CN109212108A - Gas chromatography-mass spectrometry that is a kind of while measuring three kinds of trace quinolines herbicides in rice and soybean - Google Patents
Gas chromatography-mass spectrometry that is a kind of while measuring three kinds of trace quinolines herbicides in rice and soybean Download PDFInfo
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Abstract
The present invention relates to the methods of Trace toxicants analysis detection, and in particular to a kind of gas chromatography-mass spectrometry for measuring trace quinmerac, dichloro quinolinic acid and imazaquin in rice and soybean simultaneously.Method and step includes with object in alkaline 10% acetonitrile solution ultrasonic extraction sample, target compound in extracting solution is enriched with new adsorbent 2- naphthalene sulfonic acids root-magnalium type hydrotalcite product of roasting, realizes that object is eluted completely, efficiently extracted with low dose of organic solvent to compound with hydrochloric acid solution dissolution adsorbent, and quickly analyzes measurement with gas chromatography after derivation.New adsorbent used by this method realizes the rapidly and efficiently absorption to object by the way of dispersive solid-phase extraction, can save a large amount of adsorption time compared with gel permeation chromatography and solid phase extraction；The complete De contamination of object can be realized using acid dissolution adsorbent；Only being applicable in a small amount of organic solvent extraction has the advantages that significant safe and environment-friendly and economic advantages.
Description
Technical field
The present invention relates to the methods of harmful trace species analysis detection, and in particular to measures rice and soybean simultaneously to a kind of
The gas chromatography-mass spectrometry of middle trace quinmerac, dichloro quinolinic acid and imazaquin residual quantity.
Background technique
Quinoline acids herbicide is when one kind important in pro-herbicide, and selling the type used in the market includes chloromethane quinoline
Quinoline acid, dichloro quinolinic acid and imazaquin and its ester type compound etc. it is a variety of, belong to middle lower toxicity herbicide, to human body,
Animal and aquatic products have certain toxicity.China sets the maximum residue limit (MRL) in brown rice to dichloro quinolinic acid at present
For 1.0mg/kg, setting the maximum residue limit (MRL) in soybean to imazaquin is 0.05mg/kg, it is desirable that stringent.
Dichloro quinolinic acid is to kill rice field malignant weed --- the specific drug of barnyard grass, chloromethane quinoline in quinoline acids herbicide
Quinoline acid and imazaquin be usually used in the broadleaf weeds such as knotweed, Chenopodiaceae, Amaranthus retroflexus, beggar-ticks, Siberian cocklebur, piemarker in soybean and rice field,
Also there is certain control efficiency to gramineae weeds such as Brachiaria Griseb, herba digitariae, wild broomcorn millet, setarias.
The currently standard method of the substance residual quantity involved in food is mainly " SN/T 2228-2008 inlet and outlet
The detection method gas chromatography-mass spectrography of 31 kinds of acid herbicide residual quantities in food ", wherein there is the inspection of regulation dichloro quinolinic acid
Survey method, without regard to the detection to other two kinds of herbicides.Carrying out pre-treatment using gel permeation chromatography in the standard can
To remove most impurity, play preferable pre-treatment effect, but the pretreatment process there are time-consuming and inefficient, need to expend
The shortcomings such as a large amount of organic solvents are not suitable with the rapid screening detection of big throughput sample, it would be highly desirable to need new pre-treating method
To solve the problems, such as rapidly and efficiently to detect screening.The detection of quinoline acids herbicide is mainly concerned with efficiently in document report food
Liquid chromatography, pre-treatment, which is focused primarily upon, to be extracted using organic solvent and is purified using solid phase extraction, but is extracted using solid phase
Follow the example of as purification means that there are the bothersome inefficient and optional limited deficiencies of solid phase extraction material type.
Since 2011, inventor research team is to layered di-hydroxyl composite metal oxidate (Layered Double
Hydroxides, LDHs) and its modified material conduct extensive research, be prepared for the modified LDHs of inhomogeneity intercalant anion
And its (layered double oxide, LDO) material, and carried out based on this with these synthetic materials for difference
The application study of the screening of absorption enrichment performance, the investigation and optimization of target compound.Inventor applies 2- in the research of early period
Naphthalene sulfonic acids root-magnalium type hydrotalcite adsorbent in water a variety of quinoline acids herbicides and its intermediate carried out adsorptivity and ground
Study carefully, achieves good Selective adsorption effect.On this basis, inventor is further enriched with three kinds to the adsorbent developed
The performance and methods for using them of target compound is optimized, and establishes using benzene sulfonic acid root-magnalium type hydrotalcite as adsorbent
The gas chromatography-mass spectrometry of trace quinmerac, dichloro quinolinic acid and imazaquin residues detection in rice and soybean
Usage.
Summary of the invention
Gel infiltration color is used in quinoline acids herbicide residue amount detection pre-treatment in order to overcome in existing standard method
Spectrum time-consuming and inefficient needs to expend a large amount of organic solvents, is not suitable in big throughput sample screening and literature method using solid phase
The various symptims and signs of deficiency such as extraction column time-consuming is inefficient, solid-phase extraction column type is limited, the technical problem to be solved in the present invention is that providing one kind
It is based on new adsorbent dispersive solid-phase extraction quick adsorption, be suitable for rice and soybean in trace quinmerac, two chloroquines
The gas chromatography-mass spectrometry that quinoline acid and imazaquin residual quantity detect simultaneously.
The present invention is achieved through the following technical solutions above-mentioned target.
Gas chromatography-mass spectrometry that is a kind of while measuring three kinds of trace quinolines herbicides in rice and soybean,
It is characterized in that, includes the following steps:
The extraction and absorption of step 1 compound: rice and soybean sample are sealed after crushed 60 meshes, when use in
Sample 5.00g is weighed in tool plug plastic centrifuge tube, 10% aqueous solution 20mL of alkalinity is added into centrifuge tube, is surpassed after closed and vortex
Sound extracts, centrifugation, and supernatant is transferred in another tool plug plastic centrifuge tube, extracts primary and combined extract again；To from
N-hexane 10mL is added in heart pipe, is centrifuged after oscillation, discards upper liquid, and 2- naphthalene sulfonic acids root-magnesium of 0.50g is added into centrifuge tube
Aluminium profiles hydrotalcite adsorbent, it is closed and be vortexed after oscillation certain time make the target compound in adsorbent adsorbing and extracting liquid；
The De contamination of step 2 compound: it will be centrifuged in tool plug centrifuge tube, discard supernatant liquid, add 3.00mL's thereto
Hydrochloric acid solution dissolved solid adsorbent completes the De contamination for being adsorbed compound；
The extraction of step 3 compound and derivatization: a certain amount of anhydrous sodium sulfate and organic molten is added into above-mentioned centrifuge tube
Agent extraction is vortexed, centrifugation, divides and takes supernatant into derivative bottle, adds 0.40mL methanol thereto and 0.2mL concentration is 2moL/L
Trimethyl silicone hydride diazomethane hexane solution, bath temperature be 30 DEG C to 50 DEG C, the derivatization time be 30min；
The analysis of step 4 compound is tested: into derivative bottle, addition terminate liquid removes extra derivating agent, and is added appropriate solid
Body sodium bicarbonate and anhydrous sodium sulfate, be vortexed, draw upper layer organic solution filtering after using gas chromatography-mass spectrometry according to
Following condition carries out analysis test:
A) chromatographic column: DB-5MS capillary column, 30m × 0.25mm, 0.25 μm of film thickness；Column flow rate: 1.50mL/min.
B) injector temperature: 260 DEG C；Input mode: Splitless injecting samples；Sample volume: 2 μ L.
C) temperature program:, being warming up to 260 DEG C (keeping 4min) with 20 DEG C/min rate by 40 DEG C (keep 1min), with 10 DEG C/
Min rate is warming up to 280 DEG C (keeping 8min).
D) EI bombards source: 70ev；Chromatography-mass spectroscopy connector temperature: 280 DEG C；Quadrupole rod temperature: 230 DEG C；Ion source temperature
Degree: 150 DEG C.
E) carrier gas: high-purity helium (purity >=99.999%).
F) mass spectrometric data acquisition mode: selection ion scan mode (SIM), solvent delay time: 8min.
G) the qualitatively and quantitatively ion of compound is as follows:
Wherein,
Three kinds of herbicides described in step 1 are quinmerac, dichloro quinolinic acid and imazaquin, alkaline 10% water
Solution is that pH=9.0 is adjusted with the sodium hydroxide solution of 0.01mol/L, and the ultrasonic extraction time is 15min, the duration of oscillation of absorption
For 15min.
Hydrochloric acid solution described in step 2 is that concentrated hydrochloric acid and water are formulated according to volume ratio 1:1, dosage 3.00mL.
The anhydrous sodium sulfate added in step 3 be 2.0g, organic extraction solvent be 5.00mL ethyl acetate and take entirely in
Derivative reaction.
Terminate liquid described in step 4 is the hydrochloric acid solution in step 2, and additive amount 0.05mL, solid sodium bicarbonate adds
Dosage is 0.10g, and the additive amount of anhydrous sodium sulfate is 1.0g, and filter membrane is organic phase filter membrane, 0.22 μm of aperture.
Above-mentioned steps mesoscale eddies is vortex 1min to 2min, is centrifuged to run 3min with 4500rpm revolving speed.
The case where illustrating is needed in the method for the present invention R&D process:
In view of three kinds of herbicides such as quinmerac, dichloro quinolinic acid and imazaquins during method exploitation
With certain faintly acid, it is dissolvable in water alkaline aqueous solution.Therefore, inventor is according to the dissolubility feature of object, in conjunction with mesh
Mark is dissolvable in water the feature of organic solvent and alkaline aqueous solution, has selected the acetonitrile that can be dissolved with water with water composition mix extraction molten
Agent.By experiment in investigated it is sorbent used institute can adsorbed target object optimal pH range be 4-9, use
The sodium hydroxide solution of 0.01mol/L adjusts the pH=9.0 of extracting solution, to increase Extraction solvent to the extraction efficiency of object,
Impurity is extracted in reduction altogether.
Due to using different intercalant anions to be modified LDHs material, have adjusted material interlamellar spacing and intercalation from
The type of son, so that different modification LDHs is divided by object is adsorbed when LDHs material is used as absorbent fields
The influence of many factors such as sub- size, structure, polarity and functional group shows different selective absorption performances.In order to realize to three
Kind of object has preferable adsorption effect, selected in experiment LDHs and its product of roasting material of a variety of developments for adsorbent into
The screening of row absorption property；It is excellent according to the size of sample size in experiment meanwhile in order to make adsorbent to the quick and complete absorption of object
The usage amount of adsorbent is changed.
Inventor compares methanol-sulfuric acid process, methanol-hydrogen sodium oxide molybdena, trimethyl silicone hydride diazomethane method in an experiment
Etc. a variety of derivatization methods, finds gentle using trimethyl silicone hydride diazomethane method reaction condition and spread out to three kinds of objects
Biochemical effects are best.But due to achieving preferable clean-up effect using adsorbent of the present invention, the present invention is not to spreading out
Production object carries out further Solid phase extraction again.
Meanwhile considering for object dosing accuracy, this method can not obtain object isotope to carry out
Object is quantified using matrix calibration curve under the premise of Isotopically labelled internal standard, is mentioned with eliminating systematic error as far as possible
High quantitative accuracy.
The present invention has the advantages that
(1) new adsorbent 2- naphthalene sulfonic acids root-magnalium type hydrotalcite of the present invention can be extracted using dispersed solid phase
The mode taken quickly adsorbs trace quinmerac, dichloro quinolinic acid and imazaquin residual quantity in extracting solution,
A large amount of adsorption time can be saved compared to the gel permeation chromatography of standard method and Solid Phase Extraction mode；
(2) present invention is dissolvable in water the feature of acid using 2- naphthalene sulfonic acids root-magnalium type hydrotalcite adsorbent, molten using hydrochloric acid
Liquid dissolves the adsorbent after adsorbed target object, can make object complete De contamination from adsorbent；
(3) present invention be only applicable in extractant of a small amount of organic solvent as object, compared to standard law method with
Literature procedure needs to have the advantages that significant safe and environment-friendly and economic advantages using a large amount of organic solvents.
Detailed description of the invention
Fig. 1 is the extraction standard of quinmerac in specific embodiment, dichloro quinolinic acid and imazaquin residual quantity
Solution chromatogram, concentration are 500.0 μ g/kg, wherein 1 being quinmerac, 2 being dichloro quinolinic acid, 3 being imazaquin.
Specific embodiment
Further to disclose rather than the present invention is limited, the present invention is described in further detail below in conjunction with example.
(1) reagent chemicals involved in the embodiment of the present invention are as follows:
Totally three kinds of compound solid standard items, purity are greater than for quinmerac, dichloro quinolinic acid and imazaquin allowance
Equal to 98.0%, German Dr.Ehrenstorfer GmbH Science and Technology Co., Ltd.；
Methanol, ethyl acetate, acetonitrile, anhydrous sodium sulfate, sodium hydroxide, sodium bicarbonate analyze pure, Chinese medicines group；
Hydrochloric acid, excellent pure grade, Chinese medicines group；Water is to meet level-one water as defined in GB/T 6682.
Trimethyl silane diazomethane solution, 2.0M are dissolved in n-hexane, Alfa Aesar company.
Rice used in experiment and soybean sample purchase Fuqing locality supermarket, grind and cross 60 meshes, seal, 4
It saves at DEG C, is warmed to room temperature using preceding take out back.
(2) instrument involved in the embodiment of the present invention is as follows:
KH-75A type electric heating constant-temperature blowing drying box, Guangzhou Kang Heng Instrument Ltd.；
7890B-5977C type gas chromatograph-mass spectrometer (GC-MS), Anjelen Sci. & Tech. Inc of the U.S..
(3) chromatographic test condition:
A) chromatographic column: DB-5MS capillary column, 30m × 0.25mm, 0.25 μm of film thickness；Column flow rate: 1.50mL/min.
B) injector temperature: 260 DEG C；Input mode: Splitless injecting samples；Sample volume: 2 μ L.
C) temperature program:, being warming up to 260 DEG C (keeping 4min) with 20 DEG C/min rate by 40 DEG C (keep 1min), with 10 DEG C/
Min rate is warming up to 280 DEG C (keeping 8min).
D) EI bombards source: 70ev；Chromatography-mass spectroscopy connector temperature: 280 DEG C；Quadrupole rod temperature: 230 DEG C；Ion source temperature
Degree: 150 DEG C.
E) carrier gas: high-purity helium (purity >=99.999%).
F) mass spectrometric data acquisition mode: selection ion scan mode (SIM), solvent delay time: 8min.
G) the qualitatively and quantitatively ion of compound is as follows:
| Serial number | Compound name | Quota ion | Qualitative ion |
| 1 | Quinmerac derivative | 204.1 | 177.0,235.0 |
| 2 | Dichloroquinoline acid derivative | 224.0 | 226.0,197.0 |
| 3 | Imidazole quinoline acid derivative | 227.1 | 297.1,296.1 |
(4) determination of the production of matrix calibration curve and detection limit, quantitative limit
The above-mentioned quinmerac of precise, dichloro quinolinic acid and imazaquin simultaneously dissolve constant volume with methanol, are configured to
Concentration is the standard reserving solution of 1000mg/L, is saved at -4 DEG C.Standard reserving solution is gradually diluted with deionized water when use, is matched
The standard solution that concentration gradient is 10.0 μ g/L, 20.0 μ g/L, 40.0 μ g/L, 100.0 μ g/L and 200.0 μ g/L is made.
Blank sample 5.00g is weighed in five 50mL tool plug centrifuge tubes, above-mentioned standard is added respectively and uses liquid 5.00mL,
The matrix calibration curve of series of concentrations is prepared, the alkalinity 10% acetonitrile solution 20mL of pH=9 is added into centrifuge tube, it is close
Supernatant is transferred in another 50mL tool plug plastic centrifuge tube, extracts again by ultrasonic extraction 15min after closing and being vortexed, centrifugation
Primary and combined extract；N-hexane 10mL is added into centrifuge tube, is centrifuged after oscillation, is discarded upper liquid, adds into centrifuge tube
Add 2- naphthalene sulfonic acids root-magnalium type hydrotalcite adsorbent of 0.50g, oscillation certain time proposes adsorbent absorption after closed and vortex
Take the target compound in liquid；
It will be centrifuged in tool plug centrifuge tube, and discard supernatant liquid, the hydrochloric acid solution of addition 3.00mL (press with water by concentrated hydrochloric acid thereto
Prepared according to volume ratio 1:1) dissolved solid adsorbent, complete the De contamination for being adsorbed compound；
2.0g anhydrous sodium sulfate and the extraction of 5.00mL ethyl acetate are added into above-mentioned centrifuge tube, are vortexed, centrifugation, are divided and take
Clear liquid adds 0.40mL methanol and 0.2mL concentration thereto into derivative bottle as the trimethyl silicone hydride diazomethane of 2moL/L
Hexane solution, bath temperature are 50 DEG C, and the derivatization time is 30min；
0.05mL hydrochloric acid solution (concentrated hydrochloric acid and water are prepared according to volume ratio 1:1) extra derivative of removal is added into derivative bottle
Agent, and solid sodium bicarbonate 0.10g and anhydrous sodium sulfate 1.0g is added, it is vortexed, organic solution 0.22 μ in upper layer is drawn after standing
M organic phase filter membrane filters and gas chromatography-mass spectrometry is applied to carry out analysis test.
Using quinoline acids herbicide sample solution concentration as X-axis, quinoline acids herbicidal derivatives are in gas-chromatography
Chromatographic peak peak area on instrument is that Y-axis draws extraction standard curve and is used for quantified by external standard method.
(LOD, LOD=3S/N) is limited by the detection of method of the three times value of signal-to-noise ratio S/N, ten times with signal-to-noise ratio S/N are
The quantitative limit (LOQ, LOQ=10S/N) of method, and the volume of addition matrix is combined to calculate the detection limit of each compound in water
And quantitative limit.
Above-mentioned extraction standard curvilinear correlation parameter, LOD and LOQ relevant information are shown in Table 1.
1. trace quinmerac of table, dichloro quinolinic acid and imazaquin residual quantity matrix
Standard curve, detection limit and quantitative limit relevant information
(5) 2- naphthalene sulfonic acids root-magnalium type hydrotalcite adsorbent synthesis
In order to which those skilled in the art can repeat to realize related experiment of the invention, a kind of present invention there is presently provided
Used in key substance 2- naphthalene sulfonic acids root-magnalium type hydrotalcite adsorbent synthetic method, it is as follows:
1. reagent chemicals involved by synthetic adsorbent are as follows:
2- sodium naphthalene sulfonate analyzes pure, Shanghai Shao Yuan reagent Co., Ltd；
Mg6Al2(OH)16CO3·4H2O analyzes pure, U.S.'s Aldrich.
2. instrument involved by synthetic adsorbent is as follows:
EXCEL type microwave dissolver, Shanghai EU Apparatus Technology Development Co., Ltd., resolution tank volume are 100mL；Microwave
Muffle furnace (sintering furnace), U.S. CE M company；VD53 type vacuum oven, Buchbinder, Germany scientific & technical corporation；HJ-5 multifunction constant temperature stirs
Mix device, Jintan high honour instrument manufacturing Co., Ltd；FS-12 type separating funnel oscillator, new Micron Technology Co., Ltd of Japan；3K-
15 type centrifuges, German sigma scientific & technical corporation；BF518945C-1 type chamber type electric resistance furnace (Muffle furnace), the U.S. match Mo Feishier section
Skill company.
3. specific step is as follows for synthetic adsorbent:
(a) it roasts: by the magnalium type hydrotalcite Mg of purchase6Al2(OH)16CO3·4H2O is placed in Muffle furnace, with the speed that heats up
It is 500 DEG C that 5 DEG C/min of rate, which is heated to temperature, roasts 6h, obtains Mg6Al2O8(OH)2；
(b) it weighs: weighing the Mg of 13.812g intercalator 2- sodium naphthalene sulfonate and 7.236g in micro-wave diminishing pot6Al2O8
(OH)2。
(c) deionized water: being boiled and is kept 30min by microwave crystallization hydrothermal synthesis, is added 60mL later and is equipped with to above-mentioned
It is closed in the micro-wave diminishing pot of intercalator sum, micro-wave diminishing pot is placed in microwave dissolver, microwave adds at 130~150 DEG C
Hot 30min completes synthesis；
(d) washing and drying: all solids in microwave tank are poured out with liquid, to boil the removal two of 30min or more
The heated stirring of the deionized water of carbonoxide, oscillation are washed and are centrifuged, and 12h is dried in vacuo at 90 DEG C, and grinding saves.
Embodiment 1
The present embodiment 1 uses the blank sample matrix of rice to carry out recovery testu to verify the feasible of the method for the present invention
Property, it is handled according to the following steps:
1. the extraction of compound is adsorbed:
Have in plug centrifuge tube in 50mL and weigh blank sample 5.00g, and respectively addition 5.00mL concentration is respectively thereto
The parallel mark-on sample of three levels six is prepared in three kinds of compound standard solution of 10.0 μ g/L, 20.0 μ g/L and 200.0 μ g/L
Product add the 10% acetonitrile solution 20mL of alkalinity of pH=9, ultrasonic extraction 15min after closed and vortex into centrifuge tube, from
Supernatant is transferred in another 50mL tool plug plastic centrifuge tube, extracts primary and combined extract again by the heart；Into centrifuge tube
N-hexane 10mL is added, is centrifuged after oscillation, discards upper liquid, 2- naphthalene sulfonic acids root-magnalium type water of 0.50g is added into centrifuge tube
Talcum adsorbent, it is closed and be vortexed after oscillation certain time make the target compound in adsorbent adsorbing and extracting liquid；
2. the De contamination of compound:
To be centrifuged in above-mentioned tool plug centrifuge tube, discard supernatant liquid, thereto add 3.00mL hydrochloric acid solution (concentrated hydrochloric acid with
Water is prepared according to volume ratio 1:1) dissolved solid adsorbent, complete the De contamination for being adsorbed compound；
3. extraction and the derivatization of compound:
2.0g anhydrous sodium sulfate and the extraction of 5.00mL ethyl acetate are added into above-mentioned centrifuge tube, are vortexed, centrifugation, are divided and take
Clear liquid adds 0.40mL methanol and 0.2mL concentration thereto into derivative bottle as the trimethyl silicone hydride diazomethane of 2moL/L
Hexane solution, bath temperature are 50 DEG C, and the derivatization time is 30min；
4, analysis test:
0.05mL hydrochloric acid solution (concentrated hydrochloric acid and water are prepared according to volume ratio 1:1) extra derivative of removal is added into derivative bottle
Agent, and solid sodium bicarbonate 0.10g and anhydrous sodium sulfate 1.0g is added, it is vortexed, organic solution 0.22 μ in upper layer is drawn after standing
M organic phase filter membrane filters and gas chromatography-mass spectrometry is applied to carry out analysis test.
The recovery of standard addition experiment relevant parameter of the present embodiment 1 is shown in Table 2.
The addition concentration and rate of recovery experimental data (n=6) of 2 Rice Samples of table
Embodiment 2
The present embodiment 2 uses the blank sample matrix of soybean to carry out recovery testu to verify the feasible of the method for the present invention
Property, it is handled according to the following steps:
1. the extraction of compound is adsorbed:
Have in plug centrifuge tube in 50mL and weigh blank sample 5.00g, and respectively addition 5.00mL concentration is respectively thereto
The parallel mark-on sample of three levels six is prepared in three kinds of compound standard solution of 10.0 μ g/L, 20.0 μ g/L and 200.0 μ g/L
Product add the 10% acetonitrile solution 20mL of alkalinity of pH=9, ultrasonic extraction 15min after closed and vortex into centrifuge tube, from
Supernatant is transferred in another 50mL tool plug plastic centrifuge tube, extracts primary and combined extract again by the heart；Into centrifuge tube
N-hexane 10mL is added, is centrifuged after oscillation, discards upper liquid, 2- naphthalene sulfonic acids root-magnalium type water of 0.50g is added into centrifuge tube
Talcum adsorbent, it is closed and be vortexed after oscillation certain time make the target compound in adsorbent adsorbing and extracting liquid；
2. the De contamination of compound:
To be centrifuged in above-mentioned tool plug centrifuge tube, discard supernatant liquid, thereto add 3.00mL hydrochloric acid solution (concentrated hydrochloric acid with
Water is prepared according to volume ratio 1:1) dissolved solid adsorbent, complete the De contamination for being adsorbed compound；
3. extraction and the derivatization of compound:
2.0g anhydrous sodium sulfate and the extraction of 5.00mL ethyl acetate are added into above-mentioned centrifuge tube, are vortexed, centrifugation, are divided and take
Clear liquid adds 0.40mL methanol and 0.2mL concentration thereto into derivative bottle as the trimethyl silicone hydride diazomethane of 2moL/L
Hexane solution, bath temperature are 30 DEG C, and the derivatization time is 30min；
4, analysis test:
0.05mL hydrochloric acid solution (concentrated hydrochloric acid and water are prepared according to volume ratio 1:1) extra derivative of removal is added into derivative bottle
Agent, and solid sodium bicarbonate 0.10g and anhydrous sodium sulfate 1.0g is added, it is vortexed, organic solution 0.22 μ in upper layer is drawn after standing
M organic phase filter membrane filters and gas chromatography-mass spectrometry is applied to carry out analysis test.
The recovery of standard addition experiment relevant parameter of the present embodiment 2 is shown in Table 3.
The addition concentration and rate of recovery experimental data (n=6) of 3 Rice Samples of table
Embodiments of the present invention above described embodiment only expresses, the description thereof is more specific and detailed, but can not
Therefore limitations on the scope of the patent of the present invention are interpreted as.It should be pointed out that for the ordinary skill in the art,
Without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection model of the invention
It encloses, therefore the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (6)
1. a kind of gas chromatography-mass spectrometry for measuring three kinds of trace quinolines herbicides in rice and soybean simultaneously, special
Sign is, includes the following steps:
(1) extraction and absorption of compound: rice and soybean sample are sealed after crushed 60 meshes, in tool plug modeling when use
Sample 5.00g is weighed in material centrifuge tube, 10% acetonitrile solution 20mL of alkalinity, ultrasound after closed and vortex are added into centrifuge tube
It extracts, centrifugation, supernatant is transferred in another tool plug plastic centrifuge tube, extracts primary and combined extract again；To centrifugation
N-hexane 10mL is added in pipe, is centrifuged after oscillation, discards upper liquid, and 2- naphthalene sulfonic acids root-magnalium of 0.5g is added into centrifuge tube
Type hydrotalcite adsorbent, it is closed and be vortexed after oscillation certain time make the target compound in adsorbent adsorbing and extracting liquid；
(2) De contamination of compound: it will be centrifuged in tool plug centrifuge tube, discard supernatant liquid, it is molten to add a certain amount of hydrochloric acid thereto
Liquid dissolved solid adsorbent completes the De contamination for being adsorbed compound；
(3) extraction of compound and derivatization: adding a certain amount of anhydrous sodium sulfate and organic solvent extraction into above-mentioned centrifuge tube,
It is vortexed, centrifugation, divides and take supernatant into derivative bottle, the front three that addition 0.40mL methanol and 0.20mL concentration are 2moL/L thereto
Base silane diazomethane hexane solution, bath temperature are 30 DEG C to 50 DEG C, and the derivatization time is 30min；
(4) the analysis test of compound: into derivative bottle, addition terminate liquid removes extra derivating agent, and appropriate solid carbonic acid is added
Hydrogen sodium and anhydrous sodium sulfate, be vortexed, draw upper layer organic solution filtering after using gas chromatography mass spectrometry according to following condition into
Row analysis test:
A) chromatographic column: DB-5MS capillary column, 30m × 0.25mm, 0.25 μm of film thickness；Column flow rate: 1.50mL/min.
B) injector temperature: 260 DEG C；Input mode: Splitless injecting samples；Sample volume: 2 μ L.
C) temperature program: 40 DEG C (keeping 1min), 260 DEG C (keeping 4min) are warming up to 20 DEG C/min rate, with 10 DEG C/min
Rate is warming up to 280 DEG C (keeping 8min).
D) EI bombards source: 70ev；Chromatography-mass spectroscopy connector temperature: 280 DEG C；Quadrupole rod temperature: 230 DEG C；Ion source temperature: 150
℃。
E) carrier gas: high-purity helium (purity >=99.999%).
F) mass spectrometric data acquisition mode: selection ion scan mode (SIM), solvent delay time: 8min.
G) the qualitatively and quantitatively ion of compound is as follows:
2. a kind of gas-chromatography-for measuring three kinds of trace quinolines herbicides in rice and soybean simultaneously as described in claim 1
Mass Spectrometry, which is characterized in that three kinds of herbicides described in step (1) are quinmerac, dichloro quinolinic acid and imidazoles
Quinolinic acid, alkaline 10% aqueous solution of acetonitrile are to adjust pH=9.0, ultrasonic extraction time with the sodium hydroxide solution of 0.01mol/L
For 15min, the duration of oscillation of absorption is 15min.
3. a kind of gas-chromatography-for measuring three kinds of trace quinolines herbicides in rice and soybean simultaneously as described in claim 1
Mass Spectrometry, which is characterized in that hydrochloric acid solution described in step (2) is concentrated hydrochloric acid and water prepare according to volume ratio 1:1 and
At dosage 3.00mL.
4. a kind of gas-chromatography-for measuring three kinds of trace quinolines herbicides in rice and soybean simultaneously as described in claim 1
Mass Spectrometry, which is characterized in that the anhydrous sodium sulfate added in step (3) is 2.0g, and organic extraction solvent is 5.00mL's
Ethyl acetate.
5. a kind of gas-chromatography-for measuring three kinds of trace quinolines herbicides in rice and soybean simultaneously as described in claim 1
Mass Spectrometry, which is characterized in that terminate liquid described in the step (4) is the hydrochloric acid solution in claim 3, addition
Amount is 0.05mL, and solid sodium bicarbonate additive amount is 0.10g, and the additive amount of anhydrous sodium sulfate is 1.0g, and filter membrane is organic phase filter
Film, 0.22 μm of aperture.
6. a kind of gas-chromatography-for measuring three kinds of trace quinolines herbicides in rice and soybean simultaneously as described in claim 1
Mass Spectrometry, which is characterized in that the vortex is vortex 1min to 2min, is centrifuged to run 3min with 4500rpm revolving speed.
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