United States
Environmental Protection
Agency
Environmental Monitoring and
Support Laboratory
Cincinnati OH 45268
Research and Development
EPA/600/S4-85/070 Jan. 1986
SER& Project Summary
EPA Method Study 31: Trace
Metals by Atomic Absorption
(Furnace Techniques)
T. R. Copeland and J. P. Maney
An interlaboratory study in which 10
laboratories participated was conduct-
ed to provide precision and accuracy
statements for the analysis of 18 metals
by graphite furnace atomic absorption
spectrometry. Samples were prepared
and analyzed using procedures speci-
fied in "Methods for Chemical Analysis
of Water and Wastes." EPA 600/4-
797 020, U.S. Environmental Protec-
tion Agency, Environmental Monitoring
and Support Laboratory, Cincinnati,
OH, March 1979.
The study design was based on You-
den's non-replicate design for collabo-
rative tests of analytical methods. Three
Youden pair samples of the test metals
were spiked into six types of test waters
and then analyzed. The test waters were
three industrial effluents supplied by
ERCO and three waters supplied by the
subcontractor laboratories (laboratory
pure water, finished drinking water, and
surface water). The resulting data were
statistically analyzed using the com-
puter program entitled "Interlaboratory
Method Validation Study" (IMVS).
The statistical analyses included re-
jection of outliers, estimation of mean
recovery (accuracy), estimation of single-
analyst and overall precisions, and tests
for the effects of water type on accuracy
and precision.
This Project Summary was developed
by EPA's Environmental Monitoring and
Support Laboratory, Cincinnati. OH. to
announce key findings of the research
project that is fully documented in a
separate report of the same title (see
Project Report ordering information at
back).
Introduction
The Safe Drinking Water Act (SDWA)
and the National Pollutant Discharge
Elimination System (NPDES) require that
waters and waste be analyzed to deter-
mine their chemical content. The EPA
was given a mandate to prepare methods
which would be approved for the analysis
of parameters of concern listed by these
laws and resulting regulations.
The EPA staff of the Environmental
Monitoring and Support Laboratory of
Cincinnati, Ohio, provided the procedures
for monitoring metal parameters in
wastes and waters in the document
entitled, "Methods for Chemical Analysis
of Water and Wastes." The second edi-
tion of this manual, which was published
in March 1979, added atomic absorption
furnace methods to quantitate lower
levels of metal parameters than those
determinable by the flame atomic absorp-
tion methods specified in the first edition.
Energy Resources Co. Inc. (ERCO) was
contracted by EPA to conduct a method
study to define the accuracy and precision
of the atomic absorption furnace proce-
dure for the following 18 trace metals:
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
(Method
(Method
(Method
(Method
(Method
(Method
(Method
(Method
(Method
(Method
(Method
202.2)
204.2)
206.2)
208.2)
210.2)
213.2)
218.2)
219.2)
220.2)
236.2)
239.2)
-------
Manganese
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
(Method
(Method
(Method
(Method
(Method
(Method
(Method
243.2)
249.2)
270.2)
272.2)
279.2)
286.2)
289.2)
Ten laboratories were selected by ERCO
for participating in the method study
following their successful analysis of
performance evaluation samples. These
laboratories then collected drinking, sur-
face, and laboratory pure waters while
ERCO supplied them with three different
types of industrial effluents. These waters
and effluents were analyzed to determine
background levels of the elements of
interest and subsequently specified vol-
umes of unknown metal concentrates
were added and the samples reanalyzed.
The added level of each metal was
determined by difference.
Youden's non-replicate collaborative
test design was applied to 10 participating
laboratories. Formal statistical tech-
niques compatible with the Youden de-
sign were used to identify outliers, est-
imate the method's accuracy and preci-
sion, and test for the effect of water type.
The formal statistical analyses were
carried out using U.S. EPA's IMVS com-
puter program.
Procedure
The study consisted of two distinct
analysis phases. Phase I involved the
selection of participating laboratories. An
EPA-supplied list of laboratories and
previous ERCO experience were used to
solicit interested laboratories. Based on
prior experience of the laboratories in
graphite furnace analysis; assurance of
adequate facilities, instrumentation, and
personnel to complete the analyses in a
timely manner; and cost estimates, 12
laboratories were selected to receive two
pre-award performance evaluation sam-
ples. These samples contained acid solu-
tions of eight of the 18 metals of interest
in sealed glass ampules.
These solutions were spiked into lab-
oratory pure water supplied by the indi-
vidual participating laboratories and an-
alyzed by the graphite furnace atomic
absorption procedures to be employed in
the interlaboratory study. The analytical
results were submitted to ERCO for
evaluation.
Based upon the individual laboratories'
analytical results and the above criteria,
10 laboratories were selected for partic-
ipation in the study.
Phase II consisted of the actual inter-
laboratory study. This study required the
analysis of six different water matrices,
spiked at six different concentrations
(three Youden pairs) of all 18 analytes of
interest. In addition, each participating
laboratory performed an analysis of the
six waters with no spiked compounds
added. Each participating laboratory then
issued a report of all results to ERCO.
The final step in the study was the
statistical analysis of all data by Battelle
Memorial Laboratories using EPA's INVS
system.
Results and Discussion
The object of this study was to char-
acterize the performance of graphite
furnace atomic absorption procedures in
terms of accuracy, overall precision,
single-analyst precision, and the effect of
water types on accuracy and precision.
Through the statistical analysis of 8,640
analytical values, estimates of accuracy
and precision were made and expressed
as regression equations, which are pre-
sented in Table 1.
Of all 8,640 analytical values, 23%
were rejected as outliers. The accuracy of
the methods is obtained by comparing the
mean recovery to the true values of
concentration. The range of accuracy
values (expressed as a percent relative
error) was from 0.13% to 17,720%. This
wide range was very dependent upon the
individual analyte with the highest error
being for zinc.
The overall standard deviation indicates
the precision associated with the meas-
urements generated by the 10 laborator-
ies. The overall precision (expressed as a
percent relative standard deviation)
ranged from 0.55% to 171 %. The highest
relative standard deviation (worst preci-
sion) occurred for silver.
Statistical comparisons of the effect of
water type were performed on all an-
alytes. These indicated a practical effect
of water matrix on the accuracy and/or
precision of the methods in the following
cases:
Arsenic in effluents 2 and 3
Beryllium in surface water
Nickel in effluents 2 and 3
Selenium in effluents 1 and 3
Silver in effluent 2
and Thallium in surface water and
effluent 2
Conclusions and
Recommendations
Statistically significant matrix effects
were found for several methods. Accuracy
and precision were, in general, poorest
for the low concentration levels. Many
laboratories could not achieve the recom-
mended method detection limits. For
several analytes accuracy and precision
for the highest concentration levels were
also poor, indicating that non-linearity
might not have been detected by some
analysts. Environmental contamination
with Al, Fe, and Zn affected the accuracy
and precision of these analyses. For four
of the six waters, zinc had the highest
percentage of data rejected. On average,
23% of the data were rejected. For
individual laboratories, data rejection
ranged from 12% to 36%. From all of the
above it must be concluded that accurate
and precise results may be obtained only
by analysts thoroughly experienced in the
use of graphite furnace methods.
It is recommended that instrumental
parameters such as graphite type, back-
ground correction, sheath gas, and use of
matrix modifiers be specified so that
variability from these effects is minimized
and separated from sample matrix effects.
It is further recommended that more
rigorous checks be made to determine if
the method of standard additions is
required for a particular analyte/matrix
combination.
-------
Table 1. EPA Method Study—Trace Metals by AA. Regression Equations for Accuracy and Precision for Compound 1
Water Type Aluminum Water Type Aluminum
Applicable cone, range
Lab pure water
Single-analyst precision
O verall precision
Accuracy
Drinking water
Single-analyst precision
Overall precision
Accuracy
Surface Water
Single-analyst precision
Overall precision
Accuracy
Water Type
(28.00-125.OO; iig/L
SR = 0.23X + 6.45
S = 0.42X+ 5.83
X = 0.70C +32.36
SR = 0.72X+21.97
S = 0.2SX + 14.45
X = 1.IOC+ 39.21
SR = 0.33X+ 5.29
S = O.SOX - 0.27
X = -0.34C + 33.60
Aluminum
Applicable cone, range
Lab pure water
Single-analyst precision
Overall precision
Accuracy
Effluent 3
Single-analyst precision
Overall precision
Accuracy
Water Type
(26.80-120.00) ug/L
SR = 0.23X+ 6.21
S = 0.42X + 5.80
X = 0.70C + 31.13
SR - 0.24X+ 3.18
S = 0.14X +26.59
X = 1.03C +32.88
Aluminum
Applicable cone, range
Lab pure water
Single-analyst precision
Overall precision
Accuracy
Effluent 1
Single-analyst precision
Overall precision
Accuracy
Water Type
(11.00-58.301 mg/L
SR = 0.36X - 2.87
S = 0.39X - 2.27
X = 0.85C + 1.87
SR = 0./6X + 0,88
S = 0.26X + 2.24
X = 1.12C- 2.89
Antimony
Applicable cone, range
Lab pure water
Single-analyst precision
Overall precision
Accuracy
Effluent 2
Single-analyst precision
Overall precision
Accuracy
Water Type
(0.46-2.18) mg/L
SR - 0.39X- 0.14
S = 0.39X - 0.09
X = 0.85C + 0.08
SR = -0.04X + 0.76
S = 0.07X+ 0.18
X - 0.85C+ 0.12
Antimony
Applicable cone, range
Lab pure water
Single-analyst precision
Overall precis/on
Accuracy
Effluent 1
Single-analyst precision
Overall precision
Accuracy
Effluent 2
Single-analyst precision
Overall precision
Accuracy
Effluent 3
Single-analyst precision
Overall precision
Accuracy
Water Type
(10.50-230.00) ug/L
SR = 0.14X+ 1.09
S = 0.40X + 0.88
X = 0.65C + 0.56
SR = 0.24X- 0.50
S = 0.17X + 3.89
X = 0.88C- 1.28
SR = 0.72X + 4.23
S = 0.09X + 9.56
X = 0.73C + 5.80
SR - 0.22X + 0.37
S = 0.33X + 0.87
X = 0.61C+ 0.31
Arsenic
Applicable cone, range
Lab pure water
Single-analyst precision
Overall precision
Accuracy
Drinking Water
Single-analyst precision
Overall precision
Accuracy
Surface water
Single-analyst precision
Overall precision
Accuracy
Water Type
(11.00-240.00) ug/L
SR = 0.23X + 0.02
5 = 0.34X + 0.86
X = O.SOC - 2.66
SR = 0.21 X- 0.14
S = 0.18X+ 0.73
X - 0.87C- 2.14
SR = 0.16X+ 0.14
S = O.2OX + 0.87
X = O.81C-0.97
Arsenic
Applicable cone, range
Lab pure water
Single-analyst precision
Overall precision
Accuracy
Effluent 1
Single-analyst precision
Overall precision
Accuracy
19.78-227.00) ug/L
SR = 0.08X + 2.82
S = 0.17X+ 1.98
X = 1.02C+ 3.30
SR = 0.07X + 5.85
S = 0.15X+ 4.01
X = 1.15C + 8.87
Applicable cone, range
Lab pure water
Single-analyst precision
Overall precision
Accuracy
Drinking Water
Single-analyst precision
O verall precision
Accuracy
110.20-237.00) ug/L
SR = 0./OX+ 0.70
5 = 0.//X+ 1.98
X = 0.52C + 0.63
SR = 0.06X + 1.96
S = 0.12X+ 1.49
X = 0.93C + 0.62
-------
Table 1. (Continued)
Water Type
Arsenic
Water Type
Arsenic
Applicable cone, range
Effluent 2
Single-analyst precision
Overall precision
Accuracy
Effluents
Single-analyst precision
Overall precision
Accuracy
Water Type
(9.78-227.00) fjg/L
SR = 0.16X +0.97
S = 0.14X +3.70
X = 0.94C-0.68
SR = 0.07X + 0.53
S = 0.15X+2.56
X = 0.87C - 0.30
Barium
Applicable cone, range
Surface Water
Single-analyst precision
Overall precision
Accuracy
Water Type
/10.20-237.00) ug/L
SR = 0.09X + 0.80
S = 0.13X +2.75
X = 0.91C-1.29
Barium
Applicable cone, range
Lab pure water
Single-analyst precision
Overall precision
Accuracy
Effluent 1
Single-analyst precision
Overall precision
Accuracy
Effluent 2
Single-analyst precision
Overall precision
Accuracy
Effluent3
Single-analyst precision
Overall precision
Accuracy
Water Type
(56.50-418.00) ug/L
SR = 0.12X +4.80
S = 0.36X-8.62
X = 0.84C + 83.77
SR = 0.19X +70.20
S = 0.27X + 32.68
X = 0.97C + 67.43
SR = 0.29X-13.14
S = 0.58X-27.91
X = 0.84C + 42.52
SR = 0.69X-39.17
S = 0.34X + 9.88
X - 0.24C + 65.63
Beryllium
Applicable cone, range
Lab pure water
Single-analyst precision
Overall precision
Accuracy
Drinking Water
Single-analyst precision
0 verall precision
Accuracy
Surface water
Single-analyst precision
Overall precision
Accuracy
Water Type
(59.10-437.00) ug/L
SR = 0.15X - 1.72
S = 0.14X +75.63
X = 0.84C + 30.67
SR = 0.11X +2.22
S = 0.37X - 10.56
X = 0.92C + 36.50
SR - 0.20X-0.16
S = 0.28X + 7.58
X = 0.93C + 30.17
Beryllium
Applicable cone, range
Lab pure water
Single-analyst precision
Overall precision
Accuracy
Effluent 1
Single-analyst precision
O verall precision
Accuracy
Effluent 2
Single-analyst precision
Overall precision
Accuracy
Effluents
Single-analyst precision
Overall precision
Accuracy
Water Type
10.45-10.90) ug/L
SR = 0.7 2X + 0.05
S = 0.29X + 0.05
X - 1.15C-0.25
SR = 0.07X + 0.10
S = 0.19X +0.20
X - 0.92C + 0.11
SR = 0.12X-0.05
S = 0.07X + 0.19
X = J.08C + 0.01
SR = 0.13X-0.00
S - 0.20X + 0.08
X = 0.92C - 0.03
Cadmium
Applicable cone, range
Lab pure water
Single-analyst precision
Overall precision
Accuracy
Drinking water
Single-analyst precision
Overall precision
Accuracy
Surface water
Single-analyst precision
Overall precision
Accuracy
Water Type
10.47-11.40) ug/L
SR = 0.1 OX+ 0.08
S = 0.11X + 0.18
X = O.98C - 0.05
SR = 0.03X + 0.11
S = 0.14X +0.07
X = J.01C-0.07
SR = 0.7 OX+ 0.02
S = 0.29X-0.08
X = 0.90C + 0.10
Cadmium
Applicable cone, range
Lab pure water
Single-analyst precision
Overall precision
Accuracy
(0.43-12.00J fjg/L
SR = 0.09X + 0.25
S = 0.17X + 0.20
X = 1.02C + 0.24
Applicable cone, range
Lab pure water
Single-analyst precision
0 verall precision
Accuracy
(0.45-12.50) ug/L
SR = 0.1 OX+ 0.05
S = 0.27X-0.05
X = 0.95C + 0.09
-------
Table 1. (Continued)
Water Type
Cadmium
Water Type
Cadmium
Applicable cone, range
Effluent 1
Single-analyst precision
Overall precision
Accuracy
Effluent 2
Single-analyst precision
Overall precision
Accuracy
Effluent 3
Single-analyst precision
Overall precision
Accuracy
Water Type
(0.43-12.00) ug/L
SR = 0.14X +0.42
S = 0.32X^0.15
X = 0.75C + 0.39
SR = 0.12X + 0.09
S = 0.23X + 0.07
X = 0.81C + 0.15
SR = 0.15X^0.04
S = 0.27X^0.14
X = 0.96C + O.JO
Chromium
Applicable cone, range
Drinking water
Single-analyst precision
Overall precision
Accuracy
Surface water
Single-analyst precision
Overall precision
Accuracy
(0.45-12.50) ug/L
Sft = 0.17X + 0.11
S = 0.26X^0.10
X = 0.92C + 0.24
Water Type
SR = 0.22X-0.13
S = 0.38X^0.10
X = 1.04C + 0.15
Chromium
Applicable cone, range
Lab pure water
Single-analyst precision
Overall precision
Accuracy
Effluent 1
Single-analyst precision
Overall precision
Accuracy
Effluent 2
Single-analyst precision
Overall precision
Accuracy
Effluents
Single-analyst precision
Overall precision
Accuracy
Water Type
(9.87-236.00) fjg/L
SR = 0.18X^0.73
S = 0.20X + 1.14
X - 0.89C+O.1J
SR = 0.14X^0,88
S = 0.21 X +3.87
X = 0.87C+7.09
SR = 0.17X-0.32
5 = 0.14X + 2.S5
X = 0.95C + 1.03
SR = O.oax + 0.28
S = 0.22X + 0.41
X = 0.92C - 0.68
Cobalt
Applicable cone, range
Lab pure water
Single-analyst precision
0 verall precision
Accuracy
Drinking water
Single-analyst precision
Overall precision
Accuracy
Surface water
Single-analyst precision
Overall precision
Accuracy
Water Type
(10.30-246.00) ug/L
SR = 0.12X-0.41
S = 0.14X +0.35
X = 0.94C + 0.40
SR = 0.06X^2.73
S = 0.12X^4.14
X = /.OOC + 0.89
SR = 0.12X- 0.12
S - 0.26X - 0.04
X = 0.91 C +0.47
Cobalt
Applicable cone, range
Lab pure water
Single-analyst precision
Overall precision
Accuracy
Drinking water
Single-analyst precision
Overall precision
Accuracy
Surface water
Single-analyst precision
Overall precision
Accuracy
Water Type
129.70-420.00)/jg/L
SR = 0.09X + 0.50
S = 0.25X - 2.99
X = 0.88C + 1.36
SR = O.J2X+ 1.60
S = 0.23X+ 1.24
X = 0.92C + 0.44
SR - 0.14X- 1.00
S = 0.18X-0.14
X = 0.92C + 2.07
Cobalt
Applicable cone, range
Lab pure water
Single-analyst precision
O verall precision
Accuracy
Effluent 1
Single-analyst precision
Overall precision
Accuracy
Water Type
(24.80-407.00) ug/L
SR = 0.1IX + 0.02
S = 0.25*-2.69
X = 0.89C+ 1.11
SR = 0.16X +0.58
S = 0.20X-0.89
X - 0.88C + 4.50
Cobalt
Applicable cone, range
Lab pure water
Single-analyst precision
Overall precision
Accuracy
(21.10-461.00) ug/L
SR = 0.09X + 0.03
S = 0.25X- 1.99
X = 0.89C + 0.25
Applicable cone, range
Lab pure water
Single-analyst precision
O verall precision
Accuracy
(29.30-435.00) ug/L
SR = 0.09X + 0.16
S - 0.25X-3.31
X - 0.88C + 1.32
-------
Table 1. (Continued)
Water Type
Cobalt
Water Type
Cobalt
Applicable cone, range
Effluent 2
Single-analyst precision
O verall precision
Accuracy
Water Type
Applicable cone, range
(21. 10-461. 00) ijg/L
SR = 0.09X^3.21
S = 0.73X + 1.76
X = 0.95C + 0.43
Copper
(10.10-234.OO)/jg/L
Applicable cone, range
fffluent 3
Single-analyst precision
Overall precision
Accuracy
Water Type
Applicable cone, range
(29.30-435.00} ng/L
SR = 0.06X + 2.06
S = 0.1 5X + 1.28
X = 0.82C + 1.43
Copper
(0.30-1 .67) mg/L
Lab pure water
Single-analyst precision
Overall precision
Accuracy
Effluent 1
Single-analyst precision
Overall precision
Accuracy
Effluent 3
Single-analyst precision
O verall precision
Accuracy
SR = 0.07X + 4.37
S = 0.11X + 4.97
X = 0.92C-0.81
SR = 0.22X - 0.44
S = 0.21X+ 1.21
X = 0.96C-0.10
SR = 0.13X+ 1.95
S = 0.29X + 4.96
X = 0.81 C +0.42
Lab pure water
Single-analyst precision
0 verall precision
Accuracy
Effluent 2
Single-analyst precision
O verall precision
Accuracy
SR = 0.13X-0.02
S = 0.13X-0.00
X = 0.93C + 0.01
SR = 0.05X + 0.02
S = 0.13X +0.01
X = 1.02C - 0.07
Water Type
Copper
Applicable cone, range
(10.60-245.00) fjg/L
Lab pure water
Single-analyst precision
Overall precision
Accuracy
Drinking water
Single-analyst precision
Overall precision
Accuracy
Surface water
Single-analyst precision
Overall precision
Accuracy
SR = 0.22X - 0.46
S = 0.21 X+ 1.29
X = 0.96C-0.77
SR = 0.15X +2.63
S = 0.34X + 3.39
X = 0.91 C +6.09
SR = 0.06X+1.18
S = 0.18X +1.44
X = 1.00C - 0.26
Water Type
Iron
Water Type
Iron
Applicable cone, range
(26.10-455.00) ng/L
Applicable cone, range
(25.00-435.00) /jg/L
Lab pure water
Single-analyst precision
Overall precision
Accuracy
Drinking water
Single-analyst precision
Overall precision
Accuracy
Surface water
Single-analyst precision
Overall precision
Accuracy
SR = 0.30X+26.73
S = 0.35X + 73.23
X = 1.40C+11.73
SR = 0.30X + 7.06
S = 0.36X + 9./5
X = 1.20C + 70.35
SR = 0.35X - 3.95
S = 0.34X + 37.42
X = 1.IOC+ 96.38
Lab pure water
Single-analyst precision
Overall precision
Accuracy
Effluents
Single-analyst precision
Overall precision
Accuracy
SR - 0.30X + 25.23
S = 0.35X+ 12.73
X = 1.41C+ 11.24
SR = 0.23X+16.21
S = 0.31X + 31.14
X = 1.09C + 37.18
-------
Table 1. (Continued)
Water Type
Iron
Water Type
Iron
Applicable cone, range
Lab pure water
Single-analyst precision
Overall precision
Accuracy
Effluent 1
Single-analyst precision
Overall precision
Accuracy
Water Type
(1.03-S.59) mg/L
SR = 0.04X^0.13
S = 0.05X + 0.27
X = 1.01C + O.07
SR = 0.28X + 0.04
S = 0.41X-0.13
X = 1.16C-0.25
Lead
Applicable cone, range
Lab pure water
Single-analyst precision
Overall precision
Accuracy
Effluent 2
Single-analyst precision
0 verall precision
Accuracy
Water Type
(0.37-2.61) mg/L
SR = 0.06X + 0.03
S = 0.07X + 0.08
X = 1.42C-0.17
SR = 0.18X-0.03
S = 0.22X-0.01
X = r.OOC + 0.04
Lead
Applicable cone, range
Lab pure water
Single-analyst precision
Overall precision
Accuracy
Effluent 1
Single-analyst precision
Overall precision
Accuracy
Effluent 2
Single-analyst precision
Overall precision
Accuracy
Effluent 3
Single-analyst precision
Overall precision
Accuracy
(10.40-243.00) ug/L
SR = 0.17X-0.88
S = 0.17X+1.36
X = 1.06C-2.26
SR = 0.22X-0.14
S = 0.23X-0.06
X = 0.81 C + 2.05
SR = 0.14X+ 1.00
S = 0.22X+1.40
X = 0.86C-2.12
SR = 0.22X^1.48
S - 0.34X^1.86
X = 0.70C+ 1.63
Applicable cone, range
Lab pure water
Single-analyst precision
0 verall precision
Accuracy
Drinking water
Single-analyst precision
0 verall precision
Accuracy
Surface water
Single-analyst precision
Overall precision
Accuracy
(10.90-254.00) ug/L
SR = 0.20X^0.42
S = 0.28X - 0.66
X = 0.83C + 1.35
SR - 0.07X + 1.39
S = 0.2 IX + 2.56
X - 0.85C + 0.50
SR = 0.19X^0.11
S - 0.18X +1.73
X - 0.92C - 0.96
Water Type
Applicable cone, range
Lab pure water
Single-analyst precision
O verall precis/on
Accuracy
Drinking water
Single-analyst precision
Overall precision
Accuracy
Manganese
(0.44-1 4.80) ug/L
SR
S =
X =
SR
S =
X =
= 0.27X + 0.31
0.44X + 0.48
1.00C+1.46
= 0.1 6X + 0.51
0.38X + 0.52
0.90C+ 1.38
Water Type
Applicable cone, range
Lab pure water
Single-analyst precision
Overall precision
Accuracy
Effluent 1
Single-analyst precision
Overall precision
Accuracy
Manganese
(91. 00-484.00) ug/L
SR
S =
X -
SR
S =
X =
= 0.03X+11.34
O.O5X + 1 1.20
0.55C + 12.98
= 0.04X + 40.27
0.1 IX + 32.01
0.97C - 6.66
Surface water
Single-analyst precision
0 verall precision
Accuracy
Water Type
Manganese
Water Type
Manganese
Applicable cone, range
Lab pure water
Single-analyst precision
0 verall precision
Accuracy
Effluent 2
Single-analyst precision
Overall precision
Accuracy
(111.00-666.00) ug/L
SR = 0.05X^8.13
S = 0.07X + 9.19
X = 0.93C + 9.38
SR = 0.26X + 3.47
S = 0.32X - 6.30
X = 0.78C-8.22
Applicable cone, range
Lab pure water
Single-analyst precision
O verall precision
Accuracy
£ffluent3
Single-analyst precision
Overall precision
Accuracy
(0.42-14.20) ug/L
SR = 0.27X + 0.37
S = 0.43X + 0.47
X = 1.00C+1.40
SR = O.23X + 0.52
S = 0.48X - 0.28
X = 0.46C + 2.56
-------
Table 1. (Continued)
Water Type
Nickel
Water Type
Nickel
Applicable cone, range
Lab pure water
Single-analyst precision
Overall precision
Accuracy
Effluent 1
Single-analyst precision
Overall precision
Accuracy
Effluent 2
Single-analyst precision
Overall precision
Accuracy
Effluent 3
Single-analyst precision
Overall precision
Accuracy
Water Type
(26.20-461.00) ug/L
SR = 0.17X +0.34
S - 0.26X + 1.89
X = 0.84C + 6.46
SR = 0.1 OX+ 3.46
S = 0.16X +4.72
X = 0.67C + 70.56
SR = 0.13X + 2.39
S = 0.24X + 5.60
X = O.S5C-4.74
SR = 0.04X + 1.88
S = 0.18X+ 9.11
X = 0.84C - 9.99
Selenium
Applicable cone, range
Lab pure water
Single-analyst precision
O verall precision
Accuracy
Drinking water
Single-analyst precision
Overall precision
Accuracy
Surface water
Single-analyst precision
Overall precision
Accuracy
Water Type
(27.40-482.00) ug/L
SR = 0.21 X-2.45
S = 0.23X + 1.98
X = 0.93C - 2.02
SR = 0.12X +4.43
S = 0.27X + 2.20
X = 0.81 C +0.75
SR = 0.1 OX+ 4.38
S = 0.16X +9.37
X = 0.81 C +2.47
Selenium
Applicable cone, range
Lab pure water
Single-analyst precision
Overall precision
Accuracy
Effluent 1
Single-analyst precision
Overall precision
Accuracy
Effluent 2
Single-analyst precision
Overall precision
Accuracy
Effluent 3
Single-analyst precision
Overall precision
Accuracy
Water Type
(10.00-235.00) ug/L
SR = 0.06X + 0.65
S = 0.17X + 0.14
X = 0.93C - 0.20
SR = 0.05X + 3.19
S = 0.19X+ 1.76
X = 0.88C-2.45
SR = 0.1 IX+ 3.14
S = 0.19X + 2.78
X = 1.11C-2.78
SR - 0.17X +0.20
S = 0.40X + 2.55
X = 0.84C-2.14
Silver
Applicable cone, range
Lab pure water
Single-analyst precision
Overall precision
Accuracy
Drinking water
Single-analyst precision
Overall precision
Accuracy
Surface water
Single-analyst precision
Overall precision
Accuracy
Water Type
(10.50-246.00) ug/L
SR = 0.1 OX+ 0.50
S = 0.14X + 2.18
X = 0.98C + 1.28
SR = 0.05X + 2.23
S = 0.16X + 3.16
X = 1.07C + 0.19
SR = 0.15X +0.25
S = 0.17X+ 1.64
X = 1.00C-0.66
Silver
Applicable cone, range
Lab pure water
Single-analyst precision
Overall precision
Accuracy
Effluent 1
Single-analyst precision
Overall precision
Accuracy
Effluent 2
Single-analyst precision
Overall precision
Accuracy
Effluents
Single-analyst precision
Overall precision
Accuracy
(8.48-56.50) ug/L
SR = 0.19X-0.95
S = 0.17X + 0.35
X = 0.79C + 2.78
SR = 0.06X + 0.78
S = 0.28X - 1.05
X = 0.90C + 0.96
SR = 0.28X+1.11
S = 0.65X + 0.26
X = 0.49C + 0.03
SR = 0.34X-2.10
S = 0.38X-1.06
X = 0.70C + 4.27
Applicable cone, range
Lab pure water
Single-analyst precision
Overall precision
Accuracy
Drinking water
Single-analyst precision
Overall precision
Accuracy
Surface water
Single-analyst precision
Overall precision
Accuracy
(0.45-13.60) ug/L
SR = 0.15X +0.03
S = 0.18X + 0.15
X = 0.96C + 0.17
SR = -0.02X + 0.77
S = 0.20X + 0.17
X = 0.82C + 0.81
SR = 0.1 OX-0.07
S = 0.56X + 0.06
X = 0.87C + 2.46
8
-------
Table 1. (Continued)
Water Type
Thallium
Water Type
Thallium
Applicable cone, range
Lab pure water
Single-analyst precision
Overall precision
Accuracy
Effluent 1
Single-analyst precision
Overall precision
Accuracy
Effluent 2
Single-analyst precision
Overall precision
Accuracy
Effluent 3
Single-analyst precision
Overall precision
Accuracy
(10.00-241.00)ijg/L
SR = 0.15X +0.03
S = 0.12X +0.96
X = 0.87C-1.24
SR = 0.09X + 0.41
S = 0.30X - 0.04
X = 0.76C- 1.12
SR = 0.16X-0.20
S = 0.14X+ 1.58
X = 0.62C- 1.06
SR = 0.06X + 0.00
S = 0.19X +0.33
X = 0.81 C-1.70
Applicable cone, range
Lab pure water
Single-analyst precision
Overall precision
Accuracy
Drinking water
Single-analyst precision
Overall precision
Accuracy
Surface water
Single-analyst precision
Overall precision
Accuracy
(10.50-252.00)/jg/L
SR = 0.06X + 0.41
S = 0.1 IX+ 0.13
X = 0.88C-0.10
SR = 0.09X-0.29
S = 0.26X- 1.14
X = 0.89C - 0.89
SR = 0.1 OX+ 0.02
S = 0.25X-0.14
X = 0.84C-1.15
Water type
Vanadium
Water type
Vanadium
Applicable cone, range
Lab pure water
Single-analyst precision
Overall precision
Accuracy
Drinking water
Single-analyst precision
Overall precision
Accuracy
Surface water
Single-analyst precision
Overall precision
Accuracy
(151.00-982.00) fig/7.
SR = 0.12X + 2.14
S = 0.53X-44.69
X = 0.75C +26.06
SR = 0.04X + 21.95
S = 0.18X + 14.92
X = 1.00C-14.73
SR = 0.1 SX-5.47
S = 0.15X +0.56
X = 0.96C- 11.91
Applicable cone, range
Lab pure water
Single-analyst precision
Overall precision
Accuracy
Effluent 1
Single-analyst precision
Overall precision
Accuracy
Effluent 2
Single-analyst precision
Overall precision
Accuracy
(144.00-939.00)vg/L
SR = 0.12X + 1.96
S = 0.53X-42.61
X = 0.75C +25.26
SR = 0.04X + 19.60
S = 0.24X + 4.39
X = 1.05C-7.45
SR = 0.13X+14.33
S = 0.11X+19.77
X = 0.94C-17.68
Water type
Vanadium
Applicable cone, range
Lab pure water
Single-analyst precision
Overall precision
Accuracy
Effluent 3
Single-analyst precision
O verall precision
Accuracy
(1.36-6.031 mg/L
SR = 0.05X + 0.01
S = 0.1 IX-0.01
X = 0.96C + 0.04
SR = 0.12X- 0.04
S = 0.21X-0.13
X = 0.99C-0.18
Water type
Zinc
Water type
Zinc
Applicable cone, range
Lab pure water
Single-analyst precision
Overall precision
Accuracy
(0.54-17.40) ug/L
SR = 0.56X- 1.19
S = 1.03X-1.03
X = 2.93C+J.02
Applicable cone, range
Lab pure water
Single-analyst precision
Overall precision
Accuracy
(1.31-6.41) mg/L
SR = 0.24X + 0.04
S = 0.30X + 0.11
X = 1.18C-0.31
-------
Table 1. (Continued)
Water type
Zinc
Water type
Zinc
Applicable cone, range
Drinking water
Single-analyst precision
Overall precision
Accuracy
Surface water
Single-analyst precision
Overall precision
Accuracy
(0.54-17.40) fjg/L
SR = 0.31 X + 6.80
S = 0.99X + 0.69
X = 1.29C+14.50
SR = 0.59X-5.51
S = 1.06X-0.04
X = 2.43C + 7.16
Applicable cone range
Effluent 1
Single-analyst precision
Overall precision
Accuracy
(1.31-6.41 jmg/L
SR = 0.35X + O.J9
S = 0.69X + 0.10
X = 0.42C + 0.84
Water type
Zinc
Water type
Zinc
Applicable cone, range
(24.60-189.00) ug/L
X = Mean recovery.
C = True value for the concentration.
Applicable cone, range
(0.51 -16.70) ug/L
Lab pure water
Single-analyst precision
Overall precision
Accuracy
Effluent 2
Single-analyst precision
Overall precision
Accuracy
SR = 0.24X+1.21
S = 0.31 X+ 1.45
X = 1. 11 C -2.76
SR = 0.86X- 19.95
S = 0.77X-3.46
X = 1.04C + 9.S8
Lab pure water
Single-analyst precision
O verall precision
Accuracy
Effluents
Single-analyst precision
Overall precision
Accuracy
SR
S =
X =
= 0.56X-J.04
1.00X-0.63
2.93C + 0.86
1.27X- 11.00
8.83C + 54.05
T. R. Copeland and J. P. Maney are with ERCO, Cambridge, MA 02138.
Edward L. Berg and Robert L. Graves are the EPA Project Officers (see below).
The complete report, entitled "EPA Method Study 31: Trace Metals by Atomic
Absorption (Furnace Techniques)," (Order No. PB 86-121 704/AS; Cost:
$28.95, subject to change) will be available only from:
National Technical Information Service
5285 Port Royal Road
Springfield, VA 22161
Telephone: 703-487-4650
The EPA Project Officers can be contacted at:
Environmental Monitoring and Support Laboratory
U.S. Environmental Protection Agency
Cincinnati, OH 45268
10
•&U. S. GOVERNMENT PRINTING OFFICE: 1986/646-116/20749
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