CN106226432A - A kind of edible rice safe mass stage division - Google Patents
A kind of edible rice safe mass stage division Download PDFInfo
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- CN106226432A CN106226432A CN201610648567.9A CN201610648567A CN106226432A CN 106226432 A CN106226432 A CN 106226432A CN 201610648567 A CN201610648567 A CN 201610648567A CN 106226432 A CN106226432 A CN 106226432A
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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
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/3103—Atomic absorption analysis
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- 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
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
- G01N2030/025—Gas 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
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
- G01N2030/027—Liquid chromatography
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Abstract
The present invention relates to a kind of edible rice safe mass stage division, be also applied for edible paddy is carried out safe mass classification.Set up a kind of rice safe mass stage division to instruct the production of China's rice product, consumption the most necessary, but currently there are no a kind of rice safe mass stage division.Present invention is characterized in that the step of described method is as follows: (1) takes food with rice sample, the persticide residue in detection edible rice；(2) take food with rice sample, the heavy metal cadmium content in detection edible rice；(3) persticide residue obtained according to detection and heavy metal cadmium content, carry out safe mass classification to edible rice.The detection speed of the present invention is fast, accuracy is high, and reagent saves, environmentally friendly, also have stability and reproducible, and Producer can fix a price by credit rating, the optional purchase of consumer, can really embody high quality and favourable price.
Description
Technical field
The present invention relates to a kind of edible rice safe mass stage division, be also applied for edible paddy is carried out safe mass
Classification.
Background technology
Oryza sativa L. is the topmost cereal crops of China, and its total output accounts for the 40% of total output of grain, and the whole nation has more than 60%
Population with rice as staple food, the product quality of rice is healthy closely bound up with our people's.The development of modern agriculture
Drastically increase the yield of China's rice, and excess uses environmental pollution and the rice Product quality and safety that fertilizer and pesticide causes
Problem is the most outstanding day by day, and the event such as the most poisonous rice, cadmium rice goes out cruelly, along with socioeconomic further development and people are raw
Flat the improving constantly of running water, people are more and more higher to the requirement of quality of rice, and safe mass has become people's focus of attention.Though
The method the most also having detection/prediction rice safe mass, if publication date is on 03 19th, 2014, Publication No.
In the Chinese patent of CN103645201A, disclose and a kind of quickly detect the method for heavy metal cadmium in rice based on XRF,
And for example publication date is on 06 10th, 2015, in the Chinese patent of Publication No. CN104686267A, discloses a kind of the most pre-
Survey the method for heavy metal cadmium content in rice, but currently there are no a kind of rice safe mass stage division.Therefore, one is set up
Planting rice safe mass stage division instructs the production of China's rice product, consumption the most necessary.
Summary of the invention
It is an object of the invention to overcome above-mentioned deficiency present in prior art, and provide a kind of detection speed fast, accurate
Exactness is high, and reagent saves, environmentally friendly, also have stability and reproducible, and Producer can be fixed a price by credit rating, and consumer can
Select to buy, can really embody the edible rice safe mass stage division of high quality and favourable price.
The present invention solves the problems referred to above and be the technical scheme is that the feature of this edible rice safe mass stage division
It is: the step of described method is as follows:
(1) take food with rice sample, the persticide residue in detection edible rice；
(2) take food with rice sample, the heavy metal cadmium content in detection edible rice；
(3) persticide residue obtained according to detection and heavy metal cadmium content, carry out safe mass classification to edible rice.
As preferably, in step of the present invention (1), use organophosphor in gas chromatography determination edible rice sample, organic
Chlorine and Determining pyrethroid pesticide residues, the detecting step of persticide residue is as follows: organophosphor, organochlorine and chrysanthemum in edible rice sample
Ester pesticides is saltoutd through magnesium sulfate through acetonitrile extraction, extracting solution, after PSA dispersive solid-phase extraction purifies, after air inlet chromatography
Detect with FPD detector, carry out qualitative according to retention time, area quantified by external standard method；Or, organochlorine in edible rice sample
Saltout through magnesium sulfate through acetonitrile extraction, extracting solution with pyrethrin pesticide, after Fu Luoli silicon column solid phase extraction purifies, air inlet phase color
Detect with ECD detector after spectrometer, carry out qualitative according to retention time, area quantified by external standard method.
As preferably, the present invention uses organophosphor, organochlorine and chrysanthemum esters in gas chromatography determination edible rice sample
The step of persticide residue is as follows:
1. extract
Edible rice dry sample, weighs edible rice sample size-reduced for 5.0g, is placed in 250mL plastic centrifuge tube, adds
25.0mL distilled water, stands 30min, adds 25.0ml acetonitrile, is homogenized 2min, adds 10g anhydrous slufuric acid in high speed dispersor
Magnesium and 1g sodium chloride, be homogenized 1 minute in low speed dispersion machine, and centrifugal force is 2500g, centrifugal 3min, makes acetonitrile and aqueous phase layering；
2. purify
Organophosphor purifies: pipettes 4.0ml upper strata acetonitrile solution and purifies in 15ml graduated centrifuge tube, to be measured；
Organochlorine and chrysanthemum ester purify: pipette 10ml upper strata acetonitrile solution in 15ml graduated centrifuge tube, in centrifuge tube in advance
Adding 0.5g sodium chloride, vortex mixed 1min, stratification, accurately absorption 5ml acetonitrile solution is in boiling flask, and rotary evaporation is extremely
Near dry, dissolve with the mixed liquor of the acetone+n-hexane of 2mL and obtain solution to be clean；
By Fu Luoli silicon post successively with the 5.0mL acetone+mixed liquor of n-hexane, the pre-drip washing of 5.0mL n-hexane, conditioning,
When solvent liquid level arrives post adsorption layer surface, pour above-mentioned solution to be clean immediately into, receive eluting with 15mL graduated centrifuge tube
Liquid, rinses drip washing Fu Luoli silicon post after beaker with the mixed liquor of 5mL acetone+n-hexane, and is repeated once；Leacheate will be filled
Centrifuge tube is placed on Nitrogen evaporator, and under the conditions of bath temperature 50 DEG C, nitrogen blows and is evaporated to, less than 5mL, be settled to n-hexane
5.0mL, mixes on vortex mixer, to be measured；
During for using automatic solid-phase extractor to purify, take the above-mentioned supernatant 8mL saltoutd, at rotary evaporation extremely
After the most dry, the mixed liquor adding acetone+n-hexane dissolves and is settled to 8mL, and instrument loading 2.5mL, with 4mL acetone+n-hexane
Mixed liquor drip washing Fu Luoli silicon post at twice, the centrifuge tube filling leacheate is placed on Nitrogen evaporator, bath temperature 50 DEG C
Under the conditions of, nitrogen blows and is evaporated to, less than 2mL, be settled to 2.5mL with n-hexane, mixes on vortex mixer, to be measured；
In the mixed liquor of acetone+n-hexane, the volume ratio of acetone and n-hexane is 1:9；
3. organophosphor measures
Chromatographic condition is as follows:
Chromatographic column: DB-1701 quartz capillary column, 30m × 0.25mm × 0.25um；
Column temperature: initial temperature 90 DEG C, rises to 270 DEG C with 25 DEG C/min immediately, keeps 3min；
Injection port: temperature 250 DEG C, pressure 25psi；
Sample size: 1ul；
Input mode: pulse does not shunts, pulsating pressure 50psi, keep 1min, purge time 0.9min；
Detector temperature: 240 DEG C；
Gas: carrier gas N2, constant voltage 25psi；H2Flow velocity 120ml/min；Air velocity 88ml/min；
Sample determination
Chromatographic condition in pressing 3. is to standard working solution and sample solution equal-volume sample introduction, qualitative according to retention time, face
Long-pending quantified by external standard method；
4. organochlorine and chrysanthemum ester measure
Chromatographic condition is as follows:
Chromatographic column: DB-17 or DB-1 quartz capillary column, 30m × 0.25mm × 0.25um；
Column temperature: initial temperature 90 DEG C, rises to 150 DEG C with 25 DEG C/min immediately, then rises to 270 DEG C with 10 DEG C/min, keeps 8min；
Injection port: temperature 250 DEG C, pressure 30psi；
Sample size: 1ul；
Input mode: shunting, split ratio is 5:1；
Detector temperature: 300 DEG C, post flow+tail wind drift amount=30mL/min；
Gas: carrier gas N2, constant voltage 30psi；
5. sample determination
Chromatographic condition in pressing 4. is to standard working solution and sample solution equal-volume sample introduction, qualitative according to retention time, face
Long-pending quantified by external standard method；
6. result calculates
In edible rice sample, tested pesticide concentration is in terms of mass fraction W, and numerical value is milligrams per kilogram to represent, by following public affairs
Formula calculates:
V1-standard specimen sampling volume, μ l；
V2-sample feeding volume, μ l；
A-standard specimen peak area；
A1-sample peak area；
M-sample quality (g)；
V3-solvent adds volume (ml)；
V4-point take solvent volume (ml)；
V-constant volume (ml).
As preferably, in step of the present invention (1), use in liquid chromatograph/concatenation mass spectrometric determination edible rice sample and have
Machine phosphorus, organic nitrogen, carbamate chemicals residual amount step as follows: edible rice sample Pesticides through acetonitrile extraction, extracts
Liquid is saltoutd through magnesium sulfate, after PSA dispersive solid-phase extraction purifies, with liquid chromatograph concatenation mass spectrograph detection, according to retention time
Carrying out qualitative with qualitative ion and quota ion and qualitative ion ratio, quota ion area external standard method is carried out quantitatively.
As preferably, the present invention uses organophosphor in liquid chromatograph/concatenation mass spectrometric determination edible rice sample, organic
Nitrogen, carbamate chemicals residual amount step as follows:
1. extract
Edible rice dry sample, weighs edible rice sample size-reduced for 5.0g, is placed in 250mL plastic centrifuge tube, adds
25.0mL distilled water, stands 30min；Add 25.0ml acetonitrile, high speed dispersor is homogenized 2min, adds 10g anhydrous slufuric acid
Magnesium and 1g sodium chloride, be homogenized 1 minute in low speed dispersion machine, and centrifugal force is 2500g, centrifugal 3min, makes acetonitrile and aqueous phase layering；
2. purify
Pipette 4.0ml upper strata acetonitrile solution in 15ml graduated centrifuge tube, purify, to be measured；
3. instrument condition
Chromatographic condition is as follows:
Chromatographic column: ZORBAX SB C18 (100mm × 2.1mm, 1.8 μm)；
Column temperature: 55 DEG C；
Mobile phase A: the 5mmol/L ammonium acetate solution containing 0.1% formic acid；Mobile phase B: acetonitrile；
Flow velocity: 0.3mL/min；
Mass Spectrometry Conditions is as follows:
Ion source: ESI；
Capillary voltage: 4kV；
Nitrogen flow rate: 10L/min；
Mass spectrum acquisition rate: 500ms/cycle；
Nebulizer pressure: 35psi；
Dry temperature: 350 DEG C；
4. sample determination
By the instrument condition in 3. to standard working solution and sample solution equal-volume sample introduction, according to retention time and qualitative from
Son and quota ion and qualitative ion ratio carry out qualitative, and quota ion area external standard method is carried out quantitatively；
5. result calculates
In sample, tested pesticide concentration is in terms of mass fraction W, and numerical value, milligrams per kilogram to represent, is calculated by following equation:
V1-standard specimen sampling volume, μ l；
V2-sample feeding volume, μ l；
A-standard specimen peak area；
A1-sample peak area；
M-sample quality (g)；
V3-solvent adds volume (ml)；
V4-point take solvent volume (ml)；
V-constant volume (ml).
As preferably, in step of the present invention (2), use the heavy metal cadmium in graphite oven atomic absorption detection edible rice
The step of content is as follows: edible rice sample, after acid is cleared up, imports atomic absorption spectrphotometry through graphite furnace automatic sampler
In meter graphite furnace, after graphite furnace high temperature atomic, Atomic Absorption specific wavelength spectral line in the optical path, its absorbance contains with it
Amount is directly proportional.
As preferably, the present invention uses the step of the heavy metal cadmium content in graphite oven atomic absorption detection edible rice
As follows:
1. prepared by sample
Removing the foreign material in edible rice sample, with quartering division to 50g after mixing, ground at least 98% passes through hole
The sieve of footpath 0.180mm, standby after mixing；
2. Specimen eliminating
Weigh edible rice sample 0.5g to be placed in digester, add 5mL concentrated nitric acid, place 15min, build sealing lid,
Put in microwave digestion system, rotate rotating disk 1min, clear up；After clearing up completely when screen instruction temperature is less than 50 DEG C,
Open the door of microwave dissolver, the most slowly unclamp explosion-proof membrane cover to discharge pressure, take off temperature sensor, open sealing lid,
By in digestion solution transfer also constant volume to 25mL volumetric flask, mix to be measured；Do reagent blank simultaneously；
3. Specification Curve of Increasing
Utilize the automatic dilution function of graphite furnace automatic sampler, allow it automatically by the top mark aqueous standard method of cadmium element
Curve, and add corresponding matrix modifier；Set the condition of instrument；Input relevant parameter, and design the dense of standard curve
Degree gradient；Draw standard curve；
4. calculate
X=(c-c0) × V × 1000/m × 1000 × 1000
In formula: each constituent content, mg/kg in X-sample；
C treatments of the sample liquid measures concentration, ng/mL；
C0 sample blank Digestive system concentration, ng/mL；
V treatments of the sample liquid cumulative volume, mL；
M-sample quality, g.
As preferably, in step of the present invention (3), the persticide residue obtained according to detection and heavy metal cadmium content are to edible
The step that rice carries out safe mass classification is as follows: the lowest class index reached with Product checking index is for judging grade, i.e.
Testing result agriculture is residual, cadmium all reaches one-level is judged to one-level；If one of which is two grades, it is judged to two grades；The like.
As preferably, in step of the present invention (3), the persticide residue obtained according to detection and heavy metal cadmium content are to edible
Rice carries out safe mass classification and is divided into level Four, specific as follows:
| Edible rice grade | Pesticide residues | Cadmium (mg/kg) |
| High-quality one-level | Do not detect | ≤0.01 |
| High-quality two grades | Detection one | ≤0.05 |
| High-quality three grades | Detect two kinds | ≤0.1 |
| Regular grade | Detect multiple | ＜ 0.2 |
The present invention compared with prior art, has the following advantages and effect: 1, propose quality of rice safe class concept, for
The agricultural industry criteria of system revision later provides scientific basis；2, be conducive to instructing the production of China's rice product, consumption.Producer
Can fix a price by credit rating, consumer can be chosen purchase, can really embody high quality and favourable price.3, High Quality Environment could produce excellent
Matter rice, has had quality grading, and High Quality Environment is worth and emerges from, and is conducive to preserving the ecological environment and the sustainable development of agricultural
Exhibition.4, the detection method of persticide residue and heavy metal cadmium content has that speed is fast, accuracy is high, and reagent saves, environmentally friendly,
Also have stability and reproducible feature.
Accompanying drawing explanation
Fig. 1 is the preparation process schematic diagram of cadmium standard solution and standard curve in the embodiment of the present invention.
Detailed description of the invention
The present invention is described in further detail below in conjunction with the accompanying drawings and by embodiment, and following example are to this
Bright explanation and the invention is not limited in following example.
Embodiment.
2003-2012 whole nation quality of rice is generally investigated and nearly ten thousand parts of samples of risk assessment detection by the present embodiment by us
On the comprehensive analysis foundation of product, selection pesticide residues and heavy metal cadmium are as value parameter, according to the system of sample detection data
Meter result determines graded index, its stage division such as following table:
Edible rice safe mass stage division
| Edible rice grade | Pesticide residues | Cadmium (mg/kg) |
| High-quality one-level | Do not detect | ≤0.01 |
| High-quality two grades | Detection one | ≤0.05 |
| High-quality three grades | Detect two kinds | ≤0.1 |
| Regular grade | Detect multiple | ＜ 0.2 |
One, value parameter explanation
(1), pesticide residues: pesticide residues are problems the most complicated, and on Oryza sativa L., common pesticides reaches hundreds of, and often
Year, the pesticide used was all in change, and novel pesticide continues to bring out, and was difficult to be used as value parameter with certain concrete pesticide, but according to
Whole nation quality of rice generaI investigation and risk assessment monitoring result are seen, China's rice residual recall rate of product agriculture is up to more than 20%, much
Product detection Multiple Pesticides, pesticide detection number reflect production process Pesticides use, the reality of safety interval control etc.
Border situation, therefore, using pesticide detection number as graded index simple possible.The pesticide parameter of concrete detection can be sent out according to the Ministry of Agriculture
Depending on the annual quality of rice security risk assessment detection parameter of cloth, as 52 kinds of pesticide of detection in 2015 are: Bayer 71628, methyl pair
Sulfur phosphorus, Isofenphos methyl, Azodrin, quintiofos, Rogor, phosphamidon, Malathion, phonamiphos, triazophos, fenifrothion, water amine
Sulfur phosphorus, phosmet, orthene, Bravo, clofenotane, Gamma Hexaochlorocyclohexane, triazolone, Buprofezin, tricyclazole, Triadimenol, pungent
Sulfur phosphorus, Acetochlor, isopropyl methoxalamine, Mobucin, butachlor, chlorpyrifos-methyl, phenthoate dimephenthoate cidial, dichlorvos, chlopyrifos, parathion,
Diazinon, decis, cypermethrin, iprobenfos, Ethodan, Difenoconazole, imidacloprid, Isoprothiolane, metrifonate, pyridine worm
Amidine, avilamycin, carbendazim, paclobutrazol, ethiprole, alachlor, thiophanate-methyl, carbaryl, metalaxyl, carbofuran, miaow are fresh
Amine, Diacloden.
(2), heavy metal: on Oryza sativa L., the heavy metal of generally detection has cadmium, lead, arsenic, hydrargyrum, chromium etc., interim cadmium be recall rate,
Exceeding standard rate is the highest, is showing the statistical result of 2003-2012 whole nation quality of rice Survey Sample, and the recall rate of cadmium reaches
97%, in rice, the height of cadmium content substantially reflects the pollution situation in water and soil compression ring border, rice district, place, therefore, it can cadmium to contain
The height of amount is as graded index.During in graded index, 0.2mg/kg is GB rice, the highest limitation of cadmium, is Cd concentration of brown rice
Requirement up to standard；0.1mg/kg is the average of Survey Sample cadmium, and as the starting point of premium grade, sample compliance rate is 65%；
The sample compliance rate of 0.01mg/kg is 16%；The sample compliance rate of 0.05mg/kg is 48%.
Two, the detection of value parameter
(1) mensuration of organophosphor, organochlorine and Determining pyrethroid pesticide residues in rice: gas chromatography.
1 method summary
In sample, organophosphor, organochlorine and pyrethrin pesticide are saltoutd through magnesium sulfate through acetonitrile extraction, extracting solution, divide through PSA
After dissipating Solid phase extraction, detect with FPD detector after air inlet chromatography, carry out qualitative according to retention time, area external standard
Standard measure.
In sample, organochlorine and pyrethrin pesticide are saltoutd through magnesium sulfate through acetonitrile extraction, extracting solution, solid through Fu Luoli silicon post
After phase extracting and purifying, detecting with ECD detector, carry out qualitative according to retention time after air inlet chromatography, area external standard is legal
Amount.
2 measurement ranges
Organophosphorus insecticide includes: dichlorvos, Bayer 71628, orthene, thimet, omethoate, Azodrin, pleasure
Really, chlopyrifos, parathion-methyl, Malathion, fenifrothion, parathion, quintiofos, isocarbophos, triazophos, fenthion,
Diazinon, cadusafos, methidathion, phosmet, Isofenphos methyl etc..
Organochlorine and pyrethrin pesticide include: Gamma Hexaochlorocyclohexane, clofenotane, cypermethrin, fenvalerate, Fenpropathrin, chlorine chrysanthemum
Ester, lambda-cyhalothrin, cyfloxylate, decis, Biphenthrin, taufluvalinate, flucythrinate, triazolone, hundred bacterium
Clearly, RP-26019, dicofol, procymidone, pentachloronitrobenzene, vinclozolin etc..
3 reagent
3.1 acetonitriles: the residual level of agriculture, the U.S. world (TEAIA).
3.2 acetone: the residual level of agriculture, the U.S. world (TEAIA).
3.3 normal hexane: the residual level of agriculture, the U.S. world (TEAIA).
3.4 toluene: the residual level of agriculture, the U.S. world (TEAIA).
3.5 magnesium sulfate: two kinds of magnesium sulfate are used in this experiment, and one is purity ＞ 97%, graininess (20～50 mesh), lark
Prestige ACROS product, because it has graininess, will not cause dust in experimentation, be mainly used in saltouing.Another kind of residual for agriculture
Level, powder (100 mesh), U.S.'s Alfa Products, because of its powder, soaking effect is good, for dehydration (because of its be
Sealed tube is carried out, it is not necessary to consider dust problem).
3.6 sodium chloride: the residual level of agriculture, Germany's CNW product.
3.7 γ-gulonolactone.
3.8 protective agent solution: weigh γ-gulonolactone 100mg in 10ml volumetric flask, add 2ml water and are allowed to molten
Solve, be then settled to 10ml with acetonitrile, mixing, cross the 0.22 organic filter membrane of μm, standby.
3.9 standard sample of pesticide: country's certified reference material (usual concentration is 1000 or 100mg/L)；Import sterling standard specimen
(the high concentration list mark storing solution of 1000mg/L need to be configured to).
3.10 standard working solution: organophosphorus pesticide standard mixed solution acetontrile becomes the standard of 0.25mg/L to work
Solution, is placed in-20 DEG C of preservations.Before measuring, standard specimen presses standard working solution+protective agent mixed liquor (volume ratio 10:1) addition protection
Agent mixed solution, mixing.
Organochlorine and chrysanthemum ester standard mixed solution normal hexane are configured to the standard working solution of 0.1mg/L, are placed in-20 DEG C
Preserve.
4 instruments
4.1 gas chromatograpies (attached FPD and ECD detector).
4.2 high speed dispersor.
4.3 centrifuge.
4.4 balance.
4.5 turbine mixer.
5 analytical procedures
5.1 extract
Rice Samples dry sample, weighs the size-reduced sample of 5.0g, is placed in 250mL plastic centrifuge tube, adds 25.0mL and steams
Distilled water, stands 30min.Add 25.0ml acetonitrile, high speed dispersor high speed be homogenized 2min, add 10g anhydrous magnesium sulfate and
1g sodium chloride, in low speed dispersion machine, low speed is homogenized 1 minute (substituting shaking step), and centrifugal force is 2500g, centrifugal 3min, makes
Acetonitrile and aqueous phase layering.
5.2 purify
5.2.1 organophosphor
Pipette 4.0ml upper strata acetonitrile solution in 15ml graduated centrifuge tube, centrifuge tube adds 100mgPSA and C-in advance
18,1200mg anhydrous magnesium sulfate, after vortex mixed 1min, 3000 revs/min of centrifugal 5min.Accurately draw 0.8ml acetonitrile solution
In sample injection bottle, and add protective agent solution 0.08ml, shake up, to be measured.
5.2.2 organochlorine and chrysanthemum ester
Pipette 10ml upper strata acetonitrile solution in 15ml graduated centrifuge tube, centrifuge tube adds 0.5g sodium chloride, whirlpool in advance
Rotation mixing 1min, stratification.Accurately draw 5ml acetonitrile solution, to use to nearly dry (about 0.3mL) in boiling flask, rotary evaporation
Acetone+the n-hexane (volume ratio of acetone and n-hexane is 10:90) of about 2mL dissolves, to be clean.
By Fu Luoli silicon post successively with 5.0mL acetone+n-hexane (volume ratio of acetone and n-hexane is 10:90), 5.0mL
The pre-drip washing of n-hexane, conditioning, when solvent liquid level arrives post adsorption layer surface, pour above-mentioned solution to be clean immediately into, use
15mL graduated centrifuge tube receives eluent, rinses with 5mL acetone+n-hexane (volume ratio of acetone and n-hexane is 10:90) and burns
Drip washing Fu Luoli silicon post after Bei, and be repeated once.The centrifuge tube filling leacheate is placed on Nitrogen evaporator, bath temperature 50 DEG C
Under the conditions of, nitrogen blows and is evaporated to, less than 5mL, be settled to 5.0mL with n-hexane, mixes on vortex mixer, to be measured.
During for using automatic solid-phase extractor to purify, take the above-mentioned supernatant 8mL saltoutd, at rotary evaporation extremely
Nearly dry rear (about 0.5mL), the acetone+n-hexane (volume ratio of acetone and n-hexane is 10:90) adding 7.5mL dissolves (constant volume
Volume is 8mL), instrument loading 2.5mL, with 4mL acetone+n-hexane (volume ratio of acetone and n-hexane is 10:90) at twice
Drip washing Fu Luoli silicon post, is placed in the centrifuge tube filling leacheate on Nitrogen evaporator, and under the conditions of bath temperature 50 DEG C, nitrogen blows evaporation
To less than 2mL, it is settled to 2.5mL with n-hexane, vortex mixer mixes, to be measured.(holding extension rate is constant).
5.3 organophosphors measure
5.3.1 chromatographic condition
5.3.1.1 chromatographic column: DB-1701 quartz capillary column, 30m × 0.25mm × 0.25um.
5.3.1.2 column temperature: initial temperature 90 DEG C, rises to 270 DEG C with 25 DEG C/min immediately, keeps 3min.
5.3.1.3 injection port: temperature 250 DEG C, pressure 25psi.
5.3.1.4 sample size: 1ul.
5.3.1.5 input mode: pulse does not shunts, pulsating pressure 50psi, keep 1min, purge time 0.9min.
5.3.1.6 detector temperature: 240 DEG C.
5.3.1.7 gas: carrier gas N2, constant voltage 25psi；H2Flow velocity 120ml/min；Air velocity 88ml/min.
5.3.2 sample determination
By 5.3 instrument conditions, to standard working solution and sample solution equal-volume sample introduction, qualitative according to retention time, area
Quantified by external standard method.
5.4 organochlorine and chrysanthemum ester measure
5.4.1 chromatographic condition
5.4.1.1 chromatographic column: DB-17 or DB-1 quartz capillary column, 30m × 0.25mm × 0.25um.
5.4.1.2 column temperature: initial temperature 90 DEG C, rises to 150 DEG C with 25 DEG C/min immediately, then rises to 270 DEG C with 10 DEG C/min, protects
Hold 8min.
5.4.1.3 injection port: temperature 250 DEG C, pressure 30psi.
5.4.1.4 sample size: 1ul.
5.4.1.5 input mode: shunting, split ratio is 5:1.
5.4.1.6 detector temperature: 300 DEG C, post flow+tail wind drift amount=30mL/min.
5.4.1.7 gas: carrier gas N2, constant voltage 30psi.
5.4.2 sample determination
By 5.4 instrument conditions, to standard working solution and sample solution equal-volume sample introduction, qualitative according to retention time, area
Quantified by external standard method.
6 results calculate
In sample, tested pesticide concentration is in terms of mass fraction W, and numerical value represents with milligrams per kilogram (mg/kg), by following public affairs
Formula calculates:
V1-standard specimen sampling volume, μ l.
V2-sample feeding volume, μ l.
A-standard specimen peak area.
A1-sample peak area.
M-sample quality (g).
V3-solvent adds volume (ml).
V4-point take solvent volume (ml)
V-constant volume (ml).
Result of calculation retains two position effective digitals, retains three position effective digitals when result is more than 1mg/kg.Measured value
The revision of the convention of computing and Effective Numerical is carried out by numerical value rule for rounding off.
(2) in rice, the persticide residue such as organophosphor, organic nitrogen, carbamate measures: liquid chromatograph/concatenation mass spectrum
Method.
1 method summary
Rice sample Pesticides is saltoutd through magnesium sulfate through acetonitrile extraction, extracting solution, after PSA dispersive solid-phase extraction purifies,
With phase chromatography-use concatenation mass spectrograph detection, carry out according to retention time and qualitative ion and quota ion and qualitative ion ratio
Qualitative, quota ion area external standard method is carried out quantitatively.
2 measurement ranges
80 kinds of pesticide include: 3-hydroxyl carbofuran, avilamycin, orthene, Acetamiprid, Acetochlor, alachlor, tears
Go out prestige, Aldicarb sulfone, Tinidazole glucose injection, atrazine, Fluoxastrobin, Buprofezin, butachlor, carbaryl, carbendazim, carbofuran, fluorine
Pyridine urea, d ichlorbenzuron, chlopyrifos, chlorpyrifos-methyl, cyflufenamid, diazinon, dichlorvos, Difenoconazole, diflubenzuron, Rogor,
Dimethomorph, Ethodan, fenamiphos, fenifrothion, fenthion, ethiprole, Cascade, bis(4-fluorophenyl)methyl(1H-1,2,4-triazol-1-ylmethyl)silane, HEXAFLUMURON, Hexythiazox, press down
Mould azoles, imidacloprid, indoxacarb, RP-26019, isocarbophos, Mobucin, Isoprothiolane, lufenuron, Malathion, metalaxyl, methylamine
Phosphorus, methidathion, Methomyl, methoxyfenozide, isopropyl methoxalamine, Azodrin, omethoate, paclobutrazol, parathion, methyl are to sulfur
Phosphorus, Pendimethalin, thimet, Phosalone, phosmet, phoxim, Aphox, Prochloraz, propargite, N-phenyl isopropyl carbamate, third
Ring azoles, pyridaben, pyrimethanil, quintiofos, Quizalotop-ethyl, multiple killing teichomycin-A, multiple killing teichomycin-B, tebufenozide, probenazole, thiophene worm
Piperazine, thiophanate-methyl, triazolone, Triadimenol, triazophos, metrifonate, tricyclazole.
3 reagent
3.1 acetonitriles: the residual level of agriculture, the U.S. world (TEAIA).
3.2 acetonitriles: liquid chromatographic grade, MERCK.
3.3 magnesium sulfate: two kinds of magnesium sulfate are used in this experiment, and one is purity ＞ 97%, graininess (20～50 mesh), lark
Prestige ACROS product, because it has graininess, will not cause dust in experimentation, be mainly used in saltouing.Another kind of residual for agriculture
Level, powder (100 mesh), U.S.'s Alfa Products, because of its powder, soaking effect is good, for dehydration (because of its be
Sealed tube is carried out, it is not necessary to consider dust problem).
3.4 sodium chloride: analytical pure, Germany's CNW product.
3.5PSA: U.S.'s Varian.
3.6C-18: U.S.'s Varian.
3.7 ammonium acetates: U.S. Sigam-FLUKA.
3.8 formic acid: the chromatographically pure U.S. world (TEAIA).
3.9 standard sample of pesticide: country's certified reference material (usual concentration is 1000 or 100mg/L)；Import sterling standard specimen
(the high concentration list mark storing solution of 1000mg/L need to be configured to).
3.10 standard working solution: organophosphorus pesticide standard mixed solution acetontrile becomes the standard of 0.25mg/L to work
Solution, is placed in-20 DEG C of preservations.Before measuring, standard specimen is added by standard working solution+protective agent mixed liquor (10:1 mixing by volume)
Enter protective agent mixed solution, mixing.
Standard mixed solution acetontrile becomes the standard working solution of 0.1mg/L, is placed in-20 DEG C of preservations.
4 instruments
4.1Agilent6410B LC/MS/MS。
4.2 high speed dispersor.
4.3 centrifuge.
4.4 balance.
4.5 turbine mixer.
5 analytical procedures
5.1 extract
Rice Samples dry sample, weighs the size-reduced sample of 5.0g, is placed in 250mL plastic centrifuge tube, adds 25.0mL and steams
Distilled water, stands 30min.Add 25.0ml acetonitrile, high speed dispersor high speed be homogenized 2min, add 10g anhydrous magnesium sulfate and
1g sodium chloride, in low speed dispersion machine, low speed is homogenized 1 minute (substituting shaking step), and centrifugal force is that 2500g is centrifuged 3min, makes second
Nitrile and aqueous phase layering.
5.2 purify
Pipette 4.0ml upper strata acetonitrile solution in 15ml graduated centrifuge tube, centrifuge tube adds 100mgPSA and C-in advance
18,1200mg anhydrous magnesium sulfate, after vortex mixed 1min, 3000 revs/min of centrifugal 5min.Through 0.22 μm filtering with microporous membrane,
To be measured.
5.3 instrument condition
5.3.1 chromatographic condition:
5.3.1.1 chromatographic column: ZORBAX SB C18 (100mm × 2.1mm, 1.8 μm)；
5.3.1.2 column temperature: 55 DEG C；
5.3.1.3 mobile phase A: the 5mmol/L ammonium acetate solution containing 0.1% formic acid；Mobile phase B: acetonitrile；
5.3.1.4 gradient elution program:
| Time (min) | Solvent orange 2 A (%) | Solvent B (%) |
| 0 | 80 | 20 |
| 13 | 10 | 90 |
| 15 | 10 | 90 |
| 15.1 | 80 | 20 |
| 21 | 80 | 20 |
5.3.1.5 flow velocity: 0.3mL/min；
5.3.1.6 sample size: auto-programming sample introduction (1 μ L sample liquid+4 μ L mobile phase A mixing, wash sample introduction after pin)；
5.3.2 Mass Spectrometry Conditions:
5.3.2.1 ion source: ESI；
5.3.2.2 capillary voltage: 4kV；
5.3.2.3 nitrogen flow rate: 10L/min；
5.3.2.4 mass spectrum acquisition mode: dynamically multiple-reaction monitoring (Dynamic MRM)；
5.3.2.5 mass spectrum acquisition rate: 500ms/cycle；
5.3.2.6 nebulizer pressure: 35psi；
5.3.2.7 be dried temperature: 350 DEG C.
5.3.2.8 mass spectrum acquisition parameter
5.4 sample determination
By 5.3 instrument conditions, to standard working solution and sample solution equal-volume sample introduction, according to retention time and qualitative ion
And quota ion and qualitative ion ratio carry out qualitative, quota ion area external standard method is carried out quantitatively.
6 results calculate
In sample, tested pesticide concentration is in terms of mass fraction W, and numerical value represents with milligrams per kilogram (mg/kg), by following public affairs
Formula calculates:
V1-standard specimen sampling volume, μ l.
V2-sample feeding volume, μ l.
A-standard specimen peak area.
A1-sample peak area.
M-sample quality (g).
V3-solvent adds volume (ml).
V4-point take solvent volume (ml)
V-constant volume (ml).
Result of calculation retains two position effective digitals, retains three position effective digitals when result is more than 1mg/kg.Measured value
The revision of the convention of computing and Effective Numerical is carried out by numerical value rule for rounding off.
(3) Cadmium detrmination in rice: graphite oven atomic absorption.
1 method summary
Sample is after acid is cleared up, in graphite furnace automatic sampler imports atomic absorption spectrophotometer graphite furnace, through stone
After ink stove high temperature atomic, Atomic Absorption specific wavelength spectral line in the optical path, its absorbance is directly proportional to its content.
2 instrument and equipments
2.1 U.S. CE M company MARS5 microwave dissolver.
2.2 power & light company of U.S. Sollar M6 Atomic Absorption Spectrometers (band FS95 graphite furnace automatic sampler).
2.3 cadmiums, lead, chromium, nickel hollow cathode lamp.
2.4 small-sized electric bruishers.
2.5 steel cylinder nitrogen (99.999%) or argon (99.999%).
2.6 circulating water devices (temperature is 15 DEG C).
2.7 volumetric flask, 25mL.
2.8 balances, sensibility reciprocal is 0.001g.
3 reagent
In this method, in addition to particular provisions, agents useful for same is that top grade is pure, and test water is high purity water.
3.1 nitric acid (technique is ultrapure).
3.2 perchloric acid.
3.3 nitric acid (1+99) (technique is ultrapure): measure 1.0mL nitric acid (4.1), add in 100mL volumetric flask, fixed with water
Hold.
3.4 palladium nitrate solutions (0.5g/L): weigh 0.05g Palladous nitrate., with nitric acid (4.3) dissolved dilution to 100mL.
3.5 magnesium nitrate solutions (10g/L): weigh 1.0g magnesium nitrate, be diluted to 100mL with water dissolution.
3.6 ammonium sulfate (20g/L): weigh 2.0g ammonium sulfate, be diluted to 100mL with water dissolution.
3.7 cadmium Standard Reserving Solution: State Environmental Protection Administration's standard sample institute produces, and concentration is 100mg/L.Open
Store in afterwards in refrigerator, preserve 1 year.
Cadmium standard solution and the compound method of standard curve and preservation are as shown in Figure 1.
4 operating procedures
Prepared by 4.1 samples
Removing foreign material in sample, with quartering division to about 50g after mixing, ground at least 98% passes through aperture
0.180mm (80 mesh) nylon mesh, stores in polyethylene bottle or polyethylene plastic bag after mixing, standby.
4.2 Specimen eliminating microwave digestion methods
Weigh rice sample 0.5g, be placed in digester, add 5mL concentrated nitric acid, place 15min, build sealing lid, put into
In microwave digestion system, rotate rotating disk about 1min, check whether pressure transducer kinks.The program arranged according to table 1 is cleared up.Disappear
After changing completely when screen instruction temperature is less than 50 DEG C, open the door of microwave dissolver, the most slowly unclamp explosion-proof membrane cover to release
Bleed off pressure power, take off temperature sensor, open sealing lid, by digestion solution transfer also constant volume to 25mL volumetric flask, mix to be measured.With
Time do reagent blank.
Table 1 plant sample micro-wave digestion program
| Project | Power | Temperature DEG C | Pressure p si | Pressure rising time min | Retention time min |
| Parameter | Automatically | 180 | 350 | 15 | 10 |
Note: originally clearing up program based on temperature control, Stress control is auxiliary；The matrix Ying Ji of the batch sample simultaneously cleared up
This is identical.
5 measure
5.1 Instrument measuring conditions are according to table 2
Table 2 Instrument measuring condition
The drafting of 5.2 standard curves
Utilize the automatic dilution function of graphite furnace automatic sampler (FS95), allow it automatically be joined by the top mark solution of cadmium element
Standard curve processed, compound concentration is shown in Table 3, and adds corresponding matrix modifier.
The compound concentration of table 3 standard curve and the kind of matrix modifier and dosage
5.3 instrument automatic result of calculation mode is measured
Set the optimum condition of instrument.Input following parameter: sample number into spectrum, sample quality, dilution volume, sample size,
And design the Concentraton gradient of standard curve.After adjusting light path and regulating zero point, enter standard series and measure, draw standard bent
Line.Before proceeding to sample determination, blank value measuring state can be entered back into, with sample blank Digestive system sample introduction, allow instrument take
Its average is as the blank value at the button end.Subsequently can sequentially determining sample.Measure complete after, select " printed report " can will survey
Determine result and carry out automatic printing.
6 calculate
X=(c-c0) × V × 1000/m × 1000 × 1000
In formula: each constituent content, mg/kg in X-sample；
C treatments of the sample liquid measures concentration, ng/mL；
C0 sample blank Digestive system concentration, ng/mL；
V treatments of the sample liquid cumulative volume, mL；
M-sample quality, g.
Result is stated: 1. the computing of measured value and the revision of the convention of Effective Numerical are carried out by numerical value rule for rounding off；2. significant figure
The figure place of the significant figure that figure place is minimum with measuring instrument precision in method is identical, or reservation more than Limited Doses in sanitary standard one
Position.
Above detection method has that speed is fast, accuracy is high, and reagent saves, environmentally friendly, also have stability and repeatability
Good feature.
Three, grade judges
The lowest class index reached with Product checking index is for judging grade.I.e. testing result agriculture is residual, cadmium all reaches one
Level be judged to one-level；If one of which is two grades, it is judged to two grades；The like.
Four, effect and meaning
1, propose quality of rice safe class concept, provide scientific basis for the agricultural industry criteria of system revision later；
2, be conducive to instructing the production of China's rice product, consumption.Producer can be fixed a price by credit rating, and consumer is optional
Select purchase, can really embody high quality and favourable price.
3, High Quality Environment could produce high quality white rice, has had quality grading, and High Quality Environment is worth and emerges from, and is conducive to protecting
Protect ecological environment and the sustainable development of agricultural.
Although the present invention is open as above with embodiment, but it is not limited to protection scope of the present invention, any ripe
Know the technical staff of this technology, in the change made without departing from the spirit and scope of the invention and retouching, all should be belonged to this
The protection domain of invention.
Claims (9)
1. an edible rice safe mass stage division, it is characterised in that: the step of described method is as follows:
(1) take food with rice sample, the persticide residue in detection edible rice；
(2) take food with rice sample, the heavy metal cadmium content in detection edible rice；
(3) persticide residue obtained according to detection and heavy metal cadmium content, carry out safe mass classification to edible rice.
Edible rice safe mass stage division the most according to claim 1, it is characterised in that: in step (1), use gas
Phase chromatography measures organophosphor, organochlorine and Determining pyrethroid pesticide residues in edible rice sample, the detection step of persticide residue
It is rapid as follows: in edible rice sample, organophosphor, organochlorine and pyrethrin pesticide are saltoutd through magnesium sulfate through acetonitrile extraction, extracting solution,
After PSA dispersive solid-phase extraction purifies, detect with FPD detector after air inlet chromatography, carry out qualitative according to retention time, face
Long-pending quantified by external standard method；Or, in edible rice sample, organochlorine and pyrethrin pesticide are through acetonitrile extraction, and extracting solution is through magnesium sulfate salt
Analysis, after Fu Luoli silicon column solid phase extraction purifies, detects with ECD detector after air inlet chromatography, carries out according to retention time
Qualitative, area quantified by external standard method.
Edible rice safe mass stage division the most according to claim 1, it is characterised in that: use gas chromatography to survey
Determine the step of organophosphor, organochlorine and Determining pyrethroid pesticide residues in edible rice sample as follows:
1. extract
Edible rice dry sample, weighs edible rice sample size-reduced for 5.0g, is placed in 250mL plastic centrifuge tube, adds
25.0mL distilled water, stands 30min, adds 25.0ml acetonitrile, is homogenized 2min, adds 10g anhydrous slufuric acid in high speed dispersor
Magnesium and 1g sodium chloride, be homogenized 1 minute in low speed dispersion machine, and centrifugal force is 2500g, centrifugal 3min, makes acetonitrile and aqueous phase layering；
2. purify
Organophosphor purifies: pipettes 4.0ml upper strata acetonitrile solution and purifies in 15ml graduated centrifuge tube, to be measured；
Organochlorine and chrysanthemum ester purify: pipette 10ml upper strata acetonitrile solution in 15ml graduated centrifuge tube, add in advance in centrifuge tube
0.5g sodium chloride, vortex mixed 1min, stratification, accurately absorption 5ml acetonitrile solution is in boiling flask, and rotary evaporation is to closely
Dry, dissolve with the mixed liquor of the acetone+n-hexane of 2mL and obtain solution to be clean；
Fu Luoli silicon post is used the 5.0mL acetone+mixed liquor of n-hexane, the pre-drip washing of 5.0mL n-hexane successively, and conditioning, when molten
When agent liquid level arrives post adsorption layer surface, pour above-mentioned solution to be clean immediately into, receive eluent with 15mL graduated centrifuge tube, use
The mixed liquor of 5mL acetone+n-hexane rinses drip washing Fu Luoli silicon post after beaker, and is repeated once；The centrifugal of leacheate will be filled
Pipe is placed on Nitrogen evaporator, and under the conditions of bath temperature 50 DEG C, nitrogen blows and is evaporated to, less than 5mL, be settled to 5.0mL with n-hexane,
Mix on vortex mixer, to be measured；
During for using automatic solid-phase extractor to purify, take the above-mentioned supernatant 8mL saltoutd, at rotary evaporation near dry
After, the mixed liquor adding acetone+n-hexane dissolves and is settled to 8mL, and instrument loading 2.5mL, with mixing of 4mL acetone+n-hexane
Close liquid drip washing Fu Luoli silicon post at twice, the centrifuge tube filling leacheate is placed on Nitrogen evaporator, in 50 DEG C of conditions of bath temperature
Under, nitrogen blows and is evaporated to, less than 2mL, be settled to 2.5mL with n-hexane, mixes on vortex mixer, to be measured；
In the mixed liquor of acetone+n-hexane, the volume ratio of acetone and n-hexane is 1:9；
3. organophosphor measures
Chromatographic condition is as follows:
Chromatographic column: DB-1701 quartz capillary column, 30m × 0.25mm × 0.25um；
Column temperature: initial temperature 90 DEG C, rises to 270 DEG C with 25 DEG C/min immediately, keeps 3min；
Injection port: temperature 250 DEG C, pressure 25psi；
Sample size: 1ul；
Input mode: pulse does not shunts, pulsating pressure 50psi, keep 1min, purge time 0.9min；
Detector temperature: 240 DEG C；
Gas: carrier gas N2, constant voltage 25psi；H2Flow velocity 120ml/min；Air velocity 88ml/min；
Sample determination
Chromatographic condition in pressing 3. is to standard working solution and sample solution equal-volume sample introduction, qualitative according to retention time, outside area
Mark standard measure；
4. organochlorine and chrysanthemum ester measure
Chromatographic condition is as follows:
Chromatographic column: DB-17 or DB-1 quartz capillary column, 30m × 0.25mm × 0.25um；
Column temperature: initial temperature 90 DEG C, rises to 150 DEG C with 25 DEG C/min immediately, then rises to 270 DEG C with 10 DEG C/min, keeps 8min；
Injection port: temperature 250 DEG C, pressure 30psi；
Sample size: 1ul；
Input mode: shunting, split ratio is 5:1；
Detector temperature: 300 DEG C, post flow+tail wind drift amount=30mL/min；
Gas: carrier gas N2, constant voltage 30psi；
5. sample determination
Chromatographic condition in pressing 4. is to standard working solution and sample solution equal-volume sample introduction, qualitative according to retention time, outside area
Mark standard measure；
6. result calculates
In edible rice sample, tested pesticide concentration is in terms of mass fraction W, and numerical value is milligrams per kilogram to represent, based on following equation
Calculate:
V1-standard specimen sampling volume, μ l；
V2-sample feeding volume, μ l；
A-standard specimen peak area；
A1-sample peak area；
M-sample quality (g)；
V3-solvent adds volume (ml)；
V4-point take solvent volume (ml)；
V-constant volume (ml).
Edible rice safe mass stage division the most according to claim 1, it is characterised in that: in step (1), use liquid
Organophosphor in phase chromatograph/concatenation mass spectrometric determination edible rice sample, organic nitrogen, carbamate chemicals residual amount step such as
Under: edible rice sample Pesticides is saltoutd through magnesium sulfate through acetonitrile extraction, extracting solution, after PSA dispersive solid-phase extraction purifies, uses
Liquid chromatograph concatenation mass spectrograph detection, it is fixed to carry out according to retention time and qualitative ion and quota ion and qualitative ion ratio
Property, quota ion area external standard method is carried out quantitatively.
Edible rice safe mass stage division the most according to claim 1, it is characterised in that: use liquid chromatograph/string
Connect organophosphor in mass spectrometric determination edible rice sample, organic nitrogen, carbamate chemicals residual amount step as follows:
1. extract
Edible rice dry sample, weighs edible rice sample size-reduced for 5.0g, is placed in 250mL plastic centrifuge tube, adds
25.0mL distilled water, stands 30min；Add 25.0ml acetonitrile, high speed dispersor is homogenized 2min, adds 10g anhydrous slufuric acid
Magnesium and 1g sodium chloride, be homogenized 1 minute in low speed dispersion machine, and centrifugal force is 2500g, centrifugal 3min, makes acetonitrile and aqueous phase layering；
2. purify
Pipette 4.0ml upper strata acetonitrile solution in 15ml graduated centrifuge tube, purify, to be measured；
3. instrument condition
Chromatographic condition is as follows:
Chromatographic column: ZORBAX SB C18 (100mm × 2.1mm, 1.8 μm)；
Column temperature: 55 DEG C；
Mobile phase A: the 5mmol/L ammonium acetate solution containing 0.1% formic acid；Mobile phase B: acetonitrile；
Flow velocity: 0.3mL/min；
Mass Spectrometry Conditions is as follows:
Ion source: ESI；
Capillary voltage: 4kV；
Nitrogen flow rate: 10L/min；
Mass spectrum acquisition rate: 500ms/cycle；
Nebulizer pressure: 35psi；
Dry temperature: 350 DEG C；
4. sample determination
By the instrument condition in 3. to standard working solution and sample solution equal-volume sample introduction, according to retention time and qualitative ion and
Quota ion and qualitative ion ratio carry out qualitative, and quota ion area external standard method is carried out quantitatively；
5. result calculates
In sample, tested pesticide concentration is in terms of mass fraction W, and numerical value, milligrams per kilogram to represent, is calculated by following equation:
V1-standard specimen sampling volume, μ l；
V2-sample feeding volume, μ l；
A-standard specimen peak area；
A1-sample peak area；
M-sample quality (g)；
V3-solvent adds volume (ml)；
V4-point take solvent volume (ml)；
V-constant volume (ml).
Edible rice safe mass stage division the most according to claim 1, it is characterised in that: in step (2), use stone
The step of heavy metal cadmium content in Graphite furnace atomic absorption spectrometry detection edible rice is as follows: edible rice sample after acid is cleared up,
In graphite furnace automatic sampler imports atomic absorption spectrophotometer graphite furnace, after graphite furnace high temperature atomic, at light
Road Atom absorbs specific wavelength spectral line, and its absorbance is directly proportional to its content.
Edible rice safe mass stage division the most according to claim 1, it is characterised in that: use sampling Graphite Furnace Atomic to inhale
The step of the heavy metal cadmium content in receipts method detection edible rice is as follows:
1. prepared by sample
Removing the foreign material in edible rice sample, with quartering division to 50g after mixing, ground at least 98% passes through aperture
The sieve of 0.180mm, standby after mixing；
2. Specimen eliminating
Weigh edible rice sample 0.5g to be placed in digester, add 5mL concentrated nitric acid, place 15min, build sealing lid, put into
In microwave digestion system, rotate rotating disk 1min, clear up；After clearing up completely when screen instruction temperature is less than 50 DEG C, open
The door of microwave dissolver, the most slowly unclamps explosion-proof membrane cover to discharge pressure, takes off temperature sensor, opens sealing lid, will disappear
Solve liquid transfer constant volume in 25mL volumetric flask, mix to be measured；Do reagent blank simultaneously；
3. Specification Curve of Increasing
Utilize the automatic dilution function of graphite furnace automatic sampler, make it automatically that the top mark aqueous standard method of cadmium element is bent
Line, and add corresponding matrix modifier；Set the condition of instrument；Input relevant parameter, and design the concentration of standard curve
Gradient；Draw standard curve；
4. calculate
X=(c-c0) × V × 1000/m × 1000 × 1000
In formula: each constituent content, mg/kg in X-sample；
C treatments of the sample liquid measures concentration, ng/mL；
C0 sample blank Digestive system concentration, ng/mL；
V treatments of the sample liquid cumulative volume, mL；
M-sample quality, g.
Edible rice safe mass stage division the most according to claim 1, it is characterised in that: in step (3), according to inspection
The step that the persticide residue recorded and heavy metal cadmium content carry out safe mass classification to edible rice is as follows: examine with product
Survey the lowest class index of reaching of index for judging that grade, i.e. testing result agriculture be residual, cadmium all reach one-level be judged to one-level；If
One of which is two grades and is then judged to two grades；The like.
Edible rice safe mass stage division the most according to claim 1, it is characterised in that: in step (3), according to inspection
The persticide residue recorded and heavy metal cadmium content carry out safe mass classification to edible rice and are divided into level Four, specific as follows:
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