JP2011085562A - Simple analyzer for water quality, and method of analyzing water quality using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a simplified analyzer, dispensing with troublesome pretreatment and posttreatment, and allowing the concentration of objective substances contained in a sample liquid to be measured simply and rapidly on site, and to provide a method of analysis which uses the analyzer. <P>SOLUTION: The simplified analyzer includes a tubular guide 100, including a through-hole 12, with its upstream-side opening made wide-mouthed, while letting a specimen liquid run therethrough from the upstream-side opening to its downstream-side opening; and a filtering film 20 provided in the middle of the through-hole 12 for causing an object substance to stick thereto or collecting it. The filtering film 20 is placed on the outside so that it is directly visible in the face from the upstream-side opening of the through-hole 12. The tubular guide is fit in the upstream-side opening of the through-hole to a block-out portion of the filtering film, and supplying the sample liquid to an outside-placed remainder of the filtering film. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a simple water quality analyzer and a water quality analysis method using the same.

  The water quality can be analyzed with high accuracy using various devices provided, for example, if the sample liquid to be inspected is brought back to a laboratory or laboratory. However, in water treatment facilities such as sewage treatment plants and industrial wastewater treatment facilities, it is necessary to grasp the water quality at that time in order to properly manage the operation of water treatment facilities. For this reason, it is necessary to obtain a water quality analysis result immediately after sampling the sample liquid. In addition, since it takes time to take the sample solution and analyze it, there is a concern that the quality of the sample may change during this period, such as the sample solution decays or the target substance decomposes. In response to such a demand, for example, a simple analyzer (pack test: registered trademark) described in Patent Document 1 is widely used.

  The pack test (registered trademark) is an analysis tool in which a coloring reagent prepared so as to develop color in response to a specific substance (target substance) is sealed in a polyethylene tube. When using, pull out the line (plug member) sandwiched between the welds at the end of the polyethylene tube to form a through-hole with the inside, crush the polyethylene tube with your fingers to push out the air inside, and the solution to be inspected Inhale like a dropper. The inhaled liquid to be examined chemically reacts with the reagent and develops color. By comparing visually with a color sample color-coded for each concentration after a predetermined time has elapsed, the numerical value corresponding to the closest color can be read, and the concentration of the target substance contained in the liquid to be inspected can be obtained. Of course, depending on the case, the concentration can be obtained by taking out the developed liquid to be inspected and reading it with a photometer or the like.

  On the other hand, a method for measuring the concentration of a target substance in a sample solution by filtering the target substance (formaldehyde) that has been hydrophobized with a membrane filter and comparing the colors on the membrane filter after filtration is proposed. (Patent Document 2).

Japanese Patent No. 4125603 JP 2007-218866 A

  However, the color development of the reagent enclosed in the tube, such as Pack Test (registered trademark), is determined by the molar extinction coefficient, and it is impossible to freely change the color development sensitivity. That is, there is a limit to the concentration range that can be measured by itself, for example, the color does not develop at a concentration below a certain level, or the color develops very little, and it is difficult to measure accurately even by using a photometer.

Further, in the concentration measurement method described in Patent Document 2, since there is no dedicated instrument or device, a filter holder hermetic type filtration device that has been conventionally used for the purpose of “removing foreign matters in the liquid” is used. Is used. For example, the membrane filter is sandwiched by a filter holder that is separated into two parts by a screw structure. For this reason, a thin and easy-to-break membrane filter must be set in the filter holder every time it is used in the field. Then, after passing the sample solution, in order to confirm the color of the membrane filter, it is necessary to open the filter holder and take out the membrane filter.
In addition, there is a problem that when measuring pressure through a syringe or the like, the sample solution leaks from the membrane filter and passes through a small gap between the membrane filter and the filter holder, resulting in errors in concentration measurement. .
Furthermore, when analyzing a sample solution containing a low concentration of the target substance, it is necessary to pass a large amount of the sample solution through a membrane filter, which requires a large amount of sample solution and takes time for filtration. A good analytical method was desired.

  Therefore, the present invention has been devised in view of the above points, and does not require the complicated pre-treatment and post-treatment as described above, and enables the concentration measurement of the target substance contained in the sample liquid on-site easily and quickly. A simple analyzer and an analysis method using the same are provided.

  In order to solve the above-mentioned problems, a simple analyzer for measuring the concentration of a target substance of the present invention has a through-hole that allows an upstream opening to be widened and passed from an upstream opening to a downstream opening. A filtration membrane that adsorbs or collects a target substance provided in the middle of the through hole, and the filtration membrane is exposed so that it can be viewed directly from an opening on the upstream side of the through hole, and is upstream of the through hole. A cylindrical guide member is provided, which is fitted into the opening on the side, closes a part of the filtration membrane, and supplies the sample liquid to the exposed remaining portion of the filtration membrane.

  According to the above configuration, the sample liquid is supplied in a state of being concentrated per unit area to the exposed remaining portion of the filtration membrane through the guide member fitted into the upstream opening. The target substance in the supplied sample solution is adsorbed or collected on the exposed residue of the filtration membrane. The color development of the target substance adsorbed or collected can be confirmed from the opening on the upstream side, and the concentration of the target substance is measured.

  Further, the simple analyzer of the present invention is characterized in that an inner peripheral side end face of the guiding member contacting the filtration membrane 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 filtration membrane in a ring shape, so that the sample solution is supplied only to the inner peripheral side of the guide member, and the target substance in the sample solution is the portion concerned. Only concentrated.

  Furthermore, the simple analyzer of the present invention is characterized in that the filtration membrane has a membrane filter.

  According to the above configuration, the target substance is adsorbed or collected on the membrane filter.

  Furthermore, in the simple analyzer of the present invention, the material of the membrane filter is cellulose mixed ester, cellulose acetate, polyurethane foam, polytetrafluoroethylene, polyethersulfone, polycarbonate, filter paper.

  According to the above configuration, an optimum membrane filter is selected.

  Furthermore, the simple analyzer of the present invention is characterized in that the sample solution is subjected to at least one of a hydrophobic treatment, a precipitation treatment, and a color development treatment of a target substance.

  According to the above configuration, the sample liquid is treated so that the target substance or the product derived from the target substance is adsorbed or collected on the filter membrane and the portion of the filter membrane supplied with the sample liquid is colored. Is done.

  Furthermore, in the simple analyzer of the present invention, the target substances are phosphoric acid, silicic acid, formaldehyde, nickel, chlorophyll a, iron, manganese, copper, chromium, aluminum, lead, ammonium, nitrous acid, nitric acid, residual chlorine, Fluorine, free cyanide, sulfide, hydrazine, phenol.

  According to the above configuration, the optimum substance is selected as the concentration measurement target substance.

  The target substance analysis method of the present invention is a method for measuring the concentration of a target substance in a sample solution based on the color change and concentration of the filtration membrane using the simple analyzer.

  According to the above configuration, the concentration of the target substance can be easily measured without the need for a measurement method or a quantitative analysis apparatus consisting of complicated processes.

  Further, in the method for analyzing a target substance of the present invention, the color change and shading of the filtration membrane are visually confirmed by comparing with a colorimetric member using the simple analyzer. A plurality of color display portions arranged in accordance with the measured concentration of the substance, and a fitting hole for receiving the outline of the simple analyzer main body provided substantially at the center of each color display portion; The filter membrane viewed directly from the wide-mouth opening of the simplified analyzer main body and the surrounding color display section are adjacently directly colorimetrically characterized.

  According to the above configuration, the filter membrane and the color display portion of the density colorimetric member are brought close to each other as much as possible, and colorimetry is performed 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 filter membrane in the middle of the through hole of the simple analyzer is positioned in the center of the color display part for colorimetry It becomes possible. In addition, since the depth direction of the color display portion of the density colorimetric member and the depth direction of the filtration membrane can be matched, colorimetrics that match the focal lengths on substantially the same plane are possible, making it more accurate and quick. Direct comparison can be made.

  In addition, although the expressions “upstream” and “downstream” are used, this is an expression 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 analyzer of the present invention, it is possible to provide an on-site portable analyzer capable of measuring the concentration of a target substance easily and quickly. Since a simple membrane is provided with a filter membrane that adsorbs or collects the target substance in the sample in advance, there is no need to set the membrane filter by pinching it with a pair of tweezers and setting it. The concentration can be measured quickly by passing the sample solution immediately using this simple analyzer on site. At that time, since the filtration membrane exposed through the wide opening on the upstream side can be directly viewed, it is possible to immediately compare with the color sample without taking out the membrane filter, or to measure the concentration of the target substance by measuring with a reflectometer. It is like that.

Furthermore, by supplying the sample liquid by fitting the guide member to the opening on the upstream side, the target substance in the sample liquid can be efficiently condensed and adsorbed or collected on the filtration membrane. 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 filtration membrane can be adjusted, and the measurement concentration range of the target substance is widened.
Further, when the guide member is fitted on the filtration membrane, the filtration membrane can be prevented from floating and wrinkled, and the sample liquid can be prevented from leaking from the peripheral portion of the filtration membrane. By comparing the color of the exposed residue supplied with the sample liquid on the filtration membrane by the guide member and the color of the blocked portion where the sample liquid was not supplied, the presence or absence of the target substance can be easily determined. The supply amount of the sample solution can be adjusted while checking the color change.

  Moreover, since the filtration membrane should just have an area which can confirm the color change by presence of the target substance visually, the magnitude | size of a filtration membrane can be made small. As a result, since the simple analyzer can be made small, it is easy to carry to the site and work on the site is also easy.

  In addition, the analysis method of the present invention can quickly measure the concentration of a target substance in a sample solution on site without an apparatus or a measuring instrument. Equipped with a filtration membrane in the middle of the through-hole and can be viewed directly from the opening of the wide mouth, that is, even when using a three-dimensional simple analyzer, the simple analyzer is received in the fitting hole of the density colorimetric member and filtered. The direct comparison between the film and the color display unit can be performed quickly and accurately from the same focal length.

The perspective view which shows the simple analyzer which is an example of embodiment of this invention. The principal part expanded sectional view of the simple analyzer. The perspective view of the simple analyzer which removed the guidance member. The partial notch exploded perspective view of the simple analyzer which removed the guidance member. The perspective view which showed 2nd Example of the simple analyzer. 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 the target substance using the simple measurement system of this invention. The principal part expanded sectional view of a colorimetric process. Photograph showing the concentration measurement result and colorimetry of nickel in Example 3 Photograph showing concentration measurement result of phosphoric acid in Example 5 Concentration measurement result and colorimetric result of chlorophyll a in Example 7

  Hereinafter, a simple analyzer for a target substance according to an embodiment of the present invention and a method for analyzing a target substance using the analyzer will be described with reference to the drawings.

<Simple analyzer configuration>
As shown in FIG. 1 and FIG. 2, the simple analyzer 1 includes a filter membrane 20 that adsorbs or collects a target substance provided in the middle of a through-hole 12 in a filter unit 10 having a through-hole 12, and a filter unit. 10 is provided with a cylindrical guide member 100 that is fitted to the tube 10 and supplies a sample solution. In this embodiment, the filtration membrane 20 is comprised from the basic filter material 20a and the 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 to 4, 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 perimeter on 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 FIGS. 1 and 4), 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. Has been. 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 to 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 filtration membrane 20 to be visually confirmed. In order to confirm the color change of the filtration membrane 20, the diameter of the portion α where the sample solution is supplied and the color changes 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 medium 20a made of a disc-shaped continuous porous membrane is disposed on the step 12c of the through hole 12, and a disc-shaped membrane filter 20b is disposed thereon. Therefore, when the through-hole 12 is viewed from the upstream side, the entire surface of the filtration membrane 20 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 configured by sintering a synthetic resin material such as polyethylene or a glass fiber material. Although not specifically limited, the thickness of the basic filter medium 20a is preferably about 2 to 5 mm.
Further, when the filtration membrane 20 has a two-layer structure as in the present embodiment, the basic filtration material 20a is a filtration 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 able to adsorb or collect the target substance or a product derived from the target substance on the filter 20b, and the material thereof includes cellulose mixed ester, cellulose acetate, polyurethane foam, polytetrafluoroethylene, polyethersulfone, Examples include polycarbonate, filter paper, and the like, which are appropriately selected depending on the characteristics of the target substance to be measured or the hydrophobic treatment or precipitation treatment method applied to the sample solution. Although it is not particularly limited, an example of the selection of the material of the membrane filter is as follows. For phosphoric acid or silicic acid that has been colored by the molybdenum blue method (Analytical Chemistry, 33,453, 1984) and then hydrophobized, it is a cellulose mixed ester. For formaldehyde that has been subjected to color development by the MBTH method (Japanese Patent Laid-Open No. 2007-218866) and hydrophobized, it is preferable to use a cellulose mixed ester, and α-furyldioxime method (Chem. Lett., 37, 7). , 2008), it is desirable that nickel be precipitated by cellulose acetate, and nitrite ions that have been colored by the naphthylethylenediamine method (industrial water, 433, 2, 1994) and then hydrophobized should be mixed with cellulose. Esters are preferred.

  In the above description, the filtration membrane 20 has a two-layer structure of the basic filter material 20a and the membrane filter 20b, but this configuration is not necessarily essential. For example, if the basic filter medium 20a alone can adsorb or collect the target substance or the target substance hydrophobized or precipitated, on the basic filter medium 20a, the filter membrane 20 can be used as the basic filter medium 20a. A single-layer structure may be used.

  The guiding member 100 is a member that can supply the sample solution to the exposed remaining portion of the filtration membrane 20 and change the amount of the sample solution supplied to the filtration membrane 20 per unit area. As shown in FIGS. 1 and 2, 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 front end surface 100d of the guide member 100 is configured to be in close contact so as to press the peripheral edge of the surface of the filtration membrane 20. At that time, the convex portion 100e further presses the filtration membrane 20 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. The height of the convex portion 100e from the distal end surface 100d depends on the thickness of the filtration membrane, but is preferably about 0.2 mm to 2 mm, for example.

Since the opening area of the hollow portion 100a of the guiding member 100 is smaller than the surface area of the filtration membrane 20, connecting the guiding member 100 to the large-diameter hole portion 12b of the simple analyzer 1 allows passage of the sample liquid. It becomes possible to narrow down to a part of the surface of the filtration membrane 20 and change the concentration degree 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 in order to easily confirm the coloring of the filtration membrane 20 visually. Specifically, when the inner diameter d1 is 3 mm, a small sample solution of 35 ml is sufficient to set the filtration amount per unit area to 500 ml / cm ² .

  In addition, since the sample member is passed through the hollow portion 100a, the guiding member 100 does not mean that a slight gap between the peripheral edge of the filtration membrane 20 and the large-diameter hole portion 12b (a gap is always generated). ) It is possible to prevent the sample liquid from passing through γ. The guiding member 100 of the present embodiment has a structure in which the convex portion 100e further presses the filtration membrane 20 on the inner peripheral side with respect to the gap γ, and can further 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 does not pass are formed on the surface of the filtration membrane 20 (see FIG. 3). Therefore, a portion (annular portion β) where the ground color of the filtration membrane 20 remains as it is can be formed, and it is possible to easily confirm the presence or absence of color development with a simple analyzer alone. In other words, the simple analyzer 1 can be used alone without using a color sample or the like as long as it is determined whether or not the target substance is present in the sample solution.

  Furthermore, mounting the guide member 100 not only adjusts the concentration level of the sample solution, but also exhibits a function of preventing the filtration membrane 20 from falling off. Further, when the filter membrane 20 is configured by laminating a membrane filter on the basic filter material 20a, the membrane is prevented from being turned over by supplying the sample liquid by being pressed by the guide member 100, It also functions to prevent out of shape such as floating and twisting.

  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.

  In addition, the guide member 100 is not limited to the pipe shape 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.

  The target substance contained in the sample liquid is adsorbed or collected on the filtration membrane 20, and the filtration membrane 20 is colored by the color of the target substance. Although it is not particularly limited, as an example, chlorophyll a concentration measurement will be described. When environmental water such as a lake is supplied to the filtration membrane 20 as a sample solution, phytoplanktons are collected on the filtration membrane 20, The filtration membrane is colored by the color of chlorophyll a that phytoplankton has.

  On the other hand, when the target substance is colorless, or even if it is a colored target substance, the target substance in the sample solution can be subjected to a color development treatment in order to improve the visibility of coloring. Moreover, about the sample liquid containing the target substance which is hard to be adsorbed by the filtration membrane 20, the sample liquid can be subjected to a hydrophobic treatment or a precipitation treatment. At this time, the substances adsorbed or collected on the filtration membrane 20 include not only the target substance itself but also complexes derived from the target substance, products derived from the target substance, such as ion aggregates and secondary products of the target substance. .

  The coloring process of the target substance is not particularly limited, but refers to a process of generating a colored compound by adding a reagent or the like. As an example, in the α-furyldioxime method for measuring nickel concentration, When α-furyldioxime is added to a sample solution containing nickel ions, a complex with orange nickel ions is formed (Chem. Lett., 37, 792, 2008).

  Hydrophobing treatment of the target substance is not particularly limited, and examples include adding a surfactant, octadecylsilylated silica gel, ion exchange resin, and the like. As an example, a treatment including a hydrophobization treatment and a color development treatment will be described. The MBTH method for measuring the formaldehyde concentration will be described. A certain amount of 3-methyl-2-benzothiazolone hydrazone (MBTH) is added to a sample solution. The formaldehyde contained in the sample solution is changed to azine. Thereafter, an iron (III) chloride solution is added to formaldehyde-derived azine as a blue cationic dye, and unreacted MBTH is converted to oxidized MBTH. When sodium tetraphenylborate is added to these, an ion aggregate (blue) of a blue cationic dye and sodium tetraphenylborate and an ion aggregate (yellow) of oxidized MBTH and sodium tetraphenylborate are formed. These ion aggregates are hydrophobic, float in the sample solution, and are collected on the filtration membrane 20 when passed through the filtration membrane 20 (Japanese Patent Laid-Open No. 2007-218866).

  The precipitation treatment of the target substance is not particularly limited, and examples thereof include addition of a coprecipitation agent, precipitation generation due to pH change, and salting out. As an example, a process including a precipitation process and a color development process will be described. The α-furyldioxime method for measuring nickel concentration will be described. A fixed amount of α-furyldioxime is added to the sample liquid to add it to the sample liquid. To form a complex with nickel ions contained in This orange complex forms a precipitate, and when it is passed through the filtration membrane 20, it is effectively adsorbed on the filtration membrane 20 (Chem. Lett., 37, 792, 2008).

  Any one or two or more of the hydrophobic treatment, precipitation treatment, and color development treatment of the target substance may be used, and the treatment can be selected according to the characteristics of the target substance and the filtration membrane.

  Although the target substance is not particularly limited, examples include substances used for water quality analysis and water inspection in environmental water, tap water, sewage, drainage, etc., and substances used as indicators for water management. For example, phosphoric acid, silicic acid, formaldehyde, Nickel, chlorophyll a, iron, manganese, copper, chromium, aluminum, lead, ammonium, nitrous acid, nitric acid, residual chlorine, fluorine, free cyanide, sulfuric acid, sulfide, hydrazine, phenol, silver, gold, boron, calcium, Examples include chloride, chlorine dioxide, hydrogen peroxide, magnesium, ozone, palladium, sulfurous acid, zinc, barium, and potassium.

<Simple measurement system for target substance using simple analyzer>
Next, a system that simply measures the concentration of the target substance 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 includes a visualization unit that adsorbs or collects a target substance or a product derived from a target substance contained in a sample solution to the filtration membrane 20 to visualize the presence of the target substance on the filtration membrane 20, and the visualization unit. An identification means for identifying the color of the visualized target substance or the product derived from the target substance is provided.

  The visualizing means includes, for example, a beaker (container) 50 in which a sample solution to which a target substance selected from a hydrophobic treatment, a precipitation treatment, or a color development treatment has been applied, and a sample solution that has passed through the filtration membrane 20 The collected syringe 30, the connection tube 40 that connects the beaker 50 and the syringe 30, and the simple analyzer 1 that is connected to the end of the connection tube 40 are provided. 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 guiding member 100 is fitted into the large-diameter hole portion 12b of the simple analyzer 1 as shown in the figure, and the tip portion of the guiding member 100 is opened to the sample solution.

  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, the visualization means may be configured such that a predetermined volume of the sample solution is put into a syringe, and the nozzle portion 32 of the syringe 30 and the large-diameter hole portion 12b of the simple analyzer 1 are connected using the guide member 100. The sample solution is pushed in by the syringe 30 and supplied to the simple analyzer 1 and supplied to the filtration membrane 20.

  On the other hand, the identification unit uses a density colorimetric member 90 for comparing the colors of the target substance or the product derived from the target substance visualized by the visualization unit. The density colorimetric member 90 includes a plurality of color display units 92 arranged in stages according to the concentration of the target substance or the product derived from the target substance, and a density display 94 corresponding to the color display unit 92. ing. 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 unit 92 is created by confirming color development using a sample solution having a known concentration in advance.

  The color display units 92 are arranged apart from each other, for example, according to the concentration of the target substance. More specifically, the concentration display 94 is arranged so that the concentration of the target substance increases in the left-right direction (X direction), that is, from the left side to the right side, and accordingly, the color of the color display unit 92 has a low concentration. The color is lighter in order from the light color shown to the dark color showing the high density.

  As the identification means, in addition to using the density colorimetric member 90, the concentration of the target substance can also be measured by checking the color (color intensity) of the filtration membrane 20 using a reflectometer or the like.

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

  The outline of the method for measuring the concentration of the target substance is to supply a sample solution that has been selected from the hydrophobic treatment, the precipitation process, or the color development process of the target substance on the filter membrane 20 of the simple analyzer 1. The target substance or the product derived from the target substance is adsorbed or collected on the filtration membrane 20. The density (strength) of coloring or coloring of the filtration membrane 20 is confirmed, and the concentration of the target substance is measured. Since there is a correlation between the concentration of the target substance and the color shading, the concentration of the target substance is visually compared with the color of the color display portion 92 of the density colorimetric member 90 prepared using a sample whose concentration is known in advance. It can be determined by doing.

First, the sample solution is appropriately subjected to hydrophobic treatment, precipitation treatment or color development treatment of the target substance. The sample liquid that has been subjected to the above treatment is placed in a container 50 such as a beaker, and the piston of the syringe 30 is pulled while the lower end of the guide member 100 is immersed (see FIG. 6). As a result, the sample liquid 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 the target substance or the product derived from the target substance contained in the constant volume of the sample liquid is adsorbed or collected on the filtration membrane 20.
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. 7, the simple analyzer 1 is removed from the guiding member 100 and the connection tube 40, and a spot formed on the surface of the filtration membrane 20 (adsorbed or collected target substance or generation derived from the target substance). The colored portion of the object) is compared with the color display portion 92 of the density colorimetric member 90. As a result of the comparison, the concentration display 94 corresponding to the closest one becomes the concentration of the target substance contained in the sample solution.
When the blank sample is uncolored, the presence or absence of the target substance in the sample liquid is compared by comparing the color development between the spot and the portion blocked by the guiding member 100 and not supplied with the sample liquid. Will be confirmed immediately.

  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. 8). Further, since the collar portion 16 is formed at a position substantially aligned with the position of the filtration membrane 20, when the collar portion 16 is positioned, the color display portion 92 on the density colorimetric member 90 and the filtration membrane 20 are positioned. The surface is aligned with the surface of the surface to some extent, and more accurate colorimetry is possible. In particular, since the surface of the filtration membrane 20 and the color display portion 92 are close to each other, 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, it is also possible to drop and insert the conical portion 13 of the filter unit 10 into the fitting hole 96 to perform colorimetry. In this case, the color of the filtration membrane 20 in the opening 17 and the color display portion 92 around the collar portion are displayed. And colorimetrically.

Since the total amount of the target substance adsorbed or collected per unit area of the filtration membrane 20 is proportional to the supply amount of the sample solution, the amount of the target substance that is adsorbed or collected increases as the supply amount of the sample solution increases. , Lower concentration can be measured.
The amount of the sample solution is preferably 0.5 ml to 200 ml from the viewpoint of the time required for the filtration treatment.

  Further, when a target substance is measured using a simple measurement system, interference may be caused by other metal ions that coexist in the sample solution. In such a case, in order to prevent this, interference can be eliminated by adding a masking reagent that forms a complex with the coexisting metal in the sample solution. For example, metal ions that can coexist include Na +, K +, Ca (II), Mg (II), Fe (II), Fe (III), Cu (II), Zn (II), and the like. 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.

  In addition, when there are suspended matters or suspended substances in the sample solution 70, they tend to adhere to the filtration membrane 20 and cause clogging or coloring unevenness. Therefore, the suspended matter or the like is removed beforehand with a mesh or filter. It is desirable.

  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. .

  In carrying out the present invention, 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 to 4 and made of polypropylene resin was used. The basic filter material was obtained by sintering polyethylene powder in a filter unit. As the membrane filter, a disk-shaped membrane filter made of cellulose mixed ester having a diameter of 7 mm, a pore diameter of 8 μm, and a thickness of 110 μm was used and placed on a basic filter material. 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.

1. Simple analysis of nickel <Coloration treatment and precipitation treatment of nickel>
3 mg of ammonium citrate was added to 1.5 ml of each sample solution containing 30 ppb and 100 ppb of nickel ions, and further adjusted to pH 4 to 6 with aqueous ammonia. Thereto was added 1.5 mg of gum arabic, 0.12 mg of 1,2-cyclohexanedione dioxime, and a 1,2-cyclohexanedione dioxime-nickel pink precipitate complex was formed.

<Simple analysis and colorimetric analysis of nickel>
The sample solution obtained in Example 2 was prepared in a beaker, and the sample solution was sucked into a syringe. The induction member was fitted into the large-diameter hole of the simple analyzer obtained in Example 1, and the induction member and the above syringe were connected. The syringe piston was pushed at a constant speed, and 1.5 ml of the sample solution was introduced into the simple analyzer. The filtration area of the filtration membrane was 0.07 cm ² (diameter 3 mm), and the filtration amount per unit area was 21 ml / cm ² . Further, the time taken for suction filtration of 1.5 ml was about 1 minute.
When the guide member was removed from the large-diameter hole portion and the filter membrane was viewed from the opening of the wide mouth, the portion to which the sample solution was supplied by the guide member was round and pink. (This coloring is shown in FIG. 9) When the large diameter portion of the simple analyzer is fitted in the fitting hole of the density colorimetric member prepared in advance, the color display portion and the color on the filter membrane are colorimetrically (colorimetric) 9 is shown in Fig. 9. The black circle portion indicates a fitting hole into which a simple analyzer is not fitted), and the nickel ion concentration in each of the sample solutions can be determined to be about 30 ppb and about 50 ppb.

2. Simple analysis of phosphoric acid <Coloring treatment and hydrophobic treatment of phosphoric acid>
According to the description of JIS K 0102 46.1.1, 46.1.2 (1998), 25 ml of each sample solution containing 5 ppb, 10 ppb, 20 ppb, and 50 ppb of phosphate ion is hexamolybdate hexaammonium tetrahydrate. , Sulfuric acid and L (+)-ascorbic acid were added to form blue molybdenum blue.

<Simple analysis of phosphoric acid>
5 ml of the sample solution obtained in Example 2 was transferred to a beaker, and 0.25 mg of benzyldimethyltetradecyl ammonium chloride dihydrate was added. The induction member was fitted into the large-diameter hole of the simple analyzer obtained in Example 1, and the induction member and the syringe were connected. The tip of the guide member was put into the sample solution of the beaker, the piston of the syringe was pulled up at a constant speed, and 5 ml of the sample solution was introduced into the simple analyzer. The filtration area of the filtration membrane was 0.07 cm ² (diameter 3 mm), and the filtration amount per unit area was 71 ml / cm ² .
When the guide member is removed from the large-diameter hole and the filter membrane is viewed from the opening of the wide mouth, the portion supplied with the sample solution by the guide member is colored round blue and clear blue color is recognized from the 5 ppb sample solution. (This coloring is shown in FIG. 10.) The blue coloring increased in a certain proportion as the phosphate ion concentration increased.

3. Simplified analysis of chlorophyll a In carrying out the present invention, the same filter unit and induction member as in Example 1 were used. The basic filter material was obtained by sintering polyethylene powder in a filter unit. As the membrane filter, a disk-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 was used.

<Simple analysis and colorimetric analysis of chlorophyll a>
About 20 ml of each sample solution containing about 2 ppb and about 5 ppb of phytoplankton at a chlorophyll a concentration was prepared.
The guide member was fitted into the large-diameter hole of the simple analyzer obtained in Example 6, and the conical part and the syringe were connected using a connection tube. The sample liquid was put into a beaker, the lower end of the guiding member was put into various sample liquids, the syringe piston was pulled up at a constant speed, and 10 ml was sucked. The filtration area of the filtration membrane was 0.07 cm ² (diameter 3 mm), and the filtration amount per unit area was 142 ml / cm ² . In addition, the time taken for 10 ml of suction filtration was 2 to 3 minutes.
When the guide member was removed from the large-diameter hole portion and the filtration membrane was viewed from the wide opening, the portion to which the sample solution was supplied by the guide member was colored round and green. (This coloring is shown in FIG. 11.) 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 filter membrane are colorimetrically (the colorimetric state is shown). It is shown in Fig. 11. Black circles indicate fitting holes into which a simple analyzer is not fitted), and can be determined to be about 2 ppb and about 5 ppb.

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 ... Filtration membrane 20a ... Basic filter material 20b ... Membrane filter 30 ... Syringe 32 ... Nozzle 40 ... Connection 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 part 100c ... Step surface 100e ... convex part 100d ... tip end face L1 ... full length W1 of filter unit 10 ... full width W2 of filter unit 1 ... width d1 of wide opening 17 ... inside guide member Small clearance between the peripheral portion and the large diameter portion 12b of the annular portion gamma ... filtration membrane 20 central beta ... sample liquid inside diameter alpha ... sample liquid parts 100a passes does not pass

Claims (9)

  It has a through-hole that allows the upstream opening to be wide and passes from the upstream opening to the downstream opening, and a filter membrane that adsorbs or collects the target substance provided in the middle of the through-hole. The filtration membrane is exposed so that it can be seen directly from the opening on the upstream side of the through-hole, and is fitted into the opening on the upstream side of the through-hole to block a part of the filtration membrane to allow the sample liquid to pass. A simple analyzer for measuring the concentration of a target substance, comprising a cylindrical guide member that is supplied to the exposed remainder of a filtration membrane.   The simple analyzer according to claim 1, wherein an inner peripheral end surface of the guide member in contact with the filtration membrane is formed in a protruding ring shape.   The simple analyzer according to claim 1, wherein the filtration membrane includes a membrane filter.   The simple analyzer according to claim 3, wherein the material of the membrane filter is cellulose mixed ester, cellulose acetate, polyurethane foam, polytetrafluoroethylene, polyethersulfone, polycarbonate, filter paper.   5. The sample solution according to claim 1, wherein at least one of a hydrophobic treatment, a precipitation treatment, and a color development treatment of a target substance is performed on the sample solution. Simple analyzer.   The target substances are phosphoric acid, silicic acid, formaldehyde, nickel, chlorophyll a, iron, manganese, copper, chromium, aluminum, lead, ammonium, nitrous acid, nitric acid, residual chlorine, fluorine, free cyanide, sulfide, hydrazine, It is a phenol, The simple analyzer as described in any one of Claims 1-5.   A method for measuring a concentration of a target substance in a sample solution based on a change in color and density of the filtration membrane, wherein the target substance is analyzed using the simple analyzer according to any one of claims 1 to 6. .   The color change and shading of the filtration membrane 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 A fitting hole for receiving the outer shape of the simple analyzer body provided substantially at the center, and a filter membrane directly received from the wide opening of the simple analyzer body received in the fitting hole and the surroundings 8. The method for analyzing a target substance according to claim 7, wherein the color display unit is directly colorimetrically adjacent to the color display unit.   9. The method for analyzing a target substance according to claim 8, wherein the color display portions are arranged in accordance with the concentration of the target substance.