\f/
United States
Environmental Protection
Agency
Environmental Monitoring and
Support Laboratory
Cincinnati OH 45268
Research and Development
EPA/600/S4-85/051 Dec. 1985
Project Summary
EPA Method Study 27,
Method 200.7 Trace Metals by
ICP
Robert Maxfield and Bill Mindak
An interlaboratory study was con-
ducted to determine the precision and
accuracy measurements of US EPA
Method 200.7 for the analysis of
twenty-seven elements in water and
wastewater. US EPA Method 200.7 is
entitled "Inductively Coupled Plasma—
Atomic Emission Spectrometric
Method for Trace Element Analysis of
Water and Waste" and includes instruc-
tions for quality control, sample prepa-
ration and analysis of samples by Induc-
tively Coupled Plasma (ICP).
The study design was based upon
Youden's non-replicate plan for collab-
orative tests of analytical methods.
Each water type was spiked with three
Youden pairs of the twenty-seven test
elements and analyzed using both a
"hard" and "soft" digestion procedure.
The test waters included reagent water
as a "control" against which other test
data were compared. The resulting
data were analyzed using a US EPA
computer program routine entitled
"Interlaboratory Method Validation
Study (IMVS)." The data analysis pro-
duced measures of precision and accu-
racy for the ICP method for each water
type/element/digestion combination.
These data were used to compare the
performance of the method between
water types and digestions.
The study was conducted under the
auspices of the Environmental Protec-
tion Agency, Quality Assurance Branch,
Environmental Monitoring and Support
Laboratory, Cincinnati, Ohio under EPA
Contract No. 68-03-3007. This report
covers a period from September 10,
1980 to December 31, 1983, all analyti-
cal work was completed as of January
31,1982.
This Project Summary was devel-
oped by EPA's Environmental Monitor-
ing and Support Laboratory, Cincinnati,
OH, to announce key findings of the re-
search project that is fully documented
in a separate report of the same title
(see Project Report ordering informa-
tion at back).
Introduction
In October, 1973, EPA promulgated
"Guidelines Establishing Test Proce-
dures for the Analysis of Pollutants" in
40 CFR part 136 of the Federal Register
under the authority of Section 304(h) of
the Clean Water Act. These guidelines
were amended in December, 1976, to
provide test procedures for 115 well
known pollutants and pollutant parame-
ters including metals and a number of
organic compounds. In December 1979,
the same regulation was amended and
an interim ICP method for trace element
analysis of water and waste was in-
cluded. This technique was proposed as
an alternative to existing 304(h) meth-
ods for metals analyses and provided
for simultaneous multi-element deter-
mination of metals in solutions. In
March, 1983, a revised version of the
ICP method was published as Method
200.7 in EPA's "Methods for Chemical
Analysis of Water and Wastes."
This report describes an interlabora-
tory study of Method 200.7 conducted
for 27 metals in water and wastewater.
The primary objective of the study was
to assess the method with respect to
(1) accuracy; (2) overall precision;
(3) single-analyst precision and the per-
formance of th.e method for the analy-
ses of various water types. The study
was designed and supported under the
-------
auspices of the Environmental Monitor-
ing and Support Laboratory (EMSL)—
Cincinnati. The interlaboratory study in-
cluded twelve participating laboratories
that employed US EPA Method 200.7 to
analyze approximately 100 study sam-
ples each.
Participating laboratories were sup-
plied with spiking solutions, effluent
water samples and instructions on
preparation of the samples. Laborato-
ries analyzed six (6) water types for
twenty-seven (27) elements utilizing
both the hard and soft digestion proce-
dures described in US EPA Method
200.7. Laboratories then reported data
and provided comments on the perfor-
mance of the method. Approximately
30 thousand data points were gener-
ated by the participating laboratories
during the study.
Raw data from the twelve (12) labora-
tories were treated for individual and
laboratory outliers. Acceptable data
were statistically analyzed to produce
measures of precision and accuracy and
to test for the effect of different water
types. The actual data analysis was per-
formed using IMVS software provided
by the EPA. Statistical data have been
summarized in this report and are pre-
sented along with a descriptive sum-
mary of the study findings.
Analytical Methodology
The ICP method employed in the
study is entitled "Inductively Coupled
Plasma Atomic Emission Spectrometric
Method for Trace Element Analysis of
Water and Wastes—US EPA Method
200.7." The method was included in the
March 1983 revision of EMSL's
"Methods for Chemical Analysis of
Water and Wastes." This method is
comprehensive in scope describing pro-
cedures for interference correction,
safety, sample and standard prepara-
tion, and quality control in addition to
the actual analytical procedure. Of the
four sample preparation procedures de-
scribed in the method only the "Total"
(hard) and "Total Recoverable" (soft)
methods were investigated in this inter-
laboratory study. The hard digestion de-
scribed in paragraph 9.3 of the method
involves evaporation of the sample to
near dryness after addition of nitric acid.
Conversely, the soft digestion described
in paragraph 9.4 requires evaporation
of the sample to a reduced volume with
nitric and hydrochloric acids. Method
200.7 applies to 25 of the 27 elements
included in the method study. The two
elements not included in Method 200.7,
but included in the study were stron-
tium and lithium.
Selection of Laboratories
Over forty (40) laboratories from
across the United States were contacted
to determine their interest in participat-
ing in the ICP interlaboratory method
study. The list of laboratories was com-
piled from ICP manufacturer user
groups, EPA referrals, and direct in-
quiries. Interested parties responded to
an invitation for bid, with technical pro-
posals and cost data. Proposals were
carefully reviewed and ranked on the
basis of cost, technical experience, and
facilities.
As an integral part of the laboratory
selection process a performance evalu-
ation study was conducted. This study
was designed to familiarize laboratories
with the conduct of an interlaboratory
program and to evaluate the laborato-
ries proficiency with the method on
samples similar to those that would be
used in the full study. Each laboratory
was provided with an effluent sample, a
Youden pair of spiking solutions and in-
structions for splitting, spiking, prepar-
ing and analyzing the samples. Data
were generated by the laboratories for 9
of the 27 elements that would be in-
cluded in the full study. Samples were
also digested by both the hard and soft
procedures that were used in the full
study. All laboratories provided accept-
able data for the performance study and
no laboratories were eliminated from
the method study on the basis of these
results. Negotiations with the interested
firms resulted in contracts with eleven
laboratories. One volunteer laboratory
also participated in the program; there-
fore the method study included a total
of twelve (12) laboratories.
List of Participants
Harris Laboratories
Lincoln, Nebraska
Analytics
Richmond, Virginia
Raltech
Madison, Wisconsin
Battelle Columbus Laboratory
Columbus, Ohio
Radian Corporation
Austin, Texas
Vettar Research Incorporated
Costa Mesa, California
Weyerhauser Technology Center
Federal Way, Washington
ERCO
Cambridge, Massachusetts
Monsanto Research Corp.
Dayton, Ohio
Johnson Controls
Milwaukee, Wisconsin
GCA Technology Division
Bedford, Massachusetts
Physical and Chemical Methods
Branch,
Environmental Monitoring
Support Laboratory and
U.S. Environmental Protection Agency
Cincinnati, Ohio
Selection and Collection of
Water Samples
Selection of the types of industrial ef-
fluents that would be desirable for use
in the validation program was based
upon several criteria. Selection of efflu-
ents which were regulated under
NPDES statutes for the metals of inter-
est was of prime interest. Other desir-
able characteristics were that at least
one of the three effluents selected
should be high in suspended solids and
all should present an analytical chal-
lenge to the analyst and the ICP method.
Small volumes of treated discharge
water were initially collected from eight
different sources including one publicly
owned treatment work facility, two iron
and steel plants and six different inor-
ganic chemical manufacturing facilities.
Background levels of the metals of inter-
est were determined and studied rela-
tive to anticipated spike levels and the
degree of difficulty in ICP analyses. The
three effluents selected were treated
discharges from three chemical manu-
facturing industries: copper sulfate,
sodium hydrosulfate and chromium
pigments.
For the study, approximately fifty (50)
gallons of each of the selected effluents
were collected in five (5) gallon
polyethylene containers. Individual one
(1) gallon bottles of each effluent sam-
ple, labeled E1, E2 and E3, were dis-
tributed to the twelve (12) participating
laboratories. The three other types of
water samples used in the study were
collected individually by each partici-
pating laboratory as follows:
-------
Reagent Water (RW)—Laboratory
deionized Water
Drinking Water (DW)—Local tap
water
Surface Water (SW)—Local clean
river or lake water
Preparation of Spike Solutions
High concentration aqueous solu-
tions each containing one of twenty-
seven (27) metals of interest were indi-
vidually prepared from high purity
metals, salts and oxides. High concen-
tration stock solutions were prepared
for each of the 27 elements. An aliquot
of each stock solution was diluted and
checked against a commercially pre-
pared solution in order to verify the
preparation. A three vial system was
used to develop a twenty-seven (27) ele-
ment spike; the HCI matrix ampul con-
tained 16 elements, the HN03 matrix
ampul contained 9 elements, and a
water matrix ampul contained 2 ele-
ments. Ampules were prepared at five
(5) concentration levels with a Youden
pair at each level. Youden pairs differed
in concentration by between 5-25 per-
cent for all elements. Spike solutions
were prepared by appropriate dilution
of the stock standards followed by vial-
ing in either borosilicate glass ampules
(HCI and HN03 matrices) or in linear
polyethylene ampules (H20 matrix). All
ampules of one type were prepared in a
single preparation run, with the am-
pules being filled, sealed, and labeled in
one working day. Spike levels were cho-
sen to cover a range of concentrations
over several orders of magnitude with
the lowest Youden pair below the drink-
ing water maximum contaminant levels
(MCL). This was not possible in all cases
because the MCL is at or below the ICP
detection limit for some elements. For
those elements where an MCL does not
exist, the lowest Youden pair was pre-
pared at approximately 1.5 to 5 times
the ICP detectable limit. The higher con-
centration Youden pairs were chosen
based upon the concentrations in the
effluents with the understanding that
where the effluents had high concentra-
tions of some elements (for example,
sodium at 30,000,000 |xg/L in effluent 1)
the spike levels would not be high
enough above the background level to
provide usable data in the statistical
analysis of the ICP method study data.
Test Design
The test design upon which this inter-
laboratory study was designed is based
on a form of the analysis of variance
applying the approach and methods of
the Youden Unit block design. In the
Youden non-replicate approach to de-
termining the precision and accuracy of
an analytical method, pairs of samples
of similar, but different concentrations
are analyzed. The pair of samples is re-
ferred to as a unit block or a Youden
pair. The key in the Youden approach is
to estimate precision from analyses of
Youden pairs rather than through the
use of replicate analyses. This feature of
the Youden approach allows the sepa-
ration of the random and systematic
errors without the potential for bias due
to replicate analyses.
A summary of the ICP method study
test design using Youden's non-
replicate technique is given below:
1. Five (5) Youden pairs of spike ma-
terials were prepared.
2. Six water types were included:
Reagent water
Drinking water
Surface water
Three (3) industrial effluents
3. Each water type was spiked with
three (3) of the five (5) Youden
pairs with the exception of reagent
water to which all five (5) of the
Youden pairs were spiked.
4. Each water sample was prepared
for analysis by both a hard and soft
digestion procedure.
5. Analyses were performed for
twenty-seven (27) elements.
6. Twelve (12) laboratories partici-
pated in the study.
Conduct of Study
The twelve participating laboratories
were shipped the following materials in
order to perform the interlaboratory
study:
1. One (1) gallon each of three (3) in-
dustrial effluents.
2. Dosing solutions for six (6) water
types.
3. An instruction document (Ap-
pendix C) containing
a. sample preparation and analysis
instructions specific to the vali-
dation program.
b. data reporting instructions.
c. a copy of Method 200.7.
d. packing list.
e. examples of completed data
forms.
4. Sample data forms, a methodol-
ogy comment form and a general
information questionnaire.
Laboratories were given 45 days to
analyze the samples and report data.
Data were to be reported in a standard
format in ng/L on forms provided for
that purpose.
Summary/Conclusions
The ICP interlaboratory method study
required the characterization of the pre-
cision and accuracy of the analytical
method over a wide range of condi-
tions. This study developed measures
of precision and accuracy over a range
of concentrations, into different water
types and for two sample preparation
procedures. Twenty-seven different ele-
ments were included in the study and
individual measurements of precision
and accuracy were developed for each
one.
Accuracy was related to mean recov-
ery of the analyte for this method study.
Th equation used to summarize accu-
racy data over concentration for each
water type/digestion type/element was:
X=a+b-C
where
X = mean recovery of the element
C = the concentration level of the ele-
ment
The precision of the method has been
related to both the overall and single
analyst variation of the method. Equa-
tions used to summarize precision data
over concentration for each water type/
digestion type/element were:
S=d+e-X
where
S = overall standard deviation
and
SR=f+g-X
where:
SR = single-analyst standard devia-
tion
These equations which represent the
basic product of this method study are
presented in Tables 1 to 35. Regression
equations for some elements could not
be calculated over the entire concentra-
tion range studied due to insufficient
data at the lower concentration. There-
fore, new equations were calculated
using only the middle and high concen-
trations and are shown in Table 36 for
barium, calcium, lithium, potassium, sil-
icon, and sodium. In addition to sum-
marizing the precision and accuracy of
the method, the following conclusions/
recommendations have been drawn
from the data analysis.
-------
Table 1.
Hard Digestion
Water Type
Regression Equations for Accuracy and Precision i^g/L) Reagent Water Versus
Drinking Water (Aluminum, Antimony, Arsenic, Barium)
Aluminum
Antimony
Arsenic
Barium
Applicable cone, range
( 69 - 4701
I 77 - 9361
( 69-589)
( 4-3771
Reagent water, hard
Single-analyst precision SB = 0.06X + 3.00
Overall precision S - 0.06X + 27.45
Accuracy X = 0.97C - 0.42
Drinking water, hard
Single-analyst precision SR = 0.06X + 72.84
Overall precision S = 0.07X + 23.69
Accuracy X = 0.97C + 77.34
Soft Digestion
SB - 0.07X + 5.54 SB = 0.73X + 2.97
S = 0.77X + 0.92 S = 0.72X+2.80
X = 0.80C - 77.96 X = 7.03C - 77.76
SR = 0.07X + 8.46 SB = 0. »2X - 7.35
S = 0.74X + 9.63 S = 0.09X + 7.80
X = 0.77C - 5.24 X = 0.97C + 7.08
Applicable cone, range
I 69 - 4701
Reagent water, soft
Single-analyst precision SR = 0.05X + 75.88
Overall precision S - 0.08X + 33.00
Accuracy X = 0.96C + 78.02
Drinking water, soft
Single-analyst precision SB = 0.08X + 73.25
Overall precision S - 0.07X + 28.07
Accuracy X = 1.09C + 9.66
( 77 - 936)
SR = 0.07X + 1.64
S = 0.08X + 7.J8
X = 0.91C + 0.61
( 69-589)
SB = 0.08X+ 7J.37
X = 0.96C+ 77.45
Sfl = 0.72X + 3.32
( 4-377)
SB = 0.05X + 7.93
S - 0.06X + 27.75
X - 0.88C + 2.09 X = 7.05C + 6.76
X = Mean recovery
C = True value for the concentration
Table 2. Regression Equations for Accuracy and Precision (u.g/U Reagent Water Versus
Surface Water (Aluminum, Antimony, Arsenic, Barium)
Hard Digestion
Water Type
Applicable cone, range
Reagent water, hard
Single-analyst precision
Overall precision
Accuracy
Surface water, hard
Single-analyst precision
Overall precision
Accuracy
Soft Digestion
Applicable cone, range
Reagent water, soft
Single-analyst precision
Overall precision
Accuracy
Surface water, soft
Single-analyst precision
Overall precision
Accuracy
Aluminum
1 83 - 1434)
SR = 0.05X + 3.72
S = 0.07X + 9.34
X = 0.9JC + 6.62
SB = O.OOX + 40.75
S-0.70X + 67.23
X = 0.98C + 90.54
( 83 - 1434)
SR = 0.05X + 25.05
S = 0.10X + 28.72
X = 0.93C + 28.40
SR = 0.01X + 34.72
S = 0.10X + 74.75
X = 7.02C + 40.42
Antimony
(411 - 1406)
SR = 0.23X - 50.77
S - 0.27X - 24.02
X = 0.74C + 2.27
SH = 0.77X-0.74
S = 0.07X + 35.77
X = 0.88C-55.79
(477 - 7406;
SR = 0.06X + 7.85
S = 0.05X + 20.70
X = 0.92C - 22.46
SB = 0.06X + 0.97
S = 0.07X + 74.28
X = 0.95C - 34.50
Arsenic
(83-943)
SR - 0.07X + 8.28
S = 0.77X + 2.96
X - 7.03C - 72.03
SB = 0.05X + 7.79
S = 0.70X + 70.55
X = 7.00C - 76.02
( 83 -943)
SB - 0.07X + 6.72
S = 0.72X + 2.99
X = 7.07C - 2.08
SB = 0.05X + 9.29
S=0.77X + 7.82
X = 7.06C - 7.00
Barium
I 9-377)
SR = 0.18X+1.91
S = 0.23X + 2.27
X - 0.77C + 0.77
Sfl = 0.77X + 2.87
S = 0.73X + 4.73
X = 0.84C + 3.79
( 9-377)
Sfl = 0.72X+3.32
S - 0.37X + 0.06
X = 0.80C + 7.65
SB - 0.07X + 5.07
S = 0.70X + 9.40
X = 0.87C + 7.73
X = Mean recovery
C = True value for the concentration
Conclusions
• Study data sets for potassium,
lithium, sodium, thallium, and silicon
were limited due to either the small
number of laboratories reporting data
for the element, or due to an unusu-
ally high percentage of rejected data.
Regression equations and summary
statistics for these elements must,
therefore, be used with prudence.
• Low concentration level data for alu-
minum, boron, and silicon were ef-
fected by contamination of the spiking
material from the borosilicate glass
ampules used in the study. Precision
and accuracy for low concentration
spikes for these elements were poorer
than might otherwise be expected due
to this difficulty.
• High endogenous levels of some ele-
ments in specific effluents made eval-
uation of data for precision and accu-
racy difficult. This problem was
inherent in the study design and the
selection of "real world" effluents.
• The following elements have shown
some matrix effect of practical impor-
tance due to water type: aluminum,
barium*, beryllium, boron, cobalt,
copper, iron, magnesium, man-
ganese*, nickel, selenium*, silver,
strontium, vanadium, and zinc. The el-
ements denoted with an asterisk have
shown an effect only for effluent 1, a
wastewater containing approximately
3.5 percent dissolved solids, the most
difficult water type studied.
• Digestion was shown to have an effect
on accuracy or precision or both for 16
of the 27 elements studied. The soft
digestion was shown to provide better
results (precision or accuracy) than
the hard digestion for nine of the ef-
fected elements, and similarly, the
hard digestion provided better results
for two of the effected elements. Ef-
fects of digestion on the other five ele-
ments were observed to vary with
water type or statistic (for example the
soft digestion provided better accu-
racy and the hard digestion better
precision).
• High solids or MAK type nebulization
for high dissolved solids samples
such as effluent 1 was less prone to
difficulties than standard fixed cross-
flow or concentric nebulizers.
Recommendations
• The use of teflon laboratory ware is
recommended for sample preparation
when low level blanks for aluminum,
boron, or sodium and silicon are of
concern.
• Generally, the soft digestion should
be used in place of the hard digestion,
unless the carbonaceous nature of
data specific to the samples to be ana-
lyzed suggest otherwise. The soft di-
gestion generally provides equivalent
or somewhat improved accuracy and
precision relative to the hard diges-
tion and is also less time consuming
for the analyst.
• High dissolved solids samples present
a difficult challenge to the ICP analyst.
Method 200.7 provides sufficient
guidance for proper analysis of these
samples. However, the importance of
paragraph 5.2 of the method should
be stressed more definitively, and
strict warnings to the analyst should
appear in other portions of the text
referring to section 5.2.
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Table 3. Regression Equations for Accuracy and Precision (\t,g/L) Reagent Water Versus
Effluent 1 (Aluminum, Antimony, Arsenic, Barium)
Hard Digestion
Water Type Aluminum Antimony Antnic Barium
Applicable cone, range
(413-4732)
Reagent water, hard
Single-analyst precision SR = 0.03X + 19.10
Overall precision S = 0.07X + 9.17
Accuracy X = 0.92C + 5.94
Effluent I, hard dig
Single-analyst precision SR = 0.07X + 23.06
Overall precision S = 0. J JX + J18.67
Accuracy X - 0.86C - 2.69
(355 - 1406)
SR = O.OSX + 31.56
S = 0.01X + 82.23
X = 0.79C - 0.49
SR = 0.13X + 9.54
S = O.J6X + 71.01
X = 0.78C - 7.83
1518^1887)
143-377)
SR - 0.03X + S3.2J SR = -0.01X + 10.50
S-O.J7X-32.J8 S = 0.03X+JJ.47
X - J.09C - 48.24 X - 0.97C - J8.66
SR - -O.OOX + 74.69 SR = O.OSX + 7.27
S--A02X+ JJ5.76 S = 0.08X + 7.J3
X - O.S3C -7.43 X = O.S9C - 0.20
Soft Digestion
Applicable cone, range
Reagent water, soft
Single-analyst precision
Overall precision
Accuracy
Effluent 1, soft dig
Single-analyst precision
Overall precision
Accuracy
(413-4792)
SR - 0.04X + J6.27
S = O.OSX + 35.93
X = 0.93C + J9.42
SB - 0.08X + J6.70
S = O.J9X-3.96
X = 0.84C + 00.59
(355- J40«
SR = 0.03X + 26.81
S = -0.02X + 102.35
X = 0.970-62.12
SR = 0.02X + 70.37
S = 0.18X + 26.47
X = 0.96C - J09.53
( 518 - 1887)
SR - 0.03X + 38.61
S = O.J5X- J0.74
X= J.J4C- 73.43
Sfl = O.JOX + 70.32
S - 0.23X + 42.04
X = 0.92C + 5.44
( 43 -377)
SR = -0.02X + J0.2J
S = 0.05X + J4.06
X-0.99C- JJ.7J
SB - 0.03X + J0.22
S - 0.7JX - 9.3J
X = 0.30C + J6.76
X = Mean recovery
C = True value for the concentration
Table 4. Regression Equations for Accuracy and Precision (u.g/L) Reagent Water Versus
Effluent 2 (Aluminum, Antimony, Arsenic, Barium)
Hard Digestion
Water Type
Applicable cone, range
Reagent water, hard
Single-analyst precision
Overall precision
Accuracy
Effluent 2, hard dig
Single-analyst precision
Overall precision
Accuracy
Soft Digestion
Applicable cone, range
Reagent water, soft
Single-analyst precision
Overall precision
Accuracy
Effluent 2, soft dig
Single-analyst precision
Overall precision
Accuracy
Aluminum
(413-4792)
Sfl = 0.03X+ J9.JO
S = 0.07X^9.17
X - 0.92C + 5.94
SR = O.OOX + 63.16
S = 0.04X + 38.36
X = 0.94C + 36.94
( 413 - 4792)
SR = 0.04X + J6.27
S = 0.08X + 35.93
X - 0.93C + 19.42
SB - 0.02X + 24.90
S = 0.09X + 12.34
X = 0.98C - 6.48
Antimony
(355- 1406)
SR = O.OSX + 3J.56
S - O.OJX + 82.23
X = 0.79C - 0.49
SB = 0.08X - J.22
S = -O.OJX + JJ0.77
X = 0.82C + J3.20
r355- J40W
SB - 0.03X + 26.8J
S = -0.02X + J02.35
X-0.97C-fi2.»2
SR = O.OSX + J4.04
S = O.OJX + 72.58
X = 0.92C - 3.86
Arsenic
( 518 - 1887)
SR = O.OSX + 53.21
S = 0.17X - 32.18
X = 1.09C - 48.24
SR = 0.05X - 2.53
S = O.OSX - 3.94
X = 1.08C - 34.50
(518- 1887)
SR - 0.03X + 38.61
S = O.J5X- J0.74
X- 1.14C- 73.43
SB - -0.02X + 7J.89
S = O.JJX + 5.4J
x= noc-24.se
Barium
(43-377)
SR = -O.OJX + J0.50
S = 0.03X + JJ.47
X = 0.97C - J8.66
Sfl = O.OJX + 7.78
S = O.OSX + J2.6J
X = 0.83C - 6.49
(43-377^
Sfl = -0.02X + J0.2J
S = 0.06X + J4.06
X = ft99C- JJ.7J
Sfl - -0.02X + 9.5J
S-O.J2X + 5.83
X = 0.89C - J6.26
X = Mean recovery
C = True value for the concentration
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Table S. Regression Equations for Accuracy and Precision
Effluent 3 (Aluminum, Antimony, Arsenic, Barium)
Hard Digestion
Reagent Water Versus
Water Type
Applicable cone, range
Reagent water, hard
Single-analyst precision
Overall precision
Accuracy
Effluent 3, hard dig
Single-analyst precision
Overall precision
Accuracy
Soft Digestion
Applicable cone, range
Reagent water, soft
Single-analyst precision
Overall precision
Accuracy
Effluent 3, soft dig
Single-analyst precision
Overall precision
Accuracy
Aluminum
(413-47921
SR = 0.03X + 19.10
S = 0.07X + 9.17
X = 0.92C + S.94
SR = 0.06X + 21.78
S = 0.10X + 39.55
X = 0.88C+ 75.17
1413-47921
SR = 0.04X + 16.27
S = 0.08X + 35.93
X = 0.93C + 19.42
Sfl = 0.07X + 37.77
S = 0.13X + 20.68
X = 0.88C + 63.15
Antimony
1 355 - 14061
SR - 0.05X + 31.56
S = 0.01 X + 82.23
X = 0.79C - 0.49
SB = 0.1 IX + 87.44
S = -0.10X + 310.55
X = 0.80C + 186.53
(355- 14061
SR = 0.03X + 26.81
S = -0.02X + 702.35
X = 0.97C - 62.12
SR = 0.06X + 28.41
S = -0.12X + 226.50
X = 0.95C - 18.74
Arsenic
1 518 - 18871
SR = 0.03X + 53.21
S = 0.17X - 32.18
X = 1.09C - 48.24
SR = 0.03X + 17.32
S = 0.77X-4.06
X = 1.03C - 39.94
(518- 1887)
SR = 0.03X + 38.61
S = 0.75X- 10.74
X = 1.14C- 73.43
SR = 0.02X + 23.07
S = 0.13X - 25.87
X = 1.11C- 27.78
Barium
(43-3771
SR = -0.01X + 10.50
S = 0.03X + 11.47
X - 0.97C - 18.66
SH-0.74X + 11.50
S = 0.32X + 5.23
X = 0.67C - 2.35
(43-3771
SR = -0.02X + 10.21
S = 0.06X + 14.06
X = 0.99C- 11.71
SR = 0.18X + 6.88
S - 0.23X + 5.66
X = 0.62C - 2.09
X = Mean recovery
C = True value for the concentration
Table S. Regression Equations for Accuracy and Precision (v-g/U Reagent Water Versus
Drinking Water (Beryllium, Boron, Cadmium, Calcium)
Hard Digestion
Water Type
Applicable cone, range
Reagent water, hard
Single-analyst precision
Overall precision
Accuracy
Drinking water, hard
Single-analyst precision
Overall precision
Accuracy
Soft Digestion
Applicable cone, range
Reagent water, soft
Single-analyst precision
Overall precision
Accuracy
Drinking water, soft
Single-analyst precision
Overall precision
Accuracy
Beryllium
< 3-48)
SR = O.OOX + 0.39
S = 0.03X + 0.54
X = 0.95C - 0.02
SR = 0.03X + 0.40
S = 0.02X + 0.87
X = 0.94C + 0.00
I 3-48)
SR = 0.04X + 0.19
S = 0.03X + 0.70
X = 1.02C - 0.27
SR = 0.03X + 0.28
S = 0.02X + 0.72
X = 0.99C - 0.07
Boron
( 19-1179)
SR = 0.13X + 21.58
S = 0.20X+ 11.36
X = 0.790+ 11.25
SR = 0.08X + 44.04
S = 0.19X + 28.92
X = 0.76C + 43.88
( 19- 1179)
SR = 0.01X + 23.18
S = 0.12X + 16.34
X = 0.97C + J9.02
Sff = 0.04X + 7.87
S = 0.7JX + ftO».
X = 0.94C+ JJ.59
Cadmium
( 9 - 776)
SR = 0.04X + 0.82
S = 0.0SX + 7.82
X = 0.98C + 0.30
Sfl = -0.05X + 5.39
S = 0.09X + 2.65
X = 0.87C + 2.52
r 9 - 776;
SR = 0.04X + 7.04
S = 0.08X + 0.85
X = 0.99C - 0.26
SR = 0.04X + 0.53
S = 0.08X + 7.38
X = 0.98C - 0.49
Calcium
( 17 - 1906)
SR = 0.44X + 129.41
S = 0.37X + 520.97
X - 0.79C + 7034.67
( 17 - 1906)
SR = 0.02X + 70.69
S=0.72X + 5.87
X = 0.97C + 2.57
SB =-0.74X + 820.63
S = 0.28X + 425.26
X = 7.64C + 767.67
X = Mean recovery
C = True value for the concentration
-------
Table 7.
Hard Digestion
Water Type
Regression Equations for Accuracy and Precision t\ig/U Reagent Water Versus
Surface Water (Beryllium, Boron, Cadmium, Calcium)
Beryllium
Boron
Cadmium
Calcium
Applicable cone, range
I 17-78)
1330- 1179)
I 18-776)
Reagent water, hard
Single-analyst precision SR = 0.02X + 0.18
Overall precision S = 0.02X + 0.91
Accuracy X = 1.02C - 1.92
Surface water, hard
Single-analyst precision SR = O.OOX + 0.85
Overall precision S = 0.09X - 0.47
Accuracy X = 1.0OC - 0.89
SR = -0.02X + 62.67 SR = 0.02X + 7.49
S = -0.02X + 75.99 S = 0.07X + 1.40
X = 0.97C - 39.09 X = 0.980 +0.20
SR = 0.02X + 73.05 SR = 0.04X + 0.23
S = 0.11X + 38.83 S = 0.08X+1.94
X = 0.94C + 0.99 X = 1.00C + 0.28
186- 1906)
SR = 0.02X + 3.54
S = 0.73X + 79.00
X = 0.9SC - 75.74
Sfl = 0.08X + 273.73
S = 0.40X + 99.22
X = 1.25C + 348.11
Soft Digestion
Applicable com. range
Reagent water, soft
Single-analyst precision
Overall precision
Accuracy
Surface water, soft
Single-analyst precision
Overall precision
Accuracy
( 17-76)
SR = 0.04X + 0.14
S - 0.07X - 0.47
X = 7.03C - 0.73
Sfl = 0.02X + 0.43
S = 0.07X + 7.54
X = 7.04C - 2.08
f330- 7779;
Sft = 0.05X + 53.98
S = 0.07X + 73.55
X= 1. IOC -77.26
Sfl = -0.02X + 62.90
S = 0.06X + 32.76
X = 7.07C - 2.83
( 18-776)
SR = 0.03X + 7.07
S = 0.05X + 7.36
X = 7.07C + 0.45
SB = 0.03X + 0.7fl
S = 0.09X + 0.77
X = 7.02C - 0.58
/ 86 - 7906)
SB = 0.07X + 4.52
S - 0.09X + 74.63
X= 7.00C- 77.80
SB - -0.09X + 525.98
S = 0.40X + 733.52
X = 0.89C + 338.42
X = Mean recovery
C = True value for the concentration
Table 8. Regression Equations for Accuracy and Precision (pg/L) Reagent Water Versus
Effluent 1 (Beryllium, Boron, Cadmium, Calcium)
Hard Digestion
Water Type
Applicable cone, range
Reagent water, hard
Single-analyst precision
Overall precision
Accuracy
Effluent 1, hard dig
Single-analyst precision
Overall precision
Accuracy
Soft Digestion
Applicable cone, range
Reagent water, soft
Single-analyst precision
Overall precision
Accuracy
Effluent 1, soft dig
Single-analyst precision
Overall precision
Accuracy
Beryllium
1 42 - 1906)
SR = 0.02X - 0.16
S = 0.02X + 0.48
X = 0.99C - 0.09
Sfl = 0.07X + 2.53
S = 0.72X+ 7.34
X = 0.82C + 7.93
( 42 - 1906)
SR = 0.01X + 1.82
S = 0.04X + 1.14
X - O.99C + r.SO
Sfl = 0.03X + 0.70
S = 0.73X + 7.67
X = 0.79C + J.47
Boron
1 708 - 5189)
SR = 0.13X - 57.69
S = 0.12X - 27.43
X - 0.90C + 45.43
SB = -0.07X + 277.33
S = 0.08X + 765.77
X = 0.86C-5.70
( 708 - 5189)
SR - -0.01X + 726.42
S = 0.04X + 700.64
X - 0.97C + 40.42
SR = 0.03X + 775.60
S = 0.73X+ 777.55
X = 0.88C - 72.62
Cadmium
1 89 - 1943)
Sfl = 0.04X- 1.76
S = 0.04X + 6.20
X = 0.97C + 3.32
Sfl = 0.07X + 20.70
S = 0.77X + 30.84
X = 0.85C + 4.62
1 89 - 1943)
SR - 0.02X + 7.90
S = 0.05X + 2.97
X - O.SBC + 4.90
SR = 0.03X + 18.10
S = 0.09X + 24.29
X = 0.86C + 73.77
Calcium
1 1679 - 47170)
SR = 0.03X - 19.90
S = 0.04X + 55.59
X = 7.07C - 82.98
Sfl = 0.77X + 7095.00
S = 0.27X + 7538.84
X - 0.76C + 2753.22
1 1679 - 47170)
SR = 0.01X + 42.01
S - 0.06X - 8.03
X = 7.02C - 37.70
SB - 0.09X + 7909.52
S = 0.25X + 2008.47
X = 0.75C + 4207.35
X = Mean recovery
C = True value for the concentration
-------
Table 9.
Hard Digestion
Water Type
Regression Equations for Accuracy and Precision (\i.g/U Reagent Water Versus
Effluent 2 (Beryllium, Boron, Cadmium, Calcium)
Beryllium
Boron
Cadmium
Calcium
Applicable cone, range
( 42 - 1906)
Reagent water, hard
Single-analyst precision SR = 0.02X - 0.16
Overall precision S = 0.02X + 0.48
Accuracy X = 0.99C - 0.09
Effluent 2, hard dig
Single-analyst precision SR = 0.02X + 0.09
Overall precision S = O.OBX + 0.23
Accuracy X = 0.96C + 0.16
Soft Digestion
Applicable cone, range ( 42 - 1906)
Reagent water, soft
Single-analyst precision SR - 0.01X + 1.82
Overall precision S = 0.04X + 1.14
Accuracy X = 0.99C + 1.50
Effluent 2, soft dig
Single-analyst precision SR = 0.02X + 0.12
Overall precision S = 0.07X - 0.87
Accuracy X = 0.97C - 0.03
1708 - 5189)
( 89 - 1943)
SR = 0.13X- 57.69 SR = 0.04X - 1.76
S = 0.12X - 27.43 S = 0.04X + 6.20
X = 0.90C + 45.43 X = 0.97C + 3.32
SR = 0.04X + 86.14 SR = 0.04X -0.64
S = 0.14X - 6.67 S = 0.08X + 2.81
X = 0.92C -8.42 X - 0.95C + 6.25
I 708 - 5189)
I 89 - 1943)
Sfl = -0.01X + 126.42 Sff = 0.02X + 1.90
S = 0.04X + 100.64 S = O.OBX + 2.91
X = 0.97C + 40.42 X - 0.98C + 4.90
SR = -O.OOX + 66.34 SR - 0.03X + 2.89
S = 0.08X +27.11 S = 0.04X + 9.96
X = 1.00C - 27.90 X = 0.97C + 2.08
11679 - 47170)
SR = 0.03X - J9.90
S = 0.04X + 55.59
X = 1.01C - 82.98
SR = 0.04X + 250.16
S = 0.15X + 149.94
X = 0.96C + 368.06
I 1673 - 47170)
SR = 0.01X + 42.01
S = 0.06X - 8.03
X = 1.02C - 37.70
Sfl » 0.02X + 243.27
S = 0.06X + 215.03
X = 1.03C + 39.25
X - Mean recovery
C = True value for the concentration
Table 10.
Hard Digestion
Water Type
Regression Equations for Accuracy and Precision (\ig/L) Reagent Water Versus
Effluent 3 (Beryllium, Boron, Cadmium, Calcium)
Beryllium
Boron
Cadmium
Calcium
Applicable cone, range
( 42 - 1906)
Reagent water, hard
Single-analyst precision SR = 0.02X - 0.16
Overall precision S = 0.02X + 0.48
Accuracy X = 0.99C - 0.09
Effluent 3, hard dig
Single-analyst precision • SR = 0.03X +1.09
Overall precision S = 0.09X + 0.10
Accuracy X - 0.92C - 2.01
Soft Digestion
Applicable cone, range I 42 - 1906)
Reagent water, soft
Single-analyst precision SR = 0.01X + 1.82
Overall precision S = 0.04X + 1.14
Accuracy X = 0.99C + J.50
Effluent 3, soft dig
Single-analyst precision SR = O.OJX + 0.93
Overall precision S = 0.06X - 0.40
Accuracy X - 0.93C - 0.55
I 708 - S189)
I 89 - 1943)
SR = 0.13X- 57.69 SR = 0.04X - 1.76
S = 0.12X- 27.43 S = 0.04X + 6.20
X = 0.90C + 46.43 X = 0.97C + 3.32
SR - 0.03X + 75.20 SB = 0.04X + 2.97
S = 0. J2X + 51.93 S = 0.07X + 2.00
X = 0.86C + 26.80 X - 0.90C + 7.21
< 708 - S18S)
I 89 - 1943)
SR = -0.01X + 126.42 SR - 0.03X + 1.90
S = 0.04X + 100.64 S = O.OBX -I- 2.91
X = 0.97C + 40.42 X = 0.98C + 4.90
Sfl = 0.03X + 29.54 Sfl = 0.02X + 0.83
S - 0.06X + 36.75 S = 0.04X + 11.81
X - 0.92C + 4.59 X = 0.95C + 9.29
11679 - 47170)
Sfl - 0.03X - J9.90
S - 0.04X + 55.59
X = 1.01C - 82.98
Sfl - 0.08X + 7449.24
S = 0.39X + 207.95
X- 1.10C+ 17515.96
( 1679 - 47170)
Sfl - O.OJX + 42.01
S - 0.06X - 8.03
X - ?.02C - 37.70
Sfl = -0.04X + 9730.09
S = 0.22X + 5993.79
X = 0.96C + 11220.57
X = Mean recovery
C = True value for the concentration
-------
Table 11. Regression Equations for Accuracy and Precision (\i.g/L) Reagent Water Versus
Drinking Water (Chromium, Cobalt, Copper, Iron)
Hard Digestion
Water Type
Applicable cone, range
Reagent water, hard
Single-analyst precision
Overall precision
Accuracy
Drinking water, hard
Single-analyst precision
Overall precision
Accuracy
Soft Digestion
Applicable cone, range
Reagent water, soft
Single-analyst precision
Overall precision
Accuracy
Drinking water, soft
Single-analyst precision
Overall precision
Accuracy
Chromium
1 13-470)
SR = -0.03X + 9.78
S = 0.72X + 3.35
X = 0.920 + 4.17
SR = 0.03X + 2.28
S = 0.10X + 1.11
X = 0.96C + 1.28
1 13-470)
SR = 0.08X + 0.70
S = 0.06X + 2.71
X = 0.98C - 0.61
SR = 0.06X + 2.10
S = 0.03X + 5.67
X = 0.95C + 1.36
Cobalt
1 17-281)
SR = 0.04X + 0.87
S - 0.04X + 4.27
X = 0.93C - 4.57
SR = 0.04X + 1.92
S = 0.09X + 1.75
X = 0.87C - 1.33
( 17-281)
SR = 0.04X + 0.77
S = 0.03X + 2.90
X = 0.95C - 2.02
SR = 0.03X + 0.66
S = 0.03X + 2.56
X = 0.92C - 1.39
Copper
( 8-189)
SR = 0.02X + 2.36
S = 0.06X + 2.66
X = 0.94C - 0.45
SR = 0.02X + 2.23
S = 0.09X + 5.41
X = 0.96C + 2.43
1 8-189)
SR = 0.05X + 1.17
S = 0.04X + 2.55
X = 0.93C - 3.67
Sfl = 0.08X + 2.47
S = 0.10X + 3.66
X = 1.00C + 1.95
Iron
1 13 - 187)
SR = -0.08X + 12.91
S = 0.08X + 11.22
X = 0.78C + 9.78
SR = 0.14X + 14.30
S = 0.35X + 3.41
X = 0.94C + 21.43
( 13 - 187)
SR = 0.11X + 10.37
S = 0.12X+ 12.08
X = 0.95C + 6.44
SR = -0.15X + 50.71
S = 0.24X + 16.60
X = 0.66C + 38.31
X = Mean recovery
C = True value for the concentration
Table 12.
Hard Digestion
Water Type
Regression Equations for Accuracy and Precision (u.g/L) Reagent Water Versus
Surface Water (Chromium, Cobalt, Copper, Iron)
Chromium
Cobalt
Copper
Iron
Applicable cone, range
( 25-470)
Reagent water, hard
Single-analyst precision SR = 0.01X + 3.74
Overall precision S = 0.02X + 4.72
Accuracy X = 0.98C - 0.96
Surface water, hard
Single-analyst precision SR = 0.01X + 2.83
Overall precision S = 0.07X + 2.77
Accuracy X = 0.98C + 2.18
1 58-843)
SR = 0.04X + 1.17
S = 0.06X + 0.21
X = 0.93C - 4.34
SR = 0.03X + 1.45
S = 0.03X + 4.30
X - 0.94C - 2.97
1 17 - 189)
SR = 0.02X + 2.02
S = 0.02X + 3.66
X = 0.94C - 1.23
SR = O.OOX + 4.40
S = 0.04X + 3.87
X = 0.98C - 1.56
1 74 - 2340)
SR = 0.04X + 2.34
S = 0.04X + 77.09
X = 0.99C- JJ.60
S = O.T4X + 26.28
X = 0.98C + 34.94
Soft Digestion
Applicable cone, range
Reagent water, soft
Single-analyst precision
Overall precision
Accuracy
Surface water, soft
Single-analyst precision
Overall precision
Accuracy
( 25-470)
SR = 0.04X + 3.56
S = 0.07X + 2.55
X = 1.01C - 1.85
Sfl = 0.02X + 5.78
S = 0.05X + 6.83
X = 0.98C + 0.30
( 58-843)
SR = 0.05X - 0.22
S = 0.06X + 2.29
X = 0.93C - 7.07
Sfl = 0.02X + 4.80
S = 0.05X + 4.89
X = 0.93C - 0.28
( 17 - 189)
SR = 0.03X + 1.73
S = 0.05X + 2.55
X = 0.98C - 4.68
Sfl = 0.07X + 4.43
S - 0.03X + 4.95
X = 0.98C - 7.38
1 74 - 2340)
Sfl = 0.08X + 70.52
S = 0.70X+ 73.84
X = 7.03C - 3.35
Sfl = 0.07X + 53. 75
S = 0.05X + 57.00
X= 7.07C+ 70.73
X = Mean recovery
C = True value for the concentration
-------
Table 13.
Hard Digestion
Regression Equations for Accuracy and Precision (pg/L) Reagent Water Versus
Effluent 1 (Chromium, Cobalt, Copper, Iron)
Water Type
Applicable cone, range
Reagent water, hard
Single-analyst precision
Overall precision
Accuracy
Effluent 1, hard dig
Single-analyst precision
Overall precision
Accuracy
Soft Digestion
Applicable cone, range
Reagent water, soft
Single-analyst precision
Overall precision
Accuracy
Effluent 1, soft dig
Single-analyst precision
Overall precision
Accuracy
Chromium
( 169 - 14061
SR = 0.09X - 13.32
S = 0.08X - 9.65
X = 0.99C - 2.20
SR = 0.06X + 4.97
S = 0.1 2X + 20.86
X = 0.83C + 79.33
( 169 - 14061
SR = O.OSX + 1.67
S = 0.04X + 13.17
X = 1.01C + 0.88
SB = O.OSX + 73.45
S = 0.76X + 76.57
X = 0.86C - 7.93
Cobalt
(247-23401
SR = O.OSX + 8.09
S = O.OSX + 6.24
X = 0.90C + 2.28
SR = O.OSX + 2.39
S = 0.77X + 5.77
X = 0.87C - 2.62
1247-2340)
SR = 0.02X + 7.68
S = 0.07X - 2.94
X = 0.90C + 8.24
SR = O.OSX + 12.03
S = 0.17X + 5.70
X = 0.79C + 9.84
Copper
( 166 - 1887)
Sfl = 0.07X + 3.34
S - O.OSX + 6.S6
X = 0.9BC - 2.91
SR = -0.01X + 593.39
S = 0.43X + 284.35
X = 0.44C + 857.82
1 166 - 1887)
SR = 0.07X + 6.55
S = O.OSX + 2.27
X = 0.98C - 2.27
SR = 0.50X - 44.46
S = 0.53X - 72.79
X = 0.35C + 6S6.77
Iron
1 164 - 93591
SR = 0.06X - 3.30
S = O.OSX + 2.43
X = 0.97C-6.79
Sfl = 0.02X + 49.67
S = 0.7 OX + 57.82
X = 0.82C - 70.64
1 164 - 9359)
SR = 0.04X + 26.47
S = 0.06X + 26.72
X = 7.00C + 6.88
Sfl = 0.06X + 79.97
S = 0.75X + 25.82
X = 0.87C + 77.04
X = Mean recovery
C = True value for the concentration
Table 14. Regression Equations for Accuracy and Precision (\i.g/U Reagent Water Versus
Effluent 2 (Chromium, Cobalt, Copper, Iron)
Hard Digestion
Water Type
Applicable cone, range
Reagent water, hard
Single-analyst precision
Overall precision
Accuracy
Effluent 2, hard dig
Single-analyst precision
Overall precision
Accuracy
Soft Digestion
Applicable cone, range
Reagent water, soft
Single-analyst precision
Overall precision
Accuracy
Effluent 2, soft dig
Single-analyst precision
Overall precision
Accuracy
Chromium
( 169 - 14061
Sfl - 0.09X - 73.32
S = 0.08X - 9.65
X = 0.99C - 2.20
Sfl = 0.02X + 4.29
S = 0.02X + 27.80
X = 0.95C - 0.52
( 769 - 1406)
Sfl = O.OSX + 7.67
S = 0.04X+ 73.77
X = J.07C + 0.88
Sfl = 0.07X + 3.90
S = 0.03X + 2.66
X = 0.97C + 3.89
Cobalt
1247-2340)
Sfl = 0.03X + 8.09
S = O.OSX + 6.24
X = 0.90C + 2.28
Sfl = 0.0 7X + 3.70
S = 0.06X + 2.09
X = 0.89C + 4.75
1 247 - 2340)
SR = 0.02X + 7.68
S = 0.07X - 2.94
X = 0.90C + 8.24
Sfl = 0.02X + 3.50
S = 0.06X - 3.29
X = 0.89C + 5.48
Copper
1 166 - 1887)
Sfl = 0.07X + 3.34
S = 0.03X + 6.56
X = 0.95C - 2.97
Sfl = 0.02X + 2.95
S = 0.06X + 5.88
X = 0.95C - 2.59
1 166 - 1887)
Sfl = 0.07X + 6.55
S = O.OSX + 2.27
X = 0.98C - 2.27
SB = 0.02X + 6.27
S = 0.04X + 75.87
X = 0.9SC + 7.07
Iron
( 164 - 9359)
Sfl = 0.06X - 3.30
S = O.OSX + 2.43
X - 0.97C - 6. 79
Sfl = 0.07X + 50.87
S = 0.06X + 66.77
X = 0.99C + 75.70
1 164 - 93S9)
SR = 0.04X + 26.47
S = 0.06X + 26.72
X = 7.00C + 6.88
Sfl = 0.02X + 95.60
S - 0.04X + 276.95
X = 0.96C + 720.82
X = Mean recovery
C = True value for the concentration
10
-------
Table 15. Regression Equations for Accuracy and Precision (u.g/L) Reagent Water Versus
Effluent 3 (Chromium, Cobalt, Copper, Iron)
Hard Digestion
Water Type
Applicable cone, range
Reagent water, hard
Single-analyst precision
Overall precision
Accuracy
Effluent 3, hard dig
Single-analyst precision
Overall precision
Accuracy
Soft Digestion
Applicable cone, range
Reagent water, soft
Single-analyst precision
Overall precision
Accuracy
Effluent 3, soft dig
Single-analyst precision
Overall precision
Accuracy
Chromium
( 169 - 1406)
SR = 0.09X - 13.32
S = O.OSX - 9.65
X = 0.99C - 2.20
Sfl = O.OOX + 36.49
S = 0.07X + 23.36
X = 0.89C+ 72.73
1 169 - 1406)
Sfl = 0.05X + 7.67
S = 0.04X+ 73.77
X = 7.07C + 0.88
Sfl = 0.04X + 75.34
S = 0.07X + 21.17
X = 0.87C + 75.64
Cobalt
(247-2340)
Sfl = 0.03X + 8.09
S = 0.05X + 6.24
X = 0.90C + 2.28
Sfl = 0.06X - 7.25
S = O.J4X- 72.63
X = 0.89C- 77.76
( 247 - 2340)
Sfl = 0.02X + 7.68
S = 0.07X - 2.94
X = 0.90C + 8.24
SB = O.OSX + 72.05
S = 0.09X + 5.75
X = 0.97C - 0.95
Copper
( 766 - 7887;
Sfl = 0.07X + 3.34
S = 0.03X + 6.56
X = 0.95C - 2.9J
Sfl = O.OSX + 5.00
S = 0.08X+ 77.48
X = 0.92C- 77.90
( 166 - 1887)
Sfl = 0.07X + 6.55
S = 0.05X + 2.27
X = 0.98C - 2.27
Sfl = 0.02X + 7.37
S = O.OSX + 4.46
X = 0.93C-3.77
Iron
( 104 - 9359)
Sfl = 0.06X - 3.30
S = 0.08X + 2.43
X = 0.97C-6.79
SB = O.OSX +47. 77
S = 0.70X + 47.09
X = 0.97C-33.79
( 104 - 9359)
Sfl = 0.04X + 26.47
S = 0.06X + 26.72
X = 1.00C + 6.88
Sfl = 0.07X + 29.00
S = 0.70X + 45.75
X = 0.96C - 7.37
X = Mean recovery
C = True value for the concentration
Table 16.
Hard Digestion
Water Type
Regression Equations for Accuracy and Precision (u.g/L) Reagent Water Versus
Drinking Water (Lead, Lithium, Magnesium, Manganese)
Lead
Lithium
Magnesium
Manganese
Applicable cone, range
Reagent water, hard
Single-analyst precision
Overall precision
Accuracy
I 42-943)
SR = 0.04X + 3.16
S = 0.09X + 3.57
X = 0.96C - 7.28
I 4-49)
I 34- 18491
( 4-287)
Sfl = 0.02X + 7.25 Sfl = 0.02X + 0.43
S = 0.70X + 8.99 5 = 0.04X^0.82
X = 0.92C +7.57 X = 0.93C + 0.77
Drinking water, hard
Single-analyst precision Sfl = 0.02X + 70.08
Overall precision S = 0.08X + 9.28
Accuracy X = 0.98C - 4.49
Soft Digestion
Applicable cone, range ( 42 - 943)
Reagent water, soft
Single-analyst precision Sfl = O.OSX + 3.46
Overall precision S = 0.10X + 2.93
Accuracy X = 1.01C + 3.00
Drinking water, soft
Single-analyst precision SR = O.OSX + 4.90
Overall precision S = 0.06X + 19.74
Accuracy X = 0.94C + 15.34
Sfl = -0.39X + J4.63 Sfl = 0.27X + 63.64
S = 0.22X + 2.38 S = 0.25X + 67.35
X = 0.660 + 9.58 X = 0.69C+774.74
(4-49)
( 34 - 1849)
Sfl = 0.02X + 7.37
S = 0.77X + 0.67
X = 0.92C + 0.27
( 4-287)
Sfl = -O.OOX + J0.68 Sfl = 0.07X + 0.48
S = 0.04X + 74.78 S = O.OSX + 0.35
X = 0.96C + 3.60 X = 0.99C - 0.09
Sfl = 0.09X + 72.26 Sfl = 0.72X + 0.37
S = 0.76X+770.54 S = 0.72X+7.fJ
X = 0.77C + 274.55 X = 0.97C - 0.36
X = Mean recovery
C = True value for the concentration
11
-------
Table 17.
Hard Digestion
Water Type
Regression Equations for Accuracy and Precision (u.g/L) Reagent Water Versus
Surface Water (Lead, Lithium, Magnesium, Manganese)
Lead
Lithium
Magnesium
Manganese
Applicable cone, range I 85 - 9431 (17-97) I 73 - 4623) f 17 - 943)
Reagent water, hard
Single-analyst precision SR = 0.03X + 4.56 SR = 0.14X - 0.40 SR = 0.03X + 0.24 SR = 0.02X + 0.50
Overall precision S = 0.01X + 18.87 S = 0.2SX - 0.30 S = 0.04X + 17.24 S = 0.04X + 0.93
Accuracy X = 0.97C - 3.09 X = 0.89C + 1.01 X = 1.01C - 5.94 X = 0.97C - 1.46
Surface water, hard
Single-analyst precision Sfl = 0.02X + 7.44 Sfl = 0.02X + 1.27 SR = 0.02X + 58.13 SR = 0.01X + 3.44
Overall precision S = 0.05X + 8.36 S - 0.21X - 0.18 S = 0.10X + 41.28 S = 0.03X + 4.63
Accuracy X = 0.98C - 4.58 X = 0.98C +1.44 X = 1.03C + 84.36 X = 0.95C + 2.06
Soft Digestion
Applicable cone, range ( 85 - 9431 117-971 (73- 4623) (17-943)
Reagent water, soft
Single-analyst precision
Overall precision
Accuracy
Surface water, soft
Single-analyst precision
Overall precision
Accuracy
SR = 0.05X + 4.18
S = 0.10X + 3.09
X = 0.990+ 11.21
SR = 0.02X + 6.38
S = 0.06X + 8.77
X = 0.98C + 3.92
SR = 0.13X- 1.07
S = 0.27X + 3.24
X = 0.87C + 4.88
Sfl = 0.23X - 2.05
S = 0.22X - 2.27
X = 0.90C + 3.77
Sfl = 0.05X - 0.47
S = 0.08X + 6.78
X = 7.00C - 3.67
Sfl = 0.75X + 0.24
S = 0.79X + 709.84
X = 0.96C + 704.38
Sfl = 0.04X + 0.29
S = 0.06X + 0.86
X = 0.98C - 0.78
Sfl - 0.04X + 2.90
S = 0.07X + 5.85
X = 0.97C - 0.02
X = Mean recovery
C = True value for the concentration
Table 18.
Hard Digestion
Water Type
Regression Equations for Accuracy and Precision (u.g/L) Reagent Water Versus
Effluent 1 (Lead, Lithium, Magnesium, Manganese)
Lead
Lithium
Magnesium
Manganese
Applicable cone, range
(434-4717)
Reagent water, hard
Single-analyst precision SR = 0.06X - 16.36
Overall precision S = 0.06X - 8.04
Accuracy X - 0.97C + 1.13
(43- 1943)
SR - 0.05X - 0.97
S = 0.70X-0.67
X = 1.05C - 5.20
( 1632 - 13868)
Sfl = 0.04X - 18.38
S = 0.07X - 56.61
X - 1.01C - 9.04
(253- 1887)
SR - 0.02X + 1.01
S = 0.04X T 4.07
X = 0.94C + 5.29
Effluent 1, hard dig
Single-analyst precision
Overall precision
Accuracy
Soft Digestion
Applicable cone, range
Reagent water, soft
Single-analyst precision
Overall precision
Accuracy
Effluent 1, soft dig
Single-analyst precision
Overall precision
Accuracy
SR = 0.10X - 2.85
S = 0.16X + 32.43
X - 0.76C + 13.85
( 434 - 4717)
SR = 0.02X + 16.32
S = 0.05X + 7.37
X = 0.99C + 73.49
Sfl = 0.07X + J6. 12
S = 0.09X + 88.80
X = 0.80C + 9.80
SR - 0.02X + 29.24
S - 0.25X + 55.30
X= 7.75C + 53.56
( 43 - 1943)
SR = -0.04X + 20.24
S - 0.07X + J4.55
X = 1.01C + 6.38
SR = 0.07X + 0.79
S - 0.37X - »6.9J
X = 7.33C + 48.88
Sfl - 0.28X - 7.74
S = 0.23X + 1026.00
X = 0.660+ 1961.15
I 1632 - 13868)
SR = 0.02X + 43.59
S = 0.07X - 28.66
X = J.02C - 67.39
Sfl = 0.07X + 1060.43
S = 0.73X+ 7508.77
X = 0.79C + 659.79
Sfl - -0.07X + 54.30
S = 0.04X + 54.37
X = 0.84C - J6.77
( 283 - 1887)
Sfl = 0.04X + 7.75
S = 0.05X - 0.20
X = 0.96C + 7.36
Sfl = 0.03X + 22.60
S = 0.17X + 39.81
X = 0.82C + 8.97
X = Mean recovery
C = True value for the concentration
12
-------
Table 19. Regression Equations for Accuracy and Precision <\ig/L) Reagent Water Versus
Effluent 2 (Lead, Lithium, Magnesium, Manganese)
Hard Digestion
Water Type
Applicable cone, range
Reagent water, hard
Single-analyst precision
Overall precision
Accuracy
Effluent 2, hard dig
Single-analyst precision
Overall precision
Accuracy
Soft Digestion
Applicable cone, range
Reagent water, soft
Single-analyst precision
Overall precision
Accuracy
Effluent 2, soft dig
Single-analyst precision
Overall precision
Accuracy
Lead
1434-4717)
SR = 0.06X - 16.36
S = 0.06X - 8.04
X = 0.97C + 1.13
SB = 0.07X + 42.72
S = O.OSX + 27.62
X = 0.96C - 77.40
1 434 - 4717)
SR - 0.02X + 76.32
S = 0.05X + 7.37
X = 0.99C + 73.49
SB = 0.07X + 73.66
S = 0.04X + 79.75
X = 0.98C - 7.46
Lithium
(43- 1943)
SR = O.OSX - 0.97
S = 0.70X-0.6»
X = 7.05C - 5.20
SB - O.OOX + 7.65
S = 0.75X + 7.79
X = 7.07C + 4.42
(43- 7943;
SB = -0.04X + 20.24
S - 0.07X + 74.55
X = 7.07C + 6.38
SB = 0.02X + 72.77
S = 0.72X + 9.87
X = 7.08C - 0.87
Magnesium
( 1632 - 13868)
SR = 0.04X - 18.38
S - 0.07X - 56.67
X = 7.07C - 9.04
SB = 0.03X + 794.06
S = 0.73X + 97.79
X= 1.00C + 201.74
( 1632 - 13868)
SR = 0.02X + 43.59
S = 0.07X - 28.66
X = 7.Q2C - 67.39
SB = 0.06X + 740.72
S = 0.74X + 74.73
X = 0.97C + 92.67
Manganese
( 253 - 1887)
SR - 0.02X + 7.07
S - 0.04X - 4.07
X = 0.94C + 5.29
SB = 0.07X + 9.06
S = 0.06X+ 7.78
X = 0.93C + 7.76
1 253 - 1887)
SR = 0.04X + 1.75
S = 0.05X - 0.20
X = 0.96C + 7.36
SB - 0.07X + 2.94
S = 0.06X - 6.56
X - 0.95C + 7.08
X = Mean recovery
C = True value for the concentration
Table 20.
Hard Digestion
Water Type
Regression Equations for Accuracy and Precision (p.g/L) Reagent Water Versus
Effluent 3 (Lead, Lithium, Magnesium, Manganese)
Lead
Lithium
Manganese
Applicable cone, range
1434-4717)
Reagent water, hard
Single-analyst precision SR = 0.06X - 16.36
Overall precision S = 0.06X - 8.04
Accuracy X = 0.97C + 1.13
Effluent 3, hard dig
Single-analyst precision SR = O.OOX + 68.83
Overall precision S = 0. 70X + 37.36
Accuracy X = 0.83C + ft 16
Soft Digestion
Applicable cone, range 1434-4717)
Reagent water, soft
Single-analyst precision SR = 0.02X + 16.32
Overall precision S = O.OSX + 7.3f
Accuracy X = 0.99C + 13.49
Effluent 3, soft dig
Single-analyst precision SR = O.OSX - 4.34
Overall precision S = O.OSX + 9.94
Accuracy X = 0.89C + 15.57
(43 - 19431
SR - O.OSX - 0.97
S = 0.10X-0.61
X = 1.0SC - 5.20
SR = 0.15X + 7.54
S = 0.22X + 18.42
X= J.T5C + 9.56
143 - 7943>
11632 - 13868)
SR - 0.04X - 18.38
S - 0.07X - 56.61
X = I.OTC - 9.04
1253-1887)
SR = 0.02X + 1.01
S - 0.04X - 4.07
X = 0.94C + 5.29
SR " 0.02X + 394.55 SR = 0.03X + 8.44
S = O.OSX + 243.70 S = 0.07X + 2.96
X = 0.96C - 85.39 X = 0.92C + 2.»7
11632 - 13868)
SR = -0.04X + 20.24 SB » 0.02X + 43.59
S = 0.07X + 74.55 S = 0.07X - 28.66
X = J.07C + 6.38 X = J.02C - 67.39
f253- 1887)
SR = 0.04X + 7.75
S = O.OSX - 0.20
X = 0.96C + 7.36
SB = -O.MX + 79.97 SB - O.OOX + 228.25 SB = O.OOX + 75.79
S = 0.26X + 72.63 S = 0.04X + 243.84 S = 0.06X + 3.52
X=».73C-5.57 X = 0.97C + 77.73 X = 0.940-3.14
X = Mean recovery
C = True value for the concentration
13
-------
Table 21.
Hard Digestion
Water Type
Regression Equations for Accuracy and Precision (pg/L) Reagent Water Versus
Drinking Water (Molybdenum, Nickel, Potassium, Selenium)
Molybdenum
Nickel
Potassium
Selenium
Applicable cone, range
Reagent water, hard
Single-analyst precision
Overall precision
Accuracy
Drinking water, hard
Single-analyst precision
Overall precision
Accuracy
Soft Digestion
Applicable cone, range
( 17 - 1094)
SR = 0.03X + 1.98
S = O.OSX + 1.72
X = 0.9SC + 0.69
Sfl = 0.02X + 1.64
S = 0.02X + 5.47
X = 0.960 + 2.17
( 17 - 1094)
Reagent water, soft
Single-analyst precision SR = O.OSX + 2.96
Overall precision S = O.OSX + 3.66
Accuracy X = 0.96C-2.75
Drinking water, soft
Single-analyst precision SR = 0.02X + 1.40
Overall precision S = 0.01X + 6.47
Accuracy X = 0.98C + 4.89
117 - 189)
SR = 0.09X + 7.49
S = O.OSX + 4.08
X = 0.91C + 2.02
SR = -O.OOX + 4.23
S = O.OSX + 6.42
X = 0.89C + 5.05
(17 - 189)
SR = 0.04X + 2.13
S = 0.03X + 6.38
X = 0.94C + 2.84
SR = 0.06X + 2.80
S = -0.02X + 11.04
X = 0.93C + 4.67
1347 - 18871
I 69 - 755)
SR = -O.OOX + 739.13 SR = 0.02X + 11.61
S = 0.13X + 56.49 S = 0.09X+ 18.36
X - 0.77C + 21.02 X = 0.92C - 1.57
SR = 0.14X + 211.90 SR = O.OSX + 0.48
S = O.OSX + 206.35 S = 0.72X + 0.86
X = 0.85C + 182.38 X = 0.89C + 3.48
(347 - 1887) I 69 - 755)
SR = 0.03X + 7.35
S-0.75X + 5.56
X = 0.94C+ 1.17
SR = 0.06X + 729.43 SB = -0.07X + 27.86
S = 0.12X + 746.75 S = O. 73X + 37.43
X - O.S8C - 73.83 X = 0.90C + 39.74
X = Mean recovery
C = True value for the concentration
Table 22.
Hard Digestion
Wafer Type
Regression Equations for Accuracy and Precision (\Lg/L) Reagent Water Versus
Surface Water (Molybdenum, Nickel, Potassium, Selenium)
Molybdenum
Nickel
Potassium
Selenium
Applicable cone, range
I 73 - 1094)
Reagent water, hard
Single-analyst precision SR = 0.04X + 0.97
Overall precision S = O.OSX - 7.77
Accuracy X = 0.97C - 2.93
Surface water, hard
Single-analyst precision
Overall precision
Accuracy
Soft Digestion
Applicable cone, range
SR = 0.06X - 2.60
S = O.OSX - 2.27
X = 0.96C + 7.30
I 73 - 1094)
I 43-943)
SR = O.OOX + 9.75
S = 0.04X + 6.48
X = 0.98C - 2.93
SR = 0.01X + 3.39
S = 0.03X + 6.43
X = 0.98C+ 7.77
I 43-943)
( 830 - 7S47)
I 83 - 755)
SR = -0.03X + 186.14 SR = 0.04X + 3.82
S = 0.06X + 730.84 S = 0.77X + 73.74
X - 0.92C - 772.69 X = 0.92C - 0.48
Sfl = O.OOX + 207.46 Sfl = 0.03X + 7.53
S = aOSX + 770.56 S = 0. J3X + 75.97
X = 0.98C + 770.49 X - 0.97C + 6.37
I 830 - 7547)
( 83 - 755)
Reagent water, soft
Single-analyst precision
Overall precision
Accuracy
Surface water, soft
Single-analyst precision
Overall precision
Accuracy
SR = 0.06X + 0.58
S = O.OSX + 6.49
X = 0.99C - 6.78
Sfl = 0.02X + 4.55
S = 0.02X + 7.08
X = 1.02C - 5.90
SR = O.OSX + 7.98
S = 0.06X + 3.33
X = 7.00C - 0.66
Sfl = 0.04X + 0.35
S = O.OSX + 3.29
X = 0.96C + 4.20
Sfl = 0.06X + 24.79
S = 0.07X + 767.35
X = 0.93C - 783.77
Sfl = 0.78X- 64.57
S=0.70X+ 407.87
X = 0.88C + 799.63
Sfl = 0.06X + 4.00
S = 0.74X+ 75.64
X = 0.97C + 0.36
Sfl = O.OSX + 3.05
S = 0.72X-0.02
X = 0.95C - 3.25
X = Mean recovery
C = True value for the concentration
14
-------
Table 23.
Hard Digestion
Water Type
Regression Equations for Accuracy and Precision (it,g/L) Reagent Water Versus
Effluent 1 (Molybdenum, Nickel, Potassium, Selenium) •
Molybdenum
Nickel
Potassium
Selenium
Applicable cone, range
1329 - 1830!
Reagent water, hard
Single-analyst precision SR = 0.05X - 6.25
Overall precision S = 0.08X - 3.97
Accuracy X = 1.00C - 5.06
1166 - 47170)
SR = 0.03X + 1.89
S = 0.06X + 2.63
X = 0.97C - 1.59
(1660 - 14151)
SR = 0.01X + 58.84
S = O.OSX + 85.57
X = 0.95C - 277.33
(425 - 7475;
SB = 0.03X + 6.50
S = 0.04X + 43.25
X = 0.95C - 1 17
Effluent 7, hard dig
Single-analyst precision
Overall precision
Accuracy
Soft Digestion
Applicable cone, range
Reagent water, soft
Single-analyst precision
Overall precision
Accuracy
SR = OMX + 12.22
S = 0.16X - 8.40
X = 0.75C + 27.43
(329 - 7830;
SB = 0.07X + 2.73
S = 0.70X-7.86
X = 0.96C + 9.63
SB = 0.79X + 3747.96 SB = 0.77X + 393.55 SB = 0.78X - 32.45
S = 0.49X + J36.87 S = 0.45X - 245.80 S = 0.75X + 44.08
X = -0.27C + 8222.09 X = 7.00C + J648.44 X = 0.74C + 229.79
066 - 47J70;
SB = 0.03X + 5.82
S = 0.06X + 8.53
X = J.OOC + 3.08
(7660 - 74757;
(425 - 74J5;
SB = 0.07X + 770.07 SB = -0.07X + 40.37
S = 0.07X + 730.50 S = 0.04X + 84.89
X = 0.94C - 794.86 X = 7.00C - 8.74
Effluent 1, soft dig
Single-analyst precision SR = 0.01X + 28.36
Overall precision S = 0.16X + 14.10
Accuracy X = 0.74C + 18.07
SR = 0.20X + 7236.60 SB = -0.02X+ 1375.77SR = 0.14X + 1.81
S = 0.43X + 1023.56 S = OMX + 2538.38 S = 0.17X + 9.75
X = -0.59C + 8767.05 X = 7.09C + 3770.99 X = 0.77C + 788.20
X = Mean recovery
C = True value for the concentration
Table 24.
Hard Digestion
Water Type
Regression Equations for Accuracy and Precision (\ig/L) Reagent Water Versus
Effluent 2 (Molybdenum, Nickel, Potassium, Selenium)
Molybdenum
Nickel
Potassium
Selenium
Applicable cone, range
(329 - 1830)
Reagent water, hard
Single-analyst precision SR = 0.05X - 6.25
Overall precision S = 0.08X - 3.97
Accuracy X = 1.00C - 5.06
1166 - 47170)
SR = 0.03X + 7.89
S = 0.06X + 2.63
X = 0.97C - 7.59
(7660 - 74757;
SB = 0.07X + 58.84
S = 0.08X + 85.57
X = 0.95C - 277.33
(425 - 7475;
SB = 0.03X + 6.50
S = 0.04X + 43.25
X = 0.95C- 7.77
Effluent 2, hard dig
Single-analyst precision
Overall precision
Accuracy
Soft Digestion
Applicable cone, range
Reagent water, soft
Single-analyst precision
Overall precision
Accuracy
Effluent 2, soft dig
Single-analyst precision
Overall precision
Accuracy
SR = 0.03X - 0. 12
S = 0.06X + 0.37
X = 0.98C + 1.81
(329 - 1830)
SR = 0.07X + 2.13
S = 0.10X-7.86
X = 0.96C + 9.63
SB = 0.02X + 8.76
S = 0.08X + 4.70
X = 7.03C + 9.07
SB = -O.OOX + 34.52
S = 0.06X + 73.53
X = 0.93C + 78.09
(766 - 47770;
SB = 0.03X + 5.82
S = 0.06X + 8.53
X = J.OOC + 3.08
SB = 0.02X + 6.47
S = 0.06X+8.73
X = 0.97C + 72.35
SB = 0.09X + 373.84
S = 0.79X+ 754.60
X= 1.17C -416.31
(1660 - 14151)
SB = 0.07X + 770.07
S = 0.07X + 730.50
X = 0.94C - 794.86
SB = 0.08X - 8.78
S = 0.22X + 72.29
X= 7.20C- 77.86
Sfl= -0.09X+ 776.73
S = -0.04X + 96.93
X = 0.95C - 50.28
(425 - 7475;
SB = -0.07X + 40.37
S = 0.04X + 84.89
X = 7.00C-8.74
Sfl=0.02X+ 76.78
S = 0.06X + J9.46
X = 0.97C - 26.58
X = Mean recovery
C = True value for the concentration
15
-------
Table 25.
Hard Digestion
Water Type
Regression Equations for Accuracy and Precision (\ig/L) Reagent Water Versus
Effluent 3 (Molybdenum, Nickel, Potassium, Selenium)
Molybdenum
Nickel
Potassium
Selenium
Applicable cone, range
1329 - 1830)
Reagent water, hard
Single-analyst precision SR = 0.05X - 6.25
Overall precision S = 0.08X - 3.97
Accuracy X = 1.00C - 5.06
Effluent 3, hard dig
Single-analyst precision SR = O.OOX + 71.10
Overall precision S = 0.05X + 55.78
Accuracy X = 0.91C + 14.48
Soft Digestion
Applicable cone, range (329 - 1830)
Reagent water, soft
Single-analyst precision SR = 0.07X + 2.13
Overall precision S = 0.10X - 7.86
Accuracy X = 0.96C + 9.63
Effluent 3, soft dig
Single-analyst precision SR = 0.03X + 13.20
Overall precision S = 0.08X + 73.35
Accuracy X - O.S3C + 24.21
1166 - 47170)
SR = 0.03X + 7.89
S = 0.06X + 2.63
X = 0.97C - 1.59
SR = 0.03X + 6.12
S = 0.08X + 7.73
X = 0.93C - 8.21
1166 - 47170)
SR = 0.03X + 5.82
S = 0.06X + 8.53
X = 1.00C + 3.08
SR - 0.02X + 12.75
S = 0.06X + 13.79
X = 0.92C + 4.70
11660 - 14151)
<425 - 1415)
SR = 0.01X + 58.84 SR = 0.03X + 6.50
S - 0.08X + 85.57 S = 0.04X + 43.25
X = 0.95C - 277.33 X = 0.95C -1.17
SR - 0.07X + 1778.07 SR = O.OOX + 48.17
S - 0.37X + 828.33 S = 0.06X + 62.87
X = 7.39C + 448.58 X = 0.89C + 49.08
(1660 - 141511
1425 - 1415)
SR = 0.01X + 170.07 SB - -0.01X + 40.37
S = 0.07X + J30.50 S = 0.04X + 84.89
X = 0.94C - 194.86 X =1.000-8.14
SR = 0.21X + 275.65 SB = 0.02X + 27.73
S - 0.49X + 20.96 S = 0.03X + 43.40
X - 7.00C - 277.29 X = 0.96C + 22.60
X = Mean recovery
C = True value for the concentration
Table 26. Regression Equations for Accuracy and Precision (\t.g/U Reagent Water Versus
Drinking Water (Silicon, Silver, Sodium, Strontium)
Hard Digestion
Water Type Silicon Silver Sodium Strontium
Applicable com, range 1189 - 2359)
Reagent water, hard
Single-analyst precision
Overall precision
Accuracy
Drinking water, hard
Single-analyst precision
Overall precision
Accuracy
Soft Digestion
Applicable cone, range
Reagent water, soft
Single-analyst precision
Overall precision
Accuracy
Drinking water, soft
Single-analyst precision
Overall precision
Accuracy
SR = 0.17X+ 11.86
S = 0.43X + 37.13
X = 0.57C - 38.25
( 8-94)
SR = 0.25X - 1.77
S = 0.32X - 0.95
X = 0.47C + 4.27
t 35-940)
SR = 0.10X + 95.00
S = 0.43X + 75.56
X - 7.07C +• 39.90
( 4-38)
SR = -0.03X + 0.89
S = 0.78X + 0.38
X = 0.96C - 0.35
SB = 0.73X + 765.46 SB = 0.72X + 0.30
S = 7.75X - J60.04 S = 0.35X - 0.70
X = - 7.06C + 2559.96 X = 0.50C + 4.54
SB = 2.76X - 7450.62 SB = 0.02X + 7.88
S = 7.57X-794.77 S = 0.74X+7.72
X - 0.42C + 796.76 X = 0.92C + 0.87
(188 - 2359)
SB = 0.75X + 36.02
S - 0.30X + 57.73
X = 0.87C - 29.67
SB = 0.28X + 50.97
S = 0.49X - 87.33
X = 7.04C + 42.28
( 8-94)
SR = 0.27X - 7.68
S = 0.36X - 0.95
X = 0.44C + 7.00
Sfl = 0.77X + 2.20
S = 0.24X + 7.58
X = 0.53C + 5.26
(35-940)
SR = 0.08X + 55.44
S = 0.20X + 24.24
X= 1.ISC+ 21.65
I 4-38)
SB = 0.05X + 0.49
S = 0.05X + 7.04
X = 7.05C + 0.48
SB - 0.33X + 36.39 SB = O.OSX + 7.59
S - 0.65X - 43.87 S = 0.75X + 7.70
X - -0.56C + 474.79 X = 7. »OC + 7.74
X = Mean recovery
C = True value for the concentration
16
-------
Table 27.
Hard Digestion
Water Type
Regression Equations for Accuracy and Precision <\t.g/L) Reagent Water Versus
Surface Water (Silicon, Silver, Sodium, Strontium)
Silicon
Silver
Sodium
Strontium
Applicable cone, range
Reagent water, hard
Single-analyst precision
Overall precision
Accuracy
Surface water, hard
Single-analyst precision
Overall precision
Accuracy
Soft Digestion
Applicable cone, range
Reagent water, soft
Single-analyst precision
Overall precision
Accuracy
Surface water, soft
Single-analyst precision
Overall precision
Accuracy
(849 - 47171
SR = 0.26X - 63.85
S - 0.35X + 53.58
X = O.S7C - 12.21
( 17 - 1891
SR = 0.22X - 2.06
S - 0.64X - 8.71
X = 0.29C + 3.78
(83-94341
( 9-23S9)
SR = -0.04X + 3/6.57 SR - 0.16X - 0.33
S = 1.08X - 208.75 S = 0.46X - 3.07
X = 0.07C + 766.05 X = 1.02C -4.12
SR = -O.OOX + 120.31 SR - 0.02X + 0.21
S = 0.75X + 58.74 S = 0.04X + 0.24
X - 0.94C + 25.04 X - 1.02C + 0.28
SR = -0.13X + 564.21 SR = 0.01X + 1.87
S = 0.22X + 180.83 S = 0.07X + 7.69
X = 0.82C + 484.40 X = 0.980+1.13
(849 - 4717)
( 17 - 1891
SR = 0.33X - 7 76.80 SR = 0.7SX + 7.3S
S = 0.42X - 48.64 S = 0.83X - 72.00
X - 0.97C - 95.22 X = 0.23C + 73.92
Sfl = 0.02X + 726.77 SR = 0.07X + 0.77
S = 0.56X - 282.63 S - 0.08X + 7.45
X = 0.76C + 739.06 X = 0.79C + 3.44
I 83-94341
SR = 0.14X + 22.14
S-0.76X + 19.01
X = 1.01C + 40.86
I 9-2359)
Sfl = 0.07X + 0.02
S = 0.07X + 0.65
X = 7.03C + 0.44
SR - 0.08X + 239.62 SR = 0.04X + 1.08
S = 0.30X + 233.14 S - 0.08X + 2.91
X - 1.24C + 382.20 X - 0.99C + 0.00
X = Mean recovery
C - True value for the concentration
Table 28. Regression Equations for Accuracy and Precision (\ig/L) Reagent Water Versus
Effluent• t (Silicon, Silver, Sodium, Strontium)
Hard Digestion
Water Type
Applicable cone, range
Reagent water, hard
Single-analyst precision
Overall precision
Accuracy
Silicon
(1887 - 9434)
SR = 0.34X - 211.12
S = 0.84X - 753.40
X = 0.30C + 847.87
Silver
(66
SR
S =
X =
'•- 189)
* -0.05X + 70.96
0.92X - 22.60
-0.09C + 62.94
Sodium
(826 - 47170)
SR = O.OSX + 17.94
S = 0.06X + 772.47
X = 0.97C + 67.99
Strontium
( 33
SR-
S-
X-
- 4717)
* 0.02X - 0.07
0.04X + 0.86
0.99C + 7.94
Effluent 1, hard dig
Single-analyst precision SR = 0.38X - 98.54
Overall precision S = 0.51X + 196.70
Accuracy X = 0.54C + 933.77
Soft Digestion
Applicable cone, range
(1887 - 9434)
SR = 0.24X - 6.64
S = O.OSX + 18.32
X = 0.55C + 6.66
(66-189)
(826 - 47170)
SR = 0.05X + 70.25
S = 0.75X + 8.75
X = 0.80C + 5.00
( 33 - 4717)
Reagent water, soft
Single-analyst precision SR = 0.24X - 41.61
Overall precision S = 0.40X - 282.48
Accuracy X = 1.26C - 690.74
Effluent 1, soft dig
Single-analyst precision SR = 0.22X + 92.08
Overall precision S = 0.46X - 412.90
Accuracy X = 0.93C - 66.97
SR = -0.05X + 70.77 SR = 0.04X + 782.64 SR = 0.04X + 0.67
S - 0.73X - 72.72 S = 0.07X + 769.70 S - 0.06X - 0.62
X = -0.73C + 66.00 X - 7.07C + 49.53 X - 7.07C + 3.55
SR = -0.33X + 44.09
S = 0.79X+ 75.72
X = 0.47C + 78.88
SR = 0.03X -I- 8.68
S = 0.74X- 73.09
X = 0.85C + 8.77
X = Mean recovery
C = True value for the concentration
17
-------
Table 29.
Hard Digestion
Regression Equations for Accuracy and Precision (\ig/L) Reagent Water Versus
Effluent 2 (Silicon, Silver, Sodium, Strontium)
Water Type
Applicable cone, range
Reagent water, hard
Single-analyst precision
Overall precision
Accuracy
Effluent 2, hard dig
Single-analyst precision
Overall precision
Accuracy
Soft Digestion
Applicable cone, range
Reagent water, soft
Single-analyst precision
Overall precision
Accuracy
Effluent 2, soft dig
Single-analyst precision
Overall precision
Accuracy
Silicon
11887 - 94341
SR = 0.34X- 211.12
S » 0.84X - 753.40
X - 0.30C + 847.87
11887 - 34341
Sft - 0.24X - 41.61
S - 0.40X - 282.48
X - 1.26C - 890.74
SR = 0.3SX - 472.39
S - 0.43X - 433.10
X - 0.92C + 354.58
Silver
(66-189)
SR = -0.05X + 10.96
S - 0.92X - 22.60
X - -0.09C + 82.94
SR = 0.06X + 0.70
S - -O.OOX + 19.72
X « 0.86C - 16.00
1 66-189)
SR = -O.OSX + 10.11
S = 0.73X - 12.72
X = -0.13C + 66.00
SR - 0.01X + 6.12
S*0.10X + 5.41
X = 0.79C - 5.99
Sodium
(826 - 47170)
SR - 0.05X + 17.94
S - 0.06X + 172.41
X = 0.97C + 61.99
SR » 0.10X + 5218.65
S = 0.14X + 8082.26
X = 0.42C + 12346.46
(826 - 47170)
SR ' 0.04X + 182.64
S = 0.07X + 169.70
X - 1.01C + 49.53
Strontium
( 33 - 4717)
SR - 0.02X - 0.07
S - 0.04X + 0.86
X = 0.99C + 1.94
SR = 0.01X + 15.26
S = 0.04X + 13.67
X = 0.97C + 1.08
( 33 - 4717)
SR = 0.04X + 0.67
S = 0.06X - 0.62
X - 1.01C + 3.55
SB = -0.03X + 7620.41 SR - 0.03X + 4.62
S = 0.06X + 7734.48 S = 0.06X + 6.42
X = 0.63C + 9172.71 X - 0.97C - 0.71
X = Mean recovery
C = True value for the concentration
Table 30.
Hard Digestion
Water Type
Regression Equations for Accuracy and Precision (\ig/U Reagent Water Versus
Effluent 3 (Silicon, Silver, Sodium, Strontium)
Silicon
Silver
Sodium
Strontium
Applicable cone, range
Reagent water, hard
Single-analyst precision
Overall precision
Accuracy
Effluent 3, hard dig
Single-analyst precision
Overall precision
Accuracy
Soft Digestion
Applicable cone, range
Reagent water, soft
Single-analyst precision
Overall precision
Accuracy
Effluent 3, soft dig
Single-analyst precision
Overall precision
Accuracy
(1887 - 9434)
SR - 0.34X - 211.12
S * 0.84X - 753.40
X - 0.30C + 847.87
SR = 0.19X + 369.96
S - 0.44X + 84.73
X - 0.86C - 254.75
(1887 - 94341
SR - 0.24X - 41.61
S «• 0.40X - 282.48
X = 1.26C - 690.74
(66-189)
(826 - 47170)
SR - -O.OSX + 10.96 SR = 0.05X + 17.94
S - 0.92X - 22.60 S - 0.06X + 172.41
X = -0.09C + 62.94 X - 0.97C + 61.99
( 33 - 47171
SR - 0.02X - 0.07
S = 0.04X + 0.86
X = 0.99C + 1.94
SR = -0.10X + 21.55 SR-1.17X- 27291.25 SR - 0.16X - 24.48
S --0.06X + 26.97 S - 0.23X + 9468.66 S = 0.28X + 117.64
X - 0.75C + 3.39 X - 0.83C + 24666.49 X - 0.76C + 190.69
(66-189)
(826 - 47170)
SR = -0.06X +10.11 SR" 0.04X + 182.64
S = 0.73X- 12.72 S = 0.07X + 169.70
X=°-0.13C + 66.00 X = 1.01C + 49.53
SR = -0.05X + 860.72 SR » -0.03X + 18.54
S-O.J9X + 267.27 S - 0.11X + 11.47
X " 0.84C + 328.18 X *° 0.88C - 1.98
( 33 - 4717)
SR - 0.04X + 0.67
S = 0.06X - 0.62
X - 1.01C + 3.55
SR = 0.07X + 292.44
S = 0.39X + 2.24
X = 0.63C + 234.98
X ™ Mean recovery
C = True value for the concentration
18
-------
Tab/a 31.
Hard Digestion
Water Type
Regression Equations for Accuracy and Precision (\ig/U Reagent Water Versus
Drinking Water (Thallium, Vanadium, Zinc)
Thallium
Vanadium
Zinc
Applicable cone, range
Reagent water, hard
Single-analyst precision
Overall precision
Accuracy
Drinking water, hard
Single-analyst precision
Overall precision
Accuracy
Soft Digestion
Applicable cone, range
Reagent water, soft
Single-analyst precision
Overall precision
Accuracy
Drinking water, soft
Single-analyst precision
Overall precision
Accuracy
I 79 - 477)
Sfl = 0.07X + 5.86
S - 0.22X + 7.08
X = 0.37C - 3.08
SR - 0.01X + 40.21
S = 0.01X + 51.06
X - 0.90C + 23.92
I 79 - 477)
I 13 - 75)
I 7-152)
Sfl - -0.01X + 1.58 SB = -0.02X + 9.68
S - 0.01X + 2.20 S = 0.20X + 3.21
X - 0.95C -1.52 X - 0.88C + 0.73
SB = -0.29X + 17.63 SR - 0.19X + 3.10
S = 0.08X + 5.39 S = 0.»7X + 7.35
X - 0.78C + 9.31 X » 0.92C + 5.43
I 13 - 75)
SR = -0.06X + 56.97 Sfl = 0.04X + 0.74
S = 0.23X + 4.18 S = 0.09X + 1.42
X = 0.89C + 9.63 X - 0.97C + 0.16
SR = 0.16X+ 13.45
S = 0.27X + 8.74
X = 0.90C + 0.73
Sfl = 0.04X + 0.70
S - O.OJX + 6.33
X = 0.95C + J.53
( 7-152)
Sfl - -0.02X + 8.61
S - 0.07X + 6.58
X - 0.89C + 2.76
SR = 0.12X + 2.15
X = 0.97C + 5.59
X = Mean recovery
C = True value for the concentration
Table 32.
Hard Digestion
Regression Equations for Accuracy and Precision lu.g/L) Reagent Water Versus
Surface Water (Thallium, Vanadium, Zinc)
Water Type
Applicable cone, range
Reagent water, hard
Single-analyst precision
Overall precision
Accuracy
Surface water, hard
Single-analyst precision
Overall precision
Accuracy
Soft Digestion
Applicable cone, range
Reagent water, soft
Single-analyst precision
Overall precision
Accuracy
Surface water, soft
Single-analyst precision
Overall precision
Accuracy
Thallium
(126 - 953)
Sfl = O.OOX + 24.72
S = 0.07X + 25.10
X = 0.93C - 16.28
SR = 0.06X - 1.59
S = 0.06X + 3.70
X = 0.90C - J5.59
1126 - 953)
SR = 0.02X + 33.8J
S = 0.07X + 30.95
X - 0.87C + 7Z93
Sfl = 0. MX- J.80
S = 0.»5X-0.5S
X - 0.84C - 6.86
Vanadium
( 41 - 1877)
Sfl = 0.03X - 0.28
S = 0.05X + 3.80
X - 0.97C - T.85
Sfl - 0.02X + 4.71
S = 0.06X + 3.W
X = ».OOC - 2.07
1 41 - 1877)
SR - 0.05X + 0.78
S = 0.06X + 5.4?
X = 0.97C - J.32
Sfl = O.OIX + J.86
S - 0.05X 4- 4.97
X-0.98C- 1.14
Zinc
1 68-759)
Sfl - O.OOX + 8.29
S - 0.02X + J0.9J
X = 0.97C - 3.04
Sfl"-O.OOX + 5.»7
S = 0.05X + 7.T7
X - 0.98C + 0.57
( 68 - 759)
SR - 0.06X + 2.52
S " O.OSX + 7.98
X - J.02C - 8.32
Sfl = O.OIX + 9.04
S = O.OOX + J6.57
X = 1.01C - 8.67
X = Mean recovery
C - True value for the concentration
19
-------
Table 33. Regression Equations for Accuracy and Precision (\ig/L) Reagent Water Versus
Effluent 1 (Thallium, Vanadium, Zinc)
Hard Digestion
Water Type
Thallium
Vanadium
Zinc
Applicable cone, range
Reagent water, hard
Single-analyst precision
Overall precision
Accuracy
Effluent 1, hard dig
Single-analyst precision
Overall precision
Accuracy
Soft Digestion
Applicable cone, range
Reagent water, soft
Single-analyst precision
Overall precision
Accuracy
Effluent 1, soft dig
Single-analyst precision
Overall precision
Accuracy
1420 - 1434)
S« = 0.02X + 12.17
S-O.MX- 1.18
X = 0.92C - 22.S6
SR = 0.23X - 35.03
S = 0.21X + 82.44
X = 0.71C- 12.19
(420 - 14341
SR = 0.01X + 42.63
S = O.SSX - 193.73
X - 1.08C - 87.34
SR = 0.12X + 26.26
S = 0.12X + 93.74
X = 0.78C - 38.96
SR = 0.03X + 0.00
S = 0.06X + 5.21
X = 0.97C - 4.31
SR = 0.06X + 2.96
S-O.MX + 12.38
X - 0.88C - 13.3S
(66
SR = 0.04X + 2.03
X = 0.970-4.18
SR = 0.03X + 4.68
S = 0.»6X + 9.07
X - 0.89C - 6.85
(133 - 7076)
SR = 0.01X + 3.26
S = 0.04X + 0.71
X = 0.98C - 10.37
SR = 0.04X + 44.01
S = 0.07X + 56.42
X = 0.92C + 72.42
1133 - 7076)
SR * OMX + 3.97
S - O.OSX + 6.56
X = 1.01C - 6.85
SR - O.OSX + 23.60
S = 0.14X + 17.40
X = 0.86C- 18.10
X = Mean recovery
C = True value for the concentration
Table 34. Regression Equations for Accuracy and Precision (u.g/L) Reagent Water Versus
Effluent 2 (Thallium, Vanadium, Zinc)
Herd Digestion
Water Type
Applicable cone, range
Reagent water, hard
Single-analyst precision
Overall precision
Accuracy
Effluent 2, hard dig
Single-analyst precision
Overall precision
Accuracy
Soft Digestion
Applicable cone, range
Reagent water, soft
Single-analyst precision
Overall precision
Accuracy
Effluent 2, soft dig
Single-analyst precision
Overall precision
Accuracy
Thallium
(420 - 1434)
Sfl = 0.02X+ 12. 17
S = 0.11X- 1.18
X - 0.92C - 22.56
SR => 0.03X + 62.49
S = 0.26X + 55.19
X = 0.86C - 89.13
(420 - 1434)
SR - O.OJX + 42.83
S - O.SSX - J93.73
X = f.OSC - 87.34
SR = O.OSX - 9.09
S = 0.27X - 38.90
X = 0.93C + »».93
Vanadium
( 66-4698)
SR = 0.03X + 0.00
S - 0.06X + 5.21
X = 0.97C - 4.31
SR = 0.02X + 1.30
S = 0.06X - 0.64
X = 0.95C + J.38
( 66-4698)
SR = 0.04X + 2.03
S = 0.08X + 3.1S
X = 0.970-4.18
SR - O.OSX + 1.29
S = 0.06X - 0.73
X = 0.97C - 0.25
Zinc
(133 - 7076)
SR = O.OJX + 3.26
S = 0.04X + 0.7J
X - 0.98C - J0.37
SB = 0.02X + 2.36
S - 0.06X + 3.94
X = 0.99C - 0.55
(133 - 7076)
SR = OMX + 3.97
S - 0.05X + 6.56
X = 1.01C - 6.85
Sfl - 0.02X + 5.7J
S = 0.04X + 5.28
X = 1.01C - 4.24
X = Mean recovery
C = True value for the concentration
20
-------
Table 35.
Hard Digestion
Regression Equations for Accuracy and Precision (u.g/L) Reagent Water Versus
Effluent 3 (Thallium, Vanadium, Zinc)
Water Type
Applicable cone, range
Reagent water, hard
Single-analyst precision
Overall precision
Accuracy
Effluent 3, hard dig
Single-analyst precision
Overall precision
Accuracy
Soft Digestion
Applicable cone, range
Reagent water, soft
Single-analyst precision
Overall precision
Accuracy
Effluent 3, soft dig
Single-analyst precision
Overall precision
Accuracy
Thallium
(420 - 1434)
SR = 0.02X+ 12.17
S = 0.11X- 1.18
X = 0.92C - 22.S6
SR = 0.11X + 23.85
S = 0.12X + 75.08
X - 0.83C - 49.53
(420 - 14341
SB = 0.01X + 42.83
S = 0.55X - 193.73
X = 1.08C - 87.34
SR = -0.02X+ 119.72
S = 0.40X - 72.58
X= 1.21C- 64.18
Vanadium
( 66-4698)
SR = 0.03X + 0.00
S = 0.06X + 5.21
X = 0.97C - 4.31
SR = 0.04X + 5.24
S = O.OSX + 3.36
X = 0.88C - 4.94
( 66-46981
SR = 0.04X + 2.03
S = 0.08X + 3.15
X = 0.97C-4.18
SR = 0.02X + 4.27
S = 0.09X + 9.88
X = 0.92C - 7.44
Zinc
(133 - 7076)
SR - 0.01X + 3.26
S - 0.04X + 0.71
X - OMC - 10.37
SR = 0.03X + 5.64
S = 0.06X + 8.12
X = 0.95C - 14.94
(133 - 7076)
SR = 0.04X + 3.97
S = O.OSX + £.56
X = 1.01C - 6.85
SR = 0.02X + 8.53
S = 0.07X + 3.46
X - 0.95C - 2.92
X = Mean recovery
C = True value for the concentration
Table 36. Supplemental Regression
Equations (u.g/U
Lithium
Reagent Water, Soft Digestion
S = 0.2390X + 3.9536
SR = 0.1891X - 7.5674
Barium
Reagent Water, Hard Digestion
S = O.W37X + 2.8817
SR = 0.00196X + 2.6852
X = 0.8966C - 0.2891
Range = 8.5 to 377
Reagent Water, Soft Digestion
S = 0.1366X + 0.5327
SR = 0.0218X + 3.5843
X = 0.9456C + 0.7248
Range = 8.5 to 377
Drinking Water, Hard Digestion
S = 0.1897X+ 1.7292
SR = 0.0144X + 2.8119
X = 0.9070C - 1.7284
Range = 8.5 to 377
Reagent Water, Soft Digestion
S = 0.1520X + 2.298
SR = 0.0413X + 0.5865
X = 0.9505C + 3.565
Range = 8.5 to 377
X = 0.6478C + 8.4588
Range = 17.1 to 48.6
Drinking Water, Soft Digestion
S = 0.5267X + 4.8841
SR = 0.0232X + 4.1162
X = 0.8162C + 3.7051
Range = 17.1 to 48.6
Potassium
Reagent Water, Soft Digestion
S =-0.1373X + 317.3
SR = -0.0186X + 124.6
X = 0.9529C - 191.3
Range = 830 to 1890
Silicon
Effluent 2, Hard Digestion
S = 0.8502X + 0.0
SR = O.OX + 0.0
X = 0.4324C + 309.4
Range = 7890 to 9430
Sodium
Effluent 3, Soft Digestion
S = 0.7394X - 1533.
SR = +O.OX + 0.0
X =-0.8622 + 40135.
Range = 826 to 47200
Calcium
Reagent Water, Hard Digestion
S = 0.2266X + 6.7739
SR = 0.0212X + 3.5984
X = 0.8229C - 0.4907
Range = 19.1 to 1910
21
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R. Max field andB. Mindak are with Versar, Inc.. Springfield, VA 22151.
Edward L. Berg and Robert L. Graves are the EPA Project Officers (see below).
The complete report. entitled"EPA Method Study 27. Method 200.7, Trace Metals
by ICP," (Order No. PB 85-248 656; Cost: $58.95, 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
22
-sir U.S. GOVERNMENT PRINTING OFFICE:1985/464-l 16/20720
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*2 £ 8
o £
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