JP4780109B2 - Analytical pretreatment apparatus and analysis pretreatment method for organic chemicals - Google Patents

Description

  The present invention uses a plurality of solid phase cartridges in the analysis of organic chemical substances to remove impurities in the solution containing the substance to be analyzed, thereby improving the accuracy and workability of quantitative analysis by gas chromatography. The present invention relates to an analysis pretreatment apparatus and an analysis pretreatment method therefor.

  For the analysis of organic chemical substances, particularly agricultural chemicals, an analysis method by liquid chromatography has been employed (for example, see Patent Document 1). Liquid chromatography has also been applied to the analysis of agricultural chemicals used in golf courses (see, for example, Patent Document 2). Since then, the safety of residual pesticides attached to agricultural products has become a problem, and not only liquid chromatography but also gas chromatography has come to be used. Furthermore, a method using both gas chromatography and an infrared absorption spectrum or a method using a microtrap as a pretreatment for gas chromatography analysis has been proposed (see, for example, Patent Document 3 and Patent Document 4). On the other hand, analysis methods such as dioxin have been studied as the environmental problems are closed up (see, for example, Patent Document 5). In addition, research for connecting a solid-phase cartridge and a gas chromatograph has been conducted, and a method of automating using a valve without using a packing for degrading a substance to be analyzed has been proposed (for example, Non-Patent Document 1). reference.).

JP-A-6-331618 JP-A-5-306998 JP-A-8-170941 JP 2002-328121 A JP 2002-48688 A Ryoichi Sasano et al., "Journal of Chromatography A" Elsevier Science, (USA), 896 (2000) p.41-49

  As environmental issues have become more important, efforts have been made to improve the accuracy and workability of organic chemicals such as pesticide residues and environmental hormones. However, contaminants are always mixed in the solution containing the analysis target substance extracted from the analysis target sample such as air, drinking water, waste water, vegetable and animal foods. How to remove them well and improve the analysis accuracy of the substances to be analyzed was a big problem in the analysis of these organic chemical substances. In order to solve these problems, the present invention proposes a rational analysis pretreatment and proposes an automatic analysis pretreatment apparatus capable of performing the pretreatment.

As a result of intensive studies to solve the above problems, the present inventor has come to propose the present invention. That is, a solution comprising an injection part for injecting an analysis target substance, a first liquid feed pump for sending out a solvent for flushing out the analysis target substance injected into the injection part, and an analysis target substance and the solvent for flushing out A first solid phase cartridge for adsorbing non-polar contaminants contained in the sample, a second solid phase cartridge for adsorbing the analyte, and the polarity of the solution containing the analyte from which the contaminant is removed. A second liquid-feeding pump for sending out the polarity-changing solvent for changing, and a solution containing the substance to be analyzed from which impurities are removed, and the solvent for polarity-changing from the second liquid-feeding pump is sent out and mixed. And a sample acquisition control means for acquiring the analysis target substance by supplying the mixed liquid to the second solid phase cartridge and adsorbing the analysis target substance. An analysis pre-processing device quality.
When the analysis target substance is injected into the injection part by the sample acquisition control means, the analysis target substance is pushed away by the solvent sent out by the first liquid feeding pump, and is included in the solution composed of the analysis target substance and the solvent for flushing away. The nonpolar contaminants are removed by adsorption to the first solid phase cartridge. A solvent for changing polarity is added to the solution that has passed through the first solid phase cartridge by a second liquid feed pump and supplied to the second solid phase cartridge, and the substance to be analyzed is adsorbed to the second solid phase cartridge to obtain a sample. Acquisition is completed, and sample acquisition control ends. When the acquisition of the sample is completed, the second solid phase cartridge is moved to another apparatus, and then the elution solvent is supplied to elute the sample adsorbed on the second solid phase cartridge and flow with the eluted sample. The sample may be taken out by adsorbing ionic impurities in the solution to a third solid phase cartridge or the like. In addition, the sample taken out is put into the inlet of the gas chromatograph and the sample is analyzed.
By using the reverse-phase solid-phase extraction method by adding a polarity-changing solvent that changes the polarity of the solution as described above, the sample can be continuously obtained and automation can be performed.

In addition, a sample reservoir for storing the analysis target substance, a first solid phase cartridge for adsorbing nonpolar impurities, a second solid phase cartridge for adsorbing the analysis target substance, and an ionic contaminant A third solid phase cartridge for adsorption; a solvent for flushing out the analyte; a polarity changing solvent for altering the polarity of the solution containing the analyte; and the second solid phase cartridge. At least three solvent reservoirs for respectively storing the elution solvent for eluting the analyzed analyte, and at least two inlets for receiving the elution solvent and the analyte from the sample reservoir, respectively. , At least three liquid feed pumps provided to supply the solvent stored in the solvent reservoir to the inlet, and the liquid pump supplies the solvent to the inlet. A switching means for switching the position of the inlet in order to receive the specific solvent and cause it to flow out to a predetermined flow path connected to the specific solid phase cartridge of the three solid phase cartridges, and the analysis The sample reservoir is connected to the outlet side of the injection port connected to a liquid feed pump for flushing out the target substance, and a predetermined amount of the analyte is sucked by the liquid feed pump and then flushed away. The solution containing the substance to be analyzed and the solvent is supplied to the first solid phase cartridge, and the polarity changing solvent is added to the solution that has passed through the first solid phase cartridge. Sample acquisition control means for supplying to the sample and the elution solvent for eluting the sample adsorbed on the second solid phase cartridge by the sample acquisition control means And a sample delivery control means for supplying a solution flowing together with the eluted sample to the third solid phase cartridge, and adsorbing ionic impurities to the third solid phase cartridge to take out the sample. It may also be a pre-analytical processing apparatus for organic chemical substances.
The sample acquisition control means sucks a predetermined amount of the substance to be analyzed in the sample storage section through the inlet by the liquid feed pump, and then pushes out a solvent for flushing out the substance to be analyzed by the liquid feed pump. It supplies to a solid phase cartridge, and a foreign substance is made to adsorb | suck and remove to a 1st solid phase cartridge. The polarity changing solvent is added to the solution that has passed through the first solid phase cartridge and supplied to the second solid phase cartridge, and the substance to be analyzed is adsorbed to the second solid phase cartridge to complete the acquisition of the sample. Next, the elution solvent is supplied by the sample delivery control means to elute the sample adsorbed on the second solid phase cartridge, and ionic impurities such as fatty acids in the solution flowing together with the eluted sample are thirdly removed. The sample is adsorbed on the solid phase cartridge, and the sample is removed to complete the sample removal. The sample taken out is put into the inlet of the gas chromatograph and the sample is analyzed.
By using the reverse-phase solid-phase extraction method by adding a polarity-changing solvent that changes the polarity of the solution as described above, the sample can be continuously obtained and automation can be performed.
Also, by configuring the elution solvent injection port and the analysis target substance injection port from different injection ports, it is not necessary to clean the pipes that make up the elution solvent flow path, and the analysis target substance is a sample. It is only necessary to wash only the tubes that make up the flow path through which the gas passes, and not only can the control configuration be simplified accordingly, but also the number of washing steps can be reduced so that the sample can be taken out with high accuracy. .

  Provided with a solvent storage part for storing the solvent for washing and a liquid feed pump for sending out the solvent in the solvent storage part, the corresponding inlet from the solvent storage part for storing the solvent for extruding the substance to be analyzed A switching valve is provided in the middle of the flow path to control the operation of the liquid feeding pump so that the analyte to be aspirated by the liquid feeding pump ends the suction operation before entering the port of the switching valve. Configured to supply the cleaning solvent to the switching valve so as to be able to flow out to the flow path, and to supply the cleaning solvent and to push out the analyte By providing the switching control means for switching the switching valve to the sample acquisition operation state for supplying the solvent, the analyte can be prevented from entering the port of the switching valve. Therefore, it is only necessary to clean the inside of the flow path, so that when the next sample is taken out, the previous analysis target substance remaining in the port is not sent out by the solvent, and the sample is analyzed accurately. Thus, automation of sample analysis can be realized.

  Moreover, you may provide the drying means for drying the 2nd solid-phase cartridge which adsorb | sucked the said sample.

  The filler of the first solid phase cartridge is octadecylsilane silica gel (C18), the filler of the second solid phase cartridge is octadecylsilane silica gel (C18) or stildivinylbenzene polymer (SDB), and the third The filler of the solid phase cartridge is preferably ethyldiamine-N-propylsilane silica gel (PSA), and the solvent for extruding the substance to be analyzed is a solution composed of acetonitrile and water, and includes a solution of acetonitrile and water. It is preferable that the ratio is 4: 1 to 1: 1, the elution solvent is a solution composed of hexane and acetone, and the ratio of hexane and acetone is 1: 1 to 4: 1.

In the second aspect of the present invention, a solution containing the analysis target substance is supplied to the first solid phase cartridge by a solvent for flushing out the analysis target substance, and a polarity changing solvent is supplied to the eluate from which impurities are removed. mixed mixture Te was supplied to the second solid phase cartridge, the analyte I analytical pretreatment method der organic chemicals Ru is adsorbed, the second solid phase cartridge was adsorbed analyte A sample that is dried, and then the elution solvent is supplied to the second solid phase cartridge, and the solution that flows along with the eluted substance to be analyzed is supplied to the third solid phase cartridge to adsorb ionic impurities and supplied to the gas chromatograph. It is characterized by taking a constant volume container and making it constant volume. The filler of the first solid phase cartridge is octadecylsilane silica gel (C18), the filler of the second solid phase cartridge is octadecylsilane silica gel (C18) or stildivinylbenzene polymer (SDB), and the third The filler of the solid phase cartridge is preferably ethylamine-N-propylsilane silica gel (PSA), and the solvent for pushing away the analyte is a solution comprising acetonitrile and water, and the ratio of acetonitrile to water Is 4: 1 to 1: 1, and the solvent supplied to the second solid phase cartridge is a solution composed of hexane and acetone, and the ratio of hexane and acetone is 1: 1 to 4: 1. Is particularly preferable, and the polarity-changing solvent is preferably water or saline. In the case of saline, the solvent is preferably set to 5 to 25% by weight. Properly, particularly preferred case of a 20 wt%.

  Conventionally, the pretreatment method in the analysis of organic chemical substances such as residual agricultural chemicals has been very complicated, and thus cannot be automated. Further, even if it is automated, the elution solvent and the substance to be analyzed (sample) are mixed with each other, so that the pretreatment is insufficient and a satisfactory effect cannot be obtained. The analysis pretreatment apparatus and analysis pretreatment method for organic chemicals using the solid phase cartridge of the present invention are difficult to automate by using a reverse phase solid phase extraction method in the pretreatment process. Concentration operation by rotary evaporator and nitrogen purge could be omitted, and the amount of sample could be reduced. Therefore, by using the pre-analysis apparatus of the present invention, it is possible to exert almost the same effect as the operation that has been performed manually, so that the accuracy of the analysis of organic chemical substances is improved, and the pre-analysis method for analysis Can be implemented efficiently.

It is a conceptual diagram of an analysis pretreatment apparatus. It is a block diagram which shows the detail of an analysis pretreatment apparatus, and has shown the state which is conditioning the 2nd and 3rd solid-phase cartridge with acetone. It is a block diagram which shows the detail of an analysis pre-processing apparatus, and has shown the state which is conditioning the 2nd and 3rd solid-phase cartridge with the solution which consists of hexane and acetone. It is a block diagram which shows the detail of an analysis pre-processing apparatus, and has shown the state which is conditioning the 1st and 2nd solid-phase cartridge with acetone. It is a block diagram which shows the detail of an analysis pre-processing apparatus, and has shown the state which is conditioning the 1st and 2nd solid-phase cartridge with the solution which consists of acetonitrile and water. It is a block diagram which shows the detail of an analysis pretreatment apparatus, and has shown the state holding the sample in a flow path. It is a block diagram which shows the detail of an analysis pre-processing apparatus, and has shown the state which has extruded the sample currently hold | maintained with the solution which consists of acetone and water. It is a block diagram which shows the detail of an analysis pre-processing apparatus, and has shown the state which has dried the 2nd solid-phase cartridge in the drying unit. It is a block diagram which shows the detail of an analysis pre-processing apparatus, and has shown the state which has eluted the to-be-analyzed substance from the dried 2nd solid-phase cartridge. It is a block diagram which shows the detail of an analysis pre-processing apparatus, and has shown the state which wash | cleans the flow path of a sample with acetone. It is a block diagram which shows the detail of an analysis pretreatment apparatus, and has shown the state which is conditioning the flow path of a sample with the solution which consists of acetonitrile and water.

  Although the organic chemical substance referred to in the present invention is not particularly limited, trace components such as residual agricultural chemicals and environmental hormones are preferred as objects of analysis for carrying out the present invention. Examples of residual pesticides include ashram, oxine copper, mecoprop, thiuram, ciduron, iprodione, chlorothalonil, pencyclon, bensulide and the like. Examples of environmental hormones include phenols such as nonylphenol and bisphenol A, phthalates, PCBs and dioxins, organotin compounds such as tributyltin and triphenyltin, and synthetic estrogens such as ethylestradiol and estriol. can do.

  Samples to be analyzed in the present invention are various waters such as air, drinking water, drainage, vegetable and animal foods, etc., which are attached to organic chemical substances and their surfaces. This refers to the sample to be analyzed for organic chemicals. For example, vegetables that should be analyzed for residual agricultural chemicals or environmental hormones adhering to the surface of vegetables.

  The substance to be analyzed in the present invention refers to an organic chemical substance that is contained in the sample to be analyzed and whose content is to be analyzed. For example, organic chemicals such as environmental hormones contained in the atmosphere, environmental hormones contained in water, organic chemicals such as residual agricultural chemicals, and organic chemicals contained in food ingredients and food surfaces. This refers to the target organic chemicals to be analyzed, such as attached organic chemicals.

  In the present invention, the sample to be analyzed can be used as an analysis sample as it is in various waters such as air, drinking water, and wastewater. However, in plant foods and animal foods, the organic material to be analyzed is usually used. Extract chemical substances with a solvent to make a constant volume, and prepare a sample for analysis. For example, vegetables and fruits are shredded, and cereals and beans are pulverized, sufficiently swelled with water, acetonitrile as a solvent, homogenized, filtered, and extracted with organic chemicals. And After the sample for analysis is adsorbed on the column of the liquid chromatograph, it is eluted with a mobile phase liquid different from the mobile phase liquid that has flowed into the liquid chromatograph. The pretreatment method according to the present invention is performed on a solution containing only the substance to be treated.

  The solid phase cartridge referred to in the present invention refers to a solid phase cartridge using a stildivinylbenzene polymer (SDB), octadecylsilane silica gel (C18), ethyldiamine-N-propylsilane silica gel (PSA) or the like as a filler, A filler having a good separability is used depending on the target organic chemical substance and impurities to be removed. Graphite carbon may be used to remove the pigment.

  In the present invention, the polarity-changing solvent means that a solution containing impurities and an analysis target substance is passed through the first solid phase cartridge, the impurities are adsorbed on the first solid phase cartridge, and then the analysis target substance is In order to adsorb to the second solid phase cartridge, a different solvent is mixed with the effluent of the first solid phase cartridge.

FIG. 1 shows an outline of an automatic pretreatment apparatus for taking out an analysis target substance contained in the analysis target sample. This automatic pretreatment apparatus includes a first apparatus for acquiring an analysis target substance, and a second apparatus for taking out an eluate from which ionic impurities such as fatty acids in the acquired analysis target substance are removed. Yes.
The first device includes an injection part F for injecting an analysis target substance, a first liquid feed pump P1 for injecting a solvent through a pipe L1 to push the analysis target substance injected into the injection part F, A first solid phase cartridge S1 for adsorbing nonpolar contaminants flowing from the injection section F through the tube L2, and the polarity of the solution containing the analyte to be supplied supplied to the tube L3 through the first solid phase cartridge S1 A second liquid-feeding pump P2 for merging the polarity-changing solvent for changing the amount into the tube L3 via the tube L4, a mixer M (which may be omitted) for stirring the combined solution, and stirring The supplied solution is supplied via the tube L5, and the second solid phase cartridge S2 for adsorbing the analysis target substance in the supplied solution and the polarity not adsorbed on the second solid phase cartridge S2 are used. And a pipe L6 for discharging contaminants from the composition to the outside, so that it is possible to obtain the analyte. In other words, a sample acquisition control means is provided in a control device (not shown), and when the substance to be analyzed is injected into the injection part F by this sample acquisition control means, the solvent sent out by the first liquid feed pump P1. As a result, the substance to be analyzed is swept away, and the nonpolar contaminants contained in the solution comprising the substance to be swollen and the solvent to be swept away are adsorbed and removed by the first solid phase cartridge S1. Subsequently, a solvent for polarity change is added to the solution that has passed through the first solid phase cartridge S1 by the second liquid feeding pump P2, and the solvent is supplied to the second solid phase cartridge S2. The sample acquisition is completed, and the sample acquisition control is completed.
The second device was eluted from the second solid phase cartridge S2 and the third liquid feed pump P3 for supplying the elution solvent to the second solid phase cartridge S2 from which the substance to be analyzed was obtained via the tube L7. The solution is supplied through the tube L8, and the third volume solid phase cartridge S3 for adsorbing ionic impurities such as fatty acids and the solution flowing together with the analyte to be analyzed that has passed through the third solid phase cartridge S3 have a constant volume. And a tube L9 for discharging to the test tube W, the substance to be analyzed can be taken out. As a means for moving the second solid phase cartridge S2 of the first device to the second device, the rotating body is provided with the second solid phase cartridge S2, and the rotating body is rotated and moved to the second device side. Any means may be used, such as moving by means of sliding movement. Although not shown, the second solid phase cartridge S2 is dried by a drying means before the analysis target substance obtained by the second solid phase cartridge S2 is eluted with the elution solvent.

More specific examples of the automatic pretreatment apparatus are shown in FIGS.
This automatic pretreatment apparatus is configured to complete the pretreatment work from six steps of a conditioning process, a sample acquisition process, a drying process, a sample removal process, a sample pipe cleaning process, and a sample pipe conditioning process.
Specifically, the sample vial B5 as a sample reservoir for storing the analysis target substance, the first solid phase cartridge S1 for adsorbing nonpolar impurities, and the second solid phase for adsorbing the analysis target substance Cartridge S2, a third solid phase cartridge S3 for adsorbing ionic impurities such as fatty acids, and a solvent (a solution composed of acetonitrile and water for sweeping away the substance to be analyzed, with a ratio of 4: 1 but it may be set to any ratio as long as it is in the range of 4: 1 to 1: 1), and the polarity changing solvent for changing the polarity of the solution containing the substance to be analyzed (Water or saline), an elution solvent for eluting the analyte to be adsorbed on the second solid phase cartridge S2 (a solution comprising hexane and acetone, the ratio of which is 1: 1) However, as long as it is in the range of 1: 1 to 4: 1, any ratio may be set). Each of the first to first constituting three (four or more) solvent reservoirs may be stored. The same number of the third bottles B1, B2, B3 and the bottles for receiving the solvent from the bottles are provided (if the number of injection ports for the elution solvent and the substance to be analyzed is different, the number is not necessarily the same. (In this case, there may be three, but two may be used) three inlets A, B, and C, and three first to three provided to supply the solvent stored in the bottle to the corresponding inlets. A third liquid feed pump P1, P2, P3 and a predetermined solvent connected to a specific solid phase cartridge among the three solid phase cartridges by receiving a specific solvent supplied to the injection port by the liquid supply pump Switch the position of the inlet to flow into the The sample vial B5 is connected to the outlet side of the inlet A connected to the switching means H for switching and the first liquid-feeding pump P1 for flushing out the analyte, and a predetermined amount of the analyte Is sucked by the first liquid feeding pump P1, and then sent out by the solvent in the first bottle B1 to supply a solution containing the substance to be analyzed and the solvent to the first solid phase cartridge S1, and the first solid phase cartridge S1. Sample acquisition control means N for adding the solvent for changing polarity in the second bottle B2 to the solution that has passed through the phase cartridge S1 and supplying it to the second solid phase cartridge S2 by the second liquid feeding pump P2, and the sample The acquisition control means N supplies the elution solvent in the third bottle B3 by the third liquid feed pump P3 for eluting the sample adsorbed on the second solid phase cartridge S2, and A sample delivery control means R for supplying the solution flowing together to the third solid phase cartridge S3, adsorbing ionic impurities such as fatty acids to the third solid phase cartridge S3, and taking out the sample into the extract vial B6; It has. T shown in FIG. 2 is a sample loading unit including the sample vial B5 and a cleaning container B7 described later. The elution solvent may be a mixed solvent of acetone, hexane, and toluene.

  In addition, a fourth bottle B4 that constitutes a solvent storage unit that stores a solvent for washing (acetone) and a fourth liquid feed pump P4 for sending out the solvent in the fourth bottle B4 are provided, and the analysis target substance is swept away. A switching valve V is provided in the middle portion of the flow path from the first bottle B1 for storing the solvent to the inlet A corresponding to the first bottle B1, and the analysis target substance sucked by the first liquid feeding pump P1 is It is configured to control the operation of the first liquid pump P1 so that the suction operation ends before entering the port 6 of the switching valve V (in practice, by setting the operation time of the first liquid pump P1) A set amount is sucked), the cleaning solvent is supplied to the switching valve V so as to be able to flow into the flow path LA, and the cleaning operation state for supplying the cleaning solvent and the analysis target Washed away material The switching control means X for switching the switching valve V to the sample acquisition operation state for supplying the solvent is provided so that only the inside of the flow path LA between the switching valve V and the inlet A can be cleaned. I have to.

  The switching valve V includes six ports 1 to 6 and can be switched between two positions, the position shown in FIG. 2 and the position shown in FIG. That is, the first position where the port 1 and the port 2, the port 3 and the port 4, the port 5 and the port 6 are in communication with each other, the port 1 and the port 6, the port 2 and the port 3, and the port 4 and the port 5 are Each can be switched to the second position in the communication state. The bottles B1 to B4 and the liquid feed pumps P1 to P4 are used as a bottle storage place U, and a solvent control unit for controlling a solvent such as switching control means X for switching the switching valve V is provided. After the cleaning solvent passes through the flow path LA, it is discharged to the waste liquid receiver B8 through the cleaning container B7.

  In addition, a drying unit K is provided as a drying means for drying the second solid phase cartridge S2 that has adsorbed the sample. Although this drying unit K is comprised from the nitrogen cylinder K1 and the flow volume control part K2 for controlling the flow volume of the nitrogen from this nitrogen cylinder K1, other structures may be sufficient.

  Each of the bottles B1 to B4 is provided with a valve v that can flow only in the four directions shown in the upper left of the paper surface of FIG.

  The four inlets A to D are provided in a rotating body (not shown) that is rotatable around a vertical axis, and by rotating the rotating body by a predetermined angle, an outlet of a specific inlet is predetermined. The switching means H is configured so that it can be connected to the flow path of the liquid. However, by sliding the four inlets at once or separately in the horizontal direction, the outlets of the specific inlets to the predetermined flow path. You may comprise so that it can connect.

Using the automatic pretreatment apparatus configured in this manner, as described above, the sample passes through the six steps of the conditioning process, the sample acquisition process, the drying process, the sample removal process, the sample pipe cleaning process, and the sample pipe conditioning. The taking out will be described.
First, the conditioning process is shown in FIG. 2 to FIG. 5. First, as shown in FIG. 2, the valve V is switched to the first position and the rotating body is rotated to exit the inlet B shown in FIG. Is connected to the flow path LB1 leading to the second solid phase cartridge S2, and then the acetone (cleaning solvent) is flowed from the fourth bottle B4 to the valve V by the fourth liquid feeding pump P4. To the injection port B. The supplied acetone flows from the inlet B to the waste liquid receiver B8 through the second solid phase cartridge S2 and the third solid phase cartridge S3 in this order.
Secondly, as shown in FIG. 3, the valve V is switched to the second position and the rotating body is rotated so that the outlet of the inlet C is connected to the flow path LC1 leading to the second solid phase cartridge S2. After that, a solution (elution solvent) composed of hexane and acetone is flowed from the third bottle B3 to the valve V from the third bottle B3 by the third liquid feeding pump P3, and is supplied to the inlet C via the flow path LC. The supplied solution flows from the inlet C to the waste liquid receiver B8 through the second solid phase cartridge S2 and the third solid phase cartridge S3 in this order.
Third, as shown in FIG. 4, the valve V is switched to the first position, and the rotating body is rotated so that the outlet B of the inlet B leads to the first solid phase cartridge S1 (different from LB1). Then, acetone (cleaning solvent) is caused to flow from the fourth bottle B4 to the valve V through the fourth liquid pump P4 to the inlet B via the flow path LB. Supply. The supplied solution flows from the inlet B to the waste liquid receiver B8 through the first solid phase cartridge S1, the T-shaped joint portion J to which the polarity changing solvent is supplied, and the second solid phase cartridge S2. .
Fourth, as shown in FIG. 5, the valve V is switched to the second position and the rotating body is rotated so that the outlet of the inlet B leads to the first solid phase cartridge S1 (LB3 (LB1, LB2). Are connected to different flow paths), and then a solution (a solvent for extruding the substance to be analyzed) consisting of acetonitrile and water is flowed to the valve V from the first bottle B1 by the first liquid pump P1. , And supplied to the inlet B through the flow path LB. The supplied solution flows from the inlet B to the waste liquid receiver B8 through the first solid phase cartridge S1, the T-shaped joint portion J to which the polarity changing solvent is supplied, and the second solid phase cartridge S2. .

The sample acquisition process is shown in FIGS. 6 and 7. First, as shown in FIG. 6, the valve V is switched to the first position and the rotating body is rotated so that the outlet of the inlet A leads to the sample vial B5. After the state connected to the path LA1, the sample acquisition control means N causes the sample vial B5 to be analyzed in a predetermined amount via the inlet A by the first liquid feed pump P1 (do not fill the path LA). After the suction, as shown in FIG. 7, the rotating body is rotated so that the inlet A is connected to the flow path LA2 communicating with the first solid phase cartridge S1, and then the liquid feeding A solvent (solution consisting of acetonitrile and water) for pushing away the substance to be analyzed is pushed out by the pump P1 and supplied to the inlet A, the flow path LA2, and the first solid phase cartridge S1, and the first solid phase cartridge S1 has no polarity. sex Contaminants adsorbed and removed. Subsequently, the saline solution (which may be water or a polarity changing solvent) in the second bottle B2 is passed through the first solid phase cartridge S1 and the solution flowing through the flow path LA3 by the second liquid feeding pump P2. In addition, the sample is supplied to the second solid phase cartridge S2, and the substance to be analyzed is adsorbed to the second solid phase cartridge S2, thereby completing the sample acquisition. An amount of the analyte in the sample vial B5 that does not fill the flow path LA via the inlet A with the first liquid feed pump P1 (actually about 1/3 or 1/2 of the flow path LA) Therefore, the analysis target substance can be held only in the flow path LA, and the analysis target substance and the solvent can be mixed into the port of the valve V. I am trying not to.
Thereafter, the process proceeds to the drying step, and as shown in FIG. 8, the rotating body is rotated to connect the drying unit K and the inlet D, and the outlet of the inlet D and the second solid phase cartridge S2 are connected. Are connected to each other through the flow path LD1, and then the second solid phase cartridge S2 is dried through the flow path LD, the inlet D, and the flow path LD1 with nitrogen.

Next, the process moves to the sample removal step, and as shown in FIG. 9, the rotating body is rotated so that the outlet of the inlet C is connected to the flow path LC1 leading to the second solid phase cartridge S2. The delivery control means R supplies the elution solvent (solution consisting of hexane and acetone) in the third bottle B3 with the delivery pump P3 to elute the sample adsorbed on the second solid phase cartridge S2, and elution The ionic impurities such as fatty acids in the solution flowing together with the sample are adsorbed on the third solid phase cartridge S3, and the sample is taken out into the extractant vial B6 to complete the taking out of the sample. The sample taken out to the extract vial B6 is put into the inlet of the gas chromatograph to analyze the sample.
By providing the elution solvent injection port C separately from the analysis target material injection port A as described above, it is necessary to wash the tubes constituting the elution solvent flow path without mixing them together. Absent. Further, there is an advantage that the analysis target substance does not enter the port 6 of the switching valve V when the analysis target substance is aspirated, the cleaning of the port can be made unnecessary, and the sample can be taken out with high accuracy.

  After the removal of the sample is completed, the process moves to the sample line cleaning step. As shown in FIG. 10, the valve V is switched to the second position and the rotating body is rotated so that the outlet of the inlet A leads to the flow path LA3 (the flow path is different from LA1 and LA2) leading to the cleaning container B7. After being connected, acetone (cleaning solvent) is flowed from the fourth bottle B4 to the port 6 from the port 1 to the port 6 through the flow path LP4 by the fourth liquid feeding pump P4, and the flow path LA is passed through the flow path LA. To the injection port A. The supplied cleaning solvent flows from the inlet A to the waste liquid receiver B8 through the flow path LA3, the cleaning container B7, and the flow path LA4 in this order to complete the cleaning process.

  Next, as shown in FIG. 11, conditioning in the cleaned pipeline (flow path) is performed, and a series of control operations is completed. That is, the valve V is switched to the first position and the rotating body is rotated so that the outlet of the injection port A is connected to the flow path LA3 (the flow path is different from LA1 and LA2) leading to the cleaning container B7. After that, a solution consisting of acetonitrile and water (solvent for extruding the substance to be analyzed) is flowed from the first bottle B1 to the port 5 to the port 6 of the valve V through the flow path LP1 by the first liquid feeding pump P1. , And supplied to the inlet A through the flow path LA. The supplied solution flows from the inlet A to the waste liquid receiver B8 through the flow path LA3, the cleaning container B7, and the flow path LA4 in this order, and the last step is completed.

The automatic pretreatment apparatus of the present invention can quickly perform pretreatment of analytical samples in gas chromatographic analysis of organic chemical substances, and promptly and precisely measure multi-component residual pesticides and environmental hormones. It is possible to quickly evaluate the safety of the target food.
Further, the filler of the third solid phase cartridge S3 may be composed of only PSA, and may be added with graphite carbon for removing the dye. In this case, PSA and graphite carbon may be divided and filled, or may be filled in a mixed state in which both are completely mixed.

Claims (17)

  Included in a solution comprising an injection part for injecting an analysis target substance, a first liquid feed pump for sending out a solvent for pushing away the analysis target substance injected into the injection part, and an analysis target substance and the solvent for pushing away The polarity of the first solid phase cartridge for adsorbing the nonpolar contaminants, the second solid phase cartridge for adsorbing the analyte, and the solution containing the analyte from which the contaminants are removed are changed. A second liquid-feeding pump for sending out the polarity-changing solvent for feeding, and a mixture in which the solvent for polarity-changing from the second liquid-feeding pump is fed into and mixed with the solution containing the analysis target substance from which impurities are removed A sample acquisition control means for supplying the liquid to the second solid phase cartridge and acquiring the analysis target substance by adsorbing the analysis target substance; Pretreatment device.   A sample storage part for storing an analysis target substance, a first solid phase cartridge for adsorbing nonpolar impurities, a second solid phase cartridge for adsorbing the analysis target substance, and an ionic contaminant Third solid phase cartridge, solvent for flushing out the analyte, polarity changing solvent for altering the polarity of the solution containing the analyte, and analysis adsorbed on the second solid phase cartridge At least three solvent reservoirs for respectively storing elution solvents for eluting the target substance, at least two inlets for receiving the elution solvent and the analyte substance from the sample reservoir, and At least three liquid feed pumps provided to supply the solvent stored in the solvent storage section to the inlet, and the liquid pump supplied to the inlet A switching means for switching the position of the inlet for receiving a predetermined solvent and flowing it out to a predetermined flow path connected to a specific solid phase cartridge of the three solid phase cartridges; The sample reservoir is connected to the outlet side of the inlet connected to a liquid feed pump for pushing away the substance, and a predetermined amount of the substance to be analyzed is sucked by the liquid feed pump, and then pushed away. A solution containing the substance to be analyzed and the solvent is supplied to the first solid phase cartridge by being sent out by a solvent, and a polarity changing solvent is added to the solution that has passed through the first solid phase cartridge to add to the second solid phase cartridge. A sample acquisition control means for supplying, and the elution solvent for eluting the sample adsorbed on the second solid phase cartridge by the sample acquisition control means. And a sample delivery control means for supplying a solution flowing together with the sample to the third solid phase cartridge, and adsorbing ionic impurities to the third solid phase cartridge to take out the sample. Analytical pretreatment equipment for organic chemicals.   In Claim 2, the solvent storage part which stores the solvent for washing | cleaning, and the liquid feed pump for sending out the solvent of this solvent storage part are provided, and the solvent storage part which stores the solvent for pushing out the said to-be-analyzed substance is changed to this A switching valve is provided in the middle of the flow path to the corresponding inlet, and the feeding pump is configured so that the aspirating operation is terminated before the analyte to be aspirated by the feeding pump enters the port of the switching valve. A cleaning operation state in which the cleaning solvent is supplied to the switching valve so as to be able to flow out to the flow path, and the cleaning solvent is supplied and the analysis target An organic chemical pre-analysis processing apparatus comprising switching control means for switching the switching valve to a sample acquisition operation state for supplying a solvent for extruding a substance.   4. The organic chemical substance pretreatment analysis apparatus according to claim 2, further comprising a drying unit for drying the second solid phase cartridge that has adsorbed the sample.   5. The filler according to claim 1, wherein the filler of the first solid phase cartridge is octadecylsilane silica gel (C18), and the filler of the second solid phase cartridge is octadecylsilane silica gel (C18) or stildivinylbenzene heavy weight. Analytical pretreatment equipment for organic chemical substances that are combined (SDB).   The analysis pretreatment apparatus for organic chemical substances according to any one of claims 2 to 4, wherein the filler of the third solid phase cartridge is ethyldiamine-N-propylsilane silica gel (PSA).   5. The organic chemical substance according to claim 1, wherein the solvent for extruding the substance to be analyzed is a solution composed of acetonitrile and water, and the ratio of acetonitrile to water is 4: 1 to 1: 1. Analysis pretreatment equipment.   5. The analytical pretreatment apparatus for organic chemical substances according to claim 2, wherein the elution solvent is a solution composed of hexane and acetone, and the ratio of hexane to acetone is 1: 1 to 4: 1. . A solution containing the analysis target substance is supplied to the first solid phase cartridge by a solvent for flushing out the analysis target substance, and a mixed liquid is supplied by supplying a solvent for polarity change to the eluate from which impurities are removed. A method for pre-analysis of an organic chemical substance that is supplied to a second solid phase cartridge and adsorbs the analysis target substance, wherein the second solid phase cartridge on which the analysis target substance is adsorbed is dried, and then an elution solvent is used. A sample that is supplied to the second solid phase cartridge and flows along with the eluted analyte to be supplied to the third solid phase cartridge to adsorb ionic impurities and is supplied to the gas chromatograph is taken in a constant volume container, Analytical pretreatment method for organic chemicals characterized by constant volume . In claim 9, the filler of the first solid phase cartridge is octadecylsilane silica gel (C18), filler of the second solid phase cartridges with octadecylsilane silica gel (C18) or still divinylbenzene polymer (SDB) Analytical pretreatment method for certain organic chemicals. 10. The analytical pretreatment method for an organic chemical substance according to claim 9 , wherein the filler of the third solid phase cartridge is ethyldiamine-N-propylsilane silica gel (PSA). The analysis pretreatment method for an organic chemical substance according to claim 9 , wherein the solvent for sweeping away the substance to be analyzed is a solution composed of acetonitrile and water, and the ratio of acetonitrile to water is 4: 1 to 1: 1. . 10. The pretreatment method for analyzing an organic chemical substance according to claim 9 , wherein the elution solvent is a solution composed of hexane and acetone, and the ratio of hexane to acetone is 1: 1 to 4: 1. The analysis pretreatment method for an organic chemical substance according to claim 9 , wherein the polarity changing solvent is water or saline. A solution containing the analysis target substance is supplied to the first solid phase cartridge by a solvent for flushing out the analysis target substance, and a mixed liquid is supplied by supplying a solvent for polarity change to the eluate from which impurities are removed. An analysis pretreatment method for an organic chemical substance that is supplied to a second solid phase cartridge and adsorbs the analyte, wherein the filler of the first solid phase cartridge is octadecylsilane silica gel (C18), An analytical pretreatment method for an organic chemical substance in which the solid phase cartridge is filled with octadecylsilane silica gel (C18) or stildivinylbenzene polymer (SDB). A solution containing the analysis target substance is supplied to the first solid phase cartridge by a solvent for flushing out the analysis target substance, and a mixed liquid is supplied by supplying a solvent for polarity change to the eluate from which impurities are removed. An analysis pretreatment method for an organic chemical substance that is supplied to a second solid phase cartridge and adsorbs the analysis target substance, wherein the solvent for sweeping the analysis target substance is a solution comprising acetonitrile and water, and acetonitrile Analytical pretreatment method for organic chemicals in which the ratio of water to water is 4: 1 to 1: 1. A solution containing the analysis target substance is supplied to the first solid phase cartridge by a solvent for flushing out the analysis target substance, and a mixed liquid is supplied by supplying a solvent for polarity change to the eluate from which impurities are removed. An analysis pretreatment method for an organic chemical substance that is supplied to a second solid phase cartridge and adsorbs the analysis target substance, wherein the organic chemical substance pretreatment method is such that the polarity changing solvent is water or saline.

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