Estimation of measurement uncertainty in chemical analysis

Self-test 10.3

Here you can test your understanding how the uncertainty component accounting for systematic effects can be estimated in practice.

1. Which are the possibilities of estimating the bias component of measurement uncertainty (component that accounts for the systematic effects) of an analytical procedure in your laboratory?

2. The laboratory wants to estimate the bias component of uncertainty of protein determination in different products by the Kjeldahl method. There are two certified reference materials available: Ham with protein content (19.6 ± 0.6) g/100g (k=2, norm) and cheese with protein content (26.3 ± 0.7) g/100g (k=2, norm). The laboratory has carried out four bias determinations with the following results (each found value is found as a mean from a number of parallel measurements):
Reference (g/100g)Found value (g/100g)
26.326.9
26.327.2
19.620.1
19.620.4
Please calculate the bias component of uncertainty (please give 2 or 3 decimals). Absolute uncertainties can be used in this case.

The bias component is found as follows:

10-3-2-vihje1.pngFor finding the RMSbias and u(Cref) the bias values from the individual bias determinations (four altogether) and combined standard uncertainties of the reference materials used for the individual determinations (again, four altogether) have to be combined using the root mean square approach:

10-3-2-vihje1b.png

The individual bias values are found as differences of the lab value and the reference value. The combined standard uncertainties of the reference values can be found by dividing the expanded uncertainties with the coverage factor.

The individual bias values are (all in g/100g): 0.6, 0.9, 0.5, 0.8. The RMSbias found from these data is 0.7176 g/100g (decimal places are deliberately given in excess).

The individual u(Crefi) values are (all in g/100g): 0.35, 0.35, 0.3, 0.3. The u(Cref) found from these data is 0.3260 g/100g (decimal places are deliberately given in excess).

The u(bias) found from these data is 0.7882 g/100g (decimal places are deliberately given in excess). u(bias) is not yet the final uncertainty but rather an interim result for future calculations, so it should not be rounded to 1 or 2 significant digits.

3. Which of the following statements about the previous exercise are true? Please mark the true statements in the tick-boxes.

4. For determining within-lab long-term reproducibility and bias of determination of heavy metals in soil laboratory has a sewage sludge control sample. Sample preparation has been carried out with this sample (by microwave digestion) and the resulting solution is kept in refrigerator and analyzed on all days when determination of heavy metals is carried out. The solution is analyzed twice on the same day and standard deviation is calculated from the two results. These standard deviations are pooled over a time period of approximately one year. This pooled standard deviation is used as estimate of within-lab long-term reproducibility. The absolute differences between the two results are averaged over a time period of one year and the average absolute difference is used as bias estimate.

There are several flaws in the above described approach. Which statements are true?

5. Which of the following issues are important in determining bias?


 

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