Common Contributors to Measurement Uncertainty – Chemical Analyses

(representative list - may not be all inclusive for all types of analyses)
(QC sample types in this list are typical of those utilized in AIHA-LAP, LLC laboratories)
additional tabbed sheets for examples

Representative
and Applicable
Contributors to Uncertainty QC Data

Transportation/Storage/Handling:

shipping time, container and temperature NA / (FS)

lab storage time, conditions and temperature NA / (LCS, FS)

contamination in lab storage areas NA / LCS, FB

Laboratory Subsampling

sample nonhomogeneity DUP

blending techniques DUP
sample size DUP
Sample Preparation:
volumetric glassware LCS, DUP
dispensing device LCS, DUP
balance LCS, DUP
temperature LCS, DUP
sample extraction LCS, DUP
extractant background LCS, DUP, MB
Lab Environmental Conditions:
temperature variance LCS, DUP
humidity variance LCS, DUP
Analysts:
different analysts LCS, DUP
analyst training level and experience LCS, DUP

data interpretation by analyst LCS, DUP

Measuring Instruments:
instrument stability LCS, DUP
 carry over effects LCS, DUP
day to day calibration differences LCS
interferences LCS
Calibration Standards/Reference
Materials:
preparation variances LCS
calibration stock material uncertainty CERTIFICATE

LCS reference material uncertainty CERTIFICATE

Test Procedure Variations:
variation within and between reagent lots LCS
extraction or digestion times, temperatures,
and conditions LCS
sample dependent modifications LCS
desorption efficiencies within and between
lots for sorbents LCS
Data Manipulation:
sampling media/blank correction LCS, MB
instrument blank correction LCS
accuracy of calculations LCS

area or air volume sampled NA

Where:
DUP = Duplicate, resulting from sub-sampling of a bulk (NOTE: NOT LCS/LCSD duplicate spiked sampling media)
FB = Field Blank
FS = Field Spike - Not typically conducted unless part of sampling method validation. Should be considered only when labora
is responsible for field sampling.
LCS = Laboratory Control Standard, matrix matched and typically taken through the entire analytical process with each sample
batch
MB = Method or Matrix Blank
NA = Not Applicable
utors to Measurement Uncertainty – Chemical Analyses
ve list - may not be all inclusive for all types of analyses)
al of those utilized in AIHA-LAP, LLC laboratories) See
additional tabbed sheets for examples

Comments to Clarify Contributor Effects

NOTE: This is not part of analytical uncertainty, but must be considered by labs
providing sampling and when providing guidance regarding sample packaging and
shipping. Usually no impact if recommended shipping conditions and holding times in
referenced methods are maintained. Improper packing materials, bulks shipped w/samples,
etc. may adversely affect data. Field blanks, field spiked samples or duplicate field samples
shipped with samples or included in method validation studies may reflect these contributors.
Field variability (FS/DUP) is only considered when lab is responsible for sampling.

Usually no impact if recommended storage conditions and holding times in reference

methods are maintained. Impact is monitored per sample batch only if LCS samples are
prepared on receipt and stored with field samples. Field spiked samples or stability study
samples included in some method validation studies may also reflect these contributors. Field
variability (FS/DUP) is only considered when lab is responsible for sampling.

Usually no impact if recommended storage conditions and holding times in reference

methods are maintained. Improper storage such as sorbent tubes stored with bulk solvent
samples or near solvent sources may adversely affect data. Impact is monitored only if LCS is
prepared on receipt & stored with field samples. Field blank can be used to assess
contamination from collection, transport, and storage.
NOTE: This primarily applies to bulk/solid samples which requires use of laboratory duplicate
sample data to determine impact on uncertainty. It is not applicable for LCS/LCSD media
spike duplicates.

Sample composition, etc.

Stirring, sieving, grinding, etc.

Large enough to allow adequate subsampling.

NA for Class A; applies for graduated tubes or cylinders, etc.

Pipettes, and other types of dispensers that are not Class A.
Balance error is often insignificant compared to other MU sources.
Hot plate or ashing temperatures.
Applies to LCS or DUP if it goes throughthe entire sample preparation process.
Analyte or interferant is present in acids, solvents, etc.

Room temp during bulk asbestos, gravimetry, etc. processes.

Gravimetry involving hydroscopic media, etc.

Must use inter-analyst instead of intra-analyst repeat data, where applicable.

Must use inter-analyst instead of intra-analyst repeat data, where applicable.
Chromatographic peak ID, interference corrections, etc. Must use inter-analyst instead of
intra-analyst repeat data, where applicable.

Baseline drift, repeatability of averaged readings, lab environmental stability, etc.

 Impact of high samples on following sample readings; can be monitored by proper use of
CCBs.
Variation in instrument response and calibration process
Due to matrix, inter-element effects, co-eluting GC peaks, etc.

Due to analysts, balances, dispensing devices used, etc

Obtain from certificate or estimate, can be ignored if less than 1/3 of the largest contributor.
Only has impact when LCS data are used to correct customer sample results. Obtain from
certificate or estimate. Can be ignored if less than 1/3 of the largest contributor. Note that use
of an LCS with a large uncertainty can result in over estimation of overall analytical
uncertainty.

Similar to extractant background effects under Sample Preparation above.

May affect complete dissolution of analyte or loss of material in some cases.

Changes in conditions due to sample size, customer requests, etc.

May vary by lot or manufacturer; also applies to diffusion rates for passive monitors.

When significant and when data are blank corrected.

When allowed.
Manual, spreadsheet, LIMS, etc.
Typically provided by the customer. This is not part of analytical uncertainty, but must be
considered by labs providing sampling and providing combined sampling and analytical
uncertainty.

pling of a bulk (NOTE: NOT LCS/LCSD duplicate spiked sampling media)

d unless part of sampling method validation. Should be considered only when laboratory

ix matched and typically taken through the entire analytical process with each sample
 Example of Contributors to Measurement Uncertainty
Chemical Analyses of Sorbent Tubes using Chromatography
See Example Calculations (to the right of the table)
Contributors to Uncertainty
Transportation/Storage/Handling
shipping time, container & temperature
lab storage time, conditions & temperature
contamination in lab storage areas
Laboratory Subsampling
sample nonhomogeneity
blending techniques
sample size
Sample Preparation:
volumetric glassware
dispensing device
balance
temperature
sample extraction
extractant background
Lab Environmental Conditions:
temperature variance
humidity variance
Analysts:
different analysts
analyst training level & experience
data interpretation by analyst
Measuring Instruments:
instrument stability
carry over effects
day to day calibration differences
interferences
Calibration Standards/Reference Materials:
preparation variances
calibration stock material uncertainty
LCS reference material uncertainty
Test Procedure Variations
variation within and between reagent lots
extraction or digestion times and temps
sample dependent modifications
desorption efficiencies within and between lots
for sorbent tubes
Data Manipulation:
sampling media blank correction
instrument blank correction
Accuracy of calculations
Representative and
Applicable QC Data Comments to Clarify Contributor Effects
NA Limited impact on most sorbent tubes
Usually no impact if recommended storage conditions and hold times are maintained. LCS
samples are representative if prepared on receipt & stored with field samples - usually no
impact if recommended storage conditions and holding times are maintained. Field spiked
samples or stability study samples included in some method validation studies may also reflect
NA these contributors.
Usually no impact if appropriate storage conditions are maintained. Field blank can be used to
NA assess contamination from collection, transport, and storage
NA Not applicable to sorbent tube analysis
NA Not applicable to sorbent tube analysis
NA Not applicable to sorbent tube analysis
LCS Same type of glassware used for samples and LCS
LCS Same type of dispensing device
NA Not applicable to sorbent tube analysis
NA Not applicable to sorbent tube analysis
LCS Applies to LCS if goes through sample preparation
LCS, MB Analyte or interferant in solvents or other prep reagents used, etc.
LCS LCS results reflect any temperature effects on chromatography instrument
NA Not applicable to sorbent tube analysis
LCS LCS results reflect variability due to different analysts, as applicable, on different days
LCS LCS results reflect variability due to different analysts, as applicable, on different days
LCS LCS results reflect variability due to different analysts, as applicable, on different days
LCS LCS results reflect instrument variability on different days
LCS LCS results reflect instrument variability on different days
LCS LCS results reflect instrument variability on different days
LCS LCS results reflect instrument variability on different days
LCS Due to analysts, dispensing devices used, etc
CERTIFICATE Obtain from certificate or estimate
Use if customer sample data corrected for desorption efficiency. Obtain from certificate or
CERTIFICATE estimate.
LCS LCS subjected to same treatment as customer samples
LCS LCS subjected to same treatment as customer samples
LCS LCS subjected to same treatment as customer samples
LCS LCS subjected to same treatment as customer samples
LCS LCS subjected to same treatment as customer samples
LCS LCS subjected to same treatment as customer samples
LCS LCS subjected to same treatment as customer samples
LCS = Laboratory Control Standard, typically taken through the entire analytical process with each sample batch
MB = Method or matrix blank
NA = Not Applicable
 Examples of Analytical Measurement Uncertainty for Analysis of Organic Solvents on Charcoal Tubes

mg n-Butanol on Charcoal Tube using CS2

mg Toluene on Charcoal Tube using CS2
Desorption per NIOSH 1401Mod
Desorption per NIOSH 1501
LCS/LCSD = 0.0810 mg n-butanol spike /tube
LCS/LCSD = 0.0867 mg toluene spike/tube
(includes correction for DE = 0.80)

LCSD
LCS mg LCS %Rec LCSD mg %Rec LCS mg LCS %Rec LCSD mg LCSD %Rec

0.0876 101.0 0.0884 102.0 0.0862 106.4 0.0832 96.0

0.0824 95.0 0.0850 98.0 0.0799 98.6 0.0812 93.7

0.0867 100.0 0.0858 99.0 0.0839 103.6 0.0825 95.2

0.0832 96.0 0.0841 97.0 0.0923 114.0 0.0874 100.8

0.0789 91.0 0.0789 91.0 0.0847 104.6 0.0819 94.5
0.0798 92.0 0.0806 93.0 0.0702 86.7 0.0907 104.6
0.0850 98.0 0.0850 98.0 0.0632 78.0 0.0676 78.0
0.0824 95.0 0.0867 100.0 0.0933 115.2 0.0870 100.3
0.0858 99.0 0.0867 100.0 0.1005 124.1 0.0924 106.6
0.0850 98.0 0.0850 98.0 0.0987 121.9 0.0933 107.6
0.0876 101.0 0.0858 99.0 0.0826 102.0 0.0919 106.0
0.0832 96.0 0.0884 102.0 0.0913 112.7 0.0756 87.2
0.0884 102.0 0.0919 106.0 0.0770 95.1 0.0920 106.1
0.0867 100.0 0.0893 103.0 0.0910 112.3 0.0960 110.7
0.0902 104.0 0.0884 102.0 0.0832 102.7 0.0928 107.0
0.0850 98.0 0.0876 101.0 0.0984 121.5 0.0884 102.0
0.0876 101.0 0.0902 104.0 0.0872 107.7 0.0861 99.3
0.0834 96.2 0.0892 102.9 0.0809 99.9 0.0655 75.5
0.0819 94.5 0.0812 93.7 0.0926 114.3 0.0956 110.3
0.0797 91.9 0.0784 90.4 0.0979 120.9 0.0889 102.5

40 point Mean % Rec 98.2 40 point Mean % Rec 103.1

40 point Std Dev 4.0 40 point Std Dev 11.5

RSD 4.05% RSD 11.2%

Reference material used for calibration indicates assay Reference materials used for calibration and LCS
of 99.5%. Expanded uncertainty of reference material preparation indicate assay of 99.5%. Expanded uncertainty
estimated at 0.5% (95%) Divide by 2 to yield 0.25 % Rel. of reference materials estimated at 0.5% (95%). Divide by 2
SD. Insignificant compared to 4.0% can be eliminated to yield 0.25 % Rel. SD. Insignificant compared to 11.2%
from calculation can be eliminated from calculation
Expanded MU @ Expanded MU @
95% Conf k=2 8.1% % 95% Conf k=2 22.3% %
Bias @ 98.2% Rec = -1.8% Bias @ 103.1% Rec = 3.1%

Example of reporting for 0.085 mg toluene: Example of reporting for 0.085 mg n=butanol: 0.085 mg n-
0.085 mg toluene with an analytical uncertainty of +/- butanol with an analytical uncertainty of +/- 0.019 mg at the
0.007 mg at the 95% confidence level with probable bias 95% confidence level with probable bias of 0.003 mg
of -0.002 mg

No significant background in method blank. No significant background in method blank.

 ation and LCS
%. Expanded uncertainty
0.5% (95%). Divide by 2
nt compared to 11.2%

n=butanol: 0.085 mg n-
nty of +/- 0.019 mg at the
bias of 0.003 mg
Example of Contributors to Measurement Uncertainty

Chemical Analyses of Lead (Pb) in Paint using ICP-AES

See Example Calculations (to the right of the table)
Representative
and Applicable
Contributors to Uncertainty QC Data
Transportation/Storage/Handling

shipping time, container & temperature NA

lab storage time, conditions & temperature NA
contamination in lab storage areas NA
Laboratory Subsampling
sample nonhomogeneity DUP
blending techniques DUP
sample size DUP
Sample Preparation:
volumetric glassware LCS, DUP
dispensing device LCS, DUP
balance LCS, DUP
temperature LCS, DUP
sample extraction LCS, DUP
extractant background LCS, DUP, MB
Lab Environmental Conditions:
temperature variance NA
humidity variance NA

Analysts:
different analysts LCS, DUP
analyst training level & experience LCS, DUP
data interpretation by analyst LCS, DUP
Measuring Instruments:
instrument stability LCS

carry over effects LCS, DUP

day to day calibration differences LCS

interferences DUP, MS
Calibration Standards/Reference Materials:
preparation variances LCS, DUP
calibration stock material uncertainty CERTIFICATE
LCS reference material uncertainty NA
Test Procedure Variations

variation within and between reagent lots LCS

extraction or digestion times and temps LCS

sample dependent modifications LCS

desorption efficiencies within and between lots for
sorbent tubes NA
Data Manipulation:

sampling media blank correction NA

instrument blank correction LCS

Accuracy of calculations LCS

DUP = Duplicate, resulting from sub-sampling of a bulk (NOTE: NOT LCS/LCSD duplicate spiked sampling media)
FB = Field Blank
FS = Field Spike
LCS = Laboratory Control Standard, matrix matched and typically taken through the entire analytical process, with each
sample batch
MB = Method or matrix blank
NA = Not Applicable
ement Uncertainty
Examples of Analytic
Paint using ICP-AES Pb in Paint using hotblock acid digestion and
See Example Calculations (to the right of the table) Analysis in accordance with EPA SW846 305
(Mod)
LCS Recovery of Paint SRM 2582 at 208.8 +/-
Comments to Clarify Contributor Effects or SRM 2581 at 4490 +/- 110 mg/Kg P

True
LCS value
No impact on bulk paint samples from transportation, storage or normal handling mg/Kg mg/Kg
195.4 208.8
189.6 208.8
4157 4490
Sample composition, etc. 4186 4490
Stirring, sieving, grinding, etc 184 208.8
Large enough to allow adequate subsampling 184 208.8
4641 4490
NA for Class A; applies for graduated tubes or cylinders, etc. 4831 4490
pipettes, and other types of dispensers not Class A 179 208.8
balance error is often insignificant compared to other MU sources 177 208.8
Hot plate or ashing temperatures 4539 4490
Applies to LCS or DUP if goes through sample preparation 4858 4490
Analyte or interferant in acids, or other reagents 198 208.8
207 208.8
No impact on bulk paint samples 4458 4490
No impact on bulk paint samples 4514 4490
Analyst contributors affect all aspects of analysis from subsampling through data
manipulation 184 208.8
187 208.8
4551 4490
4580 4490
179 208.8
Baseline drift, repeatability of averaged readings, etc 186 208.8
Impact of high samples on following sample readings; can be monitored by proper
use of CCBs 4245 4490
4302 4490
Due to matrix, inter-element effects, etc. Cannot be routinely determined for
typical industrial hygiene sampling media 188 208.8
202 208.8
Due to analysts, balances, dispensing devices used, etc 4217 4490
Obtain from certificate or estimate 4300 4490
Sample results not corrected for LCS recovery 203 208.8
190 208.8
Similar to extractant background effects under Sample Preparation above 30 point Mean % Rec.

May affect complete dissolution of analyte or loss of material in some cases 30 point Std Dev

Changes in conditions due to sample size, customer requests, etc RSD

 No sampling media with bulk samples
when allowed

Manual, spreadsheet, LIMS, etc

g of a bulk (NOTE: NOT LCS/LCSD duplicate spiked sampling media)

matched and typically taken through the entire analytical process, with each Example analytical unc
Expanded analytical un

Bias = 4400 mg/kg X -0.

Example of reporting fo
4400 mg/Kg Pb in paint
confidence level and a
 Examples of Analytical Measurement Uncertainty for Lead in Paint

otblock acid digestion and ICP-AES

ance with EPA SW846 3050 & 6010 Sample duplicata data in mg/Kg for Pb in Paint using
(Mod) hotblock acid digestion and ICP-AES in accordance with
int SRM 2582 at 208.8 +/- 4.9 mg/Kg EPA SW-846 3050 & 6010 (Mod)
81 at 4490 +/- 110 mg/Kg Pb

mg/Kg mg/Kg Std Dev

LCS % Rec Sample Sple Dup (S) CV CV2
93.6 1604 1502 72.12 0.0464 0.0022
90.8 511 602 64.35 0.1156 0.0134
92.6 9470 8794 478.00 0.0523 0.0027
93.2 161 93 48.08 0.3786 0.1433
88.1 1683 1411 192.33 0.1243 0.0155
88.1 956 830 89.10 0.0998 0.0100
103.4 23470 26570 2192.03 0.0876 0.0077
107.6 625 730 74.25 0.1096 0.0120
85.7 723 472 177.48 0.2970 0.0882
84.8 23000 22000 707.11 0.0314 0.0010
101.1 14190 13900 205.06 0.0146 0.0002
108.2 10350 9142 854.18 0.0876 0.0077
94.8 5702 5854 107.48 0.0186 0.0003
99.1 109 122 9.19 0.0796 0.0063
99.3 7079 6427 461.03 0.0683 0.0047
100.5 196 186 7.07 0.0370 0.0014

88.1 14510 14300 148.49 0.0103 0.0001

89.6 15710 17150 1018.23 0.0620 0.0038
101.4 1187 1192 3.54 0.0030 0.0000
102.0 9265 9246 13.44 0.0015 0.0000
85.7 4240 3918 227.69 0.0558 0.0031
89.1 1979 1574 286.38 0.1612 0.0260

94.5 2357 3068 502.75 0.1853 0.0344

95.8 2254 3062 571.34 0.2150 0.0462

90.0 53160 44300 6264.97 0.1286 0.0165

96.7 24810 23000 1279.86 0.0535 0.0029
93.9 22860 22930 49.50 0.0022 0.0000
95.8 1133 1125 5.66 0.0050 0.0000
97.2 151 96 38.89 0.3149 0.0992
91.0 7774 4366 2409.82 0.3970 0.1576
94.7 ∑ CV2 0.7064

6.3 CV pooled = √ (∑CV2/30) = 0.1534 15.3%

6.7%
 Reference material used for calibration indicates concentration and expanded
uncertainty of 1001 +/- 5 ug/mL at 95% confidence level. Expanded uncertainty
divided by 2 to yield 0.25 % Rel. SD. Insignificant compared to 15.2% and can
be eliminated from calculation. No significant background in
method blank.

Combined Rel. Std Dev (SDc) = √ [ SD1 2 + SD22]

SDc = √[(6.7)2 + (15.3)2] = 16.7%

Expanded MU @ 95% Conf (k=2) = 33.4%

Bias @ 94.7% Rec of LCS = -5.3%

Example analytical uncertainty for 4400 mg/Kg Pb in paint sample:

Expanded analytical uncertainty of 4400 mg/Kg Pb in paint = 4400 X 0.334 = 1470 mg/kg

Bias = 4400 mg/kg X -0.053 = 233.2 mg/kg

Example of reporting for 4400 mg/Kg Pb in paint:

4400 mg/Kg Pb in paint with an analytical uncertainty of +/- 1500 mg/Kg at the 95%
confidence level and a probable bias of -230 mg/Kg
RSD