WO2009049366A1 - Water analysis - Google Patents
Water analysis Download PDFInfo
- Publication number
- WO2009049366A1 WO2009049366A1 PCT/AU2008/001529 AU2008001529W WO2009049366A1 WO 2009049366 A1 WO2009049366 A1 WO 2009049366A1 AU 2008001529 W AU2008001529 W AU 2008001529W WO 2009049366 A1 WO2009049366 A1 WO 2009049366A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- chloride
- oxidation
- cod
- oxygen demand
- organic
- Prior art date
Links
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
- G01N33/1806—Water biological or chemical oxygen demand (BOD or COD)
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/305—Electrodes, e.g. test electrodes; Half-cells optically transparent or photoresponsive electrodes
Definitions
- This invention relates to a method for the determination of oxygen demand of water using photoelectrochemical cells.
- the invention relates to a photoelectrochemical method of determining chemical oxygen demand in water samples having high chloride content, such as sea water.
- BOD 5 biochemical oxygen demand
- COD chemical oxygen demand
- BOD 5 involves the use of heterotrophic microorganisms to oxidise organic material and thus estimate oxygen demand.
- COD uses strong chemical oxidising agents such as dichromate or permanganate to oxidise organic material.
- the BOD 5 analysis is carried out over five days and oxygen demand is determined by titration or with an oxygen probe. COD is determined by the measurement of dichromate or permanganate depletion by titration or spectrophotometry.
- seawater is typically used in cooling towers to cool the condenser and for a number of other applications.
- the monitoring of seawater is required to avoid potential environmental concerns related to its usage and discharge.
- the ability to measure COD in seawater is an enormous industry application that is yet to be catered for.
- Titanium(IV) oxide has been extensively used for the photooxidation of organic compounds.
- TiO 2 is non- photocorrosive, non-toxic, inexpensive, relatively easily synthesised in its highly active catalytic nanoparticulate form, and is highly efficient in photooxidative degradation of organic compounds.
- a problem encountered in conducting assays using this method is dealing with interference from competing oxidisable chemical species other than organic carbon. Filtration of samples reduces interference from many species but the presence of chloride still remains a significant interference that must be dealt with.
- Chloride is commonly oxidized by photocatalysis to chlorine according to the following equation:
- the produced chlorine can be readily converted into hypochlorite under UV illumination (Equation 2) and production of other possible products including CIO 2 " , CIO 3 ' and CIO 4 ' may also occur.
- Equation 2 UV illumination
- CIO 3 ' and CIO 4 ' may also occur.
- the photoxidation kinetics of Cl " has proven to be slow.
- the method involves the use of expensive and toxic chemicals and requiring separation.
- the system will need a sophisticated component to achieve in situ separation of precipitated AgCI or Hg 2 CI 2 , which, on one hand will significantly undermine the accuracy and reliability of the system, and on the other hand will increase both the capital and operational costs.
- Chloride is a problem for organic content measurement in aqueous samples as current methods of analysis can't easily distinguish between organic and chloride content and hence it creates an erroneous measurement.
- WO2007/016740 discloses an improvement in the photoelectrochemical method for detecting chemical oxygen, previously described in WO2004/088305, which deals with the interference by chloride.
- PCT/AU2007/000735 discloses a similar method for dealing with difficult to oxidise organic compounds.
- the analytical signal is generated in exactly the same way as for the photoelectrochemical method disclosed in WO2004/088305.
- the present invention provides a method of determining chemical oxygen demand in water samples containing chloride ions by a photoelectrochemical method in which the photo electrode is activated by light pulses and the pulse parameters and the light source intensity are set to favour oxidation of the organic species in the water sample and to suppress any oxidation signal from the chloride ions present in the sample.
- the speed of organic oxidation and sensitivity may be optimised, without triggering chloride oxidation and the ensuing photocatalytic cyclic chloride oxidation reaction.
- the measurement of 1 mg/L organic content is achievable in seawater.
- the effectiveness of the method of this invention means that potassium Chloride may be used as the supporting electrolyte without compromising the effectiveness of the measurements.
- the photohole is a very powerful oxidizing agent (+3.1 V) that will readily lead to the seizure of an electron from a species adsorbed to the solid semiconductor.
- both organic compounds and water can be oxidized by the photoholes or surface trapped photoholes but usually organic compounds are more favorably oxidized, which leads to the mineralization of a wide range of organic compounds.
- N and X represents a nitrogen and a halogen atom respectively.
- the numbers of carbon, hydrogen, oxygen, nitrogen and halogen atoms in the organic compound are represented by y, m, j, k and q.
- n refers to the number of electrons transferred during the photoelectrocatalytic degradation, which equals 4y ⁇ 2j+m-3k-q
- i the photocurrent from the oxidation of organic compounds.
- F is the Faraday constant
- V and C are the sample volume and the concentration of organic compound respectively.
- the measured charge, Q is a direct measure of the total amount of electrons transferred that result from the complete degradation of all compounds in the sample. Since one oxygen molecule is equivalent to 4 electrons transferred, the measured Q value can be easily converted into an equivalent O 2 concentration (or oxygen demand).
- the equivalent COD value can therefore be represented as:
- COD (mg I L of O 2 ) -Q— x 32000 l J 4FV
- This COD equation can be used to quantify the COD value of a sample since the charge, Q, can be obtained experimentally and for a given photoelectrochemical cell, the volume, V, is a known constant.
- the net charge by pulsing is calculated according to the Equation 3, where the charge of the last pulse, nominated as Q b iank is subtracted from each pulse and from this the sum of all pulses results in Q net (see Figure 4).
- the present invention provides a photoelectrochemical assay apparatus to determine oxygen demand of a water sample which consists of a) a flow through measuring cell b) a photoactive working electrode and a counter electrode disposed in said cell, c) a UV light source, adapted to illuminate the photoactive working electrode in pulses d) a control means to control the pulsed illumination of the working electrode, the applied potential and the signal measurement 2008/001529
- control means sets the duration of the pulse, the gap between pulses and the light intensity.
- pulse duration is from 0.01 to 5 seconds and the interval between pulses is at least 1 second.
- a reference electrode is also located in the measuring cell and the working electrode is a nanoparticulate semiconductor electrode, preferably titanium dioxide.
- the flow rate is adjusted to optimise the sensitivity of the measurements.
- This cell design is based on that disclosed in application WO2004/088305 with a means to store the organic/electrolyte solution.
- the sample collection device may include a filter to remove any large particulates, or precipitated substances, that may interfere with the operation of the cell.
- the method of this invention may be combined with the organic addition method disclosed in WO2007/016740, the contents of which are incorporated herein by reference. The combination is useful when chloride content is high.
- the limitation of the organic addition method is that some prior knowledge of the level of chloride or difficult to oxidise organics is required before the appropriate level of catalytic organics may be added.
- the method embodied by this invention avoids this constraint by the use of pulsed light.
- the reaction of the chloride is discriminated against by the pulsed waveform, and the COD may be determined in high saline matrices.
- Figure 1 is a graph illustrating varying LED intensities applied to a 1 : 50 dilution of a seawater sample resulting in a chloride content of 425 mg/L Cl " ;
- Figure 2 illustrates calibration, showing the linear relationship between concentration as COD and charge response for standards ranging from 0 - 50 mg/L COD in a background of 0 - 150 mg/L Cl " in the cell a. Pulsing technique, b. standard PeCOD analysis where there is a clear effect by a significant presence of chloride;
- Figure 3 illustrates the signal response for saline and non-saline Potassium
- KHP Hydrogen Phthalate
- Figure 5 illustrates the influence of chloride presence on the analytical signal.
- Figure 5a shows the normal response for KHP in the presence (upper trace) and absence (lower trace) of 1000 mg/L chloride with direct light;
- Figure 5b shows the response for 5a above (chloride present) with a pulsed regime
- Figure 6 illustrates the calibration over a concentration range for saline samples at various dilutions, with and without organic addition. Analyses were performed using a pulse of 0.1 sec on and 1 sec off;
- Figure 7 illustrates the calibration over a concentration range for saline and non- saline sample; a.) comparing pulsed and non-pulsed methods, b.) Comparison of saline and non-saline samples for the pulsed analysis method. Analyses were performed using a pulse of 0.1 sec on and 1 sec off;
- Figure 8 provides comparative data for COD (PeCODTM ) and BODsugar refinery samples in salt water;
- FIG. 9 illustrates the relationship between PeCODTM COD and BOD values.
- PeCODTM is the trademark of the applicant that is used to designate the water analysers made in accordance with WO2004/088305.
- Figure 1 shows that when a dilution of 1 to 50 of seawater is made, resulting in a chloride content of 425 mg/L Cl " , and when the applied UV light level applied is low, the onset of chloride oxidation is delayed and a window of opportunity exists where organics can be oxidised prior to the oxidation of chloride. At a LED intensity of 20% it was observed that 5 mg/L of organic could be easily observed above the chloride content.
- the sensors were made according to the colloidal method disclosed in
- KCI is a common electrolyte used in electrochemistry, and subsequently the potential for its use as a replacement electrolyte to the currently used NaNO 3 was investigated. KCI is a good electrolyte (due to its enhanced ionic mobility) and potentially it can provide a high background of chloride that would mask any chloride present in a sample. Preliminary experiments investigated the ability to detect low COD concentrations in a 1M KCI electrolyte.
- Figure 4a shows that 10 ppm of COD could be detected in KCI and hence a high chloride background using the pulsing technique. However, further tests showed the reproducibility to be poor and the ability of the signal to return to baseline could not be repeatedly achieved.
- KHP Potassium Hydrogen Phthalate
- the linearity and response over a concentration range was investigated for both saline and non-saline standards with Potassium Hydrogen Phthalate (KHP) in the range 0-300 mg/L. The responses are shown in Figure 3.
- KHP Potassium Hydrogen Phthalate
- Sodium perchlorate is a preferred electrolyte that for the PeCODTM instrument. It can achieve excellent linearity, use lower concentrations and is also hygroscopic. For this reason it was also investigated for its use in the application of analysis of COD in a chloride matrix.
- the initial pulsing parameters in pulsing mode were 0.5 sees for the LED on time and 2.5 sees for the off time, which is a 1 :5 ratio.
- Alteration of the pulsing settings to 0.1 sec on and 1 sec off resulted in a 1 :10 ratio, which resulted in improved signal-to-noise, and in observations which showed that these settings had the biggest effect in controlling the level of chloride oxidation.
- Further studies showed that increased off time did not significantly improve the sensitivity and consequently it was decided to maintain the 0.1 on and 1.0 off time in order to also achieve increased sample throughput.
- Example 1 The determination of COD in seawater is presented. Results obtained by the pulsing method are compared to results obtained without pulsing. Three examples are presented - COD analysis with direct light and no chloride present, COD with direct light and chloride present, and COD with pulsed light and chloride present.
- Figure 5a shows the normal response obtained for COD determination of 10 mg/L KHP with direct light with and without chloride present (at 1000 mg/L). It will be seen that the tailing of the organic response down to its baseline is interrupted by the onset of the chloride oxidation. Since the response never returns to its baseline, the generation of an analytical signal is compromised.
- Figure 5b shows the response for the solution analysed in 5a above, with the pulsed regime (chloride present).
- the protocol was as follows: with the current settings at 0.1 on and 1.0 off time, linearity was tested for a range of dilutions with seawater samples (See Figure 6). A 1 :50 dilution of seawater without organic addition is seen to be preferred. Smaller dilutions are possible (i.e. 1:10), but they then require organic addition. With such high chloride backgrounds, and no organic present, chloride oxidation begins to dominate.
- the Ti ⁇ 2 sensor life is extended due to pulsing efficiency of oxidation and the absence of chloride interference.
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2008801119129A CN101918823A (en) | 2007-10-17 | 2008-10-17 | Water analysis |
AU2008314501A AU2008314501B2 (en) | 2007-10-17 | 2008-10-17 | Water analysis |
EP08800162A EP2201356A4 (en) | 2007-10-17 | 2008-10-17 | Water analysis |
ZA2010/02406A ZA201002406B (en) | 2007-10-17 | 2010-04-06 | Water analysis |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2007905660A AU2007905660A0 (en) | 2007-10-17 | Water Analysis | |
AU2007905660 | 2007-10-17 |
Publications (1)
Publication Number | Publication Date |
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WO2009049366A1 true WO2009049366A1 (en) | 2009-04-23 |
Family
ID=40566923
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/AU2008/001529 WO2009049366A1 (en) | 2007-10-17 | 2008-10-17 | Water analysis |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP2201356A4 (en) |
CN (1) | CN101918823A (en) |
AU (1) | AU2008314501B2 (en) |
WO (1) | WO2009049366A1 (en) |
ZA (1) | ZA201002406B (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010132957A1 (en) * | 2009-05-22 | 2010-11-25 | Aqua Diagnostic Holdings Pty Ltd | Water analysis |
DE102013108556A1 (en) * | 2013-08-08 | 2015-02-12 | Endress + Hauser Conducta Gesellschaft für Mess- und Regeltechnik mbH + Co. KG | Method and analyzer for determining the chemical oxygen demand of a fluid sample |
CN112798533A (en) * | 2021-02-07 | 2021-05-14 | 深圳市中志环境科技有限公司 | Multi-factor water quality monitor and multi-factor water quality monitoring method |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104132978A (en) * | 2014-07-24 | 2014-11-05 | 南京大学 | Apparatus for photocatalysis-induced electrochemiluminescence based on bipolar electrodes |
CN106970131B (en) * | 2017-03-28 | 2019-01-18 | 北京北大明德科技发展有限公司 | A kind of photoelectrocatalysis type water-soluble organic compound concentration sensor and preparation method |
CN110487864B (en) * | 2019-09-03 | 2020-10-27 | 中南大学 | Photoelectrochemical detection method for chloride ion concentration in water body |
CN111505068B (en) * | 2020-04-01 | 2021-07-30 | 中国科学院水生生物研究所 | Biosensor method and device for monitoring COD concentration in constructed wetland in real time |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004088305A1 (en) * | 2003-04-04 | 2004-10-14 | Aqua Diagnostic Pty Ltd | Photoelectrochemical determination of chemical oxygen demand |
WO2007016740A1 (en) * | 2005-08-11 | 2007-02-15 | Aqua Diagnostic Pty. Ltd. | Water analysis using a photoelectrochemical method |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4963815A (en) * | 1987-07-10 | 1990-10-16 | Molecular Devices Corporation | Photoresponsive electrode for determination of redox potential |
DE19914810A1 (en) * | 1999-03-31 | 2000-10-26 | Forschungszentrum Juelich Gmbh | Photoelectrochemical sensor |
-
2008
- 2008-10-17 EP EP08800162A patent/EP2201356A4/en active Pending
- 2008-10-17 WO PCT/AU2008/001529 patent/WO2009049366A1/en active Application Filing
- 2008-10-17 AU AU2008314501A patent/AU2008314501B2/en not_active Ceased
- 2008-10-17 CN CN2008801119129A patent/CN101918823A/en active Pending
-
2010
- 2010-04-06 ZA ZA2010/02406A patent/ZA201002406B/en unknown
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004088305A1 (en) * | 2003-04-04 | 2004-10-14 | Aqua Diagnostic Pty Ltd | Photoelectrochemical determination of chemical oxygen demand |
WO2007016740A1 (en) * | 2005-08-11 | 2007-02-15 | Aqua Diagnostic Pty. Ltd. | Water analysis using a photoelectrochemical method |
Non-Patent Citations (1)
Title |
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See also references of EP2201356A4 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010132957A1 (en) * | 2009-05-22 | 2010-11-25 | Aqua Diagnostic Holdings Pty Ltd | Water analysis |
AU2010251701B2 (en) * | 2009-05-22 | 2012-11-15 | 579453 Ontario Inc. | Water analysis |
DE102013108556A1 (en) * | 2013-08-08 | 2015-02-12 | Endress + Hauser Conducta Gesellschaft für Mess- und Regeltechnik mbH + Co. KG | Method and analyzer for determining the chemical oxygen demand of a fluid sample |
CN112798533A (en) * | 2021-02-07 | 2021-05-14 | 深圳市中志环境科技有限公司 | Multi-factor water quality monitor and multi-factor water quality monitoring method |
Also Published As
Publication number | Publication date |
---|---|
AU2008314501B2 (en) | 2011-02-17 |
AU2008314501A1 (en) | 2009-04-23 |
ZA201002406B (en) | 2011-03-30 |
EP2201356A4 (en) | 2011-12-14 |
EP2201356A1 (en) | 2010-06-30 |
CN101918823A (en) | 2010-12-15 |
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