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WO1994000595A1 - Analyse de phosphate - Google Patents

Analyse de phosphate Download PDF

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Publication number
WO1994000595A1
WO1994000595A1 PCT/US1993/006045 US9306045W WO9400595A1 WO 1994000595 A1 WO1994000595 A1 WO 1994000595A1 US 9306045 W US9306045 W US 9306045W WO 9400595 A1 WO9400595 A1 WO 9400595A1
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WO
WIPO (PCT)
Prior art keywords
orthophosphate
concentration
sample
aqueous sample
phosphatase
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US1993/006045
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English (en)
Inventor
L. Frederick Roensch
Stephen P. Hall
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Diversey Corp Canada
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Diversey Corp Canada
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Filing date
Publication date
Application filed by Diversey Corp Canada filed Critical Diversey Corp Canada
Priority to AU46496/93A priority Critical patent/AU4649693A/en
Publication of WO1994000595A1 publication Critical patent/WO1994000595A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/18—Water
    • G01N33/182—Specific anions in water
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12Q—MEASURING OR TESTING PROCESSES INVOLVING ENZYMES, NUCLEIC ACIDS OR MICROORGANISMS; COMPOSITIONS OR TEST PAPERS THEREFOR; PROCESSES OF PREPARING SUCH COMPOSITIONS; CONDITION-RESPONSIVE CONTROL IN MICROBIOLOGICAL OR ENZYMOLOGICAL PROCESSES
    • C12Q1/00—Measuring or testing processes involving enzymes, nucleic acids or microorganisms; Compositions therefor; Processes of preparing such compositions
    • C12Q1/34—Measuring or testing processes involving enzymes, nucleic acids or microorganisms; Compositions therefor; Processes of preparing such compositions involving hydrolase
    • C12Q1/42—Measuring or testing processes involving enzymes, nucleic acids or microorganisms; Compositions therefor; Processes of preparing such compositions involving hydrolase involving phosphatase
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12Q—MEASURING OR TESTING PROCESSES INVOLVING ENZYMES, NUCLEIC ACIDS OR MICROORGANISMS; COMPOSITIONS OR TEST PAPERS THEREFOR; PROCESSES OF PREPARING SUCH COMPOSITIONS; CONDITION-RESPONSIVE CONTROL IN MICROBIOLOGICAL OR ENZYMOLOGICAL PROCESSES
    • C12Q2334/00—O-linked chromogens for determinations of hydrolase enzymes, e.g. glycosidases, phosphatases, esterases

Definitions

  • This invention relates generally to chemical analysis and more particularly to a quick, non-boiling method to determine polyphosphate or phosphonate concentration in an aqueous sample.
  • polyphosphates are tetra-potassium pyrophosphate (K 4 P 2 0 7 ) , sodium tripolyphosphate (Na 5 P 3 Oj 0 ) , sodium hexametaphosphate, and other salts thereof.
  • pyrophosphate, tripolyphosphate, andhexametaphosphate are the most common polyphosphates used in water treatment systems.
  • polyphosphates include glassy phosphate (NaP0 3 ) 2 ⁇ , (NaP0 3 ) , (NaP0 3 ) 9 , (NaP0 3 ) 5 , trimetaphosphate (NaP0 3 ) 3 , sodium pyrophosphate (Na 2 H 2 P 2 0 7 ) , and another tripolyphosphate (Na 3 H 2 P 3 O, 0 ) .
  • These polyphosphates have many uses in water treatment systems as discussed below. The primary use of polyphosphate in industrial water treatment is for scale inhibition, corrosion inhibition and iron/manganese stabilization at 3 - 6 pp as P0 4 . At higher levels polyphosphates are good detergents and suspension agents.
  • polyphosphates are also used in open recirculating and in once-through water systems for corrosion inhibition or scale control in industrial and potable water systems.
  • Polyphosphates are also used in open recirculating and once-through cooling water systems.
  • the most common and largest dollar value industrial once-through cooling and process applications are in the paper and steel industries where corrosion control and iron stabilization are needed.
  • polyphosphates hydrolyze to form orthophosphate.
  • some hydrolysis (reversion) of polyphosphate to orthophosphate will take place, depending on the presence of bacteria, pH, bulk water temperature, and the skin temperature of the heat transfer surfaces.
  • Phosphonates are organic phosphorus compounds which have a carbon to phosphorus bond which gives them greater stability against oxidation.
  • phosphonates in the water treatment industry include AMP (amino methylene phosphonic acid or nitrilo tris (methylene phosphonic acid) ; HEDP (hydroxyethylidene diphosphonic acid) ; PBTC (phosphonobutane tricarboxylic acid) ; HPA (hydroxyphosphonoacetic acid) ; and HDTMP (hexamethylene diamine[tetra] methylene phosphonic acid) .
  • AMP amino methylene phosphonic acid or nitrilo tris
  • HEDP hydroxyethylidene diphosphonic acid
  • PBTC phosphonobutane tricarboxylic acid
  • HPA hydroxyphosphonoacetic acid
  • HDTMP hexamethylene diamine[tetra] methylene phosphonic acid
  • phosphonates tend to be resistant to microbiological oxidation — a constant concern in open recirculating systems. Since their introduction to water treatment some 20 years ago, the major difficulty in their application has been product control and water analysis. Although these phosphonates are relatively stable to hydrolysis, they can be converted into orthophosphate in the presence of oxidizing agents, such as ozone, chlorine or bromine. It is generally preferable to maintain polyphosphates and phosphonates in their form as polyphosphates and phosphonates in water treatment systems rather than have them break down or revert into orthophosphate. Orthophosphate is effective in certain respects but tends to be more likely to form calcium phosphate scale.
  • a treatment program may, for example, comprise adding or maintaining preselected levels of orthophosphate and/or pyrophosphate and/or tripolyphosphate and/or hexametaphosphate and/or phosphonates.
  • polyphosphates particularly pyrophosphate
  • overfeed is expensive and can cause scaling and underfeed can cause production problems and equipment degradation or eventual loss due to increased corrosion rates.
  • phosphonates overfeed can cause hard, tightly adherent calcium phosphonate to form; underfeed can result in calcium carbonate scale formation. Both these conditions can impact production, heat exchange efficiency and ultimately, in industrial situations, plant profitability.
  • extra phosphonate is added solely to allow for easier testing of the phosphonate concentration, an expensive and unadvisable technique.
  • the polyphosphate is converted into orthophosphate, the concentration of all orthophosphate in the sample (both that present originally and that produced by conversion of polyphosphate into orthophosphate) is measured using the procedure described above, the initial reading or measurement for orthophosphate is subtracted from the second to obtain the difference, then that difference in orthophosphate readings is correlated with the concentration of polyphosphate present.
  • the polyphosphate is converted into orthophosphate by boiling with, for example, sulfuric acid for 30 minutes.
  • the microwave procedure will not work on inorganic polyphosphates in the absence of acid.
  • polyphosphate and phosphonate water treatment programs daily or other regular testing is desirable to maintain the phosphate concentration within predetermined levels.
  • Polyphosphate determination requires time-consuming boiling with acid.
  • phosphonates chromate or molybdate is sometimes added to permit easier analysis and monitoring, but these present cost and environmental concerns; the thorium nitrate test is partially successful but is subject to severe interferences such as ortho P0 4 - and thorium is radioactive and is an environmental and handling concern.
  • the thorium nitrate test forms a complex without breaking the carbon-phosphorus bond.
  • the microwave and ultraviolet methods require expensive equipment, require an electrical power supply, are not readily portable, and may present environmental and handling concerns.
  • the present invention which utilizes an enzymatic method for polyphosphate and phosphonate determination.
  • the enzymatic method does not use acid, does not require boiling, requires equipment which is much less expensive and much easier to handle than the boiling digestion, microwave, or ultraviolet procedures. There is much less, if any, environmental concern using the enzymatic method. Also, the enzymatic procedure is much faster compared to the boiling acid digestion method.
  • the advantages of the enzymatic procedure are used to provide a self-contained test kit which is portable and enables repetitive field tests, for example, up to fifty on-site tests at plants or facilities having water treatment systems. It is believed that enzymes such as those disclosed herein have been used for many years in connection with enzyme kinetic studies.
  • orthophosphate precursor is a compound from which orthophosphate can be obtained by hydrolysis or oxidation, such as by hydrolyzing pyrophosphate or tripolyphosphate or other polyphosphates, or oxidizing phosphonates, to orthophosphate, or mixtures of such compounds.
  • the method includes treating the aqueous sample by contacting it with an effective amount of phosphatase to cause said orthophosphate precursor to yield orthophosphate in the treated aqueous sample, measuring the concentration of orthophosphate present in the treated aqueous sample, and utilizing the measurement obtained in the measuring step in determining the concentration of orthophosphate precursor present in the aqueous sample.
  • the aqueous sample will contain orthophosphate, and the concentration of orthophosphate in the aqueous sample is determined and accounted for in determining the concentration of orthophosphate precursor present in the aqueous sample.
  • a portable test kit for performing phosphate analysis in aqueous samples is also disclosed.
  • the test kit includes a container of phosphatase and means for measuring the concentration of orthophosphate present in an aqueous sample.
  • the means can include a color comparator.
  • Other means include a portable spectrophotometer, and a filter photometer.
  • FIG. 1 shows a perspective view of a portable test kit according to the present invention.
  • FIG. 2 shows a perspective view of means for measuring the concentration of orthophosphate in an aqueous sample.
  • the inventors have found that enzymes can be used to convert polyphosphates and phosphonates to orthophosphate in connection with the determination of polyphosphate and phosphonate concentrations in water samples.
  • the procedure for determining polyphosphate and phosphonate concentrations in water samples is basically the same as that utilized in the prior art (see, for example, the references cited above) , except that enzymatic means are substituted for boiling with acid, UV light, and microwaves, for converting polyphosphates and phosphonates to orthophosphate in the test protocol.
  • Preferred embodiments of the invention are disclosed in the following Examples. If and when required, the samples were appropriately diluted to bring them within the range of the instruments used.
  • the enzymatic method of the present invention is particularly effective for determining polyphosphate, particularly pyrophosphate, concentrations in aqueous samples in the range of zero to fifty mg/1 as P0 4 , subject to the limitations of the colorimetric quantitation method utilized.
  • EXAMPLE 1 An aqueous sample from a customer was pbtained. The only phosphorus compounds the customer used were pyrophosphates (principally tetrapotassiumpyrophosphate) thus thephosphorus compounds the sample was believed to contain were only or principally orthophosphate and pyrophosphate, although other polyphosphates may have been present.
  • pyrophosphates principally tetrapotassiumpyrophosphate
  • the concentration of orthophosphate was performed to determine the concentration of orthophosphate. Briefly, one PhosVer 3 Phosphate Reagent powder pillow from Hach Company, P.O. Box 389, Loveland, CO 80539, sized for a 5 ml. sample, was mixed with a 5 ml.
  • the Hach PhosVer 3 Phosphate Reagent powder pillow contains less than 85% potassium pyrosulfate [7790-62-7]; less than 25% L- ascorbic acid [50-81-7]; less than 5% sodium molybdate [7631- 95-0]; and less than 1% each of other components.
  • This blue sample tube, along with a blank (tube with sample water, but without the powder pillow added) were inserted in a color comparator, known in the art and available from Hach Company. The disk was rotated to obtain a color match. The reading on the scale indicated a concentration of orthophosphate of 17 mg/1 (as P0 4 ) .
  • Example 1 This would be the orthophosphate present originally plus the orthophosphate produced when the enzyme hydrolyzed the polyphosphate to orthophosphate.
  • 17 By subtracting 17 from 140, it was determined that there were 123 mg/1 (as P0 4 ) of polyphosphate present in the sample.
  • the procedure of Example 1 described above was carried out at room temperature and without boiling; no heating was required or utilized and no filtration after addition of the enzyme was necessary or utilized.
  • the sample of Example 1 was also tested using the prior art technique of boiling with acid (basically as outlined in Standard Methods f cited above) to convert or hydrolyze the polyphosphate to orthophosphate. Sulfuric acid was used with persulfate and the sample was boiled for 30 minutes under pressure from 98 to 137 kPa.
  • a colorimetric method utilizing a Hach PhosVer 3 powder pillow and a DR-2000 spectrophotometer was used to determine phosphate concentration. This method determined orthophosphate concentration of 15 mg/1 (as P0 4 ) ; orthophosphate plus polyphosphate concentration of 137 mg/1 (as P0 4 ) ; and, by subtraction, polyphosphate concentration of 122 mg/1 (as P0 4 ) . Comparing the results using enzyme hydrolysis with prior art acid boiling hydrolysis, it can be seen that the enzyme method of the present invention gave almost identical results.
  • Example 2 The procedure utilized in Example 1 was used on a second sample from a customer where the only phosphorus compound the customer used was pyrophosphate. The results were as follows and are expressed in terms of mg/1 as P0 4 . Boiling with Acid Method Enzyme Hydrolysis Method orthophosphate 11 13 orthophosphate plus polyphosphate 16 17 polyphosphate 5 4
  • a sample containing tetrapotassium pyrophosphate was prepared. No breakdown of pyrophosphate to orthophosphate was detected, prior to hydrolysis. Analysis utilizing the boiling with acid technique for 40 minutes without pressure showed a concentration of pyrophosphate of 4.0 mg/1 (as P0 4 ) . Analysis utilizing the method and enzyme of Example 1 was conducted, showing a concentration of pyrophosphate of 4.6 mg/1 (as P0 4 ) . Analysis utilizing the method of Example 1 was also conducted, except that the enzyme used was Product 1-4503 and 10 units were used. The result showed a concentration of pyrophosphate of 4.9 mg/1 (as P0 4 ) . These results are close enough for commercial purposes, as described in Example 2.
  • EXAMPLE 4 A test was run to determine if the enzymatic hydrolysis method would work on sodium tripolyphosphate.
  • a sample of sodium tripolyphosphate was prepared. Analysis by means of the boiling with acid technique (as described above) was conducted, and showed a concentration of tripolyphosphate of 3.4 mg/1 (as P0 4 ) .
  • the sample was also checked utilizing the procedure and enzyme utilized in Example 1, except that the 5 units of sweet potato phosphatase was permitted to react with the sample for one minute. The result showed a concentration of tripolyphosphate of 3.0 mg/1 (as P0 4 ) . Additional testing showed that approximately 1 minute was required to obtain adequate recovery, and that additional time delay did not increase the yield. The difference between 3.0 and 3.4 mg/1 is not deemed significant, particularly since the margin of error on the hand-held comparator is at least 10%.
  • the sample was also checked utilizing the procedure and enzyme utilized in Example 1, except that the 5 units of sweet potato phosphatase was permitted to react with the sample for different time periods. A two minute time delay or waiting period resulted in a reading for the concentration of hexametaphosphate of 1.5 mg/1 (as P0 4 ) .
  • the sweet potato phosphatase (P-1435) showed no activity towards AMP; however, an indeterminate amount (more than 5 units) of Sigma Chemical Co.
  • Product P-3627 acid phosphatase, Type I From Wheat germ (contains lipase) was added to AMP. The large amount of enzyme turned the sample yellow. The sample was then allowed to sit at ambient temperature for 15 minutes.
  • EXAMPLE 7 A test was run utilizing an alkaline or base phosphatase, specifically Sigma Product No. P-5521; (EC 3.1.3.1) ; Type VII- S: From Bovine Intestinal Mucosa; CAS [9001-78-9] .
  • a sample containing tetrapotassium pyrophosphate was prepared.
  • Analysis utilizing the boiling with acid technique showed a concentration of pyrophosphate of 3.1 mg/1 (as P0 4 ) .
  • Analysis utilizing the method of Example 1 was also conducted, except that the enzyme used was Product P-5521, an indeterminate amount of that enzyme was used, and it was permitted to react for 5 minutes. The result showed a concentration of pyrophosphate of 3.4 mg/1 (as P0 4 ) .
  • a sample of sweet potato phosphatase (Product P-1435) was allowed to sit at room temperature for about 5 months. It was then tested and found to retain its activity. Thus the enzyme is believed to be sufficiently stable for test kit purposes. Routine test procedures may be used to identify other phosphatases which would work effectively in the practice of the present invention. For example, known phosphatases can be tested to identify those effective at hydrolyzing, oxidizing, or otherwise breaking down preselected polyphosphates or phosphonates to yield orthophosphate. Also, well-known testing procedures can be utilized to identify and isolate additional phosphatases which are effective at breaking down particular or preselected polyphosphates and phosphonates to yield orthophosphate.
  • a nutrient medium can be prepared in which the only orthophosphate source is a particular polyphosphate or phosphonate, for example, PBTC. Then a wide spectrum of bacteria, etc. can be placed in the medium to select out those which can survive and grow in the medium. A bacterium which is thus selected can then be grown in quantity and processed to extract and isolate the phosphatase responsible for breaking down the polyphosphate or phosphonate in question (here, PBTC) to yield orthophosphate.
  • No buffers (other than what may have been present in the enzyme suspension) were used or added in any Examples; it was not necessary to adjust the pH in any Examples. In some cases it may be necessary to use or add buffers or to adjust the pH.
  • an enzyme for example, an alkaline phosphatase
  • an enzyme for example, an alkaline phosphatase
  • concentrations of enzyme can be used for shorter periods, and lesser concentrations can be used for longer periods, so long as greater concentrations do not constitute an interference necessitating filtration or impart color which would interfere with colorimetric quantitation or make it more difficult.
  • Lesser concentrations are preferred, principally since less color is imparted. It is believed that any colorimetric quantitation method as known in the art can be used with the disclosed enzyme procedure. Several of these colorimetric methods are described in Standard Methods, cited above, and are incorporated herein by reference.
  • vanadomolybdic acid method which is most useful for routine analyses in the range of 3 to 60 mg/1 as P0 4
  • the stannous chloride method which is more suited for the range of 0.03 to 15 mg/1 as P0 4
  • the ascorbic acid method which is more suited for the range of 0.03 to 50, and more preferably, 0.03 to 15, mg/1 as P0 4 .
  • concentrations in excess of 50, eg, 60 - 70, mg/1 as P0 4 the ascorbic acid colorimetric method becomes subject to inaccuracies due to deviations from Beer's Law.
  • Other non- colorimetric methods can also be used to determine orthophosphate concentration, including the inductively- coupled plasma method, nuclear magnetic resonance, and gravimetric methods.
  • FIG. 1 shows a preferred portable test kit 10 according to the present invention, the test kit being easily portable in one hand.
  • the test kit has a carrying case 12 within which is contained an eye dropper 14, two test tubes 16 with stoppers 18, a bottle 22 containing enzyme such as phosphatase, which can, for example, be powdered or a liquid suspension, a bottle 24 containing a reagent composition such as Hach PhosVer 3 powder pillows or other reagents for colorimetric quantitation, and a color comparator 20.
  • the eye dropper can be used to help fill the test tubes with samples, water, and/or enzyme.
  • the sample is measured for orthophosphate concentration to establish a baseline, as described above.
  • the enzyme and powder pillows are added to the contents of the test tubes and mixed sequentially, and the samples are read in the color comparator, as shown in FIG. 2.
  • FIG. 2 The enzyme and powder pillows are added to the contents of the test tubes and mixed sequentially, and the samples are read in the color comparator, as shown in FIG. 2.
  • FIG. 2 shows a color wheel 28 in a case 29 of the color comparator 20.
  • the blank test tube 16A and the sample test tube 16B are placed in the comparator and viewed in strong light through the openings 30, 32.
  • the color wheel is turned until a color match is achieved, at which point a reading on the color wheel is taken through the opening 26, which correlates the strength of the blue color to the concentration of orthophosphate in the sample.
  • the enzymatic procedure of the present invention can also be utilized (a) in quality control laboratories to determine polyphosphate and phosphonate concentrations in production samples from such products as phosphate concentrates, phosphate additives, etc., and (b) to test for phosphate and phosphonate concentrations in water samples where phosphorus compounds are added to water systems to test for such process variables as volume of vessel or system, bleed rate, and to act as a tracer so the concentration of another additive, such as a polymer, which is hard to test directly, can be monitored.
  • concentrations of phosphorus compounds are initially measured to establish a baseline.
  • the volume of the vessel or system can be calculated. For example, if the baseline shows no phosphorus compounds, and 1.4 kg. of tetrasodium pyrophosphate (71.4% P0 4 ) is added to the system, and after it is allowed to mix, a sample is drawn from the system and found, via the enzymatic procedure, to contain 1 mg/1 P0 4 , the volume of the system is 1 million liters.
  • the bleed rate of a system (the rate at which water leaks out of the system) can be calculated using a similar methodology.
  • a polymer such as polyacrylate
  • a phosphorus compound such as pyrophosphate
  • the concentration of the polymer can then be determined by measuring the concentration of the pyrophosphate.
  • the pyrophosphate acts as a tracer to a compound to be traced.
  • Phosphorus compounds are particularly useful for all the above procedures since they are nontoxic when added properly, relatively inexpensive, easy to use, and frequently must be added anyway for corrosion and scale inhibition. Previously, chromium, lithium, molybdate, organic dyes, etc.

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Abstract

Procédé et trousse portable permettant d'effectuer des tests et de déterminer la concentration de polyphosphate ou de phosphonate dans un échantillon aqueux. Le polyphosphate ou le phosphonate est traité avec une enzyme, en particulier une phosphatase, pour produire l'orthophosphate. La concentration d'orthophosphate est déterminée en utilisant des procédés connus. La concentration de polyphosphate ou de phosphonate dans un échantillon aqueux peut alors être déterminée. L'invention est particulièrement utile dans l'industrie de traitement des eaux et dans des systèmes de traitement des eaux.
PCT/US1993/006045 1992-06-25 1993-06-24 Analyse de phosphate Ceased WO1994000595A1 (fr)

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Application Number Priority Date Filing Date Title
AU46496/93A AU4649693A (en) 1992-06-25 1993-06-24 Phosphate analysis

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US90388792A 1992-06-25 1992-06-25
US07/903,887 1992-06-25

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009132727A1 (fr) * 2008-04-29 2009-11-05 Adiquimica S.A. Procédé d’analyse quantitative en ligne de la teneur en composés antitartre contenant du phosphore dans l’eau de mer d’une usine de désalinisation par osmose inversée et procédé et équipement de régulation correspondants
NL2003505C2 (en) * 2009-09-17 2011-03-21 Univ Delft Tech Method and filter system for treatment of wastewater that contains phosphorus and nitrogen.
KR101340767B1 (ko) * 2012-04-12 2013-12-11 서울시립대학교 산학협력단 저농도의 인산염 인 농도 검출방법
KR101340695B1 (ko) * 2012-04-12 2013-12-12 서울시립대학교 산학협력단 저농도의 인산염 인 농도 검출시약 및 검출키트
KR101350081B1 (ko) * 2012-04-12 2014-01-15 서울시립대학교 산학협력단 고농도의 인산염 인 농도 검출방법
US20240102984A1 (en) * 2022-09-23 2024-03-28 Hach Company Powder composition, kit, and method for determining orthophosphate concentration

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US3716456A (en) * 1971-05-14 1973-02-13 Corning Glass Works Anion monitoring system
US4062652A (en) * 1974-02-07 1977-12-13 Rolfo Fontana Gudrun B Reagent unit intended for microanalyses of standard type and device and method for its production
US4647672A (en) * 1985-06-25 1987-03-03 Kansas State University Research Foundation Ascorbate 2-polyphosphate esters and method of making same
US4889797A (en) * 1986-05-28 1989-12-26 Fuji Photo Film Co., Ltd. Dry analytical element having a spread control area for assaying enzyme activity
US5051401A (en) * 1989-04-07 1991-09-24 University Of South Alabama Inhibition of mineral deposition by phosphorylated and related polyanionic peptides

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3666399A (en) * 1970-07-31 1972-05-30 Fmc Corp Enzymatic peroxydiphosphate hydrolysis
US3716456A (en) * 1971-05-14 1973-02-13 Corning Glass Works Anion monitoring system
US4062652A (en) * 1974-02-07 1977-12-13 Rolfo Fontana Gudrun B Reagent unit intended for microanalyses of standard type and device and method for its production
US4647672A (en) * 1985-06-25 1987-03-03 Kansas State University Research Foundation Ascorbate 2-polyphosphate esters and method of making same
US4889797A (en) * 1986-05-28 1989-12-26 Fuji Photo Film Co., Ltd. Dry analytical element having a spread control area for assaying enzyme activity
US5051401A (en) * 1989-04-07 1991-09-24 University Of South Alabama Inhibition of mineral deposition by phosphorylated and related polyanionic peptides

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Title
Abstract No. 1049545, issued 23 October 1983, Moscow Lomonosov Univ, "Determination of Activity in Inorganic Pyro-Phosphatase- by Measuring Change in Potential of Copper Selective Electrode in Pyro-Phosphatase Reaction in Presence of Magnesium and Copper Ions". *
BARMAN, "Enzyme Handbook", Volume 1, published 1968, by SPRINGER-VERLAG (NEW YORK), pages V-IX, 1-15, and 521-524. *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009132727A1 (fr) * 2008-04-29 2009-11-05 Adiquimica S.A. Procédé d’analyse quantitative en ligne de la teneur en composés antitartre contenant du phosphore dans l’eau de mer d’une usine de désalinisation par osmose inversée et procédé et équipement de régulation correspondants
NL2003505C2 (en) * 2009-09-17 2011-03-21 Univ Delft Tech Method and filter system for treatment of wastewater that contains phosphorus and nitrogen.
KR101340767B1 (ko) * 2012-04-12 2013-12-11 서울시립대학교 산학협력단 저농도의 인산염 인 농도 검출방법
KR101340695B1 (ko) * 2012-04-12 2013-12-12 서울시립대학교 산학협력단 저농도의 인산염 인 농도 검출시약 및 검출키트
KR101350081B1 (ko) * 2012-04-12 2014-01-15 서울시립대학교 산학협력단 고농도의 인산염 인 농도 검출방법
US20240102984A1 (en) * 2022-09-23 2024-03-28 Hach Company Powder composition, kit, and method for determining orthophosphate concentration

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