National Association of Testing Authorities, Australia

Measurement Uncertainty Revisited

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National Association of Testing Authorities, Australia

Approaches for estimating MU

Bottom-up approach combines the uncertainties associated with all individual operations of an analytical procedure to calculate a combined uncertainty. Good for physical measurements However Chemical methods are influenced by numerous factors, some positive and some negative, that tend to cancel out.and that often other chemical methods are influenced by factors that overwhelm the weight and volume uncertainties presented in published examples Top-down calculation/estimate using available validation and QC data. (consideration of precision and bias) www.nata.com.au

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Top-down approach
TWO COMPONENTS TO ACCURACY:

Precision; a measure of random error the expected level of agreement between replicate test results

Trueness; a measure of systematic error (bias) how close a test result is to the true result

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EXAMPLE: Determination of Aflatoxin M1 in Milk

Data (total 20 tests) from QC samples analysed with each batch of samples. Milk spiked with Aflatoxin M1 at 2.0 g/L Mean result = 1.74 g/L (87% recovery) Standard deviation, s = 0.144 g/L (8.3% RSD)

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Expression for Combined Uncertainty

Bias (b) = observed result expected result

What is the uncertainty associated with this bias?

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b = - 0.26g/L ub = 0.032
Is this Bias, taking into account the uncertainty associated with it, significant? Is |b| > 2 ub ? Yes
So we need to: (1) Correct for bias as well as consider ub in our estimate of MU, or
(2) Expand our estimate of uncertainty to account for uncorrected bias, or (3) Report the uncertainty as a range
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Option (1) : Correcting for Recovery (bias)

Uncorrected measurement = 1.74 g/L Corrected measurement = 1.74 x 100/ % Rec = 1.74 x 100/87 = 2.00 g/L

(Or corrected measurement = 1.74 + 0.26 = 2.00 g/L)

We still need the uncertainty associated with this Measurement?

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Option (1) : Correcting for Recovery (bias)

= 0.30 g/L
AM1 2.00 0.30 g/L
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Option (2) : Not Correcting for Recovery (bias)

g/L
AM1 1.74 0.56 g/L

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Option (3) Reporting MU as a range

Same calculations as option 2, however distribution is asymmetrical Negative bias Positive bias

x 2uAM1 < x < x + 2uAM1 + |b|

x 2uAM1 - |b|< x < x + 2uAM1

1.74g/L with a range of (1.44 - 2.30) g/L

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Option (1) Option (2)

AM1 2.00 0.30 g/L

AM1 1.74 0.56 g/L
(1.18 2.30)

Option (3)

AM1 = 1.74 (1.44 to 2.30) g/L

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Reality Check
Now that you have estimated the measurement uncertainty is it realistic? Some options for checking: Input from an experienced analyst for that test method Proficiency Testing Program results Horwitz trumpet Publications such as journal papers, websites with MU examples
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Proficiency Testing Program results

Lab code A B C D . . X Median NormIQR Result 17.844 14.1 10 14.1 . . 11.9 13.9 1.97 MU 0.0152 3 5 0.7 . . 1.43 0.50 z-score 2.00 0.10 -1.98 0.10 . . -1.02

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Error normalised - En Ratio

En =

LAB REF U2LABU2REF

En < 1

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Further Work
Now that you have realistic MU what can you do with it? (Besides reporting it to your customers and ensuring you meet their requirements) Establish the critical parameters (using the bottom up approach) for the test method to Improve MU Establish/justify calibration frequencies

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Questions?
Thank you

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