Contributors to Uncertainty

Representative
and Applicable
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
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) See
additional tabbed sheets for examples
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)
NA = Not Applicable
FB = Field Blank
FS = Field Spike - Not typically conducted unless part of sampling method validation. Should be considered only when laboratory
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
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.
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) See
additional tabbed sheets for examples
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.
DUP = Duplicate, resulting from sub-sampling of a bulk (NOTE: NOT LCS/LCSD duplicate spiked sampling media)
NA = Not Applicable
FB = Field Blank
FS = Field Spike - Not typically conducted unless part of sampling method validation. Should be considered only when laboratory
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
Contributors to Uncertainty
Representative and
Applicable QC Data Comments to Clarify Contributor Effects
Transportation/Storage/Handling
shipping time, container & temperature
NA
Limited impact on most sorbent tubes
lab storage time, conditions & temperature
NA
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
these contributors.
contamination in lab storage areas
NA
Usually no impact if appropriate storage conditions are maintained. Field blank can be used to
assess contamination from collection, transport, and storage
Laboratory Subsampling

sample nonhomogeneity
NA
Not applicable to sorbent tube analysis
blending techniques
NA
Not applicable to sorbent tube analysis
sample size
NA
Not applicable to sorbent tube analysis
Sample Preparation:
volumetric glassware
LCS
Same type of glassware used for samples and LCS
dispensing device
LCS
Same type of dispensing device
balance
NA
Not applicable to sorbent tube analysis
temperature
NA
Not applicable to sorbent tube analysis
sample extraction
LCS
Applies to LCS if goes through sample preparation
extractant background
LCS, MB
Analyte or interferant in solvents or other prep reagents used, etc.
Lab Environmental Conditions:
temperature variance
LCS
LCS results reflect any temperature effects on chromatography instrument
humidity variance
NA
Not applicable to sorbent tube analysis
Analysts:
different analysts
LCS
LCS results reflect variability due to different analysts, as applicable, on different days
analyst training level & experience
LCS
LCS results reflect variability due to different analysts, as applicable, on different days
data interpretation by analyst
LCS
LCS results reflect variability due to different analysts, as applicable, on different days
Measuring Instruments:
instrument stability LCS
LCS results reflect instrument variability on different days
carry over effects
LCS
LCS results reflect instrument variability on different days
day to day calibration differences
LCS
LCS results reflect instrument variability on different days
interferences
LCS
LCS results reflect instrument variability on different days
Calibration Standards/Reference Materials:
preparation variances
LCS
Due to analysts, dispensing devices used, etc
calibration stock material uncertainty
CERTIFICATE
Obtain from certificate or estimate
LCS reference material uncertainty
CERTIFICATE
Use if customer sample data corrected for desorption efficiency. Obtain from certificate or
estimate.
Test Procedure Variations
variation within and between reagent lots
LCS
LCS subjected to same treatment as customer samples
extraction or digestion times and temps
LCS
LCS subjected to same treatment as customer samples
sample dependent modifications
LCS
LCS subjected to same treatment as customer samples
desorption efficiencies within and between lots
for sorbent tubes
LCS
LCS subjected to same treatment as customer samples
Data Manipulation:
sampling media blank correction
LCS
LCS subjected to same treatment as customer samples
instrument blank correction
LCS
LCS subjected to same treatment as customer samples
Accuracy of calculations
LCS
LCS subjected to same treatment as customer samples
Example of Contributors to Measurement Uncertainty
Chemical Analyses of Sorbent Tubes using Chromatography
See Example Calculations (to the right of the table)
LCS = Laboratory Control Standard, typically taken through the entire analytical process with each sample batch
MB = Method or matrix blank
NA = Not Applicable
LCS mg LCS %Rec LCSD mg
LCSD
%Rec LCS mg LCS %Rec LCSD mg
0.0876 101.0 0.0884 102.0 0.0862 106.4 0.0832
0.0824 95.0 0.0850 98.0 0.0799 98.6 0.0812
0.0867 100.0 0.0858 99.0 0.0839 103.6 0.0825
0.0832 96.0 0.0841 97.0 0.0923 114.0 0.0874
0.0789 91.0 0.0789 91.0 0.0847 104.6 0.0819
0.0798 92.0 0.0806 93.0 0.0702 86.7 0.0907
0.0850 98.0 0.0850 98.0 0.0632 78.0 0.0676
0.0824 95.0 0.0867 100.0 0.0933 115.2 0.0870
0.0858 99.0 0.0867 100.0 0.1005 124.1 0.0924
0.0850 98.0 0.0850 98.0 0.0987 121.9 0.0933
0.0876 101.0 0.0858 99.0 0.0826 102.0 0.0919
0.0832 96.0 0.0884 102.0 0.0913 112.7 0.0756
0.0884 102.0 0.0919 106.0 0.0770 95.1 0.0920
0.0867 100.0 0.0893 103.0 0.0910 112.3 0.0960
0.0902 104.0 0.0884 102.0 0.0832 102.7 0.0928
0.0850 98.0 0.0876 101.0 0.0984 121.5 0.0884
0.0876 101.0 0.0902 104.0 0.0872 107.7 0.0861
0.0834 96.2 0.0892 102.9 0.0809 99.9 0.0655
0.0819 94.5 0.0812 93.7 0.0926 114.3 0.0956
0.0797 91.9 0.0784 90.4 0.0979 120.9 0.0889
98.2 103.1
4.0 11.5
RSD 4.05% RSD 11.2%
8.1% % 22.3%
Bias @ 103.1% Rec = 3.1%
No significant background in method blank. No significant background in method blank.
40 point Mean % Rec 40 point Mean % Rec
Example
of reporting for 0.085 mg n=butanol: 0.085 mg n-butanol with
an analytical uncertainty of +/- 0.019 mg at the 95% confidence
level with probable bias of 0.003 mg
Reference material used for calibration indicates assay of
99.5%. Expanded uncertainty of reference material
estimated at 0.5% (95%) Divide by 2 to yield 0.25 % Rel. SD.
Insignificant compared to 4.0% can be eliminated from
calculation
Reference materials used for calibration and LCS preparation
indicate assay of 99.5%. Expanded uncertainty of reference
materials estimated at 0.5% (95%). Divide by 2 to yield 0.25 %
Rel. SD. Insignificant compared to 11.2% can be eliminated
from calculation
Example of reporting for 0.085 mg toluene:
0.085 mg toluene with an analytical uncertainty of +/- 0.007
mg at the 95% confidence level with probable bias of -0.002
mg
mg Toluene on Charcoal Tube using CS
2
Desorption per NIOSH 1501
LCS/LCSD = 0.0867 mg toluene spike/tube
Expanded MU @
95% Conf k=2
Bias @ 98.2% Rec = -1.8%
Examples of Analytical Measurement Uncertainty for Analysis of Organic Solvents on Charcoal Tubes
mg n-Butanol on Charcoal Tube using CS
2
Desorption per NIOSH 1401Mod
LCS/LCSD = 0.0810 mg n-butanol spike /tube
(includes correction for DE = 0.80)
40 point Std Dev 40 point Std Dev
Expanded MU @
95% Conf k=2
LCSD %Rec
96.0
93.7
95.2
100.8
94.5
104.6
78.0
100.3
106.6
107.6
106.0
87.2
106.1
110.7
107.0
102.0
99.3
75.5
110.3
102.5
%
No significant background in method blank.
Example
of reporting for 0.085 mg n=butanol: 0.085 mg n-butanol with
an analytical uncertainty of +/- 0.019 mg at the 95% confidence
level with probable bias of 0.003 mg
Reference materials used for calibration and LCS preparation
indicate assay of 99.5%. Expanded uncertainty of reference
materials estimated at 0.5% (95%). Divide by 2 to yield 0.25 %
Rel. SD. Insignificant compared to 11.2% can be eliminated
from calculation
Examples of Analytical Measurement Uncertainty for Analysis of Organic Solvents on Charcoal Tubes
mg n-Butanol on Charcoal Tube using CS
2
Desorption per NIOSH 1401Mod
LCS/LCSD = 0.0810 mg n-butanol spike /tube
(includes correction for DE = 0.80)
Contributors to Uncertainty
Representative
and Applicable
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
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)
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)
MB = Method or matrix blank
NA = Not Applicable
FB = Field Blank
FS = Field Spike
LCS = Laboratory Control Standard, matrix matched and typically taken through the entire analytical process, with each
sample batch
Comments to Clarify Contributor Effects
No impact on bulk paint samples from transportation, storage or normal handling LCS mg/Kg
195.4
189.6
4157
Sample composition, etc.
4186
Stirring, sieving, grinding, etc
184
Large enough to allow adequate subsampling
184
4641
NA for Class A; applies for graduated tubes or cylinders, etc.
4831
pipettes, and other types of dispensers not Class A
179
balance error is often insignificant compared to other MU sources
177
Hot plate or ashing temperatures
4539
Applies to LCS or DUP if goes through sample preparation
4858
Analyte or interferant in acids, or other reagents
198
207
No impact on bulk paint samples
4458
No impact on bulk paint samples
4514
Analyst contributors affect all aspects of analysis from subsampling through data
manipulation
184
187
4551
4580
179
Baseline drift, repeatability of averaged readings, etc
186
Impact of high samples on following sample readings; can be monitored by proper
use of CCBs
4245
4302
Due to matrix, inter-element effects, etc. Cannot be routinely determined for
typical industrial hygiene sampling media
188
202
Due to analysts, balances, dispensing devices used, etc
4217
Obtain from certificate or estimate
4300
Sample results not corrected for LCS recovery
203
190
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
Changes in conditions due to sample size, customer requests, etc
30 point Std Dev
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)
Examples of Analytical Measurement Uncertainty for Lead in Paint
Pb in Paint using hotblock acid digestion and ICP-AES Analysis in
accordance with EPA SW846 3050 & 6010 (Mod)
LCS Recovery of Paint SRM 2582 at 208.8 +/- 4.9 mg/Kg or SRM
2581 at 4490 +/- 110 mg/Kg Pb
No sampling media with bulk samples
when allowed
Manual, spreadsheet, LIMS, etc
DUP = Duplicate, resulting from sub-sampling of a bulk (NOTE: NOT LCS/LCSD duplicate spiked sampling media)
MB = Method or matrix blank
NA = Not Applicable
FB = Field Blank
FS = Field Spike
LCS = Laboratory Control Standard, matrix matched and typically taken through the entire analytical process, with each
sample batch
True value
mg/Kg LCS % Rec
mg/Kg
Sample
mg/Kg Sple
Dup
Std Dev
(S) CV
208.8
93.6
1604 1502 72.12 0.0464
208.8
90.8
511 602 64.35 0.1156
4490
92.6
9470 8794 478.00 0.0523
4490
93.2
161 93 48.08 0.3786
208.8
88.1
1683 1411 192.33 0.1243
208.8
88.1
956 830 89.10 0.0998
4490
103.4
23470 26570 2192.03 0.0876
4490
107.6
625 730 74.25 0.1096
208.8
85.7
723 472 177.48 0.2970
208.8
84.8
23000 22000 707.11 0.0314
4490
101.1
14190 13900 205.06 0.0146
4490
108.2
10350 9142 854.18 0.0876
208.8
94.8
5702 5854 107.48 0.0186
208.8
99.1
109 122 9.19 0.0796
4490
99.3
7079 6427 461.03 0.0683
4490
100.5
196 186 7.07 0.0370
208.8
88.1
14510 14300 148.49 0.0103
208.8
89.6
15710 17150 1018.23 0.0620
4490
101.4
1187 1192 3.54 0.0030
4490
102.0
9265 9246 13.44 0.0015
208.8
85.7
4240 3918 227.69 0.0558
208.8
89.1
1979 1574 286.38 0.1612
4490
94.5
2357 3068 502.75 0.1853
4490
95.8
2254 3062 571.34 0.2150
208.8
90.0
53160 44300 6264.97 0.1286
208.8
96.7
24810 23000 1279.86 0.0535
4490
93.9
22860 22930 49.50 0.0022
4490
95.8
1133 1125 5.66 0.0050
208.8
97.2
151 96 38.89 0.3149
208.8
91.0
7774 4366 2409.82 0.3970
30 point Mean % Rec. 94.7
CV
2
6.3
CV pooled = (CV
2
/30) =
RSD 6.7%
30 point Std Dev
Sample duplicata data in mg/Kg for Pb in Paint using hotblock acid
digestion and ICP-AES in accordance with EPA SW-846 3050 &
6010 (Mod)
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.
Examples of Analytical Measurement Uncertainty for Lead in Paint
Pb in Paint using hotblock acid digestion and ICP-AES Analysis in
accordance with EPA SW846 3050 & 6010 (Mod)
LCS Recovery of Paint SRM 2582 at 208.8 +/- 4.9 mg/Kg or SRM
2581 at 4490 +/- 110 mg/Kg Pb
Combined Rel. Std Dev (SDc) = [ SD1
2
+ SD2
2
]
SDc = [(6.7)
2
+ (15.3)
2
] = 16.7%
33.4%
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
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
Bias @ 94.7% Rec of LCS = -5.3%
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.
Expanded MU @ 95% Conf (k=2) =
CV
2
0.0022
0.0134
0.0027
0.1433
0.0155
0.0100
0.0077
0.0120
0.0882
0.0010
0.0002
0.0077
0.0003
0.0063
0.0047
0.0014
0.0001
0.0038
0.0000
0.0000
0.0031
0.0260
0.0344
0.0462
0.0165
0.0029
0.0000
0.0000
0.0992
0.1576
0.7064
0.1534
15.3%
RSD

Sample duplicata data in mg/Kg for Pb in Paint using hotblock acid
digestion and ICP-AES in accordance with EPA SW-846 3050 &
6010 (Mod)