CN102539559A - Method for quantitatively detecting residual sulfonylurea herbicide trace amount in soil - Google Patents
Method for quantitatively detecting residual sulfonylurea herbicide trace amount in soil Download PDFInfo
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Abstract
The invention discloses a method for quantitatively detecting residual sulfonylurea herbicide trace amount in soil, which comprises the steps of adding soil to be detected into 0.1mol/L sodium bicarbonate water solution with pH7.8, oscillating for 1h, centrifuging for 5min at a speed of 12000r/min, obtaining sediments and primary liquid supernatant, taking the primary liquid supernatant to be adjusted to be in pH2.5 by 0.1M hydrochloric acid water solution, preparing a sample to be detected, and detecting the sample to be detected by a capillary electrophoresis apparatus; and obtaining contents of metsulfuron-methyl, chlorsulfuron and chlorimuron-ethyl in the sample to be detected according to standard curves of the metsulfuron-methyl, the chlorsulfuron and the chlorimuron-ethyl. The method is high in detecting sensitivity, and reaches detection limit with 10-3 microgram/kg grade, wherein the value of the limit of detection with 10-3g/kg grade is higher than that of the detection limit of other methods of an efficient liquid chromatogram and the like (not more than microgram/kg).
Description
(1) technical field
The present invention relates to sulfonylurea herbicide trace residue detection method in a kind of soil, the method for sulfonylurea herbicide trace residue in particularly a kind of detection by quantitative soil.
(2) background technology
Along with the liberation of agrotechnical modernization and yield-power, chemical herbicide has become the main means of control farmland weed harm.Since the eighties in last century, E.I.Du Pont Company released first ultra high efficiency sulfonylurea herbicide (green sulphur is grand); Sulfonylurea herbicide has become the important herbicide of world today's farmland weed control; Also be widely used in China, use tribenuron-methyl+metsulfuron-methyl mixture controlling weeds as 31% rice field is arranged at jiangsu wuxi.This type herbicide consumption is low especially, and the amount of application of per hectare only needs 2～75g active component; And selectivity is strong, and very big to the sensitivity differences of Different Crop, its minimal residue can produce poisoning to late stubble sensitive crop.The residual life of swelling in soil like green sulphur, is longer, has jeopardized non-target plant, and stubble is that the wheatland of corn, soybean, cotton is disabled behind China dry farming area.In wheat rice continuous cropping district, because of the poisoning to paddy rice also can take place in improper use, nineteen ninety-five Shenyang the major accident of the grand hazard rice of green sulphur once took place, cause 533.4hm
2The rice field is injured, wherein 267hm
2Total crop failure; Hebei province in 1992 uses the wheatland behind the metsulfuron-methyl, causes the large tracts of land poisoning for back stubble corn; 1994 in Jiangsu Province the rape field use ethametsulfuron, make the poisoning of back stubble paddy rice occurrence of large-area.In China the report of many sulfonylurea herbicides to late stubble sensitive crop generation poisoning incident arranged, similar report is abroad also arranged.Given this, MRL standard (MRLs) has been formulated to herbicide residue in the farm imports in succession in developed country or areas such as the U.S., European Union, Japan.U.S.'s regulation, from February, 2007, residual the limiting the quantity of of the sulfonylurea herbicide in the rice product is 0.05mg/kg.
The MRL of the flupyrsulfuron-methyl-sodium of the positive list regulation broccoli of Japan, flazasulfuron, azimsulfuron, bensulfuron-methyl is 0.02mg/kg.Foramsulfuron and flazasulfuron are 0.01mg/kg in European Union's regulation lichee.Therefore, it is significant to the residual poisoning of control sulfonylurea herbicide to inquire into the residual analysis determining method of sulfonylurea herbicide.
At present; Measure residual mainly contain high performance liquid chromatography (HPLC), vapor-phase chromatography (GC), chromaticness couplet spectrometry (LC/MS), ELISA and the bioassay method etc. of sulfonylurea herbicide in water and soil; Present these detection methods, its detectability is generally between mg/kg～μ g/kg.
Yet because the sulfonylurea herbicide consumption is low, the low and this low-residual concentration of its corresponding residual concentration characteristic just causes certain difficulty for the assay determination of this compounds in soil, water body, the crop.Therefore, the research of searching sulfonyl urea compound high-sensitivity detecting method has become one of focus of Related Research Domain.
Since capillary electrophoresis technique was born, the research work Showed Very Brisk was particularly advanced about ten years, the report that has a large amount of relevant capillary electrophoresis techniques to use.Capillary electrophoresis technique has been widely used in aspects such as Single Molecule Detection, DNA, protein, Pharmaceutical Analysis, and sensitivity is higher.But relevant capillary electrophoresis technique is applied to sulfonylurea herbicide residue detection report seldom.
The present invention combines with quantitative compensation sulfonylurea herbicide to be measured with extraction is concentrated according to the highly sensitive advantage of capillary electrophoresis technique, has set up multiple sulfonylurea herbicide trace (10 in a kind of while detection by quantitative soil
-3μ g/kg level) capillary electrophoretic analysis method of residue detection has obtained satisfied result.
(3) summary of the invention
The object of the invention provides multiple sulfonylurea herbicide trace (10 in a kind of while detection by quantitative soil
-3μ g/kg level) capillary electrophoretic analysis method of residue detection.
The technical scheme that the present invention adopts is:
The method of sulfonylurea herbicide trace residue in a kind of detection by quantitative soil, said method is: soil sample to be measured is added in the 0.1mol/L sodium bicarbonate aqueous solution of pH7.8 vibration 1h; The centrifugal 5min of 12000r/min must precipitate and primary supernatant, gets after primary supernatant transfers pH to 2.5 with the 0.1M aqueous hydrochloric acid solution; The pretreated C18 post of packing into is used eluent methylene chloride again, collects to drench fluid; The pouring fluid is concentrated into dried, and concentrate obtains lysate with the dissolving of volumetric concentration 60% methanol aqueous solution; With adding the hybrid standard storing solution in the lysate, add volumetric concentration 60% methanol aqueous solution constant volume again and process mixed liquor, make the grand standard chlorine Sulfometuron Methyl final concentration that reaches of the green sulphur of adding in the mixed liquor of standard metsulfuron-methyl, standard be 5mg/L; Obtain testing sample, testing sample is tested with HPCE; Grand and the chlorimuronethyl typical curve according to metsulfuron-methyl, green sulphur obtains metsulfuron-methyl in the testing sample, green sulphur is grand or the content of chlorimuronethyl, again according to formula (1) calculate wait survey metsulfuron-methyl in the soil sample, green sulphur is grand or the content of chlorimuronethyl; Said hybrid standard storing solution is the mixed solution that the grand and standard chlorine Sulfometuron Methyl final concentration of standard metsulfuron-methyl, the green sulphur of standard is 100mg/L.
Metsulfuron-methyl, the grand content that reaches chlorimuronethyl concentration of green sulphur calculate according to formula (1) in the soil: amount
formula (1) that soil sulfometuronmethyl, rimsulfuron 25 or chlorine sulphur are grand
In the formula (1): ρ-calculate metsulfuron-methyl in the acquisition liquid to be measured, the grand concentration (mg/L) that reaches chlorimuronethyl of green sulphur according to typical curve;
V
1---constant volume (mL);
The quality of m---oven-dried soil (g);
Said HPCE test condition is: HPCE adopts the UV detecting device; The quartz capillary of internal diameter 75 μ m, effective column length 50cm; When HPCE is started shooting at every turn; With 0.1mol/L hydrochloric acid flushing pillar, wash capillary column 10min, 5min and 20min respectively with 0.1mol/L NaOH, deionized water, damping fluid successively then earlier.Wash capillary column 2min with damping fluid before each sample introduction; With 0.1mol/L NaOH flushing capillary column 10min, use deionized water rinsing 5min again, detection wavelength: 214nm, separation voltage: 25kV, temperature when finish analyzing: 35 ℃, sample introduction 3800Pa * 10 second, sample size 10 μ L.
Said buffer solution is pH5.0 glacial acetic acid-ammonium acetate buffer solution, and said buffer solution is made up of the following raw material of final concentration: 50mmol/L glacial acetic acid, 50mmol/L ammonium acetate, 80mmol/L SDS, volumetric concentration 14% methyl alcohol, volumetric concentration 20% isopropyl alcohol.
Further, said method is: will wait in the 0.1mol/L sodium bicarbonate aqueous solution of surveying soil sample adding pH7.8 vibration 1h; The centrifugal 5min of 12000r/min must precipitate and primary supernatant, and said deposition repeats vibration extraction 1h with the 0.1mol/L sodium bicarbonate aqueous solution of pH7.8 again; Centrifugal, repeat 2 times, incorporate the supernatant that repeats to extract for 2 times into described primary supernatant; Total supernatant of getting merging is transferred the pretreated C18 post of packing into behind the pH to 2.5 with the 0.1M aqueous hydrochloric acid solution, uses eluent methylene chloride again, collects and drenches fluid; The pouring fluid is concentrated into dried, and concentrate obtains lysate with the dissolving of volumetric concentration 60% methanol aqueous solution; With adding the hybrid standard storing solution in the lysate, add volumetric concentration 60% methanol aqueous solution constant volume again and process mixed liquor, make the grand standard chlorine Sulfometuron Methyl final concentration that reaches of the green sulphur of adding in the mixed liquor of standard metsulfuron-methyl, standard be 5mg/L; Obtain testing sample, testing sample is tested with HPCE; Grand and the chlorimuronethyl typical curve according to metsulfuron-methyl, green sulphur obtains metsulfuron-methyl in the testing sample, green sulphur is grand or the content of chlorimuronethyl, again according to formula (1) calculate wait survey metsulfuron-methyl in the soil sample, green sulphur is grand or the content of chlorimuronethyl; Said hybrid standard storing solution is the mixed solution that the grand and standard chlorine Sulfometuron Methyl final concentration of standard metsulfuron-methyl, the green sulphur of standard is 100mg/L; The pre-service of said C18 post discards leacheate for using methyl alcohol and redistilled water drip washing C18 post successively.
Compared with prior art, beneficial effect of the present invention is mainly reflected in: the inventive method detection sensitivity is high, and detectability reaches 10
-3μ g/kg level is higher than the detection limit value (being no more than μ g/kg) of other existing methods such as high performance liquid chromatography.
(4) description of drawings
Fig. 1 typical curve: A is that peak area and metsulfuron-methyl concentration linear standard curve, B are that peak area and chlorimuronethyl linear standard curve, C are the grand concentration linear standard curve of peak area and green sulphur
Metsulfuron-methyl, chlorimuronethyl and the grand capillary electrophoretic separation collection of illustrative plates of green sulphur in the different samples of Fig. 2, wherein a does not add the sulfonylurea herbicide pedotheque (to organize a); B adds 10 * 10
-3μ g/kg sulfonylurea herbicide pedotheque (group b); C adds 10 * 10
-3Add the sample (group c) of 5mg/L sulfonylurea herbicide in the μ g/kg sulfonylurea herbicide pedotheque, 1 is the metsulfuron-methyl absorption peak among b and the c, and 2 is the chlorimuronethyl absorption peak, and 3 is the grand absorption peak of green sulphur.
(5) embodiment
Below in conjunction with specific embodiment the present invention is described further, but protection scope of the present invention is not limited in this:
1, medicament and material
Metsulfuron-methyl, grand, the chlorimuronethyl standard items (U.S. Chemical Service company) of green sulphur.
Methyl alcohol, isopropyl alcohol (chromatographically pure level); Ammonium acetate, glacial acetic acid, hydrochloric acid, soda mint, NaOH sodium dodecylsulphonate (SDS) (analyzing pure level); The C18 post.
2, key instrument
HPCE (Beckman P/ACE System 5000), pH meter.
3, solution preparation and testing conditions
(1) solution preparation
1. sulphur is grand, green sulphur grand and the accurate weighing metsulfuron-methyl of chlorimuronethyl hybrid standard storing solution, green sulphur is grand and each 10mg of chlorimuronethyl is miscible in 100mL methanol-water (60: 40; V/v) in the mixed solvent, the grand and chlorimuronethyl concentration of metsulfuron-methyl, green sulphur is respectively 100mg/L hybrid standard storing solution, 4 ℃ keep in Dark Place in refrigerator.
2. damping fluid takes by weighing the 3g glacial acetic acid and the 3.65g ammonium acetate is dissolved in certain water gaging, moves in the volumetric flask of 1L, in this volumetric flask, adds 27.6g SDS, 140mL methyl alcohol and 200mL isopropyl alcohol simultaneously; Use the distilled water constant volume; Regulate pH to 5.0, obtain glacial acetic acid-ammonium acetate buffer, i.e. glacial acetic acid 50mmol/L, ammonium acetate 50mmol/L, SDS80mmol/L; 14% methyl alcohol (v/v), 20% isopropyl alcohol (v/v).
3. 0.1mol/L hydrochloric acid and 0.1mol/L sodium hydroxide solution pipette 9mL and analyze pure concentrated hydrochloric acid to the volumetric flask of L, use the distilled water constant volume, obtain 0.1mol/L hydrochloric acid; Take by weighing the 4g dissolution of sodium hydroxide in certain water gaging, move in the volumetric flask of 1L, use the distilled water constant volume, obtain the 0.1mol/L sodium hydroxide solution.
4. 0.1mol/L soda mint (pH7.8) solution takes by weighing the 8.4g soda mint and is dissolved in certain water gaging, moves in the volumetric flask of 1L, use the distilled water constant volume, regulates pH to 7.8, acquisition 0.1mol/L soda mint (pH7.8) solution.
5. the methanol aqueous solution of volumetric concentration 60% is methanol-water (60: 40; V/v) solution: in the volumetric flask of 1L, add 600mL methyl alcohol and 400mL water, promptly obtain methanol-water (60: 40; V/v) solution.
(2) testing conditions
It is the UV detecting device that HPCE adopts accessory, the quartz capillary of internal diameter 75 μ m, effective column length 50cm.When HPCE is started shooting at every turn, with 0.1mol/L hydrochloric acid flushing pillar, wash capillary column 10min, 5min and 20min respectively with 0.1mol/L NaOH, deionized water, damping fluid successively then earlier.Wash capillary column 2min with damping fluid before each sample introduction; With 0.1mol/L NaOH flushing capillary column 10min, use deionized water rinsing 5min again when finishing to analyze.Detect wavelength: 214nm, separation voltage: 25kV, temperature: 35 ℃, sample introduction 3800Pa * 10 second, sample size 10 μ L.
Embodiment 1 typical curve is drawn
Pipette respectively in 100mg/L hybrid standard storing solution to the 7 5mL volumetric flask of 25,50,100,200,300,400 and 500 μ L, with methanol-water (60: 40; V/v) mixed solvent constant volume, obtain metsulfuron-methyl, green sulphur is grand and chlorimuronethyl concentration be respectively 0.5,1.0,2.0,4.0,6.0,8.0 with the mixed standard solution of 10mg/L, adopt above-mentioned testing conditions to carry out Capillary Electrophoresis and detect.Adopt peak area and metsulfuron-methyl, the grand chlorimuronethyl concentration drawing typical curve separately that reaches of green sulphur, the working stamndard curve is used for metsulfuron-methyl, green sulphur is grand and the residual quantitative Analysis of chlorimuronethyl, and the result sees Fig. 1.
Take by weighing the heavy soil sample of 100g oven-dried soil in the 500mL triangular flask, add 200mL 0.1mol/L soda mint (pH7.8) WS, build vibration 1h with rubber stopper, in the centrifugal 5min of 12000r/min.Obtain supernatant, extract residue and extract twice with identical sodium bicarbonate solution again, the gained supernatant is merged.Supernatant after the merging is transferred pH to 2.5 with the 0.1M hydrochloric acid solution; And the C18 post of packing into (the C18 post is earlier through with activation of 10mL methyl alcohol and the passivation of 10mL redistilled water; Discard and drench fluid), use 10mL eluent methylene chloride C18 post again, collect and drench fluid; Be concentrated into driedly with rotary evaporator, concentrate was with 1mL methanol-water (60: 40; V/v) mixed solvent dissolving changed in the 5mL volumetric flask, and in volumetric flask, adds the 100mg/L hybrid standard storing solution of 25 μ L, with methanol-water (60: 40; V/v) the mixed solvent constant volume makes the metsulfuron-methyl of adding in the volumetric flask, green sulphur is grand and the chlorimuronethyl final concentration is 5mg/L; Test with Capillary Electrophoresis behind the constant volume; Method of testing is the same; According to typical curve, calculate metsulfuron-methyl, the grand chlorimuronethyl concentration that reaches of green sulphur, swell and the chlorimuronethyl residual concentration according to metsulfuron-methyl, green sulphur in formula (1) the calculating soil.
Metsulfuron-methyl, the grand content that reaches chlorimuronethyl concentration of green sulphur calculate according to formula (1) in the soil: amount
formula (1) that soil sulfometuronmethyl, rimsulfuron 25 or chlorine sulphur are grand
In the formula (1): ρ-typical curve calculates and obtains metsulfuron-methyl in the liquid to be measured, green sulphur is grand and the concentration (mg/L) of chlorimuronethyl;
V
1---constant volume (mL);
The quality of m---oven-dried soil (g);
Trace metsulfuron-methyl, the grand mensuration that reaches chlorimuronethyl of green sulphur in the embodiment 3 paddy soil samples
(1) soil: the pedotheque that is used to detect picks up from rice field, Greater, Hangzhou, Zhejiang province.This soil sample was not used sulfonylurea herbicide, and the soil texture is a sandy loam, clay content 18.0%, silt content 55.2%, grains of sand content 26.8%, pH4.74, the content of organic matter 1.82%.
(2) the hybrid standard storing solution of 1mg/L
Respectively accurate weighing metsulfuron-methyl, green sulphur is grand, each 1mg of chlorimuronethyl is miscible in the 1L redistilled water, obtains to contain metsulfuron-methyl, green sulphur is grand, chlorimuronethyl concentration is respectively 1mg/L hybrid standard storing solution.
(3) detection sensitivity
Experiment is divided into 3 groups; Group a, group b and group c, wherein organizing a is control group, does not add the hybrid standard storing solution of 1mg/L; Group b and group c are experimental group, and the hybrid standard storing solution that adds 1mg/L is respectively processed and contained that metsulfuron-methyl, green sulphur are grand, chlorimuronethyl concentration is 10 * 10 respectively
-3The soil sample of μ g/kg is organized simultaneously in the pouring fluid of extract behind C18 post wash-out of c and is added 1mg/L hybrid standard storing solution, makes that the metsulfuron-methyl of adding, green sulphur are grand, the chlorimuronethyl final concentration is 5 μ g/L.
Take by weighing 3 parts of 500g (oven-dried soil meter) soil sample respectively in 3 beakers; Be respectively group a, group b and group c; In group a, group b and group add 0,5 among the c respectively, the 1mg/L hybrid standard storing solution of 5mL; Abundant mixing, group a obtain to contain that metsulfuron-methyl, green sulphur are grand, chlorimuronethyl is 0 μ g/kg, and group b and group c obtain to contain that metsulfuron-methyl, green sulphur are grand, chlorimuronethyl is 10 * 10
-3μ g/kg.3 groups of soil samples are crossed the 1mm sieve, in-20 ℃ of refrigerated storage.Take by weighing respectively the freezing soil sample of 100g (group a), the freezing soil sample of 200g (group b with group c), in 3 500mL triangular flasks, group a～group c adds 200mL 0.1mol/L sodium bicarbonate solution respectively; Build vibration 1h with rubber stopper,, obtain supernatant in the centrifugal 5min of 12000r/min; Extract residue and extract twice with the 0.1mol/L sodium bicarbonate solution again, each group gained supernatant is merged respectively, the supernatant after merging is respectively transferred pH to 2.5 with the 0.1mol/L hydrochloric acid solution; (the C18 post passes through with activation of 10mL methyl alcohol and the passivation of 10mL redistilled water to be respectively charged into the C18 post; Discard and drench fluid), use 10mL eluent methylene chloride C18 post more respectively, collect respectively and drench fluid (group a～group c); Be concentrated into driedly respectively with rotary evaporator, residue was with 1mL methanol-water (60: 40; V/v) mixed solvent dissolving (wherein organize metsulfuron-methyl among a, green sulphur sample concentration coefficient grand, chlorimuronethyl is 100, metsulfuron-methyl among group b and the group c, green sulphur are grand, chlorimuronethyl is 10 * 10
-3The sample concentration coefficient of μ g/kg is 200), change over to respectively (group a～group c) in 3 5mL volumetric flasks, and in the volumetric flask of group c, add the 100mg/L hybrid standard storing solution of 25 μ L, group a～group c uses methanol-water (60: 40 respectively; V/v) mixed solvent constant volume; With the Capillary Electrophoresis test, method of testing is calculated metsulfuron-methyl, the grand chlorimuronethyl concentration that reaches of green sulphur with the above according to typical curve behind the constant volume; Calculate metsulfuron-methyl in the pedotheque, the grand chlorimuronethyl concentration that reaches of green sulphur according to formula (1) again, the result sees Fig. 2.
Measure separating effect and see Fig. 2; Fig. 2 is that metsulfuron-methyl in the different samples (1), green sulphur grand (3) separate spectrogram with the capillary electrophoresis separation of chlorimuronethyl (2); Can find out from a of Fig. 2 during not adding the soil testing sample of herbicide, do not have metsulfuron-methyl, green sulphur is grand and the retention time of chlorimuronethyl and absorption peak occur, and shows by metsulfuron-methyl, green sulphur is grand and chlorimuronethyl pollutes.Can know that from the b of Fig. 2 soil adds 10 * 10
-3Behind the grand and chlorimuronethyl of μ g/kg metsulfuron-methyl, green sulphur; Concentrate 100 times after capillary electrophoresis separation metsulfuron-methyl occurs in metsulfuron-methyl, the grand position of corresponding retention time with chlorimuronethyl of green sulphur, green sulphur is grand and the absorption peak of chlorimuronethyl through extracting; But absorption intensity a little less than; Unstability of base line, it is bigger disturbed by soil constitution.In order to strengthen the grand and chlorimuronethyl separating effect of metsulfuron-methyl, green sulphur; Strengthen the absorption peak absorption intensity; Treating after soil extract concentrates 100 times added the 5mg/L metsulfuron-methyl in the test in the test sample, green sulphur is grand and chlorimuronethyl, and its capillary electrophoresis separation spectrogram is seen the c of Fig. 2, can find out that therefrom metsulfuron-methyl, green sulphur swell and the chlorimuronethyl separating effect is better; The absorption peak absorption intensity is bigger; Baseline is steady, and it is less disturbed by soil constitution, and metsulfuron-methyl, green sulphur swell and chlorimuronethyl absorption peak peak area is increased to 35% of whole capillary electrophoresis separation spectrogram absorption peak peak area; Metsulfuron-methyl in the soil to be measured in view of the above, green sulphur is grand and chlorimuronethyl content can calculate through working curve and obtains, and visible corresponding interference can be got rid of through the testing compound of adding quantitative concentrations.This shows and adopt the method to have higher sensitivity, can detect in the soil 10
-3The metsulfuron-methyl of μ g/kg, green sulphur swell and the chlorimuronethyl trace residue.
(4) recovery
Take by weighing 30 parts of 500g (oven-dried soil meter) soil sample respectively in 30 beakers; Be divided into 3 groups, be respectively group d, group e and group f, in group d, group e and group add 5,10 among the f respectively, the 1mg/L hybrid standard storing solution of 25mL; Abundant mixing obtains to contain that metsulfuron-methyl, green sulphur are grand, chlorimuronethyl is 10 * 10
-3μ g/kg (group d), 20 * 10
-3μ g/kg (group e) and 50 * 10
-3The soil sample of μ g/kg (group f) is crossed the 1mm sieve with 3 groups of soil samples, in-20 ℃ of refrigerated storage.Take by weighing freezing soil sample of 100g (group e and group f) and the freezing soil sample of 200g (group d) respectively, in 30 500mL triangular flasks, add 200mL 0.1mol/L sodium bicarbonate solution respectively; Build vibration 1h with rubber stopper,, obtain supernatant in the centrifugal 5min of 12000r/min; Extract residue and extract twice with the 0.1mol/L sodium bicarbonate solution again, each group gained supernatant is merged respectively, the supernatant after merging is respectively transferred pH to 2.5 with the 0.1mol/L hydrochloric acid solution; (the C18 post passes through with activation of 10mL methyl alcohol and the passivation of 10mL redistilled water to be respectively charged into the C18 post; Discard and drench fluid), use 10mL eluent methylene chloride C18 post more respectively, collect respectively and drench fluid (group d～group f); Be concentrated into driedly with rotary evaporator, residue is used 1mL methanol-water (60: 40 respectively; V/v) (wherein grand, the chlorimuronethyl of metsulfuron-methyl, green sulphur is 20 * 10-3 μ g/kg or 50 * 10 in mixed solvent dissolving
-3The sample concentration coefficient of μ g/kg is 100, and metsulfuron-methyl, green sulphur swell, chlorimuronethyl is 10 * 10
-3The sample concentration coefficient of μ g/kg is 200), change over to respectively in 30 5mL volumetric flasks, and in volumetric flask, add the 100mg/L hybrid standard storing solution of 25 μ L, use methanol-water (60: 40 more respectively; V/v) mixed solvent constant volume, with the Capillary Electrophoresis test, assay method is with embodiment 2 behind the constant volume.
The recovery that metsulfuron-methyl, green sulphur swell and chlorimuronethyl extraction back is measured in 30 duplicate samples is seen table 1.Can find out that from table 1 metsulfuron-methyl, green sulphur swell and chlorimuronethyl three's average recovery rate is respectively: 97.7 ± 1.6%, 96.0 ± 1.4% and 98.6 ± 2.3%; And 10～50 * 10
-3The recovery did not receive metsulfuron-methyl in μ g/kg enclosed, green sulphur is grand and the influence of chlorimuronethyl concentration, showed that capillary electrophoresis method is that trace and multiple sulfonylurea herbicide are mixed residual effective separation and method for measuring.
The grand recovery of metsulfuron-methyl, chlorimuronethyl and green sulphur in the table 1. variable concentrations sample
Claims (5)
1. the method for sulfonylurea herbicide trace residue in the detection by quantitative soil is characterized in that said method is: will wait and survey in the 0.1mol/L sodium bicarbonate aqueous solution that soil sample adds pH7.8 vibration 1h; The centrifugal 5min of 12000r/min must precipitate and primary supernatant, gets primary supernatant and transfers pH to 2.5 with the 0.1M aqueous hydrochloric acid solution; The pretreated C18 post of packing into is used eluent methylene chloride again, collects to drench fluid; The pouring fluid is concentrated into dried, and concentrate obtains lysate with the dissolving of volumetric concentration 60% methanol aqueous solution; With adding the hybrid standard storing solution in the lysate, add volumetric concentration 60% methanol aqueous solution again and process mixed liquor, make the grand standard chlorine Sulfometuron Methyl final concentration that reaches of the green sulphur of adding in the mixed liquor of standard metsulfuron-methyl, standard be 5mg/L; Obtain testing sample, testing sample is tested with HPCE; Grand and the chlorimuronethyl typical curve according to metsulfuron-methyl, green sulphur obtains metsulfuron-methyl in the testing sample, green sulphur is grand or the content of chlorimuronethyl; Said hybrid standard storing solution is the mixed solution that the grand and standard chlorine Sulfometuron Methyl final concentration of standard metsulfuron-methyl, the green sulphur of standard is 100mg/L.
2. detection method as claimed in claim 1; It is characterized in that said HPCE test condition is: HPCE adopts the UV detecting device; The quartz capillary of internal diameter 75 μ m, effective column length 50cm; When HPCE is started shooting at every turn, with 0.1mol/L hydrochloric acid flushing pillar, wash capillary column 10min, 5min and 20min respectively with 0.1mol/L NaOH, deionized water, damping fluid successively then earlier.Wash capillary column 2min with damping fluid before each sample introduction; With 0.1mol/L NaOH flushing capillary column 10min, use deionized water rinsing 5min again, detection wavelength: 214nm, separation voltage: 25kV, temperature when finish analyzing: 35 ℃, sample introduction 3800Pa * 10 second, sample size 10 μ L.
3. detection method as claimed in claim 2; It is characterized in that said buffer solution is pH5.0 glacial acetic acid-ammonium acetate buffer solution; Said buffer solution is made up of the following raw material of final concentration: 50mmol/L glacial acetic acid, 50mmol/L ammonium acetate, 80mmol/L SDS; Volumetric concentration 14% methyl alcohol, volumetric concentration 20% isopropyl alcohol.
4. detection method as claimed in claim 1; It is characterized in that said deposition repeats vibration extraction 1h with the 0.1mol/L sodium bicarbonate aqueous solution of pH7.8 again; Centrifugal; Repeat 2 times, incorporate the supernatant that repeats to extract for 2 times into described primary supernatant, total supernatant of getting merging is transferred the pretreated C18 post of packing into behind the pH to 2.5 with the 0.1M aqueous hydrochloric acid solution.
5. like claim 1 or 4 described detection methods, it is characterized in that the pre-service of said C18 post for using methyl alcohol and redistilled water drip washing C18 post successively, discards leacheate.
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| CN105699550A (en) * | 2016-02-26 | 2016-06-22 | 环境保护部南京环境科学研究所 | Analysis method applied to measuring residual quantity of sulfonylurea herbicide in plants |
| CN109254068A (en) * | 2018-07-13 | 2019-01-22 | 湖南人文科技学院 | A kind of method of quick detection organic heterocyclic class herbicide residue |
| CN114235522A (en) * | 2021-12-08 | 2022-03-25 | 中国科学院东北地理与农业生态研究所 | Kit and method for detecting ureide content and allantoic acid content in plant |
| CN114660190A (en) * | 2021-12-24 | 2022-06-24 | 浙江中一检测研究院股份有限公司 | Method for detecting pesticide residue of weedicide in soil |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102901782A (en) * | 2012-10-30 | 2013-01-30 | 湖南省烟草公司郴州市公司 | Residue detection method for quinclorac in tobacco leaf and tobacco planting soil |
| CN102901782B (en) * | 2012-10-30 | 2013-10-30 | 湖南省烟草公司郴州市公司 | Residue detection method for quinclorac in tobacco leaf and tobacco planting soil |
| CN105699550A (en) * | 2016-02-26 | 2016-06-22 | 环境保护部南京环境科学研究所 | Analysis method applied to measuring residual quantity of sulfonylurea herbicide in plants |
| CN105699550B (en) * | 2016-02-26 | 2017-08-25 | 环境保护部南京环境科学研究所 | A kind of analysis method for being applied to determine sulfonylurea herbicide residual quantity in plant |
| CN109254068A (en) * | 2018-07-13 | 2019-01-22 | 湖南人文科技学院 | A kind of method of quick detection organic heterocyclic class herbicide residue |
| CN114235522A (en) * | 2021-12-08 | 2022-03-25 | 中国科学院东北地理与农业生态研究所 | Kit and method for detecting ureide content and allantoic acid content in plant |
| CN114235522B (en) * | 2021-12-08 | 2023-05-02 | 中国科学院东北地理与农业生态研究所 | Kit and method for detecting ureide content and allantoin content in plants |
| CN114660190A (en) * | 2021-12-24 | 2022-06-24 | 浙江中一检测研究院股份有限公司 | Method for detecting pesticide residue of weedicide in soil |
| CN114660190B (en) * | 2021-12-24 | 2024-05-14 | 浙江中一检测研究院股份有限公司 | Method for detecting herbicidal ether pesticide residues in soil |
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