ESTIMATION OF ANALYTICAL MEASUREMENT UNCERTAINTY

Laboratory Quality and Accreditation Office

Uncertainty Calculator Standard Operating Procedure

TABLE OF CONTENTS PAGE

SCOPE 3
REFERENCES 4
TERMINOLOGY 5
SUMMARY OF METHOD 9
PROCEDURE 12
CALCULATIONS 14
REPORT 23
PRECISION, BIAS, AND QUALITY CONTROL 23
APPENDIX A: GENERAL UNCERTAINTY BUDGET 29
APPENDIX B: EXAMPLE UNCERTAINTY BUDGET 26
APPENDIX C: EXAMPLE SPREADSHEET 28
APPENDIX D: SOFTWARE VALIDATION 31

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1. SCOPE

1.1 This Standard Operating Procedure (SOP) describes the rationale and methodology for
estimating analytical measurement uncertainty using the Quality Control-based Nested
Approach for Estimating Analytical Measurement Uncertainty Spreadsheet. Other
approaches that meet the requirements of ISO/IEC 170215 may also be used to estimate
analytical measurement uncertainty.

1.2 This SOP applies to test methods that are within the scope of ISO/IEC 17025-1999
Standard: General Requirements for the Competence of Testing and Calibration
Laboratories and it is based on the general rules outlined in Guide to the Expression of
Uncertainty in Measurement (GUM). The GUM approach is recommended in ISO/IEC
17025. (17025, 5.4.6.3 Note 3). According to ISO/IEC 17025, a laboratory “shall have
and shall apply procedures for estimating uncertainty of measurement.” (17025,
5.4.6.2) and where appropriate, an estimation of uncertainty must be reported with the
test result. (17025, 5.10.3.1c) This SOP is for use by environmental testing laboratories
in the development and implementation of their quality systems. To be recognized as
competent for carrying out specific environmental tests, this SOP describes the
requirements that a laboratory must successfully demonstrate for the estimation of
analytical measurement uncertainty.

1.3 When estimating analytical measurement uncertainty, all significant components of

uncertainty must be identified and quantified. (17025, 5.4.6.3) Components that affect
analytical measurement uncertainty include sampling, handling, transport, storage,
preparation, and testing. (17025, 5.4.1) Components of uncertainty that do not
contribute significantly to the total uncertainty of the test result can be neglected.
(17025, 5.6.2.2.1)

1.4 Estimation of analytical measurement uncertainty is not required for qualitative tests
with pass/fail or detect/non-detect results. However, decision uncertainty may be

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required by estimating Type I and Type II errors. Certain biological tests, spot tests,
and immunoassay tests are included in this category.

1.5 Estimation of analytical measurement uncertainty is not required for well-recognized

quantitative test methods where the reference method specifies:
1.5.1 bias and precision acceptance limits,
1.5.2 form of presentation of the test result, and
1.5.3 procedure for estimating analytical measurement uncertainty
Certain methods with well-characterized uncertainties are included in this category
(e.g., NIOSH 7400). (17025, 5.4.6.2 Note 2)

1.6 Estimation of analytical measurement uncertainty is required for quantitative test

methods where the estimation of uncertainty is not specified in the method. The QC-
based Nested Approach for Estimating Analytical Measurement Uncertainty
Spreadsheet can be used to estimate analytical measurement uncertainty when Quality
Control data is available. Certain performance-based methods (published regulatory or
consensus methods) are included in this category.

2. REFERENCES

2.1 ISO 17025-1999, General Requirements for the Competence of Testing and Calibration
Laboratories, The International Organization of Standardization (ISO) and the
International Electrotechnical Commission (IEC), December 1999.

2.2 American National Standard for Expressing Uncertainty - U.S. Guide to the Expression
of Uncertainty in Measurement, (US GUM), American National Standards Institute
(ANSI) in 1997.

2.3 ISO Guide to the Expression of Uncertainty in Measurement (GUM), 1993.

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2.4 Quality Assurance of Chemical Measurements, Taylor, John Keenan, Lewis Publishers,
1987.

2.5 Environmental Analytical Measurement Uncertainty Estimation: Nested Hierarchical

Approach, Defense Technical Information Center #ADA396946, Ingersoll, William
Stephen, 2001.

2.6 QC-based Nested Approach for Estimating Measurement Uncertainty Spreadsheet,

Microsoft Excel Spreadsheet, Ingersoll, William Stephen, 2002.

3. TERMINOLOGY

3.1 Acceptance limits- data quality limits specified by the test method or generated by the
laboratory.

3.2 Accuracy- the agreement of a single analytical measurement result to a reference value.
Accuracy is a combination of random and systematic components. Random
components affect the precision of the test result and systematic components affect the
bias of the test result. See bias and precision.

3.3 “Backing-out”- the rearrangement of the “square root-of-the-sum-of-the-squares”

equation to solve for an unknown component standard uncertainty.

3.4 Bias- the deviation of the mean of replicate analytical measurements from a reference
analyte concentration. Relative bias is represented by analytical measurement mean
minus the reference analyte concentration and the difference divided by the reference
analyte concentration. See accuracy and precision.

3.5 Combined standard uncertainty- the standard uncertainty of the analytical measurement
result that is the sum in quadrature (square-root-of-the-sum-of-the-squares) of the
component standard uncertainties.

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3.6 Coverage factor- the numerical factor used as a multiplier of the combined standard
uncertainty to expand the uncertainty corresponding to a specific level of confidence.
The Student’s t-distribution is used for determining the coverage factor.

3.7 Duplicate samples- two samples taken from the same population and carried through
certain stages of sampling and testing. Duplicate sample include field co-located
duplicate samples, field-split duplicate samples, and laboratory duplicate subsamples.

3.8 Expanded uncertainty- the quantity defining an interval enveloping the analytical
measurement that captures a large fraction of the distribution of analyte concentrations
that could be attributable to the quantity measured. The combined standard uncertainty
is multiplied by the coverage factor to calculate the expanded uncertainty.

3.9 Field samples- sampled and tested to represent the large-scale population distribution.
Sampling usually includes primary sampling stage where the sample is extracted from
the sample location and secondary sampling stage where the collected sample is
reduced to a subsample after physical preparation such as milling and blending.
Testing usually includes chemical preparation such as extraction and separation, and
instrumental analysis.

3.10 Field co-located duplicate samples- samples collected near (0.5 to 3 feet) the field
sample. Co-located duplicate samples are used to quantify the variance of the sampling
strategy, sample collection, preparation, and testing stages.

3.11 Field-split duplicate sample- a field sample homogenized in the field and split into two
or more portions that are sent to the laboratory as separate samples. Field-split
duplicate samples are used to quantify the variance of the sample collection,
preparation, and testing stages.

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3.12 Hypothesis testing- the formulation of a decision such as not rejecting the null
hypothesis, or rejecting the null hypothesis and accepting the alternative hypothesis.
An example of hypothesis testing is that the null hypothesis (H0) is H0 > the Action
Level (AL) and the alternative hypothesis (HA) is HA < AL.

3.13 Independent Calibration Verification (ICV)- a standard solution used to verify the
calibration curve derived from a source independent of the instrument calibration
standard. The ICV is use to quantify second source standard variance and bias. Also
called the Quality Control Sample.

3.14 Instrument Calibration Standard (ICS)- a reference material used to standardize an

analytical instrument.

3.15 Instrument Performance Check (IPC)- the analyses of one of the ICSs to verified initial
and continuing calibration. The IPC is used to quantify the instrumental testing
repeatability variance and bias.

3.16 Laboratory control sample (LCS)- a clean-matrix reference material with an established
analyte concentration derived from a source independent of the instrument calibration
standard. The LCS is carried through the entire chemical preparation and testing
procedures. The LCS is used to quantify the variance and bias of the chemical
preparation and instrumental testing stages without matrix interference. Same a
laboratory fortified blank. Also called a Laboratory fortified blank (LFB).

3.17 Laboratory duplicate subsample- a portion of the collected sample that is carried
through the chemical preparation and testing. The Laboratory duplicate subsample is
used to quantify the variance of the chemical preparation and instrumental testing
stages with matrix interferences.

3.18 Matrix spiked sample- a subsample spiked with reference material with an established
concentration derived from a source independent of the instrument calibration standard.

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Matrix spiked sample are carried through the chemical preparation and testing stages.
Matrix spiked samples are used to quantify the variance and bias of the chemical
preparation and testing stages with matrix interference. Also called a Laboratory
fortified matrix (LFM).

3.19 Precision- the dispersion of replicate analytical measurements. Precision is represented

by the variance, relative variance, standard deviation, relative standard deviation, or
range. See accuracy and bias.

3.20 QC-based Nested Approach Spreadsheet- the Microsoft Excel spreadsheet used to
automatically calculate analytical measurement uncertainty.

3.21 Quality Assurance (QA)- the program used to establish confidence in the quality of data
generated by the laboratory. Quality Control is a component of Quality Assurance.

3.22 Quality Control (QC)- the program that includes planning, implementing, monitoring,
assessing, and adjusting processes that the laboratory uses to measure its capability and
performance in generating quality data.

3.23 Quality Control Chart- a graph of analytical measurement results for a specific QC
standard plotted sequentially with upper and lower control limits (±3σ). A central line
that is the best estimate of the average variable plotted, and upper and lower warning
limits (±2σ) are usually included in the Quality Control Chart.

3.24 Reference material- a traceable standard with an established analyte concentration.

3.25 Replicate analytical measurements- two or more results representing the same sample
parameter. Replicate analytical measurements are used to quantify the analytical
measurement repeatability precision.

3.26 Replicate samples- two or more samples representing the same population parameter.

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3.27 Standard uncertainty- the analytical measurement uncertainty expressed as a standard

deviation. The relative standard deviation represents the relative standard uncertainty.

3.28 Type I error- error that results in hypothesis testing for rejecting the null hypothesis
when it should not be rejected.

3.29 Type II error- error that results in hypothesis testing for not rejecting the null
hypothesis when it should be rejected.

3.30 Type A evaluation of uncertainty- the method of evaluation of uncertainty by the

statistical analysis of a series of test results.

3.31 Type B evaluation of uncertainty- the method of evaluation of uncertainty by means

other than statistical analysis.

3.32 Uncertainty- the parameter associated with the analytical measurement results that
characterizes the dispersion of the values that could be reasonable attributed to the
quantity measured.

3.33 Uncertainty interval- the range of analyte concentrations that an analytical

measurement could represent at a specified level of confidence. The relative standard
deviation is used to represent the relative standard uncertainty in the QC-based Nested
Approach.

4. SUMMARY OF METHOD

4.1 The concept of analytical measurement uncertainty is widely recognized among

analytical chemists. Replicate preparation and testing of a sample generates a range of
results. This variability of results represents the analytical measurement uncertainty.

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4.2 This SOP includes requirements and information for assessing competence, and for
determining compliance by the organization or accrediting authority granting the
accreditation or approval. Accrediting authorities may use this SOP in assessing the
competence of environmental laboratories.

4.3 If more stringent standards or requirements are included in a mandated test method or
by regulation, the laboratory shall demonstrate that such requirements are met. If it is
not clear which requirements are more stringent, the standard from the method or
regulation must be followed.

4.4 Samples are routinely prepared and tested only once and replicate preparation and
testing of environmental samples is not practical. However, any rigorous statistical
determination of uncertainty based on a single test measurement is not possible. “There
is no statistical basis for a confidence level statement of one measurement unless
supported by a control chart or other evidence of statistical control.” (Taylor, J.K., 28).

4.5 The estimation of analytical measurement uncertainty is formalized in the U.S. Guide to
the Expression of Uncertainty in Measurement, (US GUM), published by American
National Standards Institute (ANSI) in 1997. The US GUM is the ANSI adoption of
the ISO Guide to the Expression of Uncertainty in Measurement (GUM), published in
1993, and it establishes general rules to evaluate and express uncertainty for
quantitative analytical measurements.

4.6 The general rules outline the process for identifying components of uncertainty,
quantifying component standard uncertainty, combining standard uncertainties,
expanding combined uncertainty, and reporting uncertainty.

4.7 The QC-based Nested Approach for Estimating Analytical Measurement Uncertainty
Spreadsheet was developed to automate estimation of analytical measurement
uncertainty.

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4.8 Readily available laboratory Quality Control Chart data can be used to estimate the
analytical measurement uncertainty for single test results. Using the laboratory
generated Quality Control Limits, a mathematical model can be constructed to
systematically “back-out” component uncertainties.

4.9 Laboratory-generated quality control data is used to populate a Microsoft Excel

spreadsheet that automatically partitions sources of uncertainty, quantifies uncertainty
for each component, and calculates the expanded uncertainty with optional bias
correction. A histogram is generated to identify significant and negligible sources of
uncertainty.

4.10 The steps for estimating uncertainty are incorporated into the following conceptual
algorithm:
4.10.1 Specify the analyte of interest that is to be quantified
4.10.2 Identify the sources of analytical measurement uncertainty
4.10.3 Quantify the components of analytical measurement uncertainty
4.10.4 Calculate the combined and expanded analytical measurement uncertainty
4.10.4.1 The first step is to state what is to be quantified (the analyte of
interest). A summary of the chemical preparation and testing methods
is included.
4.10.4.2 The second step is to identify the sources of analytical measurement
variability or uncertainty. The sources of uncertainty can be
partitioned into the following general components:
Large-scale site population variability
Small-scale sample location variability
Field sampling and laboratory subsampling variability
Sample chemical preparation variability
Sample test measurement variability
An Uncertainty Budget can be developed to tabulate analytical
uncertainty.

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4.10.4.3 The third step is to quantify the components of analytical measurement

uncertainty. A frequent approach to evaluating and expressing
uncertainty of a measurement is the use of the statistical concept of the
confidence interval. The confidence interval is the range of results that
reasonably captures the analyte concentration with a specified
probability. When the confidence interval is constructed by the
statistical analysis of replicate results, the approach is a Type A
evaluation of standard uncertainty (US GUM, Section 4.2). When the
confidence interval is not constructed by statistical analysis of
replicate results, the approach is a Type B evaluation of standard
uncertainty (US GUM, Section 4.3).
For statistical analysis (Type A evaluation), the standard deviation is
calculated for the percent deviation (relative bias) for each quality
control standard or sample. The standard deviation of analytical
measurement results represents the standard uncertainty.
4.10.4.4 The fourth step is to combine the individual uncertainties and then
apply a “coverage factor” which is chosen on the basis of the desired
level of confidence to be associated with the interval around the
measurement. Coverage factors are usually 2 or 3, corresponding to
intervals with levels of confidence of approximately 95% and 99%,
respectively.

5 PROCEDURE

5.1 If the reference method results in qualitative or semi-quantitative measurements, then

the report result is an estimate and analytical measurement uncertainty is not quantified.

5.2 If the reference method specifies the procedure for estimation of analytical
measurement uncertainty, then follow the reference method procedure.

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5.3 If the reference method does not specify the procedure for estimating analytical
measurement uncertainty, then use this procedure.

5.4 The analytical measurement uncertainty for each quantitative field of testing must be
estimated per analyte of interest, sample matrix, and analytical technology.

5.5 The automated calculation of laboratory analytical measurement uncertainty requires

the following Quality Control standards:
5.5.1 Instrument Calibration Standard or Instrument Performance Check
5.5.2 Independent Calibration Verification or Quality Control Sample
5.5.3 Laboratory Control Sample or Laboratory Fortified Blank
5.5.4 Matrix Spiked Sample or Laboratory Fortified Matrix

5.6 Acquire twenty analyses for each of the QC standards described in Section 6.5. Twenty
analyses are required for the automated calculation of analytical measurement
uncertainty. These data may be acquired from Quality Control Charts.

5.7 Subtract the reference analyte concentration from the analytical measurement result and
divide the difference by the reference analyte concentration.

5.8 Multiply relative error by 100 to calculate the percent deviation. The percent deviation
is relative deviation from the reference analyte concentration multiplied by 100. Input
the percent deviation data into the QC-based Nested Approach Spreadsheet in the
appropriate column. See Appendix A for the mathematical algorithm used to calculate
analytical measurement uncertainty.

5.9 Input the following information into the spreadsheet:

5.9.1 Analyte, matrix, and technology
5.9.2 Confidence level
5.9.3 Analytical measurement
5.9.4 Units

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5.10 The confidence level is usually 95%, but other confidence levels can be selected
according to client requirements. The QC-based Nested Approach Spreadsheet
presents the confidence interval associated with the analytical measurement. Bias-
correction is also presented for comparison. The bias-correction is based on the
recovery efficiency of the laboratory chemical preparation and instrumental analysis
components.

5.11 Representative sampling and subsampling eliminates sampling bias and imprecision
associated materialization error.

5.12 The Uncertainty Budget of the general analytical measurement components of

uncertainty can be tabulated from the QC-based Nested Approach Spreadsheet
histogram. An example Uncertainty Budget is presented in Appendix B.

5.13 The Uncertainty Budget of specific analytical measurement components of uncertainty

can be tabulated by itemizing sources of uncertainty that may or may not affect total
analytical measurement uncertainty. An example Uncertainty Budget with specific
sources of uncertainty is presented in Appendix C.

5.14 An example spreadsheet is presented in Appendix D with copper in wastewater by ICP

quality control results.

5.15 The data from Appendix D is used in Appendix E to validate the QC-based calculator
spreadsheet software.

6. CALCULATIONS

A.1 The mathematical model for uncertainty propagation is the Taylor series expansion.
A.1.1 The Equation A.1 is the Taylor series expansion for determining the estimated
combined variance (uc2):
n n −1 n
uc2 (y) = ∑
i =1
(∂ f/∂ xi)2 u2(xi) +2 ∑ ∑
i =1 j = i +1
(∂ f/∂ xi)(∂ f/∂ xj )u(xi,, xj)

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Equation A.1

A.1.2 The Taylor series expansion equation can be simplified to calculate the combined
standard uncertainty in Equation A.2:
n n −1 n
u2c(y) = ∑i =1
[c1u(x1)]2 + [c2u(x2)]2 +…+[cn u(xn)]2 + 2 ∑ ∑
i =1 j = i +1
cicju(xi)u(xj)rij

Equation A.2
The symbol ci represents ∂ f /∂ xi , symbol rij represents the correlation of xi and
xj. The second term is the co-variance associated with xi and xj . The estimated co-
variances or the estimated correlation coefficients are required if the variable xi
and xj components are dependent. If the variable xi and xj are independent, then
the co-variant term is equal to zero and the co-variant term drops out of the
equation. The combined standard uncertainty estimate uc uses the quadrature
equation or “square-root-sum-of-squares” method for combining the standard
uncertainties. This equation is the law of propagation of uncertainty.
A.1.3 There two primary approaches for applying the law of propagation of uncertainty:
additive and multiplicative.
A.14 If y is an additive function of x1 , x2 ,…xn , then Equation A.3 is used:

u ( y) = [c u ( x )] + [c2 u ( x2)]2 + ... + [ck u ( xn)]2

2
c 1 1

Equation A.3
A.1.5 If y is a multiplicative function of x1 , x2 ,…xn, then Equation A.4 is used to
determine the relative combined standard uncertainty uc,r where y ≠ 0 and |y| is
the absolute value of y:

u c,r
( y ) = [u c ( y )] / | y |= [c1 u ( x1) / x1] 2 + [c2 u ( x2) / x2] 2 + ... + [ck u ( xn) / xn] 2

Equation A.4
A.1.6 The QC-based Nested Approach Spreadsheet is based on multiplicative
combination of component efficiencies; therefore Equation A.5 is used to estimate
analytical measurement uncertainty.
A.2 The QC-based Nested Approach for Estimating Analytical Measurement Uncertainty is
an automated system for calculating analytical measurement uncertainty.

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A.2.1 The data inputted into the Microsoft Excel QC-based Nested Approach
Spreadsheet are the percent deviation of the Quality Control Chart data.
A.2.2 The ICS, ICV, LCS, and MIS standards are used to calculate analytical
measurement uncertainty for the laboratory.
A.2.3 Calculate the percent deviation for ICS, ICV, LCS and MIS quality control data
(that have a reference value) by equation A.5.1 and calculate the percent deviation
for FDS and CLS quality control data (that don’t have a reference value) by
equation A.5.2.
A.2.3.1Calculate the percent deviation (%Di) for each individual ICS, ICV, LCS, and
MIS result by subtracting the reference analyte concentration (T) from the each
individual analytical measurement (Xi), dividing the difference by T, and
multiplying the quotient by 100 in Equation A.5:
 (X − T )
% Di =  i  * (100 )
 T 
Equation A.5.1
A.2.3.2When data for field duplicate samples (FDS) and co-located duplicate samples
(CLS) are available, calculate the percent deviation (%Di) or relative percent
difference (RPD) for the FDS and the CLS by subtracting the second duplicate
analytical measurement (X2) from the first duplicate analytical measurement (X1),
dividing the difference by the average of the first and second duplicate samples,
multiplying the quotient by 100, and taking the absolute value of the result in
Equation A.6:

 X 1 − X 2   100 
% Di =  *  
(
 1 X + X 2 ) 2   1 
Equation A.5.2

A.2.4 On page 1 input the %D of 20 Quality Control analytical measurements for the
ICS, ICV, LCS, MIS, FDS, and CLS in the appropriate column of the
spreadsheet.
A.2.5 On page 1, when the data is inputted, the spreadsheet automatically calculates:
Relative standard uncertainty (ur) of the 20 (n) individual %Di results

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Average bias (% B ) based on the average (% D ) of the n individual %Di

results
Average recovery (% R ) of the n individual %Di results
The following equations are used to calculate:

% B in Equation A.6

% R in Equation A.7
ur in Equation A.8
 % D1 + % D2 + ... + % Dn 
% B = %D =  
 n 
Equation A.6
(
% R = 100 + % D )
Equation A.7
1/ 2
 n 
( )
2
 ∑ % Di − % D 
 
u r =  i =1 
n −1
 
 
 
Equation A.8
A.2.6 On page 2, when the data is inputted, the spreadsheet automatically calculates
standard uncertainty (s or ur), recovery, and systematic error for components:
IME – Intrinsic Measurement Effect
SPE – Spike Preparation Effect
PME – Preparation Method Effect
MIE – Matrix Interference Effect
SCE – Sample Collection Effect
SLE – Sample Location Effect
A.2.7 The relative standard deviation of the Instrumental Calibration Standard (ICS)
represents the uncertainty associated with instrumental repeatability Intrinsic
Measurement Effects (IME) in Equation A.9.
ICS
ur = IMEur

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Equation A.9
A.2.8 The relative standard deviation of the Independent Calibration Verification (ICV)
is a combination of IME and the Spike Preparation Effects (SPE) in Equation
A.10.

ICV u r = ( IME u r ) 2 + ( SPE u r ) 2

Equation A.10
Equation A.10 is rearranged to “back-out” the SPE standard uncertainty from the
known ICV and IME standard uncertainties:

SPE u r = ( ICV u r ) 2 − ( IME u r ) 2

A.2.9 The relative standard deviation of the Laboratory Control Sample (LCS) is a
combination of IME, SPE, and the Preparation Method Effects (PME) in Equation
A.11.

LCS u r = ( IME u r ) 2 + ( SPE u r ) 2 + ( PME u r ) 2

Equation A.11
Equation A.11 is rearranged to “back-out” the PME standard uncertainty from the
known ICV, IME, and SPE standard uncertainties:

PME u r = ( LCS u r ) 2 − ( ( IME u r ) 2 + ( SPE u r ) 2 )

A.2.10 The relative standard deviation of the Matrix Spiked Sample (MIS) is a
combination of IME, SPE, PME, and the Matrix Interference Effects (MIE) in
Equation A.12.

MIS u r = ( IME u r ) 2 + ( SPE u r ) 2 + ( PME u r ) 2 + ( MIE u r ) 2

Equation A.12
Equation A.12 is rearranged to “back-out” the MIE standard uncertainty from the
known MIS, IME, SPE, and PME standard uncertainties:

MIE u r = ( MIS u r ) 2 − ( ( IME u r ) 2 + ( SPE u r ) 2 + ( PME u r ) 2 )

A.2.11 The relative standard deviation of the Field-split Duplicate Sample (FSR) is a
combination of IME, PME, MIE, and the Sample Collection and Subsampling
Effects (SCE) in Equation A.13.

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FSR u r = ( IME u r ) 2 + ( SCE u r ) 2 + ( PME u r ) 2 + ( MIE u r ) 2

Equation A.13
Equation A.13 is rearranged to “back-out” the MIE standard uncertainty from the
known FSR, IME, PME, and MIE standard uncertainties:

SCE u r = ( FSR u r ) 2 − ( ( IME u r ) 2 + ( PME u r ) 2 + ( MIE u r ) 2 )

A.2.12 The relative standard deviation of the Field Co-located Duplicate Sample (CLR)
is a combination of IME, PME, MIE, SCE, and the small-scale Sample Location
Effects (SLE) in Equation A.14.

CLR u r = ( IME u r ) 2 + ( SCE u r ) 2 + ( PME u r ) 2 + ( MIE u r ) 2 + ( SLE u r ) 2

Equation A.14
Equation A.14 is rearranged to “back-out” the SLE standard uncertainty from the
known CLR, IME, PME, MIE and SCE standard uncertainties:

SLE u r = (CLR u r ) 2 − ( ( IME u r ) 2 + ( PME u r ) 2 + ( MIE u r ) 2 + ( SCE u r ) 2 )

A.2.13 The large-scale natural variability of the analyte distribution inherent in the
sampling site is not measured directly, but is derived by a process of sampling and
testing. This process confounds the natural site population parameter mean and
standard deviation. The relative standard deviation of the collection of Site Field
Samples (SFS) is a combination of IME, PME, MIE, SCE, SLE, and the large-
scale Sampling Site Effects (SSE) in Equation A.15.

SFS u r = ( IME u r ) 2 + ( SCE u r ) 2 + ( PME u r ) 2 + ( MIE u r ) 2 + ( SLE u r ) 2 + ( SSE u r ) 2

Equation A.15
Equation A.15 is rearranged to “back-out” the SSE standard uncertainty from the
known SFS, IME, PME, MIE, SCE, and SLE standard uncertainties:

SSE u r = ( SFS u r ) 2 − ( ( IME u r ) 2 + ( PME u r ) 2 + ( MIE u r ) 2 + ( SCE u r ) 2 + ( SLE u r ) 2 )

A.2.14 The spreadsheet has a logic test to make the calculations more robust. If a
component in the logic hierarchy has a standard uncertainty less than the standard
uncertainty of a component lower in the logic hierarchy, then the spreadsheet
reports zero for the higher component.

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A.2.15 The component recovery ( % R IME ) for IME is calculated by using Equation A.16.
% R IME = 100 + % D ICS
Equation A.16
A.2.16 The component recovery ( % R SPE ) for SPE is calculated by using Equation A.17.

(
 100 + % D ICV
% R SPE = 
) 
 ( % R IME / 100 ) 
Equation A.17
A.2.17 The component recovery ( % R PME ) for PME is calculated by using Equation A.18.

% R PME = 
(
100 + % D LCS ) 

( )(
 % R IME / 100 % R SPE / 100 ) 

Equation A.18
A.2.18 The component recovery ( % R MIE ) for MIE is calculated by using Equation A.19.

% R MIE = 
(
100 + % D LCS ) 

( )( )(
 % R IME / 100 % R SPE / 100 % R PME / 100 ) 

Equation A.19
A.2.19 The component systematic error ( % B IME ) for IME is calculated by using
Equation A.20.
(
% B IME = % R IME − 100 )
Equation A.20
A.2.20 The component systematic error ( % B SPE ) for SPE is calculated by using Equation
A.21.
(
% B SPE = % R SPE − 100 )
Equation A.21
A.2.21 The component systematic error ( % B PME ) for PME is calculated by using
Equation A.22.
(
% B PME = % R PME − 100 )
Equation A.22
A.2.22 The component systematic error ( % B MIE ) for MIE is calculated by using
Equation A.23.

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Uncertainty Calculator Standard Operating Procedure

(
% B MIE = % R MIE − 100 )
Equation A.23
A.2.23 The analyst must select from the menu and input the percent confidence. The
following table (Table A.1) is a list of available confidence levels with
corresponding coverage factors based on 20 analytical measurements.

TABLE A.1: CONFIDENCE LEVELS AND COVERAGE FACTORS

Confidence Level Two-Tailed Distribution Coverage Factor
(Percent Confidence) (Student’s t-Value for 19 Degrees of Freedom)
80 1.328
90 1.729
95 2.093
99 2.861

A.2.24 After selection of the confidence level, the spreadsheet automatically presents the
coverage factor and calculates the Relative Analytical Measurement Uncertainty
and the Relative Systematic Error.
A.2.25 The combining relative standard uncertainty in percent for routine single test
RST
measurements ( ur) is a combination of IME, PME, and MIE in Equation A.24.
RST u r = ( IME u r ) 2 + ( PME u r ) 2 + ( MIE u r ) 2
Equation A.24
A.2.26 The combined standard uncertainty is expanded to the specified confidence level
RST
by multiplying the ur by the appropriate coverage factor.
A.2.27 The combined relative bias in percent for the routine single test measurements
(% B ) is a combination of IME, PME, and MIE in Equation A.25.
RST

%B = 100 * ( ( (% R
RST / 100 )(% R
IME / 100 )(% R / 100 ) ) − 1 )
PME MIE

Equation A.25

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Uncertainty Calculator Standard Operating Procedure

A.2.28 On page 3 the analyst must enter the analytical measurement and the units of the
analytical measurement.
A.2.29 The spreadsheet automatically calculates and presents the uncertainty interval
expanded to the specified level of confidence for the test result. The calculation of
the confidence interval (CI) for the analytical measurement result (Cm) is
presented in Equation A.26.
CI = Cm ± (Cm)*(k* RSTur)
Equation A.26
A.2.30 The spreadsheet automatically calculates and presents the bias corrected results
(CmBC) and the bias-corrected confidence interval (CIBC) expanded to the specified
confidence level for the test result in Equations A.27a and A.27b.
 Cm 
CmBC =  
((
 100 + % B RST ) )
/ 100 
Equation A.27a
CIBC = CmBC ± (CmBC)*(k* RSTur)
Equation A.27b

7. REPORT

7.1 Documentation of a analytical measurement may require the following:

7.1.1 Description of the methods used to calculate the measurement result and
estimation of analytical measurement uncertainty
7.1.2 Uncertainty Budget of uncertainty components
7.1.3 Correction factors used to normalize (correct for bias) the data
7.1.4 Report the analytical measurement result with estimated expanded uncertainty
and the level of confidence

8 PRECISION, BIAS, AND QUALITY CONTROL

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Uncertainty Calculator Standard Operating Procedure

8.1 The estimation of analytical measurement is an integral component of the Quality

Assurance-Quality Control system. “One of the prime objectives of quality assurance
is to evaluate measurement uncertainty.” (Taylor, J.K., 10)

8.2 A component of Quality Control is laboratory generated Quality Control Charts. The
use of the QC-based Nested Approach Spreadsheet is based on the bias and precision
limits of Quality Control Charts.

8.3 Quality Control Charts must represent the laboratory’s capability and performance, and
the analytical measurement system must have a stable pattern of variation. “Until a
measurement operation has attained a state of statistical control, it cannot be regarded
in any logical sense as measuring anything at all.” (Taylor, J.K., 13)

8.4 The QC-based estimation of analytical measurement uncertainty per analyte, matrix,
and technology must be calculated when Quality Control Charts are updated. Usually
Quality Control Charts are updated annually or when there is a major change in primary
analytical personnel, analytical instrumentation, or analytical procedures.

8.5 Though it is recognized that other sources of uncertainty contribute to total analytical
measurement uncertainty, the laboratory is usually only responsible for reporting
estimations of uncertainty for the analysis components of the laboratory. If the
laboratory has access to field-split duplicates data or field co-located duplicate data,
then sample collection and subsampling, and sampling strategy components can be
quantified.

8.6 Each analyst is responsible for calculating estimations of uncertainty and Quality
Control assessment of the reasonableness of the calculations. The automated Microsoft
Excel spreadsheet (QC-based Nested Approach for Estimating Analytical Measurement
Uncertainty) calculates the analytical measurement uncertainty based on Quality
Control Chart data.

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Uncertainty Calculator Standard Operating Procedure

8.7 The person responsible for Quality Assurance must review analytical measurement
uncertainty calculations at least annually. The estimation of analytical measurement
uncertainty must be uniform and consistent to ensure data quality and data
comparability

APPENDIX A: GENERAL UNCERTAINTY BUDGET

The general components of sampling and testing that are sources of analytical measurement
uncertainty are tabulated in the following table (Table A-1).
TABLE A-1: SOURCES OF UNCERTAINTY
Uncertainty Sources Source Analytical Sample Analytical
Symbol Sample Symbol
Intrinsic IME Instrument Calibration Standard ICS
(Instrumental)
Measurement Effects
Spike Preparation SPE Initial Calibration Verification Standard ICV
Effects

Preparation Method PME Laboratory Control Sample LCS

Effects

Matrix Interference MIE Matrix Interference Sample MIS

Effects Matrix Spike/ Duplicate Sample MS/MSD

Sample Collection SCE Field Replicate (Duplicate) Sample FSR

Effects (Collected from same location and during same
sampling event time)

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Uncertainty Calculator Standard Operating Procedure

Sample Location SLE Co-Located (Same Location) Sample CLR

Effects (Collected 0.5 – 3 feet away from field sample)

Sampling Site SSE Site field sample collected from the environmental SFS
Population Effects site for the study

An example of general uncertainty budget components of sampling and testing that contribute
the analytical measurement are presented in the follow table (Table A-2).
TABLE A-2: GENERAL UNCERTAINTY BUDGET

Component Symbol Relative Probability Distribution Sensitivity Relative

Standard Coefficient Uncertainty
Uncertainty Contribution
Intrinsic IME 2% Normal 1 1
Instrumental
Measurement
Effects
Laboratory PME 4% Normal 1 2
Preparation Method
Effects
Sample Matrix MIE 6% Normal or Lognormal 1 3
Interference Effects

Sample Collection SCE 8% Normal or Lognormal 1 4

and Subsampling
Effects
Sampling Strategy SSE 9% Normal or Lognormal 1 4.5
Effects

Sampling Site Media SME 14% Normal or Lognormal 1 7

Contamination
Effects

APPENDIX B: EXAMPLE UNCERTAINTY BUDGET FOR METHOD 3050B

Uncertainty Source Uncertainty Interval Evaluation Distribution
(99.7% CL) Type
Weighing-Boat Weight 5 +/-0.05 g Type A Normal
(Top Loader Balance)
Sample Weight Wet (Tared) 996 +/-10 g Type A Normal
(Top Loader Balance)
Drying Temperature 30 +/-4 o C Type B U-shaped
(Thermometer)
Drying Time 24 +/- 2 hours Type B Rectangular
(Analog Clock)
Particle Size Reduction - #10 sieve 2 mm 1+/- 1 mm Type B Triangular
(Milling Machine)
Homogenization 30+/-2 rpm Type B Triangular
(Tumbler Blending Machine)
Tumbler Time 18+/-2 hours Type B Rectangular
(Analog Clock)
Weight of the Dried Sample + Boat Dry 664 +/- 7 g Type A Normal
(Top Loader Balance)
Weighing-Boat Weight 1+/-0.001 g Type A Normal
(Analytical Balance)
Weight of the Subsample (Tared) 2+/-0.002 g Type A Normal

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Uncertainty Calculator Standard Operating Procedure

(Analytical Balance)
Quantitative Transfer Efficiency 99+/-1% Type B Triangular
(From Weighing-Boat to Beaker)
Spike Volume 0.5 +/- 0.005 mL Type A Normal
(Eppendorf Pipette)
Spike Concentration 995 +/- 10 mg/L Type B Rectangular
(Manufacture’s Reagent Purity)
Hot-Plate/Hot-Block/Microwave 95 +/-5 o C Type B U-shaped
Digestion Temperature (Thermometer)
Extraction Time 4.75+/-0.25 hours Type B Rectangular
(Analog Clock)
Nitric Acid Volume 10 +/- 1 mL Type B Triangular
(Transfer Pipette)
Nitric Acid Concentration 69.5 +/- 0.5 % Type B Rectangular
(Manufacture’s Reagent Purity)
Hydrogen Peroxide Volume 10+/-3 mL Type B Triangular
(Transfer Pipette)
Hydrogen Peroxide Concentration 30.5+/-1.5% Type B Rectangular
(Manufacture’s Reagent Purity)
Hydrochloric Acid Volume 10+/-1 mL Type B Triangular
(Transfer Pipette)
Hydrochloric Acid Concentration 36.5+/-0.5% Type B Rectangular
(Manufacture’s Reagent Purity)
Extraction Efficiency 96+/-2% Type B Triangular
(Matrix Interference)
Quantitative Transfer Efficiency 99.5+/-0.5% Type B Triangular
(From Beaker to Graduated Cylinder)
Dilution Volume 100+/-3 mL Type A Normal
(Graduated Cylinder)

EXPLANTIONS OF DISTRIBUTIONS FOR METHOD 3050B

Normal Distribution

The normal distribution is usually determined statistically. The normal distribution is based on
the central limit theorem where random sampling results in a normal distribution of data
regardless of the underlying distribution of the quantity measured.

S = a/3 or approximately 0.33 a

Where S is the standard deviation and a is ½ the range of values.

Triangular Distribution

The triangular is more conservative than normal. The triangular is used when the variation limits
are known (lowest and highest), and it is known that it is a better probability (most likely) of
finding values close to the mean value that further away from it.

S = a/(6)0.5 or approximately 0.41 a

Rectangular Distribution

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Uncertainty Calculator Standard Operating Procedure

Rectangular is more conservative than the triangular. The upper and lower bounds of range of
data is estimated, but the distribution is not known so all results are assumed to be equally likely.
For example, the throw of a dice has a rectangular distribution. 1, 2, 3, 4, 5,and 6 are equally
likely and the probability is 1/6 or 0.167 that 1 to 6 will occur. There is a zero probability that <1
or >6 will occur. It is often used when information is derived from calibration certificates and
manufacturer’s specifications.

S = a/(3)0.5 or approximately 0.58 a

U-shaped Distribution (Sine Wave)

U-shaped is more conservative than rectangular and the U-shaped returns a higher equivalent
standard deviation value for the same variation width, +/- a. U-shaped distribution is not as rare
as it seems. Cyclic events, such as temperature of a hot plate, oven, or furnace, often yield
uncertainty contributors that fall into this sine-wave pattern. Another example is the power cycle
of a microwave digestion system. If we assume that the amplitude of the signal is sinusoidal,
the distribution for incident voltage is the U-shaped distribution. There is a better probability of
finding values close to the variation limits than around the mean value.

S = a/(2)0.5 or approximately 0.71 a

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Uncertainty Calculator Standard Operating Procedure

APPENDIX C: QC-BASED NESTED APPROACH FOR ESTIMATING ANALYTICAL

MEASUREMENT UNCERTAINTY EXAMPLE SPREADSHEET

C-1: Page 1

C1.1 The analyte of interest, sample matrix, and analytical technology is entered as
“Copper in Wastewater by ICP”.

C1.2 For the ICS, ICV, LCS, and MIS, 20 replicate analytical measurement results are
entered.

QC-based Nested Approach for Estimating Analytical Measurement Uncertainty Page 1

What are the analyte, matrix, and technology? Copper in Wastewater by ICP
Enter 20 replicate results for the following quality control samples as relative deviation (%):
ICS - Instrument calibration standard
ICV - Second source calibration verification standard
LCS - Laboratory control sample
MIS - Matrix interference sample (matrix spike, organic surrogate, radiochemical tracer)
FDS - Field-split duplicate sample
CLS - Co-located duplicate sample

ICS ICV LCS MIS FDS CLS

1.1 0.5 4.0 12.0 0.0 0.0
0.8 0.1 0.5 1.4 0.0 0.0
0.4 1.0 1.5 8.0 0.0 0.0
2.0 1.2 1.7 3.7 0.0 0.0
1.0 0.2 0.1 12.0 0.0 0.0
1.2 0.4 2.2 0.4 0.0 0.0
1.7 1.2 0.4 3.6 0.0 0.0
3.7 0.9 0.3 0.1 0.0 0.0
1.1 0.1 0.5 2.7 0.0 0.0
3.1 1.3 15.0 17.0 0.0 0.0
2.0 0.9 20.0 30.0 0.0 0.0
0.7 1.0 0.4 3.7 0.0 0.0
0.4 2.0 4.0 1.5 0.0 0.0
0.9 0.2 0.6 5.0 0.0 0.0
1.4 1.0 1.5 1.4 0.0 0.0
1.9 1.4 5.0 20.0 0.0 0.0
2.0 1.5 24.0 3.5 0.0 0.0
1.5 1.7 3.0 5.0 0.0 0.0
1.6 3.0 13.0 -24.0 0.0 0.0
1.1 3.1 11.0 -13.0 0.0 0.0
Std. Dev. 0.84 0.85 7.2 11.1 0.0 0.0
Bias 1.5 1.1 5.4 4.7
Recovery 101.5 101.1 105.4 104.7

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C-2: Page 2

C-2.1 The confidence level is selected from: 80%, 90%, 95%, and 99%.

C-2.2 The confidence level is entered as “95”.

QC-based Nested Approach Copper in Wastewater by ICP Page 2

Components of Analytical Uncertainty

IME - Intrinsic instrumental measurement effects
SPE - Spike preparation effects
PME - Preparation method effects
MIE - Matrix interference effects
SCE- Sample collection effects
SLE - Sample location effects

Component Percent Standard Uncertainty Component Percent Recovery Component Systematic Error
IME ~ 0.8 % relative standard deviation IME ~ 101 IME ~ 1 percent

SPE ~ 0.1 % relative standard deviation SPE ~ 100 SPE ~ 0 percent

PME ~ 7.1 % relative standard deviation PME ~ 104 PME ~ 4 percent

MIE ~ 8.5 % relative standard deviation MIE ~ 99 MIE ~ -1 percent

2.093
SCE ~ 0.0 % relative standard deviation 2.093
2.093
SLE ~ 0.0 % relative standard deviation WRONG CL
WRONG CL
What is the Confidence Level (CL)? Enter ONLY one of these percentages: 80, 90, 95, 99 95 %
Your specified t-value is 2.093 for a Two-Tailed Normal Distribution Confidence Interval

Relative Analytical Measurement Uncertainty for routine field samples

(Only the IME, PME, and MIE are combined for the analytical measurement uncertainty)
23.3 % relative uncertainty

Relative Systematic Error associated with the measurement of routine field samples
(Only the IME, PME, and MIE biases are combined for the analytical measurement systematic error)
5.1 % relative systematic error

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C-3: Page 3

C-3.1 The analytical measurement result is entered as “10”.

C-3.2 The units are entered as “mg/L”.

QC-based Nested Approach Copper in Wastewater by ICP Page 3

Partitioning of Uncertainty
Percent Relative Uncertainty

9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
IME SPE PME MIE SCE SLE
Components

What is the analytical measurement result? 10

What are the analytical measurement units? mg/L

If the sample measurement is 10 mg/L ,

then the uncertainty interval is 7.7 - 12.3 mg/L at the 95 % Confidence Level (Expanded Uncertainty)

For the above result, if the systematic measurement error (bias) is corrected, and
the corrected measurement is 9.5 mg/L ,
then the uncertainty interval is 7.3 - 11.7 mg/L at the 95 % Confidence Level (Expanded Uncertainty)

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Uncertainty Calculator Standard Operating Procedure

APPENDIX D: SOFTWARE VALIDATION BASED ON DATA IN APPENDIX C

Replicate ICS ICV

Number %D %D -% D (%D-% D ) 2 %D %D -% D (%D-% D )2
1 1.1 -0.4 0.14 0.5 -0.6 0.40
2 0.8 -0.7 0.52 0.1 -1.0 1.07
3 0.4 -1.1 1.25 1.0 -0.1 0.02
4 2.0 0.6 0.31 1.2 0.1 0.00
5 1.0 -0.5 0.24 0.2 -0.9 0.87
6 1.2 -0.3 0.07 0.4 -0.7 0.54
7 1.7 0.3 0.07 1.2 0.1 0.00
8 3.7 2.3 5.06 0.9 -0.2 0.06
9 1.1 -0.4 0.18 0.1 -1.0 1.07
10 3.1 1.6 2.63 1.3 0.2 0.03
11 2.0 0.5 0.27 0.9 -0.2 0.06
12 0.7 -0.8 0.61 1.0 -0.1 0.02
13 0.4 -1.1 1.17 2.0 0.9 0.75
14 0.9 -0.6 0.34 0.2 -0.9 0.87
15 1.4 -0.1 0.01 1.0 -0.1 0.02
16 1.9 0.4 0.18 1.4 0.3 0.07
17 2.0 0.5 0.27 1.5 0.4 0.13
18 1.5 0.0 0.00 1.7 0.6 0.32
19 1.6 0.1 0.01 3.0 1.9 3.48
20 1.1 -0.4 0.14 3.1 2.0 3.86

ICS ICV
 % D1 + % D2 + ... + % Dn   % D1 + % D2 + ... + % Dn 
Equation A.6 %D =   %D =  
 n   n 
% D =12.7/20=1.5% % D = 32.6/20 =1.1%

Equation A.7 ( )
% R = 100 + % D =100+1.5=101.5% ( )
% R = 100 + % D =100+1.1=101.1%
 n 
( )
2
 n   ∑ % Di − % D
( )
2

 ∑ % Di − % D   
  u r =  i =1  = 13 .65
Equation A.8 u r =  i =1  = 13 .47 1
1  
   
   
 
 n 
( )
2
   ∑ % Di − % D
∑ (% D )
2

n
−%D  

i
  
ur =  i =1
 = 0 . 71
u r =  i =1  = 0.72
n −1 n −1
   




 
 
1/ 2
 n 
( )
1/ 2 2
 n 
( )
2
 ∑ % Di − % D   ∑ %Di − %D 
   
u r =  i =1  = 0 .84 % ur =  i=1  = 0.85%

n −1
 n −1
   
   
 

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Replicate LCS MIS

Number %D %D -% D (%D-% D ) 2 %D %D -% D (%D-% D )2
1 4.0 -1.4 2.06 12.0 7.3 53.29
2 0.5 -4.9 24.35 1.4 -3.3 10.89
3 1.5 -3.9 15.48 8.0 3.3 10.89
4 1.7 -3.7 13.95 3.7 -1.0 1.00
5 0.1 -5.3 28.46 12.0 7.3 53.29
6 2.2 -3.2 10.47 0.4 -4.3 18.49
7 0.4 -5.0 25.35 3.6 -1.1 1.21
8 0.3 -5.1 26.37 0.1 -4.6 21.16
9 0.5 -4.9 24.35 2.7 -2.0 4.00
10 15.0 9.6 91.49 17.0 12.3 151.29
11 20.0 14.6 212.14 30.0 25.3 640.09
12 0.4 -5.0 25.35 3.7 -1.0 1.00
13 4.0 -1.4 2.06 1.5 -3.2 10.24
14 0.6 -4.8 23.38 5.0 0.3 0.09
15 1.5 -3.9 15.48 1.4 -3.3 10.89
16 5.0 -0.4 0.19 20.0 15.3 234.09
17 24.0 18.6 344.66 3.5 -1.2 1.44
18 3.0 -2.4 5.93 5.0 0.3 0.09
19 13.0 7.6 57.23 -24.0 -28.7 823.69
20 11.0 5.6 30.97 -13.0 -17.7 313.29

LCS MIS
 % D1 + % D2 + ... + % Dn   % D1 + % D2 + ... + % Dn 
Equation A.6 %D =   %D =  
 n   n 
% D =12.7/20=5.4% % D = 32.6/20 =4.7%
Equation A.7 ( )
% R = 100 + % D =100+5.4=105.4% ( )
% R = 100 + % D =100+4.7=104.7%
 n   n 
( ) ( )
2 2
 ∑ % Di − % D   ∑ % Di − % D 
   
Equation A.8 u r =  i =1  = 979 .73 u r =  i =1  = 2360 .42
   
   
   
 n   n 
( )
2

( )
2
 ∑ % Di − % D   ∑ % Di − % D 
   
u r =  i =1  = 51 .56 u r =  i =1  = 124 .23
n −1 n −1
   
   
   
1/ 2 1/ 2
 n   n 
( ) ( )
2 2
 ∑ % Di − % D   ∑ %Di − %D 
   
u r =  i =1  = 7.18% u r =  i =1  = 11.14%
n −1 n −1
   
   
   

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ICS
ur = IMEur=0.84%
Equation A.9
ICS
If ur > ICVur, then SPEur is estimated as zero, else:

SPE u r = ( ICV u r ) 2 − ( IME u r ) 2 = 0.85 2 − 0.84 2 = 0.10%

Equation A.10
ICV
If ur > LCSur, then PMEur is estimated as zero, else:

PME u r = ( LCS u r ) 2 − ( ( IME u r ) 2 + ( SPE u r ) 2 )= 7.2 2 − (0.84 2 + 0.10 2 ) = 7.1%

Equation A.11
LCS
If ur > MISur, then MIEur is estimated as zero, else:

MIE u r = ( MIS u r ) 2 − ( ( IME u r ) 2 + ( SPE u r ) 2 + ( PME u r ) 2 )= 11.12 − (0.84 2 + 0.10 2 + 7.12 ) = 8.5%

Equation A.12
% R IME = 100 + % D ICS = 100 + 1.5 = 101.5%
Equation A.16

% R SPE = 
(
 100 + % D ICV )  = (100 + 1.1)
= 99.7%
 ( % R IME / 100 )  (101.5 / 100)

Equation A.17

% R PME = 
(
100 + % D LCS ) 
=
(100 + 5.4)
( )( )  (101.5 / 100)(99.7 / 100) = 104.3%
 % R IME / 100 % R SPE / 100 
Equation A.18

% R MIE = 
(
100 + % D MIS ) 
=
(100 + 4.7)
( )( )( )  (101.5 / 100)(99.7 / 100)(104.3 / 100) = 99.3%
 % R IME / 100 % R SPE / 100 % R PME / 100 

Equation A.19
( )
% B IME = % R IME − 100 =(101.5-100)=1.5%
Equation A.20

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( )
% B SPE = % R SPE − 100 = (100 − 100) = −0.3%
Equation A.21
( )
% B PME = % R PME − 100 = (104 − 100) = 4.3%
Equation A.22
( )
% B MIE = % R MIE − 100 = 99 − 100 = −0.7%
Equation A.23

RST u r = ( IME u r ) 2 + ( PME u r ) 2 + ( MIE u r ) 2 = 0.84 2 + 7.18 2 + 11.14 2 = 11.13%

Equation A.24
% B RST = 100 * ( ( (% R IME )( )(
/ 100 % R PME / 100 % R MIE / 100 ) )−1 )
% B RST = 100 * ( (101.5 / 100)(104.3 / 100 )(99.3 / 100 ) ) − 1 ) = 5.1%
Equation A.25
CI = Cm ± (Cm)*(k* RSTur)= 10 ± (10*2.093*0.1113) = 10 ± 2.3 mg/L
Equation A.26
 Cm  10
CmBC =  = = 9.5mg / L
((
 100 + % B RST ) ) 
/ 100  ((100 + 5.1) / 100)

Equation A.27a
CIBC = CmBC ± (CmBC)*(k* RSTur)= 9.5 ±(9.5*2.093*0.1113) = 9.5 ± 2.2 mg/L
Equation A.27b

34