CN110687225B - HPLC-MS/MS detection method for residual quantity of metazosulfuron-methyl in cereal grains and oil - Google Patents
HPLC-MS/MS detection method for residual quantity of metazosulfuron-methyl in cereal grains and oil Download PDFInfo
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Abstract
The invention discloses an HPLC-MS/MS detection method for the residual quantity of metazosulfuron in cereals and oil plants. Adding sodium chloride into a sample, performing ultrasonic extraction by using acetonitrile, centrifuging, and purifying an extracting solution by using a multi-walled carbon nanotube solid-phase extraction column to obtain a solution to be detected; then qualitative and/or quantitative analysis of metazosulfuron-ethyl was performed by 1290-G6460C high performance liquid chromatography-tandem electrospray triple quadrupole mass spectrometer and Agilent ZORBAX Eclipse Plus C18 chromatography column. The method for detecting the metazosulfuron in the cereal grains and the oil material by using the HPLC-MS/MS for the first time is simple, convenient and easy to operate, and can meet the requirements of rapid detection and confirmation of the metazosulfuron residual quantity in the cereal grains and the oil material.
Description
Technical Field
The invention relates to a detection method, in particular to an HPLC-MS/MS detection method for the residual quantity of metazosulfuron in cereals and oil plants, belonging to the technical field of pesticide residue detection.
Background
Metazosulfuron (metazosulfuron), CAS number: 868680-84-6, formula: c 15 H 18 ClN 7 O 7 S, the structural formula is shown as follows. The metazosulfuron is a sulfonylurea systemic herbicide developed by Nissan chemical company, is mainly used for preventing and killing piemarker, amaranthus retroflexus, crab grass and cockspur grass in paddy fields and wheat fields, is widely applied to paddy fields at present, has good activity and has higher activity (although the action mechanism is the same, the receptors are different) on weeds which the traditional sulfonylurea herbicide generates resistance. Acute percutaneous LD50 of metazosulfuron to WIST rats>2000mg/kg body weight, slight irritation to eyes and skin of New Zealand white rabbit, and acute toxicity to carp LC50>95.1mg/L and acute toxicity to earthworm LC50>1000a.i.mg/kg dry soil, acute toxicity to daphnia EC50(48h)>101mg/L, honeybee LD50 (mouth and contact)>100 mu g/bee, earthworm LC50>1000mg/kg (soil). Toxicity grade: and (III) class.
The reported detection method of metazosulfuron at present only utilizes a liquid chromatography technology to detect a metazosulfuron technical product, and no related report of metazosulfuron detection by utilizing a liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) technology is found at present, and no related report of metazosulfuron in the aspect of crop residue detection is found. At present, the maximum residual limit value of the metazosulfuron on the paddy rice and the brown rice is 0.05mg/kg, but the maximum residual limit value is lack of the residual detection standard of the metazosulfuron.
Disclosure of Invention
Aiming at the problems, the invention provides an HPLC-MS/MS detection method of metazosulfuron in cereals and oil plants. The method combines an improved QuEChERs method with an HPLC-MS/MS technology to establish an analysis method for rapidly detecting the residual quantity of the metazosulfuron in the cereal grains and the oil. The method is simple and convenient, is easy to operate, and can meet the requirement of rapid detection and confirmation of the residual amount of the metazosulfuron in cereals and oil plants.
The technical scheme of the invention is as follows: an HPLC-MS/MS detection method of metazosulfuron-methyl in cereals and oil plants is characterized in that,
1) pretreatment
Taking a sample (grain or oil), adding sodium chloride, ultrasonically extracting by acetonitrile, centrifuging, and purifying an extracting solution (supernate) by using a multi-wall carbon nano tube solid phase extraction column to obtain a solution to be detected;
2) detection
And (3) carrying out qualitative and/or quantitative analysis on the metazosulfuron-ethyl by the liquid to be detected by adopting a high performance liquid chromatography-triple quadrupole tandem mass spectrometer.
The high performance liquid chromatography conditions of the step 2) are as follows: agilent ZORBAX Eclipse Plus C18; column temperature: 35 ℃; sample introduction amount: 3 mu L of the solution; the gradient elution conditions are shown in table 1.
TABLE 1 gradient elution parameters of metazosulfuron mobile phase
The mass spectrum conditions are as follows: an ion source: electrospray ion source ESI; capillary voltage: 4.0 KV; taper hole voltage: 35V; the monitoring mode is as follows: multiple Reaction Monitoring (MRM); flow rate of drying gas: 8.0L/min; the scanning mode is as follows: positive ion scan, ion source temperature 350 ℃.
The retention time, the qualitative ion pair, the quantitative ion and the declustering voltage/collision voltage of the metazosulfuron are shown in table 2.
TABLE 2 analysis parameters of metazosulfuron under tandem mass spectrometry multiple reaction monitoring mode
The pretreatment of the step 1) is specifically as follows:
extraction: weighing 5g of sample, placing the sample in a centrifuge tube, adding 1g of sodium chloride, adding 10mL of acetonitrile, uniformly mixing, performing ultrasonic extraction, and performing refrigerated centrifugation at 8000r/min at-20 ℃; transferring the supernatant to another clean centrifuge tube, extracting the residue with 10mL acetonitrile once, performing refrigerated centrifugation at 8000r/min at-20 deg.C, and mixing the two acetonitrile extractive solutions for purification;
the purification method comprises the following steps: and (3) taking 5mL of the solution, purifying by using a filled multi-walled carbon nanotube solid phase extraction small column (the upper end of which is filled with anhydrous sodium sulfate with the height of 1 cm), eluting by using acetonitrile, collecting effluent, concentrating at 40 ℃ to be nearly dry, fixing the volume to 1.0mL by using methanol, and filtering by using a filter membrane to obtain the solution to be detected.
Furthermore, the mass concentration of the matrix matching standard solution and the peak area of the monitored ion are used as a standard curve, and a linear equation shown in table 3 is adopted to quantify the metazosulfuron in the brown rice and the peanut.
The invention has the beneficial effects that:
1) the invention firstly utilizes HPLC-MS/MS to detect the metazosulfuron in cereals and oil plants
The invention establishes an analysis method for rapidly detecting metazosulfuron residues in cereals and oil materials by combining an improved QuEChERS with an HPLC-MS/MS technology. The method is simple and convenient, is easy to operate, can meet the requirements of rapid detection and confirmation of the residual amount of the metazosulfuron in the cereals and the oil plants, and provides a basis for detecting the residual amount of the metazosulfuron in the cereals and the oil plants.
2) Rapid analysis, high sensitivity
The method adopts 1290-G6460C high performance liquid chromatography-tandem electrospray triple quadrupole mass spectrometer and Agilent ZORBAX Eclipse Plus C18 chromatographic column, optimizes the detection parameters (such as mobile phase, qualitative ion pair and quantitative ion pair) of the high performance liquid chromatography-mass spectrometer, improves the separation efficiency, shortens the sample analysis period (the retention time of a target peak is 2.30min), and is suitable for rapid analysis of the metazosulfuron-methyl residue in grain and oil. The average addition recovery rate of the method is not lower than 82%, the linear range is 0.001-0.5 mg/L, and the limit of quantitation (LOQ) is 0.001 mg/kg; the method is simple, high in sensitivity and good in selectivity.
Drawings
FIG. 1 is total ion current, qualitative ion and quantitative ion diagram detected by metazosulfuron-ethyl;
FIG. 2 is a total ion current, qualitative ion and quantitative ion diagram detected by metazosulfuron-methyl in peanut;
FIG. 3 is a total ion current, qualitative ion and quantitative ion diagram detected by the metazosulfuron in the brown rice;
FIG. 4 is a standard curve of metazosulfuron in methanol solution;
FIG. 5 is a standard curve of metazosulfuron in peanut matrix;
FIG. 6 is a standard curve of metazosulfuron in brown rice matrix.
Detailed Description
1 materials and methods
1.1 test materials
99.1% metazosulfuron, first standard; acetonitrile: chromatographically pure, fish; methanol: superior pure, fish; formic acid: chromatographically pure, CNW; ultrapure water: child haha; QuEChERS material: agilent.
1.2 Main instruments
1290-G6460C high Performance liquid chromatography-tandem electrospray triple quadrupole Mass spectrometer (Agilent, USA); G6460C mass spectrometry system (Agilent, USA); an ultrasonic extractor (ultrasonic instruments ltd, kunshan); high speed refiners (IKA WORK INC T25 Basic, Germany); rotary evaporator (Heidolph LABOROTA 4001, germany); high speed centrifuges (heel Force, hong Kong); laboratory glassware is commonly used.
1.3 instrumental detection conditions
A chromatographic column: agilent ZORBAX Eclipse Plus C18(50 mm. times.2.1 mm, 1.8 μm); column temperature: 35 ℃; sample introduction amount: 3 mu L of the solution; an ion source: electrospray ion source ESI; the scanning mode is as follows: a source of positive ions; capillary voltage: 4.0 KV; taper hole voltage: 35V; ion source temperature: at 350 deg.c. The detection mode is as follows: multiple Reaction Monitoring (MRM); flow rate of drying gas: 8.0L/min. The gradient elution conditions are shown in table 1, above.
And comparing the retention time with the qualitative ion pair information to perform qualitative analysis, and performing quantitative analysis on quantitative ion pairs (parent ions and daughter ions with the highest response value), wherein the retention time, the monitored ions and the declustering voltage/collision voltage of the metazosulfuron are shown in the table 2. The total ion current, the qualitative ion and the quantitative ion map detected by the metazosulfuron are shown in figure 1, and the total ion current, the qualitative ion and the quantitative ion map in the peanut and the brown rice are shown in figures 2-3.
1.4 preparation of Standard solution and drawing of Standard Curve
Accurately weighing 0.001g (accurate to 0.0001 g) of metazosulfuron-ethyl standard in a 10mL volumetric flask, adding methanol to a constant volume to prepare a standard stock solution of 100 mu g/mL, and storing at-20 ℃ in a dark place. Diluting the metazosulfuron standard stock solution with methanol to obtain 0.001, 0.005, 0.01, 0.05, 0.1, 0.5 μ g/mL series of standard solutions.
Processing blank matrix (brown rice, peanut) by 1.5 extraction and purification method to obtain blank matrix extraction purification solution. The standard stock solution of metazosulfuron-ethyl is diluted by blank matrix extraction and purification solution to prepare 0.001, 0.005, 0.01, 0.05, 0.1 and 0.5 mu g/mL matrix matching standard solution.
And then, measuring according to the condition of 1.3, and making a standard curve by matching the mass concentration of the standard solution and the matrix of the metazosulfuron-ethyl with the mass concentration of the standard solution and the peak area of the monitored ion.
1.5 sample pretreatment method
1.5.1 cereal grain (brown rice)
The extraction method comprises the following steps: weighing 5g of sample (accurate to 0.01g) and placing in a 50mL centrifuge tube, adding 1g of sodium chloride and 10mL of acetonitrile, shaking for 5min by a vortex oscillator, mixing uniformly, performing ultrasonic extraction for 15min, and performing refrigerated centrifugation at 8000r/min at-20 ℃ for 10 min. Transferring the supernatant to another clean centrifuge tube, extracting the residue with 10mL acetonitrile, centrifuging at-20 deg.C at 8000r/min for 10min, mixing the two acetonitrile extractive solutions, and purifying.
The purification method comprises the following steps: and accurately weighing 75mg of multi-walled carbon nanotube MWCNTs into a 6mL plastic SPE column tube, fixing a filler in the SPE small column up and down by using a matched 6mL small column sieve plate, and pressing the MWCNTs tightly to keep the height of the filled small column at about 0.3 cm. And (3) filling anhydrous sodium sulfate with the height of about 1cm into the upper end of the filled MWCNTs SPE small column, pre-leaching the small column by using 6mL of acetonitrile, and discarding the leaching solution. And (3) completely transferring the extracting solution to the activated multi-walled carbon nano tube solid phase extraction small column, and collecting the effluent liquid by using a clean 15mL graduated centrifuge tube until all the extracting solution completely passes through the solid phase extraction small column. Then, the elution was carried out with 8mL of acetonitrile, and the flow rate was controlled at 0.5mL/min, and all the effluent was collected. Then concentrating to near dryness at 40 ℃ on a rotary evaporator, metering the volume to 1.0mL by using methanol, and passing through a 0.45 mu m organic filter membrane for the measurement of ultra performance liquid chromatography-tandem mass spectrometry.
1.5.2 oil (peanut)
The extraction method comprises the following steps: weighing 5g of sample (accurate to 0.01g) and placing in a 50mL centrifuge tube, adding 1g of sodium chloride and 10mL of acetonitrile, shaking for 5min by a vortex oscillator, mixing uniformly, performing ultrasonic extraction for 15min, and performing refrigerated centrifugation at 8000r/min at-20 ℃ for 10 min. Transferring the supernatant to another clean centrifuge tube, extracting the residue with 10mL acetonitrile, centrifuging at-20 deg.C at 8000r/min for 10min, mixing the two acetonitrile extractive solutions, and purifying.
The purification method comprises the following steps: and (3) filling anhydrous sodium sulfate with the height of about 1cm into the upper end of the filled MWCNTs SPE small column, pre-leaching the small column by using 6mL of acetonitrile, and discarding the leaching solution. And (3) completely transferring the extracting solution to the activated multi-walled carbon nano tube solid phase extraction small column, and collecting the effluent liquid by using a clean 15mL graduated centrifuge tube until all the extracting solution completely passes through the solid phase extraction small column. Then, the elution was carried out with 8mL of acetonitrile, and the flow rate was controlled at 0.5mL/min, and all the effluent was collected. Then concentrating to near dryness at 40 ℃ on a rotary evaporator, metering the volume to 1.0mL by using methanol, and passing through a 0.45 mu m organic filter membrane for the measurement of ultra performance liquid chromatography-tandem mass spectrometry.
2 results and analysis
2.1 determination of pretreatment method
The method selects a QuEChERS method, and the extraction solvent is acetonitrile. Many of the matrix components of cereal grains and oils have similar properties to pesticides, so that conventional solvents cannot separate the analyte from the matrix, and lipids are not compatible with liquid systems. The comprehensive consideration of acetonitrile has better effects of precipitating protein and reducing impurity interference, and the step of purifying by the QuEChERS technology also takes acetonitrile as a solvent, so the acetonitrile is selected as an optimal extraction solvent in the experiment.
2.2 determination of purification conditions
Although proteins and lipids are insoluble in acetonitrile, a part of the proteins and lipids are extracted, and thus further purification is required. By consulting the literature, three materials of PSA, C18 and GCB, gel chromatography and permeation chromatography (GPC), a C18SPE purifying small column and MWCNTs SPE small columns are selected for purification. Through comprehensive consideration of comparison of purification effect, matrix effect elimination, test cost control, treatment time and the like in practical tests, the MWCNTs SPE small column is finally selected for purification, so that a matrix co-extract can be well removed, the matrix effect is reduced (as can be seen from figures 1-3, the matrix effect is very small and can be ignored), the machine pollution is greatly reduced, and the purification effect meets the test requirements.
2.2 Linear Range and detection limits of the method
Within the range of 0.001-0.5 mg/L, the peak area and the mass concentration of the metazosulfuron are in a good linear relationship, and the linear equation, the correlation coefficient and the lowest detection limit of the metazosulfuron are shown in Table 3 and figures 4-6. The peak area and the mass concentration of the metazosulfuron are in a good linear relationship within the range of 0.001-0.5 mg/L.
TABLE 3 Linear equation, correlation coefficient and minimum detection limit of metazosulfuron-ethyl in different matrices
2.2.2 accuracy and precision
The method comprises the steps of adding standard solutions (n is 3) of 0.01 mu g/mL, 0.1 mu g/mL and 1 mu g/mL into blank brown rice and peanut samples respectively to obtain samples with the addition levels of 0.01, 0.1 and 1mg/kg, carrying out sample pretreatment by a method of 1.5, and then carrying out measurement on the metazosulfuron by a high performance liquid chromatography-triple quadrupole tandem mass spectrometer under the condition of 1.3. The recovery rate and precision of the experimental method were examined. The specific results are shown in Table 4.
TABLE 4 results of the additive recovery of metazosulfuron
As can be seen from Table 4, the average addition recovery rate of the metazosulfuron in cereals and oil crops is 82-91% at three addition levels of 0.01, 0.1 and 1mg/kg, the variation coefficient RSD is 1.5-7.1%, the analysis requirement of pesticide residue is met, and the metazosulfuron can be applied to actual residue.
3 determination of actual samples
10 parts of peanuts and 10 parts of brown rice sold in the Jinan market are randomly extracted, HPLC-MS/MS detection is carried out on the residual quantity of the metazosulfuron-ethyl by adopting the method, and the content of the metazosulfuron-ethyl is less than 0.01mg/kg and meets the regulation.
Claims (5)
1. An HPLC-MS/MS detection method of metazosulfuron in oil is characterized in that,
1) pretreatment
Extraction: weighing 5g of oil material sample, placing the oil material sample in a centrifuge tube, adding 1g of sodium chloride, adding 10mL of acetonitrile, uniformly mixing, performing ultrasonic extraction, and performing refrigerated centrifugation at-20 ℃; transferring the supernatant to another clean centrifugal tube, extracting the residue once with 10mL acetonitrile, freezing and centrifuging at-20 ℃, and combining the two acetonitrile extracting solutions for purification;
the purification method comprises the following steps: taking 5mL of acetonitrile extracting solution, transferring the acetonitrile extracting solution to a filled multi-walled carbon nanotube solid phase extraction small column for purification, collecting effluent liquid by using a centrifugal tube until all the extracting solution completely passes through the solid phase extraction small column, then eluting by using acetonitrile, controlling the flow rate to be 0.5mL/min, collecting all effluent liquid, then concentrating the effluent liquid at 40 ℃ till the effluent liquid is nearly dry, fixing the volume to 1.0mL by using methanol, and filtering by using a filter membrane to obtain a solution to be detected;
2) detection of
Qualitative and quantitative analysis is carried out on the metazosulfuron-methyl by the liquid to be detected by adopting a high performance liquid chromatography-triple quadrupole tandem mass spectrometer;
the high performance liquid chromatography adopts chromatographic columns as follows: an Agilent ZORBAX Eclipse Plus C18 chromatographic column, 50mm × 2.1mm, 1.8 μm; column temperature: 35 ℃; sample introduction amount: 3 mu L of the solution; gradient elution was carried out with 0.1% formic acid water and methanol as mobile phases, and the gradient elution conditions are shown in the following table:
2. the HPLC-MS/MS detection method for metazosulfuron in oil as claimed in claim 1, characterized in that the mass spectrum conditions are as follows: an ion source: electrospray ion source ESI; capillary voltage: 4.0 KV; taper hole voltage: 35V; the monitoring mode is as follows: multiple reaction monitoring, MRM; flow rate of drying gas: 8.0L/min; the scanning mode is as follows: positive ion scan, ion source temperature 350 ℃.
3. The HPLC-MS/MS detection method for metazosulfuron in oil as claimed in claim 2, which is characterized in that the retention time and the qualitative ion pair are used for qualitative analysis, and the quantitative ion pair is used for quantitative analysis, wherein the retention time, the qualitative ion pair, the quantitative ion, the declustering voltage/collision voltage of metazosulfuron are shown in the following table:
4. the HPLC-MS/MS detection method of metazosulfuron-methyl in oil as claimed in claim 1, which is characterized by refrigerated centrifugation at 8000r/min at-20 ℃.
5. An HPLC-MS/MS detection method for metazosulfuron in oil as claimed in any one of claims 1 to 3, characterized in that the quantification in step 2) is: and (3) taking the mass concentration of the matrix matching standard solution and the peak area of the monitored ion as a standard curve to quantify the metazosulfuron-methyl.
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