CN103293266B - GC-MS/MS (gas chromatography-tandem mass spectrometry) method for analyzing dinitroaniline pesticide residue in tobacco and tobacco product - Google Patents
GC-MS/MS (gas chromatography-tandem mass spectrometry) method for analyzing dinitroaniline pesticide residue in tobacco and tobacco product Download PDFInfo
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Abstract
The invention relates to a GC-MS/MS (gas chromatography-tandem mass spectrometry) method for analyzing dinitroaniline pesticide residue in tobacco and a tobacco product, which is characterized by comprising the following steps: drenching a sample with water, and adding acetonitrile and an internal standard substance; performing vortex extraction and salting-out stratification, and performing secondary salting-out and liquid-liquid extraction with a sodium chloride water solution and n-hexane; and taking the n-hexane supernatant, and determining according to a GC-MS/MS method. The method provided by the invention simplifies the existing sample treatment method, provides a cleaner on-machine solution, and reduces the maintenance of instruments in the operating process. The sample pretreatment process of the method provided by the invention omits a purification step of substrate d-SPE (dispersive solid phase extraction); and instead, the acetonitrile extracting solution is taken, and liquid-liquid extraction and secondary salting-out are performed by using the n-hexane and the sodium chloride water solution, so that the polar coextraction substrate in the supernatant is greatly reduced. By using GC-MS/MS having high sensitivity and high interference rejection, the detection limit of a target substance can be greatly reduced, and the advantages of high sensitivity and favorable repetitiveness are achieved.
Description
Technical field
The invention belongs to tobacco and tobacco product Pesticide Residues detection technique field, relate generally to the determination techniques of nitro pesticide residue in tobacco and tobacco product.
Background technology
Organic agricultural chemicals divides and mainly includes machine phosphorus, organochlorine, pyrethroid, carbamates, organic nitrogen (comprising amide-type and nitro class) etc. by chemical constitution character.Wherein, dinitroaniline agricultural chemicals is also the important indicator that tobacco Pesticide Residues detects, and the residual recall rate of the representative agriculture such as pendimethalin is higher.
Residues of pesticides refer to that the applications of pesticide are after crops, remain in trace pesticide and metabolin and catabolite etc. in environment, crops and biosome.In the storage process of growing seedlings after growth and harvesting of tobacco, inevitably use herbicide, plant growth regulator, pesticide, acaricide and germifuge etc.And tobacco sucks product as one simultaneously, its security requirement is high, and therefore, the residues of pesticides in tobacco have obtained paying close attention to widely.
In view of harmfulness and the importance of residues of pesticides, a lot of countries and regions have proposed the Pesticide Residue in multiple kinds of crops and quality control method, as method simultaneously, the SANCO/10684/2009 of European Union etc. of Japan.International tobacco scientific research Cooperation Centre (CORESTA) has proposed the guiding residue limits of 99 kinds of agricultural chemicals in tobacco (GRLs, Guidance Residue Levels) in Dec, 2003, and revise in June, 2008, is now 118 kinds.
The detection method of dinitroaniline pesticide residue analysis in tobacco is mainly contained to vapor-phase chromatography (GC) and gas chromatography-mass spectrography (GC-MS).Gas chromatography-tandem mass spectrum (GC-MS/MS) has no report for analyzing separately dinitroaniline pesticide residue.Mass spectrum has improved the reliability of method on qualitative as detecting device, and second order ms (MS/MS) is one-level mass spectrum (MS) relatively, and its antijamming capability is stronger, lower to the requirement of sample pre-treatments.
For adapting to high selectivity and the strong anti-interference ability of second order ms, in pre-treating method, applying maximum is exactly simple and quick QuEChERS method.From 2003, after Anastassiades etc. have proposed to be applicable to the QuEChERS method of multi-residue analysis in fruits and vegetables, the method developed rapidly and updates, and was applied to the mensuration of tobacco and tobacco product Pesticide Residues.The party's general theory of law is, after acetonitrile extraction, purify with PSA, then or dilution or solvent replace, upper machine testing.
summary of the invention:
Object of the present invention is intended to further simplify existing method and obtain cleaner upper machine solution, provide a kind of sample after water infiltration, add acetonitrile and internal standard compound, then extraction of ocean eddies, the layering of saltouing, then carry out with sodium-chloride water solution and normal hexane that secondary is saltoutd and liquid-liquid extraction, get normal hexane supernatant, carry out method for measuring with gas chromatography-tandem mass spectrometry (GC-MS/MS).The method can fast, accurately detect the dinitroaniline pesticide residue in tobacco and tobacco product, and measurement result is accurate, reproducible.
The object of the invention is to be achieved through the following technical solutions: in tobacco of the present invention and tobacco product, the assay method of dinitroaniline persticide residue comprises the following steps:
The preparation of a, inner mark solution: preparation TPP(triphenyl) concentration is the acetone soln of 20 μ g/mL;
B, take sample: take 2.0 g tobacco samples in 50 mL tool plug centrifuge tubes, be accurate to 0.1 g;
C, add water infiltration sample: accurately add 10 mL water, infiltrate 10 min;
D, oscillation extraction: accurately add 10 mL acetonitriles and 100 μ L inner mark solutions, on whirlpool mixing shaker with 2000 rpm vortex 1 min;
E, the layering of saltouing: add the pack of saltouing (containing 4 g anhydrous magnesium sulfates, 1 g sodium chloride, 1 g sodium citrate and 0.5 g DisodiumHydrogen Citrate), immediately on whirlpool mixing shaker with 2000 rpm, 2 min that vibrate, on supercentrifuge with centrifugal 3 min of 5000 rpm;
F, liquid-liquid extraction: get 1 mL acetonitrile extract in 15 mL centrifuge tubes, and add 1 mL normal hexane and 5 mL 20% sodium-chloride water solutions, on whirlpool mixer oscillator with speed oscillation 2 min of 2000 rpm, on supercentrifuge, with centrifugal 3 min of 5000 rpm, get upper strata hexane solution stand-by;
G, preparation standard operation solution: take respectively 0.010 g(and be accurate to 0.1 mg) various standard sample of pesticide, be placed in same 10 mL volumetric flasks, with acetone solution constant volume, then use normal hexane-acetone (9:1, v/v) dilution to be also finally mixed with the standard operation solution of the various agricultural chemicals with concentration gradient;
H, prepare matrix and join mark working solution: after blank tobacco sample is processed by identical pre-treatment mode, after getting respectively 1 mL upper strata hexane solution nitrogen and drying up, redissolve with the pesticide standard working solution of 1 mL variable concentrations gradient;
I, GC-MS/MS measure: the matrix of drawing the variable concentrations preparing is joined mark working solution, cross after the organic filter membrane of 0.22 μ m, inject GC-MS/MS;
The calculating of j, pesticide residue determination result: carry out the quantitative test of agricultural chemicals object with internal standard method, select quasi-molecular ions Area Ratio to carry out regretional analysis to its respective concentration with the secondary of agricultural chemicals and interior mark TPP, obtain typical curve; Sample after extracting is measured, recorded the secondary that detects agricultural chemicals and interior mark TPP and select quasi-molecular ions Area Ratio, substitution typical curve, tries to achieve the content of dinitroaniline agricultural chemicals in sample.
In the present invention, the manner of formulation of standard operation solution is as follows: take respectively 0.01 g(and be accurate to 0.1 mg) various standard sample of pesticide, be placed in same 10 mL volumetric flasks, with acetone solution constant volume, being mixed with each pesticide concentration is the mixed standard solution I of 1 mg/mL; Then accurately pipette 1 mL mixed standard solution I, be placed in 100 mL volumetric flasks, with acetone constant volume, being mixed with each pesticide concentration is the mixed standard solution II of 10 μ g/mL; Then accurately pipette 2 mL mixed standard solution II, be placed in 10 mL volumetric flasks, with normal hexane-acetone (9:1, v/v) constant volume, being mixed with each pesticide concentration is the mixed standard solution III of 2 μ g/mL; Accurately pipette the mixed standard solution III of 0.01 mL, 0.025 mL, 0.05 mL, 0.1 mL, 0.25 mL, 0.5 mL and 1 mL, be placed in 10 mL volumetric flasks, accurately add 100 μ L inner mark solutions, with normal hexane-acetone (9:1, v/v) constant volume, obtains series standard working solution.The series standard solution concentration of preparation is: 2 ng/mL, 5 ng/mL, 10 ng/mL, 20 ng/mL, 50 ng/mL, 100 ng/mL, 200 ng/mL.
In the time that GC-MS/MS measures, the chromatographic condition of employing is: chromatographic column: (30 mm × 0.25, m × 0.25 μ m) for TR-Pesticide II quartz capillary column; Injector temperature: 250 DEG C; Temperature programme: 90 DEG C of initial temperatures, keep rising to 180 DEG C with 25 DEG C/min after 5 min, keep 15 min; Then rise to 280 DEG C with 5 DEG C/min, keep 6.5 min; Program after post: 300 DEG C, keep 5 min; Splitless injecting samples, does not shunt time 1 min; Carrier gas: helium (purity is 99.999%); Constant current mode, flow velocity is 1.2 mL/min; Sample size: 1 μ L.Total run time is 55 min.
The mass spectrum condition adopting is: EI ionizes pattern, ionization energy 70 eV; Filament current: 50 μ A; Ion source temperature: 250 DEG C; Transmission line temperature: 280 DEG C; Q2 collides gas: argon gas (purity 99.999%), and collision pond pressure is 1.0 mTorr; Solvent delay 5 min; Scan mode: multiple-reaction monitoring (MRM).Dinitroaniline agricultural chemicals and interior target retention time and mass spectrum parameter are in table 1.
table 1 dinitroaniline agricultural chemicals object and interior target retention time and MRM parameter
| Sequence number | Universal Chinese character title | English name | Quota ion pair | Qualitative ion pair | Collision energy (eV) | Retention time (min) |
| 1 | Benfluralin | Benfluralin | 292.1/160.1 | 292.1/264.1 | 21;10 | 12.17 |
| 2 | Butralin | Butralin | 266.1/220.1 | 266.1/190.1 | 10;15 | 22.91 |
| 3 | Flumetralim | Flumetralin | 143.0/107.0 | 143.0/108.0 | 20;20 | 28.18 |
| 4 | Isopropalin | Isopropalin | 280.2/238.1 | 280.2/180.1 | 10;15 | 24.05 |
| 5 | Pendimethalin | Pendimethalin | 252.1/162.1 | 252.1/191.1 | 12;7 | 24.41 |
| 6 | Trefanocide | Trifluralin | 306.1/264.1 | 306.1/160.1 | 10;20 | 12.10 |
| IS | TPP | Triphenyl phosphate | 326.1/325.1 | 326.1/233.1 | 10;10 | 35.01 |
Method of the present invention has been simplified existing sample treatment, and cleaner upper machine solution is provided, and has reduced instrument maintenance in use.Compared with prior art the inventive method has following excellent results:
(1) in the inventive method sample pretreatment process, used for reference the step of " with water infiltration sample " in existing method to improve the effect of extracting of acetonitrile to agricultural chemicals object; Saved the step of " putting into refrigerator before adding the bag of saltouing " simultaneously, found through investigating, dinitroaniline agricultural chemicals is mostly thermally-stabilised, can not cause because of the combination heat release of anhydrous magnesium sulfate and water degraded, so locate to save the running time.
(2) in the inventive method sample pretreatment process, save the purifying step of Dispersive solid phase extraction (d-SPE), but get acetonitrile extract, carry out liquid-liquid extraction and secondary is saltoutd with normal hexane and sodium-chloride water solution, ensured nonpolar and recovery low pole object.Meanwhile, because normal hexane is nonpolar strong, therefore the polarity coextraction matrix in supernatant liquor also greatly reduces, upper machine solution is cleaner, has reduced instrument maintenance in use.
(3) the inventive method has adopted the GC-MS/MS of high sensitivity and strong anti-interference ability to detect, and therefore has advantages of that operation is accurate, highly sensitive and reproducible.
1. the detectability of the inventive method:
The matrix of variable concentrations agricultural chemicals is joined to mark working solution and inject GC-MS/MS, calculate detectability (LOD) with 3 times of signal to noise ratio (S/N ratio)s (S/N=3), detectability is between 0.61 ng/g～3.03 ng/g.
2. the repeatability of the inventive method and recovery of standard addition:
In blank tobacco sample, add the standard solution (concentration is 50 ng/mL) of 6 kinds of agricultural chemicals, then carry out respectively pre-treatment and GC-MS/MS and analyze, and calculate its recovery according to adding scalar sum measured value, the results are shown in Table 2.As can be seen from Table 2, the recovery of 6 kinds of agricultural chemicals is between 89.54%～101.62%, and relative standard deviation (RSD), between 3.12%～8.56%, illustrates that the recovery of the inventive method is high, reproducible.
the recovery of table 2 dinitroaniline agricultural chemicals and repeatability (n=6)
Brief description of the drawings
Fig. 1 is assay method process flow diagram of the present invention (this figure is as Figure of abstract).
Embodiment
The present invention is described further below in conjunction with example, but is not restriction the present invention.
Example 1:
1. instrument and reagent:
Dinitroaniline agricultural chemicals: benfluralin, butralin, flumetralim, isopropalin, pendimethalin, trefanocide, interior mark: TPP, is standard items; Acetonitrile, acetone, normal hexane, be chromatographic grade reagent; Distilled water, meets the requirement of one-level water in GB/T 6682.
U.S. Thermo Fisher TSQ Quantum GC gas chromatography-triple quadrupole rods tandem mass spectrometry instrument; Switzerland Mettler AE 163 electronic balances (sensibility reciprocal: 0.0001g); U.S. Labnet VtexMixer VX200 oscillator; Germany Sigma high speed freezing centrifuge.
2. sample preparation:
Take approximately 2 g samples, be accurate to 0.01 g, in 50 mL tool lid centrifuge tubes, add 10 mL water, vibrate to sample by water fully infiltrate rear leave standstill 10 min.Pipette 10 mL acetonitriles to centrifuge tube, add mark working fluid in 100 μ L, and be placed on whirlpool mixing shaker with 2000 r/min velocity fluctuation 1 min.In centrifuge tube, add 4 g anhydrous magnesium sulfates, 1 g sodium chloride, 1 g sodium citrate and 0.5 g DisodiumHydrogen Citrate, immediately on whirlpool mixing shaker with 2000 rpm, 2 min that vibrate, on supercentrifuge with centrifugal 3 min of 5000 rpm;
Get 1 mL acetonitrile extract in 15 mL centrifuge tubes, include 1 mL normal hexane and 5 mL 20% sodium-chloride water solutions, on whirlpool mixer oscillator, with speed oscillation 2 min of 2000 rpm, on supercentrifuge, with centrifugal 3 min of 5000 rpm, get upper strata hexane solution stand-by;
3. prepare standard operation solution:
Take respectively 0.01 g(and be accurate to 0.1 mg) various standard sample of pesticide, be placed in same 10 mL volumetric flasks, with acetone solution constant volume, being mixed with each pesticide concentration is the mixed standard solution I of 1 mg/mL; Then accurately pipette 1 mL mixed standard solution I, be placed in 100 mL volumetric flasks, with acetone constant volume, being mixed with each pesticide concentration is the mixed standard solution II of 10 μ g/mL; Then accurately pipette 2 mL mixed standard solution II, be placed in 10 mL volumetric flasks, with normal hexane-acetone (9:1, v/v) constant volume, being mixed with each pesticide concentration is the mixed standard solution III of 2 μ g/mL; Accurately pipette the mixed standard solution III of 0.01 mL, 0.025 mL, 0.05 mL, 0.1 mL, 0.25 mL, 0.5 mL and 1 mL, be placed in 10 mL volumetric flasks, accurately add 100 μ L inner mark solutions, with normal hexane-acetone (9:1, v/v) constant volume, obtains series standard working solution.The series standard solution concentration of preparation is: 2 ng/mL, 5 ng/mL, 10 ng/mL, 20 ng/mL, 50 ng/mL, 100 ng/mL, 200 ng/mL.
4. prepare matrix and join mark working solution:
Blank tobacco sample, by after identical pre-treatment mode processing (with reference to step " 2. sample preparation "), after getting respectively 1 mL upper strata hexane solution nitrogen and drying up, is redissolved with the pesticide standard working solution of 1 mL variable concentrations gradient;
5. assay method:
The agricultural chemicals matrix of the variable concentrations preparing is joined to mark working solution and inject GC-MS/MS, carry out the quantitative test of agricultural chemicals with internal standard method, select quasi-molecular ions Area Ratio to carry out regretional analysis to its respective concentration with the secondary of agricultural chemicals and interior mark TPP, obtain typical curve; Sample after extracting is measured, recorded the secondary selection quasi-molecular ions Area Ratio that detects agricultural chemicals and interior mark TPP, substitution typical curve, tries to achieve the content of the dinitroaniline agricultural chemicals in sample in table 3.
table 3the testing result of sample A Pesticides object
| Sequence number | Universal Chinese character title | The content (μ g/g) of sample Pesticides object |
| 1 | Benfluralin | —— |
| 2 | Butralin | —— |
| 3 | Flumetralim | 0.71 |
| 4 | Isopropalin | —— |
| 5 | Pendimethalin | 0.09 |
| 6 | Trefanocide | —— |
Note: "-" represents not detect
In the time that GC-MS/MS measures, the chromatographic condition of employing is: chromatographic column: (30 mm × 0.25, m × 0.25 μ m) for TR-Pesticide II quartz capillary column; Injector temperature: 250 DEG C; Temperature programme: 90 DEG C of initial temperatures, keep rising to 180 DEG C with 25 DEG C/min after 5 min, keep 15 min; Then rise to 280 DEG C with 5 DEG C/min, keep 6.5 min; Program after post: 300 DEG C, keep 5 min; Splitless injecting samples, does not shunt time 1 min; Carrier gas: helium (purity is 99.999%); Constant current mode, flow velocity is 1.2 mL/min; Sample size: 1 μ L.Total run time is 55 min.
The mass spectrum condition adopting is: EI ionizes pattern, ionization energy 70 eV; Filament current: 50 μ A; Ion source temperature: 250 DEG C; Transmission line temperature: 280 DEG C; Q2 collides gas: argon gas (purity 99.999%), and collision pond pressure is 1.0 mTorr; Solvent delay 5 min; Scan mode: multiple-reaction monitoring (MRM).Dinitroaniline agricultural chemicals and interior target retention time and mass spectrum parameter are in table 1.
Example 2:
As described in Example 1, select another tobacco sample B, record the content of dinitroaniline agricultural chemicals object in sample in table 4.
table 4the testing result of sample B Pesticides object
| Sequence number | Universal Chinese character title | The content (μ g/g) of sample Pesticides object |
| 1 | Benfluralin | —— |
| 2 | Butralin | 0.06 |
| 3 | Flumetralim | —— |
| 4 | Isopropalin | —— |
| 5 | Pendimethalin | 0.19 |
| 6 | Trefanocide | —— |
Note: "-" represents not detect
Example 3:
As described in Example 1, select another tobacco sample C, record the content of dinitroaniline agricultural chemicals object in sample in table 5.
table 5the testing result of sample C Pesticides object
| Sequence number | Universal Chinese character title | The content (μ g/g) of sample Pesticides object |
| 1 | Benfluralin | —— |
| 2 | Butralin | 0.03 |
| 3 | Flumetralim | 2.70 |
| 4 | Isopropalin | —— |
| 5 | Pendimethalin | —— |
| 6 | Trefanocide | —— |
Note: "-" represents not detect
Example 4:
As described in Example 1, select another tobacco sample D, record the content of dinitroaniline agricultural chemicals object in sample in table 6.
table 6the testing result of sample D Pesticides object
| Sequence number | Universal Chinese character title | The content (μ g/g) of sample Pesticides object |
| 1 | Benfluralin | —— |
| 2 | Butralin | —— |
| 3 | Flumetralim | 0.38 |
| 4 | Isopropalin | —— |
| 5 | Pendimethalin | —— |
| 6 | Trefanocide | —— |
Note: "-" represents not detect.
Claims (3)
1. analyze the GC-MS/MS method of dinitroaniline pesticide residue in tobacco and tobacco product for one kind, it is characterized in that: be by sample after water infiltration, add acetonitrile and internal standard compound, then extraction of ocean eddies, the layering of saltouing, carry out with sodium-chloride water solution and normal hexane afterwards that secondary is saltoutd and liquid-liquid extraction, get normal hexane supernatant, carry out method for measuring with gas chromatography-tandem mass spectrometry (GC-MS/MS), concrete steps are as follows:
The preparation of a, inner mark solution: preparation TPP(triphenyl) concentration is the acetone soln of 20 μ g/mL;
B, take sample: take 2.0 g tobacco samples in 50 mL tool plug centrifuge tubes, be accurate to 0.1 g;
C, add water infiltration sample: accurately add 10 mL water, infiltrate 10 min;
D, oscillation extraction: accurately add 10 mL acetonitriles and 100 μ L inner mark solutions, on whirlpool mixing shaker with 2000 rpm vortex 1 min;
E, the layering of saltouing: add containing 4 g anhydrous magnesium sulfates, 1 g sodium chloride, the pack of saltouing of 1 g sodium citrate and 0.5 g DisodiumHydrogen Citrate, immediately on whirlpool mixing shaker with 2000 rpm, 2 min that vibrate, on supercentrifuge with centrifugal 3 min of 5000 rpm;
F, liquid-liquid extraction: get 1 mL acetonitrile extract in 15 mL centrifuge tubes, and add 1 mL normal hexane and 5 mL 20% sodium-chloride water solutions, on whirlpool mixer oscillator with speed oscillation 2 min of 2000 rpm, on supercentrifuge, with centrifugal 3 min of 5000 rpm, get upper strata hexane solution stand-by;
G, preparation standard operation solution: take respectively the various standard sample of pesticide of 0.010 g, be accurate to 0.1 mg, be placed in same 10 mL volumetric flasks, with acetone solution constant volume, then use 9:1, normal hexane-acetone diluted of v/v is also finally mixed with the series standard working solution of the various agricultural chemicals with concentration gradient;
H, prepare matrix and join mark working solution: after blank tobacco sample is processed by identical pre-treatment mode, after getting respectively 1 mL upper strata hexane solution nitrogen and drying up, redissolve with the pesticide standard working solution of 1 mL variable concentrations gradient;
I, GC-MS/MS measure: the matrix of drawing the variable concentrations preparing is joined mark working solution, cross after the organic filter membrane of 0.22 μ m, inject GC-MS/MS;
In the time that GC-MS/MS measures, the chromatographic condition of employing is: chromatographic column: TR-Pesticide II quartz capillary column specification 30 mm × 0.25, m × 0.25 μ m; Injector temperature: 250 DEG C; Temperature programme: 90 DEG C of initial temperatures, keep rising to 180 DEG C with 25 DEG C/min after 5 min, keep 15 min; Then rise to 280 DEG C with 5 DEG C/min, keep 6.5 min; Program after post: 300 DEG C, keep 5 min; Splitless injecting samples, does not shunt time 1 min; Carrier gas: the helium that purity is 99.999%; Constant current mode, flow velocity is 1.2 mL/min; Sample size: 1 μ L, total run time is 55 min;
The mass spectrum condition adopting is: EI ionizes pattern, ionization energy 70 eV; Filament current: 50 μ A; Ion source temperature: 250 DEG C; Transmission line temperature: 280 DEG C; Q2 collides gas: the argon gas that purity is 99.999%, and collision pond pressure is 1.0 mTorr; Solvent delay 5 min; Scan mode: multiple-reaction monitoring (MRM);
The calculating of j, pesticide residue determination result: carry out the quantitative test of agricultural chemicals object with internal standard method, select quasi-molecular ions Area Ratio to carry out regretional analysis to its respective concentration with the secondary of agricultural chemicals and interior mark TPP, obtain typical curve; Sample after extracting is measured, recorded the secondary that detects agricultural chemicals and interior mark TPP and select quasi-molecular ions Area Ratio, substitution typical curve, tries to achieve the content of dinitroaniline agricultural chemicals in sample.
2. the GC-MS/MS method of dinitroaniline pesticide residue in analysis tobacco according to claim 1 and tobacco product, is characterized in that: dinitroaniline agricultural chemicals refers to following 6 kinds: benfluralin, butralin, flumetralim, isopropalin, pendimethalin, trefanocide.
3. the GC-MS/MS method of dinitroaniline pesticide residue in analysis tobacco according to claim 1 and tobacco product, is characterized in that: the series standard working solution concentration with the various agricultural chemicals of concentration gradient is specially: 2 ng/mL, 5 ng/mL, 10 ng/mL, 20 ng/mL, 50 ng/mL, 100 ng/mL, 200 ng/mL.
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| CN106353435A (en) * | 2016-11-03 | 2017-01-25 | 湖南农业大学 | Method for determining butralin residual quantity in peanut plant or peanut shell on basis of GC-ECD |
| JP6727722B2 (en) | 2016-11-29 | 2020-07-22 | 株式会社日立製作所 | Standard sample preparation method for air flow analysis system |
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