JP2011085561A - Simple analyzer for mercury ions, and method of analyzing mercury ions using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a simplified analyzer dispensing, with handling work for a film that contains particulate dithizone for selectively capturing mercury ions, and allowing the quantity of mercury ions to be determined on site, in a simple and rapid manner. <P>SOLUTION: The simplified analyzer includes a through-hole 12 with its upstream-side opening 17, made wide-mouthed while letting a sample liquid run therethrough from the upstream-side opening 17 to its downstream-side opening 18; a filtering material 20 provided in the middle of the through hole 12; and a mercury-ion capture film 22, made by fixing solid components contained in a dispersion liquid on the surface of the filtering material 20, by supplying the dispersion liquid that contains the particulate dithizone to the upstream-side opening 17. The capture film 22 is placed on the outside so that direct viewing can be made, in a directly visible way from the upstream-side opening 17 of the through-hole 12. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a simple analyzer for measuring the concentration of mercury ions and a method for analyzing mercury ions using the analyzer.

The present applicant has developed “Pak Test” (registered trademark) as a simple analyzer used for on-site water quality inspection and has been well received and improved (Patent Document 1). This pack test (registered trademark) is an analyzer in which a coloring reagent that reacts with a substance to be analyzed is sealed in a resin tube. A sample solution is sucked into a tube and reacted with a coloring reagent, and the concentration of the substance to be analyzed is measured based on the color of the coloring.
By the way, the environmental standard and the drainage standard related to water pollution of heavy metals are set to an extremely low concentration level of the order of ppb (= μg / L). Therefore, in the field, the coloration due to the reaction with the color reagent of Pack Test (registered trademark) is detected in combination with other devices such as a photometer, or the sample solution collected on the field is once put in the laboratory. It was required to take it home and measure with a precision detector.

  Among heavy metals, mercury is highly harmful to the human body and the environment, and is defined as 5 ppb or less as an industrial wastewater standard and 0.5 ppb or less as an environmental standard. Therefore, management of mercury ions contained in waste water, environmental water, drinking water, etc. is required, and a method for easily measuring the mercury ion concentration on site has been proposed (Patent Document 2). In this method, a mercury ion detection film having a thin film made of fine particles of dithizone which is a mercury ion detection reagent is used. The mercury ion detection reagent is colored by immersing the mercury ion detection film in the sample solution or passing the sample solution, and the mercury ion is measured according to the degree of color development.

Japanese Patent No. 4125603 Japanese Patent No. 4185882

  However, since the mercury ion detection film is thin and easily broken, careful handling is required for the immersion and removal from the sample liquid, and it is difficult to work in the field. On the other hand, when measuring mercury ions by passing a sample solution, it is necessary to set the film in a predetermined filter holder, but when the film is torn or wrinkled, there is a portion where mercury ions are not captured. Will occur and affect the analysis results. And after passing, in order to confirm color development on the film, the filter holder must be opened and the film must be taken out.

  Further, in the analysis of a sample solution containing mercury ions with a low concentration of about several ppb, it is difficult to detect colorimetrically by the method of immersing the film in the sample solution. In the method using liquid flow, colorimetric detection is possible by concentrating, but since the film is originally colored in gray, in order to change the color of the film to the extent that colorimetry is possible A large amount of sample solution was required and filtration took time, and it was not possible to efficiently measure mercury ions.

  Thus, it takes time to handle the mercury ion detection film and it is difficult to measure mercury ions at a low concentration, and it is not always possible to measure mercury ions simply and quickly on site.

  Therefore, the present invention has been devised in view of the above points, and its purpose is from the fine particle dithizone, which makes it unnecessary to handle a mercury ion detection film at the time of analysis, and enables simple and quick measurement of mercury ions at the site. Another object of the present invention is to provide a simple analyzer preliminarily provided with a mercury ion trapping film and a mercury ion analysis method using the same.

  In order to solve the above-described problems, a mercury ion simple analyzer according to the present invention has a wide opening at the upstream side and a through hole that passes from the upstream opening to the downstream opening, and the through hole. And a mercury ion-trapping film in which the fine particle dithizone is fixed on the surface of the filter material by supplying a dispersion containing fine particle dithizone to the upstream opening. The mercury ion trapping film is exposed so that it can be viewed directly from the opening on the upstream side of the through hole.

  According to the above configuration, when a sample solution containing mercury ions is supplied to the opening on the upstream side of the simple analyzer in the field, the mercury ions are selectively captured by the mercury ion capturing film fixed on the filter medium. Is done. Color development due to mercury ions trapped in the film can be visually confirmed from the opening on the upstream side, and the concentration of mercury ions is measured.

  Further, the mercury ion simple analyzer of the present invention is fitted into the opening on the upstream side of the through hole to block a part of the mercury ion trapping film, and the sample liquid is left on the exposed portion of the mercury ion trapping film. A cylindrical guide member to be supplied is provided.

  According to the above configuration, the sample solution is supplied to the exposed residue of the mercury ion trapping film through the guide member fitted in the upstream opening, and the sample solution is concentrated per unit area with respect to the exposed residue. Supplied.

  In addition, the inner peripheral side end face of the induction member in contact with the mercury ion trapping film is formed in a protruding ring shape.

  According to the above configuration, the protruding tip surface of the guide member presses the inner diameter side of the mercury ion trapping film in a ring shape, so that the sample liquid is supplied only to the inner peripheral side of the guide member, and mercury ions are only in that portion. Concentrated.

  Moreover, the mercury ion analysis method of the present invention is a method for measuring the mercury ion concentration by visually confirming the color change and the light and shade of the mercury ion capturing film using the simple analyzer.

  According to the above configuration, the mercury ion concentration can be measured by colorimetry visually without using a machine or a measuring device.

  Further, the mercury ion analysis method of the present invention uses the above-mentioned simple analyzer to visually check the color change and shade of the mercury ion trapping film and compare it with a colorimetric member to measure the mercury ion concentration. The colorimetric member includes a plurality of color display units arranged in accordance with a measured concentration of a target substance, and a fitting for receiving an outline of the simple analyzer body provided at substantially the center of each color display unit. A mercury ion trapping film directly viewed from the wide-mouth opening of the simple analyzer main body received in the fitting hole and the surrounding color display portion are directly colorimetrically adjacent to each other. And

  According to the above configuration, the mercury ion trapping film and the color display portion of the density colorimetric member are brought close to each other as much as possible to perform colorimetry from substantially the same plane. Since the simple analyzer body can be received in the fitting hole provided in the center of the color display part, the mercury ion trapping film in the middle of the through hole of the analyzer is positioned in the center of the color display part and colorimetric It becomes possible to do. In addition, since the depth direction of the color display portion of the density colorimetric member and the depth direction of the mercury ion trapping film can be matched, colorimetrics that match the focal length on substantially the same plane are possible, and more accurate. A quick direct comparison can be made.

  In the present invention, “containing fine particle dithizone” is a concept that may include not only a part of fine particle dithizone but also a case of being composed of only fine particle dithizone.

  The expressions “upstream” and “downstream” are used, which are expressions based on the flow of the sample liquid when the simple analyzer is used. That is, the side on which the sample liquid is supplied is the “upstream” side, and the side on which the sample liquid is collected is the “downstream” side.

According to the simple mercury ion analyzer of the present invention, it is possible to provide an on-site portable analyzer capable of easily and quickly measuring the concentration of mercury ions.
In particular, since a mercury ion trapping membrane that can selectively trap only mercury ions is fixed on the filter material in advance, the mercury ion trapping membrane can be picked with tweezers and immersed in a sample solution for measurement. There is no need to set the sample by inserting it into a holder, and the sample solution containing mercury ions can be immediately filtered by using this simple analyzer on site to quickly measure the concentration. At that time, since the mercury ion trapping film exposed through the wide opening on the upstream side can be directly viewed, it is possible to determine the mercury ion concentration by immediately comparing with the color sample without taking out the mercury ion trapping film. Yes.

  Since the mercury ion trapping film only needs to have an area that allows visual confirmation of color development due to the presence of mercury ions, the size of the trapping film can be reduced. As a result, the amount of sample liquid filtration per unit area of the mercury ion trapping membrane can be increased, and low concentration mercury ions can be measured. In addition, since the simple analyzer can be made small, it is easy to carry to the site and work on the site is also easy.

  Further, by feeding the sample liquid by fitting the guiding member into the opening on the upstream side, it is possible to prevent the mercury ion capturing film from floating and to prevent the sample liquid from leaking from the peripheral edge of the mercury ion capturing film. it can. Further, by changing the inner diameter of the sample solution supply part of the guide member, the supply amount of the sample solution per unit area of the mercury ion trapping film can be adjusted, and the measurement range of mercury ions can be widened. After the reaction of the mercury ion detection reagent, the presence of mercury ions is determined by comparing the coloration of the exposed portion of the mercury ion trapping film supplied with the sample solution by the guide member and the clogged portion where the sample solution is not supplied. Therefore, it is possible to easily determine whether or not the sample liquid is supplied, and to adjust the supply amount of the sample liquid while observing the color of the mercury ion trapping film.

  In addition, the analysis method of the present invention can quickly measure mercury ions in a sample solution on-site without an apparatus or a measuring instrument. A mercury ion-trapping film is provided in the middle of the through-hole and can be viewed directly from the opening of the wide mouth, that is, even when a three-dimensional simple analyzer is used, the simple analyzer is received in the fitting hole of the density colorimetric member. Thus, the direct comparison between the mercury ion trapping film and the color display portion can be performed quickly and accurately from the same focal length.

The perspective view of the simple analyzer which is an example of embodiment of this invention. The partial notch exploded perspective view of the simple analyzer. The perspective view which shows a simple analyzer and a guidance member. The principal part expanded sectional view which shows the connection state of the simple analyzer of FIG. 1, and a guidance member. The perspective view which showed 2nd Example of the guide member. The front view which shows the manufacturing method of a simple analyzer. The principal part expanded sectional view which shows the manufacturing method of FIG. The schematic perspective view of the simple measurement system comprised using the simple analyzer. The perspective view which shows the colorimetric process which measures the density | concentration of mercury ion using the simple measurement system of this invention. The principal part expanded sectional view of a colorimetric process.

  Hereinafter, a simple mercury ion analyzer and a mercury ion analysis method using the same according to embodiments of the present invention will be described with reference to the drawings.

<Simple analyzer configuration>
As shown in FIGS. 1 and 2, the simple analyzer 1 includes a filter unit 10 having a through-hole 12 and a mercury ion-trapping membrane containing a filter medium 20 provided in the middle of the through-hole 12 and fine particle dithizone. 22. In the present embodiment, the filter medium 20 includes a basic filter medium 20a and a membrane filter 20b. 1 and 2, the upper side is the upstream side, and the lower side is the downstream side.

  As shown in FIGS. 1 and 2, the filter unit 10 in the present embodiment is a cylindrical body having a through hole 12 extending vertically, and is integrally formed with a synthetic resin material or the like. As for this filter unit 10, the collar part 16 is projected over the outer periphery of the high-order outer peripheral surface of about 1/3 of the up-down direction. The outer peripheral surface of the filter unit 10 can be divided into a large-diameter portion 11 and a conical portion 13 with the flange portion 16 as a boundary, and a large-diameter cylindrical large-diameter portion 11 in which the upstream side from the flange portion 16 rises substantially perpendicularly from the flange portion 16. And a wide opening 17 is opened at the upstream end of the large-diameter portion 11. On the other hand, on the downstream side (lower side in FIG. 2), a conical portion 13 whose outer diameter gradually decreases in the downward direction is provided, and an opening 18 is opened at the downstream end of the conical portion 13. . The opening 18 on the downstream side has a narrow opening. Further, a protrusion 14 is formed on the outer peripheral surface slightly upstream of the flange 16 over the entire periphery. The filter unit 10 is formed in a size that can be easily carried on site, and the wide opening width W2 may be a size that allows the color change of the mercury ion capturing film 22 to be visually confirmed. In order to confirm a change in the color of the mercury ion trapping film 22, the diameter of the portion α where the color changes when the sample liquid is supplied needs to be 2.5 mm or more. The wide opening width W2 is preferably 2.5 mm to 10 mm in order to increase the visibility and make the simple analyzer 1 portable enough to be carried on site. Although not particularly limited, in this embodiment, the total length L1 of the filter unit 10 is about 16 mm, the total width W1 is about 11 mm, and the wide opening width W2 is about 7 mm. In addition, the filter unit 10 may be comprised other than the resin material, for example, can be comprised also with a metal, earthenware, etc.

  The through hole 12 has a stepped portion 12c projecting in a ring shape on the way from the upstream opening 17 to the downstream opening 18. On the upstream side of the stepped portion 12c, a substantially vertical large-diameter hole portion 12b is opened to a wide opening so that it can be directly viewed from the outside, and a first tapered hole that expands in a tapered shape at the upper end of the large-diameter hole portion 12b. A portion 12a is provided. Further, the inner peripheral surface on the downstream side from the stepped portion 12c is tapered so that the diameter of the through hole 12 is narrowed to form a second tapered hole portion 12d, and the downstream side of the second tapered hole portion 12d is a through hole. A small-diameter hole portion 12e in which the inner diameter of 12 is narrowed is provided. As above-mentioned, the 1st taper hole part 12a, the large diameter hole part 12b, the step part 12c, the 2nd taper hole part 12d, and the small diameter hole part 12e connect, and the through-hole 12 is comprised as a whole.

  A basic filter material 20a made of a disk-shaped continuous porous membrane is disposed on the step 12c of the through-hole 12, and a disk-shaped membrane filter 20b is disposed thereon, and is laminated on the membrane filter 20b. A disc-shaped mercury ion trapping film 22 is arranged as shown. Therefore, when the through hole 12 is viewed from the upstream side, the entire surface of the mercury ion trapping film 22 can be directly visually recognized through the wide opening 17.

The outer edge of the lower surface of the basic filter material 20a is in close contact with the step portion 12c, and the outer peripheral surface is in close contact with the inner peripheral surface of the large-diameter hole portion 12b over the entire circumference. In the present embodiment, the basic filter material 20a is formed by sintering a synthetic resin material such as polyethylene. Although not specifically limited, the thickness of the basic filter medium 20a is preferably about 2 to 5 mm.
Further, when the filter medium 20 has a two-layer structure as in the present embodiment, the basic filter medium 20a is a filter membrane and at the same time plays a role of appropriately holding the membrane filter 20b. However, if the membrane filter 20b can be appropriately held, the basic filter material 20a does not necessarily need to be a sintered filter, and for example, a fine mesh can be used.

  The membrane filter 20b is disposed on the basic filter material 20a and covers the entire surface of the basic filter material 20a. The membrane filter 20b only needs to be capable of laminating fine particle dithizone contained in the dispersion on the filter 20b. Examples thereof include a stretched porous film made of cellulose ester, polycarbonate, polyester, and a porous polymer sheet. Specifically, the pore size of the membrane filter 20b is 1 μm or less, preferably in the range of 0.2 μm to 0.8 μm. The thickness of the membrane filter 20b is desirably about 5 μm to 1 mm.

  In the above description, the filter medium 20 has a two-layer structure of the basic filter medium 20a and the membrane filter 20b, but this configuration is not necessarily essential. For example, if the basic filter medium 20a can fix the fine particle dithizone on the basic filter medium 20a to form the mercury ion trapping membrane 22, the filter medium 20 has a single layer structure of the basic filter medium 20a. May be.

  The mercury ion capturing film 22 is a film having a function of capturing mercury ions (Hg ions) contained in the sample solution. The mercury ion capturing film 22 is a thin film composed of fine particles of dithizone which is a mercury ion detection reagent, and the particle diameter of dithizone constituting the film is 5 to 500 nm. The lower surface of the mercury ion trapping film 22 is integrally attached to the surface of the membrane filter 20b and extends over the entire surface with substantially the same thickness. Specifically, the thickness of the mercury ion trapping film is 0.1 μm to 10 μm.

  The guiding member 100 is a member that can supply the sample solution to the exposed remainder of the mercury ion trapping film 22 and change the supply amount of the sample solution per unit area to the mercury ion trapping film 22. As shown in FIGS. 3 and 4, in the present embodiment, it is configured as a cylindrical (pipe-shaped) member formed with a hollow portion 100a through which a sample solution passes, and has a large-diameter hole portion of the simple analyzer 1 at one end. The small diameter portion 100b that can be forcibly fitted to 12b is reduced in diameter, and the step surface 100c is located in the reduced diameter portion. The cylindrical shape includes a cylindrical shape, a rectangular tube shape, and an expanded cylindrical shape, that is, a trumpet shape. Further, at the tip of the small diameter portion 100b, a tip surface 100d and an end surface of a convex portion 100e protruding from the inner peripheral side are formed in a ring shape. When the small-diameter portion 100b of the guide member 100 is fitted into the large-diameter hole portion 12b of the simple analyzer 1, the upstream end surface 10a of the filter unit 10 comes into contact with the step surface 100c and is positioned. At this time, the leading end surface 100d of the guiding member 100 is configured to be in close contact so as to press the peripheral edge of the surface of the mercury ion capturing film 22. At that time, the convex portion 100e further presses the mercury ion trapping film 22 in a ring shape on the inner peripheral side of the distal end surface 100d. The ring shape includes a circular shape (annular), an elliptical shape, and a square shape. Although the height of the convex part 100e from the front end surface 100d depends on the thickness of the mercury ion trapping film, it is preferably about 0.2 mm to 2 mm, for example.

Since the opening area of the hollow part 100a of the guiding member 100 is smaller than the surface area of the mercury ion trapping film 22, the guiding member 100 is connected to the large-diameter hole 12b of the simple analyzer 1 to It is possible to narrow the passage to a part of the surface of the mercury ion capturing film 22 and change the degree of concentration per unit area. For example, the concentration level can be adjusted as appropriate by arranging a plurality of guide members 100 having different inner diameters d1 of the hollow portion 100a as a series. In other words, the concentration level can be secured even when the sample solution is precious and cannot be secured in large quantities, which means that the concentration can be measured.
The inner diameter d1 of the hollow portion 100a is preferably 5 mm or less from the relationship between the amount of sample solution supplied and the time required for filtration, and is preferably 2.5 mm or more from the viewpoint of easy visual confirmation of the color development state after mercury ion capture. Specifically, when the inner diameter d1 is 3 mm, a small sample solution of 3.5 ml is sufficient for the filtration amount per unit area to be 50 ml / cm 2.

  Further, the guiding member 100 can prevent the sample liquid from passing through a gap (which does not necessarily mean that a gap is generated) γ that can be generated by drying and shrinking the peripheral edge of the mercury ion trapping film 22. it can. That is, since the mercury ion capturing membrane 22 is dried by laminating fine dithizone containing moisture on the filter medium 20, that is, the basic filter medium 20a or the membrane filter 20b, there is a possibility that shrinkage may occur in the drying process. . This is because if a slight gap is generated between the peripheral edge of the mercury ion trapping film 22 and the large-diameter hole 12b due to the shrinkage, a part of the sample solution passes through the gap and affects the concentration measurement. The guiding member 100 has a structure in which the convex portion 100e can further press the mercury ion capturing film 22 on the inner peripheral side with respect to the gap γ to prevent permeation and diffusion to the outer peripheral side.

  Furthermore, when the guide member 100 is used, a central portion α through which the sample solution passes and an annular portion β through which the sample solution 70 does not pass are formed on the surface of the mercury ion capturing film 22 after the color development treatment (see FIG. 1). For this reason, a portion (annular portion β) where the background color of the mercury ion capturing film 22 remains as it is after the color development treatment can be formed, and it is possible to easily confirm the presence or absence of color development even with a simple analyzer alone. The background color of the mercury ion trapping film 22 of the present invention is light gray, and when the mercury is trapped, it exhibits a pink color. However, it may be difficult to recognize the color change compared to the ground color of white. Therefore, the color change can be easily confirmed by leaving the ground color portion (annular portion β). In other words, the simple analyzer 1 can be used alone without using a color sample as long as it is determined whether or not mercury ions are present in the sample solution.

  Furthermore, mounting the guide member 100 not only adjusts the concentration level of the sample solution 70 but also exhibits a function of preventing the mercury ion trapping film 22 from falling off. Further, the mercury ion trapping membrane 22 is formed by laminating a thin and hydrophobic solid component on the filter medium 20, that is, the basic filter medium 20a or the membrane filter 20b. Prevents the film from turning over due to the supply of the sample solution and also prevents the deformation of the mold.

  The guide member 100 may have a structure that can be attached to and detached from the simple analyzer 1 or a structure that cannot be attached or detached (a fitting-in structure or an integrally formed structure). Of course, in the case where the guiding member 100 has a structure that cannot be detached, even when the guiding member 100 has a structure that can be detached, the guiding member 100 is made of a colorless transparent resin or the like without removing the guiding member 100 from the simple analyzer 1. Colorimetric analysis can be performed quickly.

  The guide member 100 is not limited to the pipe-shaped member as described above, and may be configured as a so-called donut-shaped guide member 110 as shown in FIG. With such a configuration, the entire guide member 110 can be stored in the large-diameter hole portion 12b of the simple analyzer 1, and the configuration can be made compact.

<Simple analyzer manufacturing method>
Next, a method for manufacturing the simple analyzer 1 will be described with reference to FIGS. 6 and 7. In addition, the manufacturing method of the simple analyzer 1 is not limited to the method of the following description.

  The fine particle dithizone dispersion can be obtained, for example, by adding a solution obtained by dissolving dithizone in a hydrophilic organic solvent such as acetone or methanol to stirred water. In this dispersion, fine dithizone particles having a length of 1 μm or less and a width of 100 nm or less are uniformly dispersed in water. If necessary, large particles (micron level) may be removed by filtering with a filter having a pore size of submicron level.

  The basic filter medium 20a and the membrane filter 20b, which are formed to a size that can be fitted into the large-diameter hole 12b, are superposed on each other to form the filter medium 20, and are pushed into the step 12c of the large-diameter hole 12b and fixed. As shown in FIG. 6, one end of the connection tube 40 is pushed into and connected to the large diameter portion 11 of the filter unit 10. At this time, the protrusion 14 formed on the outer peripheral surface of the large-diameter portion 11 of the filter unit 10 functions as a stopper for preventing the connection tube 40 from coming off. Then, a predetermined volume of the dispersion 60 containing dithizone of a predetermined amount of fine particles is placed in the syringe 30, and the syringe 30 is connected to the other end of the connection tube 40. The dispersion liquid 60 is pushed in at a constant speed with the syringe 30 and laminated on the membrane filter 20b. The membrane filter 20b allows liquid to pass through, but does not allow the fine particle dithizone or the like in the dispersion liquid 60 to pass through and is left on the upstream side, so that the mercury ion trapping film 22 is formed.

  As shown in FIG. 7, when the dispersion liquid 60 containing fine particle dithizone is supplied from the opening 17, the fine particle dithizone dispersed in the dispersion liquid 60 as a solid component is fixed on the membrane filter 20b. Is done. The dispersion liquid 60 is supplied to the large-diameter hole portion 12b while being converged on the inner peripheral edge side by the first tapered hole portion 12a, and is fixed while being engaged while being drawn into the pores of the membrane filter 20b. At this time, since the porosity of the membrane filter 20b is set so as to be uniform over the entire surface, the solid components in the dispersion 60 are sequentially laminated in a uniform state to capture light gray mercury ions. A film 22 is formed. In addition, since the thickness of the mercury ion trapping film 22 formed varies depending on the amount of the dispersion 60 to be supplied, it is necessary to adjust the supply amount as appropriate.

After supplying the slurry 60, a certain amount of air is sucked from the small-diameter hole 12e, thereby removing the liquid contained in the mercury ion trapping membrane 22, the basic filter material 20a, and the membrane filter 20b. If necessary, an excessive liquid may be removed by pressing the surface of the mercury ion trapping film 22 using a member having a size that can be fitted into the large-diameter hole 12b.
Thereafter, although not shown, the filter unit 10 on which the mercury ion capturing film 22 is formed is dried with a dryer, and the simple analyzer 1 is obtained.

<Simple mercury ion measurement system using a simple analyzer>
Next, a system that simply measures the concentration of mercury ions using the simple analyzer 1 described above will be described.

  The simple analysis is realized by the simple measurement system shown in FIG. The simple measurement system captures mercury ions contained in the sample liquid 70 and visualizes the presence of mercury ions on the mercury ion capturing film 22, and identification for identifying the color of mercury ions visualized by the visualization means. Means are provided.

  The visualization means includes, for example, a beaker (container) 50 to which a sample solution 70 containing mercury ions is supplied, a syringe 30 from which the sample solution 70 in which the mercury ions are captured from the mercury ion capturing film 22 is collected, and these beakers 50. And the connection tube 40 that connects the syringe 30 and the simple analyzer 1 that is connected to the end portions of the connection tube 40. Specifically, one end of the connection tube 40 is fitted and connected to the nozzle portion 32 of the syringe 30 and the other end is connected to the conical portion 13 of the simple analyzer 1. The connecting tube 40 is desirably a cylindrical body made of a thermoplastic resin having flexibility, and is in close contact by being pushed into the tapered portion of the nozzle portion 32 or the conical portion 13. Further, the large-diameter hole portion 12b of the simple analyzer 1 may be opened to the sample solution 70, but the guide member 100 may be fitted into the large-diameter hole portion 12b as illustrated.

  As the syringe 30, various commercially available syringes can be used. Although not particularly limited, specifically, a syringe with a stopper (such as manufactured by Fujiwara Seisakusho Co., Ltd.) that can fix the cylinder position inside the syringe is desirable from the viewpoint that the suction speed of the sample solution can be made substantially constant and the suction is not time-consuming.

  Further, in the visualization means, the sample solution 70 may be put into a syringe in a certain volume, and the nozzle portion 32 of the syringe 30 and the large-diameter hole portion 12b of the simple analyzer 1 may be connected using the connection tube 40 or the guide member 100. Good. The sample solution 70 is pushed in by the syringe 30 and supplied to the simple analyzer 1.

  On the other hand, the identification means uses a density colorimetric member 90 for comparing the colors of mercury ions visualized by the visualization means. The density colorimetric member 90 includes a plurality of color display units 92 arranged stepwise according to the concentration of mercury ions, and a density display 94 corresponding to the color display unit 92. The density colorimetric member 90 has a sheet shape shown in the figure, and a fitting hole 96 for fitting the large diameter portion 11 of the simple analyzer 1 is formed at the center of each color display portion 92. For this reason, the color display portion 92 basically has an annular shape surrounding the fitting hole 96. The color of the color display portion 92 is created by confirming color development using a sample solution 70 having a known concentration in advance.

  The color display portions 92 are arranged apart from each other, for example, according to the concentration of mercury ions. More specifically, the concentration display 94 is arranged so that the concentration of mercury ions increases in the left-right direction (X direction), that is, from the left to the right, and the color of the color display unit 92 is also changed from gray to pink accordingly. It becomes darker in order.

<Measurement method using simple measurement system>
Subsequently, a specific measurement method using the simple measurement system will be described along a procedure.

  As an outline of the method for measuring the concentration of mercury ions, the sample liquid 70 is supplied onto the mercury ion capturing film 22 of the simple analyzer 1 and the mercury ions contained in the sample liquid 70 are captured on the mercury ion capturing film 22. The color density (color intensity) of the mercury ion capturing film 22 is confirmed, and the mercury ion concentration is measured. Since there is a correlation between the concentration of mercury ions and the density of the developed color, the concentration of mercury ions is visually compared with the color of the color display portion 92 of the density colorimetric member 90 created using a sample whose concentration is known in advance. Can be determined by comparison.

First, the piston of the syringe 30 is pulled while the lower end of the guide member 100 is immersed in the sample solution 70 of the container 50 such as a beaker, and the sample solution 70 is sucked up (see FIG. 8). Thereby, the sample liquid 70 moves to the syringe 30 side through the through hole 12 of the simple analyzer 1. The syringe 30 operates the piston at a constant speed for a desired distance to supply a constant volume, and mercury ions contained in the constant volume of the sample liquid 70 are concentrated by the mercury ion trapping film 22.
Thereafter, the syringe 30 is removed from the connection tube 40, and the filtrate collected in the syringe 30 is discarded.

Next, as shown in FIG. 9, the simple analyzer 1 is removed from the guiding member 100 and the connection tube 40, and the concentration of spots (the traces of the trapped mercury ions developed) formed on the surface of the mercury ion trapping film 22 is concentrated. The color display unit 92 of the colorimetric member 90 is compared. As a result of comparison, the concentration display 94 corresponding to the closest one is the concentration of mercury ions contained in the sample liquid 70.
The presence or absence of mercury ions in the sample liquid is immediately confirmed by comparing the color development between the spot and the portion blocked by the guiding member 100 and not supplied with the sample liquid 70.

  Since the fitting holes 96 are provided in the color display portions 92 of the density colorimetric member 90, the large-diameter portion 11 of the simple analyzer 1 is fitted into the fitting holes 96. At this time, since the flange 16 is formed on the outer periphery of the filter unit 10, the upper surface is sandwiched between the protrusions 14 with the flange 16 in contact with the lower surface of the density colorimetric member 90. The simple analyzer 1 fitted in the fitting hole 96 is positioned (see FIG. 10). Further, since the collar portion 16 is formed at a position substantially aligned with the position of the mercury ion trapping film 22, when the collar portion 16 is positioned, the color display portion 92 on the density colorimetric member 90 and the mercury are arranged. The height direction with the surface of the ion trapping film 22 is aligned to some extent, and more accurate colorimetry is possible. In particular, since the surface of the mercury ion capturing film 22 and the color display portion 92 are close to each other, the colorimetry is performed quickly and accurately. Further, the simple analyzer 1 may be fitted from the upper side instead of the lower side of the density colorimetric member 90. That is, the cone portion 13 of the filter unit 10 can be dropped into the fitting hole 96 and inserted for colorimetry. In this case, the color of the mercury ion capturing film 22 in the opening 17 and the color display around the collar portion are displayed. The color is compared with the portion 92.

  Since the total amount of mercury ions captured per unit area of the mercury ion capturing film 22 is proportional to the supply amount of the sample solution 70, the larger the supply amount of the sample solution 70, the more the amount of mercury ions captured by the simple analyzer 1 Increases and lower concentrations can be measured. The amount of the sample solution 70 is desirably 200 ml or less from the viewpoint of the time required for the filtration process.

Further, when measuring mercury ions using a simple measurement system, interference may be caused by other metal ions coexisting in the sample solution 70. In such a case, in order to prevent this, the interference can be eliminated by adding a masking reagent that forms a complex with the coexisting metal in the sample solution 70. For example, the metal ions that can coexist include Na +, K +, Ca (II), Mg (II), Fe (II), Fe (III), Cu (II), and Zn (II). Examples of these metal ion masking agents include iminodiacetic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid (EDTA), ethylenediamine, acetylhydroxamic acid, amino acid, citric acid, and tartaric acid. These may be used alone or as needed. The above may be used in combination.
On the other hand, by making the sample solution acidic, mercury ions can be selectively trapped on the mercury ion trapping film and interference of other metal ions can be eliminated.

  In addition, when there is a suspended matter or suspended substance in the sample solution 70, the suspended matter is likely to adhere to the mercury ion capturing film 22 and cause clogging or uneven coloring. It is desirable to remove etc.

  The present invention is not limited to the above-described embodiments, and variously modified forms are included in the technical scope without departing from the gist of the invention described in the claims. .

  A filter unit having a total length of about 16 mm, a total width of about 11 mm, and a wide opening width of about 7 mm shown in FIGS. 1 and 2 and made of polypropylene resin was used. The basic filter material was obtained by sintering polyethylene powder in a filter unit. The membrane filter was a disc-shaped membrane filter made of cellulose mixed ester having a diameter of 7 mm, a pore diameter of 0.65 μm, and a thickness of 110 μm. The above filter was placed on a basic filter medium, and distilled water was allowed to flow through and adhered. Moreover, the guide member used the length 30mm shown in FIG. 3, the external width 8mm, the internal diameter 3mm, and the thing made from a polypropylene resin.

  0.5 g of dithizone was dissolved in 0.1 ml of acetone, and 0.1 ml of this solution was taken in a syringe. 10 ml of distilled water in a beaker was stirred at 1000 rpm using a magnetic stirrer, and 0.1 ml of the above solution was vigorously injected from a syringe at a stroke to obtain a dispersion containing fine dithizone.

  0.4 ml of the obtained dispersion was immediately sucked with a syringe, and the dispersion was supplied at a constant speed from the opening of the wide mouth, and was laminated on the membrane filter. Water remaining on the basic filter medium and the membrane filter is removed by suction from the downstream opening with a syringe, placed horizontally on the filter holder, and filtered through several ml of distilled water to wash the formed thin film, and 50 ° C. The sample was allowed to stand for 1 hour under the conditions and dried to obtain a simple analyzer.

The guiding member is fitted into the large-diameter hole portion of the simple analyzer of Example 1, and the conical portion and the syringe are connected using a connection tube. A sample solution containing 10 ppb mercury ions is prepared in a beaker, the lower end of the guiding member is put into various sample solutions, the piston of the syringe is pulled at a constant speed, and 3.5 ml is sucked. The filtration area of the mercury ion trapping membrane is 0.07 cm ² (diameter 3 mm), and the filtration amount per unit area is 50 ml / cm ² .

  When the guide member is removed from the large-diameter hole and the mercury ion trapping membrane is seen from the opening of the wide mouth, the portion where the sample solution is not supplied remains light gray, but the sample solution is supplied by the guide member. A light pink round coloring can be confirmed in the part. The large-diameter portion of the simple analyzer is fitted into the fitting hole of the density colorimetric member, and the color display portion and the color on the mercury ion trapping film are brought close to each other and colorimetric to determine the mercury ion concentration in the sample.

DESCRIPTION OF SYMBOLS 1 ... Simple analyzer 2 ... Simple measurement system 10 ... Filter unit 10a ... Upstream end surface 11 of filter unit 10 ... Large diameter part 12 ... Through-hole 12a ... 1st taper hole part 12b ... Large diameter hole part 12c ... Step part 12d ... 2nd taper hole part 12e ... Small diameter hole part 13 ... Conical part 14 ... Protrusion part 16 ... Eaves part 17 ... Wide opening 18 ... Downstream opening 20 ... Filter medium 20a ... Basic filter medium 20b ... Membrane filter 22 ... Mercury ion capture film 30 ... Syringe 32 ... Nozzle 40 ... Connecting tube 50 ... Container 90 ... Concentration colorimetric member 92 ... Color display part 94 ... Concentration display 96 ... Fitting hole 100, 110 ... Induction member 100a ... Hollow part 100b ... Small diameter portion 100c ... Step surface 100e ... Convex portion 100d ... Lead end face L1 ... Full length W1 of filter unit 10 ... Full width W2 of filter unit 1 ... Wide opening 17 Gap may be caused by drying shrinkage of the periphery of the width d1 ... guide member of the hollow portion 100a of the inner diameter alpha ... center beta ... sample liquid does not pass through the annular portion gamma ... mercury ions capture membrane 22 sample liquid passes

Claims (7)

  A through-hole that allows the upstream opening to have a wide opening and pass from the upstream opening to the downstream opening, a filter medium provided in the middle of the through-hole, and fine particles with respect to the upstream opening And a mercury ion trapping film in which the fine particle dithizone is fixed on the surface of the filter medium by supplying a dispersion containing dithizone, and the mercury ion trapping film is an opening upstream of the through-hole. This is a simple analyzer for measuring the mercury ion concentration that is displayed so that it can be seen directly from the center.   A cylindrical guide member is provided, which is fitted into the opening on the upstream side of the through-hole, closes a part of the mercury ion trapping film, and supplies the sample liquid to the remaining exposed portion of the mercury ion trapping film. The simple analyzer for measuring the mercury ion concentration according to claim 1.   The simple analyzer according to claim 2, wherein an inner peripheral side end face of the induction member in contact with the mercury ion capturing film is formed in a protruding ring shape.   The simple analyzer according to any one of claims 1 to 3, wherein the filter medium includes a sintered filter and a membrane filter.   A method for measuring the mercury ion concentration by visually confirming a change in color and density of the mercury ion trapping film, and analyzing the mercury ion using the simple analyzer according to any one of claims 1 to 4. Method.   The color change and density of the mercury ion trapping film is visually confirmed by comparing with a colorimetric member, and a plurality of color display units in which the colorimetric member is arranged according to the measured concentration of the target substance, and each color display unit And a fitting hole for receiving the outer shape of the simple analyzer main body provided substantially at the center of the mercury analyzer, and a mercury ion trapping film that is directly viewed from the wide opening of the simple analyzer main body received in the fitting hole. 6. The method for analyzing mercury ions according to claim 5, wherein the color display part and the surrounding color display part are directly colorimetrically adjacent to each other. 7. The method for analyzing mercury ions according to claim 6, wherein the color display portions are arranged in accordance with the concentration of mercury ions.

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