Phys., 49, 857 (1968). 4.5.3 Assay of O3concentrations. • Summarizing results of the evaluation (see appendix E). /XIPLAYER_CM4 12 0 R “Characterization and mitigation of water vapor effects in the measurement of ozone by chemiluminescence with, 12. /Contents 5 0 R The photometer must be inter-compared annually, either directly or via transfer standards, with a NIST standard reference photometer (SRP) or calibration photometers used by other agencies or laboratories. Examples of conversion factors 30 Appendix C. Examples for the estimation of measurement uncertainty of results 32 Appendix D. Example of rounding, reporting and interpreting results 39 Appendix E. Glossary 41 6.2.2 Achieving quality objectives . of Chem. The user's quality control program shall … Ozone analyzers must be calibrated as follows, using O3 standards obtained directly according to section 4.5.3 or by means of a certified transfer standard. This filter must be changed weekly (or at least often as specified in the manufacturer's operation/instruction manual), and the sample inlet system used with the analyzer must be kept clean, to avoid loss of O3 in the O3 sample air prior to the concentration measurement. Appendix A Nevada Administrative Code for Laboratory Certification Appendix B Application Form for Nevada Brownfields Program Appendix C EPA Region 9 Templates for Sampling and Analysis Plan and Field Sampling Plan (reference and web link) Appendix D Data Quality Indicators and Measurement Quality Objectives Assoc., 63 (7), 855-863 (2013). 1.1 This chemiluminescence method provides reference measurements of the concentration of ozone (O3) in ambient air for determining compliance with the national primary and secondary ambient air quality standards for O3 as specified in 40 CFR part 50. A number of advantages are realized by locating the calibration photometer in a clean laboratory where it can be stationary, protected from the physical shock of transportation, operated by a responsible analyst, and used as a common standard for all field calibrations via transfer standards. II, Appendix D, Measurement Quality Objectives and Validation Templates zero drift data validation tolerances: these are trace gas analyzer tolerances, where trace gas analyzers are not required and standard analyzers are in 4.3.2 Air flow controllers. H: Audit Information . It is the operator's responsibility to verify that all of the information required for equation 4 is obtained, either automatically by the photometer or manually. AMBIENT AIR MONITORING AND QUALITY ASSURANCE/QUALITY CONTROL GUIDELINES . “Methods for gas-phase measurements of ozone, ozone precursors and aerosol precursors.” Atmos. The Ultraviolet Spectrum”, J. Chem. A review of the collected data is necessary in order to identify if data measurement objectives established in the seven-step data quality objective … 4.2 Applicability. Appendix A — Preparation and Preliminary Phase The first step in a quality assessment, after the scope, objectives, and administrative arrangements are agreed, is for the quality assessment team leader to undertake the preparation and planning work set out in Tool 1 (Self-assessment with Independent Validation use Tool 1A). Laboratory Quality Control Frequency of Analysis Measurement Quality Objective Calibration Standard Per analytical method or manufacturer’s specifications Per analytical method or manufacturer’s specifications Continuing Calibration Verification /XIPLAYER_CM5 13 0 R CONDUCT OF EXPERIMENTAL STUDIES OF METHOD PERFORMANCE 8 3.3. 4.5.3.2 Verify that the flow rate through the photometer absorption cell, F, allows the cell to be flushed in a reasonably short period of time (2 liter/min is a typical flow). For certification of transfer standards which provide their own source of O3, the transfer standard may replace the O3 generator and possibly other components shown in Figure 2; see Reference 12 for guidance. 13. Quality Assurance Handbook for Air Pollution Measurement Systems "Volume IV: Meteorological Measurements Version 2.0" EPA-454/B-08-002 , March 2008 (PDF) (191 pp, 5.1 MB, About PDF) QA Handbook Appendix D: Measurement Quality Objectives and Validation Templates; March 2017 (PDF) (54 pp, 400 K, About PDF) Brownfields A stable O3 generator is used to produce O3 concentrations over the required calibration concentration range. 4 0 obj APPENDIX A APPENDIX B APPENDIX C APPENDIX D . If substantial adjustment of the span control is necessary, recheck the zero and span adjustments by repeating steps 4.5.5.2 to 4.5.5.4. Upon initial operation of the photometer, the following steps must be carried out with all quantitative results or indications recorded in a chronological record, either in tabular form or plotted on a graphical chart. Figure 2 shows a commonly used configuration and serves to illustrate the calibration procedure, which follows. << /Length 2226 4.5.5.4 Adjust the O3 analyzer's span control to obtain the desired response equivalent to the calculated standard concentration. The flow rate through the O3 generator (Fo) and the dilution air flow rate (FD) are measured with a flow or volume standard that is traceable to a NIST flow or volume calibration standard. See Reference 13 for additional information. 4.5.5.5 Generate additional O3 concentration standards (a minimum of 5 are recommended) over the calibration scale of the O3 analyzer by adjusting the O3 source or by Option 1. VI. ... Validation and Reconciliation with DQIs. Quality objectives are goals for the value of products, services and processes. >> 1 0 obj Appendix A LTMS Analytical Requirements Appendix B Summary Table of Quality Objectives and Criteria for Measurement Data Appendix C FORM TEMPLATES Field Data Sheet Discharge Field Sheet Chain of Custody Appendix D Summary of Sample Container, Volume, Initial Preservation, and Holding Time Recommendations for Water Samples 4.5.3.4 Ensure that the flow rate of zero air, Fz, is at least 1 liter/min greater than the flow rate required by the photometer. The transmittance is defined as the ratio I/I0, where I is the intensity of light which passes through the cell and is sensed by the detector when the cell contains an O3 sample, and I0 is the intensity of light which passes through the cell and is sensed by the detector when the cell contains zero air. In addition to the QC checks required for meeting the measurement quality objectives and validation templates, semi-annual system Compute the linear regression slope and intercept and plot the regression line to verify that no point deviates from this line by more than 2 percent of the maximum concentration tested. A. Coxom, “Kinetic Studies of Oxy-halogen Radical Systems”, Proc. A. Clyne and J. 8. References 8-11 describe the chemiluminescence measurement principle. 2.1 This reference method is based on continuous automated measurement of the intensity of the characteristic chemiluminescence released by the gas phase reaction of O3 in sampled air with either ethylene (C2H4) or nitric oxide (NO) gas. US EPA QA Handbook Appendix D :Validation Templates . 8.2 Study Site 7. 4.5.3.5 With zero air flowing in the output manifold, actuate the two-way valve to allow the photometer to sample first the manifold zero air, then Fz. The linearity error must be less than 5%. Data Quality Objectives and Criteria for Measurement of Data Data Precision, Accuracy, Measurement Range Appendix E shows objectives for measurement range, method detection limit, precision, and accuracy when applicable and the sample matrix for each parameter tested for this project. and measurement efforts mandated or supported by EPA have in place a centrally managed Quality Assurance (QA) Program Plan. A complete UV calibration system consists of an O3 generator, an output port or manifold, a photometer, an appropriate source of zero air, and other components as necessary. A device to indicate temperature must be used that is accurate to ±1 °C. I: Example of Reports to Management . CASTNET uses the measurement quality objectives and validation templates described in the EPA QA Handbook Validation Template8 (reproduced in Appendix B of this plan) to ensure that the highest quality data are being submitted to the AQS. 4.5.5 Calibration of ozone analyzers. The user's quality control program … The calculated O3 concentrations must be corrected for O3 losses, which may occur in the photometer, and for the temperature and pressure of the sample. [Available at, 14. Figure 1-1 Figure 1-2 Figure 1-3 Figure 1-4 Figure 1-5 Figure 2-1 Figure 2-2 Figure 2-3 Figure 2-4 Figure 2-5a The criteria include d on the tables were from 40 CFR Part 50 Appendices L and N, 40 CFR Part 58 Appendix A, and Method 2.12; a fe w criteria were also added that were neither in CFR nor Method 2.12, but which the workgroup felt s hould be included. /Filter /FlateDecode /XObject << /XIPLAYER0 6 0 R Appendix H: Data Quality Checklist - MDRO/CDI Data v. Appendix I: Data Quality Checklist - SSI Events/Procedures . D: Measurement Quality Objectives and Validation Templates . 4.5.3.6 Adjust the O3 generator to produce an O3 concentration as needed. (This can be readily achieved by prudent selection of optical filter and detector response characteristics.) A7. Validation templates in Appendix D of Redbook Validation templates include instrument/method-specific recommendations as well as MQOs The MQOs are all calculated from the difference between your instrument’s indicated value and the known (audit) value = d … A manual or automatic two-way valve, or other means is used to switch the photometer flow between zero air and the O3 concentration. Air flow controllers are devices capable of regulating air flows as necessary to meet the output stability and photometer precision requirements. 2.2 The measurement system is calibrated by referencing the instrumental chemiluminescence measurements to certified O3 standard concentrations generated in a dynamic flow system and assayed by photometry to be traceable to a National Institute of Standards and Technology (NIST) standard reference photometer for O3 (see Section 4, Calibration Procedure, below). 2.3 An analyzer implementing this measurement principle is shown schematically in Figure 1. 8.0 Quality Objectives & Criteria for Measurement Data 6. Record the stable zero air response as “Z”. b) need to consider processes in terms of added value, c) obtaining results of process performance and effectiveness and d) understanding, meeting and integrating Customer, … A transfer standard is certified by relating the output of the transfer standard to one or more O3 calibration standards as determined according to section 4.5.3. W. B. DeMore and O. Raper, “Hartley Band Extinction Coefficients of Ozone in the Gas Phase and in Liquid Nitrogen, Carbon Monoxide, and Argon”, J. Phys. Phys., 59, 1203 (1973). 4.5.3.8 Actuate the two-way valve to allow the photometer to sample the O3 concentration until the absorption cell is thoroughly flushed and record the stable measured value of I. %����� 4.5.5.3 Generate an O3 concentration standard of approximately 80% of the desired upper range limit (URL) of the O3 analyzer. A device to indicate barometric pressure must be used that is accurate to ±2 torr. Each O3 concentration generated by dilution is calculated from: Additional information on calibration and pollutant standards is provided in Section 12 of Reference 14. The use of a particle filter on the sample inlet line of a chemiluminescence O3 FRM analyzer is required to prevent buildup of particulate matter in the measurement cell and inlet components. 4.5.2 Preparation. With this option, accurate flow measurements are required. objectives provide a mechanism for ongoing control and evaluating and measuring data quality throughout the project. ... – Findings against the agency self-assessment template in terms of compliance with existing strategies and 9. >> A quality measure (also called a quality indicator or performance measure) is an objective measurement of the proportion of patients who received the indicated process(es) of care and/or whether patients had the desired outcome(s) of care . Quality Measurement Manual ... Quality measures assess the quality of patient care in an objective fashion Though the principles of quality management and continuous G: Example Procedure for Calibrating Data Acquisition System . Check the photometer system for integrity, leaks, cleanliness, proper flow rates, etc. endobj Identification of critical measurements, data quality objectives, data quality indicator goals, the schedule for completing testing, and milestones shall be addressed. Other configurations may require appropriate variations in the procedural steps. 4.1 Principle. Chem., 68, 412 (1964). QA Handbook for Air Pollution Measurement Systems - Volume II. 4.3.3 Ozone generator. >> It is part of an overall Gateway Review Framework and measures progress and recommendations in terms of seven focus areas for ICT projects in NSW. Roy. It may also assist service providers in developing their Quality Management Plans (QMP). Because the low-pressure mercury lamp radiates at several wavelengths, the photometer must incorporate suitable means to assure that no O3 is generated in the cell by the lamp, and that at least 99.5% of the radiation sensed by the detector is 254 nm radiation. 4.5.5.7 Option 1: The various O3 concentrations required in steps 4.5.3.11 and 4.5.5.5 may be obtained by dilution of the O3 concentration generated in steps 4.5.3.6 and 4.5.5.3. [Available at, 13. 2.5 Sampling considerations. Ambient Air Quality Monitoring Program. See the photometer instruction manual and Reference 13 for guidance. The user's quality control program shall provide guidelines for initial establishment of these variables and for subsequent alteration as operational experience is accumulated. The quantities defined above are related by the Beer-Lambert absorption law. APPENDIX D. ANALYSING UNCERTAINTY SOURCES 102 ... uncertainty should be integrated with existing quality assurance measures, since these measures frequently 7. Boylan, P., Helmig, D., and Park, J.H. Quality Control Checks The EPA Quality Assurance Handbook for Air Pollution Measurement Systems, Vol. stream EPA-454/B-13-003, May 2013. Some commercial photometers may automatically evaluate all or part of equation 4. Appendix D to Part 50 - Reference Measurement Principle and Calibration Procedure for the Measurement of Ozone in the Atmosphere (Chemiluminescence Method), R = dilution ratio = flow of original concentration divided by the total flow. Offsetting the analyzer's zero adjustment to +5% of scale is recommended to facilitate observing negative zero drift (if any). Denominator Validation Template . Appendix D). 84A P P E N D I X D Research Problem Statements for Priority 1 NeedsDemonstration Project Using Both Infrared and High-Speed Ground-Penetrating Radar for Uniformity Measurements on New Hot-Mix Asphalt Layers Problem Statement There is a continuing need to improve monitoring of new hot-mix asphalt (HMA) surfaces. ; Crow, W.; Spicer, C.W. 3.2 A small sensitivity to variations in the humidity of the sample air is minimized by a sample air dryer. (London), 78, 932 (1961). >> Data Quality Checklists iii. 4.5.5.1 Allow sufficient time for the O3 analyzer and the photometer or transfer standard to warm-up and stabilize. Principal DQIs: PARCC ... Data Validation Data Quality Assessment Quality Assurance Project Plan QA PLANNING FOR The dynamic calibration system may be modified as shown in Figure 3 to allow for dilution air to be metered in downstream of the O3 generator. 2.4 An analyzer implementing this measurement principle and calibration procedure will be considered a federal reference method (FRM) only if it has been designated as a reference method in accordance with part 53 of this chapter. Oceanic Technol., 9 (2), 142-148(1992). The configuration must provide a stable O3 concentration at the system output and allow the photometer to accurately assay the output concentration to the precision specified for the photometer (4.3.1). Rate Constants and Activation Energies”, Int'l Jour. Quality Assurance Handbook for Air Pollution Measurement Systems "Volume IV: Meteorological Measurements Version 2.0" EPA-454/B-08-002 , March 2008 (PDF) (191 pp, 5.1 MB, About PDF) QA Handbook Appendix D: Measurement Quality Objectives and Validation Templates; March 2017 (PDF) (54 pp, 400 K, About PDF) Brownfields 4.3.4 Output manifold. Appendix A LTMS Analytical Requirements Appendix B Summary Table of Quality Objectives and Criteria for Measurement Data Appendix C FORM TEMPLATES Field Data Sheet Discharge Field Sheet Chain of Custody Appendix D Summary of Sample Container, Volume, Initial Preservation, and Holding Time Recommendations for Water Samples /Resources 3 0 R 4.3 Apparatus. 4.5.2.4 Inter-comparison. 4.5.2.2 System check. 8. 4.5.2.5 Ozone losses. Transfer standards must meet the requirements and specifications set forth in Reference 12. ; Walega, J.G. As the performance and stability record of the photometer is established, the frequency of these steps may be reduced to be consistent with the documented stability of the photometer and the guidance provided in Reference 12. Proper operation of the photometer is of critical importance to the accuracy of this procedure. Quality Manager June 2005 Positive Improvement in added-value measurements from Customers Notes. Am., 43, 870 (1953). 4.5.3.3 Ensure that the flow rate into the output manifold is at least 1 liter/min greater than the total flow rate required by the photometer and any other flow demand connected to the manifold. These tables describe operational and systematic criteria for O 3 0 Date:05/13 Page 1 of 48. The frequency of calibration, as well as the number of points necessary to establish the calibration curve and the frequency of other performance checking will vary by analyzer; however, the minimum frequency, acceptance criteria, and subsequent actions are specified in Reference 3, Appendix D: Measurement Quality Objectives and Validation Template for SO 2 (page 9 of 30). and quantitative measurement instruments that meet acceptable standards of quality, such as reliability and validity (see appendix A for a detailed description of this study’s research methodology and analyti­ cal approach). The quality objectives should relate of come directly from the quality policy It is assumed that all conditions of the system, except for the contents of the absorption cell, are identical during measurement of I and I0. E.C.Y. A mixing chamber between the O3 generator and the output manifold is also required. APPENDIX D CONTENT OF PROJECT PLAN DOCUMENTS D.1 Introduction ... of a project plan document since it is closely associated with the data quality objective (DQO) ... D Data Validation and Usability ; D1 Verification and Validation Requirements : D5.1: 8 : D2 : It is a basic quality management process to establish a set of quality objectives. %PDF-1.4 5.1 The frequency of calibration, as well as the number of points necessary to establish the calibration curve, and the frequency of other performance checking will vary by analyzer; however, the minimum frequency, acceptance criteria, and subsequent actions are specified in Appendix D of Reference 14: Measurement Quality Objectives and Validation Templates. The system must have a vent designed to insure atmospheric pressure in the manifold and to prevent ambient air from entering the manifold. Ridley, B.A. 1. 6.3 Planning of changes 1 Goal Statements & Objective Statements 6. For each O3 concentration standard, record the O3 concentration and the corresponding analyzer response. The calibration photometer must be dedicated exclusively to use as a calibration standard. 5. Section IV. Manufacturers of analyzers should include in their instruction/operation manuals information and guidance as to these variables and on other matters of operation, calibration, routine maintenance, and quality control. Monthly HAI Reporting Plan ii. /MediaBox [0 0 792 612] The concentration of O3 in an absorption cell is determined from a measurement of the amount of 254 nm light absorbed by the sample. Appendix D RSEPA Master QAPP: Final Revision 0 of RSEPA. PN 1599 . /Parent 2 0 R 10. The two photometer readings must be equal (I = I0). Since the accuracy of the measured flow-rates will affect the linearity error as measured this way, the test is not necessarily conclusive. for Air Pollution Measurement Systems, Vol. The length of the light path through the absorption cell must be known with an accuracy of at least 99.5%. Table A1: Measurement Quality Objectives* - Conventional Analytes in Fresh and Marine Waters. The exact procedure varies depending on the nature and design of the transfer standard. Air Waste Manage. 2 0 obj 5.1 The frequency of calibration, as well as the number of points necessary to establish the calibration curve, and the frequency of other performance checking will vary by analyzer; however, the minimum frequency, acceptance criteria, and subsequent actions are specified in Appendix D of Reference 14: Measurement Quality Objectives and Validation Templates. Define terms ... measurements from measurement errors or interferences Goal •Verify Level 1 review and ensure data quality control requirements are met Goal E: Characteristics of Spatial Scales Related to Each Pollutant . 4.5.3.10 Calculate the O3 concentration from equation 4. Appendix G: Data Quality Checklist - CLABSI/CAUTI Data iv. 3.1 Except as described in 3.2 below, the chemiluminescence measurement system is inherently free of significant interferences from other pollutant substances that may be present in ambient air. The photometer consists of a low-pressure mercury discharge lamp, (optional) collimation optics, an absorption cell, a detector, and signal-processing electronics, as illustrated in Figure 2. In July 2014 EPA made changes to Appendix D, Measurement Quality Objectives and Validation Templates (AMTIC Version) of the 2013 Quality Assurance Handbook, Volume II relating to gaseous monitoring zero drift and other changes. APPENDIX D. DATA QUALITY INDICATORS .....D-1 AD1. Document No: TR 18 Issue No: 1 Page 5 of 37 2.21 Uncertainty of Measurement: Parameter associated with the result of a measurement that characterizes the dispersion of the values that could reasonably be attributed to the measurand. Requirement Frequency Acceptance Criteria Critical Criteria One Point QC Check. This procedure is applicable to the calibration of ambient air O3 analyzers, either directly or by means of a transfer standard certified by this procedure. /Count 20 Appendix D Measurement Quality Objectives and Validation Templates AMTIC Version 4.4.1 Zero air. Technical Assistance Document for the Calibration of Ambient Ozone Monitors, EPA publication number EPA-600/4-79-057, September, 1979. The calibration procedure is based on the photometric assay of O3 concentrations in a dynamic flow system. 1 Date:03/17 Page 1 of 54 Appendix D Measurement Quality Objectives and Validation Templates Table of Contents (click on link to go to individual tables) Validation Template Page O3 5 CO 8 NO2, NOx, NO 10 SO2 13 PM2.5 Filter Based Local Conditions 16 Continuous PM2.5 Local Conditions 21 Additional information on verifying linearity is contained in Reference 13. << /Type /Catalog 5.1 The frequency of calibration, as well as the number of points necessary to establish the calibration curve, and the frequency of other performance checking will vary by analyzer; however, the minimum frequency, acceptance criteria, and subsequent actions are specified in Appendix D of Reference 14: Measurement Quality Objectives and Validation Templates. Appendix A Assessment Monitoring Minimum Requirements Appendix B Summary Table of Quality Objectives and Criteria for Measurement Data Appendix C FORM TEMPLATES Field Data Sheet Chain of Custody Discharge Field Sheet Appendix D Summary of Sample Container, Volume, Initial Preservation, and Holding Time Recommendations for i. 18.1 Data Review and Verification 13. Each O3 concentration is determined from the measurement of the transmittance (I/I0) of the sample at 254 nm with a photometer of path length l and calculated from the equation. Kinetics, VI, 725 (1974). Some guidelines for quantitatively determining this loss are discussed in Reference 13. 1. 4.5.3.11 Obtain additional O3 concentration standards as necessary by repeating steps 4.5.3.6 to 4.5.3.10 or by Option 1. F: Sample Manifold Design for Precursor Gas Monitoring . Consensus built validation templates . Additional information regarding the assembly of a UV photometric calibration apparatus is given in Reference 13. ; Grahek, F.E. METHOD VALIDATION 7 3.2. /XIPLAYER_CM6 14 0 R Page 4 List of Figures Page Figure 1. As shown in Figure 2, the zero air supplied to the photometer cell for the I0 reference measurement must be derived from the same source as the zero air used for generation of the O3 concentration to be assayed (I measurement). measure, however, that the real power of the quality measurement enterprise will eventually be felt . 18.1 Data Review and Verification 13. Appendix D: Enter title or description of attachment. 4.3.1 UV photometer. This loss must not exceed 5%. These validation templates describe operational and systematic criteria for O3 measurements, including requirements for frequency of measurements or audits, calibration schedules, and acceptance criteria for QC checks. 6. “A small, high-sensitivity, medium-response ozone detector suitable for measurements from light aircraft.” J. Atmos. It must always be used with clean, filtered calibration gases, and never used for ambient air sampling. More rigorous quality assurance over the work of the Internal Auditors. Section III. Soc. 1 Goal Statements & Objective Statements 6. 4.5.3.7 Actuate the two-way valve to allow the photometer to sample zero air until the absorption cell is thoroughly flushed and record the stable measured value of Io. /Pages 2 0 R This determination requires knowledge of (1) the absorption coefficient (α) of O3 at 254 nm, (2) the optical path length (l) through the sample, (3) the transmittance of the sample at a nominal wavelength of 254 nm, and (4) the temperature (T) and pressure (P) of the sample. Soc., A303, 207 (1968). Some portion of the O3 may be lost upon contact with the photometer cell walls and gas handling components. 3 0 obj a) continuous improvement of processes based on objective measurement and analysis. The magnitude of this loss must be determined and used to correct the calculated O3 concentration. 4.3.6 Temperature indicator. In some commercially available photometers, the operation of the two-way valve and various other operations in section 4.5.3 may be carried out automatically by the photometer. 5.1 The frequency of calibration, as well as the number of points necessary to establish the calibration curve, and the frequency of other performance checking will vary by analyzer; however, the minimum frequency, acceptance criteria, and subsequent actions are specified in Appendix D of Reference 14: Measurement Quality Objectives and Validation Templates. For “automatic” photometers which evaluate the first term of equation 4 based on a linear approximation, a manual correction may be required, particularly at higher O3 levels. or 3. J: Guidance for Use of Electronic Logbooks [Available at, National Institute of Standards and Technology, www.epa.gov/ttnamti1/files/ambient/qaqc/OzoneTransferStandardGuidance.pdf, www.epa.gov/ttnamti1/files/ambient/criteria/4-79-057.pdf, http://www.epa.gov/ttnamti1/files/ambient/pm25/qa/QA-Handbook-Vol-II.pdf, Electronic Code of Federal Regulations (e-CFR), CHAPTER I - ENVIRONMENTAL PROTECTION AGENCY, PART 50 - NATIONAL PRIMARY AND SECONDARY AMBIENT AIR QUALITY STANDARDS. This automated method is applicable to the measurement of ambient O3 concentrations using continuous (real-time) sampling and analysis. x��Y[o��~���S� 1˽��J�m��(p@K��ITx���ٛ�Yry� �ַ����WI�$߯�. Phys. An ambient air sample stream and a specific flowing concentration of either C2H4 (ET-CL method) or NO (NO-CL method) are mixed in a measurement cell, where the resulting chemiluminescence is quantitatively measured by a sensitive photo-detector. 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