CN1605864A - Method for detecting pesticide residue utilizing the relation between characteristic peak and pesticide concentration - Google Patents
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Abstract
The invention discloses a method for detecting pesticide residue utilizing the relation between characteristic peak and pesticide concentration, wherein standard pesticides are utilized to determine the characteristic ions for each pesticides, an air-mass combination instrument is employed to collect one or more characteristic fragment ionic strength of each standard pesticide, then linear equation and correlation coefficient are obtained through linear regression for the corresponding pesticide content, the color spectrum peak pureness of the tested mixed sample piece is then determined through single scanning mode, then the ion current signal produced by the interfering substance is eliminated, and the content of the tested pesticide is determined through the linear equation.
Description
Technical Field
The invention relates to a quantitative analysis method of pesticide residue, in particular to a method for detecting pesticide residue by using a gas chromatograph-mass spectrometer to respectively determine characteristic peak values of pesticides, performing linear regression on the relationship between the characteristic peak value intensity or the total intensity of a characteristic peak value group and the pesticide concentration and using the relationship between the characteristic peak value and the pesticide concentration.
Background
In the gas-mass combined analysis, whether a chromatographic peak is a single substance or not is confirmed by taking characteristic ion fragments of various components as characteristics, and then quantitative analysis is carried out through a total ion flow diagram. In actual practice, if a chromatographic peak is found to be composed of a plurality of components, it is necessary to change the chromatographic separation conditions to separate the components, but it is difficult to completely separate the components in nature into a single component peak in a chromatographic column. Therefore, the quantitative analysis method of gas-mass combination currently used cannot solve the quantitative problem of the component difficult to separate. For the difficult-to-separate substance pairs, only the total area of chromatographic peaks (mixed ion flow diagram) can be used to give a less accurate quantitative analysis result.
Disclosure of Invention
The invention aims to solve the technical problem of carrying out quantitative analysis by utilizing the linear relation between the characteristic peak intensity (fragment ionic strength) of each pesticide and the pesticide content, thereby solving the quantitative analysis of a single component in a substance difficult to separate.
In order to solve the technical problems, the invention adopts the technical scheme that: a method for detecting pesticide residue by using the relation between characteristic peak intensity and pesticide concentration comprises the following steps:
a. determining characteristic ions of each pesticide by using standard pesticides through a gas-mass spectrometer, giving a base peak of each pesticide, and listing the sequence of the strength of the characteristic ions to obtain a characteristic value of the pesticide;
b. when selecting characteristic ions for analysis, a base peak is generally selected, when the base peaks of certain compounds are the same and the retention time of chromatographic peaks of two components is also the same, the base peak cannot be selected as the characteristic ions for analysis, and second-strong characteristic ions are selected for quantitative analysis according to the strength sequence of the characteristic ion peaks;
c. collecting one or more characteristic fragment ionic strengths in each standard pesticide by a gas-mass spectrometer, and performing linear regression by using the series of data and corresponding pesticide content to obtain a linear equation and a correlation coefficient;
d. judging the chromatographic peak purity of the mixed sample to be detected in a single scanning mode, finding out the characteristic value of the pesticide to be detected in the mixed sample, and eliminating an ion current signal generated by an interfering substance;
e. and calculating the content of the pesticide to be detected by using the obtained characteristic numerical value intensity through the obtained linear equation.
The characteristic values of the pesticides are as follows:
TABLE 1 characteristic values of certain pesticides
The main fragment ions of the nominal molecular weight base peak of the serial number pesticide are from strong to weak
1 Dipterex 25641394145120411203945
2 trifluralin 335434326430643306264
3 simazine 201444420144201
4 metalaxyl 279454520624927945206249279
5Pinebing 293 57 57 85 208 57 85 208
6Butachlor 311 57 57 160 176 188 237 57 160 176 188 237
7 Methylisophosphorus 331585812119958199121
8 Methsulfuron-methyl 38169154269110140691101404215
9 Methylphosphine 260757512126075121260
10 Dimethoate 2298787931258793125
11Different absorption of sulfur and phosphorus 230 88 60 88 109 230 88 60 109 230
12Systemic phosphorus 258 88 60 88 170 258 88 60 170 258
13 iprobenfos 288919120424628891204246288
14 Methamidophos 14194476494141941414764
15 quick-acting Keling 2839667962839628367
16Fenpropathrin 349 97 55 97 125 181 265 97 55 125 181 265
17Chlorpyrifos 349 97 97 197 199 314 316 97 199 197 314 316
18 Phoxim 2981037610312910376129
19 Sterilization pill 2951047610411713026010476260130117
20-metolcarb 165108108108
21Dichlorvos 220 109 79 109 185 109 79 185
22Methyl parathion 263 109 109 125 263 109 125 263
23Parathion 291 109 97 109 291 109 97 291
24 Oxycola 21311058791101561101567958
25Cicada powder 193 121 121 136 121 136
26Fenobucarb 207 121 121 150 121 150
27Fenitrothion 277 125 79 109 125 260 277 125 109 277 260 79
28Fenvalerate 419 125 125 152 167 225 419 125 167 225 419 152
29 Hadamide 1871265512618712655187
30Long-acting phosphorus 223 127 67 97 127 127 67 97
31Malathion 330 127 93 125 127 158 173 127 173 125 93 158
32 chlorotoluron 212132132167132167
33Acephate 183 136 42 47 94 136 136 42 94 47
34Isocarbophos 289 136 94 110 120 136 289 136 120 110 94 289
35 diazinon 304137137179304137179304
36 carbaryl 201144115144144115
37 methidathion 3021458514514585
38 quinalphos 2981469711814615729814615711897298
39 bendiocarb 223151126151166223151126166223
40 Trithion 3421579712115719934215712197342199
41 Dilopyrifos 2171615716116321721916116357217219
42 cypermethrin 4151639112716318120916318191127209
43 Furandan 221164149164164149
44 pirimicarb 2381667216623816672238
45Cyhalothrin 449 181 181 197 208 181 197 208
46Deltamethrin 503 181 77 93 181 253 181 253 93 77
47 Fusha 3671829712118236718212197367
48 atrazine 21520043582002152005821543
49 Ethiophos 3842319712515323138423197153125384
50 prometryn 2412415810518422624124118422658105
51 Fluorocycloprothrin 502250181250252502250252181502
52 chlorothalonil 264266109264266268266264268109
53 Daofeng 32027479931211252742741219312579
54 times sulfur phosphorus 278278109125169278278125109169
55 herbicidal Ether 283283139202283283202139
56 Pistia phosphorus 320285125285287285287125
57 pyrasulfotole 32232265972023223229765202
58 bromothion 364331125329331331329125
In order to ensure the reliability of the detection method and avoid the unexpected components in nature from generating the same ions as the pesticide to be detected, more than two characteristic ions are used for respectively carrying out quantitative determination on a sample.
The invention is characterized in that under electron bombardment, components of a substance are separated into fragment ions representing the characteristics of the substance, and the probability of completely coinciding the characteristic fragment ions of the two components is extremely low like human fingerprints. The characteristic peak value (fragment ion strength) is selected for quantitative analysis, so that the selectivity of the analysis method can be greatly improved, and the result is more accurate. By selecting the characteristic peak values of the components, the components in the chromatographic peak difficult to separate are identified, the problem of non-separation quantitative analysis of the components difficult to separate is solved, and the detection precision is improved.
Drawings
FIG. 1 is a mass spectrum of rice.
FIG. 2 is a mass spectrum of quinalphos.
FIG. 3 is a comparison of total ion flow pattern of phenthoate and quinalphos with single scan ion flow.
FIG. 4 shows the relationship between the concentration and the ionic strength of rice plumping.
FIG. 5 is a linear relationship between the total of the rice plump ionic strength andthe concentration.
Detailed Description
The method for detecting the amount of pesticide residue according to the present invention using the relationship between the characteristic peak intensity and the pesticide concentration will be described in further detail with reference to the following embodiments:
1. the characteristic peak values of various components are found out by utilizing standard pesticides with various concentrations through a gas-mass spectrometer.
a. Conditions of analysis
A chromatographic column: DB-1(30m × 0.25mm i.d. × 0.25 μm), carrier gas: high purity helium gas
Sample inlet temperature: 320 ℃, pressure control mode: the pressure was 100kPa, the split ratio was 10/1, and the column temperature program was:
interface temperature: 320 ℃, EI source temperature: 200 ℃, detector voltage: 0.9kV, ionization voltage: 70V, emission current: 60 μ a, solvent retardation: 5min, scanning mode: single Scan (SIM)
b. Characteristic fragment ion selection of chromatographically difficult components
When selecting the fragment ions characteristic of the difficultly separated components in chromatography, special attention should be paid to the fact that the same fragment ions in the difficultly separated components cannot be taken as characteristic ions. The selection of the characteristic ions of phenthoate and quinalphos is illustrated by taking fig. 1 and fig. 2 as examples.The fragment ions of phenthoate and quinalphos are respectively m/ z 79, 93, 121, 125, 274 and 97, 118, 146, 157 and 298; when selecting the characteristic fragment ions, ions with higher ion intensity should be selected as the characteristic ions. As shown in fig. 1, fragment ions in the hufeng mass spectrum have m/z of 79, 93, 121, 125 and 27; fragment ions m/z in the quinalphos mass spectrum of fig. 2 are 97, 118, 146, 157 and 298; they are respectively phenthoate and quinalphos characteristic ions. The ion for analysis of phenthoate can be 274, and the ion for analysis of quinalphos can be 146.
As shown in Table 1, when the base peaks of some compounds are the same and the retention times of chromatographic peaks of two components are also the same (two pesticides adjacent to each other are drawn in the table), the base peaks cannot be selected as characteristic ions for analysis, and the second-most strong characteristic ions are selected for quantitative analysis according to the order of the intensity of the characteristic ion peaks. For example, the reference peak of fenpropathrin and chlorpyrifos is 97, and when two substances are mixed into one chromatographic peak, 97 cannot be used as an ion for analysis if only one component is detected.
c. Determination of chromatographic Peak purities
As shown in fig. 3, the total ion flow diagram and the single scan ion flow diagram of phenthoate and quinalphos under the above analysis conditions are compared.
As can be seen in fig. 3, the total ion flow diagram curve 1 of the components is a single chromatographic peak, and it cannot be accurately determined whether it is formed of a pure substance. By selecting characteristic fragment ions, 79, 93, 121, 125 and 274 of the phenthoate are scanned to obtain a curve 2, 97, 118, 146, 157 and 298 of the quinalphos are scanned to obtain a curve 3, so that the chromatographic peaks of the fragment ions in the total ion flow graph are obviously separated, whether a single chromatographic peak is formed by a pure substance or not can be determined, and more accurate qualitative analysis can be performed by respectively detecting the contributions of the phenthoate (79, 93, 121, 125 and 274) and the quinalphos (97, 118, 146, 157 and 298) to the total ion flow graph.
2. Preparing series of standard solutions with different concentrations to draw a working curve.
a. Preparing standard rice plumping solutions of 0.1, 0.2, 0.5, 1.0, 2.0, 5.0, 10.0 and 20.0 micrograms/milliliter.
b. And (3) respectively taking 0.6 microliter of the standard solution, and injecting the standard solution into a sample inlet of a gas chromatography-mass spectrometer.
c. Collecting characteristic ionic strength of the phenthoate 274 and mapping with corresponding pesticide concentration to obtain a straight line 4 in figure 4; collecting characteristic ionic strength of the phenthoate 121 and corresponding pesticide concentration to map to obtain a straight line 5 in a graph 4; collecting characteristic ionic strength of the phenthoate 93 and mapping with corresponding pesticide concentration to obtain a straight line 6 in the graph; collecting characteristic ionic strength of phenthoate 79 and corresponding pesticide concentration to plot to obtain a straight line 7 in figure 4; the characteristic ionic strength of phenthoate 125 and the corresponding pesticide concentration are collected and plotted to obtain a straight line 8 in figure 4.
The five groups of data are regressed to obtain the following equation:
component mass to charge ratio regression equation correlation coefficient
Daofengsan 79Y-2677.2X-1607.20.9990
93 Y＝3828.2X-2251.3 0.9990
121 Y＝4447.4X-2640.1 0.9990
125 Y＝2095.6X-1363.9 0.9988
274 Y＝6812.7X-4254.2 0.9989
3. The sum of the ion intensities of a plurality of characteristic fragments is collected by a gas chromatograph-mass spectrometer, and linear regression is carried out by utilizing the series of data and the corresponding component content to obtain the following linear equation and correlation coefficient. See fig. 5.
Component mass to charge ratio regression equation correlation coefficient
121、125、274
4. And (4) judging the purity of chromatographic peaks in a single scanning mode, indicating the characteristic numerical value of the pesticide to be detected in the mixed sample, and eliminating an ion flow signal generated by an interfering substance.
By referring to the data in table 1, looking for characteristic values of the pesticides to be tested in the mixed sample, a single scan was performed on representative fragments of phenthoate (79, 93, 121, 125, 274) and quinalphos (97, 118, 146, 157, 298), respectively, and the contribution of each compound to the total ion flow graph can be seen. When additional pesticides are suspected in the chromatographic peak, a single scan can be performed again according to the data in table 1. As can be seen from fig. 3, the characteristic values representing rice plumpness are: 79. 93, 121, 125, 274
5. And comparing the single scanning result with the result of the total ion flow diagram, and accurately identifying the purity of the chromatographic peak.
Fig. 3 is a comparison of the single scan results with the results of the total ion flow plot, and it is evident that the chromatographic peak is made up of two components. If 79, 93, 121, 125, 274 are used for detecting phenthoate, 97, 118, 146, 157, 298 are used for detecting quinalphos, and if a third component exists, the characteristic value of the component can be selected for quantitative analysis
6. And (4) carrying out quantitative analysis on the sample.
According to the sample pretreatment standard in the national pesticide detection standard, a sample containing the phenthoate pesticide is extracted and enriched, and then 0.6 microliter of the phenthoate pesticide is injected into a sample inlet of a gas chromatography-mass spectrometer.
The characteristic ionic strength with the mass-to-charge ratio of the phenthoate is collected to obtain the residual quantity of the phenthoate in the sample according to a working curve, meanwhile, the characteristic ionic strength with the mass-to-charge ratio of 121 is collected to obtain the residual quantity of the phenthoate in the sample according to the working curve, and when the relative error of the two detection results is less than 5% -10%, the selected characteristic ion is considered as an interference-free component. The minimum detection limit of the method is 0.02 micrograms/ml.
In order to ensure the reliability of the detection method and avoid the unpredictable components in nature from generating the same ions as the pesticide to be detected, more than two characteristic ions are respectively used for quantitatively determining a sample, for example, two (or more) ions in 79, 93, 121, 125 and 274 five ions are used for determining whether the characteristic value representing the rice plumpness has interfering ions or not in the determination of the rice plumpness in the sample, and the relationship between the total intensity and the concentration of the five ions can be used for quantitative analysis only if the determination results of the five ions on the rice plumpness are respectively the same.
Of course, the computer working software of the method can be developed for the workstation of the air-mass spectrometer.
Claims (3)
1. A method for detecting pesticide residue by using the relation between characteristic ionic strength and pesticide concentration is characterized by comprising the following steps:
a. determining characteristic ions of each pesticide by using standard pesticides through a gas-mass spectrometer, giving a base peak of each pesticide, and listing the sequence of the strength of the characteristic ions to obtain a characteristic value of the pesticide;
b. when selecting characteristic ions for analysis, generally selecting a base peak, and when the base peaks of certain compounds are the same and the chromatographic peak retention time of two components is also the same, selecting characteristic ions with second highest intensity according to the intensity sequence of the characteristic ion peaks for quantitative analysis;
c. collecting one or more characteristic fragment ionic strengths in each standard pesticide by a gas-mass spectrometer, and performing linear regression by using the series of data and corresponding pesticide content to obtain a linear equation and a correlation coefficient;
d. judging the chromatographic peak purity of the mixed sample to be detected in a single scanning mode, finding out the characteristic value of the pesticide to be detected in the mixed sample, and eliminating an ion current signal generated by an interfering substance;
e. and calculating the content of the pesticide to be detected by using the obtained characteristic numerical value intensity through the obtained linear equation.
2. The method for detecting the residual amount of agricultural chemicals according to claim 1, wherein the characteristic values of agricultural chemicals are as follows:
TABLE 1 characteristic values of certain pesticides
The main fragment ions of the nominal molecular weight base peak of the serial number pesticide are from strong to weak
1 Dipterex 25641394145120411203945
2 trifluralin 335434326430643306264
3 simazine 201444420144201
4 metalaxyl 279454520624927945206249279
5Pinebing 293 57 57 85 208 57 85 208
6Butachlor 311 57 57 160 176 188 237 57 160 176 188 237
7 Methylisophosphorus 331585812119958199121
8 Methsulfuron-methyl 38169154269110140691101404215
9 Methylphosphine 260757512126075121260
10 Dimethoate 2298787931258793125
11Different absorption of sulfur and phosphorus 230 88 60 88 109 230 88 60 109 230
12Systemic phosphorus 258 88 60 88 170 258 88 60 170 258
13 iprobenfos 288919120424628891204246288
14 Methamidophos 14194476494141941414764
15 quick-acting Keling 2839667962839628367
16Fenpropathrin 349 97 55 97 125 181 265 97 55 125 181 265
17Chlorpyrifos 349 97 97 197 199 314 316 97 199 197 314 316
18 Phoxim 2981037610312910376129
19 Sterilization pill 2951047610411713026010476260130117
20-metolcarb 165108108108
21Dichlorvos 220 109 79 109 185 109 79 185
22Methyl parathion 263 109 109 125 263 109 125 263
23Parathion 291 109 97 109 291 109 97 291
24 Oxycola 21311058791101561101567958
25Cicada powder 193 121 121 136 121 136
26Fenobucarb 207 121 121 150 121 150
27Fenitrothion 277 125 79 109 125 260 277 125 109 277 260 79
28Fenvalerate 419 125 125 152 167 225 419 125 167 225 419 152
29 Hadamide 1871265512618712655187
30Long-acting phosphorus 223 127 67 97 127 127 67 97
31Malathion 330 127 93 125 127 158 173 127 173 125 93 158
32 chlorotoluron 212132132167132167
33Acephate 183 136 42 47 94 136 136 42 94 47
34Isocarbophos 289 136 94 110 120 136 289 136 120 110 94 289
35 diazinon 304137137179304137179304
36 carbaryl 201144115144144115
37 methidathion 3021458514514585
38 quinalphos 2981469711814615729814615711897298
39 bendiocarb 223151126151166223151126166223
40 Trithion 3421579712115719934215712197342199
41 Dilopyrifos 2171615716116321721916116357217219
42 cypermethrin 4151639112716318120916318191127209
43 Furandan 221164149164164149
44 pirimicarb 2381667216623816672238
45Cyhalothrin 449 181 181 197 208 181 197 208
46Deltamethrin 503 181 77 93 181 253 181 253 93 77
47 Fusha 3671829712118236718212197367
48 atrazine 21520043582002152005821543
49 Ethiophos 3842319712515323138423197153125384
50 prometryn 2412415810518422624124118422658105
51 Fluorocycloprothrin 502250181250252502250252181502
52 chlorothalonil 264266109264266268266264268109
53 Daofeng 32027479931211252742741219312579
54 times sulfur phosphorus 278278109125169278278125109169
55 herbicidal Ether 283283139202283283202139
56 Pistia phosphorus 320285125285287285287125
57 pyrasulfotole 32232265972023223229765202
58 bromothion 364331125329331331329125
3. The method for detecting the residual amount of agricultural chemicals according to claim 1, wherein the quantitative determination of a sample is carried out using two or more characteristic ions, respectively, in order to ensure the reliability of the detection method and to avoid the generation of ions identical to the agricultural chemicals to be detected from unpredictable components in nature.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101915809A (en) * | 2010-07-01 | 2010-12-15 | 王冬群 | Detection method of pyrethroid pesticide remained in rice |
| CN103713029A (en) * | 2013-12-19 | 2014-04-09 | 江苏大学 | Electrochemical luminescence sensor for detecting pesticide carbaryl and preparation method thereof |
| CN106198485A (en) * | 2016-06-24 | 2016-12-07 | 北京华泰诺安探测技术有限公司 | A kind of Raman spectrum matching process |
| US10915548B2 (en) * | 2017-04-18 | 2021-02-09 | Chinese Academy Of Inspection And Quarantine | Method of online tracing pesticide residues and visualizing warning on basis of high resolution mass spectrum, internet and geographic information |
| CN113176326A (en) * | 2021-04-26 | 2021-07-27 | 上汽大众汽车有限公司 | Method for detecting methanol content of cleaning solution |
| CN114088685A (en) * | 2021-11-22 | 2022-02-25 | 生态环境部华南环境科学研究所 | Method for rapidly detecting pesticide residues in water body |
| CN114354819A (en) * | 2022-03-15 | 2022-04-15 | 四川德成动物保健品有限公司 | Method and device for detecting residual components of traditional Chinese medicine extract |
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2003
- 2003-10-09 CN CN 200310106605 patent/CN1605864A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101915809A (en) * | 2010-07-01 | 2010-12-15 | 王冬群 | Detection method of pyrethroid pesticide remained in rice |
| CN101915809B (en) * | 2010-07-01 | 2012-10-17 | 王冬群 | Detection method of pyrethroid pesticide remained in rice |
| CN103713029A (en) * | 2013-12-19 | 2014-04-09 | 江苏大学 | Electrochemical luminescence sensor for detecting pesticide carbaryl and preparation method thereof |
| CN103713029B (en) * | 2013-12-19 | 2016-05-25 | 江苏大学 | Electrochemical luminous sensor detecting for agricultural chemicals sevin and preparation method thereof |
| CN106198485A (en) * | 2016-06-24 | 2016-12-07 | 北京华泰诺安探测技术有限公司 | A kind of Raman spectrum matching process |
| CN106198485B (en) * | 2016-06-24 | 2018-10-30 | 北京华泰诺安探测技术有限公司 | A kind of Raman spectrum matching process |
| US10915548B2 (en) * | 2017-04-18 | 2021-02-09 | Chinese Academy Of Inspection And Quarantine | Method of online tracing pesticide residues and visualizing warning on basis of high resolution mass spectrum, internet and geographic information |
| CN113176326A (en) * | 2021-04-26 | 2021-07-27 | 上汽大众汽车有限公司 | Method for detecting methanol content of cleaning solution |
| CN114088685A (en) * | 2021-11-22 | 2022-02-25 | 生态环境部华南环境科学研究所 | Method for rapidly detecting pesticide residues in water body |
| CN114354819A (en) * | 2022-03-15 | 2022-04-15 | 四川德成动物保健品有限公司 | Method and device for detecting residual components of traditional Chinese medicine extract |
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