CN101598708A

CN101598708A - The how residual rapid analysis of agricultural chemicals in a kind of fruit, the vegetables

Info

Publication number: CN101598708A
Application number: CNA2009100155730A
Authority: CN
Inventors: 娄喜山; 付建; 高洪良
Original assignee: YANTAI JIEKE INSPECTION CO Ltd
Current assignee: YANTAI JIEKE INSPECTION CO Ltd
Priority date: 2009-05-19
Filing date: 2009-05-19
Publication date: 2009-12-09
Anticipated expiration: 2029-05-19
Also published as: CN101598708B

Abstract

The invention discloses a kind of fruit, the how residual rapid analysis of agricultural chemicals in the vegetables, be to take by weighing sample, add anhydrous sodium acetate and anhydrous magnesium sulfate, add acetate acetonitrile solution again, after concussion is extracted, carry out centrifugal, the acetonitrile extract that obtains after centrifugal is incorporated with in the centrifuge tube of mixed fillers, concussion, centrifugal, draw scavenging solution, concentrate evaporate to dryness, acetonitrile and water volume ratio are that 1: 1 mixed liquor is fixed molten, UPLC/MS/MS detects, and the present invention is matrix with the fruit and vegetable, utilize matrix to disperse solid phase extraction techniques that sample is carried out pre-service, realize Avermectin in the fruit and vegetable, Aldicarb, the fast detecting of 130 kinds of residues of pesticides such as fly eradication amine, it is quick to have testing result, accurately, efficiently, and cheap characteristics.

Description

The how residual rapid analysis of agricultural chemicals in a kind of fruit, the vegetables

Technical field

The invention belongs to the food detection method technical field, especially relate to the how residual rapid analysis of agricultural chemicals in a kind of fruit, the vegetables.

Background technology

Along with the safety detection of various countries' reinforcement to imported food, as the enforcement of Japanese positive list, various agricultural product limit standards are more and more lower, and the scope that agricultural chemicals relates to is more and more wider, and it is very severe that export situation becomes.When food security receives publicity day by day, each state all make every effort to seek a kind of easy fast, precise and high efficiency, cheap multi-residue analysis method, satisfy the needs of food security in the future.

In recent years, the detecting instrument development is maked rapid progress, yet when instrumental detection efficiency improves, traditional sample pretreatment technology has but restricted the further raising of detection efficiency greatly, detection at residues of pesticides in the fruit and vegetable, existing multi-residue analysis method has GB/T 19648-2006, the analytic approach simultaneously of GB/T20769-2006 and Japan etc., these methods all adopt traditional ultrasonic or homogeneous to extract, the amount of reagent of using is all bigger, add with Solid-Phase Extraction SPE post and carry out enrichment, concentrate, and purification, low and the cost of specimen preparation efficient is than higher, and waste time and energy, be badly in need of a kind of preprocess method efficiently and substitute, under the situation of food security growing interest, seek a kind of method of multi-residue analysis fast, seem particularly important.

Summary of the invention

To the objective of the invention is to improve the deficiency of prior art and provide a kind of be matrix with the fruit and vegetable, utilize matrix disperse solid phase extraction techniques to sample carry out pre-service, the fast detecting that realizes 130 kinds of residues of pesticides such as Avermectin, Aldicarb, fly eradication amine in the fruit and vegetable, testing result fast, accurately, the how residual rapid analysis of agricultural chemicals in the efficient and cheap fruit, vegetables.

The object of the present invention is achieved like this, and the how residual rapid analysis of agricultural chemicals in a kind of fruit, the vegetables is characterized in that this method may further comprise the steps:

A, extraction: take by weighing the sample for preparing, add in the centrifuge tube that contains anhydrous sodium acetate and anhydrous magnesium sulfate, add acetate acetonitrile solution again, concuss after the ultrasonic Extraction, carries out centrifugal;

B, purification: the acetonitrile extract that obtains after centrifugal is incorporated with in the centrifuge tube of mixed fillers, and scavenging solution is drawn in concussion, centrifugal, concentrates evaporate to dryness, and acetonitrile and water volume ratio are that 1: 1 mixed liquor constant volume is to be detected;

C, UPLC/MS/MS detect.

Instrument condition: liquid-phase condition: A:0.1% formic acid water, B:0.1% formic acid acetonitrile

Chromatographic column: ACQUITY UPLC ^TMBEH C18 1.7um 2.1 * 50mm Column

Chromatographic condition:

Time-min	Flow-ml/min-	％A	％B	Curve
Time-min	Flow-ml/min-	％A	％B	Curve	Initial	0.25	60	40
0.3	0.25	60	40	6	Initial	0.25	60	40
0.3	0.25	60	40	6	4	0.25	10	90	6
4.5	0.25	10	90	6	4	0.25	10	90	6
4.5	0.25	10	90	6	5.5	0.25	60	40	1

Mass spectrum condition: multiple-reaction monitoring-MRM scan pattern

Extraction is the sample 15.0g that takes by weighing even sample preparation, adds in the 50mL centrifuge tube that contains 1.5g anhydrous sodium acetate and 6g anhydrous magnesium sulfate, adds 15mL1% acetate acetonitrile solution again, concuss 1min, and behind the ultrasonic Extraction 15min, the centrifugal 1min of 5000r/min.

Purification is to shift 10mL acetonitrile extract in the 15mL centrifuge tube that the different proportion mixed fillers is housed, concussion 1min, the centrifugal 1min of 5000r/min, draw the 5mL scavenging solution, concentrate evaporate to dryness, acetonitrile and water volume ratio are 1: 1 mixed liquor constant volume 2mL, treat that UPLC/MS/MS detects.

The mixed fillers ratio of using is: leaf vegetables, fruits are 1: 1 as the mass ratio of PSA and graphitized carbon, and the oil-containing crop is that the mass ratio of graphitized carbon, PSA, C18 is 1: 2: 2.

Compared with the prior art the present invention has following distinguishing feature and good effect: it is a kind of sample pretreatment technology that the matrix that the present invention adopts is disperseed solid phase extraction techniques, its basic operation be with solid-state or liquid sample directly and the Solid-Phase Extraction material be mixed together grinding, make sample be dispersed in the surface of stationary-phase particle size, form the chromatographic stationary phase of a uniqueness.It has concentrated processes such as traditional sample homogenizing, histocyte cracking, extraction, filtration, purification, makes The pretreatment become easy, has also avoided the loss of object simultaneously.This method is easy and simple to handle, quick, solvent load is few, can carry out qualitatively, quantitative fast at nearly 130 kinds of agricultural chemicals such as Avermectin, Aldicarb, fly eradication amine in the fruit and vegetable, and detection limit can satisfy the detection demand fully, and detection efficiency can promote 3-5 doubly.

Various because of the sample type complexity, be the clean-up effect of realizing can both realizing to different substrates, solid phase extraction filler adopts mixed fillers, and promptly adsorbents such as C18, graphitized carbon, PSA, zeyssatite mix in different ratios, finish the purification to sample.For purification process, use mixing solid phase extraction filler can effectively be removed the fatty acid in the component, pigment, sterol, fat etc. disturb impurity, remove moisture with anhydrous magnesium sulfate again, and the leaching liquor that obtains can carry out the pesticide multi-residues analysis with the UPLC that has high sensitivity MS/MS detecting device.

Compare original purification method, this method is simple to operate, efficient, cost is low, the signal to noise ratio (S/N ratio), the sensitivity that detect can satisfy the demands fully, have realized how residual express-analysis such as Avermectin in the fruit and vegetable, Aldicarb, fly eradication amine, and can satisfy the requirement of detectability.We formulate following mixing solid phase extraction filler and come sample implement is purified at different sample types.

The mixed fillers type

The filler that leaf vegetables, fruits adopt: the mass ratio of PSA and graphitic carbon is 1: 1

Oil-containing crop filler: the mass ratio of graphitized carbon, PSA, C18 is 1: 2: 2

Amount of filler is fixed by concrete sample type.

Clean-up effect is seen Fig. 1.

Description of drawings

Fig. 1 sees figure for clean-up effect.

Embodiment

Embodiment 1, the how residual rapid analysis of agricultural chemicals in a kind of fruit, the vegetables, with the green asparagus is example, prepare 130 kinds of agricultural chemicals hybrid standard product solution, add 0.01mg/kg respectively, the 0.1mg/kg standard sample of pesticide is done recovery, each contents level repeats 4 times, extract then, take by weighing the sample 15.0g of even sample preparation, add in the 50mL centrifuge tube that contains 1.5g anhydrous sodium acetate and 6g anhydrous magnesium sulfate, add 15mL1% acetate acetonitrile solution again, concuss 1min, behind the ultrasonic Extraction 15min, the centrifugal 1min of 5000r/min; Purify, shift 10mL acetonitrile extract in the 15mL centrifuge tube that the different proportion mixed fillers is housed, filler is that the mass ratio of 500mg PSA and graphitized carbon is 1: 1, concussion 1min, the centrifugal 1min of 5000r/min, draw the 5mL scavenging solution, concentrate evaporate to dryness, acetonitrile and water volume ratio are 1: 1 mixed liquor constant volume 2mL; UPLC/MS/MS detects, instrument condition: liquid-phase condition: A:0.1% formic acid water, and B:0.1% formic acid acetonitrile, chromatographic column: ACQUIYT UPLCTM BEH C181.7um 2.1 * 50mm Column, chromatographic condition:

Time-min	Flow-mL/min	％A	％B	Curve
Time-min	Flow-mL/min	％A	％B	Curve	Initial	0.25	60	40
0.3	0.25	60	40	6	Initial	0.25	60	40
0.3	0.25	60	40	6	4	0.25	10	90	6
4.5	0.25	10	90	6	4	0.25	10	90	6
4.5	0.25	10	90	6	5.5	0.25	60	40	1

The average recovery rate and the relative standard deviation of resulting various agricultural chemical compounds see Table 1:

The average recovery rate of the various agricultural chemical compounds of table 1 and relative standard deviation n=4

Table1 Recovery and RSD n＝4

As can be seen from the data, the recovery is at 70%-120%, and relative standard deviation all is not more than 10%, and method detects and is limited to 0.01mg/kg.The recovery and relative standard deviation all meet agricultural residual detection requirement.

Embodiment 2, and the how residual rapid analysis of agricultural chemicals in a kind of fruit, the vegetables is an example with the green soy bean, prepare 28 kinds of agricultural chemicals hybrid standard product solution, do the 0.02mg/kg level and add recovery, each contents level repeats 4 times, extracts then, take by weighing the sample 15.0g of even sample preparation, add in the 50mL centrifuge tube that contains 1.5g anhydrous sodium acetate and 6g anhydrous magnesium sulfate, add 15mL1% acetate acetonitrile solution again, concuss 1min, behind the ultrasonic Extraction 15min, the centrifugal 1min of 5000r/min; Purify, shift 10mL acetonitrile extract in the 15mL centrifuge tube that the different proportion mixed fillers is housed, filler is that the mass ratio of 500mg graphitized carbon, PSA, C18 is mixing in 1: 2: 2, concussion 1min, the centrifugal 1min of 5000r/min, draw the 5mL scavenging solution, concentrate evaporate to dryness, acetonitrile and water volume ratio are 1: 1 mixed liquor constant volume 2mL; UPLC/MSMS detects, instrument condition: liquid-phase condition: A:0.1% formic acid water, B:0.1% formic acid acetonitrile, chromatographic column: ACQUITY UPLC ^TMBEH C18 1.7um 2.1 * 50mmColumn, chromatographic condition:

All between 70%～120%, relative standard deviation all is not more than 10% to the recovery of resulting various agricultural chemical compounds, and method detects and is limited to 0.02mg/kg, and the recovery and relative standard deviation all meet agricultural residual detection requirement, see Table 2

The average recovery rate of the various agricultural chemical compounds of table 2 and relative standard deviation n=4

Table2 Recovery and RSD n＝4

Above-described example only is that preferred implementation of the present invention is described; be not that scope of the present invention is limited; design under the prerequisite of spirit not breaking away from the present invention; various distortion and improvement that the common engineering technical personnel in this area make technical scheme of the present invention all should fall in the definite protection domain of claims of the present invention.

Claims

1, the how residual rapid analysis of agricultural chemicals in a kind of fruit, the vegetables is characterized in that this method may further comprise the steps:

C, UPLC/MS/MS detect.

Chromatographic column: ACQUITYUPLC ^TMBEH C181.7 μ m2.1 * 50mm Column

Chromatographic condition:

Time-min Flow-ml/min ％A ％B Curve Initial 0.25 60 40 0.3 0.25 60 40 6 4 0.25 10 90 6 4.5 0.25 10 90 6 5.5 0.25 60 40 1

Mass spectrum condition: multiple-reaction monitoring-MRM scan pattern.

2, the how residual rapid analysis of agricultural chemicals in a kind of fruit according to claim 1, the vegetables, it is characterized in that extracting is the sample 15.0g that takes by weighing even sample preparation, add in the 50mL centrifuge tube that contains 1.5g anhydrous sodium acetate and 6g anhydrous magnesium sulfate, add 15mL1% acetate acetonitrile solution again, concuss 1min, behind the ultrasonic Extraction 15min, the centrifugal 1min of 5000r/min.

3, the how residual rapid analysis of agricultural chemicals in a kind of fruit according to claim 1, the vegetables, it is characterized in that purifying is to shift 10mL acetonitrile extract in the 15mL centrifuge tube that the different proportion mixed fillers is housed, vibration 1min, the centrifugal 1min of 5000r/min, draw the 5mL scavenging solution, concentrate evaporate to dryness, acetonitrile and water volume ratio are the fixed molten 2mL of 1: 1 mixed liquor, treat that UPLC/MS/MS detects.

4, according to the how residual rapid analysis of agricultural chemicals in claim 1 or 3 described a kind of fruit, the vegetables, it is characterized in that the mixed fillers ratio of using is: leaf vegetables, fruits are 1: 1 as PSA and graphitized carbon mass ratio, and the oil-containing crop is that the mass ratio of graphitized carbon, PSA, C18 is 1: 2: 2.