CN101839897B - Measuring method of cloransulam-methyl residues in soybeans and soil - Google Patents
Measuring method of cloransulam-methyl residues in soybeans and soil Download PDFInfo
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Abstract
The invention relates to a measuring method of cloransulam-methyl residues in soybeans and soil, comprising the following concrete steps of: weighing 10-20g of samples and then putting in a conical flask with a plug; adding 20-60mL of pure water and standing for 10-30 min; then adding 50-70mL of acetonitrile; extracting for 30-60 min under vibration; filtering and transferring to a separating funnel; adding 20-30mL of 0.01mol/L hydrochloric acid and a saturated sodium chloride aqueous solution; vibrating for 3-10 min and standing for demixing; extracting again by using 50-100mL of acetonitrile, merging and concentrating to 10-30mL; purifying: sprinkling a solid phase extraction C18 column with the acetonitrile in advance, and purifying the extraction phase by adopting a column chromatography; collecting leaching liquid; concentrating for dryness; making at constant volume by using methanol and water the volume ratio of which is 1:1 and filtering through a filter membrane; and carrying out detection by adopting a liquid chromatogram method. The measuring method has the characteristics of simple and quick operation, high recovery rate, high sensitivity and small impurity interference and provides the reliable guarantee for rapidly and accurately measuring the cloransulam-methyl residues in the soybeans and the soil and establishing a simple and convenient and effective analysis method.
Description
Technical field
The invention belongs to the determination techniques field of persticide residue, particularly relate to the determination of residual amount method of cloransulammethyl in soybean and soil.
Background technology:
The World Health Organization (WHO) and FAO (Food and Agriculture Organization of the United Nation) (WHO/FAO) are defined as Pesticide Residue, according to good agricultural production (GAP) standard, after directly or indirectly using agricultural chemicals, the Cmax of the pesticide residue that forms in food and feed.At first according to the toxicity assessment of agricultural chemicals and residue thereof, use the agricultural chemicals standard according to GAP and safe and reasonable that country promulgates, the control needs that adapt to national various disease and pests, under tight technical supervision, under the prerequisite of effectively prevention and elimination of disease and pests, get representational high value in a series of residual datas of obtaining.Its direct effect is the restriction pesticide residue in agricultural products, and citizens is healthy.In today of world's trade integration, maximum residue limits for pesticide also becomes technology barriers important between each trading country.Soybean is the tradition outlet goods and materials of China.In the situation that the state such as European Union, Japan, Korea S and area are strictly limited and manage transgenic product, the prospect of export of China non-transgenic soybean is very good.For China soybean can enter market, various countries unblockedly, understand and the research import market to the regulation of soybean Pesticide Residue, guarantee that the soybean Pesticide Residues is controlled within the scope that importer allows just most important.
Cloransulammethyl (Cloransulam-methyl) belongs to sulfonamides herbicide, is mainly used in Soybean Field and effectively prevents and kill off the weeds such as dayflower, smartweed, Siberian cocklebur, piemarker, artemisiifolia, and effectively suppress the growth of the broad leaved weeds such as sowthistle, field thistle.Cloransulammethyl is China's herbicide commonly used, and the relevant residue detection analysis of cloransulammethyl in soil and soybean is domestic and have no open report at present.
Summary of the invention:
In order to estimate the security after cloransulammethyl uses in soybean, the present invention has set up the method for cloransulammethyl residual quantity in use ultra high efficiency liquid phase-mass spectrum/GC-MS (UPLC/MS/MS) method mensuration soybean and soil.Specifically with an organic solvent extract cloransulammethyl in soybean and soil, then add sodium chloride in extract, isolate organic solvent layer by liquid liquid, and utilize rotary evaporation to be concentrated into isolated organic solvent layer dried fully, utilize solid phase extraction to remove interfering material in extract, adopt at last ultra high efficiency liquid phase/mass spectrum/GC-MS (UPLC/MS/MS) to detect.Result shows: in the inventive method, the retention time of cloransulammethyl is 0.92min, and the range of linearity detects and is limited to 0.005mg/kg at 0.02～50mg/L, and the recovery is 79%～98%.For achieving the above object, the invention provides following technical scheme:
The residual assay method of cloransulammethyl in soybean and soil is characterized in that being undertaken by following step:
(1) extract: take sample 10-20g, be placed in tool plug conical flask, add pure water 20-60mL, standing 10-30 minute, then add the 50-70mL acetonitrile, mechanical shaking extraction 30-60 minute;
(2) separate: filtration is transferred in separating funnel, adds 20-30mL 0.01mol/L hydrochloric acid and saturated aqueous sodium chloride, vibrated 3-10 minute, and standing demix;
(3) extraction: again extract with the 50-100mL acetonitrile, merge, acetonitrile is evaporated to 10-30mL;
(4) purify: Solid-Phase Extraction C18 post is crossed column purification through the acetonitrile pre-leaching mutually with said extracted, and collect and drench fluid, concentrated near doing, use V/V methyl alcohol: water 1: 1, constant volume is also to be measured through membrane filtration;
(5) measure: adopt liquid phase chromatography to detect, wherein chromatographic column: Acquity BEH C8 (2.1mm * 100mm, 1.7 μ m, column temperature: 30 ℃, sample size 10 μ L, mobile phase: solvent orange 2 A is methyl alcohol, solvent B is 0.1% formic acid; Gradient elution; The concentration limit of soybean kernel and soil is 0.005mg/kg.It is as follows that the present invention measures the concrete grammar of cloransulammethyl residual quantity:
1, test material
Reagent and material: acetonitrile, hydrochloric acid, sodium chloride (be analyze pure), methyl alcohol (HPLC level, Fisher scientific ﹠ technical corporation), pure water (Millipore company), C18 post (Varian company produce)
Standard items: cloransulammethyl (purity 98.3%, The Dow Agrosciences, LLC. provides)
Instrument: ACQUITY Ultra Performance LCTM Ultra Performance Liquid Chromatography instrument (Waters company), the QuattroPremier XE quadrupole mass spectrometer (Waters company) of connecting, solid-phase extracting instrument (Japanese GL Sciences), high speed dispersor (IKA-WERKE), separating funnel oscillator (MMV-1000W), rotary evaporator (Laborota 4000efficient, German Heidolph) etc.
2, test method
Extract: take sample 10.0g, be placed in tool plug triangular flask, add pure water 20mL, after standing 10min, add the 50mL acetonitrile, mechanical shaking extraction 30 minutes.Filtration is transferred in separating funnel, adds 20mL 0.01mol/L hydrochloric acid and the appropriate saturated water of sodium chloride.Vibrated 3 minutes, standing demix, separating acetonitrile phase and water; With 50mL acetonitrile aqueous phase extracted again, merge the acetonitrile phase, acetonitrile is evaporated to the 30mL left and right mutually.
Purify: Solid-Phase Extraction C18 post is crossed column purification through the acetonitrile pre-leaching mutually with said extracted, and collect and drench fluid, concentrated near doing, use methyl alcohol: water (1: 1, V/V) constant volume and to be measured through membrane filtration.
3, instrumental analysis condition
3.1UPLC condition
Chromatographic column: Acquity BEH C8 (2.1mm * 100mm, 1.7 μ m), column temperature: 30 ℃, sample size 10 μ L, mobile phase: solvent orange 2 A is methyl alcohol, solvent B is 0.1% formic acid; Gradient elution.
Program sees Table 1:
The gradient elution program of table 1UPLC
| Time (min) | Flow velocity (mL/min) | A(％) | B(％) | |
| 0 0.50 2.00 2.10 3.00 | 0.3 0.3 0.3 0.3 0.3 | 90 95 95 90 90 | 10 5 5 10 10 | - 6 6 6 6 |
3.2 mass spectrum condition
Ion gun: ESI (+); Capillary voltage: 3.0Kv; Ion source temperature: 110 ℃, desolventizing temperature degree: 400 ℃; Taper hole blowback air flow: 50L/h, desolventizing airshed: 550L/h, detection mode is multiple-reaction monitoring scan pattern (MRM), sees Table 2:
Table 2 mass spectrum condition
| Parent ion | Daughter ion | Taper hole | Collision energy | |
| 430 430 | 370.3 398.1 | 30 30 | 22 18 |
At first carry out daughter ion scanning to 430 under taper hole voltage 30V, find that 370.3 and 398.1 is two of abundance maximum, therefore it is defined as the daughter ion of qualitative, quantitative.Again 370.3 and 398.1 two daughter ions are carried out the optimization of collision energy, find under the energy of 22eV, the abundance of daughter ion 370.3 is than large under other energy; Under the energy of 18eV, the abundance of daughter ion 398.1 is than large under other energy, therefore with 22eV and 18eV respectively as the collision energy of two passages.
4, the concentration limit of method
The cloransulammethyl standard items are added respectively in the operation of application said method in soybean kernel, soil, interpolation concentration is 0.005mg/kg.3 times of signal to noise ratio (S/N ratio) S/N are set as instrument detection limit with instrument, and method concentration limit (mg/kg)=instrument detection limit (ng) * dilutes volume (mL)/[sampling volume (ul) * sampling amount (g).The concentration limit that calculates at last soybean kernel and soil is 0.005mg/kg.
5, the recovery of method and relative standard deviation
Add respectively the cloransulammethyl standard items in soybean, soil, adding concentration is 0.005mg/kg and 0.02mg/kg, five repetitions, and test findings sees Table 3.Test shows, the recovery meets the residual testing requirement of agriculture, has proved that the method has the recovery and repeatability preferably.
Table 3 cloransulammethyl adds recovery test
In soybean of the present invention and soil, the good effect of the assay method of cloransulammethyl residual quantity is: the inventive method can effectively be avoided the matrix interference in sample, obtains good effect.In soybean of the present invention and soil, the assay method of cloransulammethyl residual quantity has higher accuracy, precision and sensitivity, and simple and quick, the recovery is high, and impurity disturbs I with the content of effective measurement cloransulammethyl in soybean and soil.
Description of drawings:
Fig. 1 is the soil contrast; Fig. 2 is soil interpolation figure; Fig. 3 is soybean kernel contrast figure;
Fig. 4 soybean kernel adds figure; Fig. 5 cloransulammethyl structural formula figure; Fig. 6 cloransulammethyl MS/MS mass spectrogram.
Embodiment:
In order to explain more fully enforcement of the present invention, provide the preparation embodiment of the residual assay method of cloransulammethyl in soybean and soil.These embodiments are only to explain rather than limit the scope of the invention.Wherein raw material used all has commercially available.
Embodiment 1
(1) extract: take soybean 20g, be placed in tool plug conical flask, add pure water 20mL, standing 10 minutes, then add the 50mL acetonitrile, mechanical shaking extraction 30 minutes;
(2) separate: filtration is transferred in separating funnel, adds 20mL 0.01mol/L hydrochloric acid and saturated aqueous sodium chloride, vibrated 3 minutes, and standing demix;
(3) extraction: again extract with the 50mL acetonitrile, merge, methyl alcohol is evaporated to 10mL;
(4) purify: Solid-Phase Extraction C18 post is crossed column purification through the acetonitrile pre-leaching mutually with said extracted, and collect and drench fluid, concentrated near doing, use V/V methyl alcohol: water 1: 1, constant volume is also to be measured through membrane filtration;
(5) measure: adopt liquid phase chromatography to detect, wherein chromatographic column: Acquity BEH C8 (2.1mm * 100mm, 1.7 μ m, column temperature: 30 ℃, sample size 10 μ L, mobile phase: solvent orange 2 A is methyl alcohol, solvent B is 0.1% formic acid; Gradient elution.
(6) measurement result: record cloransulammethyl content in soybean lower than 0.005mg/kg by above step.
(1) extract: take soybean 20g, be placed in tool plug conical flask, add pure water 60mL, standing 30 minutes, then add the 70mL acetonitrile, mechanical shaking extraction 60 minutes;
(2) separate: filtration is transferred in separating funnel, adds 30mL 0.01mol/L hydrochloric acid and saturated aqueous sodium chloride, vibrated 10 minutes, and standing demix;
(3) extraction: again extract with the 100mL acetonitrile, merge acetonitrile and be evaporated to 30mL;
(4) purify: Solid-Phase Extraction C18 post is crossed column purification through the acetonitrile pre-leaching mutually with said extracted, and collect and drench fluid, concentrated near doing, use V/V methyl alcohol: water 1: 1, constant volume is also to be measured through membrane filtration;
(5) measure: adopt liquid phase chromatography to detect, wherein chromatographic column: Acquity BEH C8 (2.1mm * 100mm, 1.7 μ m, column temperature: 30 ℃, sample size 10 μ L, mobile phase: solvent orange 2 A is methyl alcohol, solvent B is 0.1% formic acid; Gradient elution.
(6) measurement result: the cloransulammethyl content that records in soybean by above step is 0.012mg/kg.
Embodiment 3
(1) extract: take soil 15g, be placed in tool plug conical flask, add pure water 40mL, standing 20 minutes, then add the 60mL acetonitrile, mechanical shaking extraction 40 minutes;
(2) separate: filtration is transferred in separating funnel, adds 25mL 0.01mol/L hydrochloric acid and saturated aqueous sodium chloride, vibrated 10 minutes, and standing demix;
(3) extraction: again extract with the 80mL acetonitrile, merge acetonitrile and be evaporated to 25mL;
(4) purify: Solid-Phase Extraction C18 post is crossed column purification through the acetonitrile pre-leaching mutually with said extracted, and collect and drench fluid, concentrated near doing, use V/V methyl alcohol: water 1: 1, constant volume is also to be measured through membrane filtration;
(5) measure: adopt liquid phase chromatography to detect, wherein chromatographic column: Acquity BEH C8 (2.1mm * 100mm, 1.7 μ m, column temperature: 30 ℃, sample size 10 μ L, mobile phase: solvent orange 2 A is methyl alcohol, solvent B is 0.1% formic acid; Gradient elution.
(6) measurement result: record cloransulammethyl content in soil lower than 0.005mg/kg by above step.
After the preferred embodiment that describes in detail, being familiar with this technology personage can be well understood to, can carry out various variations and modification not breaking away under above-mentioned claim and spirit, all foundations technical spirit of the present invention is done any simple modification, equivalent variations and modification to above embodiment, all belongs to the scope of technical solution of the present invention.And the present invention also is not subjected to the restriction of example embodiment in instructions.
Claims (1)
1. the residual assay method of cloransulammethyl in soybean and soil is characterized in that being undertaken by following step:
(1) extract: take sample 10-20g, be placed in tool plug conical flask, add pure water 20-60mL, standing 10-30 minute, then add the 50-70mL acetonitrile, mechanical shaking extraction 30-60 minute;
(2) separate: filtration is transferred in separating funnel, adds 20-30mL 0.01mol/L hydrochloric acid and saturated aqueous sodium chloride, vibrated 3-10 minute, and standing demix;
(3) extraction: again extract with the 50-100mL acetonitrile, merge, acetonitrile is evaporated to 10-30mL;
(4) purify: Solid-Phase Extraction C18 post is crossed column purification through the acetonitrile pre-leaching mutually with said extracted, and collect and drench fluid, concentrated near doing, use V/V methyl alcohol: the solution constant volume of water=1: 1, and to be measured through membrane filtration;
(5) measure: adopt liquid phase chromatography to detect, wherein chromatographic column: Acquity BEH C8,2.1mm * 100mm, 1.7 μ m, column temperature: 30 ℃, sample size 10 μ L, mobile phase: solvent orange 2 A is methyl alcohol, solvent B is 0.1% formic acid; Gradient elution; The concentration limit of soybean and soil is 0.005mg/kg;
The composition of wherein said liquid phase chromatography mobile phase and flow velocity are:
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| CN102221595A (en) * | 2011-06-13 | 2011-10-19 | 天津市农业科学院中心实验室 | Method for measuring residual amounts of pirimicarb and mtabolites thereof in cabbage |
| CN103412077B (en) * | 2013-07-14 | 2014-11-05 | 崔淑华 | Method for measuring indazole flusulfamide residue amount |
| CN108956818A (en) * | 2018-07-24 | 2018-12-07 | 山东省农药科学研究院 | A kind of HPLC-MS/MS measuring method of fluridone residual quantity |
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| Analysis of triazolopyrimidine herbicides in soils using field-enhanced sample injection-coelectroosmotic capillary electrophoresis combined with solid-phase extraction;Hernandez-Borges J; Garcia-Montelongo FJ; Cifuentes A;;《JOURNAL OF CHROMATOGRAPHY A 》;20051005;第1100卷(第1期);236-242 * |
| Rapid analysis of triazollopyrimidine sullfoanillide herbicides in waters and soils by high-performance liquid chromatography with UV detection using a C-18 monolithic column;Rodriguez-Delgado Miguel Angel; Hernandez-Borges Javier;《JOURNAL OF SEPARATION SCIENCE》;20070131;第30卷(第1期);8-14 * |
| 超高效液相色谱􀀁电喷雾串联质谱法同时测定大豆中107种除草剂残留;储晓刚 等;《分析化学》;20080331;第36卷(第3期);325-329 * |
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