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
QC Data

Contributors to Uncertainty
Transportation/Storage/Handling:

shipping time, container and temperature

lab storage time, conditions and temperature

contamination in lab storage areas

NA / (FS)

NA / (LCS, FS)

NA / LCS, FB

Laboratory Subsampling

blending techniques

DUP
DUP

sample size

DUP

sample nonhomogeneity

Sample Preparation:
volumetric glassware
dispensing device
balance
temperature
sample extraction
extractant background

LCS, DUP
LCS, DUP
LCS, DUP
LCS, DUP
LCS, DUP
LCS, DUP, MB

Lab Environmental Conditions:

temperature variance
humidity variance

LCS, DUP
LCS, DUP

Analysts:
analyst training level and experience

LCS, DUP
LCS, DUP

data interpretation by analyst

LCS, DUP

different analysts

Measuring Instruments:
instrument stability

LCS, DUP

carry over effects

day to day calibration differences
interferences

LCS, DUP
LCS
LCS

Calibration Standards/Reference
Materials:
calibration stock material uncertainty

LCS
CERTIFICATE

LCS reference material uncertainty

CERTIFICATE

preparation variances

Test Procedure Variations:

variation within and between reagent lots
extraction or digestion times, temperatures,
and conditions

LCS

sample dependent modifications

LCS
LCS

desorption efficiencies within and between

lots for sorbents

LCS

Data Manipulation:
sampling media/blank correction
instrument blank correction
accuracy of calculations

area or air volume sampled

LCS, MB
LCS
LCS
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

ive list - may not be all inclusive for all types of analyses)
al of those utilized in AIHA-LAP, LLC laboratories)
additional tabbed sheets for examples

See

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)
Representative and
Applicable QC Data

Contributors to Uncertainty

Comments to Clarify Contributor Effects

Transportation/Storage/Handling

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

shipping time, container & temperature

Laboratory Subsampling
sample nonhomogeneity
blending techniques
sample size

NA
NA
NA

Not applicable to sorbent tube analysis

Not applicable to sorbent tube analysis
Not applicable to sorbent tube analysis

Sample Preparation:
volumetric glassware
dispensing device
balance
temperature
sample extraction
extractant background

LCS
LCS
NA
NA
LCS
LCS, MB

Same type of glassware used for samples and LCS

Same type of dispensing device
Not applicable to sorbent tube analysis
Not applicable to sorbent tube analysis
Applies to LCS if goes through sample preparation
Analyte or interferant in solvents or other prep reagents used, etc.

Lab Environmental Conditions:

LCS
NA

LCS results reflect any temperature effects on chromatography instrument

LCS
LCS

LCS results reflect variability due to different analysts, as applicable, on different days

analyst training level & experience

data interpretation by analyst

LCS

LCS results reflect variability due to different analysts, as applicable, on different days

LCS
LCS

LCS results reflect instrument variability on different days

carry over effects

day to day calibration differences

LCS

LCS results reflect instrument variability on different days

interferences

LCS

LCS results reflect instrument variability on different days

temperature variance
humidity variance

Not applicable to sorbent tube analysis

Analysts:
different analysts

LCS results reflect variability due to different analysts, as applicable, on different days

Measuring Instruments:
instrument stability

LCS results reflect instrument variability on different days

Calibration Standards/Reference Materials:

calibration stock material uncertainty

LCS
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.

preparation variances

Due to analysts, dispensing devices used, etc

Test Procedure Variations

LCS subjected to same treatment as customer samples

sample dependent modifications

LCS
LCS
LCS

desorption efficiencies within and between lots

for sorbent tubes

LCS

LCS subjected to same treatment as customer samples

LCS
LCS
LCS

LCS subjected to same treatment as customer samples

variation within and between reagent lots

extraction or digestion times and temps

LCS subjected to same treatment as customer samples

LCS subjected to same treatment as customer samples

Data Manipulation:
sampling media blank correction
instrument blank correction
Accuracy of calculations

LCS subjected to same treatment as customer samples

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 Toluene on Charcoal Tube using CS2
Desorption per NIOSH 1501
LCS/LCSD = 0.0867 mg toluene spike/tube

LCS mg

LCS %Rec LCSD mg

mg n-Butanol on Charcoal Tube using CS2

Desorption per NIOSH 1401Mod
LCS/LCSD = 0.0810 mg n-butanol spike /tube
(includes correction for DE = 0.80)

LCSD
%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
0.0789
0.0798
0.0850
0.0824
0.0858
0.0850
0.0876
0.0832
0.0884
0.0867
0.0902
0.0850
0.0876
0.0834
0.0819
0.0797

96.0
91.0
92.0
98.0
95.0
99.0
98.0
101.0
96.0
102.0
100.0
104.0
98.0
101.0
96.2
94.5
91.9

0.0841
0.0789
0.0806
0.0850
0.0867
0.0867
0.0850
0.0858
0.0884
0.0919
0.0893
0.0884
0.0876
0.0902
0.0892
0.0812
0.0784

97.0
91.0
93.0
98.0
100.0
100.0
98.0
99.0
102.0
106.0
103.0
102.0
101.0
104.0
102.9
93.7
90.4

0.0923
0.0847
0.0702
0.0632
0.0933
0.1005
0.0987
0.0826
0.0913
0.0770
0.0910
0.0832
0.0984
0.0872
0.0809
0.0926
0.0979

114.0
104.6
86.7
78.0
115.2
124.1
121.9
102.0
112.7
95.1
112.3
102.7
121.5
107.7
99.9
114.3
120.9

0.0874
0.0819
0.0907
0.0676
0.0870
0.0924
0.0933
0.0919
0.0756
0.0920
0.0960
0.0928
0.0884
0.0861
0.0655
0.0956
0.0889

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

40 point Mean % Rec

98.2

40 point Mean % Rec

103.1

40 point Std Dev

RSD

4.0
4.05%

40 point Std Dev

RSD

11.5
11.2%

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
Expanded MU @
95% Conf k=2
8.1%
%
Bias @ 98.2% Rec = -1.8%

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
Expanded MU @
95% Conf k=2
22.3%
%
Bias @ 103.1% Rec = 3.1%

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

Example of reporting for 0.085 mg n=butanol: 0.085 mg nbutanol with an analytical uncertainty of +/- 0.019 mg at the
95% confidence level with probable bias of 0.003 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 nnty 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
QC Data

Contributors to Uncertainty
Transportation/Storage/Handling

shipping time, container & temperature

lab storage time, conditions & temperature
contamination in lab storage areas

NA
NA
NA

Laboratory Subsampling
sample nonhomogeneity
blending techniques
sample size

DUP
DUP
DUP

Sample Preparation:
volumetric glassware
dispensing device
balance
temperature
sample extraction
extractant background

LCS, DUP
LCS, DUP
LCS, DUP
LCS, DUP
LCS, DUP
LCS, DUP, MB

Lab Environmental Conditions:

temperature variance
humidity variance

NA
NA

Analysts:
different analysts
analyst training level & experience
data interpretation by analyst

LCS, DUP
LCS, DUP
LCS, DUP

Measuring Instruments:
instrument stability
carry over effects
day to day calibration differences
interferences

LCS
LCS, DUP
LCS
DUP, MS

Calibration Standards/Reference Materials:

preparation variances
calibration stock material uncertainty
LCS reference material uncertainty

LCS, DUP
CERTIFICATE
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:

instrument blank correction

NA
LCS

Accuracy of calculations

LCS

sampling media blank correction

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

See Example Calculations (to the right of the table)
Comments to Clarify Contributor Effects

No impact on bulk paint samples from transportation, storage or normal handling

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 not Class A
balance error is often insignificant compared to other MU sources
Hot plate or ashing temperatures
Applies to LCS or DUP if goes through sample preparation
Analyte or interferant in acids, or other reagents
No impact on bulk paint samples
No impact on bulk paint samples
Analyst contributors affect all aspects of analysis from subsampling through data
manipulation

Baseline drift, repeatability of averaged readings, etc

Impact of high samples on following sample readings; can be monitored by proper
use of CCBs
Due to matrix, inter-element effects, etc. Cannot be routinely determined for
typical industrial hygiene sampling media
Due to analysts, balances, dispensing devices used, etc
Obtain from certificate or estimate
Sample results not corrected for LCS recovery

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

Pb in Paint using hotblock acid digestion and

Analysis in accordance with EPA SW846 305
(Mod)
LCS Recovery of Paint SRM 2582 at 208.8 +/or SRM 2581 at 4490 +/- 110 mg/Kg P

LCS
mg/Kg
195.4
189.6
4157
4186
184
184
4641
4831
179
177
4539
4858
198
207
4458
4514

True
value
mg/Kg
208.8
208.8
4490
4490
208.8
208.8
4490
4490
208.8
208.8
4490
4490
208.8
208.8
4490
4490

184
187
4551
4580
179
186

208.8
208.8
4490
4490
208.8
208.8

4245
4302

4490
4490

188
202
4217
4300
203
190

208.8
208.8
4490
4490
208.8
208.8

30 point Mean % Rec.

30 point Std Dev
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
(Mod)
int SRM 2582 at 208.8 +/- 4.9 mg/Kg
81 at 4490 +/- 110 mg/Kg Pb

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)

LCS % Rec
93.6
90.8
92.6
93.2
88.1
88.1
103.4
107.6
85.7
84.8
101.1
108.2
94.8
99.1
99.3
100.5

mg/Kg
Sample
1604
511
9470
161
1683
956
23470
625
723
23000
14190
10350
5702
109
7079
196

mg/Kg
Sple Dup
1502
602
8794
93
1411
830
26570
730
472
22000
13900
9142
5854
122
6427
186

Std Dev
(S)
72.12
64.35
478.00
48.08
192.33
89.10
2192.03
74.25
177.48
707.11
205.06
854.18
107.48
9.19
461.03
7.07

CV
0.0464
0.1156
0.0523
0.3786
0.1243
0.0998
0.0876
0.1096
0.2970
0.0314
0.0146
0.0876
0.0186
0.0796
0.0683
0.0370

CV2
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

88.1
89.6
101.4
102.0
85.7
89.1

14510
15710
1187
9265
4240
1979

14300
17150
1192
9246
3918
1574

148.49
1018.23
3.54
13.44
227.69
286.38

0.0103
0.0620
0.0030
0.0015
0.0558
0.1612

0.0001
0.0038
0.0000
0.0000
0.0031
0.0260

94.5
95.8

2357
2254

3068
3062

502.75
571.34

0.1853
0.2150

0.0344
0.0462

90.0
96.7
93.9
95.8
97.2
91.0

53160
24810
22860
1133
151
7774

44300
23000
22930
1125
96
4366

6264.97
1279.86
49.50
5.66
38.89
2409.82

0.1286
0.0535
0.0022
0.0050
0.3149
0.3970

0.0165
0.0029
0.0000
0.0000
0.0992
0.1576

94.7
6.3
6.7%

CV2
CV pooled = (CV2/30) =

0.7064
0.1534

15.3%

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.
Combined Rel. Std Dev (SDc) = [ SD12 + SD22]
SDc = [(6.7)2 + (15.3)2] = 16.7%
Expanded MU @ 95% Conf (k=2) =
Bias @ 94.7% Rec of LCS = -5.3%

33.4%

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