CN108828101A - The remaining method of diuron in measurement sugarcane based on 3,4- dichloroaniline - Google Patents
The remaining method of diuron in measurement sugarcane based on 3,4- dichloroaniline Download PDFInfo
- Publication number
- CN108828101A CN108828101A CN201810898171.9A CN201810898171A CN108828101A CN 108828101 A CN108828101 A CN 108828101A CN 201810898171 A CN201810898171 A CN 201810898171A CN 108828101 A CN108828101 A CN 108828101A
- Authority
- CN
- China
- Prior art keywords
- diuron
- column
- sugarcane
- temperature
- ion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention discloses the remaining methods of diuron in the measurement sugarcane based on 3,4-DCA, include the following steps：S1. the instruction ingredient 3,4- dichloroaniline of diuron thermal decomposition is determined using Gas chromatographyMass spectrometry；S2. sample pre-treatments：Sugarcane sample is extracted and purified treatment, sugarcane prepare liquid is obtained；S3. the diuron standard solution of at least six concentration is prepared；The diuron standard solution of each concentration gradient of preparation is subjected to gas chromatography-electron capture detector measurement, draws standard working curve；Measure diuron content in sugarcane prepare liquid.Using method of the invention, diuron linear relationship within the scope of 0.01-5.0 mg/L is good, related coefficient is all larger than 0.998, detection is limited to 0.007 mg/kg, the rate of recovery of the diuron in sugar-cane juice is 89.2%-111%, relative standard deviation is 2.45%-6.57%, and the accuracy of this method and precision can meet the requirement of pesticide residue analysis.
Description
Technical field
The present invention relates in technical field of food safety, more particularly in the measurement sugarcane based on 3,4-DCA
The remaining method of diuron.
Background technique
Diuron (Diuron) is a kind of phenyl ureagroup herbicides, can effectively prevent and kill off gramineae weed, broadleaf weeds and algae
Class, due to this herbicide, its drug effect is not limited by region, weather conditions, and all parts of the country are widely used in sugarcane, corn, big
The crops such as beans field, since diuron chemical property is stablized, residual life, is long, persistently exists in the environment, and has certain life
Mammal, birds and development of fetus and the toxic effect of human health are issued in object cumulative effect according on May 24th, 2015
Cloth implements " national food safety standard sugar GB13104-2014 ", and original sanitary standard is risen to food safety country mark
Standard increases food additives and pollutant（Such as pesticide residue, heavy metal）Limit standard is using regulation, wherein executing respectively
The maximum residue limit of GB2760-2014 and GB2762-2017 and maximum usage amount, therefore in order to ensure sugar products and Environmental security,
The residual quantity of diuron sugar products raw material sugar-cane juice is analyzed very necessary.
Currently, the method for diuron mainly has sour water gas chromatography-mass spectrography, superelevation liquid chromatography in detection sugarcane
With the instrument analytical methods such as liquid chromatography-mass spectrometry.Since diuron is decomposed when temperature reaches 180 DEG C or more generations, gas phase is given
Chromatography qualitative and quantitative analysis brings difficulty, and most of researchs are analyzed using liquid chromatography, but when using liquid phase
Chromatography mass spectrometry, testing cost height and Mobile-phase reagent consumption are big, are difficult to meet quick, inexpensive, environmental protection tests and want
It asks.
Summary of the invention
In order to make up the defect of prior art, it is residual to provide diuron in the measurement sugarcane based on 3,4-DCA by the present invention
The method stayed.
The technical problems to be solved by the invention are achieved by the following technical programs：
The remaining method of diuron, includes the following steps in measurement sugarcane based on 3,4-DCA：
S1. the instruction ingredient 3,4- dichloroaniline of diuron thermal decomposition is determined using Gas chromatographyMass spectrometry；
S2. sample pre-treatments：Sugarcane sample is extracted and purified treatment, sugarcane prepare liquid is obtained；
S3. the diuron standard solution of at least six concentration is prepared；The diuron standard solution of each concentration gradient of preparation is carried out
Gas chromatography-electron capture detector measurement carries out regression analysis to its respective concentration with the chromatographic peak area of standard solution, draws
Standard working curve processed；Sugarcane prepare liquid injection gas chromatography-electron capture detector is measured under the same conditions, is surveyed
The chromatographic peak area of diuron in sugarcane prepare liquid is obtained, standard working curve is substituted into, obtains diuron content in sugarcane prepare liquid.
Further, the condition of gas chromatography-electron capture detector detection is：Column model：Rtx-5；Chromatographic column
Size：30 m×250μm ×0.25μm；Carrier gas is the nitrogen that purity is greater than 99.999%；Flow rate of carrier gas is 1.2mL/min；
Injector temperature is 250 DEG C；Detector temperature is 300 DEG C；Column oven uses temperature programming, and temperature program is：Chromatographic column is initial
100 DEG C of temperature, 200 DEG C is risen to 20 DEG C/min, then rise to 230 DEG C with 8 DEG C/min, keep 2 min；Sample volume：1L；Split ratio
For:1:50.
Further, the concrete operations of step S1 are：（1）The foundation of GC conditions；The foundation of Mass Spectrometry Conditions；（2）
To certain density diuron standard solution gas chromatograph-mass spectrometer in step（1）Under conditions of detected, according to gained
Total ion chromatogram and mass spectrogram, in conjunction with U.S. NIST standard diagram library or other standard diagram library searchings, to the enemy
Each pyrolysate carries out qualitative analysis in the grand standard solution of grass, determines the primary product 3,4-DCA of diuron thermal decomposition；
（3）The diuron standard solution for preparing various concentration, by the diuron standard solution gas-chromatography-of each concentration gradient of preparation
Mass spectrograph is in step（1）Under conditions of detected, carry out Salbutamol Selected Ion Monitoring SIM quantitative analysis, quota ion be m/z 161
Ion, using diuron concentration as abscissa, using the peak height of its quota ion as ordinate, linear using least square method is returned
It comes back and draws standard working curve, the linearly dependent coefficient of the standard working curve is greater than 0.998.
Since diuron is decomposed when temperature reaches 180 DEG C or more generations, brought to gas chromatography qualitative and quantitative analysis
Difficulty, this field researcher think that always detection remaining to diuron in sugarcane sample is not suitable for using gas phase color
Spectrum-electron capture detector method.The applicant by furtheing investigate for a long time, using Gas chromatographyMass spectrometry to enemy's grass
The grand decomposition product caused by thermal decomposition during gas chromatographic analysis has carried out Qualitative and Quantitative research, passes through mass spectrogram point
Solve product chemical structure, find out diuron thermal decomposition instruction ingredient and with diuron stoste relationship, confirm gas-chromatography-
Electron capture organ detection method measures the remaining feasibility of diuron and accuracy in sugarcane sample, to establishing gas-chromatography-electronics
The remaining detection method of diuron is of great significance in acquisition detector method analysis sugarcane sample.
So far, have no both at home and abroad about in Electron-capture gas chromatography in food agricultural product by 3,
Qualitative and quantitative target report of the 4- dichloroaniline as diuron, before the application, those skilled in the art always will
How focusing on for research uses the instrument detection method in addition to Electron-capture gas chromatography method efficiently to measure enemy's grass
In grand remaining research, because of the thermal instability of diuron, those skilled in the art are not paid close attention to always using gas-chromatography-electricity
Sub- acquisition detector method measures the remaining feasibility of diuron, and the applicant is by further investigation, it is determined that 3,4-DCA
For diuron thermal decomposition instruction ingredient and quantitative analysis representative component, and in 3,4-DCA structure containing there are two electricity
The stronger chlorine element of negativity has stronger response signal, high sensitivity, thus for quickly detection trace in-electron capture detector
Amount diuron provides a kind of new approach.
Further, the foundation of GC conditions：Column model：HP-5MS ；Chromatographic column specification：30 m×250μm
×0.25μm；Carrier gas is the helium that purity is greater than 99.999%；Flow rate of carrier gas is 1.2 mL/min；Injector temperature is 250 DEG C,
Detector temperature is 300 DEG C, and column oven uses temperature programming, temperature program：100 DEG C of chromatographic column initial temperature, with 20 DEG C/min
200 DEG C are risen to, then rises to 230 DEG C with 8 DEG C/min, keeps 2 min；Sample volume：1L, split ratio are：1:5；Mass Spectrometry Conditions are built
It is vertical：Ion source：Electron bombardment ionization source；Electronics energy：70eV；Gas chromatography-mass spectrum interface temperature：250℃；Quadrupole rod temperature：150
℃；Ion source temperature：230 DEG C, acquisition mode：Salbutamol Selected Ion Monitoring SIM, the quota ion of 3,4-DCA are m/z 161
Ion, qualitative ion be m/z 161,207,126,63 ion.
Sugar-cane juice matrix is complicated, containing more organic acid, phenols, metal ion, pigment and microorganism etc., can not only reduce
The sensitivity and selectivity of testing result, but also chromatographic column, ion source and detector etc. can be caused greatly to damage.Cause
This, before carrying out instrument analysis, it usually needs avoid matrix from doing object analysis using suitable Sample Pretreatment Technique
It disturbs, improves the accuracy of testing result.
Further, sample pre-treatments are：（1）It extracts：It draws 5.00 mL of sugarcane juice to be placed in 50 mL centrifuge tubes, be added
5.0 mL acetonitriles and 2.0 g sodium citrates, revolve mixed 1 min, and ultrasonic extraction 3min puts into a centrifuge centrifuge tube with 5000
R/min is centrifuged 5 min, takes out supernatant as in nitrogen blowpipe；Continue to add 5.0 mL acetonitriles, rotation into above-mentioned centrifuge tube again
Mixed 1 min, ultrasonic extraction 3min, above-mentioned centrifuge tube is put into a centrifuge and is centrifuged 5 min with 5000 r/min, takes out supernatant
It is close dry as being blown in above-mentioned nitrogen blowpipe, with methanol constant volume to 2.0 mL, obtain extracting solution；（2）Purification：Extracting solution is transferred to only
Change in column, take out repeatedly and push away piston three times, allows extracting solution by decontaminating column, obtain eluent；Eluent is passed through 0.22 micron again
Miillpore filter is transferred in sample injection bottle and measures to upper machine.
Further, the frequency of ultrasonic extraction is 70 kHz, and the temperature of ultrasonic extraction is 30 DEG C.
It uses acetonitrile for Extraction solvent in the present invention, relative to the conventional use of Extraction solvent such as acetone, can not only incite somebody to action
Diuron in sugar-cane juice farthest extracts, and due to containing a large amount of sucrose, glucose and fruit in sugar-cane juice
Insoluble in acetonitrile, using acetonitrile as Extraction solvent, the dry of carbohydrate content can be effectively reduced in the glucides such as sugar, these ingredients
It disturbs, so that object chromatographic peak profile is symmetrical, matrix effect is low.
Magnesium sulfate is usually added in traditional extraction process simultaneously, the present invention with sodium citrate in practice, it has been found that substitute
Magnesium sulfate can substantially increase the extraction efficiency that diuron is remained in sugar-cane juice.
Further, the decontaminating column includes the filler in column tube and column tube, is equipped with a piston, the work in the column tube
Plug can be along the axial movement of the column tube；The column tube lower end is equipped with outlet tube；The filler is made of following component：NANO
3-12 parts of carbon is modified mesopore silicon oxide 2-10 parts and 0.5 part of diatomite；The NANO carbon is loaded on column tube bottom, the modification
Mesopore silicon oxide and diatomite mixed packing use polypropylene sieve plate as separation therebetween on column tube upper layer.
Further, the preparation method of the modified mesopore silicon oxide is：By ordered meso-porous silicon oxide at 75-85 DEG C
8-10 h is dried, pretreated ordered meso-porous silicon oxide is obtained；The pretreated ordered meso-porous silicon oxide that will be obtained, adds
Enter toluene, 3- aminopropyl triethoxysilane and γ-halogen propyl trimethoxy silicane is then added, in oil bath heated at constant temperature magnetic force
It is stirred to react in blender, filters after reaction, clean 1-2 h with isopropanol, it is dry, wherein organic mesopore silicon oxide and first
The mass volume ratio of benzene is 8g:1L, ordered meso-porous silicon oxide, 3- aminopropyl triethoxysilane and γ-halogen propyl trimethoxy
The molar ratio of silane is: 8.5: 0.6: 1.5.
The present invention is using 3- aminopropyl triethoxysilane and γ-halogen propyl trimethoxy silicane by organic functional
Group is introduced into mesopore silicon oxide surface, synthesizes a kind of mesoporous hydrogenated silicon oxide of new functionization, passes through tune in the synthesis process
3- aminopropyl triethoxysilane and γ-halogen propyl trimethoxy silicane adding proportion are saved, it can be to meso pore silicon oxide material table
Face functionalization degree carries out Effective Regulation, so that functional group is evenly distributed, and keeps the duct of meso pore silicon oxide material orderly
Degree is not destroyed.The modification mesopore silicon oxide synthesized in this way can effectively remove in extracting solution as purifying adsorbent
Phenolic substances, while reducing the absorption to object.
NANO carbon is the characteristics such as nano material its surface hydrophobicity, porous and distinctive pi-electron system based on carbon, is easy
It is acted on target compound π-π, therefore NANO carbon can be effectively reduced or eliminate pigment, fat, metal ion in sample etc.
Influence of the matrix to testing result is a kind of ideal adsorbent and cleanser.NANO carbon in the present invention is selected from commercial product,
What the decontaminating column in the present invention carried out based on being Cleanert NANO carbon decontaminating column by commercially available from Agela brand changes
Into.
The adsorption capacity of diatomite is very strong, and those skilled in the art usually do not use diatom when purifying sugarcane extract
Soil adsorbs pesticide residue therein to avoid diatomite, to influence to the remaining Accurate Determining of pesticide in sugarcane.This
The favorite outer a small amount of diatomite of addition of having attempted is invented as one of adsorbent, is made with NANO carbon and modified mesopore silicon oxide compatibility
With discovery has no effect on the recycling of pesticide residue, and opposite final purification effect is very prominent.
In the present invention, by optimizing the performance of ten several adsorbent materials, for the first time using NANO carbon, modified mesopore silicon oxide
With diatomite as adsorbent, further through the dosage and proportion of three kinds of materials of optimization, connected applications method, which has reached, mentions sugarcane
The purification requirement of liquid is taken, sample substrate chaff interferent can be farthest removed, can significantly reduce matrix effect, it will not adsorbed target
Pesticide.
Further, the particle size range of the filler is between 5 μm -100 μm.
Further, sieve plate is the network with certain pore size
Further, the column tube is high-density polyethylene material or glass material.
It in existing decontaminating column or is that all adsorbents are mixed to laggard luggage to fill out or be by various adsorbents point
Layer is loaded, and will be modified to be layered with NANO carbon again after mesopore silicon oxide and diatomite mixed packing in the present invention and be loaded, test
Confirm that the clean-up effect of this type of feed is more preferable.
The present invention has the advantages that：
The present invention has determined remaining feasible using GC -ECD measurement thermal instability substance diuron for the first time
Property, using method of the invention, diuron linear relationship within the scope of 0.01-5.0 mg/L is good, and related coefficient is all larger than
0.998, detection is limited to 0.007 mg/kg, and the rate of recovery of the diuron in sugar-cane juice is 89.2%-111%, and relative standard deviation is
2.45%-6.57%, the accuracy of this method and precision can meet the requirement of pesticide residue analysis.
Detailed description of the invention
Fig. 1 is the GC-ECD chromatogram of the diuron standard solution of 0.5mg/L；
Fig. 2 is the total ion chromatogram of the diuron standard solution of 0.5mg/L；
Fig. 3 is the mass spectrogram of 3,4- dichloroaniline.
Specific embodiment
The present invention will now be described in detail with reference to examples, and the examples are only preferred embodiments of the present invention,
It is not limitation of the invention.
Embodiment 1
The method for determining the instruction ingredient that diuron thermally decomposes in Electron-capture gas chromatography, its step are as follows：
（1）The foundation of GC conditions：Column model：HP-5MS ；Chromatographic column specification：30 m×250μm ×0.25μm；
Carrier gas is the helium that purity is greater than 99.999%；Flow rate of carrier gas is 1.2 mL/min；Injector temperature is 250 DEG C, detector temperature
Degree is 300 DEG C, and column oven uses temperature programming, temperature program：100 DEG C of chromatographic column initial temperature, 200 are risen to 20 DEG C/min
DEG C, then 230 DEG C are risen to 8 DEG C/min, keep 2 min；Sample volume：1L, split ratio are：1:5；The foundation of Mass Spectrometry Conditions：Ion
Source：Electron bombardment ionization source；Electronics energy：70eV；Gas chromatography-mass spectrum interface temperature：250℃；Quadrupole rod temperature：150℃；Ion source
Temperature：230 DEG C, acquisition mode：Salbutamol Selected Ion Monitoring SIM, the quota ion of 3,4-DCA are the ion of m/z 161, fixed
Property ion be m/z 161,207,126,63 ion；
（2）To a certain concentration（0.5mg/L）Diuron standard solution gas chromatograph-mass spectrometer in step（1）Under conditions of
It is detected, according to resulting total ion chromatogram and mass spectrogram, in conjunction with U.S. NIST standard diagram library or other standard drawings
Library searching carries out qualitative analysis to pyrolysate each in the diuron standard solution, determines the main of diuron thermal decomposition
Product 3,4- dichloroaniline；
- 3 it is found that do not find diuron original shape, but simultaneously when carrying out gas chromatographic detection to diuron standard solution refering to fig. 1
It is formed there are two types of decomposition product, passes through total ion chromatogram and mass spectrogram analysis, the primary product 3,4- of diuron thermal decomposition
Dichloroaniline.
（3）Prepare the diuron standard solution of various concentration（0.01-5ppm）, by the diuron of each concentration gradient of preparation
Standard solution gas chromatograph-mass spectrometer is in step（1）Under conditions of detected, carry out Salbutamol Selected Ion Monitoring SIM quantitatively divide
Analysis, quota ion are that the ion of m/z 161, using the peak height of its quota ion as ordinate, is adopted using diuron concentration as abscissa
Standard working curve is drawn with the linear regression of least square method, as a result, it has been found that 3,4-DCA corresponding signal and diuron
Concentration is directly proportional, and the linearly dependent coefficient of the standard working curve is 0.9986.
Embodiment 2
On the basis of embodiment 1, the remaining method of diuron in sugarcane is measured, is included the following steps：
S1. sample pre-treatments：Sugarcane sample is extracted and purified treatment, sugarcane prepare liquid is obtained；
S2. the diuron standard solution of 7 concentration is prepared（0.01,0.05,0.1,0.5,1.0,2.0 and 5.0 mg/L）；It will match
The diuron standard solution of each concentration gradient of system carries out gas chromatography-electron capture detector measurement, with the color of standard solution
Spectral peak area carries out regression analysis to its respective concentration, draws standard working curve；Sugarcane prepare liquid is infused under the same conditions
Enter gas chromatography-electron capture detector to be measured, measure the chromatographic peak area of diuron in sugarcane prepare liquid, substitutes into standard
Working curve obtains diuron content in sugarcane prepare liquid.
Wherein, the condition of gas chromatography-electron capture detector detection is：Column model：Rtx-5；Column size：
30 m×250μm ×0.25μm；Carrier gas is the nitrogen that purity is greater than 99.999%；Flow rate of carrier gas is 1.2mL/min；Injection port
Temperature is 250 DEG C；Detector temperature is 300 DEG C；Column oven uses temperature programming, and temperature program is：Chromatographic column initial temperature 100
DEG C, 200 DEG C are risen to 20 DEG C/min, then rise to 230 DEG C with 8 DEG C/min, keeps 2 min；Sample volume：1L；Split ratio is:1:
50。
Sample pre-treatments are：（1）It extracts：It draws 5.00 mL of sugarcane juice to be placed in 50 mL centrifuge tubes, 5.0 mL acetonitriles is added
With 2.0 g sodium citrates, mixed 1 min, ultrasonic extraction 3min are revolved, centrifuge tube is put into a centrifuge with 5000 r/min centrifugation 5
Min takes out supernatant as in nitrogen blowpipe；Continue to add 5.0 mL acetonitriles into above-mentioned centrifuge tube again, revolves mixed 1 min, ultrasound
3min is extracted, above-mentioned centrifuge tube is put into a centrifuge and is centrifuged 5 min with 5000 r/min, supernatant is taken out and is blown as above-mentioned nitrogen
Guan Zhong is blown to and closely does, with methanol constant volume to 2.0 mL, obtains extracting solution；（2）Purification：Extracting solution is transferred in decontaminating column, is taken out repeatedly
Piston three times is pushed away, allows extracting solution by decontaminating column, obtains eluent；Eluent is passed through to 0.22 micron of miillpore filter, transfer again
It is measured into sample injection bottle to upper machine.Wherein, the frequency of ultrasonic extraction is 70 kHz, and the temperature of ultrasonic extraction is 30 DEG C.
The decontaminating column includes the filler in column tube and column tube, and the column tube is high-density polyethylene material or glass material
Material, the particle size range of the filler are equipped with a piston, the piston can be along the column between 5 μm -100 μm in the column tube
The axial movement of pipe；The column tube lower end is equipped with outlet tube；The filler is made of following component：3-12 parts of NANO carbon changes
Property 2-10 parts of mesopore silicon oxide and 0.5 part of diatomite；The NANO carbon is loaded on column tube bottom, the modified mesopore silicon oxide
With diatomite mixed packing on column tube upper layer, use polypropylene sieve plate as separating therebetween, sieve plate is the net with certain pore size
Lattice structure, wherein the preparation method of the modified mesopore silicon oxide is：Ordered meso-porous silicon oxide is dried into 8- at 75-85 DEG C
10 h obtain pretreated ordered meso-porous silicon oxide；Toluene is added in the pretreated ordered meso-porous silicon oxide that will be obtained,
Then 3- aminopropyl triethoxysilane and γ-halogen propyl trimethoxy silicane is added, in oil bath constant-temperature heating magnetic stirring apparatus
In be stirred to react, filter after reaction, clean 1-2 h with isopropanol, it is dry, wherein the matter of organic mesopore silicon oxide and toluene
Amount volume ratio is 8g:1L, ordered meso-porous silicon oxide, 3- aminopropyl triethoxysilane and γ-halogen propyl trimethoxy silicane
Molar ratio is: 8.5: 0.6: 1.5.
Embodiment 3
Precision and recovery of standard addition are tested
Using without diuron sugar-cane juice as blank sample, each sample be respectively 0.01 mg/kg, 0.05 mg/kg,
The rate of recovery of the pitch-based sphere of 0.5 mg/kg is tested, and each pitch-based sphere does 6 parts of Duplicate Samples, according to the method in embodiment 2 into
Row measurement, asks its average recovery rate and relative standard deviation.
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, as long as skill obtained in the form of equivalent substitutions or equivalent transformations
Art scheme should all be fallen within the scope and spirit of the invention.
Claims (9)
1. the remaining method of diuron, includes the following steps in the measurement sugarcane based on 3,4-DCA：
S1. the instruction ingredient 3,4- dichloroaniline of diuron thermal decomposition is determined using Gas chromatographyMass spectrometry；
S2. sample pre-treatments：Sugarcane sample is extracted and purified treatment, sugarcane prepare liquid is obtained；
S3. the diuron standard solution of at least six concentration is prepared；The diuron standard solution of each concentration gradient of preparation is carried out
Gas chromatography-electron capture detector measurement carries out regression analysis to its respective concentration with the chromatographic peak area of standard solution, draws
Standard working curve processed；Sugarcane prepare liquid injection gas chromatography-electron capture detector is measured under the same conditions, is surveyed
The chromatographic peak area of diuron in sugarcane prepare liquid is obtained, standard working curve is substituted into, obtains diuron content in sugarcane prepare liquid.
2. the method as described in claim 1, which is characterized in that gas chromatography-electron capture detector detection condition be：Color
Compose column type number：Rtx-5；Column size：30 m×250μm ×0.25μm；Carrier gas is the nitrogen that purity is greater than 99.999%；
Flow rate of carrier gas is 1.2mL/min；Injector temperature is 250 DEG C；Detector temperature is 300 DEG C；Column oven uses temperature programming, rises
Warm program is：100 DEG C of chromatographic column initial temperature, 200 DEG C is risen to 20 DEG C/min, then rise to 230 DEG C with 8 DEG C/min, keep 2
min；Sample volume：1L；Split ratio is 1:50.
3. the method as described in claim 1, which is characterized in that the concrete operations of step S1 are：（1）GC conditions are built
It is vertical；The foundation of Mass Spectrometry Conditions；（2）To certain density diuron standard solution gas chromatograph-mass spectrometer in step（1）Item
It is detected under part, according to resulting total ion chromatogram and mass spectrogram, in conjunction with U.S. NIST standard diagram library or other marks
Quasi- map library searching carries out qualitative analysis to pyrolysate each in the diuron standard solution, determines diuron thermal decomposition
Primary product 3,4- dichloroaniline；（3）The diuron standard solution for preparing various concentration, by enemy's grass of each concentration gradient of preparation
Grand standard solution gas chromatograph-mass spectrometer is in step（1）Under conditions of detected, it is quantitative to carry out Salbutamol Selected Ion Monitoring SIM
Analysis, quota ion is the ion of m/z 161, using diuron concentration as abscissa, using the peak height of its quota ion as ordinate,
Standard working curve is drawn using the linear regression of least square method, the linearly dependent coefficient of the standard working curve is greater than
0.998。
4. method as claimed in claim 3, which is characterized in that the foundation of GC conditions：Column model：HP-5MS ；
Chromatographic column specification：30 m×250μm ×0.25μm；Carrier gas is the helium that purity is greater than 99.999%；Flow rate of carrier gas is 1.2
mL/min；Injector temperature is 250 DEG C, and detector temperature is 300 DEG C, and column oven uses temperature programming, temperature program：Chromatographic column
100 DEG C of initial temperature, 200 DEG C is risen to 20 DEG C/min, then rise to 230 DEG C with 8 DEG C/min, keep 2 min；Sample volume：1L, point
Stream is than being 1:5；The foundation of Mass Spectrometry Conditions：Ion source：Electron bombardment ionization source；Electronics energy：70eV；Gas chromatography-mass spectrum interface temperature：
250℃；Quadrupole rod temperature：150℃；Ion source temperature：230 DEG C, acquisition mode：Salbutamol Selected Ion Monitoring SIM, 3,4-DCA
Quota ion be m/z 161 ion, qualitative ion be m/z 161,207,126,63 ion.
5. the method as described in claim 1, which is characterized in that sample pre-treatments are：（1）It extracts：5.00 mL of sugarcane juice is drawn to set
In 50 mL centrifuge tubes, 5.0 mL acetonitriles and 2.0 g sodium citrates are added, revolve mixed 1 min, ultrasonic extraction 3min will be centrifuged
Pipe, which is put into a centrifuge, is centrifuged 5 min with 5000 r/min, takes out supernatant as in nitrogen blowpipe；It is relayed again to above-mentioned centrifuge tube
5.0 mL acetonitriles of continuous addition, revolve mixed 1 min, and ultrasonic extraction 3min puts into a centrifuge above-mentioned centrifuge tube with 5000 r/min
5 min are centrifuged, taking-up supernatant is close dry as being blown in above-mentioned nitrogen blowpipe, with methanol constant volume to 2.0 mL, obtains extracting solution；（2）
Purification：Extracting solution is transferred in decontaminating column, takes out repeatedly and pushes away piston three times, allows extracting solution by decontaminating column, obtains eluent；It will wash again
De- liquid passes through 0.22 micron of miillpore filter, is transferred in sample injection bottle and measures to upper machine.
6. method as claimed in claim 5, which is characterized in that the frequency of ultrasonic extraction is 70 kHz, the temperature of ultrasonic extraction
It is 30 DEG C.
7. method as claimed in claim 5, which is characterized in that the decontaminating column includes the filler in column tube and column tube, described
A piston is equipped in column tube, the piston can be along the axial movement of the column tube；The column tube lower end is equipped with outlet tube；Described
Filler is made of following component：3-12 parts of NANO carbon is modified mesopore silicon oxide 2-10 parts and 0.5 part of diatomite；The NANO carbon
It is loaded on column tube bottom, the modified mesopore silicon oxide and diatomite mixed packing are sieved using polypropylene therebetween on column tube upper layer
Plate is as separation.
8. the method for claim 7, which is characterized in that the preparation method of the modified mesopore silicon oxide is：It will be orderly
Mesopore silicon oxide dries 8-10 h at 75-85 DEG C, obtains pretreated ordered meso-porous silicon oxide；The pretreatment that will be obtained
Toluene is added in ordered meso-porous silicon oxide afterwards, and 3- aminopropyl triethoxysilane and γ-halogen propyl trimethoxy silicon is then added
Alkane is stirred to react in oil bath constant-temperature heating magnetic stirring apparatus, filters after reaction, cleans 1-2 h with isopropanol, dry,
Wherein the mass volume ratio of organic mesopore silicon oxide and toluene is 8g:1L, ordered meso-porous silicon oxide, 3- aminopropyl-triethoxy
Silane and γ-halogen propyl trimethoxy silicane molar ratio are: 8.5: 0.6: 1.5.
9. the method for claim 7, which is characterized in that the particle size range of the filler is between 5 μm -100 μm；Sieve plate
For the network with certain pore size；The column tube is high-density polyethylene material or glass material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810898171.9A CN108828101B (en) | 2018-08-08 | 2018-08-08 | Method for determining diuron residues in sugarcane based on 3, 4-dichloroaniline |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810898171.9A CN108828101B (en) | 2018-08-08 | 2018-08-08 | Method for determining diuron residues in sugarcane based on 3, 4-dichloroaniline |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108828101A true CN108828101A (en) | 2018-11-16 |
| CN108828101B CN108828101B (en) | 2021-05-07 |
Family
ID=64153835
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810898171.9A Active CN108828101B (en) | 2018-08-08 | 2018-08-08 | Method for determining diuron residues in sugarcane based on 3, 4-dichloroaniline |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108828101B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114200055A (en) * | 2021-12-10 | 2022-03-18 | 云南省农业科学院甘蔗研究所 | Method for rapidly identifying sugarcane raw juice brown sugar and brown granulated sugar based on characteristic aroma substance GC-IMS fingerprint |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7059206B1 (en) * | 1999-08-25 | 2006-06-13 | University Of Portsmouth | Aquatic passive sampling device and methods for its use |
| CN101832979A (en) * | 2009-12-02 | 2010-09-15 | 天津市农业科学院中心实验室 | Determination method of residual quantity of diuron and metabolin thereof in cottonseeds |
| CN103575798A (en) * | 2013-09-12 | 2014-02-12 | 浙江出入境检验检疫局检验检疫技术中心 | Method for measuring residues of ethephon, thidiazuron and diuron in cotton by using liquid chromatography tandem mass spectrometry |
-
2018
- 2018-08-08 CN CN201810898171.9A patent/CN108828101B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7059206B1 (en) * | 1999-08-25 | 2006-06-13 | University Of Portsmouth | Aquatic passive sampling device and methods for its use |
| CN101832979A (en) * | 2009-12-02 | 2010-09-15 | 天津市农业科学院中心实验室 | Determination method of residual quantity of diuron and metabolin thereof in cottonseeds |
| CN103575798A (en) * | 2013-09-12 | 2014-02-12 | 浙江出入境检验检疫局检验检疫技术中心 | Method for measuring residues of ethephon, thidiazuron and diuron in cotton by using liquid chromatography tandem mass spectrometry |
Non-Patent Citations (4)
| Title |
|---|
| K. WITTKE 等: "Determination of dichloroanilines in human urine by GC–MS,GC–MS–MS, and GC–ECD as markers of low-level pesticide exposure", 《JOURNAL OF CHROMATOGRAPHY B》 * |
| TASSIA C. EGEA 等: "Diuron degradation by bacteria from soil of sugarcane crops", 《HELIYON》 * |
| 平立凤 等: "超高效液相色谱法测定甘蔗和土壤中敌草隆残留", 《分析科学学报》 * |
| 郭永泽 等: "棉籽中敌草隆及其代谢产物残留量的测定方法", 《天津农业科学》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114200055A (en) * | 2021-12-10 | 2022-03-18 | 云南省农业科学院甘蔗研究所 | Method for rapidly identifying sugarcane raw juice brown sugar and brown granulated sugar based on characteristic aroma substance GC-IMS fingerprint |
| CN114200055B (en) * | 2021-12-10 | 2024-03-22 | 云南省农业科学院甘蔗研究所 | Method for rapidly identifying raw sugarcane juice brown sugar and brown granulated sugar based on characteristic aroma substance GC-IMS fingerprint |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108828101B (en) | 2021-05-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106706830B (en) | A method of perfluori piated carboxylic acids compound in measurement crop | |
| Zheng et al. | Ultrasound/microwave‐assisted solid–liquid–solid dispersive extraction with high‐performance liquid chromatography coupled to tandem mass spectrometry for the determination of neonicotinoid insecticides in Dendrobium officinale | |
| CN102735784A (en) | Method for simultaneously determining one hundred pesticide residuals in traditional Chinese medicine through ultrahigh performance liquid chromatography-tandem quadrupole mass spectrum | |
| CN106526009B (en) | A kind of quantitative detecting method of universal Rynaxypyr residual quantity | |
| CN106568873A (en) | Quantitative detection method for residual quantity of chlorantraniliprole in soil | |
| CN108982730B (en) | Analysis method for detecting prochloraz metabolite in plant-derived agricultural products by combining common group method with UPLC-MSMS | |
| CN104374849A (en) | Method for treating pyrethroid pesticide residue soil environment sample before measurement | |
| CN111855871A (en) | Method for measuring iprovalicarb and fluopyram in tobacco by combination of filtration type solid-phase extraction and supercritical fluid chromatography-mass spectrometry | |
| CN115184497B (en) | Method for determining content of 2, 4-epibrassinolide in dendrobium candidum | |
| de Jesus et al. | Evaluation of a novel metal–organic framework as an adsorbent for the extraction of multiclass pesticides from coconut palm (Cocos nucifera L.): An analytical approach using matrix solid‐phase dispersion and liquid chromatography | |
| JP2006505765A (en) | Extraction method of polar phytochemicals | |
| CN108828101A (en) | The remaining method of diuron in measurement sugarcane based on 3,4- dichloroaniline | |
| CN106546675B (en) | The quantitative detecting method of Rynaxypyr residual quantity in a kind of tealeaves | |
| CN114264755B (en) | Gas chromatography-triple quadrupole mass spectrometry detection method for residual amount of sulfonepyraflufen in plant-derived food | |
| CN106290662A (en) | Organochlorine pesticide and the method for quick of pyrethroid pesticide and pre-treating method thereof in Folium Camelliae sinensis | |
| CN110161136A (en) | A kind of method of persistence organic pollutant in tablet bubbling aid dispersion Magnetic solid phases extraction and determination water | |
| CN110763771A (en) | Pretreatment method for measuring organochlorine pesticide and polychlorinated biphenyl in aquatic product culture water body | |
| Ma et al. | Coconut shell biochar application in liquid-solid microextraction of triazine herbicides from multi-media environmental samples | |
| Zhang et al. | Application of three-dimensional material CZIF-8/CS-MS as adsorbents for the determination of plant growth regulators in Schisandra chinensis | |
| CN103616456A (en) | High performance liquid chromatography-tandem mass spectrum detection method of dithiophosphate pesticide metabolites | |
| CN107505421A (en) | The rapid extraction and purification method of ethiprole and its metabolite residue in a kind of birds, beasts and eggs | |
| CN104502508B (en) | A kind of GC-NCI-MS assay method of cyanogen insect amide residual quantity | |
| Gao et al. | Application of solid‐phase extraction: High‐resolution mass spectrometry analysis strategy in the characterization and quantification of amide herbicides in aquatic products | |
| CN115963189A (en) | Method for detecting multiple pesticide residues in forage grass | |
| WO2003074144A2 (en) | Process for scavenging phytochemicals |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |