMPSHN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000004458 analytical method Methods 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 29
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 19
- 239000000047 product Substances 0.000 claims description 18
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 15
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 14
- 150000002500 ions Chemical class 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000007789 sealing Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 238000000605 extraction Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000006228 supernatant Substances 0.000 claims description 10
- 238000003795 desorption Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 239000013076 target substance Substances 0.000 claims description 8
- 239000012528 membrane Substances 0.000 claims description 7
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 7
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 5
- 238000007664 blowing Methods 0.000 claims description 5
- FUKUFMFMCZIRNT-UHFFFAOYSA-N hydron;methanol;chloride Chemical compound Cl.OC FUKUFMFMCZIRNT-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000012074 organic phase Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000005070 sampling Methods 0.000 claims description 5
- GRONZTPUWOOUFQ-UHFFFAOYSA-M sodium;methanol;hydroxide Chemical compound [OH-].[Na+].OC GRONZTPUWOOUFQ-UHFFFAOYSA-M 0.000 claims description 5
- 238000001819 mass spectrum Methods 0.000 claims description 4
- 239000012159 carrier gas Substances 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 238000004949 mass spectrometry Methods 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 238000012863 analytical testing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 10
- 238000001514 detection method Methods 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000002414 normal-phase solid-phase extraction Methods 0.000 abstract description 2
- 238000010828 elution Methods 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 15
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- 230000015572 biosynthetic process Effects 0.000 description 4
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- 229910021641 deionized water Inorganic materials 0.000 description 4
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- 239000010410 layer Substances 0.000 description 4
- 238000011002 quantification Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000012086 standard solution Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910020038 Mg6Al2 Inorganic materials 0.000 description 2
- 150000003529 abscisic acid derivatives Chemical class 0.000 description 2
- 238000012271 agricultural production Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MCWXGJITAZMZEV-UHFFFAOYSA-N dimethoate Chemical class CNC(=O)CSP(=S)(OC)OC MCWXGJITAZMZEV-UHFFFAOYSA-N 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
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- 238000005457 optimization Methods 0.000 description 2
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- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- 238000012421 spiking Methods 0.000 description 2
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- 229910003023 Mg-Al Inorganic materials 0.000 description 1
- 239000005986 Prohexadione Substances 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
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- 238000010812 external standard method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
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- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
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- 230000010355 oscillation Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- BUCOQPHDYUOJSI-UHFFFAOYSA-N prohexadione Chemical compound CCC(=O)C1C(=O)CC(C(O)=O)CC1=O BUCOQPHDYUOJSI-UHFFFAOYSA-N 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
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- 238000005245 sintering Methods 0.000 description 1
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 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 simultaneously measuring trace amount of clofibric acid, acetosyringone, abscisic acid and 2,3, 5-triiodobenzoic acid in water source water. The method comprises the steps of enriching a target compound in water source water by using a novel adsorbent dodecyl benzene sulfonate-magnesium aluminum type hydrotalcite roasted product, dissolving the adsorbent by using acid to realize complete elution of the target compound, extracting the compound by using a small amount of organic solvent, and analyzing and determining by using a gas chromatography-mass spectrometry combination method after double derivatization of acid-methanol and alkali-methanol. The novel adsorbent adopted by the method realizes rapid and efficient adsorption on the target object by adopting a dispersed solid-phase extraction mode, the target object can be completely desorbed by applying an acid-soluble adsorbent, and the method has the obvious advantages of safety, environmental protection and economic advantages by only being suitable for extracting a small amount of organic solvent, and is an analysis method which can be applied to detection of five trace target objects in water.
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 five trace plant growth regulators such as prohexadione, clofibric acid, acetosyringone, abscisic acid, 2,3, 5-triiodobenzoic acid and the like in source water.
Background
Plant growth regulators are chemical agents commonly used in agricultural production and play an important role in agricultural production. However, with the use of plant growth regulators in large quantities and the possible problems of leakage and excessive discharge during production, varieties that are soluble in water and can exist stably and durably in water bodies have become increasingly a source of harmful chemicals that contaminate source water.
California acid, clofibric acid, acetosyringone, abscisic acid, and 2,3, 5-triiodobenzoic acid are five commonly used plant growth regulators. There is currently no method and standard for detecting these five trace substances in the source water, which makes it difficult to monitor the content of the trace substances in the source water.
The inventor carries out adsorption experiments on the five substances in water by using the novel dodecyl benzene sulfonate-magnesium aluminum type hydrotalcite roasted product adsorbent in earlier researches, and the result shows that the adsorbent has a good adsorption effect on a target object. On the basis, the inventor further optimizes the performance and application method of the developed adsorbent for enriching the target compound in water, and establishes a gas chromatography-mass spectrometry combined method for detecting trace amount of clofibric acid, acetosyringone, abscisic acid and 2,3, 5-triiodobenzoic acid in water source water with a dodecyl benzene sulfonate-magnesium aluminum type hydrotalcite roasted product as the adsorbent.
Disclosure of Invention
In order to overcome the defects that the trace amount of clofibric acid, acetosyringone, abscisic acid and 2,3, 5-triiodobenzoic acid in the existing water source water lack an effective detection method and standard, the invention aims to solve the technical problem of providing a gas chromatography-mass spectrometry combined method which is based on the novel adsorbent, is dispersed and solid-phase extracted for rapid adsorption and is suitable for simultaneously detecting the trace amount of clofibric acid, acetosyringone, abscisic acid and 2,3, 5-triiodobenzoic acid in the water source water.
The invention achieves the above object by the following technical means.
A gas chromatography-mass spectrometry combined method for measuring five trace plant growth regulators in water source water comprises the following steps:
adsorption of the compound of step 1: sampling a water source water sample, storing at 4 ℃, filtering before use, adding water source water into a separating funnel, adding 0.40g of dodecyl benzene sulfonate-magnesium aluminum type hydrotalcite roasted product adsorbent, and oscillating for a certain time to enable the adsorbent to enrich target compounds in water;
analytical testing of the compound of step 4: placing the derivative bottle in a refrigerator below-10 ℃ for cooling for 10min, adding 0.5mL of saturated sodium chloride aqueous solution and sodium bicarbonate powder into the derivative bottle, carrying out vortex, adding anhydrous sodium sulfate into the derivative bottle, carrying out vortex and centrifugation, completely taking the organic solution, carrying out nitrogen blowing at 40 ℃ to dry, carrying out volume fixing by using ethyl acetate, filtering, and carrying out analytical test by using a gas chromatography-mass spectrometry combination method according to the following conditions:
a) a chromatographic column: DB-5MS capillary column, 30m × 0.25mm, 0.25 μm thick; column flow rate: 1.2 mL/min.
b) Sample inlet temperature: 260 ℃; 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 160 deg.C at 10 deg.C/min (keeping 3min), heating to 250 deg.C at 15 deg.C/min (keeping 10min), and running at 280 deg.C (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 8 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 | Dimethoate derivatives | 155.1 | 214.0，111.0 |
| 2 | Clofibric acid derivatives | 169.0 | 228.0，128.0 |
| 3 | Acetylsyringone derivatives | 195.0 | 210.1，291.9 |
| 4 | Abscisic acid derivatives | 190.0 | 162.1，125.0 |
| 5 | 2,3, 5-triiodobenzoic acid derivatives | 513.8 | 482.7，454.7 |
Wherein,
the five plant growth regulators in the step 1 are difructonic acid, clofibric acid, acetosyringone, abscisic acid and 2,3, 5-triiodobenzoic acid, the water source 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 2.0 mL.
The anhydrous sodium sulfate added in the step 3 is 2.0g, the organic extraction solvent is acetonitrile, and the dosage of each extraction is 5.00 mL.
In the step 4, the addition amount of the solid sodium bicarbonate is 0.5g, the addition amount of the anhydrous sodium sulfate is 2.0g, the dosage of the ethyl acetate is 2.00mL, the filter membrane is an organic phase filter membrane, and the pore diameter is 0.22 mu m.
In the above steps, the vortex is 1min to 2min, and the centrifugation is carried out for 3min at the rotating speed of 4500 rpm.
The method of the invention needs to be explained in the research process:
layered Double Hydroxide (LDHs) is a typical Layered material with a supramolecular intercalation structure, and in the field of application of LDHs and roasted products thereof as adsorbents, different intercalation anions can be selected according to various factors such as molecular size, structure, polarity and functional groups of adsorbed targets to synthesize different types of modified LDHs materials. The modified LDHs materials have different interlayer spacing, so that the modified LDHs materials have the adsorption selection effect of limiting the molecules of a specific target substance to enter the interlayer; meanwhile, the modified material intercalation anions have different replacement difficulty degrees, so that the modified material intercalation anions show different adsorption selectivity on different targets. Therefore, in practical application, the adsorption effect of different LDHs materials and their calcination products on specific target species needs to be selected, verified and optimized through adsorption experiments.
In the process of research and development of the method, the inventor takes five targets as adsorption objects and utilizes a plurality of synthesized LDHs materials and roasting products thereof to investigate the adsorption performance of the LDHs materials, screens out adsorbents with good adsorption effects on the five targets, and selects and optimizes the dosage of the adsorbents and the selection and the proportion of extraction solvents; meanwhile, the derivatization methods of the five target substances are selected and the acid-methanol and alkali-methanol dual derivatization method is preferably selected, so that the derivatization method with good derivatization effect on the five target substances is realized; in addition, the selection and optimization of chromatographic separation conditions, the selection and optimization of mass spectrum conditions, the selectivity and anti-interference of quantitative and qualitative ions and other factors are investigated and optimized, and a relatively excellent detection method is provided on the basis.
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 dodecyl benzene sulfonate-magnesium-aluminum type hydrotalcite roasted product adopted by the invention can quickly adsorb five trace target objects 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 dodecylbenzene sulfonate-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 clofibric acid and clofibric acid in the embodiment at a concentration of 500.0. mu.g/L, wherein 1 is clofibric acid, 2 is clofibric acid, 3 is acetosyringone, 4 is abscisic acid, and 5 is 2,3, 5-triiodobenzoic 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:
adjusting the purity of compound solid standard products such as tartaric acid, clofibric acid, acetosyringone, abscisic acid, 2,3, 5-triiodobenzoic acid and the like to be more than or equal to 98.0 percent, Shanghai Aladdin science and technology Limited;
methanol, acetonitrile, ethyl acetate, sodium hydroxide, anhydrous sodium sulfate, sodium bicarbonate, sodium dodecyl benzene sulfonate, 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: 1.2 mL/min.
b) Sample inlet temperature: 260 ℃; 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 160 deg.C at 10 deg.C/min (keeping 3min), heating to 250 deg.C at 15 deg.C/min (keeping 10min), and running at 280 deg.C (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 8 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 | Dimethoate derivatives | 155.1 | 214.0，111.0 |
| 2 | Clofibric acid derivatives | 169.0 | 228.0，128.0 |
| 3 | Acetylsyringone derivatives | 195.0 | 210.1，291.9 |
| 4 | Abscisic acid derivatives | 190.0 | 162.1，125.0 |
| 5 | 2,3, 5-triiodobenzoic acid derivatives | 513.8 | 482.7，454.7 |
(4) Preparation of matrix calibration curve and determination of detection limit and quantitative limit
Accurately weighing the above compounds, dissolving with methanol to desired 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 2.00mL of the standard use solution, preparing a matrix calibration curve with a series of concentrations, then adding 0.40g of dodecyl benzene sulfonate-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 2.00mL 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 acetonitrile, whirling for 1min, centrifuging at 4500rpm for 3min, separating the supernatant into a derivatization bottle, re-extracting for one time, combining the extracts, adding 1.0mL of 1.0mol/L sodium hydroxide-methanol solution into the derivatization bottle, sealing, whirling, mixing uniformly, and placing in a 70 ℃ water bath for derivatization for 30 min; after cooling, adding 1.0mL of 2mol/L HCl-methanol solution, sealing, vortex uniformly mixing, and placing in a water bath at 70 ℃ for derivatization for 30min to complete the derivatization process of the target substance; 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 2.0g 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, fixing the volume by using 2.00mL of ethyl acetate, filtering by using a 0.22-micron organic phase filter membrane, and performing analysis and test by using a gas chromatography-mass spectrometry combination method.
And (3) taking the concentration of the target compound in the sample solution as an X axis, and taking the chromatographic peak area of the target compound derivative on a gas chromatography-mass spectrometer as a Y axis to draw a matrix standard curve and use the matrix standard curve for quantification by an external standard method.
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 five plant growth regulators
(5) Synthesis of p-methyl 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 material dodecylbenzene sulfonate-magnesium aluminum type hydrotalcite calcined product 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:
sodium dodecyl benzene sulfonate, analytically pure, group of national 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) 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: 20.909g 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, 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 performing microwave heating at 150 ℃ for 30min 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.
(e) And (3) second roasting: and (3) placing the dried dodecyl benzene sulfonate-magnesium-aluminum type hydrotalcite in a muffle furnace, heating to 500 ℃ at a heating rate of 5 ℃/min, and roasting for 6h to obtain a roasted product of the dodecyl benzene sulfonate-magnesium-aluminum type hydrotalcite serving as the adsorbent.
Example 1
In this example 1, a standard addition recovery experiment is performed by using Minjiang water as a sample matrix to verify the feasibility of the method, wherein a water sample is taken from a water intake of Minjiang in Taijiang section of Fuzhou water works and is treated according to the following steps:
1. adsorption of the compound:
adding 200mL of Minjiang water into 500mL of separating funnel, adding 2.00mL of five 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 0.40g of dodecylbenzene sulfonate-magnesium aluminum type hydrotalcite roasted product adsorbent into each funnel, and oscillating for 15min to enable the adsorbent to adsorb a target;
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 2.00mL 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 acetonitrile, whirling for 1min, centrifuging at 4500rpm for 3min, separating the supernatant into a derivatization bottle, re-extracting for one time, combining the extracts, adding 1.0mL of 1.0mol/L sodium hydroxide-methanol solution into the derivatization bottle, sealing, whirling, mixing uniformly, and placing in a 70 ℃ water bath for derivatization for 30 min; after cooling, adding 1.0mL of 2mol/L HCl-methanol solution, sealing, vortex uniformly mixing, and placing in a water bath at 70 ℃ for derivatization for 30min to complete the derivatization process of the target substance;
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 2.0g 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, fixing the volume by using 2.00mL of ethyl acetate, filtering by using a 0.22-micron organic phase filter membrane, and performing analysis and test by using a gas chromatography-mass spectrometry combination 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, reservoir water was used as a sample matrix to perform a labeling recovery experiment to verify the feasibility of the method of the present invention, and the water sample was taken from yokko tokyo reservoir and treated according to the following steps:
1. adsorption of the compound:
adding 200mL of reservoir water into a 500mL separating funnel, adding 2.00mL of five 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 0.40g of dodecylbenzene sulfonate-magnesium aluminum type hydrotalcite roasted product adsorbent into each funnel, and oscillating for 15min to enable the adsorbent to adsorb a target;
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 2.00mL 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 acetonitrile, whirling for 1min, centrifuging at 4500rpm for 3min, separating the supernatant into a derivatization bottle, re-extracting for one time, combining the extracts, adding 1.0mL of 1.0mol/L sodium hydroxide-methanol solution into the derivatization bottle, sealing, whirling, mixing uniformly, and placing in a 70 ℃ water bath for derivatization for 30 min; after cooling, adding 1.0mL of 2mol/L HCl-methanol solution, sealing, vortex uniformly mixing, and placing in a water bath at 70 ℃ for derivatization for 30min to complete the derivatization process of the target substance;
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 2.0g 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, fixing the volume by using 2.00mL of ethyl acetate, filtering by using a 0.22-micron organic phase filter membrane, and performing analysis and test by using a gas chromatography-mass spectrometry combination 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 five trace plant growth regulators in water source water is characterized by comprising the following steps:
(1) adsorption of the compound: sampling a water source water sample, storing at 4 ℃, filtering before use, adding water source water into a separating funnel, adding 0.40g of dodecyl benzene sulfonate-magnesium aluminum type hydrotalcite roasted product adsorbent, and oscillating for a certain time to ensure that the adsorbent is enriched in the tartaric acid, clofibric acid, acetosyringone, abscisic acid and 2,3, 5-triiodobenzoic 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 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 centrifuge tube, extracting twice, whirling, centrifuging, combining the supernatants into a derivatization bottle, adding 1.0mL of 1.0mol/L sodium hydroxide-methanol solution, sealing, whirling, mixing uniformly, and placing in a 70 ℃ water bath for derivatization for 30 min; after cooling, adding 1.0mL of 2mol/L HCl-methanol solution, sealing, vortex uniformly mixing, and placing in a water bath at 70 ℃ for derivatization for 30min to complete the derivatization process of the target substance;
(4) analytical testing of compounds: placing the derivative bottle in a refrigerator below-10 ℃ for cooling for 10min, adding 0.5mL of saturated sodium chloride aqueous solution and sodium bicarbonate powder into the derivative bottle, carrying out vortex, adding anhydrous sodium sulfate into the derivative bottle, carrying out vortex and centrifugation, completely taking the organic solution, carrying out nitrogen blowing at 40 ℃ to dry, carrying out volume fixing by using ethyl acetate, filtering, and carrying out analytical test by using a gas chromatography-mass spectrometry combination method according to the following conditions:
a) a chromatographic column: DB-5MS capillary column, 30m × 0.25mm, 0.25 μm thick; column flow rate: 1.2 mL/min;
b) sample inlet temperature: 260 ℃; 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 160 deg.C at a speed of 10 deg.C/min for 3min, heating to 250 deg.C at a speed of 15 deg.C/min for 10min, and running at 280 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: 8 min;
g) the quantitative and qualitative ion of the compounds are given in the following table:
2. the method for measuring the five trace plant growth regulators in the source water according to claim 1, wherein the source water in step (1) is 200mL and the shaking time is 15 min.
3. The gas chromatography-mass spectrometry combination for measuring five trace plant growth regulators in source water as claimed in claim 1, wherein the hydrochloric acid solution in step (2) is prepared from concentrated hydrochloric acid and water at a volume ratio of 1:1, and the dosage is 2.0 mL.
4. The gas chromatography-mass spectrometry combination for measuring five trace plant growth regulators in source water as claimed in claim 1, wherein the anhydrous sodium sulfate added in step (3) is 2.0g, the organic extraction solvent is acetonitrile, and the amount of acetonitrile used in each extraction is 5.00 mL.
5. The method for measuring the combined gas chromatography-mass spectrometry of five trace plant growth regulators in source water as claimed in claim 1, wherein the amount of the solid sodium bicarbonate added in step (4) is 0.5g, the amount of the anhydrous sodium sulfate added is 2.0g, the amount of the ethyl acetate used is 2.00mL, and the filtration membrane is an organic phase membrane with a pore size of 0.22 μm.
6. The method for measuring the five trace plant growth regulators in the source water of claim 1, wherein the vortex is performed for 1min to 2min and the centrifugation is performed at 4500rpm for 3 min.
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