JP5395847B2 - Residual pesticide automatic pretreatment system and residual pesticide extraction method using the same - Google Patents

Residual pesticide automatic pretreatment system and residual pesticide extraction method using the same Download PDF

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JP5395847B2
JP5395847B2 JP2011135294A JP2011135294A JP5395847B2 JP 5395847 B2 JP5395847 B2 JP 5395847B2 JP 2011135294 A JP2011135294 A JP 2011135294A JP 2011135294 A JP2011135294 A JP 2011135294A JP 5395847 B2 JP5395847 B2 JP 5395847B2
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sample
container
sample container
extraction solvent
extraction
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JP2013003003A (en
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大貴 奥田
敏広 山田
治 畠山
桂 飛石
雅美 加藤
寿晴 黒田
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日清食品ホールディングス株式会社
システム・インスツルメンツ株式会社
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  The present invention relates to an automatic pretreatment system for residual agricultural chemicals and a method for extracting residual agricultural chemicals using the same.

  In recent years, interest in food safety has increased. In particular, a positive list system that prohibits the sale of foods with pesticides remaining in excess of a certain amount of pesticides, feed additives and veterinary drugs (pesticides, etc.) remaining in food in May 2003 It has been in effect since 29th. Related to this, “Testing Methods for Substances in Agricultural Chemicals, Feed Additives or Veterinary Drug Residues in Foods” (Food Safety Issue No. 0124001 dated January 24, 2005, Ministry of Health, Labor and Welfare In the Food Safety Department Manager Notice), simultaneous testing methods for pesticides, etc. are stipulated.

  By the way, in the residual pesticide inspection, pretreatment is required for inspection objects such as agricultural products. An automatic pretreatment apparatus for residual agricultural chemicals that automatically and consistently performs this pretreatment with a single apparatus is disclosed (Patent Document 1).

JP-A-6-3233

  The pretreatment of inspection items such as agricultural products in the inspection of residual agricultural chemicals takes a lot of time and effort, and there is still a strong demand for automating this. In addition, the positive list system prohibits the sale, etc., of pesticides, etc., for which no residue standard has been established, exceeding a certain amount (0.01 ppm). Therefore, there is a need for an automatic pretreatment system that reduces the contamination of components derived from other specimens (also referred to as “cross-contamination” in the present specification).

  In the automatic pretreatment apparatus for residual agricultural chemicals described in Patent Document 1, a solution such as a solvent containing the extracted residual agricultural chemicals is sent out through the pipe (tube) in the order of the processes, so the inside of the pipe needs to be washed well And a large amount of cleaning solvent is required for cleaning the inside of the pipe. Further, since the pipe has a long flow path, there is a possibility of cross contamination and a reduction in the recovery rate, and a further improved automatic pretreatment apparatus has been demanded.

  Therefore, the present invention provides an automatic pretreatment system for residual agricultural chemicals that can automate the pretreatment of inspection items such as agricultural products in the inspection of residual agricultural chemicals, extract residual agricultural chemicals at a high recovery rate, and reduce cross-contamination. With the goal. Another object of the present invention is to provide a method for extracting residual pesticides using the automatic pretreatment system for residual pesticides.

  The present invention comprises a sample cup having a filter paper inside and having an openable and closable discharge port at the bottom, a movable sample stock table holding one or more sample cups, water or an extraction solvent. A solvent supply device for injecting into the sample cup, a cutter provided on the removable shaft, a homogenizer for crushing and stirring the sample, water and extraction solvent in the sample cup, and discharging from the outlet of the sample cup A total amount of the first sample container for receiving the filtrate, the first movable container stock table holding the first sample container, and the first sample container receiving the filtrate A volume-up device for injecting the extraction solvent so as to adjust the sample solution, a first stirring means for stirring the sample solution in the first sample container, and the sample solution with a buffer solution- Liquid extraction A second sample container, a dispensing device for dispensing a predetermined amount of the sample solution in the first sample container into the second sample container, and a second sample container in the second sample container Second stirring means for stirring the sample solution and the buffer solution, a third sample container for recovering the extraction solvent layer after liquid-liquid extraction, and the second sample container after liquid-liquid extraction There is provided an automatic pretreatment system for residual agricultural chemicals comprising a solvent recovery device that sucks up an extracted solvent layer and discharges the extracted solvent layer into the third sample container.

  Since the automatic residual pesticide pretreatment system includes a movable sample stock table and a movable container stock table, there is no need for a flow path such as a tube for transferring a filtrate containing a pesticide or the like, a sample solution, or an extraction solvent layer. Moreover, since the homogenizer having a detachable shaft is provided, the shaft can be removed and replaced for each sample. Since the above-mentioned residual pesticide automatic pretreatment system has such a configuration, pesticides and the like derived from the previously treated sample do not remain, and cross contamination can be reduced. Moreover, it becomes possible to collect agricultural chemicals and the like that have been attached to the flow path and could not be recovered, and the recovery rate is improved. Furthermore, since automatic cleaning of the flow path and the shaft is not necessary, waste liquid treatment of the organic solvent used for cleaning them is not necessary, and it is possible to reduce the environmental load and the cost of the pretreatment operation.

  In the present specification, “agricultural chemicals” means agricultural chemicals, feed additives and veterinary drugs. In the present specification, “residual agricultural chemicals” mean agricultural chemicals remaining in food, feed additives, and veterinary drugs (such as agricultural chemicals).

  The residual pesticide automatic pretreatment system may further include a buffer solution supply device that injects a buffer solution into the second sample container.

  The automatic pretreatment system for residual agricultural chemicals further includes a second movable container stock table that holds the third sample container, and a vaporizer that evaporates at least a part of the extraction solvent in the third sample container. You may have. By providing the second movable container stock table and the vaporizer, it becomes possible to concentrate or dry the pesticides in the third sample container, and it can be easily used as a solvent suitable for the subsequent analysis operation. It can be replaced, and the analysis efficiency is improved.

  The automatic residual pesticide pretreatment system may further include a funnel filled with a dehydrating agent and attached to the mouth of the third sample container. By having the above funnel, it becomes possible to remove the moisture contained in the extraction solvent layer, to remove the influence of residual moisture in the subsequent analysis operation, and to increase the evaporation efficiency when equipped with the above vaporizer. Can do.

  The automatic residual pesticide pretreatment system further includes an extraction solvent supply device for injecting a predetermined amount of the extraction solvent into the second sample container in which the predetermined amount of the extraction solvent layer has been sucked up by the solvent recovery device. May be. By providing the extraction solvent supply device, the liquid-liquid extraction can be performed again, and the recovery rate of agricultural chemicals and the like can be improved.

  The dispensing device or the solvent recovery device may be a pipette device having a detachable pipette end. Since the pipette end that comes into contact with the sample is detachable, the pipette device can be removed and replaced for each sample. Thereby, cross contamination can be further reduced. Further, by making the pipette end disposable, it is not necessary to clean the pipette end.

  The movable sample stock table may hold a plurality of sample cups. The above automatic pretreatment system for residual agricultural chemicals is not provided with a flow path such as a tube for transferring a filtrate, sample liquid or extraction solvent layer containing agricultural chemicals, etc., so that sufficient space can be secured and processing can be performed at once. The number of sample cups can be easily increased. In addition, since the number of samples that can be processed at a time increases, pretreatment efficiency can be improved.

  When the movable sample stock table is configured to hold a plurality of sample cups, the movable sample stock table is moved to an upper portion of the sample cup held by the movable stock table at a predetermined timing, and from the homogenizer or the solvent supply device. There may be further provided a tray for receiving the falling object. By providing the tray, even when the movable sample stock table and the homogenizer or the solvent supply device move relatively, it prevents the fallen objects derived from other samples from entering the sample cup. be able to. Thereby, cross contamination can be further reduced.

  The present invention is also a method for extracting residual agricultural chemicals in the automatic residual agricultural chemical pretreatment system, wherein the sample cup into which water and the extraction solvent are injected by the solvent supply device is positioned below the homogenizer. The step of moving the movable sample stock table, and the first sample container in which the sample cup in which the internal sample, water and the extraction solvent are pulverized and stirred by the homogenizer is held on the first movable container stock table. The movable sample stock table is moved so as to be positioned above the first sample container, and the first sample container receiving the filtrate discharged from the discharge port of the sample cup is positioned below the measuring device. And a step of moving the first movable container stock table and the sample liquid inside by the measuring up device. Moving the first movable container stock table so that the adjusted first sample container is located within the operating range of the first agitating means; and Moving the first movable container stock table so that the first sample container in which the sample solution has been stirred is located within the operating range of the dispensing apparatus. Provide a method.

  According to the above extraction method, the extraction operation proceeds while the sample cup and the first sample container are directly moved by the movable sample stock table and the first movable container stock table. It is not necessary to transfer a solution such as a solvent containing an agrochemical through a flow path such as a pipe (tube). Therefore, cross contamination can be sufficiently reduced, and residual agricultural chemicals can be extracted with a high recovery rate.

  In the method for extracting residual agricultural chemicals, the step of re-extracting the filtration residue remaining in the sample cup with an extraction solvent after discharging the filtrate from the sample cup is performed at least once. The solvent supply device re-injects the extraction solvent into the sample cup from which the filtrate is discharged and the filtration residue remains, and the sample cup into which the extraction solvent is re-injected by the solvent supply device is disposed below the homogenizer. Moving the movable sample stock table to position, the step of pulverizing and stirring the filtration residue and extraction solvent inside the sample cup, and the homogenizer being re-injected with the filtration residue inside. A sample cup in which the extracted solvent is pulverized and stirred is a first sample volume held on the first movable container stock table. So as to be positioned above the can is intended to include a step of moving the movable sample stock table. Thereby, the collection rate of agrochemicals etc. can be improved more.

  In addition, the method for extracting residual agricultural chemicals is to perform the step of re-extracting the buffer solution layer after liquid-liquid extraction at least once, and the step of re-extracting the buffer solution phase after liquid-liquid extraction includes: The extraction solvent supply device reabsorbs the predetermined amount of the extraction solvent in the second sample container in which the predetermined amount of the extraction solvent layer is sucked up by the solvent recovery device and the buffer solution layer and the remaining extraction solvent layer remain. The step of injecting, the step of agitating the buffer solution layer in the second sample container, the remaining extraction solvent layer, and the re-injected extraction solvent; and the solvent recovery device comprising: A step of sucking up the extraction solvent layer inside the second sample container and discharging it into the third sample container. Thereby, the collection rate of agricultural chemicals and the like can be further improved.

  The present invention provides an automatic pretreatment system for residual agricultural chemicals that can automate the pretreatment of agricultural products in the inspection of residual agricultural chemicals, extract residual agricultural chemicals with a high recovery rate, and reduce cross-contamination. Moreover, the residual agricultural chemical extraction method using the said residual agricultural chemical automatic pre-processing system is provided.

1 is a front view showing an automatic pretreatment system for residual agricultural chemicals according to an embodiment of the present invention. It is a top view of the residual pesticide automatic pretreatment system shown in FIG. It is a perspective view which shows the one aspect | mode of a sample cup. It is a perspective view which shows one aspect | mode of a homogenizer. It is a perspective view which shows the one aspect | mode of a sample crushing part. It is a perspective view which shows the one aspect | mode of a solvent supply part. It is a perspective view which shows the one aspect | mode of a 1st movable container stock table. It is a perspective view which shows the one aspect | mode of a saucer. It is a front view showing one mode of a scalpel up device. It is a perspective view which shows the one aspect | mode of a 1st stirring means. It is a front view which shows the one aspect | mode of a dispensing apparatus. It is a perspective view which shows the one aspect | mode of a chip stock table. It is a perspective view which shows operation | movement of the dispensing apparatus of FIG. It is a perspective view showing one mode of a stirrer. It is a perspective view which shows the one aspect | mode of the 2nd movable container stock table. It is a perspective view which shows the one aspect | mode of a buffer solution supply apparatus. It is a front view which shows the one aspect | mode of a solvent collection | recovery apparatus. It is a perspective view which shows the one aspect | mode of a funnel stock table. It is a perspective view which shows the one aspect | mode of a vaporization apparatus. It is a perspective view which shows the one aspect | mode of a pump mechanism. It is an operation flow which shows one mode of an extraction filtration process. It is an operation flow which shows one mode of a measuring up process and a buffer dispensing process, respectively. It is an operation flow which shows one mode of the 1st dispensing process. It is an operation flow which shows one mode of the 2nd dispensing process.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. In the description of the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted.

  The automatic pretreatment system for residual agricultural chemicals of the present invention is based on the “Method for testing substances that are ingredients of agricultural chemicals, feed additives, or veterinary drugs remaining in foods” as defined by the Ministry of Health, Labor and Welfare. No. 0124001, General Manager of Food Safety Department, Ministry of Health, Labor and Welfare of the Ministry of Health, Labor and Welfare. Among the simultaneous test methods stipulated in Chapter 2, “(a) Simultaneous test method for agricultural chemicals by GC / MS (agricultural products)” Also referred to as “MS method”), “(b) Simultaneous test method I (agricultural products) for agricultural chemicals, etc. by LC / MS” (hereinafter also referred to as “LC / MS-I method”), “(U) LC / MS Can be suitably used for the pretreatment (extraction) of “Simultaneous test method II (agricultural products)” (hereinafter also referred to as “LC / MS-II method”).

(A) The extraction procedure in a simultaneous test method (agricultural products) for agricultural chemicals and the like by GC / MS is as follows.
(1) In the case of cereals, beans and seeds Add 20 mL of water to 10.0 g of the sample and leave it for 15 minutes. 50 mL of acetonitrile is added to this and homogenized, followed by suction filtration. Add 20 mL of acetonitrile to the residue on the filter paper, homogenize, and filter with suction. Combine the resulting filtrates and add acetonitrile to make exactly 100 mL. Take 20 mL of the extract, add 10 g of sodium chloride and 20 mL of 0.5 mol / L phosphate buffer (pH 7.0), and shake for 10 minutes. After standing, discard the separated aqueous layer. Pour 10 mL of acetonitrile into an octadecylsilylated silica gel minicolumn (1,000 mg) and discard the effluent. Inject the above acetonitrile layer into this column, and then inject 2 mL of acetonitrile. Collect the entire eluate, add anhydrous sodium sulfate to dehydrate, filter off the anhydrous sodium sulfate, and remove the filtrate at 40 ° C or lower. Concentrate to remove the solvent. Add 2 mL of a mixture of acetonitrile and toluene (3: 1) to the residue and dissolve.
(2) For fruits, vegetables, herbs, tea and hops For fruits, vegetables and herbs, weigh 20.0 g of sample. In the case of tea and hops, add 20 mL of water to 5.00 g of sample and leave for 15 minutes. 50 mL of acetonitrile is added to this and homogenized, followed by suction filtration. Add 20 mL of acetonitrile to the residue on the filter paper, homogenize, and filter with suction. Combine the resulting filtrates and add acetonitrile to make exactly 100 mL. Take 20 mL of the extract, add 10 g of sodium chloride and 20 mL of 0.5 mol / L phosphate buffer (pH 7.0), and shake. After standing, discard the separated aqueous layer. Anhydrous sodium sulfate is added to the acetonitrile layer for dehydration, and the anhydrous sodium sulfate is filtered off, and then the filtrate is concentrated at 40 ° C. or lower to remove the solvent. Add 2 mL of a mixture of acetonitrile and toluene (3: 1) to the residue and dissolve.

  (A) The procedure of extraction in the simultaneous test method I (agricultural products) of agricultural chemicals by LC / MS is the same as the procedure in (a) the simultaneous test method of agricultural chemicals (agricultural products) by GC / MS. In addition, (c) The extraction procedure in the simultaneous test method II (agricultural products) such as agricultural chemicals by LC / MS uses 0.01 mol / L hydrochloric acid instead of 0.5 mol / L phosphate buffer (pH 7.0). In addition, except that the shaking time at that time is changed to 15 minutes, (a) the procedure in the simultaneous test method (agricultural products) for agricultural chemicals and the like by GC / MS is the same. In addition, it is said that numerical parameters such as the addition amount and time in the official method may be appropriately changed as long as a recovery rate equivalent to or higher than that of the official method is secured.

  FIG. 1 is a front view showing an automatic pretreatment system for residual agricultural chemicals according to this embodiment, and FIG. 2 is a plan view thereof. FIG. 2 shows a state in which a solvent amount control device 400 described later is pulled out.

  The automatic pesticide residue pretreatment system 1000 shown in FIG. 1 and FIG. 2 executes extraction filtration unit A that executes extraction of agricultural chemicals and the like from samples such as agricultural products and removal of residues from the extract, and performs measurement of the filtrate. And a dispensing unit C that performs dispensing of the solution (sample solution, buffer solution and extraction solvent), liquid-liquid extraction of the sample solution, and recovery of the extraction solvent layer. In the pesticide residue automatic pretreatment system 1000, an extraction filtration unit A, a mess-up unit B, and a dispensing unit C are arranged in the upper stage of the casing 1, and the solvent amount control device 400, tanks 3, 4, 5 and A control computer PC and the like are arranged.

  The extraction filtration unit A includes a sample cup 110, a movable sample stock table 100, a sample crushing unit 10, a solvent supply unit 20, and a first movable container stock table 200. The first movable container stock table 200 can hold a plurality of first sample containers 210 (see FIG. 5). The extraction filtration unit A may further include a tray 700 from the viewpoint of further reducing cross contamination (see FIG. 8). Hereinafter, each structure of the extraction filtration part A is demonstrated in detail based on drawing.

  The sample cup 110 shown in FIG. 3 has a filter paper 140 inside thereof, and has a discharge port 120 that can be opened and closed at the bottom. The discharge port 120 can be switched between an open state and a closed state as the handle 130 rotates in the horizontal direction.

  The movable sample stock table 100 shown in FIGS. 1 and 2 can be slid in the left-right direction by the operation of a motor (not shown), and can move horizontally. Twelve sample cups 110 are arranged on the movable sample stock table 100. In the present embodiment, the case where the number of the sample cups 110 is twelve is shown, but the present invention is not limited to this, and the number may be larger or smaller.

  The homogenizer 11 shown in FIG. 4 has a cutter 15 provided on a detachable shaft 12. The shaft 12 is attached so as to be detachable from the lid portion 13 fitted into the mouth of the sample cup 110. The lid portion 13 has an O-ring 14 that is in close contact with the mouth of the sample cup 110. The homogenizer 11 operates so that a shaft 12 is rotated by a motor (not shown), and a sample such as agricultural products in the sample cup 110 is pulverized and stirred by a cutter 15 provided at the tip of the shaft 12.

  In the sample crushing section 10 shown in FIG. 5, the same number (12) of homogenizers 11 as the number of sample cups 110 that can be held by the movable sample stock table 100 are arranged on a support member (not shown) (FIG. 5). (Only 6 are shown in the figure.) The interval at which the homogenizer 11 is arranged coincides with the interval at which the sample cups 110 are held, and operates so that the samples, water, and extraction solvent in all the sample cups 110 are pulverized and stirred simultaneously. Note that the sample crushing unit 10 is disposed above the movable sample stock table 100.

  In the solvent supply unit 20 shown in FIG. 6, the same number (12) of solvent supply devices 21 as the number of sample cups 110 that can be held by the movable sample stock table 100 are arranged on the support member (see FIG. 6). Only one is shown.) The solvent supply device 21 is fitted with a tube 22 for transferring water or extraction solvent or pressurized air, and a mouth of the sample cup 110, and a plurality of water or extraction solvent or pressurized air is injected into the sample cup 110. And a lid portion 23 having an inlet at the bottom. The tube 22 is connected to a tank 3 for storing water, a tank 4 for storing an extraction solvent, and a compressor (not shown) for sending pressurized air via an automatic one-point four-way valve (not shown). (See FIG. 1). The lid portion 23 has an O-ring 24 that is in close contact with the mouth of the sample cup 110. The intervals at which the solvent supply devices 21 are arranged coincide with the intervals at which the sample cups 110 are arranged, and operate so as to inject water, extraction solvent, or pressurized air into all the sample cups 110 simultaneously. . The solvent supply unit 20 is disposed above the movable sample stock table 100.

  In the first movable container stock table 200 shown in FIG. 7, the same number (12) of first sample containers 210 as the number of sample cups 110 that can be held by the movable sample stock table 100 are arranged, and the first The same number of interface sensors 205 as the sample containers 210 are provided. The first movable container stock table 200 can be moved in a horizontal direction along a rail (not shown) by an operation of a motor (not shown). In addition, the 1st movable container stock table 200 is provided in the position lower than the movable sample stock table 100 (refer FIG. 1). Here, as the interface sensor 205, an infrared sensor, a weight sensor, an ultrasonic sensor, or the like can be used. In addition, as the first sample container 210, a glass container, a plastic container, a metal container, or the like is used.

  The tray 700 shown in FIG. 8 is for receiving falling objects such as dripping from the homogenizer 11 or the solvent supply device 21. The receiving tray 700 may be anything that can receive the falling object, but since it can hold the falling object liquid on the receiving tray 700, it is preferable to have a wall standing on the edge. . The tray 700 is disposed below the sample crushing unit 10 and the solvent supply unit 20 and above the movable sample stock table 100, and can be moved horizontally back and forth. The tray 700 may be one sheet or two or more sheets, or may be two or more sheets that can be moved independently.

  The effect | action in the extraction filtration part A is demonstrated. The movable sample stock table 100 is provided with a sample cup 110 in which a predetermined amount of a sample such as an agricultural product is placed. Water and an extraction solvent are sequentially injected from the solvent supply unit 20 into the sample cup 110. Preferably, after the water is injected, the extraction solvent is injected after a period of time for allowing water to permeate the sample is provided. Next, the movable sample stock table 100 moves so that the sample crushing unit 10 is positioned on the sample cup 110. A homogenizer 11 provided in the sample crushing unit 10 is lowered into the sample cup 110, and the sample, water, and extraction solvent in the sample cup 110 are crushed and stirred by the cutter 15 by the rotation of the shaft 12. After crushing and stirring, the movable sample stock table 100 and, if necessary, the first movable container stock table 200 move so that the first sample container 210 is positioned under the sample cup 110. Next, the discharge port 120 of the sample cup 110 is opened, and the filtrate that has passed through the filter paper 140 inside the sample cup 110 is injected into the first sample container 210 (filtration). At this time, the lid portion 23 of the solvent supply device 21 is fitted into the mouth of the sample cup 110, and pressurized air may be injected from the tube 22 (pressure filtration). In addition, since the shaft 12 of the homogenizer 11 is detachable, it can be removed and cleaned or replaced for each crushing and stirring operation.

  The first sample container 210 into which the filtrate has been injected is transferred to the knife-up part B as the first movable container stock table 200 moves. Further, if necessary, an operation for performing “washing” may be additionally performed before being transferred to the knife-up portion B. By “washing in”, further recovery of the agricultural chemicals remaining in the filtration residue, the filter paper 140 or the sample cup 110 becomes possible, and the recovery rate of the agricultural chemicals is improved.

  The operation of “washing” in the extraction filtration unit A will be described. After the filtrate is injected from the sample cup 110 into the first sample container 210, the discharge port 120 of the sample cup 110 is closed, and the extraction solvent is injected again from the solvent supply device 21 to the sample cup 110. Next, the movable sample stock table 100 moves so that the sample crushing unit 10 is positioned on the sample cup 110. A homogenizer 11 provided in the sample crushing unit 10 is lowered into the sample cup 110, and the filter residue and the extraction solvent in the sample cup 110 are crushed and stirred by the cutter 15 by the rotation of the shaft 12. After crushing and stirring, the movable sample stock table 100 moves so that the first sample container 210 into which the filtrate is injected is positioned under the sample cup 110. Next, the discharge port 120 of the sample cup 110 is opened, and the filtrate that has passed through the filter paper 140 inside the sample cup is again injected into the first sample container 210 (filtration). At this time, the lid portion 23 of the solvent supply device 21 is fitted into the mouth of the sample cup 110, and pressurized air may be injected from the tube 22 (pressure filtration). In this “washing”, the crushing and stirring by the homogenizer 11 is omitted, and the extraction solvent is injected into the sample cup 110 from the solvent supply device 21 while the sample cup 110 is placed on the first sample container 210. It may be a simple one. Further, the above “washing” may be repeatedly performed a plurality of times.

  When the pan 700 is included, when the sample cup 110 and the homogenizer 11 or the solvent supply device 21 are separated, the pan 700 is positioned so as to be positioned between the sample crushing unit 10 or the solvent supply unit 20 and the movable sample stock table 100. Is slid in the direction (see FIG. 8). After the tray 700 is positioned at the predetermined position, the sample crushing unit 10 or the solvent supply unit 20 is moved while the tray 700 is positioned on the movable sample stock table. As a result, it is possible to prevent falling objects (drops of solvent etc.) derived from other samples from being mixed.

  The measuring up part B includes a first sample container 210, a first movable container stock table 200, a measuring up apparatus 30, and a first stirring means 40. Next, each structure of the knife-up part B is demonstrated in detail based on drawing.

  The knife-up device 30 shown in FIG. 9 includes a pipe 31 to which the extraction solvent is supplied from the tank 4, a pulley 32, and a belt 33 stretched on the pulley 32. The pipe 31 can be moved in the vertical direction by a pulley 32 and a belt 33. The knife-up device 30 can be moved in the front-rear and horizontal directions by a motor (not shown), and operates to sequentially inject the extraction solvent into the plurality of first sample containers 210.

  In the first stirring means 40 shown in FIG. 10, bubbling devices 41 of the same number (12) as the number of first sample containers 210 that can be held by the first movable container stock table 200 are arranged on the support member. (Only six are shown in FIG. 10). The interval at which the bubbling device 41 is arranged coincides with the interval at which the first sample containers 210 are arranged, and operates so as to agitate the sample liquids in all the first sample containers 210 at the same time. The bubbling device 41 includes a tube 42 connected to a compressor (not shown), a connection portion 43, and a detachable pipe 44. The bubbling device 41 can move in the vertical direction. The pipe 44 can be attached and detached at the connecting portion 43. In addition to the bubbling device 41, means such as a shaking device, an ultrasonic generator, a combination of a stirring bar and a magnetic stirrer can be used as the first stirring unit 40. Here, it is preferable that the first agitating means 40 is an agitating means such as an ultrasonic generator that does not come into contact with the sample liquid, because cleaning or replacement for each sample is unnecessary. On the other hand, if the bubbling device 41 according to the present embodiment is used as the first stirring means 40, it is preferable in that it can be efficiently stirred in a short time.

  The effect | action in the knife up part B is demonstrated. The first movable container stock table 200 moves so that the first sample container 210 into which the filtrate has been injected in the extraction filtration unit A is positioned below the measuring apparatus 30. The pipe 31 of the knife-up device 30 is lowered into the first sample container 210, and the total amount from the knife-up device 30 is based on a control signal from the interface sensor 205 provided in the first movable container stock table 200. The extraction solvent is injected into the first sample container 210 so as to be a predetermined amount. At this time, the lower end position of the pipe 31 is controlled so as to be positioned above the liquid surface of the sample liquid when the volume is increased to a predetermined amount. Thereby, since the pipe 31 does not touch the sample liquid in the 1st sample container 210, replacement | exchange or washing | cleaning of the pipe 31 for every sample is unnecessary.

  Next, the first movable container stock table 200 moves so that the first sample container 210 is positioned within the operating range of the bubbling apparatus 41 (below the bubbling apparatus 41). The pipe 44 of the bubbling device 41 is lowered into the first sample container 210, and air is bubbled in a state where the pipe 44 is immersed in the sample solution. Thereby, the sample liquid in the first sample container 210 is stirred. In addition, since the pipe 44 is detachable at the connection portion 43, it can be removed and cleaned or replaced for each sample.

  The first sample container 210 in which the sample liquid has been stirred is transferred to the dispensing unit C as the first movable container stock table 200 moves.

  The dispensing unit C includes a first sample container 210, a first movable container stock table 200, a dispensing device 50, a chip stock table 600, a second stirring means 80, and a third sample container. 310, a second movable container stock table 300, a buffer solution supply device 500, a second sample container 810, and a solvent recovery device 60. A plurality of chip stock tables 600 may be provided. The automatic pesticide residue pretreatment system according to this embodiment includes a tip stock table 600 for a dispensing device 50 and a tip stock table 600 for a solvent recovery device 60 (see FIGS. 1 and 2). The dispensing unit C may further include an extraction solvent supply device, a funnel 91, and a funnel stock table 90. Hereafter, each structure of the dispensing part C is demonstrated in detail based on drawing.

  A dispensing device 50 shown in FIG. 11 includes a support member 57, a detachable pipette end 51, a fitting portion 52 that fits into the pipette end 51, and has a vent hole therein, and a syringe (see FIG. 11). A tube 53 whose other end is connected to the fitting portion 52, and an ejecting portion 54 that pushes down the pipette end 51 in conjunction with the push bar 55 and separates the pipette end 51 from the fitting portion 52. And a control rod 56 for controlling the vertical movement of the pipette end 51, the fitting part 52 and the ejecting part 54. The dispensing device 50 (pipette device) can be moved horizontally back and forth and left and right. Further, the vertical movement of the control rod 56 that controls the vertical position is possible in the vertical direction. The two pipetting devices are controlled independently.

  A chip stock table 600 shown in FIG. 12 includes a holder unit 650 for holding an unused pipette end 51, a discard unit 640 for discarding the used pipette end 51, and a sensor unit 630 for detecting the presence or absence of the pipette end 51. It comprises. The pipette end 51 is preferably a disposable type such as a plastic tip because cleaning or the like is unnecessary.

  Here, the operation of the dispensing device 50 will be described. In the dispensing device 50, air enters and exits at the pipette end 51 in accordance with the operation of the syringe connected by the tube 53. With the tip of the pipette end 51 immersed in the sample solution, the sample solution is sucked up by drawing air with a syringe. On the other hand, the sample liquid held at the pipette end 51 is discharged by extruding air with a syringe. The dispensing device 50 moves onto the tip stock table 600 without the pipette end 51. Next, with the downward movement of the control rod 56, the fitting portion 52 and the pipette end 51 are fitted. The pipette device loaded with the pipette end 51 moves onto the first sample container 210 containing the sample liquid after the control rod 56 returns to the original position. The control rod 56 lowers the sample liquid to a position where the pipette end 51 comes into contact with the sample liquid, and sucks up the sample liquid in accordance with the operation of the syringe. After the control rod 56 returns to its original position, it moves onto the second sample container 810. The pipette end 51 is lowered by the control rod 56 so as to be positioned in the second sample container 810, and the sample liquid is discharged according to the operation of the syringe. For example, if the amount of the sample liquid in the second sample container 810 does not reach a predetermined amount by performing the above operation only once, the pipette end 51 is loaded after the sample liquid is discharged from the pipette end 51. The pipette device moves again onto the first sample container 210 after the control rod 56 returns to the original position. Thereafter, the above operation is repeated to discharge the sample liquid into the second sample container 810. This repeated operation can be executed several times to obtain a predetermined amount.

  Next, after the control rod 56 returns to the original position, it passes through the sensor unit 630 and moves to the disposal port 640 of the chip stock table 600. When passing through the sensor unit 630, the presence of the pipette end 51 is detected at the tip of the dispensing device 50 by the infrared sensor transmitter 610 and the receiving unit 620, and is the pipette end 51 attached to the tip of the dispensing device 50? It is determined whether or not. When the presence of the pipette end 51 is not sensed, the operator is notified by an alarm or the like that the dispensing operation to the second sample container 810 has not been performed correctly. Further, when there are a plurality of second sample containers 810, it is assumed that only the sample (sample) in which the pipette end 51 has not been sensed, the dispensing operation has not been performed correctly, and the subsequent operations of only the sample are stopped. It can also be programmed. Note that the sensor unit 630 may not be installed. Further, not only the sensor unit 630 senses after the dispensing operation, but also allows the sensor unit 630 to pass through when the pipette end 51 is mounted before the dispensing operation, thereby sensing an installation error of the pipette end 51. When the pipette end 51 moves over the disposal port 640 after the pipette end 51 has passed the sensor unit 630, the dispensing device 50 is pushed down relative to the control rod 56 and the pipette end 51 is fitted. The pipette end 51 is discarded from the joint portion 52 and is discarded to the disposal port 640.

  FIG. 13 is an explanatory view showing the operation of the dispensing device (pipette device) 50 according to the present embodiment. FIG. 13 shows an example of a stock table 800 that holds the second sample container 810. The pipette device 50 (not shown) is arranged so that the pipette end 51 passes between the second sample containers 810 (that is, does not pass directly above the second sample container 810). Move in the horizontal direction R. Thereby, falling objects from the pipette end 51 can be prevented from entering the second sample container 810. In the present embodiment, the number of second sample containers 810 (the number that can be held in the stock table 800) is twice the number of first sample containers 210 (24). The dispensing device 50 dispenses the sample liquid from one first sample container 210 to two second sample containers 810. Thereby, the sample for GC / MS analysis and the sample for LC / MS analysis are obtained from the same sample solution. In this embodiment, the number of second sample containers 810 is twice the number of first sample containers 210, but this point can be set as appropriate, and the second sample container The number of containers 810 can be set equal to the number of first sample containers 210, or can be set three times or four times.

  The second stirring means 80 shown in FIG. 14 includes a magnetic stirrer 81. A stirrer is provided in advance in the second sample container 810. With the stirring bar and the magnetic stirrer 81, the organic solvent (extraction solvent) and the aqueous solution (buffer solution and sample solution) in the second sample container 810 are stirred and mixed. The second stirring unit 80 is not limited to this, and a bubbling device, a shaking device, or the like can also be used. As the second sample container 810, a glass container, a plastic container, a metal container, or the like is used.

  In the second movable container stock table 300 shown in FIG. 15, the same number (24) of third sample containers 310 as the number of second sample containers 810 are arranged. The second movable container stock table 300 includes a heat block 320. The second movable container stock table 300 can be moved in the horizontal direction along the rail (not shown) by the operation of a motor (not shown). As the third sample container 310, a glass container, a plastic container, a metal container, or the like is used.

  A buffer solution supply apparatus 500 shown in FIG. 16 includes a pipe 510 to which a buffer solution is supplied from the tank 5, a pulley 520, and a belt 530 stretched on the pulley 520. The pipe 510 is moved in the vertical direction by the pulley 520 and the belt 530. The buffer solution supply device 500 can be moved in the front-rear and left-right directions by a motor (not shown), and operates to inject the buffer solution into a plurality (24) of second sample containers 810 in order. . When the buffer solution is injected, the tip of the pipe 510 is lowered into the second sample container 810, but is controlled so as not to touch the liquid surface after the buffer solution is injected. Thereby, it is not necessary to clean or replace the pipe 510 for each sample.

  A solvent recovery device (pipette device) 60 shown in FIG. 17 includes a support member 67, a detachable pipette end 61, a fitting portion 62 that fits into the pipette end 61, and has a vent hole inside, and one end. The pipette end 61 is pushed down in conjunction with the tube 63 connected to the tip of the syringe (not shown) and the other end connected to the fitting portion 62, and the pressing rod 65, and the pipette end 61 is detached from the fitting portion 62. It includes an ejecting portion 64, a pipette end 61, a fitting portion 62, and a control rod 66 that controls the vertical movement of the ejecting portion 64. The solvent recovery device 60 (pipette device) can be moved horizontally back and forth and left and right. Further, the vertical movement of the control rod 66 that controls the vertical position is possible in the vertical direction. The two pipetting devices are controlled independently. The specific operation is the same as that of the dispensing device 50. As in the case of the dispensing device 50, the pipette end 61 can be a disposable type such as a plastic tip. Furthermore, a tube stock table 600 shown in FIG. 12 may be provided for the solvent recovery device 60. The configuration and operation of the tube stock table 600 in this case are the same as those described above.

  The funnel stock table 90 shown in FIG. 18 has the same number (24) of funnels 91 filled with dehydrating agents 92 as the number of third sample containers 310. The interval at which the funnel 91 is disposed coincides with the interval at which the third sample container 310 is disposed. A funnel stock table 90 is disposed on the second movable container stock table 300 and operates to inject the extraction solvent layer into all the funnels 91 without waiting for the extraction solvent layer from the funnels 91 to be dropped. To do. Examples of the dehydrating agent 92 include anhydrous sodium sulfate, silica gel, calcium chloride, and niline pentoxide.

  The buffer solution supply device 500 shown in FIG. 16 is also used as an extraction solvent supply device for re-extraction. By switching the connection between the pipe 510 and the tank 5 for storing the buffer solution to the connection between the pipe 510 and the tank 4 for storing the extraction solvent by a valve (not shown), it operates as an extraction solvent supply device. To do. In the present embodiment, the buffer solution supply device 500 is also used as the extraction solvent supply device, but can also be provided separately.

  The effect | action in the dispensing part C is demonstrated. A predetermined amount of buffer solution is injected into the second sample container 810 in which a predetermined amount of sodium chloride has been put in advance by the buffer solution supply device 500. It should be noted that a predetermined amount of sodium chloride may be introduced into the empty second sample container 810 after a predetermined amount of buffer solution is injected by the buffer solution supply device 500. In addition, when the buffer solution supply apparatus 500 is not used, a second sample container 810 in which a predetermined amount of sodium chloride and a predetermined amount of buffer solution are put in advance may be used.

  The first movable container stock table 200 moves so that the first sample container 210 containing the sample liquid that has been measured up by the measuring up section B is positioned at a predetermined position. After reaching the predetermined position, the dispensing device 50 sucks up a predetermined amount of the sample liquid from the first sample container 210 in accordance with the operation of the dispensing device 50 described above. Next, the dispensing device 50 moves onto the second sample container 810 containing the buffer solution, and discharges the sucked sample liquid into the second sample container 810. The above operation of the dispensing device 50 is repeated until the amount of the sample liquid discharged into the second sample container 810 reaches a predetermined amount.

  Next, the buffer solution and the sample solution in the second sample container 810 are stirred by the second stirring means 80 (liquid-liquid extraction). After the stirring, the second sample container 810 is allowed to stand for a predetermined time until the aqueous layer (buffer solution layer) and the organic solvent layer (extraction solvent layer) are separated. After standing for a predetermined time, the solvent recovery device 60 moves onto the second sample container 810, and the upper layer (organic solvent layer) in the second sample container 810 is operated in the same manner as the dispensing device 50 described above. Suck up. Thereafter, the solvent recovery device 60 moves onto the third sample container 310 and discharges the sucked organic solvent layer into the third sample container 310. The above-described operation of the solvent recovery device 60 is repeated until the amount of the organic solvent layer discharged into the third sample container 310 reaches a predetermined amount.

  By these actions, the agricultural chemicals extracted into the organic solvent layer in the third sample container 310 are recovered. The collected agricultural chemicals and the like can be used as they are for subsequent analysis and inspection. In the above-described embodiment, the sample solution is discharged to the second sample container 810 in which the buffer solution has been put in advance by the dispensing device 50, but the second sample container is used by the dispensing device 50. The buffer solution may be added by the buffer solution supply device 500 after the sample solution is discharged into 810.

  The operation of the extraction solvent supply device (in the present embodiment, also used as the buffer solution supply device 500) will be described. The extraction solvent supply device injects a predetermined amount of the extraction solvent into the second sample container 810 in which the predetermined amount of the extraction solvent layer has been sucked up by the solvent recovery device 60. Here, the buffer layer, the extraction solvent layer, and the injected extraction solvent in the second sample container 810 are stirred by the second stirring unit 80 (re-extraction). After the stirring, the second sample container 810 is allowed to stand for a predetermined time until the aqueous layer (buffer solution layer) and the organic solvent layer (extraction solvent layer) are separated. After standing for a predetermined time, the solvent recovery device 60 moves onto the second sample container 810, and the upper layer (organic solvent layer) in the second sample container 810 is operated in the same manner as the dispensing device 50 described above. Suck up. Thereafter, the solvent recovery device 60 moves onto the third sample container 310 including the extracted solvent layer recovered by the previous liquid-liquid extraction, and discharges the sucked organic solvent layer into the third sample container 310. . This re-extraction can improve the recovery rate of agricultural chemicals and the like. Further, this re-extraction operation may be repeated a plurality of times in order to further improve the recovery rate. In addition, as means for recovering the extraction solvent layer containing agricultural chemicals, etc., means for recovering the remaining extraction solvent layer by discarding the aqueous layer (buffer solution layer) as in the case of using a separatory funnel, and solvent recovery Although a means for sucking up and collecting the extraction solvent layer as in the apparatus 60 can be considered, an emulsion layer may occasionally be formed between the aqueous layer and the extraction solvent layer during liquid-liquid extraction. In this case, it is advantageous that the extraction solvent layer is repeatedly collected by performing re-extraction in the means for sucking and collecting the extraction solvent layer as in this embodiment.

  The operation when the dispensing unit C further includes the funnel 91 and the funnel stock table 90 will be described. It moves so that the funnel stock table 90 in which the funnel 91 filled with the dehydrating agent 92 is set is disposed above the second movable container stock table 300 in which the third sample container 310 is set. In the liquid-liquid extraction and re-extraction operations described above, the solvent recovery device 60 discharges the extraction solvent layer into the funnel 91. As a result, the extraction solvent layer is injected into the third sample container 310 through each funnel 91. Since the funnel 91 is filled with the dehydrating agent 92, the organic solvent layer in which moisture has been absorbed by the dehydrating agent 92 is collected in the third sample container 310.

  In addition to the above, the residual pesticide automatic pretreatment system according to the present embodiment may further include a vaporizer 70, a solvent amount controller 400, and the like.

  The vaporizer 70 shown in FIG. 19 includes a tube 72 connected to a nitrogen gas cylinder, a pipe 71 connected to the tube 72, and a support base 73 that supports the tube 72 and the connection portion of the pipe 71. The support base 73 can move up and down in the vertical direction. The operation of the vaporizer 70 will be described. The second movable container stock table 300 moves so that the third sample container 310 that has recovered the extraction solvent layer is positioned below the pipe 71. The pipe 71 moves up and down as the support base 73 moves up and down. Nitrogen gas sent from the tube 72 is sent into the third sample container 310 through the pipe 71, and the extraction solvent in the third sample container 310 can be evaporated. At this time, the third sample container 310 may be heated by the heat block 320 of the second movable container stock table 300. Heating is usually performed at a low temperature of about 40 ° C. The action of the vaporizer 70 makes it possible to concentrate or dry agricultural chemicals and the like, and it can be easily replaced with a solvent suitable for the subsequent analysis operation, thereby improving analysis efficiency.

  A solvent amount control device 400 shown in FIG. 20 includes a syringe main body 410, a piston 430 that controls the volume of the syringe, a motor 440 that moves the piston 430 up and down a required distance based on a control signal, and an automatic one-point four-way valve. And a tube 420 connected to the storage tank 3, 4 or 5. The solvent amount control device 400 can suck water, extraction solvent, or buffer solution from the storage tank 3, 4, or 5 and send out a predetermined amount of water, extraction solvent, or buffer solution according to the control signal.

  Next, a residual pesticide extraction method using the residual pesticide automatic pretreatment system 1000 according to the present embodiment will be described with reference to operation flows shown in FIGS. However, numerical parameters such as time and addition amount are not limited to those described below, and can be appropriately set as long as a recovery rate equivalent to or higher than that of the official method is secured.

[Extraction filtration process]
The extraction filtration step is a step of performing solid-liquid separation by eluting agricultural chemicals or the like from a sample such as an agricultural product into an extraction solvent (for example, acetonitrile or acetone). Hereinafter, the extraction filtration step will be described more specifically based on the operation flow shown in FIG.

  The sample cup 110 is taken out, and a sample such as an agricultural product to be inspected (for example, dried leek) is weighed with a necessary amount balance or the like. The sample cup 110 into which the sample has been placed is placed on the movable sample stock table 100. When there are a plurality of sample cups 110, the above operation is performed for each.

  When the arrangement of the sample cup 110 is completed, the processes after the extraction filtration are performed by the residual pesticide automatic pretreatment system 1000. Subsequent steps (steps) are automated unless otherwise specified, and are automatically executed by the automatic residual chemical pretreatment system 1000 based on, for example, control of an automation program. As the automation program, known programs can be appropriately modified or used in combination. Hereinafter, the extraction filtration process will be described based on the operation of the apparatus in the residual agricultural chemical automatic pretreatment system 1000.

  First, the step of moving the movable sample stock table 100 is performed so that the solvent supply unit 20 is positioned above the sample cup 110. Next, a step in which the solvent supply device 21 sequentially injects water and the extraction solvent into the sample cup 110 containing the sample is executed. In this step, 20 ml of water is first injected, allowed to stand for 10 minutes to allow water to permeate the agricultural product sample, and then 50 ml of extraction solvent (acetonitrile) is injected. Thereafter, the step of moving the movable sample stock table 100 is performed so that the sample cup 110 into which water and the extraction solvent have been injected by the solvent supply device 21 is positioned below the sample crushing unit 10 (homogenizer 11). .

  Subsequently, a step in which the homogenizer 11 crushes and stirs the sample, water, and extraction solvent inside the sample cup 110 is executed. In this step, pulverization and stirring are performed for 5 minutes.

  After the pulverization and stirring, the sample cup 110 in which the internal sample, water, and the extraction solvent are pulverized and stirred by the homogenizer 11 is positioned above the first sample container 210 held by the first movable container stock table 200. Next, the step of moving the movable sample stock table 100 is executed.

  Thereafter, a step of opening the discharge port 120 of the sample cup 110 is executed by a discharge port opening / closing control unit (not shown) provided in the movable sample stock table 100. Through this step, the filtrate (water containing solute, liquid such as extraction solvent) is discharged from the discharge port 120 through the filter paper 140 provided in the sample cup 110 and is collected in the first sample container 210. And in the sample cup 110, the filtration residue (solid content, such as a crushed material of an agricultural product sample) remains. This filtration operation may be filtration by natural fall, and a step in which the solvent supply device 21 injects pressurized air sent from a compressor connected to the solvent supply device 21 into the sample cup 110 is executed. Also good. By this step, pressure is applied to the sample cup 110, and pressure filtration is performed.

  Next, a step of re-extracting the filtration residue in the sample cup 110 with an extraction solvent (filtration residue re-extraction step) is performed. In this re-extraction process, first, after the filtrate is discharged from the sample cup 110, the discharge port 120 of the sample cup 110 is closed by the discharge opening / closing control unit provided in the movable sample stock table 100. Is done. Next, the step in which the solvent supply device 21 discharges the filtrate and reinjects the extraction solvent into the sample cup 110 where the filtration residue remains is executed. The amount of extraction solvent (acetonitrile) at this time is 20 ml. The step of moving the movable sample stock table 100 is performed so that the sample cup 110 into which the extraction solvent has been reinjected by the solvent supply device 21 is positioned below the sample crushing unit 10 (homogenizer 11). The step of the homogenizer 11 crushing and stirring the filtration residue and the extraction solvent in the sample cup 110 is executed. In this step, pulverization and stirring are performed for 1 minute. After the internal filtration residue and the re-injected extraction solvent are pulverized and stirred by the homogenizer 11, the sample cup 110 is above the first sample container 210 held by the first movable container stock table 200. The step of moving the movable sample stock table 100 so as to be positioned at is performed. A step of opening the discharge port 120 of the sample cup 110 is executed by a discharge port opening / closing control unit (not shown) provided in the movable sample stock table 100. As a result, the filtrate discharged (re-extracted) from the discharge port 120 through the filter paper 140 is collected in the first sample container 210 containing the filtrate from the first filtration. The recovery rate of agricultural chemicals and the like is improved by the re-extraction process described above. In this re-extraction step, pulverization and stirring by the homogenizer 11 may be omitted. Further, the re-extraction step may be repeated a plurality of times, or the re-extraction step itself can be omitted.

  In addition, since the shaft 12 of the homogenizer 11 is detachable, the operator can remove the shaft 12 of the homogenizer 11 for each agricultural product sample and wash or replace it. Thereby, cross contamination can be reduced.

[Mess up process]
The measuring up step is a step of adjusting the sample solution by adjusting the total volume of the filtrate obtained in the extraction filtration step to a preset volume. Hereinafter, the knife-up process will be described more specifically based on the operation flow shown in FIG.

  First, the step of moving the first movable container stock table 200 so that the first sample container 210 that has received the filtrate discharged from the discharge port 120 of the sample cup 110 is positioned below the measuring apparatus 30. Is executed.

  The step of measuring the volume up to 100 ml by adding the extraction solvent (acetonitrile) to the first sample container 210 where the filtrate is collected is executed. The interface sensor 205 provided in the first movable stock table 200 is disposed at the measuring up prescribed position, and the extraction solvent (acetonitrile) is added by the measuring up apparatus 30 until the interface sensor senses the liquid level. Therefore, it is possible to increase the amount to a specified amount.

  After the scalpel up, the first movable container so that the first sample container 210 in which the sample liquid is adjusted by the scalpel up apparatus 30 is positioned below the first stirring means 40 (bubbling device 41). A step of moving the stock table 200 is executed. The step in which the first stirring means 40 (the bubbling device 41) stirs the sample liquid in the first sample container 210 is executed. When the first stirring means 40 is the bubbling device 41, the bubbling device 41 performs a step of bubbling pressurized air (or nitrogen gas) to the sample solution in the first sample container 210.

[Buffer dispensing process]
The buffer dispensing step is a step of dispensing a predetermined amount of buffer solution for liquid-liquid extraction of an extraction solvent containing agricultural chemicals and the like. Hereinafter, the buffer dispensing process will be described more specifically based on the operation flow shown in FIG.

  An operator places a second sample container 810 into which a predetermined amount of sodium chloride and a stirrer are charged on a stock table 800 provided on the second stirring means 80 (magnetic stirrer 81). Subsequently, a step of injecting 20 ml of the buffer solution (phosphate buffer) into the second sample container 810 by the buffer solution supply apparatus 500 is executed in parallel with the measuring up process.

  In the present embodiment, the number of second sample containers 810 is twice the number of first sample containers 210. By distributing the sample liquid in the first sample container 210 to the two second sample containers 810, a sample for gas chromatography (GC) analysis and a sample for liquid chromatography (LC) analysis are obtained. be able to. This point can be set as appropriate, and the number of the second sample containers 810 may be the same as the number of the first sample containers 210, or may be set to 3 times or 4 times. it can.

  The buffer dispensing step is not necessarily performed in parallel with the measuring up step, and is performed after dispensing the sample solution into the second sample container 810 in the first dispensing step described below. May be. In addition, the second sample container 810 in which a predetermined amount of buffer solution (phosphate buffer) is added in addition to a predetermined amount of sodium chloride and a stirrer in advance without using the buffer solution supply apparatus 500 is used. It may be prepared and placed on the stock table 810. The operation of charging a predetermined amount of sodium chloride, a stirrer, and a predetermined amount of buffer solution (phosphate buffer) into the second sample container 810 does not depend on the operator, and the apparatus for charging these is automatically applied to the residual agricultural chemical pretreatment system 1000. It may be automated by incorporating it into

[First dispensing process]
The first dispensing step is a step of liquid-liquid extraction of the sample solution obtained in the measuring up step with the buffer solution dispensed in the buffer dispensing step. Hereinafter, the first dispensing process will be described more specifically based on the operation flow shown in FIG.

  The first movable stock table 200 is placed so that the first sample container 210 in which the internal sample liquid is stirred by the first stirring means 40 is located within the operating range of the dispensing device 50 (pipette device). The moving step is executed. The step of setting the pipette end 51 is executed by the dispensing device 50 (pipette device) moving above the tip stock table 600. Next, the dispensing device 50 (pipette device) moves above the first sample container 210, sucks up the sample liquid, and then moves so as to be positioned above the second sample container 810, and sucked up the sample. A step of injecting the liquid into the second sample container 810 is performed. The amount of the sample solution sucked up in this step is 10 ml. This step is repeated twice, and a total of 20 ml of sample liquid is dispensed per second sample container 810. The pipette end 51 is a disposable plastic tip, and the pipette end 51 can be exchanged for each sample.

  The second stirring means 80 (the magnetic stirrer 81 and the stirring bar previously placed in the second sample container 810) is used for the sample solution and buffer solution (including sodium chloride) in the second sample container 810. The step of stirring is performed. The stirring time in this step is 10 minutes. After stirring, the second sample container 810 is allowed to stand for 10 minutes, and the extraction solvent layer and the buffer solution layer are separated.

  The solvent recovery device 60 (pipette device) is moved above the tip stock table 600 and the step of setting the pipette end 61 is executed. Next, the solvent recovery device 60 (pipette device) moves above the second sample container 810, sucks up the separated extraction solvent layer (upper layer), and then is positioned above the third sample container 310. A step of injecting the extracted and extracted solvent layer into the third sample container 310 is executed. The amount of the extraction solvent layer sucked up in this step is 5 ml. Further, this step is repeated three times, and a total of 15 ml of extraction solvent layer is injected for each third sample container 310. The pipette end 61 is a disposable plastic tip, and the pipette end 61 can be exchanged for each sample.

  In this embodiment, the mouth of the third sample container 310 is equipped with a funnel 91 (Goucher funnel) filled with a dehydrating agent 92 (anhydrous sodium sulfate), and the recovered extraction solvent layer is a dehydrating agent. 92 and goochroth are collected into the third sample container 310. Thereby, the water | moisture content of an extraction solvent layer is removed.

[Second dispensing process]
The second dispensing step is a step of re-extracting the buffer solution phase layer after the liquid-liquid extraction by repeating the first dispensing step. The second dispensing step may not be performed and may be repeated once or twice or more. Hereinafter, the second dispensing process will be described more specifically based on the operation flow shown in FIG.

  The extraction solvent supply device (in this embodiment, combined use with the buffer solution supply device 500) sucks up a predetermined amount (15 ml) of the extraction solvent layer by the solvent recovery device 60, and the buffer solution layer and the remaining extraction solvent layer (about 5 ml). A step of reinjecting a predetermined amount (5 ml) of the extraction solvent (acetonitrile, shown as “cleaning liquid” in FIG. 24) into the second sample container 810 in which is left.

  The second stirring means 80 (the magnetic stirrer 81 and the stirrer previously charged in the second sample container 810) is used for the buffer solution layer, the remaining extraction solvent layer, and the extraction in the second sample container 810. A step of stirring the solvent (cleaning liquid) is performed. After stirring, the second sample container 810 is allowed to stand for 5 minutes, and the extraction solvent layer and the buffer solution layer are separated. The solvent recovery device 60 (pipette device) is moved above the tip stock table 600 and the step of setting the pipette end 61 is executed. In addition, the sample which collect | recovered the extraction solvent layer (upper layer) with the solvent collection | recovery apparatus 60 (pipette apparatus) in the 1st dispensing process, and the extraction solvent layer ( When the sample from which the upper layer is recovered is the same sample, the pipette end 61 can be reused by the one used in the first dispensing process, so this step may be omitted. Next, the solvent recovery device 60 (pipette device) moves above the second sample container 810, sucks the separated extraction solvent layer, and then moves so as to be positioned above the third sample container 310, A step of injecting the extracted solvent layer into the third sample container 310 is executed. The amount of the extraction solvent layer sucked up in this step is 5 ml. In addition, this step is repeated twice, and a total of 10 ml of extraction solvent layer is injected for each third sample container 310 (a total of 25 ml).

  In the present embodiment, a funnel 91 (goochroth) filled with a dehydrating agent 92 (anhydrous sodium sulfate) is attached to the mouth of the third sample container 310, and the recovered extraction solvent layer is a dehydrating agent. 92 and goochroth are collected into the third sample container 310. Thereby, the water | moisture content of an extraction solvent layer is removed. In addition, it is not necessary to prepare the dehydrating agent 92 and the gourd funnel for the second dispensing step, and the same ones used in the first dispensing step should be used for each sample. it can. This further improves the recovery rate.

  The third sample container 310 after the extraction solvent layer recovery is performed by the heat block 320 (which can be heated and cooled) of the second movable container stock table 300 when the following nitrogen gas drying step is not performed. The temperature can be adjusted and held at 10 ° C.

[Chisso gas drying process]
The nitrogen gas drying step is a step of evaporating only the extraction solvent from the extraction solvent containing the agricultural chemical or the like to concentrate or dry the agricultural chemical or the like.

  The step of moving the second movable container stock table 300 is performed so that the third sample container 310 from which the extraction solvent layer has been recovered is positioned below the vaporizer 70. The step of the vaporizer 70 injecting nitrogen gas into the third sample container 310 is executed. By this step, the extraction solvent in the third sample container 310 is vaporized, and the residual pesticide is dried or concentrated. In the nitrogen gas drying step, a step of heating the third sample container 310 to 30 to 40 ° C. by the heat block 320 of the second movable container stock table 300 may be executed.

<Simultaneous testing method for agricultural chemicals (agricultural products)>
For the GC / MS method, the LC / MS-I method, and the LC / MS-II method, the pretreatment (extraction of agrochemicals, etc.) is also referred to as a residual pesticide automatic pretreatment system according to the present invention (hereinafter “the present system”). ) And “Testing methods for substances that are constituents of agricultural chemicals, feed additives or veterinary drugs remaining in food” as defined by the Ministry of Health, Labor and Welfare mentioned above (development of food safety on January 24, 2005) No. 0124001, General Manager of Food Safety Department, Ministry of Health, Labor and Welfare) (a), (b), (c) of the extraction procedure (all "(2) fruit, vegetables, herbs, tea and hops In the case of “procedure” (hereinafter also referred to as “official method”), the extracted pesticides and the like were compared with those conducted by an examiner.

[Preparation of test solution using this system]
[Pretreatment of dried leek in this system]
The leeks clearly showing that agricultural chemicals and the like were used in the cultivation process were dried with hot air to obtain dried leeks. 5.00 g of dried leek was weighed with an electronic balance, put into a sample cup 110, set on a movable sample stock table 100, and pesticide residue was automatically extracted using this system (see FIGS. 21 to 24). Method). The sample was used for GC-MS analysis and LC-MS analysis by concentrating or drying using the vaporizer 70. The operation from weighing to concentration or drying was repeated three times independently to obtain n = 3 samples.

  Specifically, 20 ml of water is injected from the solvent supply device 21 into the sample cup 110 containing 5.00 g of dried leek and allowed to stand for 10 minutes, and then 50 ml of acetonitrile is injected from the solvent supply device 21. The mixture was pulverized and stirred with the homogenizer 11 for 5 minutes. After crushing and stirring, the discharge port 120 of the sample cup 110 was opened, pressurized air was injected from the solvent supply device 21 and pressure filtration was performed, and the filtrate was received in the first sample container 210. Next, the discharge port 120 of the sample cup 110 was closed, and 20 ml of acetonitrile was added from the solvent supply device 21 this time, and the mixture was again pulverized by stirring with the homogenizer 11 for 1 minute. Thereafter, the discharge port 120 of the sample cup 110 was opened, pressurized air was injected from the solvent supply device 21 and subjected to pressure filtration, and the filtrate was received again by the first sample container 210.

  Acetonitrile was added by the measuring apparatus 30 to increase the volume of the solution in the first sample container 210 to 100 ml, and bubbling was performed for 3 minutes by the bubbling apparatus 41 to obtain a sample solution. In parallel with this measuring up operation, 10 g of sodium chloride was weighed and added to the second sample container 810, and a stir bar was added. Then, a 0.05 mol / L phosphate buffer ( 20 ml of pH 7.0) (in the case of LC / MS-II method, 20 ml of 0.01 mol / L hydrochloric acid) was injected.

  Into the second sample container 810 containing the sodium chloride and the buffer solution (phosphate buffer), the sample solution 20 ml (10 ml dispensing operation is performed twice from the first sample container 210 by the dispensing device 50 (pipette device). Dispensed). Thereafter, the stirrer previously charged in the second sample container 810 was rotated by the magnetic stirrer 81 and stirred for 5 minutes. Note that the number of the second sample containers 810 is twice as many as that of the first sample containers 210, and duplicates were prepared and used as samples for GC-MS analysis and LC-MS analysis, respectively. The magnetic stirrer 81 is stopped and allowed to stand for 5 minutes to separate the liquid in the second sample container 810 into two layers (buffer solution layer and extraction solvent layer), and the upper layer (extraction by the solvent recovery device 60 (pipette device)). The solvent layer was collected 3 times for each 5 ml, and a total of 15 ml was collected in the third sample container 310. A funnel 91 (Goucher funnel) filled with a dehydrating agent 92 (anhydrous sodium sulfate 20 g) is set above the third sample container 310, and the extracted solvent layer recovered through the funnel 91 is placed in the third sample container 310. And dehydrated. Thereafter, the goroth funnel and anhydrous sodium sulfate were washed with 5 ml of acetonitrile and collected in the third sample container 310.

  Next, 5 ml of acetonitrile is added from the extraction solvent supply device 500 (also used as the buffer solution supply device in this embodiment) to the second sample container 810 where the buffer solution layer and a small amount of the extraction solvent layer remain, and again the magnetic stirrer. The stirrer was rotated by 81 and stirred for 1 minute. The magnetic stirrer 81 was stopped and allowed to stand for 5 minutes, and 5 ml of the upper layer (extraction solvent layer) was recovered by the solvent recovery device 60 (pipette device) into the third sample container 310 through the above-mentioned funnel (re-extraction step). After repeating this re-extraction step once again, the goroth and anhydrous sodium sulfate were washed again with 10 ml of acetonitrile and collected in the third sample container 310.

  The extraction solvent recovered in the third sample container 310 as described above is concentrated to 20 ml or less (in the case of the GC / MS method and the LC / MS-I method), or is completely evaporated to dryness (LC / MS-II). Therefore, the heat block 320 of the second movable stock table 300 was heated to 35 ° C., and nitrogen gas was blown into the third sample container 310 by the vaporizer 70. Nitrogen was blown for 20 minutes in the case of concentration and 90 minutes in the case of dryness.

  As described above, pretreatment (extraction of agricultural chemicals, etc.) was performed using this system.

[Preparation of GC / MS, LC / MS test solution]
Next, each of the samples (each n = 3) obtained in [Pretreatment of dried leek in this system] was subjected to the following treatment to prepare a test solution.

  In the case of the GC / MS method and the LC / MS-I method, the liquid concentrated to 20 ml or less is injected into an octadecylsilylated silica gel mini column (1000 ml) conditioned with 10 ml of acetonitrile, and further 2 ml of acetonitrile is injected, and the total amount of the eluate is injected. Was recovered. The eluate was concentrated at 40 ° C. or lower, and the residue was dissolved by adding 2 ml of a mixture of acetonitrile and toluene (3: 1). 2 ml of the liquid obtained in the previous operation was injected into a graphite carbon / aminopropylsilylated silica gel laminated mini column (500 mg / 500 mg) conditioned with 10 ml of a mixture of acetonitrile and toluene (3: 1), and then acetonitrile and toluene (3: 1 ) 20 ml of the mixed solution was injected, and the entire eluate was collected. The filtrate was concentrated at 40 ° C. or lower, and the residue was dissolved in a mixture of acetone and n-hexane (1: 1) to make exactly 1 ml as a test solution.

  In the case of the LC / MS-II method, a solution obtained by adding 2 ml of a mixture of acetone, triethylamine and n-hexane (20: 0.5: 80) to the third sample container 310 and dissolving the dried sample is obtained. The mixture was injected into a silica gel mini column conditioned with 5 ml of methanol, 5 ml of acetone, and 10 ml of n-hexane, 10 ml of a mixture of acetone, triethylamine and n-hexane (20: 0.5: 80) was injected, and the effluent was discarded. The inside of the third sample container 310 is washed with 2 ml of a mixture of acetone and methanol (1: 1), the washing is poured into a silica gel mini column, 18 ml of a mixture of acetone and methanol (1: 1) is further poured, and the total amount of the eluate is measured. It was collected. The filtrate was concentrated at 40 ° C. or lower, and the residue was dissolved in methanol to make exactly 1 ml as a test solution.

[Preparation of test solution by official method]
[Pretreatment of dried leek by official method and preparation of test solution]
Weigh 5.00 g of dried leek in the same lot as used in [Preparation of test solution using this system] with an electronic balance, pre-treat it by an inspector according to the official method, and use GC / MS, LC / MS. A test solution was prepared. The process from the pretreatment to the preparation of the test solution was performed three times independently to obtain a test solution with n = 3. In addition, in order to reduce variation, a pre-treatment was performed by one skilled inspector who was familiar with this test method (official method).

  Specifically, in the case of the GC / MS method and the LC / MS-I method, 20 ml of water was added to 5.00 g of the dried leek and left for 15 minutes. 50 mL of acetonitrile was added thereto, and the mixture was homogenized for 3 minutes, and then suction filtered using a funnel. Acetonitrile was added to the obtained filtrate to make a constant volume of 100 ml. To a separatory funnel containing 10 g of sodium chloride and 20 mL of 0.5 mol / L phosphate buffer (pH 7.0), 20 mL of the filtrate having a constant volume was accurately collected and shaken for 10 minutes. After standing for 5 minutes, the separated aqueous layer (lower layer) was discarded. Next, an acetonitrile layer (upper layer) was injected into an octadecylsilylated silica gel minicolumn (1000 ml) conditioned with 10 ml of acetonitrile, and further 2 ml of acetonitrile was injected to collect the total amount of the eluate. The eluate was dehydrated by adding anhydrous sodium sulfate and filtered. The filtrate was concentrated at 40 ° C. or lower using an evaporator, and 2 ml of a mixture of acetonitrile and toluene (3: 1) was added to the residue to dissolve it (solution A). 2 ml of the solution A is injected into a graphite carbon / aminopropylsilylated silica gel laminated mini-column (500 mg / 500 mg) conditioned with 10 ml of a mixture of acetonitrile and toluene (3: 1), and then 20 ml of a mixture of acetonitrile and toluene (3: 1) is injected. The entire eluate was collected. The filtrate was concentrated using an evaporator at 40 ° C. or lower, and in the case of the GC / MS method, the residue was dissolved in a mixture of acetone and n-hexane (1: 1) to make exactly 1 ml as a test solution. On the other hand, in the case of the LC / MS-I method, an exactly 1 ml solution dissolved in methanol was used as a test solution.

  In the case of the LC / MS-II method, 20 ml of water was added to 5.00 g of the above dried leek and left for 15 minutes. 50 mL of acetonitrile was added thereto, and the mixture was homogenized for 3 minutes, and then suction filtered using a funnel. Acetonitrile was added to the obtained filtrate to make a constant volume of 100 ml. To a separatory funnel containing 10 g of sodium chloride and 20 mL of 0.01M hydrochloric acid, 20 ml of a fixed volume of the filtrate was accurately collected and shaken for 10 minutes. After standing for 5 minutes, the separated aqueous layer (lower layer) was discarded. Anhydrous sodium sulfate was added to the acetonitrile layer (upper layer) to dehydrate and filtered. The filtrate was concentrated using an evaporator at 40 ° C. or lower, and 2 ml of a mixture of acetone, triethylamine and n-hexane (20: 0.5: 80) was added to the residue and dissolved (solution B). Next, 2 ml of the solution B was injected into a silica gel mini-column conditioned with 5 ml of methanol, 5 ml of acetone, and 10 ml of n-hexane, and 10 ml of a mixture of acetone, triethylamine and n-hexane (20: 0.5: 80) was injected, and the effluent was discharged. The liquid was discarded. Wash the inside of the container containing the solution B with 2 ml of a mixture of acetone and methanol (1: 1), inject the washing into a silica gel mini column, and then inject 18 ml of a mixture of acetone and methanol (1: 1) The whole amount was recovered. The filtrate was concentrated using an evaporator at 40 ° C. or lower, and the residue was dissolved in methanol to make exactly 1 ml as a test solution.

[Qualitative and quantitative determination of agricultural chemicals, etc.]
For the test solutions (each n = 3) obtained in [Preparation of test solution using this system] and [Preparation of test solution by official method], GC / MS / MS measurement and LC / MS / MS measurement were performed. Qualitative and quantitative determination of agricultural chemicals in each test solution was performed.

GC / MS / MS measurement conditions are as follows.
Measuring instrument: GC / MS / MS
Column: 5% phenyl-methyl silicon (inner diameter 0.25 mm, length 30 m, film thickness 0.25 μm)
Column temperature: 50 ° C (1 minute) -25 ° C / minute-125 ° C (0 minute) -10 ° C / minute-300 ° C (10 minutes)
Inlet temperature: 240 ° C
Carrier gas: Helium Ionization mode: EI
Injection volume: 1 μl

LC / MS / MS measurement conditions are as follows.
Measuring instrument: LC / MS / MS
Column: Octadecylsilylated silica gel Column temperature: 40 ° C
Mobile phase: Solution A (5 mmol / L ammonium acetate aqueous solution) and solution B (5 mmol / L ammonium acetate methanol solution) are sent over a concentration gradient.
Mobile phase flow rate: 0.30 ml / min Ionization mode: ESI
Injection volume: 10 μl

(Create a calibration curve)
In the GC / MS method, 369 kinds of pesticides such as cypermethrin, chlorpyrifos, and ethion are used. In the LC / MS-I method, 144 kinds of pesticides such as dimelon, carbofuran, and carpentadim are used. In the / MS-II method, standard products are obtained for 64 kinds of agricultural chemicals including fluazifop, haloxyhop, triasulfuron, etc., and 10 ppb, 100 ppb, and 200 ppb standard solutions are prepared for each of these standard products. A measurement curve was prepared separately under the above measurement conditions.

[Analysis results of dried leek]
Six types of agricultural chemicals described in Table 1 were detected in both the test solution obtained in [Preparation of test solution using this system] and the test solution obtained in [Preparation of test solution by official method] (6 All pesticides other than seeds were not detected (ND). For the GC / MS method, three types of metalaxyl, Procymidone, and pyrimethanil were detected. In the LC / MS-I method, carbendazim, ometoate, and propamocarb p Three species were detected, and no agrochemicals were detected by the LC / MS-II method. As shown in Table 1, almost the same results were obtained with this system and the official method, and it became clear that this system can replace the official method.

<Addition recovery test (1): dried leek>
Prepare an additive recovery solution containing each pesticide, etc. at a predetermined concentration for 5.00 g of dried leek in the same lot as that used in the above <Simultaneous testing method for agricultural chemicals (agricultural products)>. The solution was added to the dried leek so that the concentration of each agricultural chemical and the like was 50 ppb. Thereafter, in the same manner as in the above-mentioned <Simultaneous testing method for agricultural chemicals (agricultural products)>, pretreatment using this system or pretreatment by an inspector in accordance with an official method was performed to prepare a test solution. An addition recovery test for agricultural chemicals and the like was performed by quantifying the agricultural chemicals recovered in the test solution.

  In the GC / MS method, the addition / recovery test was conducted for the 369 types of agricultural chemicals described above, the LC / MS-I method for the 144 types of agricultural chemicals, and the LC / MS-II method for the 64 types of agricultural chemicals described above. For pesticides, etc., extracted using this system, extracted by an inspector in accordance with the official method, both are performed with n = 5, and the average recovery rate and coefficient of variation (CV) to see the variation in data are shown. Calculated. The recovery was 70% to 120%, and the coefficient of variation CV (standard deviation ÷ average) was 15% or less, and the results of this system and the official method were compared. The results are shown in Tables 2 and 3.

  Table 2 shows “the number of agricultural chemicals whose recovery rate was 70% to 120% / the total number of agricultural chemicals tested”. Table 3 shows “the number of agricultural chemicals whose CV was 15% or less / the total number of agricultural chemicals tested”. As is clear from Tables 2 and 3, results using the automatic pretreatment system for residual pesticides according to the present invention are superior in both recovery rate and variation (CV), compared to those performed by a skilled tester according to the official method. was gotten.

<Additive recovery test (2): fresh cabbage>
Addition and recovery tests were conducted using fresh cabbage in which no agricultural chemicals were detected. The additive collection solution described in <Addition / recovery test (1): Dried leek> was added to 20 g of the fresh cabbage so that the concentration of each agricultural chemical and the like was 25 ppb. Thereafter, 20 ml of water was not injected, an octadecylsilylated silica gel minicolumn (1000 ml) was not used (in the case of the GC / MS method and the LC / MS-I method), the amount of the test solution (the amount of the final preparation solvent) In the same manner as in [Preparation of test solution using this system] and [Preparation of test solution by official method] above, except that the volume was adjusted to 2 ml, pretreatment using this system, or test according to the official method A pretreatment by the government was performed to obtain a test solution. Except that this test solution was used, the average recovery rate and the coefficient of variation (CV) for observing the variation in data were calculated in the same manner as in <Additional recovery test (1): Dried leek>. The results are shown in Tables 4 and 5.

<Additive recovery test (3): Flour>
An addition recovery test was conducted using wheat flour in which no agricultural chemicals were detected. The additive collection solution described in the above <Addition / recovery test (1): dried leek> was added to 10 g of the flour so that the concentration of each agricultural chemical and the like was 25 ppb. Then, in preparing the test solution, the acetonitrile layer after the separation was injected into an octadecylsilylated silica gel mini column (1000 ml) conditioned with 10 ml of acetonitrile, and further 2 ml of acetonitrile was injected to collect the total amount of the eluate. Except that the procedure after dehydration with anhydrous sodium sulfate was performed (only in the case of LC / MS-II method in the official method), the above [Preparation of test solution using this system] and [official method Preparation of a test solution by the same method as above, pretreatment using this system or pretreatment by an examiner according to an official method was carried out to obtain a test solution. Except that this test solution was used, the average recovery rate and the coefficient of variation (CV) for observing the variation in data were calculated in the same manner as in <Additional recovery test (1): Dried leek>. The results are shown in Tables 6 and 7.

  As is clear from Tables 4 to 7, even in the case of fresh cabbage and flour, it is better to use the pesticide residue automatic pretreatment system according to the present invention than a skilled examiner performs according to the official method. Also, excellent results were obtained in both recovery rate and variation (CV).

<Detection test for agricultural chemicals in pasty processed food>
Tom Tom Kum paste obtained in Thailand (a paste-like Tom Yum Kung base) was tested for detection of pesticides and the like remaining in the food. The Tom Yum Goong Paste is a food (processed food) made from lemon grass, chili, onion, garlic and the like.

  Except that 5 g of the above Tom Yum Goong Paste was used as a sample, the number of samples was n = 10, and the LC / MS-II method was not carried out, the same as in the above <Addition Recovery Test (3): Wheat Flour> A test for the detection of pesticides and the like in the Tom Yum Goong paste was performed in the same manner as in the above <Simultaneous test method for agricultural chemicals (agricultural products)> except that a test solution was prepared and this test solution was used. In the official method, pretreatment was performed independently by three skilled examiners familiar with the test method.

  As a result, four types of pesticides described in Table 8 were detected in both the test solution pretreated with this system and the test solution pretreated by the official method. In the GC / MS method, three types of ethion, cypermethrin, and triazophos were detected, and in the LC / MS-I method, one type of carbendazim was detected. As shown in Table 8, the detected concentrations were almost the same in this system and the official method, and it is clear that the official method can be substituted. In addition, the variation is generally lower in this system, and it is clear that a more reliable test result can be obtained according to this system.

  DESCRIPTION OF SYMBOLS 11 ... Homogenizer, 12 ... Shaft, 15 ... Cutter, 21 ... Solvent supply device, 30 ... Mess-up device, 40 ... First stirring means, 50 ... Dispensing device, 51 ... Pipette end, 60 ... Solvent recovery device, 61 ... pipette end, 70 ... vaporizer, 80 ... second stirring means, 91 ... funnel, 92 ... dehydrating agent, 100 ... movable sample stock table, 110 ... sample cup, 120 ... discharge port, 140 ... filter paper, 200 ... First movable container stock table 210 ... first sample container 300 ... second movable container stock table 310 ... third sample container 500 ... buffer supply device (extraction solvent supply device) 700 ... saucer, 800 ... stock table, 810 ... second sample container, 1000 ... automatic pretreatment system for residual agricultural chemicals.

Claims (12)

  1. A sample cup having a filter paper inside and having an openable opening at the bottom,
    A movable sample stock table holding one or more of the sample cups;
    A solvent supply device for injecting water or an extraction solvent into the sample cup;
    A homogenizer having a cutter provided on a detachable shaft and crushing and stirring the sample, water and extraction solvent in the sample cup;
    A first sample container for receiving the filtrate discharged from the outlet of the sample cup;
    A first movable container stock table for holding the first sample container;
    A measuring up apparatus for injecting the extraction solvent into the first sample container that has received the filtrate so that the total amount becomes a predetermined amount, and adjusting the sample solution;
    First stirring means for stirring the sample liquid in the first sample container;
    A second sample container for liquid-liquid extraction of the sample solution with a buffer;
    A dispensing device for dispensing a predetermined amount of the sample solution in the first sample container into the second sample container;
    Second stirring means for stirring the sample solution and the buffer solution in the second sample container;
    A third sample container for recovering the extraction solvent layer after liquid-liquid extraction;
    A solvent recovery device that sucks up the extraction solvent layer in the second sample container after liquid-liquid extraction and discharges it into the third sample container;
    An automatic pretreatment system for residual pesticides.
  2.   The automatic pretreatment system for residual agricultural chemicals according to claim 1, further comprising a buffer supply device for injecting a buffer into the second sample container.
  3. The second movable container stock table that holds the third sample container, and a vaporizer that evaporates at least a part of the extraction solvent in the third sample container. Automatic pretreatment system for residual pesticides.
  4.   The automatic pretreatment system for residual pesticides according to any one of claims 1 to 3, further comprising a funnel filled with a dehydrating agent and attached to the mouth of the third sample container.
  5.   5. The apparatus according to claim 1, further comprising an extraction solvent supply device that injects a predetermined amount of the extraction solvent into the second sample container in which the predetermined amount of the extraction solvent layer is sucked up by the solvent recovery device. An automatic pretreatment system for residual agricultural chemicals as described in the section
  6.   The automatic pretreatment system for residual agricultural chemicals according to any one of claims 1 to 5, wherein the dispensing device is a pipette device having a detachable pipette end.
  7.   The residual pesticide automatic pretreatment system according to any one of claims 1 to 6, wherein the solvent recovery device is a pipette device having a detachable pipette end.
  8.   The automatic pretreatment system for residual agricultural chemicals according to any one of claims 1 to 7, wherein the movable sample stock table holds a plurality of sample cups.
  9.   The residue according to claim 8, further comprising a tray that moves to a top of the sample cup held by the movable sample stock table at a predetermined timing and receives a fallen object from the homogenizer or the solvent supply device. Pesticide automatic pretreatment system.
  10. A method for extracting residual pesticides in an automatic pretreatment system for residual pesticides according to any one of claims 1 to 9,
    Moving the movable sample stock table so that the sample cup into which water and extraction solvent have been injected by the solvent supply device is located below the homogenizer;
    The movable cup so that the sample cup in which the internal sample, water, and the extraction solvent are pulverized and stirred by the homogenizer is positioned above the first sample container held by the first movable container stock table. Moving the sample stock table;
    Moving the first movable container stock table so that the first sample container receiving the filtrate discharged from the discharge port of the sample cup is located below the measuring apparatus;
    Moving the first movable container stock table so that the first sample container in which the sample liquid is adjusted by the measuring apparatus is positioned within the operating range of the first stirring means; When,
    The step of moving the first movable container stock table so that the first sample container in which the sample liquid inside is stirred by the first stirring means is positioned within the operating range of the dispensing device. And a method for extracting residual pesticides.
  11. It is the extraction method of the residual pesticide of Claim 10, Comprising:
    The extraction method is to perform at least one step of re-extracting the filtration residue remaining in the sample cup with an extraction solvent after discharging the filtrate from the sample cup.
    The re-extracting step includes
    The solvent supply device re-injects the extraction solvent into the sample cup from which the filtrate is discharged and the filtration residue remains;
    Moving the movable sample stock table so that the sample cup re-injected with the extraction solvent by the solvent supply device is positioned below the homogenizer;
    The homogenizer crushing and stirring the filtration residue and extraction solvent inside the sample cup;
    The sample cup in which the internal filtration residue and the re-injected extraction solvent are pulverized and stirred by the homogenizer is positioned above the first sample container held by the first movable container stock table. The method for extracting a residual agricultural chemical according to claim 10, further comprising: moving the movable sample stock table.
  12. A method for extracting residual pesticides in the automatic pretreatment system for residual pesticides according to claim 5,
    The extraction method is to perform the step of re-extracting the buffer layer after liquid-liquid extraction at least once,
    Re-extracting the buffer phase after the liquid-liquid extraction,
    The extraction solvent supply device reabsorbs the predetermined amount of the extraction solvent into the second sample container in which the predetermined amount of the extraction solvent layer is sucked up by the solvent recovery device and the buffer solution layer and the remaining extraction solvent layer remain. Injecting step;
    The second agitating means agitating the buffer solution layer in the second sample container, the remaining extraction solvent layer, and the reinjected extraction solvent; and
    A method for extracting residual agricultural chemicals, comprising: a step of sucking an extraction solvent layer inside a second sample container and discharging the extracted solvent layer into a third sample container.
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CN108279315B (en) * 2018-02-11 2019-01-25 江苏康盛农业发展有限公司 It is a kind of for pesticide and the shredding mechanism of residues detection
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JP2524554B2 (en) * 1992-06-20 1996-08-14 システム・インスツルメンツ株式会社 Pesticide residue automatic pretreatment apparatus
JP3024375B2 (en) * 1992-07-31 2000-03-21 味の素株式会社 Automatic pre-processing equipment
JP2001108688A (en) * 1999-10-07 2001-04-20 Dainippon Seiki:Kk Device for automatically extracting component substance in liquid sample, device for automatically measuring concentration and method for extracting component substance in liquid sample
JP4275633B2 (en) * 2005-03-04 2009-06-10 日本ハム株式会社 Pesticide residue extraction method and extraction kit

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WO2018058991A1 (en) * 2016-09-28 2018-04-05 深圳市易特科信息技术有限公司 Device for detecting toxicity of wild plant and providing alert

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