Edmund Halsz
Thermo Fisher Scientific
ILAP Meeting
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Definition
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Uncertainty and Error
While doubt about validity arises from error, error and uncertainty
are not the same
The doubt may exist about the exactness of the results, i.e., as a
result of repeatability or reproducibility attributable to time period
factors.
The doubt may exist about the validity of a result attributable to
inappropriate sample collection or handling, to heterogeneity leading
to sub-sampling error or to the presence of analytical bias.
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Parties needing measurement uncertainties
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General requirements for the competence of testing and
calibration laboratories (ISO/IEC 17025-2005)
Testing laboratories need to estimate the measurements
uncertainty
Procedures to estimate measurement's uncertainty
The degree of necessary rigour in an estimate of the uncertainty of
measurement depends on factors such as:
requirements of the testing method
customer demands
narrow limits on which the decision of conformity to a specification is based
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Evaluating Measurement Uncertainty
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U = k u
U = k u
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Potential Sources of Uncertainty in Analytical Measurements
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Quantifying Uncertainty for Chemical Analysis
u (C
j =1
ref )j
u (Cref ) =
1.96 m
u (bias ) = RMSbias + u (Cref ) 2
2
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Some Sources of Uncertainties in AS-AES
1 mm
11s
0s 30s
150s 50s
70s
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Reference Materials to Calibrate AS-AES Instruments
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Uncertainty in Certification of Reference Materials
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Uncertainty in Certification of Reference Materials
Example for steels
BAS (Bureau of Analysed Samples Ltd.):
Before 1996: SM
After 1996:ISO Guide 35; u=t*SM/ n
SM: standard deviation of means (averages); inter-laboratory standard deviation
Brammer Standard Company, Inc.:
uncertainties based on value judgments; no attempt to derive from
exact statistical measurements of imprecision
ECISS (European Committee for Iron and Steel)
SM= (sb2+sW2/4)
CKD:
GUM and ISO Guide 35, U (expanded combined uncertainty with
coverage factor 2-2.5)
ARMI (Analytical Reference Materials International)
Before 1996: Standard deviation using n-1 values
After 1996: Confidence interval ~(1/ 2.5)*SM (1/ 3)*SM
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Uncertainty in Certification of Reference Materials
Example of non-uniform certification uncertainty
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Expressing Uncertainty for AS-AES
Situation today:
Norms and guides: very few examples
Very few published papers
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Bias Uncertainty Evaluation
Calibration a posteriori experiment
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Bias Uncertainty Evaluation
Calibration a posteriori experiment
Uncertainty assessment for LAST calibration with ARL 3460
Uncertainty for each element expressed as single value, being a
constant over the complete calibration range
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Bias Uncertainty Evaluation
Calibration a posteriori experiment
B. Magnusson- Technical Research Institute of Sweden
OES users seminar, Sigtuna, SE, sept. 2004
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Building Uncertainty Budgets
U(method): 2 x interlaboratory
standard deviation,
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Uncertainty in AS-AES
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Proposal for Quantifying Bias Uncertainty in AS-AES
Explanation:
Confidence intervals capture the true value of the regression
function with a user-specified probability, the confidence level, using
the estimated regression function and the associated estimate of the
error
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Confidence Interval
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Proposal to Use Confidence Interval to Express Bias Uncertainty
Ccalculated = a Ccertified + b
1 1 (Cl C ) 2
CI (Cl ) = t ;n k SEE + + n
(C
m n
certified j C )2
j =1
Where:
m: number of replicates for an average
n: number of samples used to build calibration curve
k: total number of coefficients for polynomial and corrections
C : average of all concentrations Ccertified
t: Student factor for probability and n-k degrees of freedom
SEE: Standard Estimate of Error
1 n
SEE = (Ccalculated Ccertified )
2
n k j =1
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Confidence Interval to Express Bias Uncertainty
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Confidence Interval to Express Bias Uncertainty
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Confidence Interval to Express Bias Uncertainty
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Properties of Confidence Interval
Hyperbolic shape
Higher uncertainty at the edges
Minimum absolute uncertainty for C
Curve extension modifies / degrades bias uncertainty
Weighted regression improves uncertainty for localized (low) concentrations
Multiple segments per element line produce saw jaws
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Confidence Interval to Express Bias Uncertainty
Multiple Segments
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Expressing Combined Uncertainty for AS-AES (proposal)
C = Caverage 2u
u = CI (Caverage ) 2 + Sd 2
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Analytical Decision - Product Conformance
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Analytical Decision
Product conformance
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Analytical Decision
Product conformance
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