Standard Operating Procedure

Measurement Uncertainty in Chemical Analysis

This is an example of a Standard Operating Procedure. It is a proposal and starting point only. The type and extent of documentation depends on the process environment. The proposed documentation should be adapted accordingly and should be based on individual risk assessments. There is no guarantee that this document will pass a regulatory inspection.

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STANDARD OPERATING PROCEDURE Document Number: S-536 Version 1.xx

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Measurement Uncertainty in Chemical Analysis

Company Name:

Controls: Superseded Document Reason for Revision Effective Date Signatures: Author I indicate that I have authored or updated this SOP according to applicable business requirements and our company procedure: Preparing and Updating Standard Operating Procedures. Name: Signature: Date: Approver ________________________________ ________________________________ ________________________________ N/A, new N/A May 1, 2012

I indicate that I have reviewed this SOP, and find it meets all applicable business requirements and that it reflects the procedure described. I approve it for use. Name: Signature: Date: ________________________________ ________________________________ ________________________________

Reviewer

I indicate that I have reviewed this SOP and find that it meets all applicable quality requirements and company standards. I approve it for use. Name: Signature: Date: ________________________________ ________________________________ ________________________________

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Measurement Uncertainty in Chemical Analysis

1. PURPOSE
Typically every chemical measurement has an error. Therefore a measurement only gives an approximation of the true value of the quantity to be measured. The possible difference to the true value, or the measurement uncertainty, should be estimated and reported as part of any good analytical practice. This SOP addresses the process for estimating and documentation of measurement uncertainty.

2. SCOPE
The SOP covers the estimation and reporting of uncertainty of chemical testing.

3. GLOSSARY/DEFINITIONS
Item (Measurement) Uncertainty Explanation Parameter associated with a result of a measurement that characterizes the dispersion of the values that could reasonably be attributed to the measurand (Reference 1). Uncertainty of the result x of a measurement expressed as a standard deviation (Reference 1). Standard uncertainty of a result y of a measurement when the result is obtained from the values of a number of other quantities, equal to the positive square root of a sum of terms, the terms being the variances or co-variances of these other quantities weighted according to how the measurement result varies with these quantities (Reference 1). Quantity defining an interval about the result of the measurement that may be expected to encompass a large fraction of the distribution of values that could reasonably be attributed to the measurand (Reference 1). Numerical factor used as a multiplier of the combined standard uncertainty in order to obtain an expanded uncertainty (Reference 1).

Standard Uncertainty Combined Standard Uncertainty

Expanded Uncertainty

Coverage Factor

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Measurement Uncertainty in Chemical Analysis Traceability The property of the result of a measurement of the value of a standard whereby it can be related to stated references, usually national or international standards, through an unbroken chain of comparisons all having stated uncertainties (Reference 1). Value consistent with a definition of a given particular quantity (Reference 1). The result of a measurement minus the true value of the measurand (Reference 1). The result of a measurement minus the mean that would result from an infinite number of measurements of the same measurand carried out under repeatability conditions (Reference 1). Mean that would result from an infinite number of measurements of the same measurand carried out under repeatability conditions minus a true value of the measurand (Reference 1).

True Value

Error (of a measurement) Random Error

Systematic Error

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4. REFERENCE DOCUMENTS
4.1. EURACHEM/CITAC Guide CH 4, Quantifying Uncertainty in Analytical

Measurement, 2nd Edition, 2000.

4.2. Checklist E-186: Measurement Uncertainty in Chemical Analysis.

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5. RESPONSIBILITIES
5.1. Analysts

5.1.1. Collect measurement data to estimate measurement uncertainty. 5.1.2. Estimate measurement uncertainty. 5.1.3. Report measurement uncertainty for routine analysis.
5.2. Laboratory Supervisor

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Measurement Uncertainty in Chemical Analysis 5.2.1. Prepares a list of tests that require estimation and reporting of measurement uncertainty. 5.2.2. Reviews uncertainty data experiments, evaluations and reports.
5.3. Quality Assurance Department

5.3.1. Advises on regulations and guidelines related to measurement uncertainty. 5.3.2. Checks if processes and documentation are in compliance with internal policies and quality standards/guidelines. 5.3.3. Reviews and approves measurement uncertainty data as part of the review of test results.

6. FREQUENCY OF USE
6.1. Whenever chemical analyses are performed that may require estimation and

reporting of measurement uncertainty data.

7. PROCEDURE
7.1. Determine Tests that Require Estimation of Measurement Uncertainty

7.1.1. The laboratory supervisor proposes tests that require estimation and reporting of measurement uncertainty. In general these include:

Well-recognized quantitative test methods that specify limits to the

values of the major sources of uncertainty of measurement and specify the form of presentation of calculated results.

All other quantitative test methods including standard methods and

methods developed in-house.

All tests where reporting of measurement uncertainty is required by

clients. 7.1.2. Quality Assurance reviews and approves the list.
7.2. Document Methods and Specifications

7.2.1. For methods as defined in 7.1.1 the analyst documents the method and specifications. This includes: Scope of the method. Equipment used to run the method.
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Measurement Uncertainty in Chemical Analysis Performance acceptance criteria. Laboratories where the method is used. Required measurement uncertainty data.

7.3. Identify Uncertainty Sources

7.3.1. The analyst collects and documents information on possible sources of uncertainty. The following sources should be considered:

Sampling, sample storage. Instruments, equipment (bias, precision). Reagent purity, reference standards. Environmental and measurement conditions. Contamination, carry over. Computational effects (calibration model). Sample effects (matrix).
7.3.2. The list is reviewed and approved by the laboratory supervisor.
7.4. Define Experiments

7.4.1. The analyst suggests a list of experiments to be executed to get uncertainty estimates. Depending on findings from 7.2 and 7.3 the following should be considered: Single laboratory short-term precision. Single laboratory day-by-day precision. Precision within multiple laboratories. Recovery studies through comparison with certified reference material. Recovery studies through spiking blank and sample matrix reference material.

7.4.2. The list is reviewed and approved by the laboratory supervisor.

7.5. Define other Sources of Uncertainty

7.5.1. The analyst suggests a list of other sources that can contribute to uncertainty. Depending on findings from 7.2 and 7.3 the following should be considered: Uncertainty of certified reference material as reported in the certificate as supplied by the supplier.
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Measurement Uncertainty in Chemical Analysis Purity of reagents as found in the suppliers catalogue .

7.5.2. The laboratory supervisor reviews and approves the list.

7.6. Conduct Experiments and Evaluate Results

7.6.1. For each experiment defined and approved in 7.4 the analyst conducts the experiments. 7.6.2. For each experiment a minimum of ten analyses are performed. 7.6.3. The analyst calculates analyte recovery and the standard deviation of precision studies for each experiment.
7.7. Calculate Combined Standard and Expanded Measurement Uncertainty

7.7.1. Using data from 7.5 and 7.6.3 the analyst calculates the combined standard uncertainty data using the formula:

7.7.2. Using results from 7.7.1 the analyst calculates the expanded uncertainty formula:

Unless otherwise specified a capacity factor of 2 is used that gives a 95% confidence interval.
7.8. Report Results

7.8.1. The analyst reports the results. The following general recommendations should be considered: Present sufficient information to allow the result to be reevaluated. Document the details on how measurement uncertainty has been determined. Describe the methods used to estimate measurement uncertainty. Document all values and the sources of all assumptions and corrections.
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Measurement Uncertainty in Chemical Analysis List all components of uncertainty. Limit the numerical values of uncertainty to two digits.

7.8.2. Unless otherwise specified the analyst reports numerical values following the guidelines for reporting expanded uncertainty:

7.8.3. Reports are signed by the analyst.

7.9. Review of Experiments, Evaluations and Reports

7.9.1. Experiments, evaluations and reports are reviewed and approved by the laboratory supervisor or delegate. 7.9.2. Experiments, evaluations and reports are reviewed and approved by the QA manager or delegate.

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