CN109187136A - A kind of preparation method and application applied to laboratory pesticide residue proficiency testing sample - Google Patents
A kind of preparation method and application applied to laboratory pesticide residue proficiency testing sample Download PDFInfo
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- CN109187136A CN109187136A CN201811094865.3A CN201811094865A CN109187136A CN 109187136 A CN109187136 A CN 109187136A CN 201811094865 A CN201811094865 A CN 201811094865A CN 109187136 A CN109187136 A CN 109187136A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/286—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q involving mechanical work, e.g. chopping, disintegrating, compacting, homogenising
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/38—Diluting, dispersing or mixing samples
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/42—Low-temperature sample treatment, e.g. cryofixation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/286—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q involving mechanical work, e.g. chopping, disintegrating, compacting, homogenising
- G01N2001/2866—Grinding or homogeneising
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N2001/2893—Preparing calibration standards
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Abstract
The present invention relates to Detecting Pesticide fields, and in particular to a kind of preparation method and application applied to laboratory pesticide residue proficiency testing sample.The present invention uses Freeze Drying Technique, will shred, is homogenized uniform matrix sample freeze-drying, crushes, sieving, prepare uniform matrix freeze-dried powder, the standard sample of pesticide of uniform sprinkling certain concentration, is lyophilized again, crushes, dispenses after sieving in proportion.Proficiency testing sample preparation methods of the present invention are compared with prior art, preparation method is more reliable, it can be evenly dispersed by micro and trace pesticide, with preferable uniformity and stability, ability comparison, qualitative and quantitative analysis, the verifying of detection method, test equipment calibration and the quality control of test result of laboratory monitoring pesticide residue test item can be met and examined.
Description
Technical field
The present invention relates to Detecting Pesticide fields, and in particular to a kind of applied to laboratory pesticide residue proficiency testing
Sample preparation methods.It can be applied to qualitative and quantitative analysis, the quality of verifying, the test equipment calibration and test result of detection method
Control and examination.
Background technique
Abuse of the pesticide in agricultural product and always various circles of society and the focus of the common people are abused, wherein being used as people
Pesticide residue is especially prominent in the vegetable and fruit of the necessity of daily life, is pesticide residue case the most serious.Nearly more than ten
Great changes all have occurred in Nian Lai, the cultivated area and planting patterns of China's vegetable and fruit, and the cultivated areas such as greenhouse, greenhouse are very fast
Increase, these all provide advantage for the growth of disease pest and breeding.With being constantly progressive for planting technology, vegetable and fruit
Growth period is shorter and shorter, and environmental pollution increasingly sharpens, and the pest and disease damage of vegetable and fruit is increasingly severe.On the one hand, rural area at present
Substantially still based on the family plantation of small area, means and the method for preventing and treating pest and disease damage are extremely limited；On the other hand, it plants
Family lacks Knowledge Attainments and overall awareness, in order to ensure the stabilization of agricultural product income, with gradually adding for veterinary antibiotics pest and disease damage
Weight and overdose apply high poison, persistent pesticide, and pesticide residue level and range in veterinary antibiotics is caused to have reached phase
When serious degree.
The height exposure of pesticide residue makes the mankind be faced with the health risk of long-term exposure low concentration pesticide.State food peace
Full blast danger Evaluation Center is always using the pesticide in vegetable and fruit as the emphasis of Risk Monitoring, in addition in technical method and pesticide prison
Outside constantly improve in survey coverage area, more stress to reinforce the technical level in each monitoring laboratory and improve entirely to monitor number
According to quality, it is ensured that accuracy, reliability and the comparativity of monitoring data.Meanwhile the quality control sample of Pesticide Residues
Product are at home there is also biggish vacancy, the residual Quality Control of existing agriculture announced according to " national standard physical resources shared platform "
Sample, that there are matrix species is few for sample, and pesticide residue type is single and the problems such as without representativeness, and the Quality Control sample of matter sample
It plays an important role to the verifying, assessment and Quality Control Links of experimental method, so establishing pesticide residue material object mark
The preparation of sample and quality evaluating method provide technical support to the propulsion and development of domestic pesticide residue material object Quality Control sample, are
The quality assurance in Detecting Pesticide laboratory provides foundation.
To carry out " Quality Developing outline ", effectively promotes laboratory inspection detectability level and ensure state food
The monitoring data quality of pollutant Risk Monitoring, by National Certification and Accreditation Commission and state food security risk assessment central tissue, Shanghai
It is responsible for coordinating, implements and open in Municipal Disease Control and Prevention Center (state food security risk monitoring Reference Lab (pesticide residue))
" the residual measurement of fruits and vegetables middle peasant " the proficiency testing plan of exhibition, the project are National Certification and Accreditation Commission proficiency testing C intermediate item (numbers in 2017
41).The purpose of proficiency testing plan is Detecting Pesticide ability and level in order to evaluate laboratory, and is directed to and tests
The problem of finding in card carries out Source Tracing, proposes reform advice and suggestion, the strong pesticide residue inspection for improving laboratory
The detectability of survey.Meanwhile it can be used as participation examination the laboratory voluntarily control of evaluation experimental room quality and maintenance detectability
Horizontal tool and means.
Chinese patent literature CN100359315C discloses a kind of animal remedy residual ability verification sample and preparation method thereof, base
Matter is food-borne animal's liver, and addition veterinary drug to veterinary drug content is 50ppb-5ppm in matrix, and veterinary drug is telracycline family, chloramphenicol
Or micro or even trace veterinary drug can be uniformly distributed in test substance by the veterinary drugs such as sulfamido, the invention, sample system
Standby success rate is high.Chinese patent literature CN107227338A discloses escherichia coli proficiency testing sample in Drinking Water
And preparation method thereof, sample includes object bacteria and background flora, and the object bacteria is escherichia coli, the background flora by
Staphylococcus aureus, Bacillus cereus, Klebsiella Pneumoniae, enterobacter cloacae, proteus mirabilis, clostridium perfringen and
Citrobacter freundii composition, the invention uniformity, stability meet proficiency testing requirement, can utmostly guarantee test specimens
The stability of product.Chinese patent literature CN100494961C disclose the verification sample of orange juice ability containing food additives and its
Preparation method contains food additives preservative 0.2-0.25g/kg, sweetener 0.09-0.17g/kg, the invention energy in sample
Guarantee uniformity in the verification sample of orange juice ability containing numerous food additive component, stable contain benzoic acid, sorbic acid
With the food additive components such as saccharin sodium, the stability of sorbic acid especially ensure that.But about vegetables in the present invention and water
The preparation method of fruit pesticide residue proficiency testing standard sample, yet there are no report.
Summary of the invention
The first purpose of this invention is aiming at the shortcomings in the prior art, to provide a kind of pesticide residue laboratory capabilities and test
Demonstrate,prove sample preparation methods.
Second object of the present invention is aiming at the shortcomings in the prior art, to provide and be prepared by preparation method as described above
The trace standard of pesticide sample arrived.
Third object of the present invention is aiming at the shortcomings in the prior art, to provide trace standard of pesticide sample as described above
Purposes.
To realize above-mentioned first purpose, the technical solution adopted by the present invention is that:
A kind of pesticide residue laboratory proficiency testing sample preparation methods, comprising the following steps:
A the fruit or vegetables sample with batch) are acquired；
B) sample discards inedible position, and chopping is blocking, is crushed to pulpous state；
C) merge slurries, low-temperature homogenate；
D sample) is subjected to freeze-drying and dehydrating；
E the block sample after) taking drying, pulverizer are crushed to powder, are sieved, obtain bare substrate freeze-dried powder；
F it) takes quantitative freeze-dried powder evenly laid out on plate, is uniformly sprayed on standard pesticide substance solution with spraying apparatus
Powder surface；
G it) is freeze-dried, after removing solvent, is crushed again, sieving obtains mark-on freeze-dried powder；
H it is fitted into bottle after) mixing mark-on freeze-dried powder with bare substrate freeze-dried powder, bottle is placed in high-speed oscillator
On, oscillation is for 24 hours, it is ensured that powder uniformly mixes；
I after powder in bottle) is sub-packed in brown ml headspace bottle (specimen bottle mark, number) internal gland with packing instrument with equivalent-
20 DEG C of freezen protectives.
As an optimal technical scheme of the invention, in the above preparation method, the specific steps are as follows:
A the fruit or vegetables sample with batch) are acquired；
B) sample discards inedible position, is shredded required sample to fritter with knife, is crushed to slurry through fruits and vegetables pulverizer
Shape；
C) merge slurries, low-temperature homogenate；1000~3000 revs/min of speed, the time 30~60 minutes of homogenate；
D freeze-drying and dehydrating) is carried out；- 30 DEG C~-5 DEG C of pre-freezing temperature, 1~4h of pre-freeze time, -196 DEG C of condenser temperature
~-20 DEG C, cooling time 30min~96h；
E the block sample after) taking drying, pulverizer are crushed to powder, cross 80~120 meshes, obtain bare substrate freeze-dried powder；
F 400g freeze-dried powder) is accurately weighed, it is evenly laid out on the plastics chopping board of 0.3m × 0.4m, it is incited somebody to action with spraying apparatus
Standard pesticide substance solution is uniformly sprayed on powder surface, and sprinkling liquid and 1~5mL:100 of bare substrate powder proportions~
200g；
G it) is freeze-dried, after removing solvent, is crushed again, crossed 80~120 sieves, obtain mark-on freeze-dried powder；
H mark-on freeze-dried powder and bare substrate freeze-dried powder are mixed according to the ratio of mass ratio 1~2:1~5), are packed into 4L
In vial, vial is placed on high-speed oscillator with 100~500 beats/min of hunting of frequency for 24 hours, it is ensured that powder is equal
Even mixing；
I powder in vial accurately) is sub-packed in 20mL brown ml headspace bottle (specimen bottle mark with packing instrument with every bottle of 6g powder
Note, number) -20 DEG C~-80 DEG C freezen protectives after internal gland.
As an optimal technical scheme of the invention, further following steps: the uniformity of the standard sample is examined
And stability.
As an optimal technical scheme of the invention, the step D and G: -20 DEG C of precooling temperature~30 DEG C, when pre-cooling
Between 1~4h, -196 DEG C~-20 DEG C of condenser temperature, cooling time 30min~for 24 hours.
As an optimal technical scheme of the invention, selected standard pesticide substance is Biphenthrin, Fipronil and bromine worm
Nitrile.
As an optimal technical scheme of the invention, selected standard pesticide substance is procymidone, pentachloronitrobenzene and bromine
Cyano chrysanthemate.
As an optimal technical scheme of the invention, matrix used is cabbage.
As an optimal technical scheme of the invention, matrix used is apple.
As an optimal technical scheme of the invention, the pesticide concentration added in matrix is 0.05-1.0mg/kg.
As an optimal technical scheme of the invention, the mark-on standard sample of pesticide methanol or acetonitrile dissolution.
To realize above-mentioned second purpose, the technical solution adopted by the present invention is that:
The trace standard of pesticide sample that any preparation method as above is prepared.
To realize above-mentioned third purpose, the technical solution adopted by the present invention is that:
The purposes of trace standard of pesticide sample as described above, which is characterized in that be used for pesticide residue laboratory testing energy
Power verifying, pesticide qualitative and quantitative analysis, the verifying of detection method, test equipment calibration and the quality control of test result and examination
Etc..
The present invention also provides the bare substrate control sample of trace standard of pesticide sample, when preparation according to 1 part of mark-on sample,
The ratio aluminium foil bag vacuum-pumping and sealing that 2 parts of blank samples are one group is packed.
Pesticide standard sample of the invention and preparation method, fill the domestic gaps, and preparation method is simple, obtained sample in kind
This is uniform and stable, easy to maintain, solves pesticide material standard sample problem of easy degradation.Standard sample of the invention can be commented effectively
The Detecting Pesticide ability and level of valence laboratory can be used for the control of pesticide qualitative and quantitative analysis quality, it is ensured that vegetable
Biphenthrin, Fipronil in dish and the procymidone in chlorfenapyr and fruit, pentachloronitrobenzene and decis detect effective
Property, it is used suitable for each department such as food, environmental protection, quality inspection and health, it is ensured that food safety will bring significant economic effect
Benefit and social benefit.
Detailed description of the invention
Attached drawing 1 is the preparation flow figure of sample.
Attached drawing 2 is the chemical structural formula of standard pesticide substance.
Attached drawing 3-4 is cabbage and apple pesticide standard sample degradation tendency chart；In Fig. 3 from top to bottom successively are as follows: biphenyl
Pyrethroids, chlorfenapyr, Fipronil.
Attached drawing 5-6 is the chromatogram of pesticide standard sample of the present invention.
Specific embodiment
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair
It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after having read the content of the invention recorded, art technology
Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Fixed range.
The invention discloses the preparation methods and purposes of a kind of trace standard of pesticide sample, are applied to laboratory pesticide residue and examine
Proficiency testing is surveyed, but is not limited thereto.The preparation flow of trace standard of pesticide sample is as shown in Figure 1, by the following examples
The pesticide standard sample of preparation method preparation of the invention is illustrated, application experiment room ability compares, wherein bare substrate pair
According to sample preparation procedure and trace standard of pesticide sample preparation procedure only standard adding procedure (example in sample preparation procedure
1 and example 2 in step F) difference.Bare substrate freeze-dried powder first is prepared according to step A, B, C, D, E step, then
According to preparation trace standard of pesticide sample the step of A, B, C, D, E, F, G, I.Wherein bare substrate check sample and pesticide residue
By pesticide residue background detection confirmation, (background values is less than detection limit to standard sample, is below 0.001 mg/ before preparation
Kg), the type and concentration level that pesticide adds are according to pesticide residue Risk Monitoring data over the years referring concurrently to GB 2763-
Maximum Pesticide Residue standard, is added common fruit or vegetable type food matrix in 2016 editions food.
Embodiment 1: the preparation of apple powder trace standard of pesticide sample and the report of Detecting Pesticide proficiency testing
It is defined in fruit sample based on " state food security risk monitoring plan in 2017 " to decis (isomery
The sum of body), pentachloronitrobenzene and procymidone are monitored.This proficiency testing testing plan project is procymidone, five in apple
This 3 component qualitative, quantitatives measurements of chloronitrobenzene and decis (the sum of isomers).This proficiency testing has solicited national food
The opinion at product security risk assessment center, selects apple powder for sample substrate." Pesticide is maximum by China GB2763-2016
Residue limits " regulation decis (the sum of isomers) limitation is 0.01~10.0mg/kg, pentachloronitrobenzene limitation for 0.01~
2.0mg/Kg, procymidone limitation are 0.20~10.0mg/Kg.The detectable concentration level of proficiency testing sample is in addition to considering country's limit
Outside amount standard, the main monitoring concentration level for considering each pollutant in food contaminant Risk Monitoring requires to reach sample copy
Bottom residual concentration is horizontal, therefore the concentration level range of this proficiency testing is designed as 0.05-1.0mg/kg.This proficiency testing
Recommend the detection method used to be based in " state food pollution in 2017 and adverse factor Risk Monitoring operation manuals "
The multi-pesticide residue detection method of QuEChERS, or referring to this proficiency testing job instruction, while national standard GB/T also can be used
The standard methods such as 19648-2006 and GB/T 5009.146-2008 or Ministry of Agriculture NY/T 761-2008.Final ability verifying knot
Fruit is determined with the qualitative, quantitative result of 3 target compounds.
1 experimental method
1.1 standard sample preparation methods
1.1.1 required instrument, reagent and vessel are prepared
Instrument: oaks company of refiner China；IKA company of oscillator Germany；Freeze drier, Chinese Dong Fulong industry
Company.Reagent: distilled water；N-hexane, the residual grade of agriculture, Dr.E company of the U.S.；Acetone, the residual grade of agriculture, Dr.E company of the U.S..This experiment institute
There is the container used by washing, distilled water cleaning and hexane acetone mixed solvent (1:1, v/v) wiping, to dry
Journey.
1.1.2 sample preparation procedure
A) Organic Apple of Aksu, Xinjiang is originated from sample selection.
B fruit stone and carpopodium) are discarded, pulp fraction is taken, required sample is shredded to fritter with knife, is crushed through fruits and vegetables pulverizer
To pulpous state.
C high-speed rotating cutter head) is used, is homogenized 3000 revs/min of speed, the time 30 minutes.
D it) is transferred into the freeze-drying disk cleaned up, carries out freeze-drying and dehydrating: -5 DEG C of precooling temperature, when pre-cooling
Between 4h, -196 DEG C of condenser temperature, cooling time 48h-.After the completion, when displays temperature reaches room temperature, taking-up freeze-drying disk.
E) block sample after drying, pulverizer are crushed to powder, sieve with 100 mesh sieve.
F) (bare substrate is without carrying out the residual addition of agriculture) accurately weighs 400g freeze-dried powder, evenly laid out in 0.3m × 0.4m
Plastics chopping board on, after the apple coarse crushing being freeze-dried, be partially contained in stainless steel disc, by spraying mode by first
The mixed standard solution (decis, pentachloronitrobenzene and procymidone, Fig. 2) of three kinds of pesticides of alcohol dissolution is uniformly sprayed on freeze-drying
Mark-on freeze-dried powder of the powder surface as examination sample, sprinkling liquid and bare substrate powder ratio (1mL/100g).
G it) is freeze-dried again, progress freeze-drying and dehydrating: -5 DEG C of pre-freezing temperature, pre-freeze time 4h, condenser temperature
- 196 DEG C, cooling time is for 24 hours.After the completion, when displays temperature reaches room temperature, taking-up freeze-drying disk.After removing solvent, crush,
It sieves with 100 mesh sieve.
H) the freeze-dried powder 400g and bare substrate freeze-dried powder 1200g of mark-on are mixed according to (1:3), are packed into 4L vial
In, vial is placed on high-speed oscillator in the environment being protected from light to vibrate for 24 hours in 300 beats/min of frequency, it is ensured that powder
Uniformly mixing.
I after powder in vial accurately) is sub-packed in 20mL brown ml headspace bottle internal gland with packing instrument with every bottle of 6g powder
- 20 DEG C of freezen protectives.It is packed according to the ratio aluminium foil bag vacuum-pumping and sealing that 1 part of mark-on sample, 2 parts of blank samples are one group.
Stick on sample number into spectrum in packaging, number is serial number.The freezen protective in -20 DEG C of refrigerator-freezer.(in order to guarantee the long-term of sample
Stablize, prevent rotten and target substance decomposition, sample packing, envelope are carried out using the import Brown Glass Brown glass bottles and jars only with inner sealing lid
Membrana oralis sealing.Before packing, each sample bottle by sufficiently washing, is dried, and be cooled to room temperature at 120 DEG C).
1.2 sample homogeneities and stability test
1.2.1 sample homogeneity
The pattern detection process of uniformity follows CNAS-GL40:2016, with reference to vegetable in European Union's Reference Lab (EURL)
The production method of dish pesticide residues in fruits aptitude tests sample (PT).10 bottles of samples, each sample are taken out from refrigerator at random
Originally take two parts to do double sample detections, pattern detection sequence is in strict accordance with the random sequence being previously set (random digit corresponds to bottle number)
It does pre-treatment and sample introduction is analyzed, quantitative detection is carried out to sample using the proceduring standard curve of matrix matching.Recommend to use
Multi-pesticide residue detection method based on QuEChERS in " state food pollution in 2016 and adverse factor Risk Monitoring operation manuals "
Or using the method in this proficiency testing job instruction.
1.2.2 sample stability experiment and Acceleration study
Carrying out span to sample is the stability experiment and extreme temperature (35 DEG C) condition under the conditions of 40 days stored refrigerated
Acceleration study carrys out the stability of test sample after lower placement 4h, and each sample measures replication 2 times, method and uniformity one
It causes.Hair sample is investigated simultaneously to test to sample stability between report deadline, is reported since sending out sample the last week to testing result
After deadline five days carry out span be one and a half months it is stored refrigerated under the conditions of hair sample detection cycle stability experiment, every time
Sample measures replication 2 times.
1.2.3 experiment detection method
1.2.3.1 analysis instrument and reagent
Instrument: mass spectrum, Agilent 5975C, gas phase, Agilent 7890, autosampler: Agilent 7693；
Reagent: acetonitrile, the residual grade of agriculture, Fisher company provide；Acetone, the residual grade of agriculture, Tedia company of the U.S., toluene, agriculture are residual
Grade, Fisher company provide, n-hexane, the residual grade of agriculture, and Fisher company provides.
1.2.3.2 chromatographic condition
GC conditions: color column: DB-5MS, 30m × 0.25mm × 0.25 μm；Carrier gas: high-purity helium, flow velocity:
1.0mL/min；Injector temperature: 250 DEG C, using Splitless injecting samples, sample volume: 1 μ L.Temperature programming: 80 DEG C of initial temperature,
1min is kept, 180 DEG C is warming up to the speed of 20 DEG C/min, keeps 2min, then be warming up to 280 DEG C with the speed of 10 DEG C/min,
Keep 5min.
Mass Spectrometry Conditions: electron bombardment (EI) ion source；230 DEG C of ion source temperature；Electron energy 70eV.
1.2.3.3 detection method:
It is measured under ion (SIM) mode of selection, sets different detection windows for 3 kinds of compounds, measure it respectively
Ionic strength, actual conditions are shown in Table 1.
1 the retention time of the compound of table and selection ion (SIM)
1.3 proficiency testing plans
1.3.1 proficiency testing laboratory overview is participated in
This project requires the laboratory for participating in state food security risk monitoring relevant item detection in 2017 that must participate in
This proficiency testing, other laboratories can voluntary participation this proficiency testings.
The laboratory for participating in this proficiency testing project shares 135, be distributed in national 31 provinces, municipality directly under the Central Government, from
Control area (see Table 2 for details).In the unit participated in, to defend the most of department of planning commission, followed by quality testing department and other detection machines
Structure, in addition there are also the inspection laboratories of the departments such as some entry and exit, agricultural (see Table 3 for details).
2 proficiency testing of table registers participant Area distribution
3 proficiency testing of table registers participant industry distribution
1.3.2 the detection method of sample
This project does not force specified measuring method, but institute in its daily residual measurement work of agriculture of laboratory applications of suggesting respectively participating in the experiment
The sample-pretreating method and instrument analytical method of use carry out this assessment mode.Laboratory of participating in the experiment should fully consider laboratory
The interference of background contamination and positive blank result to measurement result accuracy.Respectively participating in the experiment laboratory can be according in job instruction
Suggestion take 1.00 grams of samples or the empirically determined sampling amount according to oneself, but need to guarantee measurement result method quantitative limit with
On.
For the validity of follow-up evaluation foodstuffs risk operation manuals method, recommend to use " state food in 2017
Pollution and adverse factor Risk Monitoring operation manuals " in multi-pesticide residue detection method based on QuEChERS or tested using this ability
The method for demonstrate,proving job instruction.Most of laboratories have been all made of the two methods from the results of view, and individual laboratories use
National standard (GB23200.8-2016 and DB34/T 1075-2009) or the method for the Ministry of Agriculture (NY/T 761-2008).Such as without gas
Matter combined instrument, it is also possible to gas chromatography, but submission method and correlated condition, parameter must be indicated.
1.4 statistics designs and evaluation method
1.4.1 the determination of public discussion value
(Robust statistic is referring to GB/ using steady statistical for the result statistics of this time proficiency testing examination
T28043-2011 and ISO-13528:2015), using the steady average value of each laboratory reported result as the public discussion value of examination
(Assigned Value), it is therefore intended that outlier (Outlier) is to the influence degree of public discussion value, i.e. public discussion value in control result
The influence that not will receive individual outliers leads to relatively large deviation, allow also for outlier it is more when contribution to public discussion value.
The uncertainty of each pesticide residue public discussion value is calculated with following formula:Wherein: xiIt is uncertainty, s*
It is steady standard deviation, n is the result sum of report.
1.4.2 the determination of standard deviation
In order to follow international uniform agreement (the IUPAC:THE INTERNATIONAL of Experiment of Analytical Chemistry room proficiency testing
HARMONIZED PROTOCOL FOR THE PROFICIENCY TESTING OF ANALYTICAL CHEMISTRY
LABORATORIES), referring concurrently in FAPAS and the food of European Union multi-pesticide residue proficiency testing result report in about examination tie
The standard deviation definition of fruit has chosen stronger Horwitz formula (the being detailed in IUPAC) meter of applicability (Fit for Purpose)
Calculate the standard deviation of the result of appraisal.It is (such as steady using relatively broad standard deviation calculation mode for domestic proficiency testing
Standard deviation, the methods of nIQR and MADe are detailed in GB/T28043-2011 and ISO-13528:2015), this laboratory reference
The proficiency testing of IUPAC is reached an agreement on, it is believed that using the standard deviation of laboratory result as the standard deviation of proficiency testing, that is, passes through system
Meter mode merely excludes in 5% laboratory outside satisfied result, can not really with equitably evaluate each laboratory and exist
Performance in proficiency testing, therefore this laboratory determines the standard deviation for using the calculated result of Horwitz formula as examination.
Horwitz formula:
When concentration < 120ppb, σp=0.22c/mr；
Concentration>120ppb and when<13.8%, σp=0.02c0.8495/mr；
Wherein: σpFor the standard deviation of proficiency testing；C is the result of appraisal, with the expression of nondimensional mass percent；
Mr (mass ratio) is nondimensional mass percent.
For example, the result of appraisal are 120ppb, σpValue are as follows:
σp=0.02 × (0.12 × 10-6)0.8495/10-6=0.026mg/kg=2.6%
1.4.3 Z value
In order to judge the score of the examination in laboratory, result is calculated using Z value.
The calculation formula of Z value are as follows: Z=(x-X)/σp,
Wherein: x is the reported result in each laboratory, and X is public discussion value, σpFor the relative deviation of proficiency testing.
Note: all | Z | > 5 Z value is counted as 5 or -5.
Evaluation of result: | Z |≤2 is satisfied, | Z | > 2 is dissatisfied.
2 experimental results
The uniformity testing of 2.1 samples
The data statistical approach of the chromatogram (Fig. 6) of pesticide standard sample, uniformity according to CNAS-GL40:2016 and " divides
Analyse the international uniform agreement of chemical laboratory proficiency testing " (The International Harmonized Protocol for
The proficiency testing of analytical chemistry laboratories, IUPAC), carry out 10
Double samples of random sample detect, and the judgment criteria of sample homogeneity is according to following formula Sam 2< c, wherein SamIt is the standard of sample room
Deviation works as Sam 2It is calculated as its value when negative value and is defined as 0, c=F1σall 2+F2Sam 2, wherein F1And F2It is that 10 samples is taken to do uniformly
Property measurement when parameter, respectively 1.88 and 1.01, σallThe uniformity concentration of=0.3*0.25* compound, when formula is set up then
Otherwise qualification is unqualified.Uniformity data statistic analysis result is shown in Table 4, and table 5, three target analytes are qualified, indicates sample
For the relative deviation in relative deviation and sample between product without significant statistical difference, sample homogeneity is intact (table 6, table 7).
The residual uniformity detection data of 4 agriculture of table (A sample)
The residual uniformity detection data of 5 agriculture of table (B sample)
The residual homogeneity statistical result of 6 agriculture of table (A sample)
The residual homogeneity statistical result of 7 agriculture of table (B sample)
2.2 sample stabilities examine (foundation)
When degradation rate tends towards stability in matrix after sample preparation, two bottles of deepfreezes (- 20 are randomly selected
DEG C) sample, carrying out span to sample is the detection and analysis under the conditions of 60 days be stored at room temperature, and does double samples analyses, analysis every time
Statistical method follows GB/T28043-2011.The testing time span of the stability contains the entire of proficiency testing examination sample
Period.
Extract 60 days first and last two days of analysis of stability are as analysis node, degradation effect of the analog sample in 60 days, such as
Orchard worker's drug compound meets | Xi-Yi|≤0.3×σp, so that it may think to examine the qualified stability of sample: wherein XiIt is first day
The test concentrations of compound, YiFor the test concentrations of last day compound, σpThe uniformity concentration of=0.25 × each compound.
The stability result of examination sample is shown in Table 8 tables 9, and statistical result is shown in Table 10 tables 11, according to as a result, three kinds of changes in sample
The concentration of object is closed as the variation of time is without significantly reducing (Fig. 4), this demonstrate that examining sample to pass through under normal temperature environment
There is preferable stability, will not be because of stability the problem of influences to participate in the result of reference test laboratory after a period of time.
8 stability test data (sample A) of table
| Date | Pentachloronitrobenzene (mg/kg) | Procymidone (mg/kg) | Decis (mg/kg) |
| day 1 | 0.118 | 0.449 | 0.630 |
| day 5 | 0.113 | 0.457 | 0.675 |
| day 10 | 0.123 | 0.447 | 0.668 |
| day 15 | 0.123 | 0.448 | 0.671 |
| day 20 | 0.119 | 0.442 | 0.669 |
| day 30 | 0.123 | 0.461 | 0.651 |
| day 40 | 0.121 | 0.445 | 0.638 |
| day 50 | 0.114 | 0.455 | 0.635 |
| day 60 | 0.116 | 0.446 | 0.635 |
9 stability test data (sample B) of table
| Date | Pentachloronitrobenzene (mg/kg) | Procymidone (mg/kg) | Decis (mg/kg) |
| day 1 | 0.270 | 0.290 | 0.647 |
| day 5 | 0.288 | 0.305 | 0.675 |
| day 10 | 0.294 | 0.294 | 0.668 |
| day 15 | 0.288 | 0.302 | 0.650 |
| day 20 | 0.285 | 0.281 | 0.623 |
| day 30 | 0.295 | 0.290 | 0.634 |
| day 40 | 0.269 | 0.276 | 0.644 |
| day 50 | 0.265 | 0.287 | 0.630 |
| day 60 | 0.263 | 0.279 | 0.615 |
10 stability statistical result (sample A) of table
11 stability statistical result (sample B) of table
2.3 sample Acceleration studies
Acceleration study mainly investigate examination sample be transported at room temperature or experimentation in the extreme temperature (35 that is likely encountered
DEG C) under stability, the setting time be 4h, data result show and (be shown in Table 11, table 12) sample at such a temperature compound have compared with
Significantly to degrade, it is proposed that the examination sample is in transport and experimentation it is ensured that temperature is room temperature (25 DEG C) or refrigerates.
11 Acceleration study degradation rate result (sample A) of table
12 Acceleration study degradation rate result (sample B) of table
| mg/kg | Sample1 | Sample2 | Sample average | Heated 1 | Heated 2 | Accelerate average | Degradation rate (%) |
| Pentachloronitrobenzene | 0.363 | 0.355 | 0.359 | 0.246 | 0.266 | 0.256 | 28.6 |
| Procymidone | 0.278 | 0.277 | 0.278 | 0.174 | 0.183 | 0.179 | 35.7 |
| Decis | 0.614 | 0.636 | 0.625 | 0.309 | 0.292 | 0.301 | 51.9 |
2.4 testing results statistics and Capacity Evaluation
2.4.1 the design and merit rating principle statisticallyd analyze
Each monomer other to each horizontal group and total amount carry out steady Z ratio scoring respectively.Three compound Z values are less than
It is determined as that result is satisfied equal to 2, any one index Z value is greater than 2 and is determined as that result is dissatisfied.
2.4.2 laboratory measurements
This proficiency testing shares 135 mechanisms and participates in, wherein 7 mechanisms do not report knot due to various reasons
Fruit, 101 mechanisms have participated in pentachloronitrobenzene measurement, and 76 mechanisms participate in procymidone measurement, and 107 mechanisms participate in bromine cyanogen chrysanthemum
Ester measurement, statistical form are shown in Table 13.By preliminary survey and repetition measurement, there are three results to be unsatisfied in final 2 laboratories, 1 laboratory 2
A result is dissatisfied, and 21, laboratory results are dissatisfied.As a result as it can be seen that most of laboratories can find the problem, and in time
Correction, improves detection level, has reached the requirement of examination, has also reached this proficiency testing plan and has promoted relevant unit's pesticide
Remain the original intention of detectability.
Table 13 participates in the evaluation result statistical form in the laboratory of preliminary survey
| Compound name | Pentachloronitrobenzene | Procymidone | Decis |
| Participate in laboratory quantity | 101 | 76 | 107 |
| As a result it is satisfied with laboratory quantity | 98 | 73 | 103 |
| As a result it is unsatisfied with laboratory quantity | 3 | 3 | 4 |
| Qualification rate | 97.0% | 96.1% | 96.3% |
Embodiment 2: trace standard of pesticide sampling report in cabbage
1. experimental method
1.1 standard sample preparation methods
1.1.1 required instrument, reagent and vessel are prepared (with embodiment 1)
1.1.2 sample preparation procedure
A) sample selection Web superstore " bright dish house keeper " purchase, in same batch, sample type belongs to be had sample source
Machine vegetables, without any additive and pesticide.
B) required sample is shredded to fritter with knife, is crushed to pulpous state through fruits and vegetables pulverizer.
C high-speed rotating cutter head) is used, is homogenized 2000 revs/min of speed, the time 60 minutes.
D it) is transferred into the freeze-drying disk cleaned up, progress freeze-drying and dehydrating: -10 DEG C of pre-freezing temperature, pre-freeze
Time 4h, -180 DEG C of condenser temperature, cooling time 96h.After the completion, when displays temperature reaches room temperature, taking-up freeze-drying disk.
E) the block sample after drying, pulverizer are crushed to powder, cross 80 meshes.
F) (bare substrate is without carrying out the residual addition of agriculture) accurately weighs 400g freeze-dried powder, evenly laid out in 0.3m × 0.4m
Plastics chopping board on, after the apple coarse crushing being freeze-dried, be partially contained in stainless steel disc, by spraying mode by first
The mixed standard solution (decis, pentachloronitrobenzene and procymidone, Fig. 2) of three kinds of pesticides of alcohol dissolution is uniformly sprayed on freeze-drying
Mark-on freeze-dried powder of the powder surface as examination sample, sprinkling liquid and bare substrate powder ratio (5mL/100g).
G it) is freeze-dried again, progress freeze-drying and dehydrating: -10 DEG C of pre-freezing temperature, pre-freeze time 4h, condenser temperature
- 180 DEG C, cooling time 96h.After the completion, when displays temperature reaches room temperature, taking-up freeze-drying disk.After removing solvent, crush,
Cross 80 sieves.
H) freeze-dried powder of mark-on is mixed with bare substrate freeze-dried powder according to (1:3), is fitted into 4L vial, by vial
It is placed on high-speed oscillator in the environment being protected from light to vibrate 12h in 400 beats/min of frequency, it is ensured that powder uniformly mixes.
I after powder in vial accurately) is sub-packed in 20mL brown ml headspace bottle internal gland with packing instrument with every bottle of 6g powder
- 20 DEG C of freezen protectives.It refrigerates and protects after (specimen bottle all does numeral mark, and coding rule is 001-050 reference sample) internal gland
It deposits.Reference sample is prepared for 50 bottles altogether, and freezen protective under conditions of being stored in -20 degrees Celsius uses preceding normal temperature unfreezing.
1.2 experimental method
1.2.1 method foundation
Referring to " measurement of 500 kinds of pesticides and related chemicals residual quantity in GB/T 19648-2006 fruits and vegetables "；It is suitable
With matrix: apple, citrus, grape, wild cabbage, celery, tomato；Experimental principle: taking 20g sample, extract through acetonitrile, auxiliary of saltouing
Liquid-liquid extraction, after respectively with C18 column and Graphon & aminopropyl series connection SPE column purification after use gas-chromatography-mass spectrometry
Instrument sample detection；Detecting instrument: gas-chromatography (DB-1701 chromatographic column)-mass spectrum (source EI)；Instrument acquisition: by 500 kinds of compounds
It is divided into 5 groups, uses Heptachlor epoxide as internal standard, with SIM mode to 3 ions of each compound application；Quantitative approach: matrix
The proceduring standard curve matched；Detection limit: Biphenthrin: 0.0063mg/kg, Fipronil: 0.050mg/kg, chlorfenapyr:
0.050mg/kg。
Referring to the QuEChERs method of AOAC 2007.01；It is applicable in matrix: fruits and vegetables and cereal without grease and high sugar；
Experimental method/principle: taking 5g sample (wet sample)/takes 1g sample that 5mL water immersion 30min (dry sample) is added, and is added and contains 1% formic acid second
Nitrile extracts, and auxiliary liquid-liquid extraction of saltouing and (ammonium acetate is first added, anhydrous magnesium sulfate is added afterwards) takes supernatant 1mL PSA and Carb
Gas-chromatography-concatenation mass spectrum sample detection is used after purification after filter membrane；Quantitative approach: the proceduring standard curve of matrix matching；
Detection limit: Biphenthrin: 0.0001mg/kg, Fipronil: 0.001mg/kg, chlorfenapyr: 0.0005mg/kg.
Comparative approach result consistency is examined using double sample t.
The measurement of 1.3 homogeneity
The pattern detection process of homogeneity follows ISO/IEC-17025, with reference to vegetable in European Union's Reference Lab (EURL)
The production method of dish pesticide residues in fruits aptitude tests sample (PT).7 bottles of samples, each sample are taken out from refrigerator at random
It is divided into double sample detections, pattern detection sequence does pre-treatment in strict accordance with the random sequence (random digit corresponds to bottle number) being previously set
With sample introduction is analyzed, detection method uses GC-MS/MS instrument referring to AOAC above 2007.01 ' method 2 ', quantitative analysis, utilizes
The proceduring standard curve of matrix matching quantifies sample.
1.4 Stability Determination
1.4.1 compound test
When degradation rate tends towards stability in matrix after sample preparation, one bottle of deepfreeze (- 20 is randomly selected
DEG C) sample, carrying out span to sample is the detection and analysis under the conditions of 42 days be stored at room temperature, and does double samples analyses, analysis every time
Method equally follows ISO/IEC-17025.What analysis of stability was extracted 60 days is used as analysis node in first and last two days, and analog sample is 42
Degradation effect in it, if agricultural chemical compound meets | Xi-Yi|≤0.3×σp, so that it may think that the stability of reference sample is closed
Lattice: wherein XiFor the compound concentration of (first day) Day1, YiFor the compound concentration of (the 42nd day) Day42, σp=0.25*ization
Close the assignment concentration of object.
1.4.2 accelerated test
Acceleration study has investigated the drop that reference sample places each agricultural chemical compound after 4h under the conditions of extreme temperature (35 DEG C)
Solve situation.
1.4.3 transportation stability
In order to verify in reference sample in the stability of long-distance transport process, two bottles of samples (lab scale sample) are by being distinguished
It transports from Shanghai City disease control to Gansu Province and Hainan Province's disease control, and measure content after being returned after transporting destination to by other side.
2. experimental result
2.1 method validation
2.1.1 the consistency of method
The chromatogram (Fig. 5) of pesticide standard sample, table 14 are listed based on AOAC 2007.01 ' method 2 ' and GB/T
' the sample content and relative deviation of the two methods of 1 ' sum of method, the results showed that the relative standard between method of 19648-2006
Deviation is less than 10%；Table 1 compares the difference of compound determination between different instruments, and relative standard deviation is respectively less than 15%.
The measurement difference of agricultural chemical compound between 14 distinct methods of table
2.1.2 instrument otherness is tested
Sample is handled referring to the second method of AOAC 2007.01, and quantitative approach uses the proceduring standard of matrix matching
Curve, select 3 kinds of different instruments (gas chromatography-electron capture detector GC-ECD, gas chromatography-mass spectrography GC-MS,
Gas-chromatography-concatenation mass spectrum GC-MS/MS) to sample and standard series, sample introduction is analyzed, compare the difference between instrument.Different instruments
Measurement result see the table below 15, and the relative standard deviation of 2 compounds of Biphenthrin and chlorfenapyr is respectively less than 10%, and Fipronil exists
There is matrix interference to cause result bigger than normal on GC-ECD, relative standard deviation 12.43%.
The measurement difference of agricultural chemical compound between the different instruments of table 15
2.3 sample homogeneity
The judgment criteria of sample homogeneity is Sam 2< c: wherein SamIt is the standard deviation of sample room, works as Sam 2It is calculated as negative value
When its value be defined as 0, c=F1σall 2+F2San 2, wherein F1And F2It is parameter when 7 samples being taken to do homogeneity measurement, respectively
2.1 and 1.4, σallThe mean concentration of=0.3*0.25* target agricultural chemical compound.The purpose of judgement of formula is to confirm sample
Between relative deviation be less than sample in relative deviation.As a result, it has been found that (being shown in Table 16 and table 17) trace standard of pesticide product is uniform
Property it is qualified.
The residual homogeneity detection data of 16 agriculture of table
The residual homogeneity statistical result of 17 agriculture of table
2.4 stability test interpretations of result
The stability statistical result of reference sample is shown in Table 18, according to as a result, in sample three kinds of compounds concentration with when
Between variation without significantly reduce (Fig. 3), this demonstrate that under normal temperature environment reference sample have after a period of time compared with
Good stability, will not be because of stability the problem of, influence to participate in the result of reference test laboratory.
18 stability statistical result of table
Acceleration study is the result shows that (being shown in Table 19), and under the experiment test of high temperature, compound has more apparent degradation, because
This analyte is not suitable for High temperature storage.
19 Acceleration study degradation rate result of table
| mg/kg | Sample1 | Sample2 | Sample average | Heated 1 | Heated 2 | Accelerate average | Degradation rate |
| Fipronil | 0.646 | 0.662 | 0.654 | 0.489 | 0.498 | 0.494 | 24.5% |
| Chlorfenapyr | 0.937 | 0.973 | 0.955 | 0.786 | 0.826 | 0.806 | 15.6% |
| Biphenthrin | 0.343 | 0.353 | 0.348 | 0.3 | 0.305 | 0.303 | 13.1% |
Transportation stability is the result shows that (being shown in Table 20 and table 21), sample are steady through transport 7 days in the case where not stored refrigerated
It is qualitative good.List in table from Shanghai to Gansu Province and Hainan Province's transport before (first day) and return the pesticide of (the 7th day) afterwards
Testing result and stability statistical result.
20 Gansu stability statistical result of table
21 Hainan stability statistical result of table
| ng/mL | D1(1.8) | D7(1.15) | |D1-D7| | 0.3σp | |D1-D7|<0.3σp |
| Fipronil | 2.683 | 2.608 | 0.074 | 0.201 | Pass |
| Chlorfenapyr | 2.209 | 2.234 | 0.025 | 0.166 | Pass |
| Biphenthrin | 0.241 | 0.236 | 0.004 | 0.018 | Pass |
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
Member, under the premise of not departing from the method for the present invention, can also make several improvement and supplement, these are improved and supplement also should be regarded as
Protection scope of the present invention.
Claims (10)
1. a kind of pesticide residue laboratory proficiency testing sample preparation methods, which comprises the following steps:
A the fruit or vegetables sample with batch) are acquired；
B) sample discards inedible position, and chopping is blocking, is crushed to pulpous state；
C) merge slurries, low-temperature homogenate；
D sample) is subjected to freeze-drying and dehydrating；
E the block sample after) taking drying, pulverizer are crushed to powder, are sieved, obtain bare substrate freeze-dried powder；
F it) takes quantitative freeze-dried powder evenly laid out on plate, standard pesticide substance solution is uniformly sprayed on powder with spraying apparatus
Surface；
G it) is freeze-dried, after removing solvent, is crushed again, sieving obtains mark-on freeze-dried powder；
H it is fitted into bottle after) mixing mark-on freeze-dried powder with bare substrate freeze-dried powder, bottle is placed on high-speed oscillator, shaken
It swings, it is ensured that powder uniformly mixes；
I powder in bottle) is sub-packed in freezen protective after brown ml headspace bottle internal gland with packing instrument with equivalent.
2. pesticide residue laboratory proficiency testing sample preparation methods according to claim 1, which is characterized in that specific steps
It is as follows:
A the fruit or vegetables sample with batch) are acquired；
B) sample discards inedible position, is shredded required sample to fritter with knife, is crushed to pulpous state through fruits and vegetables pulverizer；
C) merge slurries, low-temperature homogenate；1000~3000 revs/min of speed, the time 30~60 minutes of homogenate；
D freeze-drying and dehydrating) is carried out；- 30 DEG C~-5 DEG C of pre-freezing temperature, 1~4h of pre-freeze time, condenser temperature -196 DEG C~-20
DEG C, cooling time 30min~96h；
E the block sample after) taking drying, pulverizer are crushed to powder, cross 80~120 meshes, obtain bare substrate freeze-dried powder；
F) accurately 400g freeze-dried powder is weighed, it is evenly laid out on the plastics chopping board of 0.3m × 0.4m, with spraying apparatus by standard
Pesticidal material solution is uniformly sprayed on powder surface, sprinkling liquid and 1~5mL:100 of bare substrate powder proportions~200g；
G it) is freeze-dried, after removing solvent, is crushed again, crossed 80~120 sieves, obtain mark-on freeze-dried powder；
H mark-on freeze-dried powder and bare substrate freeze-dried powder are mixed according to the ratio of mass ratio 1~2:1~5), are packed into 4L glass
In bottle, vial is placed on high-speed oscillator with 100~500 beats/min of hunting of frequency for 24 hours, it is ensured that powder uniformly mixes
It closes；
I powder in vial accurately) is sub-packed in after 20mL brown ml headspace bottle internal gland -20 DEG C with packing instrument with every bottle of 6g powder
~-80 DEG C of freezen protectives.
3. pesticide residue laboratory proficiency testing sample preparation methods according to claim 2, which is characterized in that selected standard
Pesticidal material is Biphenthrin, Fipronil and chlorfenapyr.
4. pesticide residue laboratory proficiency testing sample preparation methods according to claim 2, which is characterized in that selected standard
Pesticidal material is procymidone, pentachloronitrobenzene and decis.
5. pesticide residue laboratory proficiency testing sample preparation methods according to claim 3, which is characterized in that matrix used
For cabbage.
6. pesticide residue laboratory proficiency testing sample preparation methods according to claim 4, which is characterized in that matrix used
For apple.
7. according to any pesticide residue laboratory proficiency testing sample preparation methods of claim 3~4, which is characterized in that
The pesticide concentration added in matrix is 0.05-1.0mg/kg.
8. according to any pesticide residue laboratory proficiency testing sample preparation methods of claim 3~4, which is characterized in that
The mark-on standard sample of pesticide methanol or acetonitrile dissolution.
9. the trace standard of pesticide sample that any preparation method of claim 1~6 is prepared.
10. the purposes of trace standard of pesticide sample as claimed in claim 9, which is characterized in that examined for pesticide residue laboratory
Survey proficiency testing, pesticide qualitative and quantitative analysis, the verifying of detection method, test equipment calibration and test result quality control with
Examination.
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Application publication date: 20190111 |