ICP Analyzer

Abstract

To automatically execute ICP analysis from device calibration to specimen analysis.SOLUTION: Provided is an ICP analysis device comprising: a mixing unit 114 including two inlet ends and one outlet end; a common passage 111 of which one end is connected to an ICP unit 150 and the other end is connected to the outlet end; a main passage 112 of which one end is connected to one of the inlet ends; an auto-sampler 120 connected to the other end of the main passage; a passage switching unit 140 for connecting one outlet port with any one of a plurality of inlet ports; a sub passage 113 of which one end is connected to the remaining inlet end of the mixing unit and the other end is connected to the outlet port; a calibration liquid pipe 142 of which one end is inserted to a calibration liquid container 145 and the other end is connected to one of the inlet ports; an inner standard pipe 143 of which one end is inserted to an inner standard element solution container 146 and the other end is connected to the other inlet port; one peristaltic pump 130 for pumping liquids in the main passage and the sub passage; and a control unit 170 for controlling the auto-sampler and the passage switching unit.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to an ICP (Inductively Coupled Plasma) analyzer.

Background Art

[0002] In an ICP mass spectrometer, a liquid sample is atomized and then introduced into an inductively coupled plasma flame to ionize the target element in the sample, and qualitative and quantitative analysis of the sample is performed by subjecting the generated ions to mass spectrometry. Further, in an ICP emission spectrometer, a liquid sample is atomized and then introduced into an inductively coupled plasma flame, and the light generated by heating and exciting the target element in the sample is subjected to spectroscopic analysis, thereby performing qualitative and quantitative analysis of the sample. Here, analyzers using inductively coupled plasma, such as an ICP mass spectrometer and an ICP emission spectrometer, are collectively referred to as an ICP analyzer, and analysis using these apparatuses is collectively referred to as ICP analysis.

[0003] In an ICP analyzer, physical properties such as the viscosity and volatility of a sample change due to the influence of components other than the target element contained in the sample, and thereby the liquid feeding and spraying conditions of the sample change, affecting the analysis result (such a phenomenon is called physical interference). To correct the influence of such physical interference, in quantitative analysis by an ICP analyzer, 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 determined based on the detection intensity ratio of the target element and the internal standard element. However, when analyzing a large number of samples at once, it is cumbersome to manually add a fixed amount of the internal standard element solution to each sample. Therefore, an ICP analyzer equipped with a mechanism for automatically adding the internal standard element solution to a sample has been developed (see, for example, Patent Document 1).

[0004] An ICP analyzer equipped with such an automatic addition mechanism for an internal standard element solution includes a main flow path for collecting a liquid sample, a sub-flow path for collecting the internal standard element solution, and a common flow path connected to the main flow path and the sub-flow path via a mixing section composed of a T-tube or the like. The liquid sample collected through the main flow path and the internal standard element solution collected through the sub-flow path merge and mix in the mixing section, and are introduced through the common flow path into a torch (plasma torch) for forming a plasma flame.

[0005] In the ICP analyzer having the above configuration, peristaltic pumps for pumping the liquid in the flexible tubes constituting each flow path are arranged in the main flow path and the sub-flow path. The peristaltic pump pumps the liquid in the tube by peristaltically squeezing the flexible tube as the rotor rotates, and due to its configuration, the liquid delivery amount changes periodically. Therefore, when one peristaltic pump is provided for each of the main flow path and the sub-flow path, a variation occurs in the mixing ratio of the sample liquid and the internal standard element solution introduced into the plasma torch due to the deviation of the rotation cycle of the rotor in each peristaltic pump, resulting in a variation in the quantitative value.

[0006] Therefore, in order to prevent such a variation in the mixing ratio, the liquid delivery of the sample liquid in the main flow path and the liquid delivery of the internal standard element solution in the sub-flow path may be performed by a single multi-channel peristaltic pump. In a multi-channel peristaltic pump, since a plurality of flexible tubes can be arranged along the outer circumference of the rotor, by using this pump, liquids with flow rates corresponding to the inner diameters of the respective tubes can be flowed through the tube constituting the main flow path and the tube constituting the sub-flow path in the same cycle.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0008] When calibrating an ICP analyzer, instead of the mixed solution of the sample and the internal standard element solution as described above, it is necessary to introduce a predetermined calibration solution into the plasma flame. Therefore, in a conventional ICP analyzer having the above-described configuration, first, with both the end of the tube constituting the main flow path and the end of the tube constituting the sub-flow path inserted into a container containing the calibration solution (hereinafter referred to as the calibration solution container), the multi-channel peristaltic pump is used to introduce the calibration solution into the plasma torch to perform the calibration work. Then, the tube constituting the main flow path is reinserted from the calibration solution container into the container containing the sample, and the tube constituting the sub-flow path is reinserted from the calibration solution container into the container containing the internal standard element solution (hereinafter referred to as the internal standard element solution container) to analyze the sample. However, since such reinsertion of the tube needs to be performed manually by the analyst, the above-described conventional ICP analyzer cannot automatically execute the process from the calibration of the apparatus to the analysis of the sample.

[0009] If the main and sub-channels are each connected to an autosampler, and the autosampler is used to switch the liquid flowing through the main channel and the liquid flowing through the sub-channel, it is possible to automatically perform everything from calibration to analysis of the sample to be measured. However, this requires the control of two separate operations: switching the main channel and switching the sub-channel, which makes the device bulky. It is also possible to automatically perform everything from calibration to sample analysis by connecting only the main channel to the autosampler and keeping the tubing constituting the sub-channel always inserted in the internal standard solution container. However, in this case, the internal standard solution is supplied to the plasma torch from the sub-channel even during calibration, which may prevent accurate calibration. In a configuration in which only the main flow path is connected to an autosampler and the tubing constituting the secondary 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 secondary flow path to the plasma torch during calibration, it is necessary to configure the main flow path and the secondary flow path to be delivered by separate peristaltic pumps. However, in this case, differences in the rotation periods of the rotors in each peristaltic pump will cause fluctuations in the mixing ratio of the sample liquid and the internal standard element solution introduced into the plasma torch.

[0010] The present invention has been made in view of the above points, and an object of the present invention is to enable ICP analysis to be carried out automatically from apparatus calibration to sample analysis without using a large-scale apparatus and without reducing calibration accuracy. [Means for solving the problem]

[0011] The ICP analyzer according to the present invention, which has been made to solve the above problems, is an ICP unit for generating inductively coupled plasma; a liquid mixing section having two inlet ends and one outlet end; a common flow path having one end connected to the ICP unit and the other end connected to the outlet end of the liquid mixing unit; a main flow path having one end connected to one of the two inlet ends of the liquid mixing section; An autosampler 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 having one outlet side port and a plurality of inlet side ports, and selectively connecting the outlet side port to one of the plurality of inlet side ports, A sub-flow path having one end connected to the other of the two inlet ends of the liquid mixing unit and the other end connected to the outlet side port of the flow path switching unit, A calibration liquid pipe connected to one of the plurality of inlet side ports of the flow path switching unit and guiding calibration liquid to the port, An internal standard element solution pipe connected to another one of the plurality of inlet side ports of the flow path switching unit and guiding an internal standard element solution to the port, One peristaltic pump that sends the liquid in the main flow path from the other end of the main flow path to the one end and sends the liquid in the sub-flow path from the other end of the sub-flow path to the one end, And a control unit that controls the autosampler and the flow path switching unit.

[0012] In addition, the ICP analysis method according to the present invention made to solve the above problems is, An ICP unit that generates an inductively coupled plasma, A liquid mixing unit having two inlet ends and one outlet end, A common flow path having one end connected to the ICP unit and the other end connected to the outlet end of the liquid mixing unit, A main flow path having one end connected to one of the two inlet ends of the liquid mixing unit, An autosampler 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 having one outlet side port and a plurality of inlet side ports, and selectively connecting the outlet side port to one of the plurality of inlet side ports, A sub-flow path having one end connected to the other of the two inlet ends of the liquid mixing unit and the other end connected to the outlet side port of the flow path switching unit, a calibration solution pipe connected to one of the plurality of inlet ports of the flow path switching unit and guiding the calibration solution to the port; an internal standard element solution pipe connected to another one of the plurality of inlet ports of the flow path switching unit and guiding the internal standard element solution to the port; a peristaltic pump that pumps the liquid in the main channel from the other end to the one end of the main channel and pumps the liquid in the sub channel from the other end to the one end of the sub channel; a control unit that controls the autosampler and the flow path switching unit; An ICP analysis method using an ICP analysis apparatus having setting a liquid container containing a calibration liquid and a liquid container containing a measurement target sample in the autosampler as the plurality of liquid containers; an outlet port of the flow path switching means is connected to an inlet port of the plurality of inlet ports that is connected to the calibration liquid pipe, and calibration is performed in a state in which the autosampler is used to collect the calibration liquid from a liquid container containing the calibration liquid and supply the collected calibration liquid to the other end of the main flow path; Thereafter, the outlet port of the flow path switching means is connected to one of the plurality of inlet ports that is connected to the internal standard element solution piping, and the autosampler collects the sample to be measured from a liquid container containing the sample and supplies it to the other end of the main flow path, thereby performing ICP analysis of the sample to be measured. [Effects of the Invention]

[0013] According to the present invention, in ICP analysis, it is possible to automatically perform the process from calibration of the apparatus to analysis of the sample to be measured without using a large-scale apparatus and without reducing the calibration accuracy. [Brief explanation of the drawings]

[0014]

Figure 1

Figure 2

Figure 3

[0015] An ICP mass spectrometer according to one embodiment of the present invention will now be described with reference to the drawings. Figure 1 is a diagram showing the main components of the ICP mass spectrometer according to this embodiment. This ICP mass spectrometer is broadly composed of a sample introduction section 110, an ICP section 150, a mass analysis section 160, and a control / processing section 170.

[0016] The sample introduction section 110 introduces various liquids such as a measurement target sample into the ICP section 150, and includes a common channel 111, a main channel 112, a sub-channel 113, an autosampler 120, a peristaltic pump 130, and a channel switching valve 140. One end of the common channel 111, the main channel 112, and the sub-channel 113 are connected to each other via a T-shaped tube 114 (corresponding to the "liquid mixing section" in the present invention). The other end of the common channel 111 is connected to a plasma torch 152 via a nebulizer 155 (described later), and the other end of the main channel 112 is connected to the autosampler 120. The other end of the sub-channel 113 is connected to the channel switching valve 140.

[0017] The autosampler 120 can accommodate a sample rack 121 therein, and is equipped with a sampling needle 125 for aspirating liquid from each of a plurality of liquid containers (a second rinse liquid container 122, a second calibration liquid container 123, and a measurement sample container 124, which will be described later) set on the sample rack 121, and a needle drive mechanism 126 for moving the sampling needle 125 horizontally and vertically. The other end of the main channel 112 is connected to the base end of the sampling needle 125 directly or via a pipe provided in the autosampler 120.

[0018] The flow path switching valve 140 is a three-way switching valve that includes a common port a, a first port b, a second port c, and a third port d, and that can selectively connect the common port a to either the first port b, the second port c, or the third port d. Here, the common port a corresponds to the "outlet port" in this invention, and the first port b, the second port c, and the third port d correspond to the "inlet port" in this invention. Note that the flow path switching valve 140 can be disposed, for example, inside a housing (not shown) that houses the ICP unit 150 and the mass spectrometry unit 160, but the location of the flow path switching valve 140 is not limited to this.

[0019] The other end of the sub-channel 113 is connected to the common port a of the channel switching valve 140. One end 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. 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. The first rinse liquid container 144 contains a rinse liquid (e.g., water or a predetermined organic solvent) for rinsing the sub-channel 113, the T-shaped tube 114, the common channel 111, etc., and the first calibration liquid container 145 contains a calibration liquid. As the calibration liquid, for example, a solution containing a plurality of components whose theoretical m / z values are known, each at a predetermined concentration, is used. The internal standard element solution container 146 contains an internal standard element solution containing a predetermined internal standard element (for example, an element known not to be contained in the sample to be measured) at a predetermined concentration.

[0020] The peristaltic pump 130 is for pumping the liquid in the main flow path 112 and the sub-flow path 113. The peristaltic pump 130 in this embodiment is a multi-channel peristaltic pump 130 that can simultaneously pump the liquid in at least two tubes. The peristaltic pump 130 includes a cylindrical rotor 131, a plurality of pumping rollers 132 attached to the outer periphery of the rotor 131, and a pressing member 133 provided near the outer periphery of the rotor 131. Both the main flow path 112 and the sub-flow path 113 are at least partially composed of flexible tubes. These flexible tubes are sandwiched between the outer periphery of the rotor 131 and the pressing member 133 in a state parallel to each other and orthogonal to the central axis of the rotor 131. In this state, when the rotor 131 rotates around its central axis, each of the flexible tubes is sequentially clamped between the pressing member 133 and the pumping roller 132, and the liquid flows through each flexible tube at a flow rate corresponding to its inner diameter.

[0021] The ICP unit 150 includes a plasma torch 152 that generates a plasma flame by a high-frequency magnetic field generated by a high-frequency coil 151, a plasma gas supply source 153 that supplies a plasma gas (e.g., argon gas) 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 sprays the liquid supplied from the sample introduction unit 110 into the spray chamber 157, and a nebulizer gas supply source 156 that supplies a nebulizer gas to the nebulizer 155. The liquid introduced into the ICP unit 150 through the common flow path 111 is sprayed into the spray chamber 157 from the nebulizer 155 with the help of the nebulizer gas supplied from the nebulizer gas supply source 156. The atomized liquid is introduced into the plasma torch 152, where the components in the liquid are ionized by the plasma flame.

[0022] The ions generated in the ICP unit 150 are sent to the mass spectrometry unit 160, where they are separated and detected according to m / z.

[0023] The control / processing unit 170 performs qualitative or quantitative analysis of the sample to be measured by performing arithmetic processing on the data (detection data) based on the detection signal obtained by the mass spectrometry unit 160 according to a predetermined algorithm. Further, the control / processing unit 170 comprehensively controls the operations of the respective units. Most of the functions of the control / processing unit 170 are achieved by executing a predetermined program on a computer such as a personal computer equipped with a CPU, a memory, and a large-capacity storage device. An input unit composed of a keyboard or the like and an output unit composed of a monitor or the like are further connected to the computer.

[0024] The calibration of the ICP mass spectrometer according to the present embodiment is executed according to an instruction from the user (the person in charge of analysis). For example, in an analysis site where the ICP mass spectrometer is started every morning and a large number of samples to be measured are measured in order during the day, the calibration operation is performed after the device is started and before the sample to be measured is measured. Hereinafter, the procedure of such a calibration operation and the analysis of the sample to be measured, and the operation of the sample introduction unit 110 at that time will be described with reference to the flowchart of FIG. 2.

[0025] In addition, when performing the above calibration operation and the analysis of the sample to be measured, in advance, the user sets a liquid container (hereinafter referred to as "second rinse liquid container 122") containing a rinse liquid, a liquid container (hereinafter referred to as "second calibration liquid container 123") containing a calibration liquid, and a plurality of liquid containers (hereinafter referred to as "sample containers 124 to be measured") containing the sample to be measured in the sample rack 121, and houses the sample rack 121 in the autosampler 120. As the rinse liquid contained in the second rinse liquid container 122, for example, the same rinse liquid as that contained in the first rinse liquid container 144 described above can be used. Further, as the calibration liquid contained in the second calibration liquid container 123, for example, the same calibration liquid as that contained in the first calibration liquid container 145 described above can be used. Further, the sample to be measured contained in each of the plurality of sample containers 124 to be measured is not limited to the sample to be analyzed for qualitative or quantitative analysis, and may be a standard sample for calibration curve creation.

[0026] In addition, when performing the above calibration work and analysis of the sample to be measured, the user further operates an input unit (not shown) provided in the control / processing unit 170 to register the positions (e.g., well numbers) of the second rinse liquid container 122, the second calibration liquid container 123, and each sample container 124 to be measured on the sample rack 121, and create an analysis schedule describing the execution order and analysis conditions, etc. for the samples to be measured accommodated in each sample container 124 to be measured, and store it in a predetermined storage unit (not shown) provided in the control / processing unit 170.

[0027] Thereafter, the user performs a predetermined operation on the control / processing unit 170 to start the ICP mass spectrometer (step 11). As a result, 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, under the control of the control / processing unit 170, the flow path switching valve 140 is driven so that the common port a and the first port b (the port to which the rinse liquid pipe 141 is connected) are connected, and the needle drive mechanism 126 of the autosampler 120 is driven so that 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 unit 170, and the rinse liquid is sucked from the second rinse liquid container 122 through the main flow path 112 and the rinse liquid is sucked from the first rinse liquid container 144 through the sub-flow path 113. These rinse liquids are introduced into the ICP unit 150 through the T-shaped pipe 114 and the common flow path 111.

[0028] Thereafter, the plasma torch 152 is turned on, and when a predetermined time (warm-up time) has elapsed (i.e., when step 13 becomes Yes), the flow path switching valve 140 and the needle driving mechanism 126 are driven again, and the sampling needle is moved and inserted into the second calibration liquid container 123 and the first calibration liquid container 145. As a result, the main flow path 112 and the sub-flow path 113 are connected to the second calibration liquid container 123 and the first calibration 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 first port b to the second port c (the port to which the calibration liquid piping 142 is connected), and the sampling needle 125 of the autosampler 120 is pulled up from the second rinse liquid container 122 and inserted into the second calibration liquid container 123. In this state, the peristaltic pump 130 sends a liquid, whereby the calibration liquid is sucked from the second calibration liquid container 123 via the main flow path 112 and the calibration liquid is sucked from the first calibration liquid container 145 via the sub-flow path 113, and these calibration liquids are introduced into the ICP section 150 via the T-shaped tube 114 and the common flow path 111. As a result, a plurality of known components contained in the calibration liquid are ionized in the ICP section 150, and the ions are analyzed in the mass analysis section 160, and a mass spectrum is generated in the control / processing section 170 based on the output signal from the mass analysis section 160 at this time.

[0029] Then, in the control / processing unit 170, peaks corresponding to each of the multiple known components contained in the calibration solution are identified from the multiple peaks contained in the mass spectrum, and the device is calibrated based on the m / z or height of each peak (step 15). In the calibration, the relative position of the plasma torch 152 with respect to the mass analysis unit 160 may be adjusted, or the voltage applied to the mass analysis unit 160 may be adjusted, based on the intensity of each peak in the mass spectrum obtained by analyzing the calibration solution.

[0030] When the calibration of the apparatus is completed as described above, the main flow path 112 is connected to the first measurement target sample container 124 among 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 unit 170, the connection destination of the common port a of the flow path switching valve 140 is changed from the second port c to the third port d (the port to which the internal standard element solution pipe 143 is connected), and the sampling needle 125 of the autosampler 120 is lifted from the second calibration liquid container 123 and inserted into the first measurement target sample container 124 described in the above analysis schedule. Thereby, by the action of the peristaltic pump 130, the measurement target sample is sucked from the first measurement target sample container 124 through the main flow path 112, and the internal standard element solution is sucked from the internal standard element solution container 146 through the sub-flow path 113. Then, the sucked measurement target sample and internal standard element solution flow into the common flow path through the T-shaped pipe 114, and a mixed solution formed by mixing the measurement target sample and the internal standard element solution in a predetermined ratio is generated. The mixed solution is introduced into the ICP unit 150 through the common flow path 111, the nebulizer 155, and the spray chamber 157, and thereby the components in the mixed solution are ionized and analyzed by the mass spectrometry unit 160 (step 17).

[0031] After the ionization and mass spectrometry of the measurement target sample in the first measurement target sample container 124 are completed as described above, the connection destination of the main flow path 112 is changed to the second rinse liquid container 122 (step 18). That is, the sampling needle 125 of the autosampler 120 is lifted from the first measurement target sample container 124 and inserted into the second rinse liquid container 122. Thereby, the rinse liquid is sucked from the second rinse liquid container 122 by the action of the peristaltic pump 130, and the inside of the main flow path 112, the T-shaped pipe 114, the common flow path 111, and the nebulizer 155 is rinsed with the rinse liquid.

[0032] Thereafter, the control / processing unit 170 refers to the above-described analysis schedule to determine whether analysis has been completed for all samples to be measured (step 19). If not, the sampling needle 125 of the autosampler 120 is inserted into the next sample container 124 to be measured described in the analysis schedule (step 20), and analysis of the mixed solution of the next sample to be measured and the internal standard element solution is performed by the ionization in the ICP unit 150 and the mass spectrometry unit 160 (step 17). Thereafter, for all samples to be measured set on the sample rack 121, the processes of steps 17 to 20 are repeatedly executed until the analysis is completed (that is, until it becomes Yes in step 19).

[0033] After the analysis of all samples to be measured is completed, again, the main flow path 112 and the sub-flow path 113 are connected to the second rinse solution container 122 and the first rinse solution container 144, respectively (step 21). Specifically, under the control of the control / processing unit 170, the flow path switching valve 140 is driven, the connection destination of the common port a is changed from the third port d to the first port b, and the needle drive mechanism 126 is driven to lift the sampling needle 125 of the autosampler 120 from the sample container 124 to be measured and insert it into the second rinse solution container 122.

[0034] As described above, according to the ICP mass spectrometer according to the present embodiment, since 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, it is possible to automatically execute a series of processes from the calibration of the apparatus to the analysis of the sample to be measured. In addition, compared with the case where both the change of the connection destination of the main flow path 112 and the change of the connection destination of the sub-flow path 113 are performed by the autosampler, the configuration of the sample introduction unit 110 can be simplified.

[0035] The above embodiment is merely an example of the present invention, and it goes without saying that appropriate changes, modifications, or additions within the spirit and scope of the present invention are encompassed within the scope of the present invention. For example, in the above embodiment, the end of the calibration liquid piping 142 is inserted into the first calibration liquid container 145. Alternatively, the end of the calibration liquid piping 142 may be inserted into a calibration liquid container (second calibration liquid container 123) housed in the autosampler 120. In this case, the first calibration liquid container 145 is not necessary. Furthermore, in the above embodiment, the end of the rinse liquid piping 141 is inserted into the first rinse liquid container 144. Alternatively, the end of the rinse liquid piping 141 may be inserted into a rinse liquid container (second rinse liquid container 122) housed in the autosampler 120. In this case, the first rinse liquid container 144 is not necessary.

[0036] In the above-described embodiment, either the rinse solution, the calibration solution, or the internal standard element solution is selectively flowed through the sub-channel 113. Instead, however, either the calibration solution or the internal standard element solution may be selectively flowed through the sub-channel 113. A configuration example of the ICP analyzer according to the present invention in this case is shown in FIG. 3. In the figure, components that are the same as or corresponding to those shown in FIG. 1 are given the same reference numerals with the last two digits being common, and the description thereof will be omitted as appropriate. In this configuration example, the flow path switching valve 240 includes a common port e, a first port f, and a second port g, and is a two-way switching valve that can selectively connect the common port e to the first port f or the second port g. The end of the sub-channel 213 is connected to the common port e, and one end of the calibration solution pipe 242 and the internal standard element solution pipe 243 is connected to the first port f and the second port g, respectively. The other end of the calibration solution pipe 242 is inserted into the first calibration solution container 245, and the other end of the internal standard element solution pipe 243 is inserted into the internal standard element solution container 246. When performing a series of operations from the calibration of the apparatus to the analysis of the measurement target sample automatically in such a configuration, only the calibration solution is flowed through the sub-channel 213 during calibration, and the internal standard element solution is flowed through it at other times. That is, in this configuration example, in steps 12 and 21 of the flowchart in FIG. 2, the sub-channel 213 is connected to the internal standard element solution container 246 instead of the first rinse solution container 144, and the other operations are the same as those shown in the flowchart in FIG. 2.

[0037] In the ICP analyzer shown in FIG. 3, the other end of the calibration solution pipe 242 may be inserted into a calibration solution container (second calibration solution container 223) accommodated in the autosampler 220 without providing the first calibration solution container 245.

[0038] Although the above embodiment illustrates an example in which the present invention is applied to an ICP mass spectrometer, the present invention can also be applied to an ICP optical emission spectrometer. An ICP optical emission spectrometer introduces a sample into plasma, causing elements in the sample to emit light, and then wavelength-disperses and detects the emitted light using a spectrometer. The configuration of an ICP optical emission spectrometer in which the present invention is applied is essentially the same as that shown in FIG. 1 , except that the mass analyzer 160 is replaced with a spectrometer equipped with a wavelength-dispersive element and a photodetector. In this case, however, the control / processing unit 170 generates an emission spectrum based on the detection signal from the photodetector. When the present invention is applied to an ICP optical emission spectrometer, a calibration liquid containing, for example, a plurality of components with known emission line wavelengths, each at a predetermined concentration, is used.

[0039] [Aspect] It will be appreciated by those skilled in the art that the exemplary embodiments described above are examples of the following aspects.

[0040] (Item 1) An ICP analyzer according to one aspect of the present invention comprises: an ICP unit for generating inductively coupled plasma; a liquid mixing section having two inlet ends and one outlet end; a common flow path having one end connected to the ICP unit and the other end connected to the outlet end of the liquid mixing unit; a main flow path having one end connected to one of the two inlet ends of the liquid mixing section; an autosampler that selectively collects liquid from one of a plurality of liquid containers and supplies the liquid to the other end of the main channel; a flow path switching unit having one outlet port a and a plurality of inlet ports b, c, and d, which selectively connects the outlet port to one of the plurality of inlet ports; 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 port of the flow path switching section; a calibration solution pipe connected to one of the plurality of inlet ports of the flow path switching unit and guiding the calibration solution to the port; an internal standard element solution pipe connected to another one of the plurality of inlet ports of the flow path switching unit and guiding the internal standard element solution to the port; a peristaltic pump that pumps the liquid in the main channel from the other end to the one end of the main channel and pumps the liquid in the sub channel from the other end to the one end of the sub channel; a control unit that controls the autosampler and the flow path switching unit; It has the following characteristics.

[0041] (Item 2) The ICP analyzer described in item 1 is a rinse liquid pipe connected to yet another port of the plurality of inlet ports of the flow path switching unit and for introducing the rinse liquid to the port; It may further comprise:

[0042] (Item 3) An ICP analysis method according to one aspect of the present invention includes: an ICP unit for generating inductively coupled plasma; a liquid mixing section having two inlet ends and one outlet end; a common flow path having one end connected to the ICP unit and the other end connected to the outlet end of the liquid mixing unit; a main flow path having one end connected to one of the two inlet ends of the liquid mixing section; an autosampler that selectively collects liquid from one of a plurality of liquid containers and supplies the liquid to the other end of the main channel; a flow path switching unit having one outlet port a and a plurality of inlet ports b, c, and d, which selectively connects the outlet port to one of the plurality of inlet ports; 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 port of the flow path switching section; a calibration solution pipe connected to one of the plurality of inlet ports of the flow path switching unit and guiding the calibration solution to the port; an internal standard element solution pipe connected to another one of the plurality of inlet ports of the flow path switching unit and guiding the internal standard element solution to the port; a peristaltic pump that pumps the liquid in the main channel from the other end to the one end of the main channel and pumps the liquid in the sub channel from the other end to the one end of the sub channel; a control unit that controls the autosampler and the flow path switching unit; An ICP analysis method using an ICP analysis apparatus having setting a liquid container containing a calibration liquid and a liquid container containing a measurement target sample in the autosampler as the plurality of liquid containers; an outlet port of the flow path switching means is connected to an inlet port of the plurality of inlet ports that is connected to the calibration liquid pipe, and calibration is performed in a state in which the autosampler is used to collect the calibration liquid from a liquid container containing the calibration liquid and supply the collected calibration liquid to the other end of the main flow path; Thereafter, the outlet port of the flow path switching means is connected to one of the plurality of inlet ports that is connected to the internal standard element solution piping, and the autosampler collects the sample to be measured from a liquid container containing the sample and supplies it to the other end of the main flow path, thereby performing ICP analysis of the sample to be measured.

[0043] (4) The ICP analysis method described in paragraph 3 is The ICP analyzer further comprises: a rinse liquid pipe connected to yet another port of the plurality of inlet ports of the flow path switching unit and for introducing the rinse liquid to the port; having a liquid container containing a rinse liquid is set in the autosampler as the plurality of liquid samples; Upon completion of the ICP analysis of the measurement target sample, the outlet port may be connected to one of the plurality of inlet ports that is connected to the rinse liquid piping, and the rinse liquid may be sampled by the autosampler from a liquid container containing the rinse liquid and supplied to the other end of the main flow path.

[0044] According to the ICP analysis device described in paragraph 1 or the ICP analysis method described in paragraph 3, the type of liquid supplied to the main flow path and the sub-flow path can be automatically switched using the autosampler and the flow path switching valve, so that a series of processes from the start of device calibration to the completion of analysis of the sample to be measured can be performed without user intervention.

[0045] According to the ICP analysis apparatus described in paragraph 2 or the ICP analysis method described in paragraph 4, after the analysis of the sample to be measured is completed, the consumption of the internal standard element solution can be reduced by supplying a rinse liquid (instead of the internal standard element solution) to the sub-flow path. [Explanation of symbols]

[0046] 110...Sample introduction section 111...Common flow path 112…Main channel 113…Subchannel 114...T-tube 120...Autosampler 122...Second rinse liquid container 123...Second calibration solution container 124...Measurement target sample container 130...Peristaltic pump 140...Flow path switching valve 141...Rinse liquid piping 142...Calibration solution piping 143…Internal standard element solution piping 144...First rinse liquid container 145...First calibration solution container 146...Internal standard element solution container 150...ICP section 152...Plasma torch 160…Mass spectrometry department 170...Control / processing unit

Claims

1. An ICP section that generates inductively coupled plasma, A liquid mixing section having two inlet ends and one outlet end, A common flow path with one end connected to the ICP section and the other end connected to the outlet end of the liquid mixing section, A main flow path with one end connected to one of the two inlet ends of the liquid mixing section, An autosampler 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 section having one outlet side port and a plurality of inlet side ports, and selectively connecting the outlet side port to one of the plurality of inlet side ports, A sub-flow path with 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, A calibration liquid pipe connected to one of the plurality of inlet side ports of the flow path switching section and guiding calibration liquid to the port, An internal standard element solution pipe connected to another one of the plurality of inlet side ports of the flow path switching section and guiding an internal standard element solution to the port, A single peristaltic pump that sends the liquid in the main flow path from the other end to the one end of the main flow path and sends the liquid in the sub-flow path from the other end to the one end of the sub-flow path, A control section that controls the autosampler and the flow path switching section, An ICP analyzer having the above components.

2. A rinse liquid pipe connected to yet another one of the plurality of inlet side ports of the flow path switching section and guiding rinse liquid to the port, The ICP analyzer according to Claim 1, further comprising the above component.

3. An ICP section that generates inductively coupled plasma, A liquid mixing section having two inlet ends and one outlet end, A common flow path with one end connected to the ICP section and the other end connected to the outlet end of the liquid mixing section, A main flow path with one end connected to one of the two inlet ends of the liquid mixing section, An autosampler 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 section having one outlet side port and a plurality of inlet side ports, and selectively connecting the outlet side port to one of the plurality of inlet side ports, A sub-flow path with 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, A calibration liquid pipe connected to one of the plurality of inlet side ports of the flow path switching section and guiding calibration liquid to the port, an internal standard element solution pipe connected to another one of the plurality of inlet ports of the flow path switching unit and guiding the internal standard element solution to the port; a peristaltic pump that sends the liquid in the main channel from the other end to the one end of the main channel and sends the liquid in the sub channel from the other end to the one end of the sub channel; a control unit that controls the autosampler and the flow path switching unit; An ICP analysis method using an ICP analysis apparatus having setting a liquid container containing a calibration liquid and a liquid container containing a measurement target sample in the autosampler as the plurality of liquid containers; the outlet port of the flow path switching unit is connected to an inlet port of the plurality of inlet ports that is connected to the calibration liquid pipe, and calibration is performed in a state in which the autosampler is used to collect the calibration liquid from a liquid container containing the calibration liquid and supply the collected calibration liquid to the other end of the main flow path; Thereafter, the outlet port of the flow path switching unit is connected to one of the plurality of inlet ports that is connected to the internal standard element solution pipe, and the measurement target sample is collected from a liquid container containing the measurement target sample by the autosampler and supplied to the other end of the main flow path, thereby performing ICP analysis of the measurement target sample. ICP analysis method.

4. The ICP analyzer further comprises: a rinse liquid pipe connected to yet another port of the plurality of inlet ports of the flow path switching unit and for introducing the rinse liquid to the port; It has a liquid container containing a rinse liquid is further set as one of the plurality of liquid containers in the autosampler; When the ICP analysis of the measurement sample is completed, the outlet port is connected to one of the plurality of inlet ports that is connected to the rinse liquid pipe, and the rinse liquid is collected from a liquid container containing the rinse liquid by the autosampler and supplied to the other end of the main flow path. The ICP analysis method according to claim 3.

Images