ICP analysis device and icp analysis method

Abstract

The present invention relates to an ICP analysis device and an ICP analysis method, which can automatically perform from calibration of the device to analysis of a sample in ICP analysis, having a mixing section having two inlet ports and one outlet port, a common flow path having one end connected to an ICP section and the other end connected to the outlet port, a main flow path having one end connected to one of the inlet ports, an automatic sampler connected to the other end of the main flow path, a flow path switching section connecting one outlet port to any one of a plurality of inlet ports, a sub flow path having one end connected to the remaining inlet port of the mixing section and the other end connected to the outlet port, a calibration solution pipe having one end inserted into a calibration solution container and the other end connected to one of the inlet ports, an internal standard pipe having one end inserted into an internal standard element solution container and the other end connected to the other inlet port, one peristaltic pump for delivering liquids in the main flow path and the sub flow path, and a control section for controlling the automatic sampler and the flow path switching section.

Description

TECHNICAL FIELD

[0001] The present application relates to an ICP (Inductively Coupled Plasma) analysis device and an ICP analysis method. BACKGROUND

[0002] In an ICP mass analysis device, a liquid sample is atomized and introduced into an inductively coupled plasma flame, and ions of a target element in the sample are ionized, and the generated ions are used for mass analysis, whereby qualitative analysis and quantitative analysis of the sample are performed. In an ICP emission spectroscopic analysis device, a liquid sample is atomized and introduced into an inductively coupled plasma flame, and light generated by heating and excitation of a target element in the sample is subjected to spectroscopic analysis, whereby qualitative analysis and quantitative analysis of the sample are performed. Here, an analysis device using inductively coupled plasma, such as an ICP mass analysis device and an ICP emission spectroscopic analysis device, is collectively referred to as an ICP analysis device, and analysis using these devices is collectively referred to as ICP analysis.

[0003] In an ICP analysis device, physical properties such as viscosity and volatility of a sample change due to the influence of other components other than a target element contained in the sample, and as a result, the conditions of sample delivery and atomization change, which affects the analysis results (such a phenomenon is referred to as physical interference). In order to correct the influence of such physical interference, in quantitative analysis using an ICP analysis device, an internal standard element solution containing a predetermined internal standard element at a predetermined concentration is added to a liquid sample in a predetermined amount, and then ICP analysis of the sample is performed, and the concentration of the target element in the sample is calculated based on the ratio of the detection intensities of the target element and the internal standard element. However, in the case of simultaneously analyzing a plurality of samples, it is troublesome to add a certain amount of an internal standard element solution to each sample by manual work. Therefore, an ICP analysis device provided with a mechanism for automatically adding an internal standard element solution to a sample has been developed (for example, refer to Patent Literature 1).

[0004] Such an ICP analysis device provided with an automatic internal standard element solution adding mechanism is provided with a main flow path for collecting a liquid sample, a sub flow path for collecting an internal standard element solution, and a common flow path which is connected to the main flow path and the sub flow path via a mixing portion constituted by a T-shaped pipe or the like. The liquid sample collected via the main flow path and the internal standard element solution collected via the sub flow path are mixed by being merged at the mixing portion, and are introduced to a torch (plasma torch) for forming a plasma flame via the common flow path.

[0005] In the ICP analysis device having the above-described structure, a peristaltic pump for pressure-feeding liquid in the soft tube constituting each flow path is provided in the main flow path and the sub flow path. The peristaltic pump pressure-feeds the liquid in the soft tube by peristaltically pressing the tube in conjunction with rotation of a rotor, and in its structure, the liquid feeding amount periodically varies. Therefore, in a case where one peristaltic pump is provided in each of the main flow path and the sub flow path, the mixing ratio of the sample liquid and the internal standard element solution introduced into the plasma torch fluctuates due to a deviation in the rotation period of the rotor in each peristaltic pump, and the quantitative value deviates.

[0006] Therefore, in order to prevent such fluctuation in the mixing ratio, sometimes, one multi-channel peristaltic pump is used for liquid feeding of the sample liquid in the main flow path and liquid feeding of the internal standard element solution in the sub flow path. In the multi-channel peristaltic pump, a plurality of soft tubes can be arranged along the outer periphery of the rotor, and therefore, by using this pump, liquid of a flow rate corresponding to the inner diameter of each tube can be made to flow in the tube constituting the main flow path and the tube constituting the sub flow path with the same period.

[0007] Prior art documents

[0008] Patent documents

[0009] Patent Document 1: Japanese Patent Application Publication No. 2016-061574 SUMMARY

[0010] Problems to be solved by the invention

[0011] In calibration of the ICP analysis device, a predetermined calibration liquid is introduced into the plasma flame instead of the mixed liquid of the sample and the internal standard element solution described above. Therefore, in the conventional ICP analysis device having the above-described structure, first, in a state where both the end of the tube constituting the main flow path and the end of the tube constituting the sub flow path are inserted into a container (hereinafter referred to as a calibration liquid container) in which the calibration liquid is stored, the calibration liquid is introduced into the plasma torch by the multi-channel peristaltic pump to perform a calibration operation, and then, the tube constituting the main flow path is reinserted from the calibration liquid container into a container in which the sample is stored, and the tube constituting the sub flow path is reinserted from the calibration liquid container into a container (hereinafter referred to as an internal standard element solution container) in which the internal standard element solution is stored, to perform analysis of the sample. However, this reinsertion of the tubes needs to be performed by manual work by an analysis operator, and therefore, in the above-described conventional ICP analysis device, it is not possible to automatically perform processing from calibration of the device to analysis of the sample.

[0012] Further, if configured to connect the main flow path and the sub flow path to the automatic sampler respectively, and perform both switching of the liquid flowing in the main flow path and switching of the liquid flowing in the sub flow path using the automatic sampler, it is possible to automatically perform the process from the calibration of the device to the analysis of the measurement target sample. However, in this case, control of different actions of switching of the main flow path and switching of the sub flow path is required, and the device becomes large. Alternatively, it is also possible to automatically perform the process from the calibration of the device to the analysis of the sample in a state where only the main flow path is connected to the automatic sampler and the tube configuring the sub flow path is always inserted into the internal standard element solution container, but in this case, since the internal standard element solution is supplied from the sub flow path to the plasma torch also at the time of calibration, it is possible that accurate calibration cannot be performed. In the structure where only the main flow path is connected to the automatic sampler and the tube configuring the sub flow path is always inserted into the internal standard element solution container, in order to stop the supply of the internal standard element solution from the sub flow path to the plasma torch at the time of calibration, it is necessary to configure a structure where liquid feeding in the main flow path and liquid feeding in the sub flow path are performed using respective peristaltic pumps, but in this case, since there is a deviation in the rotation period of the rotor in each peristaltic pump, the mixing ratio of the sample liquid and the internal standard element solution introduced to the plasma torch fluctuates.

[0013] The present application is made in view of the above problems, and aims to automatically perform the process from the calibration of the device to the analysis of the sample in ICP analysis without using a large device and without reducing the calibration accuracy.

[0014] Solution to the problem

[0015] The ICP analysis device of the present application made to solve the above problems has:

[0016] an ICP section that generates an inductively coupled plasma;

[0017] a liquid mixing section that has two inlet ports and one outlet port;

[0018] a common flow path that has one end connected to the ICP section and the other end connected to the outlet port of the liquid mixing section;

[0019] a main flow path that has one end connected to one of the two inlet ports of the liquid mixing section;

[0020] an automatic sampler that collects liquid from one of a plurality of liquid containers and supplies it to the other end of the main flow path;

[0021] a flow path switching section that has one outlet side port and a plurality of inlet side ports, and connects the outlet side port to one of the plurality of inlet side ports;

[0022] a sub-flow path having one end connected to the other of the two inlet ends of the liquid mixing section and the other end connected to the outlet-side port of the flow path switching section;

[0023] a correction liquid pipe connected to one of the plurality of inlet-side ports of the flow path switching section to guide a correction liquid to the one of the plurality of inlet-side ports;

[0024] an internal standard element solution pipe connected to the other of the plurality of inlet-side ports of the flow path switching section to guide an internal standard element solution to the other of the plurality of inlet-side ports;

[0025] a peristaltic pump that transports the liquid in the main flow path from the other end of the main flow path to the one end and transports the liquid in the sub-flow path from the other end of the sub-flow path to the one end; and

[0026] a control section that controls the automatic sampler and the flow path switching section.

[0027] Further, an ICP analysis method of the present application, which is achieved to solve the above-described problems, is an ICP analysis method using an ICP analysis device having:

[0028] an ICP section that generates an inductively coupled plasma;

[0029] a liquid mixing section having two inlet ends and one outlet end;

[0030] a common flow path having one end connected to the ICP section and the other end connected to the outlet end of the liquid mixing section;

[0031] a main flow path having one end connected to one of the two inlet ends of the liquid mixing section;

[0032] an automatic sampler that selectively collects a liquid from one of a plurality of liquid containers and supplies the liquid to the other end of the main flow path;

[0033] a flow path switching section having one outlet-side port and a plurality of inlet-side ports, the outlet-side port being selectively connected to one of the plurality of inlet-side ports;

[0034] a sub-flow path having one end connected to the other of the two inlet ends of the liquid mixing section and the other end connected to the outlet-side port of the flow path switching section;

[0035] a correction liquid pipe connected to one of the plurality of inlet-side ports of the flow path switching section to guide a correction liquid to the one of the plurality of inlet-side ports;

[0036] an internal standard element solution pipe connected to another of the plurality of inlet-side ports of the flow path switching section to guide an internal standard element solution to the other inlet-side port;

[0037] a peristaltic pump that conveys liquid in the main flow path from the other end of the main flow path toward the one end and conveys liquid in the sub flow path from the other end of the sub flow path toward the one end; and

[0038] a control section that controls the automatic sampler and the flow path switching section, wherein

[0039] the automatic sampler is placed with a liquid container that contains a correction liquid and a liquid container that contains a measurement target sample as the plurality of liquid containers,

[0040] the outlet-side port of the flow path switching section is connected to the inlet-side port of the plurality of inlet-side ports that is connected to the correction liquid pipe, and correction is performed in a state in which the correction liquid is collected from the liquid container that contains the correction liquid by the automatic sampler and is supplied to the other end of the main flow path,

[0041] then, the outlet-side port of the flow path switching section is connected to the inlet-side port of the plurality of inlet-side ports that is connected to the internal standard element solution pipe, and the measurement target sample is collected from the liquid container that contains the measurement target sample by the automatic sampler and is supplied to the other end of the main flow path, and thus ICP analysis of the measurement target sample is performed.

[0042] Effects of the invention

[0043] According to the present application described above, in ICP analysis, it is possible to automatically perform processing from correction of a device to analysis of a measurement target sample without using a large device and without reducing correction accuracy. BRIEF DESCRIPTION OF DRAWINGS

[0044] Figure 1 is a schematic configuration diagram of an ICP quality analysis device of an embodiment of the present application.

[0045] Figure 2 is a flowchart showing the operation of the ICP quality analysis device of the embodiment.

[0046] Figure 3 is a schematic configuration diagram of an ICP quality analysis device of another embodiment of the present application.

[0047] Explanation of reference numerals

[0048] 110, sample introduction section; 111, common flow path; 112, main flow path; 113, sub flow path; 114, T-shaped tube; 120, automatic sampler; 122, 2nd rinse solution container; 123, 2nd calibration solution container; 124, measurement target sample container; 130, peristaltic pump; 140, flow path switching valve; 141, rinse solution piping; 142, calibration solution piping; 143, internal standard element solution piping; 144, 1st rinse solution container; 145, 1st calibration solution container; 146, internal standard element solution container; 150, ICP section; 152, plasma torch; 160, mass analysis section; 2, control / processing section. DETAILED DESCRIPTION

[0049] An ICP mass spectrometer according to one embodiment of the present application will be described below with reference to the accompanying drawings. Figure 1 is a main part configuration of the ICP mass spectrometer according to the present embodiment. The ICP mass spectrometer is generally configured of a sample introduction section 110, an ICP section 150, a mass analysis section 160, and a control / processing section 170.

[0050] The sample introduction section 110 is a member that introduces various liquids such as a measurement target sample to the ICP section 150, and is provided with a common flow path 111, a main flow path 112, a sub flow path 113, an automatic sampler 120, a peristaltic pump 130, and a flow path switching valve 140. One end of each of the common flow path 111, the main flow path 112, and the sub flow path 113 is connected to each other via a T-shaped tube 114 (corresponding to the "liquid mixing section" in the present application). The other end of the common flow path 111 is connected to a plasma torch 152 via a nebulizer 155 described later, and the other end of the main flow path 112 is connected to the automatic sampler 120. In addition, the other end of the sub flow path 113 is connected to the flow path switching valve 140.

[0051] The automatic sampler 120 is capable of accommodating a sample rack 121 in its inside, and is provided with a sampling needle 125 for aspirating liquids from a plurality of liquid containers (2nd rinse solution container 122, 2nd calibration solution container 123, and measurement target sample container 124 described later) placed on the sample rack 121, and a needle driving mechanism 126 for moving the sampling needle 125 in a horizontal direction and a vertical direction. The other end of the main flow path 112 is connected to a base end side of the sampling needle 125 directly or via piping provided in the automatic sampler 120.

[0052] The flow path switching valve 140 is a three-way switching valve having a common port a, a first port b, a second port c, and a third port d, and is capable of connecting the common port a to any one of the first port b, the second port c, and the third port d. Here, the common port a corresponds to the "outlet-side port" of the present application, and the first port b, the second port c, and the third port d correspond to the "inlet-side ports" of the present application. Further, the flow path switching valve 140 can be disposed, for example, inside a housing (not shown) in which the ICP section 150 and the mass analysis section 160 are housed, but the disposition of the flow path switching valve 140 is not limited thereto.

[0053] The other end of the sub flow path 113 is connected to the common port a of the flow path switching valve 140. One ends of a rinse liquid pipe 141, a calibration liquid pipe 142, and an internal standard element solution pipe 143 are connected to the first port b, the second port c, and the third port d, respectively, and the other end of the rinse liquid pipe 141 is inserted into a first rinse liquid container 144, the other end of the calibration liquid pipe 142 is inserted into a first calibration liquid container 145, and the other end of the internal standard element solution pipe 143 is inserted into an internal standard element solution container 146. A rinse liquid (for example, water or a predetermined organic solvent) for rinsing the sub flow path 113, the T-shaped pipe 114, the common flow path 111, and the like is housed in the first rinse liquid container 144, and a calibration liquid is housed in the first calibration liquid container 145. As the calibration liquid, for example, a solution containing a plurality of components whose theoretical m / z is known at a predetermined concentration is used. Further, an internal standard element solution containing a predetermined internal standard element (for example, an element known not to be contained in a measurement target sample) at a predetermined concentration is housed in the internal standard element solution container 146.

[0054] The peristaltic pump 130 is a component for transporting liquids in the main flow path 112 and the sub flow path 113. The peristaltic pump 130 in the present embodiment is a multi-channel peristaltic pump 130 capable of simultaneously transporting liquids in at least two pipes. The peristaltic pump 130 has a cylindrical rotor 131, a plurality of press rollers 132 mounted to the outer periphery of the rotor 131, and a pressing member 133 provided near the outer periphery of the rotor 131. The main flow path 112 and the sub flow path 113 each have at least a portion thereof composed of a soft tube. These soft tubes are held between the outer periphery of the rotor 131 and the pressing member 133 in a state of being parallel to each other and orthogonal to the central axis of the rotor 131. In this state, when the rotor 131 rotates around the central axis thereof, the soft tubes are sequentially pinched between the pressing member 133 and the press rollers 132, and liquids flow in the soft tubes at a flow rate corresponding to the inner diameter thereof.

[0055] The ICP section 150 includes a plasma torch 152 that generates a plasma flame using a high-frequency magnetic field of the high-frequency coil 151, a plasma gas supply source 153 that supplies a plasma gas (e.g., argon) to the plasma torch 152, an auxiliary gas supply source 154 that supplies an auxiliary gas to the plasma torch 152, a nebulizer 155 that nebulizes a liquid supplied from the sample introduction section 110 into a nebulization chamber 157, and a nebulizer gas supply source 156 that supplies a nebulization gas to the nebulizer 155. The liquid introduced into the ICP section 150 via the common flow path 111 is nebulized into the nebulization chamber 157 from the nebulizer 155 with the aid of the nebulization gas supplied from the nebulizer gas supply source 156. The liquid thus nebulized is introduced into the plasma torch 152, and the components in the liquid are ionized by the plasma flame.

[0056] The ions generated in the ICP section 150 are transported to the mass analysis section 160, where they are separated and detected according to m / z.

[0057] The control / processing section 170 performs arithmetic processing on data (detection data) based on the detection signal obtained by the mass analysis section 160 according to a predetermined algorithm, thereby performing qualitative analysis or quantitative analysis of the measurement target sample. Furthermore, the control / processing section 170 controls the operation of the respective sections as a whole. The functions of the control / processing section 170 are mostly realized by executing a predetermined program on a computer such as a personal computer equipped with a CPU, a memory, and a mass storage device. An input section composed of a keyboard and the like and an output section composed of a display and the like are also connected to the computer.

[0058] The calibration of the ICP mass spectrometer of the present embodiment is performed according to the instruction of the user (an analyst). For example, in an analysis site where the ICP mass spectrometer is started up every morning and a plurality of measurement target samples are sequentially measured in a day, the calibration work is performed after the start-up of the device before the measurement of the measurement target samples. The flowchart of FIG. 1 is described below with reference to the calibration work and the analysis steps of the measurement target samples and the operation of the sample introduction section 110 at that time. Figure 2

[0059] ​Further, in performing the above-described correction work and analysis of the measurement target sample, the user previously places a liquid container (hereinafter referred to as "second rinse liquid container 122") that accommodates a rinse liquid, a liquid container (hereinafter referred to as "second correction liquid container 123") that accommodates a correction liquid, and a plurality of liquid containers (hereinafter referred to as "measurement target sample containers 124") that accommodate measurement target samples on the sample rack 121, and previously accommodates the sample rack 121 in the automatic sampler 120. Further, as the rinse liquid accommodated in the second rinse liquid container 122, for example, the same rinse liquid as that accommodated in the above-described first rinse liquid container 144 can be used. In addition, as the correction liquid accommodated in the second correction liquid container 123, for example, the same rinse liquid as that accommodated in the above-described first correction liquid container 145 can be used. In addition, the measurement target samples accommodated in the plurality of measurement target sample containers 124, respectively, are not limited to analyzed samples that are the objects of qualitative analysis or quantitative analysis, but can be standard samples for calibration curve preparation.

[0060] In addition, in performing the above-described correction work and analysis of the measurement target sample, the user inputs the positions (for example, hole numbers) of the second rinse liquid container 122, the second correction liquid container 123, and each measurement target sample container 124 on the sample rack 121 by further operating an input section (omitted from the drawing) provided in the control / processing section 170, creates an analysis schedule that describes the execution order and analysis conditions and the like of the analysis of the measurement target samples accommodated in each measurement target sample container 124, and stores it in a predetermined storage section (omitted from the drawing) provided in the control / processing section 170.

[0061] Then, the user activates the ICP mass analysis device by performing a predetermined operation on the control / processing section 170 (step 11). Thereby, first, the main flow path 112 and the sub flow path 113 are connected to the second rinse liquid container 122 and the first rinse liquid container 144, respectively (step 12). Specifically, the flow path switching valve 140 is driven under the control of the control / processing section 170 to a state in which the common port a is connected to the first port b (the port to which the rinse liquid pipe 141 is connected), and the needle driving mechanism 126 of the automatic sampler 120 is driven to a state in which the sampling needle 125 is inserted into the second rinse liquid container 122 on the sample rack 121. Then, in this state, the rotor 131 of the peristaltic pump 130 is driven under the control of the control / processing section 170 to suck the rinse liquid from the second rinse liquid container 122 via the main flow path 112, and the rinse liquid from the first rinse liquid container 144 via the sub flow path 113. These rinse liquids are introduced to the ICP section 150 via the T-shaped pipe 114 and the common flow path 111.

[0062] Then, at the time when the plasma torch 152 is lit and a predetermined time (warm-up time) has passed (i.e., the time when the step 13 becomes "Yes"), the flow path switching valve 140 and the needle drive mechanism 126 are driven again, and the sampling needle moves to be inserted into the 2nd correction liquid container 123 and the 1st correction liquid container 145. Thereby, the main flow path 112 and the sub flow path 113 become connected to the 2nd correction liquid container 123 and the 1st correction liquid container 145, respectively (step 14). Specifically, the connection destination of the common port a of the flow path switching valve 140 is changed from the 1st port b to the 2nd port c (the port to which the correction liquid pipe 142 is connected), and the sampling needle 125 of the autosampler 120 is lifted from the 2nd rinse liquid container 122 to be inserted into the 2nd correction liquid container 123. In this state, by the liquid delivery by the peristaltic pump 130, the correction liquid is sucked from the 2nd correction liquid container 123 via the main flow path 112, and the correction liquid is sucked from the 1st correction liquid container 145 via the sub flow path 113, and these correction liquids are introduced to the ICP section 150 via the T-junction 114 and the common flow path 111. Thereby, the plurality of known components included in the correction liquid are ionized in the ICP section 150, and the ions are analyzed in the mass analysis section 160, and the mass spectrum is generated based on the output signal from the mass analysis section 160 at this time by the control / handling section 170.

[0063] Then, in the control / handling section 170, peaks with respect to each of the plurality of known components included in the correction liquid are determined from the plurality of peaks included in the mass spectrum, and the correction of the apparatus is performed based on the m / z or height of each peak (step 15). In the correction, the relative position of the plasma torch 152 with respect to the mass analysis section 160 can be adjusted, or the applied voltage to the mass analysis section 160 can be adjusted, based on the intensity of each peak on the mass spectrum obtained by the analysis of the correction liquid.

[0064] When the calibration of the apparatus is completed according to the above, the main flow path 112 is connected to the first one of the plurality of measurement target sample containers 124 placed on the sample rack, and the sub flow path 113 is connected to the internal standard element solution container 146 (step 16). Specifically, under the control of the control / processing section 170, the connection destination of the common port a of the flow path switching valve 140 is changed from the 2nd port c to the 3rd port d (the port to which the internal standard element solution pipe 143 is connected), and the sampling needle 125 of the automatic sampler 120 is withdrawn from the 2nd calibration liquid container 123 and inserted into the first one of the measurement target sample containers 124 described in the above-mentioned analysis schedule. Thereby, by the action of the peristaltic pump 130, a state is brought about in which the measurement target sample is sucked from the first one of the measurement target sample containers 124 via the main flow path 112 and the internal standard element solution is sucked from the internal standard element solution container 146 via the sub flow path 113. Then, the measurement target sample and the internal standard element solution sucked in flow into the common flow path via the T-shaped pipe 114, and a mixed liquid in which the measurement target sample and the internal standard element solution are mixed at a predetermined ratio is generated. The mixed liquid is introduced into the ICP section 150 via the common flow path 111, the atomizer 155, and the spray chamber 157, whereby the constituent ions in the mixed liquid are ionized, and analyzed in the mass analysis section 160 (step 17).

[0065] After the ionization and mass analysis of the measurement target sample in the first one of the measurement target sample containers 124 are completed according to the above, the connection destination of the main flow path 112 is changed to the 2nd rinse liquid container 122 (step 18). That is, the sampling needle 125 of the automatic sampler 120 is withdrawn from the first one of the measurement target sample containers 124 and inserted into the 2nd rinse liquid container 122. Thereby, by the action of the peristaltic pump 130, rinse liquid is sucked from the 2nd rinse liquid container 122, and the inside of the main flow path 112, the T-shaped pipe 114, the common flow path 111, and the atomizer 155 are rinsed with the rinse liquid.

[0066] Then, the control / processing section 170 refers to the above-mentioned analysis schedule, and determines whether analysis of all of the measurement target samples has been completed (step 19), and in the case where it has not been completed, the sampling needle 125 of the automatic sampler 120 is inserted into the next one of the measurement target sample containers 124 described in the analysis schedule (step 20), and ionization by the ICP section 150 and analysis by the mass analysis section 160 are performed on the mixed liquid of the next one of the measurement target samples and the internal standard element solution (step 17). Then, the processing of steps 17 to 20 is repeatedly executed until analysis of all of the measurement target samples placed on the sample rack 121 is completed (i.e., until "Yes" in step 19).

[0067] After the analysis of all the measurement target samples is completed, the main flow path 112 and the sub flow path 113 are again connected to the 2nd rinse solution container 122 and the 1st rinse solution container 144, respectively (step 21). Specifically, the flow path switching valve 140 is driven under the control of the control / handling section 170, the connection destination of the common port a is changed from the 3rd port d to the 1st port b, and the needle driving mechanism 126 is driven, the sampling needle 125 of the autosampler 120 is lifted from the measurement target sample container 124 and inserted into the 2nd rinse solution container 122.

[0068] As described above, according to the ICP mass analysis device of the present embodiment, the connection destinations of the main flow path 112 and the sub flow path 113 are automatically changed by the autosampler 120 and the flow path switching valve 140, and thus a series of processes from the calibration of the device to the analysis of the measurement target sample can be automatically performed. In addition, compared to the case where both the connection destination change of the main flow path 112 and the connection destination change of the sub flow path 113 are performed by the autosampler, the structure of the sample introduction section 110 can be simplified.

[0069] Furthermore, the above-described embodiment is one example of the present application, and it is of course included in the present application to make changes, modifications, or additions appropriately within the scope of the gist of the present application. For example, although the end of the calibration solution pipe 142 is inserted into the 1st calibration solution container 145 in the above-described embodiment, instead, the end of the calibration solution pipe 142 can be inserted into a calibration solution container (2nd calibration solution container 123) housed in the autosampler 120. In this case, the 1st calibration solution container 145 does not need to be provided. In addition, although the end of the rinse solution pipe 141 is inserted into the 1st rinse solution container 144 in the above-described embodiment, instead, the end of the rinse solution pipe 141 can be inserted into a rinse solution container (2nd rinse solution container 122) housed in the autosampler 120. In this case, the 1st rinse solution container 144 does not need to be provided.

[0070] In addition, although the structure in which any one of the rinse solution, the calibration solution, and the internal standard element solution is made to flow in the sub flow path 113 is provided in the above-described embodiment, instead, the structure in which any one of the calibration solution and the internal standard element solution is made to flow in the sub flow path 113 can be provided. Figure 3 The structure example of the ICP analysis device of the present application in this case is shown in FIG. 12. In this figure, the same components as those in FIG. 1 are denoted by the same reference numerals, and the description thereof will be omitted. Figure 1The same or corresponding structural elements of the illustrated structures are denoted by the same reference numerals, and the description is appropriately omitted. In this structural example, the flow path switching valve 240 has a common port e, a first port f, and a second port g, and becomes a two-way switching valve that can connect the common port e to either the first port f or the second port g. The end of the sub flow path 213 is connected to the common port e, and the ends of the correction liquid pipe 242 and the internal standard element solution pipe 243 are connected to the first port f and the second port g, respectively. The other end of the correction liquid pipe 242 is inserted into the first correction liquid container 245, and the other end of the internal standard element solution pipe 243 is inserted into the internal standard element solution container 246. In such a structure, in the case where a series of operations from the calibration of the device to the analysis of the measurement target sample is automatically performed, the correction liquid flows only in the sub flow path 213 at the time of calibration, and the internal standard element solution flows in the sub flow path 213 at other times. That is, in the present structural example, in the case where the calibration of the device is performed, the internal standard element solution is not supplied to the sub flow path 213, and the internal standard element solution is not mixed with the sample solution. Therefore, the internal standard element solution does not flow into the measurement cell 150, and the internal standard element solution does not interfere with the measurement of the sample solution. As a result, the measurement accuracy of the sample solution can be improved. Figure 2 In steps 12 and 21 of the flowchart, instead of the first rinse liquid container 144, the sub flow path 213 is connected to the internal standard element solution container 246, and the other operations are the same as those shown in the flowchart of Figure 2 In steps 12 and 21 of the flowchart, instead of the first rinse liquid container 144, the sub flow path 213 is connected to the internal standard element solution container 246, and the other operations are the same as those shown in the flowchart of

[0071] Further, in the ICP analysis device shown in Figure 3 In the ICP analysis device shown in

[0072] In addition, although the example in which the present application is applied to the ICP mass analysis device is shown in the above-described embodiments, the present application can also be applied to an ICP emission spectrometry device. The ICP emission spectrometry device is a device that causes elements in a sample to emit light by introducing the sample into a plasma, and detects the light by dispersing the wavelength of the light using a spectrometer. The structure in the case where the present application is applied to the ICP emission spectrometry device is substantially the same as that shown in Figure 1 In the ICP emission spectrometry device, the emission spectrum is generated on the basis of a detection signal from the light detector in the control / processing section 170. In addition, in the case where the present application is applied to the ICP emission spectrometry device, as the correction liquid, for example, a liquid in which a plurality of components having a known wavelength of bright lines are contained at predetermined concentrations is used.

[0073] [SCHEME]

[0074] The person skilled in the art will understand that the above-described various exemplary embodiments are specific examples of the following scheme.

[0075] (1) The ICP analysis device of one aspect of the present application has:

[0076] an ICP section that generates inductively coupled plasma;

[0077] a liquid mixing section having two inlet ports and one outlet port;

[0078] a common flow path having one end connected to the ICP section and the other end connected to the outlet port of the liquid mixing section;

[0079] a main flow path having one end connected to one of the two inlet ports of the liquid mixing section;

[0080] an automatic sampler that selectively collects liquid from one of a plurality of liquid containers and supplies the other end of the main flow path;

[0081] a flow path switching section having one outlet-side port and a plurality of inlet-side ports, and selectively connecting the outlet-side port to one of the inlet-side ports;

[0082] a sub flow path having one end connected to the other of the two inlet ports of the liquid mixing section and the other end connected to the outlet-side port of the flow path switching section;

[0083] a calibration solution pipe connected to one of the inlet-side ports of the flow path switching section to direct a calibration solution to the one inlet-side port;

[0084] an internal standard element solution pipe connected to the other of the inlet-side ports of the flow path switching section to direct an internal standard element solution to the other inlet-side port;

[0085] a peristaltic pump that transports liquid in the main flow path from the other end to the one end of the main flow path, and transports liquid in the sub flow path from the other end to the one end of the sub flow path; and

[0086] a control section that controls the automatic sampler and the flow path switching section.

[0087] (2) The ICP analysis device according to (1) can further include:

[0088] a rinse solution pipe connected to the other of the inlet-side ports of the flow path switching section to direct a rinse solution to the other inlet-side port.

[0089] (3) An ICP analysis method according to an aspect of the present application is an ICP analysis method using an ICP analysis device having:

[0090] an ICP section that generates inductively coupled plasma;

[0091] a liquid mixing section having two inlet ports and one outlet port;

[0092] a common flow path having one end connected to the ICP section and the other end connected to the outlet port of the liquid mixing section;

[0093] a main flow path having one end connected to one of the two inlet ports of the liquid mixing section;

[0094] an automatic sampler that collects liquid from one of a plurality of liquid containers and supplies it to the other end of the main flow path;

[0095] a flow path switching section having one outlet-side port and a plurality of inlet-side ports, and connecting the outlet-side port to one of the plurality of inlet-side ports;

[0096] a sub flow path having one end connected to the other of the two inlet ports of the liquid mixing section and the other end connected to the outlet-side port of the flow path switching section;

[0097] a calibration solution pipe connected to one of the plurality of inlet-side ports of the flow path switching section and guiding a calibration solution to the one inlet-side port;

[0098] an internal standard element solution pipe connected to the other of the plurality of inlet-side ports of the flow path switching section and guiding an internal standard element solution to the other inlet-side port;

[0099] a peristaltic pump that transports liquid in the main flow path from the other end to the one end of the main flow path, and transports liquid in the sub flow path from the other end to the one end of the sub flow path; and

[0100] a control section that controls the automatic sampler and the flow path switching section, wherein

[0101] the liquid container containing the calibration solution and the liquid container containing the measurement target sample are placed as the plurality of liquid containers by the automatic sampler,

[0102] the outlet-side port of the flow path switching section is connected to the inlet-side port of the plurality of inlet-side ports connected to the calibration solution pipe, and calibration is performed in a state where the calibration solution is collected from the liquid container containing the calibration solution by the automatic sampler and supplied to the other end of the main flow path,

[0103] Then, the outlet side port of the flow path switching section is connected to the inlet side port of the plurality of inlet side ports connected to the internal standard element solution pipe, and the measurement target sample is collected from the liquid container containing the measurement target sample by the autosampler and supplied to the other end of the main flow path, whereby ICP analysis of the measurement target sample is performed.

[0104] (4) In the ICP analysis method according to the above 3,

[0105] The ICP analysis device further has:

[0106] a rinse liquid pipe connected to another inlet side port of the plurality of inlet side ports of the flow path switching section to guide a rinse liquid to the other inlet side port,

[0107] The autosampler further holds a liquid container containing a rinse liquid as the plurality of liquid containers,

[0108] At the time when the ICP analysis of the measurement target sample is completed, the outlet side port is connected to the inlet side port of the plurality of inlet side ports connected to the rinse liquid pipe, and the rinse liquid is collected from the liquid container containing the rinse liquid by the autosampler and supplied to the other end of the main flow path.

[0109] According to the ICP analysis device of the above 1 or the ICP analysis method of the above 3, the type of liquid supplied to the main flow path and the sub flow path can be automatically switched by the autosampler and the flow path switching valve, and thus a series of processes from the start of the device calibration to the completion of the analysis of the measurement target sample can be performed without the user's hand.

[0110] According to the ICP analysis device of the above 2 or the ICP analysis method of the above 4, after the analysis of the measurement target sample is completed, the consumption amount of the internal standard element solution can be suppressed by supplying a rinse liquid (not the internal standard element solution) to the sub flow path.

Claims

1. An ICP analysis device, wherein, This ICP analysis device has the following features: The ICP section generates inductively coupled plasma; The liquid mixing section has two inlet ends and one outlet end; A common flow path is provided, with one end connected to the ICP section and the other end connected to the outlet end of the liquid mixing section. The main flow path, one end of which is connected to one of the two inlet ends of the liquid mixing section; An automatic sampler that selectively collects liquid from one of a plurality of liquid containers and supplies it to the other end of the main flow path; A flow path switching unit has an outlet side port and multiple inlet side ports, and selectively connects the outlet side port to one of the multiple inlet side ports; A secondary flow path, one end of which is connected to the other inlet end of the two inlet ends of the liquid mixing section, and the other end of which is connected to the outlet side of the flow path switching section; A calibration fluid piping is connected to one of the plurality of inlet ports of the flow path switching unit to guide calibration fluid to that inlet port; The internal standard element solution is piped to another inlet side of the plurality of inlet side ports of the flow path switching section, thereby guiding the internal standard element solution to that other inlet side port; A peristaltic pump that delivers liquid in the main flow path from one end of the main flow path to the other end, and delivers liquid in the secondary flow path from one end of the secondary flow path to the other end; and The control unit controls the automatic sampler and the flow path switching unit.

2. The ICP analysis apparatus according to claim 1, wherein, This ICP analyzer also features: The flushing fluid piping is connected to another inlet side of the plurality of inlet side ports of the flow path switching unit to guide the flushing fluid to that inlet side port.

3. An ICP analysis method, which is an ICP analysis method using an ICP analysis apparatus, the ICP analysis apparatus having: The ICP section generates inductively coupled plasma; The liquid mixing section has two inlet ends and one outlet end; A common flow path is provided, with one end connected to the ICP section and the other end connected to the outlet end of the liquid mixing section. The main flow path, one end of which is connected to one of the two inlet ends of the liquid mixing section; An automatic sampler that selectively collects liquid from one of a plurality of liquid containers and supplies it to the other end of the main flow path; A flow path switching unit has an outlet side port and multiple inlet side ports, and selectively connects the outlet side port to one of the multiple inlet side ports; A secondary flow path, one end of which is connected to the other inlet end of the two inlet ends of the liquid mixing section, and the other end of which is connected to the outlet side of the flow path switching section; A calibration fluid piping is connected to one of the plurality of inlet ports of the flow path switching unit to guide calibration fluid to that inlet port; The internal standard element solution is piped to another inlet side of the plurality of inlet side ports of the flow path switching section, thereby guiding the internal standard element solution to that other inlet side port; A peristaltic pump that delivers liquid in the main flow path from one end of the main flow path to the other end, and delivers liquid in the secondary flow path from one end of the secondary flow path to the other end; and The control unit controls the automatic sampler and the flow path switching unit, wherein, The automatic sampler contains a liquid container holding a calibration solution and a liquid container holding the sample to be measured, which together constitute the plurality of liquid containers. The outlet of the flow path switching unit is connected to the inlet of one of the plurality of inlet ports, which is connected to the calibration fluid piping. Calibration is performed while the calibration fluid is collected from the liquid container containing the calibration fluid using the automatic sampler and supplied to the other end of the main flow path. Then, the outlet of the flow path switching unit is connected to the inlet of the internal standard element solution piping among the plurality of inlet ports, and the automatic sampler is used to collect the sample from the liquid container containing the sample to be measured and supply it to the other end of the main flow path, thereby performing ICP analysis on the sample.

4. The ICP analysis method according to claim 3, wherein, The ICP analysis device also has: The flushing fluid piping connects to another inlet port among the plurality of inlet ports of the flow path switching unit, guiding the flushing fluid to that inlet port. The automatic sampler also includes a liquid container holding the rinsing solution, serving as one of the plurality of liquid containers. At the moment when the ICP analysis of the measured sample is completed, the outlet port is connected to the inlet port of the plurality of inlet ports that is connected to the flushing fluid piping, and the flushing fluid is collected from the liquid container containing the flushing fluid using the automatic sampler and supplied to the other end of the main flow path.

Images