US20100330694A1 - bromate ion measurement method and apparatus - Google Patents

bromate ion measurement method and apparatus Download PDF

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Publication number
US20100330694A1
US20100330694A1 US12/677,146 US67714609A US2010330694A1 US 20100330694 A1 US20100330694 A1 US 20100330694A1 US 67714609 A US67714609 A US 67714609A US 2010330694 A1 US2010330694 A1 US 2010330694A1
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Prior art keywords
fluorescence intensity
sample
bromate
fluorescent substance
ions
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US12/677,146
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Shukuro Igarashi
Jun Kato
Yoshiharu Tanaka
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Ibaraki University NUC
Metawater Co Ltd
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Assigned to IBARAKI UNIVERSITY, METAWATER CO., LTD. reassignment IBARAKI UNIVERSITY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: TANAKA, YOSHIHARU, IGARASHI, SHUKURO, KATO, JUN
Publication of US20100330694A1 publication Critical patent/US20100330694A1/en
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
    • G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N2021/6432—Quenching
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N2021/7769—Measurement method of reaction-produced change in sensor
    • G01N2021/7786—Fluorescence
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/15—Inorganic acid or base [e.g., hcl, sulfuric acid, etc. ]
    • Y10T436/153333—Halogen containing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/19—Halogen containing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/19—Halogen containing
    • Y10T436/193333—In aqueous solution

Definitions

  • the present invention relates to a method and to an apparatus for measurement of bromate ions in water. More specifically, the present invention relates to a method and to an apparatus that can simply, quickly, and with high accuracy, measure minute amounts of bromate ions generated by ozone treatment in high standards purification of water.
  • Water sources such as river water, contain minute amounts of bromine ions, and when ozone treatment (water purification treatment to high standards) is performed, the bromate ions in the water react with ozone, and a reaction such as shown in FIG. 1 occurs, thereby generating bromate ions.
  • ozone treatment water purification treatment to high standards
  • An analytical method generally used for analyzing bromate ions is the ion chromatograph post-column absorption intensity method.
  • This analytical method is one in which bromate ions in a water sample are separated using a cation exchange column, sulfuric acid and an admixture of sodium nitrate and potassium bromide being added to the solution to convert the bromate ions into tribromine ions, and the tribromine ion method being used to measure the ultraviolet region absorption so as to perform quantitative determination.
  • the post column derivitization method by means of the tribromine ion method is used to measure the level of absorption of the 268 nm ultraviolet line.
  • ion chromatograph post-column a two-stage reaction occurs: in the first reaction stage, bromate is converted by a potassium bromide/sulfuric acid solution to tribromine ions, and then in the second reaction, a sodium bromide solution is used to establish the linearity of the calibration line in the low-concentration region.
  • the present invention has as an object to provide a method and an apparatus for bromate ion measurement that can more quickly and simply perform and obtain higher-sensitivity measurement results than with conventional bromate ion measurement methods.
  • the method for measuring bromate ions includes a step of mixing a fluorescent substance that is quenched by coexistence with bromate ions under acidic conditions with a sample; a step of measuring the florescence intensity after the quenching of the fluorescent substance; a step of subtracting the measured fluorescence intensity from the fluorescence intensity of a standard sample that does not contain bromate ions to calculate the fluorescence intensity difference; a step of using a pre-determined calibration line between the fluorescence intensity difference and the bromate ion concentration to calculate the bromate ion concentration from the calculated fluorescence intensity difference; and a step of determining the bromate ion concentration in the sample by measuring the fluorescence intensity after quenching of the fluorescent substance.
  • the method for measuring the bromate ions according to the present invention may have a step of adding a chelating agent to the sample before the step of mixing the fluorescent substance and the sample.
  • the fluorescent substance used in the method of measuring bromate ions according to the present invention is most preferably trifluoroperazine, and the chelating agent used in the method for measuring bromate ions according to the present invention may be ethylene diamine tetraacetate.
  • another embodiment of the present invention is an apparatus for measuring the bromate ions included in a sample, comprising means for mixing a fluorescent substance that is quenched by coexistence with bromate ions under acidic conditions with the sample; means for measuring the fluorescence intensity after the quenching of the fluorescent substance; means for subtracting the measured fluorescence intensity from the fluorescence intensity of a standard sample that does not contain bromate ions to calculate the fluorescence intensity difference; and means for using a pre-determined calibration line between the fluorescence intensity difference and the bromate ion concentration to calculate the bromate ion concentration from the calculated fluorescence intensity.
  • the apparatus for measuring bromate ions according to the present invention may be constituted so as to measure with the fluorescence intensity measuring means the admixture of the sample and the fluorescent substance that is temporarily held in the mixing means.
  • the apparatus for measuring bromate ions according to the present invention may be constituted so as to measure with the fluorescence intensity measuring means the admixture of the sample and the fluorescent substance that flows continuously in the mixing means.
  • the method for measuring bromate ions according to the present invention can simply and quickly provide high-sensitivity bromate ion concentration measurement results. Also, by adding a chelating agent as a metallic ion masking agent, it is possible to obtain high-sensitivity bromate ion concentration measurement results, regardless of a metallic ion included in the sample.
  • FIG. 1 Drawing showing the mechanism of generation of bromate ions by ozonification.
  • FIG. 2 Graph showing the fluorescent spectrum for different bromate ion concentrations.
  • FIG. 3 Graph showing the relationship between the added trifluoroperazine concentration and the fluorescence intensity difference.
  • FIG. 4 Graph showing the results of measuring the bromate ion concentration when hydrochloric acid is used as the acid solution.
  • FIG. 5 Graph showing the results of measuring the bromate ion concentration when nitric acid is used as the acid solution.
  • FIG. 6 Graph showing the results of measuring the bromate ion concentration when sulfuric acid is used as the acid solution.
  • FIG. 7 Graph showing the results of measuring the relationship between the hydrochloric acid concentration and the fluorescence intensity when hydrochloric acid is used as the acid solution.
  • FIG. 8 Graph showing the relationship between the reaction time and different bromate ion concentrations.
  • FIG. 9 Graph showing the relationship (calibration line) between the bromate ion concentration and the fluorescence intensity difference.
  • FIG. 10 Simplified schematic representation of an apparatus having a batch-type configuration for the purpose of performing measurement of bromate ions according to the present invention.
  • FIG. 11 Simplified schematic representation of an apparatus having a flow injection-type configuration for the purpose of performing measurement of bromate ions according to the present invention.
  • FIG. 12 Simplified schematic representation of means for measuring fluorescence intensity for the purpose of performing measurement of bromate ions according to the present invention.
  • FIG. 13 Simplified flowchart of an apparatus having a batch-type configuration for the purpose of measuring the bromate ions according to the present invention.
  • a sample 130 for which the bromate ion concentration is to be measured is prepared. It is preferable that a chelating agent 131 be added to the sample 130 for the purpose of masking coexisting metallic ions.
  • the sample is mixed with a fluorescent substance 132 that is extinguished by coexistence with bromate ions in the presence of acidity. After mixing, by making the pH of the sample acidic by the addition of an acid solution 133 , the fluorescent substance 132 is extinguished with dependency on the concentration of bromate ions included in the sample.
  • the bromate ion measurement method of the present invention makes use of the property of the fluorescent substance 132 that it is extinguished by the coexistence with bromate ions in the presence of acidity, and by measuring the fluorescence intensity after extinguishing using the fluorescence intensity measuring means, it is possible to determine the bromate ion concentration included in the sample from the priorly determined relationship between fluorescence intensity and bromate ions.
  • the present invention it is possible to measure the fluorescence intensity by aging 134 over approximately 2 minutes from acidifying the sample by the addition of an acid solution 133 , and it is possible to quickly perform the steps from taking the sample through the determination of the bromate ion concentration included in the sample. Therefore, according to the bromate ion concentration measurement method of the present invention, it is possible to quickly measure the bromate ion concentration in units of 0.001 mg/L, without the need for complex process steps or equipment.
  • the fluorescent substance 132 used in the present invention be a fluorescent substance having the property of being extinguished by coexistence with bromate ions in the presence of acidity, for example, phenothiazine derivatives such as phenothiazine, chlorpromazine, and methyl blue or the like.
  • phenothiazine derivatives such as phenothiazine, chlorpromazine, and methyl blue or the like.
  • trifluoroperazine (TFP) is the most preferable as the fluorescent substance used in the present invention.
  • Trifluoroperazine has phenochiadine in the basic molecular structure, and it has been reported that it is dimerization by oxidation (P. Hanson, R. O. C. Norman, J. Chem. Soc. Perhkin Trans. 2, 164-267 (1973)).
  • trifluoroperazine in trifluoroperazine as well, there is thought to be the same type of reaction mechanism by oxidation by bromate ions in accordance with the equations given below, and it is thought that the extinguishing phenomenon occurs in the fluorescence at a particular fluorescence wavelength and excitation wavelength, by trifluoroperazine causing a change in the structure.
  • the samples that can be measured by the present invention include sedimentation processed water and filtered water in the water purification process that contain minute amounts of bromate ions.
  • An acid solution 133 is used for the purpose of adjusting the sample to acidity in the present invention, and hydrochloric acid is the most preferable as the acid solution.
  • the chelating agent 131 used in the present invention be capable of masking metallic ions coexisting in the sample, and it is preferable that this be ethylene diamine tetraacetate (EDTA).
  • EDTA ethylene diamine tetraacetate
  • FIG. 10 shows a simplified schematic drawing of an apparatus having a batch-type configuration.
  • a batch-type measurement apparatus for bromate ions according to the present invention is formed by a liquid feed system 10 formed by sample supplying means 11 , pure water supplying means 12 , standard bromate ion sample supplying means 13 , chelating agent supplying means 14 , fluorescent substance supplying means 15 , acid solution supplying means 16 , a mixing cell 21 , a starter 22 , an effluent holding means 19 , a valve 17 , and a valve 18 , a constant temperature chamber 20 , a fluorescence intensity measurement means 23 , and a control section 30 that controls the fluorescence intensity measurement means 23 .
  • the pure water supplying means 12 may store pure water used as the standard sample (blank) that does not contain bromate ions for the purpose of calculating the calibration line, and it is possible to use it to supply a prescribed amount thereof to the mixing cell 21 or the reaction coil 24 as appropriate. Also, a prescribed amount of the pure water supplied by the pure water supplying means 12 may also be used for cleaning after sample measurement.
  • the standard bromate ion sample supplying means 13 can hold a standard sample that does not contain bromate ions for the purpose of calculating the calibration line, and can be used to supply a prescribed amount of the standard bromate ion sample to the mixing cell 21 or the coil 24 as appropriate.
  • the chelating agent supplying means 14 , the fluorescent substance supplying means 15 , and the acid solution supplying means 16 can respectively be used to hold chelating agent, a fluorescent substance, and an acid solution, and it is sufficient that a pump supply the chelating agent, the fluorescent substance, and the acid solution to the mixing cell 21 or the reaction coil 24 .
  • the fluorescent substance supplying means 15 desirably has a configuration that enables complete light blockage, for the purpose of preventing quenching of the fluorescent substance.
  • a mixing cell 21 that is usable in a batch-type configuration be capable of mixing the sample, and the chelating agent, the fluorescent substance, and the acid solution supplied by each of the above-noted supplying means, and it is preferable that it have a high permeability, and be very usable under acidic conditions. It is possible to use a quartz cell, for example, as the mixing cell 21 . Also, there is a stirrer 22 installed at the bottom of the mixing cell 21 , and the stirrer 2 can mix the sample and the like within the mixing cell 21 .
  • the stirrer be capable of stirring the sample or the like within the mixing cell 21 , and this can be, for example, a magnetic stirrer or an ultrasonic stirrer or the like, as known in the conventional art. It is preferable that the mixing cell 21 be provided with a rotor to enable stirring by means of the stirrer 22 .
  • a sample that is stirred and mixed with a chelating agent, a fluorescent substance, and an acid solution by the stirrer 22 is measured for fluorescence intensity of the fluorescent substance by the fluorescence intensity measurement means 23 .
  • the sample after fluorescence intensity measurement is fed as effluent to the effluent holding means 19 . It is sufficient that the effluent holding means 19 be capable of temporarily holding effluent from the mixing cell 21 after measurement which is to be disposed of.
  • the fluorescence intensity measurement means 23 be capable of measuring the intensity of fluorescence emitted by the fluorescent substance by the application of excitation light to the fluorescent substance in the sample.
  • the constant temperature chamber 20 can control the temperature of the mixing cell 21 , the stirrer 22 , the fluorescence intensity measurement means 23 , and the reaction coil 24 , and can control the temperature of the sample for which the fluorescence intensity is to be measured.
  • the range of temperature controlled by the constant temperature chamber 20 is preferably no greater than 25° C. and more preferably 5° C. to 15° C.
  • the control section 30 can oversee control of the opening and closing of valves that control the supply samples and the like from each supplying means, control of the stirring within the mixing cell 21 by the stirrer 22 , temperature control of the constant temperature chamber 20 , and control of the fluorescence intensity measurement means. Also, the control section 30 calculates the measured fluorescence intensity from the fluorescence intensity of the standard sample that does not include bromate ions, performs the step of calculating the fluorescence intensity difference, and uses the calibration line determined beforehand between the fluorescence intensity difference and the bromate ion concentration to perform the step of calculating the bromate ion concentration from the calculated fluorescence intensity difference.
  • the sample for which the bromate ion concentration is to be measured is first prepared in the sample supplying means 11 .
  • the valve 17 a and pump 18 a are controlled so as to supply the sample to the mixing cell 21 .
  • the chelating agent is supplied to the mixing cell 21 by the chelating agent supplying means 14 .
  • the fluorescent substance is supplied to the mixing cell 21 by the fluorescent substance supplying means 15 .
  • the acid solution is supplied to the mixing cell 21 by the acid solution supplying means 16 .
  • the stirrer 22 stirs the sample, the chelating agent, the fluorescent substance, and the acid solution.
  • the temperature within the mixing cell 21 is controlled.
  • the fluorescence intensity measurement means 23 measures the intensity of the fluorescence emitted from the fluorescent substance in the sample.
  • the fluorescence intensity difference is calculated by subtracting the measured fluorescence intensity from the fluorescence intensity of the standard sample that does not include bromate ions.
  • the bromate ion concentration is calculated from the fluorescence intensity difference.
  • the sample is sent as effluent to a means that receives the sample.
  • the supply of the sample and the chelating agent can be done by control of the valves 17 a - c and pumps 18 a - d by the controller section 30 .
  • the processing of the effluent from the mixing cell 21 can be controlled by the control section 30 controlling the valve 17 d and the pump 18 e.
  • FIG. 12 shows an aspect of a fluorescence intensity measurement means 23 of the present invention.
  • the fluorescence intensity measurement means 23 is formed by an excitation light source 120 , collimator lenses 121 a - c , slits 122 a - c , bandpass filters (BPFs) 123 a, b , a beam splitter 124 , photomultiplier tubes (PMTs) 125 a, b , and the mixing cell 21 .
  • BPFs bandpass filters
  • PMTs photomultiplier tubes
  • excitation light source 120 be capable of emitting a source of light to strike the fluorescent substance of the sample in the mixing cell 21 or a flow cell, and this can be a xenon lamp, a mercury xenon lamp, or a halogen lamp or the like.
  • the collimator lens 121 a can collimate the scattered light from the excitation light source 120 in the direction of the mixed sample.
  • the collimator lens 121 b can collimate the wavelength emitted from the fluorescent substance within the mixed sample in the direction of the PMT 123 b for measuring fluorescence.
  • the collimating lens 121 c can collimate a wavelength that is emitted from the fluorescent substance and passes through the BPM 123 b to the measurement position of the PMT 125 b for measuring the fluorescence.
  • Conventional known lenses can be used as such collimator lenses.
  • the slit 122 constricts the light collimated by the collimator lens from the excitation light source. As long as this configuration is adopted, it is possible to use a conventional known slit.
  • the bandpass filter (BPM) 123 a can block a particular wavelength, and send a particular wavelength to the mixed sample.
  • the BPM 123 b in the same manner, can block a particular wavelength and send a particular wavelength only to the PMT 125 b .
  • the beam splitter 124 be capable of splitting into two the incident light, and this can be a known conventional type.
  • the photomultiplier tube (PMT) 125 a can measure the temporal variations with regard to the amount of light from the excitation light source, and it is possible to use this measured value for correction at the time the fluorescence intensity is calculated. Also, the PMT 125 b measures the amount of light at the wavelength emitted from the fluorescent substance within the sample. It is possible to use a known conventional type of PMT.
  • scattered light emitted from the excitation light source 120 is collimated by the collimator lens 121 a , passes through the slit 122 a , and enters the BPM 123 a .
  • the BPM 123 a passes only the wavelength of 300 nm, and sends the wavelength of 300 nm to the beam splitter 124 .
  • the beam splitter 124 one of the two split wavelengths passes through the slit 122 b , and is sent to the PMT 125 a .
  • the PMT 125 a in order to perform correction at the time of measurement of the fluorescence intensity, the temporal variations in the amount of light from the excitation light source 120 are measured.
  • the other wavelength that passes through the beam splitter 124 enters the mixing cell 21 , and excites the fluorescent substance.
  • the wavelength emitted from the excited fluorescent substance is collimated by the collimator lens 121 b and enters the BPM 123 b .
  • the BPM 123 b blocks wavelengths other than 480 nm, and sends the 480-nm wavelength to the slit 122 c .
  • the wavelength that passes through the slit 122 c is once again collimated to the position of the PMT 125 b that measures the fluorescence intensity.
  • the PMT 125 b measures the fluorescence intensity of the wavelength emitted from the fluorescent substance.
  • FIG. 11 is a simplified schematic drawing of an apparatus having a flow injection configuration for the purpose performing measurement of bromate ions according to the present invention.
  • the flow injection type measurement apparatus for bromate ions according to the present invention is formed by sample supplying means 11 , the pure water supplying means 12 , the bromate ion standard sample supplying means 13 , the chelating agent supplying means 14 , the fluorescent substance supplying means 15 , the acid solution supplying means 16 , the pumps 18 a - d , the reaction coil 24 , the constant temperature chamber 20 , the fluorescent substance intensity measurement means 23 , and the effluent holding means 19 .
  • reaction coil 24 that can be used in the flow injection type configuration have a constitution that enables mixing while the sample, the chelating agent, the fluorescent substance, and the acid solution supplied by the supplying means are flowing continuously in the reaction coil 24 .
  • the length of the reaction coil 24 and the flow amount therein are preferably set appropriately such that the sample and the like are sufficiently mixed.
  • the sample that is mixed within the reaction coil 24 has its fluorescence intensity measured by the fluorescence intensity measurement means 23 .
  • the sample to be measured for bromate ion concentration is prepared in the sample supplying means 11 .
  • the pump 18 is controlled and the sample is supplied to the reaction coil 24 .
  • the respective valves (not shown in the drawing) are controlled to perform supply to the reaction coil 24 .
  • a chelating agent is supplied by the chelating agent supplying means 14 .
  • the fluorescent substance is supplied by the fluorescent substance supplying means 15 .
  • the acid solution is further supplied to within the reaction cell by the acid solution supplying means 16 .
  • the reaction cell 24 is constituted so as to sufficiently mix the sample, the chelating agent, the fluorescent substance, and the chelating agent flowing therewithin, and the reaction coil 24 is temperature controlled by the constant temperature chamber 20 .
  • the intensity of the fluorescence emitted by the fluorescent substance within the sample that is mixed in the reaction coil 24 is measured by the fluorescent substance intensity measurement means 23 , and the location measured by the fluorescence intensity measurement means 23 has a flow cell configuration so as to enable measurement of the sample flowing within the flow cell.
  • the sample is sent as effluent to the effluent holding means 19 .
  • the dependency of trifluoroperazine fluorescence intensity on the bromate ion concentration was measured under acidic conditions. Specifically, after sequentially adding and mixing a 3.2-ml bromate ion sample solution, 0.2 ml of TFP solution, and 0.6 ml of acid solution in a sample tube, the fluorescence was measured after 2 minutes (with an excitation wavelength of 300 nm, and a fluorescence wavelength of 485 nm) using a fluorescence spectrophotometer (product name: F4500, made by Hitachi).
  • FIG. 2 shows the fluorescence spectrum of trifluoroperazine with respect to samples with various bromate ion concentrations. From these results, it was seen that a quenching phenomenon occurred due to the bromate ion. Also, it was determined that, as the bromate ion concentration increased, the quenching of the fluorescence became greater.
  • reaction time was set to approximately 2 minutes. In the drawing, the reaction times are indicated with the addition of the acid solution taken as being 0 seconds.
  • a tolerable limit for Al +3 , Ca 2+ , K + , Na + , Ni 2+ , Mg 2+ , Cl ⁇ , NO 3 ⁇ , and SO 4 2 ⁇ was ⁇ 1000, and for Zn 2+ , IO 3 ⁇ , IO 4 ⁇ , and EDTA was ⁇ 100.
  • the tolerable limit was a low value of ⁇ 1 for Fe 2+ Fe 3+ , and Mn 2+ , by using EDTA as a masking agent, it was possible to allow the tolerable limit to be ⁇ 10 for Fe 2+ , Fe 3+ , and Mn 2+ .

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US20130337572A1 (en) * 2012-06-18 2013-12-19 Metawater Co., Ltd. Method and apparatus for measuring bromate ion
US9023654B2 (en) 2011-07-25 2015-05-05 Metawater Co., Ltd. Method and apparatus for measuring bromate ions
CN106018863A (zh) * 2016-07-29 2016-10-12 北京宝德仪器有限公司 利用标准加入法进行测量的测量装置以及测量流程
US9857304B2 (en) 2014-09-09 2018-01-02 Metawater Co., Ltd. Measuring method and measuring system of bromate ion concentration

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