United States
Environmental Protection
Agency I
Environmental Monitoring
and Support Laboratory
Cincinnati OH 45268
Research and Development
Project
EPA-600/S4-84-aiA4iMiaJ 98.
Summary
EPA Mekhod Study 14 Method
604-Phenols
Jack R. Hall, J. Ri
chard Florance, Dennis L Strother, and Marlene N. Wass
An interlaboratory study in which 20
laboratories participated was conducted
to provide precision and accuracy
statements for tie proposed EPA
Method 604-Phenols for measuring
concentrations of the Category 8
chemicals phenol, 2,4-dimethylphenol,
2-chlorophenol, i-chloro-3-methyl-
phenol, 2,4-dichlbrophenol, 2,4,6-
trichlorophenol, pentachlorophenol, 2-
nitrophenol, 4-nitrophenol, 4,6-dinitro-
2-methylphenol, anjd 2,4-dinitrophenol
in municipal and industrial aqueous
discharges.
The method provides for the determi-
nation of the phenols by gas chroma-
tography (GC) witjh flame ionization
detection (FID) or derivatization and
detection by electron capture (EC).
The study design was based on
Youden's plan for collaborative tests of
analytical methods.I Three Youden pair
samples of the tests compounds were
spiked into six types of test waters and
then analyzed. The] test waters were
distilled water, nondechlorinated tap
water, a surface iwater, and three
different industrial wastewater effluents.
A limited study was also conducted by
applying the method for the analysis of
the phenolics in dechlorinated tap
water. The resulting data were statisti-
cally analyzed usijng the computer
program "Interlaboratory Method Vali-
dation Study" (IMVS). Using the mean
recovery for each of the subject com-
pounds analyzed by the GC-FID proce-
dure, the method recoveries were in the
range of 40 to 89^6. Overall precision
was in the range of 20 to 45% and
single-analyst precision was in the
range of 15 to 37%. Using the mean
recovery for each of the subject com-
pounds, when analyzed by the GC-EC
procedure, the method recoveries were
in the range of 32 to 76%. Overall
precision was in the range of 38 to 64%
and single-analyst precision was in
the range of 29 to 48%. In general mean
recoveries, overall standard deviations,
(S) and the single-analyst standard
deviations, (SR), were directly propor-
tional to the true concentration levels.
With the exception of the FID analysis
of 2,4-dinitrophenol in three of the
wastewaters, there were no discernible
differences due to water types among
mean recoveries, overall precisions,
and single-analyst precisions.
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
EPA first promulgated guidelines
establishing test procedures for the
analysis of pollutants in 1973, following
the passage of the Federal Water Pollution
' Control Act in 1972 by Congress. Pursu-
ant to the amendment and publication of
these guidelines, EPA entered into a
Settlement Agreement—the Consent
Decree—which required the study and, if
necessary, regulation of 65 "priority"
pollutants and classes of pollutants of
known or suspected toxicity to the biota.
Subsequently, Congress passed the
Clean Water Act of 1977, mandating the
control of toxic pollutants discharged into
ambient waters by industry.
In order to facilitate the implementation
of the Clean Water Act, EPA selected for
initial study 129 specific toxic pollutants,
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113 organic and 16J inorganic. The
organic pollgtanjs werp divided into 12
categories "Based on their chemical
structure. Analytical methods were
developed by EPA for these 12 categories
through in-house and contracted research
and may eventually be required for the
monitoring of the 113 toxic pollutants in
industrial wastewater effluents, as
specified by the Clean Water Act of 1977.
This report describes the interlaboratory
study of Method 604-Phenols which is
proposed for the Category 8 chemicals:
phenol, 2,4-dimethylphenol, 2-chIoro-
phenol, 4-chloro-3-methylphenol, 2,4-
dichlorophenol, 2,4,6-trichlorophenol,
pentachlorophenol, 2-nitrophenol, 4-
nitrophenol, 4,6-dinitro-2-methylphenol,
and 2,4-dinitrophenol. The primary
objective of the study was to characterize
the behavior of Method 604-Phenols in
terms of accuracy, overall precision,
single-analyst precision, and effect of
water type on accuracy and precision.
The study was conducted with the
cooperation of 20 participating laboratories
under auspices of the Environmental
Monitoring and Support Laboratory
(EMSL)-Cincinnati.
The data were collected from the 20
laboratories according to Youden's colla-
borative testing design. Formal statistical
techniques compatible with the Youden
design were used to identify outliers,
estimate the method's accuracy and pre-
cision, and test for the effect of water
type. The formal statistical analyses were
carried out using the Interlaboratory
Method Validation Study (IMVS) computer
program. The information obtained from
the statistical analyses was summarized
and reduced to a descriptive form for the
purpose of interpretation and presentation.
Method 604-Phenols was developed by
IT Enviroscience under a contract with
the Physical and Chemical Methods
Branch, EMSL-Cincinnati. Briefly, the
method requires extraction with methylene
chloride and concentration of the extract
followed by the determination of the
phenols using GC-FID. The concentrated
extract may be more specifically analyzed
for phenols by derivatization with penta-
fluorobenzyl bromide, extract cleanup on
activated silica gel, and final measure-
ment by GC-EC.
Procedure
The interlaboratory study design was
based on Youden's plan for collaborative
evaluation of precision and accuracy for
analytical methods. According to Youden's
design, samples are analyzed in pairs. A
Youden pair consists of two samples at
similar, but distinctly different concentra-
tions. The analyst is requested to do only
a single analysis for each sample and
report only one value as in routine use of
the method.
Select/on of Laboratories
Of the 20 participating laboratories, 19
were selected as the result of competitive
bidding after evaluating their technical
capabilities and experience in trace
organic analyses of wastewater. The
twentieth laboratory was a volunteer
from within the EPA.
Preparation of Ampuls
All starting materials were reagent
grade quality or better. Distilled-in-glass
2-propanol was the solvent. Separate stock
solutions for each of the eleven phenols
were prepared by dissolving a precisely
weighed amount of the compound into
Class A volumetric glassware containing
the above mentioned solvent. Appropriate
volumes of the stock solutions were
mixed and diluted to volume in 2000-mL
volumetric flasks. The flasks were
refrigerated overnight at 4°C. The follow-
ing day, approximately 3 mL of the
refrigerated solution was transferred into
5-mL glass ampuls using an all-glass or
Teflon® delivery system. After the ampuls
were cooled in a freezer at-30°C for three
hours, they were sealed by a professional
glass blower using the pull-and-twist
technique.
True Value and Stability of
Concentrates
An important segment of this study
was to verify the true values and stability
of the phenols in the 2-propanol concen-
trates before they were used in the study.
To achieve this verification, three repli-
cate ampuls were randomly selected
from each concentrate level batch and
analyzed by triplicate injection into a gas
chromatrograph equipped with a record-
ing integrator. To check stability these
analyses were carried out at 0,45, and 90
days after the ampuls were sealed and
before the study was started. All concen-
trate values determined experimentally
were within instrumental error of the
calculated true values.
Preliminary Study
Previous EPA method studies have
shown that more realistic results can be
obtained if all participants fully understand
the analytical and sample handling
procedures before undertaking the full
study. To familiarize the analyst with the
analytical method and handling proce-
dures, each of the 20 laboratories was
sent a low-level Youden pair of sample
concentrates (different from those to be
used in the actual study) for spiking
distilled water. The analysts were also
sent instructions, a copy of the method,
and data report sheets.
The results of these analyses were
collected, statistically analyzed, and
discussed with the laboratories' repre-
sentatives in a one-day conference
meeting at EMSL-Cincinnati. The meeting
also allowed discussion of analytical
problems and clarification of any method-
ology procedures.
Actual Interlaboratory Study
A summary of the test design using
Youden's nonreplicate technique based
on pairs with slightly dissimilar analyte
concentrations is given below:
• Twenty laboratories were sent three
Youden pairs in sealed glass ampuls
containing various levels of the
eleven phenols in 2-propanol.
• When an analyst was ready to start
the analyses, the ampuls were
opened and aliquots were diluted to
volume in the appropriate water
types according to instructions.
• Each sample (ampul) was analyzed
only once.
• The six water types were analyzed
with and without spiking, and the
added level of constituent was deter-
mined by difference and reported as
/ug/L in each water sample.
• The three levels of phenols used in
the study were within the working
range of the method and represented
the range of levels one would
normally expect to encounter in
application of the method to actual
samples.
Description and Distribution of
Samples
The individual laboratories provided
their own samples of laboratory-distilled
water, tap water, and a local surface
water. The source for each surface water
is listed in the final report.
The wastewater effluent samples re-
presentative of the industries of concern
were collected by the prime contractor as
grab samples in 55-gallon stainless steel
drums which had been precleaned with
acetone, methylene chloride, and dis-
tilled water. The unfiltered wastewater
samples were mixed and transferred into
one-quart bottles using an all-Teflon sys-
tem and stored in a refrigerator at 4°C un-
til shipment to the laboratories. Each la-
boratory was sent 36 ampul concentrates
(six sets of three Youden pairs), seven
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one-quart bottles each of the three indus-
trial effluent types, instructions, and data
report sheets. The wastewater samples
were packed in ice in coolers and sent by
air freight to minimize sample change
and assure comparability of the waste-
waters from laboratory to laboratory.
Analysis and Reporting
A water spiking technique involving a
water-miscible solvent concentrate was
used in this study. Each analyst was
instructed to add separate 2.0-mL
aliquots of each concentrate to the bottle
containing approximately 1 L of water or
wastewater. .The spiked sample was
stirred for 15 minutes and then handled
as a routine sample in the method. The
results of the method's measurement for
each constituent (in micrograms per liter
of water) were then corrected by subtrac-
ting any blank sample reading and
reported on data sheets by ampul and
water type. The method utilized by the
participating laboratories. Method 604-
Phenols, was used with no reported
deviations.
The data were reviewed for complete-
ness and abnormal results. The data were
then entered into the computer for
statistical treatment. Any laboratory
reporting unusually high or low data was
requested to review its data for errors in
calculations but was not told how its re-
ported data varied from the true values.
Treatment of Data
The objective of this interlaboratory
study was to obtain information aboutthe
accuracy and precision associated with
measurements generated by Method 604-
Phenols. This objective was met through
the use of statistical analysis techniques
designed to extract and summarize the
relevant information about accuracy and
precision from the data reported by the
participating laboratories. The statistical
techniques were similar to the techniques
recommended in the ASTM Standard
Practice D2777-77.
The algorithms required to perform the
statistical analyses-were integrated into
a system of computer programs referred to
as IMVS {Interlaboratory Method Valida-
tion Study). The analyses performed by
IMVS included several tests for the
rejection of outliers (laboratories and
individual data points), summary statistics
by concentration level for mean recovery
(accuracy), overall and single-analyst
standard deviation (precision), deter-
mination of the linear relationship
between mean recovery and concentra-
tion level, determination of the linear
relationship between the precision
statistics and mean recovery, and a test
for the effect of water type on accuracy
and precision.
Results and Discussion
The IMVS computer program was
designed to output the raw data in tabular
form and to compile summary statistics
including: number of data points, true
value, mean recovery, accuracy as
percent relative e-ror, overall standard
deviation, overall percent relative standard
deviation, single-a lalyst standard devia-
tion, and single analyst percent relative
standard deviation The statistical analy-
ses performed by the IMVS program
included the deter nination of the linear
relationship between both the overall (S)
and single-analyst i SR) precision statistics
and mean recovery along with accuracy
statements based on the determination of
the linear relationship between mean
recovery (X) and concentration level. The
results of theregre
apparent linear rel
laboratory ranking
ision analyses indicate
ationships for each of
the above cases.
For all data for tie eleven compounds,
analyzed by the FID procedure, 20% of the
data were reject 3d as determined by
and individual outlier
tests. The data rejection was found to be
non-uniform among laboratories. More
than 60% of the rejected data were
generated by six of the 20 participating
laboratories. Of
the 20 participating
laboratories, one had 87% of its total raw
data rejected. For
compounds analyz
23% of the data v
all data for the nine
3d by the EC procedure,
'ere rejected as deter-
mined by laboratory ranking and individual
outlier tests. The data rejection was found
to be non-uniform among laboratories.
More than 55% ofl the rejected data was
generated by six of the 20 participating
laboratories. Of |the 20 participating
laboratories, two had more than 63% of
their total raw data rejected.
Regression equations for single-analyst
precision, overall precision, and accuracy
are presented in Tables 1 and 2.
Mean recoveries of the eleven subject
compounds when analyzed by the FID
procedure were in the range of 40 to 89%.
Overall precision was in the range of 20
to 45%, and single-analyst precision was
in the range o
recoveries of the n
when analyzed by
in the range of
15 to 37%. Mean
ne subject compounds
the EC procedure were
32 to 76%. Overall
precision was in t ie range of 38 to 64%,
and single-analys precision was in the
range of 29 to 48'k>.
With the except on of the FID analysis
of 2,4-dinitrophenol, no significant
difference in method performance was
attributable to the water type from which
the analyses were performed. A positive
bias was established for the FID analyses
of 2,4-dinitrophenol in surface waters
and two of the industrial effluents.
Examination of the chrornatograms
revealed a reduction in peak resolution
between 4,6-dinitro-2-methylphenol and
2,4-dinitrophenol when analyzing these
three water types as compared to the
peak resolution between these two
compounds in distilled water.
Conclusions and
Recommendations
Based on the results of the interlabora-
tory method study, EPA Method 604-
Phenols is a viable analytical method for
measuring trace concentrations of the
eleven Category 8 chemicals used in this
study. As a result of the collaborative
study conducted and the IMVS data
analysis, the following conclusions and
recommendations can be made concern-
ing Method 604-Phenols.
• The accuracy of the method, when
using either the FID or EC procedures,
could be expressed as a linear
function of the true concentration. In
the majority of equations the slope
represents the percent recovery
attributable to the method.
• The precision of the method using
either the FID or EC procedures could
be expressed as a linear function of
the mean recovery. In the majority of
equations the slope represents the
relative standard deviation attribu-
table to the method, both as single-
analyst and overall standard devia-
tions.
• The average mean recovery for
each compound by either FID or EC
at six concentrations in seven water
types compared well with data
generated on distilled water and
industrial effluents during develop-
ment of this method.
• Direct comparison of the FID and EC
procedures for the analysis of the
nine common Category 8 chemicals
(the two dinitrophenols are deter-
mined by GC-FID only) indicates that
the FID technique yielded fewer
outliers, lower overall and single-
analyst standard deviations, and
higher mean recoveries.
• Based on the IMVS test for the effect
of water type on precision and
accuracy, there was no statistical
significance between distilled water
and the other water types for any of
the associated parameters except for
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Table 1. Regression Equations for Accuracy and Precision for Compounds 1 -
Water Type
Applicable Cone, flange
Distilled Water
Single-Analyst Precision
Overall Precision
Accuracy
Tap Water • Non DC
Single-Analyst Precision
Overall Precision
Accuracy
Surface Water
Single-Analyst Precision
Overall Precision
Accuracy
Waste Water 1
Single-Analyst Precision
Overall Precision
Accuracy
Waste Water 2
Single-Analyst Precision
Overall Precision
Accuracy
Waste Water 3
Single-Analyst Precision
Overall Precision
Accuracy
Tap Water - DC
Single-Analyst Precision
Overall Precision
Accuracy
Phenol
(18.40 - 252.00)
SR = 0.20X - 0.88
S = 0.17X + 0.77
X =0.430+0.11
SR = 0.27X + 0.55
S = 0.61 X- 0.55
X =0.280 + 0.77
SR = 0. 19X - 0. 18
S = 0.22X - 0.04
X =0.420-0.13
SR = 0.27X + 0. 15
S =0.36X-0.11
X = 0.460 + 0.06
SR = 0.25X - 1.00
S = 0.27X + 0.69
X =0.420+1.75
SR = 0.17X + 0.24
S = 0.27X + 0.31
X = 0.400 + 0.30
SR = 0.24X - 0.53
S = 0.38X - 0.92
X = 0.440 - 1.50
2.4-Dimethylphenol
(13.00 - 151.00)
SR =O.36X - 1.38
S =0.28X + 0.30
X =0.630 - 1.82
SR = 0.66X - 0.44
S =0.75X + 0.14
X =0.350 - 1.68
SR = 0.24X - 0. 18
S = 0.31 X + 0.49
X =0.54C - 1.40
SR = 0.24X + 1. 18
S = 0.39X+1.43
X =0.510 - 1.87
SR = 0.21 X + 0.52
S =0.47X-0.53
X =0.420-0.58
SR = 0.57X - 1.16
S =0.63X-0.65
X =0.470-0.98
SR = 0.35X - 0.38
S =0.33X + 0.28
X =0.630-3.37
4
2-Chlorophenol
(12.20 - 185.00)
SR = 0.1 8X + 0,20
S = 0.21 X + 0.75
X = 0.830 - 0.84
SR=0.42X - 1.03
S = 0.47X + 0.01
X = 1.080 - 2.91
SR = 0.21 X - 0.20
S =0.28X-0.71
X = 0.830 - 0. 19
SR = 0.20X + 1.21
S = 0.20X + 2.89
X =0.820 + 0.91
SR = 0.21 X + 0.06
S = 0.25X + 0.97
X =0.720 + 0.81
SR = 0. 15X + 3.05
S = 0.21 X + 2.82
X =0.720+1.97
SR = 0.1 9X + 0.17
S = 0.25X - 0.04
X =0.720 - 1.09
4-Chloro-3-Methylphenol
(30.00 - 450.00)
SR = 0.11 X- 0.21
S = 0.1 6X+ 1.41
X = 0.870 - 1.97
SR = 0.32X + 1.36
S = 0.48X + 1.23
X =0.510 + 0.12
SR = 0. 16X + 1. 18
S =0.24X + 2.47
X = 0.82C - 1.03
SR =0.32X + 2.28
S = 0.40X - 0.02
X = 0.820 - 2.07
SR = 0.34X - 2.67
S = 0.32X + 1.80
X =0.810 - 1.74
SR = 0.17X + 1.12
S = 0.30X + 0.96
X =0.780-3.60
SR =0. 14X + 0.68
S =0. 16X + 1.68
X =0.810-4.50
Table 7. /Continued) Regression Equations for Accuracy and Precision for Compounds 5 - 8
Water Type
Applicable Cone, flange
Distilled Water
Single-Analyst Precision
Overall Precision
Accuracy
Tap Water - Non DC
Single-Analyst Precision
Overall Precision
Accuracy
Surface Water
Single-Analyst Precision
Overall Precision
Accuracy
Waste Water J
Single-Analyst Precision
Overall Precision
Accuracy
Waste Water 2
Single-Analyst Precision
Overall Precision
Accuracy
2.4-Dichlorophenol
(14.80 - 214.00)
SR=0.17X -0.02
S = 0.18X + 0.62
X =0.810 + 0.48
SR=0.24X - 1.56
S = 0.23X - 0.84
X =0.760+0.10
SR=0.17X -0.62
S =0.28X-0.75
X =0.810 + 0.23
SR = 0.31 X - 0.33
S = 0.31 X + 0.72
X =0.770+1.24
SR = 0.27X - 0.34
S = 0.26X + 1. 18
X =0.730 + 0.04
2,4,6- Trichlorophenol
(20.40 - 236.00)
SR = 0.10X + 0.53
S =0. 13X + 2.40
X = 0.860 - 0.40
SR=O.22X -0.13
S = 0.24X + 0.91
X = 0.920 + 0.81
SR = 0.17X -0.47
S = 0.24X + 0.80
X = 0.850 + 0.25
SR = 0.29X - 0.63
S = 0.26X + 3.94
X = 0.830 + 3.68
SR = 0.01 X + 12.82
S =0.35X + 4.18
X =0.760+10.29
Pentachlorophenol
(16.20 - 226.00)
SR = 0.22X - 0.58
S = 0.23X + 0.57
X =0.830 + 2.07
SR = 0.27X - 1.26
S =0.28X+1.04
X = 0.820 + 0.97
SR = 0. 16X + 2.80
S = 0.29X +1.01
X =0.770 + 3.99
SR = 0.27X + 21 .40
S =0.32X + 23.90
X =0.750 + 33.92
SR = 0.32X - 1.93
S =0.37X - 1.88
X =0.720 + 6.27
2-Nitrophenol
(25.00 - 374.00)
SR = 0. 15X + 0.44
S =0.14X + 3.84
X =0.810-0.76
SR = 0. 18X - 1.79
S = 0.21 X - 0.64
X =0.790+1.05
SR =0. 19X - 1.66
S = 0.23X - 0.94
X = 0.830 + 0.92
SR = 0.22X - 1.17
S =0.21X + 0.05
X = 0.800 + 0. 13
SR = 0.21X - 0.13
S =0. 19X + 4.88
X =0.770 + 2.90
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Table 1 . (Continued) Regression Equations for Accuracy and Precisi
Water Type 2,4-Dichlorophenol 2,4,6 -Trh
Waste Water 3
Single-Analyst Precision
Overall Precision
Accuracy
Tap Water - DC
Single-Analyst Precision
Overall Precision
Accuracy
SR=0.26X - 1.36 SR = O.
S = 0.25X + 0.70 S =0.
X =0.730+1.99 X =0.
SR = 0.24X - 1 .66 SR=0.
S =O.22X - 1.39 S =0.
X =0.770 + 0.08 X =0.
Table 1. (Continued) Regression Equations for Accuracy and Precis
Water Type
Applicable Cone. Range
Distilled Water
Single-Analyst Precision
Overall Precision
Accuracy
Tap Water - Non DC
Single-Analyst Precision
Overall Precision
Accuracy
Surface Water
Single-Analyst Precision
Overall Precision
Accuracy
Waste Water 1
Single-Analyst Precision
Overall Precision
Accuracy
Waste Water 2
Single-Analyst Precision
Overall Precision
Accuracy
Waste Water 3
Single-Analyst Precision
Overall Precision
Accuracy
Tap Water - DC
Single-Analyst Precision
Overall Precision
Accuracy
4-Nitrophenol
(28.20 - 320.00)
SR = 0.17X + 2.43
S =0.19X + 4.79
X =0.460 + 0.18
SR = 0.25X + 0.91
S = 0.31 X + 0.36
X =0.400 + 3.27
SR = 0.24X + 5.07
S = 0.32X + 3.43
X =0.400 + 4.61
SR = 0.34X - 1.44
S = 0.34X + 3.04
X =0.410 + 2.96
SR = 0.24X - 0. 15
S =0.39X + 0.53
X =0.350 + 2.78
SR = 0.26X -0.22
S =0.30X + 3.41
X = 0.390 + 3.07
SR = 0.22X + 3.95
S = 0.22X + 5.87
X =0.400+4.62
X = Mean Recovery
C = True Value for the.Concentration
on for Compounds 5-8
hloropheriol Pentachlorophenol
15X-0.56 SR = 0.25X + 2.99
20X + 1.04 S = 0.38X + 1. 13
320 + 0.94 X =0. 790 + 1.99
1 1X + 6.30 SR = 0.21 X - 1.14
15X + 5.01 S =0. 18X + 3. 71
55C + 2.14 X = 0.830 + 2.06
on for Compounds 9-11
4,6-Dinitro-2-Methylphenol
(29.80 - 338.00)
SR = 0.15X + 1.31
S =0.20X + 5.53
X =0.840 - 1.27
SR = 0.30X - 4.87
S =0.25X-0.44
X =0.840-0.24
SR = 0. 16X - 0. 16
S = 0.27X - 0.91
X = 0.840 + 1. 13
SR = O.26X - 2.89
S = 0.29X + 5.90
X = 0.900 - 0.90
SR = 0.32X - 5. 18
S = 0.37X - 3.86
X = 0.880 + 3.36
SR = 0.1 7X + 2.43
S = 0.30X + O.80
X =0.880 + 0.30
SR = 0.30X - 4.59
S = 0.31 X + O.08
X =0.84C- 1.79
2-Nitrophenol
SR = 0.1 8X- 0.04
S = 0.21 X + 2.53
X =0.770+1.78
SR = 0. 15X + 1. 19
S =0.22X+1.92
X =0.770 - 1.44
2,4-Dinitrophenol
(27.00 - 320.00)
SR=0.27X - 1.15
S =0.29X + 4.51
X =0.800-1.58
SR = 0.38X - 5.88
S =0.35X + 0.45
X =0.850+3.01
SR = 0.24X + 2.52
S =0.35X+1.85
X =0.870 + 6.11
SR = 0.34X + 0.29
S =0.40X-0.42
X =0.940+1.62
SR = 0.32X - 2.09
S =0.34X + 4.61
X =0.990 + 5.37
SR = 0.1 6X+ 14.23
S =0.24X+ 12.93
X =0.840+12.36
SR=O.22X + 6.13
S = 0.66X-3.92
X = 0.970 - 3.59
Water Type
Applicable Cone. Range
Distilled Water
Single-Analyst Precision
Overall Precision
Accuracy
Tap Water - Non DC
Single-Analyst Precision
Overall Precision
Accuracy
Phenol
f 18.40 - 252.00)
SR = 0.21X + 0.99
S =0.41X+1.40
X = 0.36C - 0.05
SR = 0.54X + 0.02
S =0.72X-0.01
X = 0.31 C- 0.73
2, 4-Dimefhylphenol
(13.00 - 1^51.00)
.
S/? = 0.3fX+ 1.03
S = 0.67X-0.24
X =0.670 - 1.15
SR = 0.77X - 0.26
S =O.79X-0.40
X =0.250+1.11
2-Chlorophenol
(12.20 - 185.00)
SR = 0.41 X - 0.59
S = 0.52X - 0.09
X = 0.550 + 0. 18
SR = 0.65X - 3.44
S =0.53X + 0.71
X = 0.80C - 2.08
4-Chloro-3-Methylpheno
(30.00 - 450.00)
SR = 0.31X+ 1.06
S -0.53X^1.18
X =0.720' -3.97
SR = 0.36X + 0. 19
S = 0.65X - 0. 16
X =0.470-3.69
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Table 2. (Continued) Regression Equations for Accuracy and Precision for Compounds 1 - 4
Water Type
Surface Water
Single-Analyst Precision
Overall Precision
Accuracy
Waste Water 1
Single-Analyst Precision
Overall Precision
Accuracy
Waste Water 2
Single-Analyst Precision
Overall Precision
Accuracy
Waste Water 3
Single-Analyst Precision
Overall Precision
Accuracy
Tap Water - DC
Single-Analyst Precision
Overall Precision
Accuracy
Phenol
Sft = 0.33X - 1. 13
S = 0.29X + 3.95
X = 0.33C + 1.98
SR = 0.54X - 1.70
S = 0.48X + 2.05
X = 0.30C + 0.40
SR = 0.37X + 0.16
S = 0.39X + 3.71
X = 0.36C + 2.94
SR = 0.29X+ 1.67
S = 0.55X + 1.05
X = 0.32C + 0.57
SR = 0.33X - 0.92
S =0.58X-0.43
X =0.28C + 0.93
Table 2. (Continued) Regression Equations for Accuracy
Water Type
Applicable Cone. Range
Distilled Water
Single-Analyst Precision
Overall Precision
Accuracy
Tap Water - Non DC
Single-Analyst Precision
Overall Precision
Accuracy
Surface Water
Single-Analyst Precision
Overall Precision
Accuracy
Waste Water 1
Single-Analyst Precision
Overall Precision
Accuracy
Waste Water 2
Single-Analyst Precision
Overall Precision
Accuracy
Waste Water 3
Single-Analyst Precision
Overall Precision
Accuracy
Tap Water - DC
Single-Analyst Precision
Overall Precision
Accuracy
2,4-Dichlorophenol
(14.80 - 214.00)
SR = 0.17X + 2.16
S = 0.37X+J.53
X =0.730-2.21
SR = 0.44X - 1.96
S =0.52X-0.33
X =0.770-3.74
SR = 0.35X + 1.51
S = 0.46X + 1.39
X = 0.71 C- 0.65
SR = 0.40X + 0.06
S = 0.43X+,0,78
X =0.710-0.20
SR=0.38X+ 1.69
S = 0.45X + 1. 15
X =0.710 + 0.60
SR = 0.33X + 0.83
S =0.43X+1.08
X =0.700-1.05
SR = 0.37 X - 0.63
S = 0.61 X- 2.82
X =0.980-4.76
2, 4-Dimethylphenol
SR = 0.26X + 2.75
S =0.42X + 2.60
X = 0.490 - 0.26
SR = 0.55X - 1.08
S =0.50X + 0.60
X =0.410-0.16
SR = 0.70X - 0.96
S =0.77X + 0.01
X = 0.520 + 0.50
SR = 0.32X + 1.55
S =0.60X+1.63
X = 0.390 + 4.52
SR =0.45X - 1.39
S =0.70X - 1.67
X = 0.590 - 0.50
and Precision for Compounds 5
2, 4, 6- Trichlorophenol
(20.4O - 236.00)
SR = 0.32X - 0.51
S = 0.34X + 2.80
X = 0.800 - 4. 16
SR = 0.42X - 3.77
S =0.44X - 1.11
X = 0.83C - 3.27
SR = 0.26X + 5.54
S = 0.38X + 3.63
X =0.630 + 2.41
SR = 0.33X + 0.21
S =0.44X+1.70
X =0.780-0.33
SR = 0.56X - 2.68
S = 0.41 X + 2.03
X =0.710-0.41
SR = 0.24X + 1.52
S = 0.32X + 2.24
X =0.660 + 2.28
SR = 0.33X - 2.02
S =0.39X-2.70
X = 0.820 - 1.61
2-Chlorophenol
SR =0.35X + 0.98
S =0.45X+1.57
X = 0.570 + 0.44
SR = 0.42X + 0.95
S = 0.47X + 2.20
X = 0.540 + 0.29
SR = 0.45X + 1.11
S =0.49X + 2.35
X =0.730-0.19
SR = 0.60X - 2.32
S = 0.68X - 1.58
X =0.710 + 0.35
SR = 0.26X - 0.81
S = 0.56X - 0.23
X = 0.500 + 0.40
-8
Pentachlorophenol
(16.20 - 226.OO)
SR = 0.33X - 0.92
S = 0.45X - 0. 15
X =0.740-2.34
SR = 0.35X + 1.06
S = 0.42X + 0.64
X =0.700 - 1.57
SR = 0.35X + 0.41
S = 0.51 X + 0.03
X =0.630-2.46
SR = 0.53X - 4.49
S =0.55X + 23.33
X =0.730 + 36.34
SR = 0.38X + 0.22
S = 0.38X + 0.32
X =0.660 + 0.48
SR = 0.34X + 0.04
S = 0.55X - 0.03
X = 0.580 + 1.27
SR = 0.1 4X + 0.02
S =0. 15X + 0.36
X =0.890 + 0.78
4-Chloro-3-Methylphenol
SR = 0.22X + 6.26
S =0.47X + 2.W
X = 0.630 + 0.58
SR = 0.52X - 3.59
S = 0.52X + 3.57
X =0.550 + 0.32
SR = 0.31 X + 0.09
S = 0.36X + 8.03
X = 0.590 + 3.19
SR = 0.40X + 2.00
S =0.54X + 2.35
X =0.460 + 3.21
SR = 0.32X - 3.35
S = 0.58X - 3.28
X = 0.540 - 5.39
2-Nitrophenol
(25.00 - 374.00)
SR=0.26X + 1.66
S = O.39X + 2.97
X =0.600-2.64
SR = 0.30X - 0.74
S = 0.45X + 0.29
X =0.580 - 1.53
SR = 0.32X + 1 .86
S = 0.45X + 2.43
X = 0.550 + 2.40
SR=0.35X -0.82
S =0.46X + 0.25
X = 0.580 + 1.06
SR = 0.37X- 1.65
S =0.42X + 2.17
X = 0.610 - 0.20
SR = 0.42X - 0.21
S = 0.51 X - 0.38
X = 0.58C - 0.98
SR=0.11X + 2.36
S =0.46X-1.40
X =0.600-1.61
-------
Table 2. (Continued) Regression Equations for Accuracy and Precis,
Water Type 4-Nitrophenol
on for Compound 9
Applicable Cone. Range
Distilled Water
Single-Analyst Precision
Overall Precision
Accuracy
Tap Water — Non DC
Single-Analyst Precision
Overall Precision
Accuracy
Surface Water
Single-Analyst Precision
Overall Precision
Accuracy
Waste Water 1
Single-Analyst Precision
Overall Precision
Accuracy
Waste Water 2
Single-Analyst Precision
Overall Precision
Accuracy
Waste Water 3
Single-Analyst Precision
Overall Precision
Accuracy
Tap Water - DC
Single-Analyst Precision
Overall Precision
Accuracy
(28.20 - 320.00!
SR = 0.37X + 0.29
S = 0.48X+1.21
X = 0.43C - 2.55
SR = O.39X -O.J6
S = 0.4JX + 1.03
X =0.35C-2.64
SR = 0.28X + 3.04
S = 0.43X + 0.08
X = 0.32C + 0.75
SR = 0.32X + 1.71
S = O.39X + 2.35
X = 0.34C + 7.34
SR = 0.20X + 2.97
S = 0.28X + 1.95
X = 0.40C + 0.45
SR = 0.50X - 1.94
S = 0.64X-0.73
X =0.360-0.37
SR = 0.1 IX+ 2.66
S = 0.41 X - O.2O
X = O.33C - 0.09
X = Mean Recovery
C = True Value for the Concentration
the three cases described for 2,4-
dinitrophenol.
Results from the limited study
comparing the method performance
on both nondechlorinated and de-
chlorinated tap water prove the need
to dechlorinate samples for phenols
analysis as soon as possible after
sample collection.
Some of the problems encountered
in applying the method during this
study included: several laboratories
had a problem with the separation of
4,6-dinitro-2-methylphenol and 2,4-
dinitrophenol when using the SP-
1240DA column during use of the
FID procedure. For each method of
detection at least one laboratory had
a problem in distinguishing between
peaks in the standard mixture. One
laboratory had trouble in concentra-
ting the extract using the Kuderna-
Danish apparatus. Some of the
laboratories had to use peak height
measurements for quantitation be-
cause occasional interference peaks
in wastewater created faulty integra-
tion when usin 3 recording integrators.
In future interlaboratory studies, very
detailed instruction should be given
to the participating laboratories to
ensure labeling of each chromato-
gram. In this study it was very
difficult to interpret much of the raw
chromatogranhic data because of
inadequate labeling. Other points to
be emphasized in future studies are
that (a) blanks and spiked samples
must be analyzed at the same
sensitivity and (b) calculations and
record keeping should be uniform or
consistent to aid in data interpreta-
tion.
r U.S. GOVERNMENT PRINTING OFFICE: 1984 - 759-102/10610
-------
Jack R. Hall, J. Richard Florence, Dennis L Strother, and Marlene N. Wass are
with IT Enviroscience, Knoxville, TN 37923.
Edward L. Berg and Robert L. Graves are the EPA Project Officers (see below).
The complete report, entitled "EPA Method Study 14, Method 604—Phenols,"
(Order No, PB 84-196 211; Cost: $22.00, 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
United States
Environmental Protection
Agency
Center for Environmental Research
Information
Cincinnati OH 45268
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POSTAGE & FEES PAID
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PERMIT No. G-35
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