United States
Environmental Protection
Agency
Environmental Monitoring and
Support Laboratory
Cincinnati OH 45268
Research and Development
EPA-600/S4-84-064 Aug. 1984
©EPA Project Summary
EPA Method Study 24,
Method 601 — Purgeable
Halocarbons by the Purge Trap
Method
Beverly J. Warner, Charles S. Friedman, Leroy Metcalfe, Thomas J.
Morrow, Arthur D. Snyder, and Carl R. McMillin
An Intel-laboratory method study to
detect 28 halocarbons in water is
described herein. In Method 601, the
halocarbons are purged by an inert gas
which is bubbled through the aqueous
sample. The vapors are trapped in a
short column containing a suitable
sorbent. The trapped components are
then thermally desorbed onto the head
of a chromatographic column and
measured by means of a halide-specif ic
detector. In this study the 28 halocarbon
compounds were divided into three
separate mixes to minimize interferen-
ces from co-eluting peaks. The spiking
solutions employed in the study con-
tained the 29 halocarbons at six con-
centrations. Six water matrices were
used in the study: a distilled, drinking,
and surface water supplied by the
cooperating laboratories; and three
industrial wastewaters supplied by
Monsanto Company. Statistical analy-
ses and conclusions in this report are
based on analytical data obtained by 20
collaborating laboratories.
Participating laboratories were selec-
ted based upon technical evaluation of
proposals and upon the analytical
results of prestudy samples. Data
obtained from the interlaboratory study
were analyzed employing EPA's com-
puter programs known as the Interlab-
oratory Method Validation Study (IMVS)
system, which are designed to imple-
ment the concepts recommended in
ASTM Standard D 2777. The statistical
analyses included rejection of outliers,
estimation of mean recovery (accuracy).
estimation of single-analyst and overall
precisions, and tests for the effects of
water type on accuracy and precision.
This Project Summary was developed
by EPA's Environmental Monitoring and
Support Laboratory, Cincinnati, OH, to
announce key findings of the research
project that is fully documented in a
separate report of the same title (see
Project Report ordering information at
back).
Introduction
The analytical laboratories of the U.S.
Environmental Protection Agency (EPA)
gather water quality data to provide
information on water resources, to assist
research activities, and to evaluate
pollution abatement activities. The
success of these pollution control activi-
ties, particularly when legal action is
involved, depends upon the reliability of
the data provided by the laboratories.
Under provisions of the Clean Water
Act, the EPA is required to promulgate
guidelines establishing test procedures
for the analysis of pollutants. The Clean
Water Act Amendments of 1977 empha-
size the control of toxic poHutants and
declare the 65 "priority" pollutants and
classes of pollutants to be toxic under
Section 307(a) of the Act. This'report is
one of a series that investigates the
analytical behavior of selected priority
pollutants. The Environmental Monitoring
and Support Laboratory (EMSL) Cincinnati
develops analytical methods and conducts
a quality assurance (QA) program for EPA
water laboratories which is designed to
-------
increase the reliability and legal defensi-
bility of water quality information collec-
tion. The responsibility for QA is assigned
to the Quality Assurance Branch (QAB),
one of whose activities is to conduct in-
terlaboratory tests of the methods. This
study reports the results of the interlab-
oratory study on Method 601 (Study 24).
Procedure
The study consisted of three distinct
phases. Phase I involved the analysis of
two prestudy samples per analyte by the
20 participating laboratories in order that
they become familiar with the method-
ology employed and to identify any
potential problems associated with the
analytical methodology. The purgeable
halocarbons, were combined into three
mixes to minimize interferences from
coeluting chromatographic peaks. These
mixes were supplied by Monsanto at two
concentrations in sealed glass ampuls.
The higher concentration mixes were
spiked into drinking water supplied by the
individual participating laboratories and
the lower concentration mixes were
spiked into a wastewater sample supplied
by Monsanto. A short report, including
the data obtained and any potential
problems encountered, was sent to Mon-
santo by each participating laboratory
at the completion of Phase I.
Phase II consisted of a prestudy confer-
ence held at EMSL-Cincinnati. Each
subcontracting laboratory sent at least
one participant to the meeting. The
analyst, or principal analyst if more than
one was involved, attended this meeting.
This meeting held after the data from the
prestudy had been evaluated, examined
the results of the prestudy and discussed
problems encountered in the methodo-
logy.
Phase III consisted of the formal inter-
laboratory study. In the case of Method
601, the analyses of three mixes at each
of six concentrations (three Youden pairs)
was required in six different water
matrices. In addition, the participating
laboratories performed an analysis of all
water blanks with no spiked compounds.
Each participating laboratory then issued
a report to Monsanto containing all data
obtained, copies of representative chromat-
ograms, and any comments.
The final step in the study was a
statistical analysis of all data by Battelle
Memorial Laboratories, Columbus, Ohio,
under contract 68-03-2624 employing
EPA's IMVS system.
Results and Discussions
The object of this study was to
characterize the performance of Method
601 in terms of accuracy, overall preci-
sion, single-analyst precision and the
effect of water types on accuracy and
precision. Through statistical analyses of
26,160 analytical values, estimates of
accuracy and precision were made and
expressed as regression equations, which
are shown in Tables 1 and 2. Table 1
presents the linear regression equations
as originally calculated by EPA's IMVS
system of computer programs. A detailed
examination of the analytical data results
in the revised equations presented in
Table 2 for 10 of the 28 compounds. Of
the 26,160 analytical values only 17%
were rejected as outliers.
The accuracy of the method is obtained
by comparing the mean recovery to the
true values of concentration. For all but
two of the 27 analytes, the average
accuracy over all six waters ranged from
83% to 108%. The two exceptions Were
*ra/7s-1,3-dichloropropene at 76% and
c/s-1,3 dichloropropene at 56%' which
were found to be unstable". ,
The overall standard deviation indicates
the precision associated with_meas|ure-
ments generated by a group of labora-
tories. The percent relative standard
deviation (%RSD) over six waters ranges
from 16% to 29% for all but four of the 27
analytes. Exceptions include c/s-1,3
dichloropropene at 40% bromomethane
gas at 42%, trans-] ,3-clichloropropene at
45%, and chloromethane gas at 50%.
The gases are expected to be less
precise due to handling problems asso-
ciated with both the sample and standard
preparations. The average precision of all
analytes in a given water was relatively
independent of water type, ranging from
24% to 29% for the six water matrices. In
Table 1. Regression Equations for Accuracy and Precision
Water Type
Trichlorofluoromethane
Chloromethane
Vinyl Chloride
i Trans-1,2-Dichloroethene
Applicable Cone. Range
Distilled Water
Single-Analyst^ Precision
Overall Precision
Accuracy
Top Water
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
(8.00 - 499.00)
SR = 0.15X +0.67
S = 0.26X + 0.91
X =0.890-0.07
SR = 0.22X - 0.03
S = 0.30X + 0.64
X =0.92C-1.21
SR = O.15X-O.42
S = 0.25X + 0.02
X =0.96C-1.11
SR = 0.18X + O.46
S = 0.31X + 0.20
X =0.96C-0.86
SR = 0.14X +0.69
S = 0.28X + 0.26
X =0.920-1.17
SR = 0.16X+1.12
S =0.29X^0.75
X =0.960-1.57
(8.00 - 499.00)
SR = 0.28X - 0.31
S = 0.52X + 1.31
X =0.770 + 0.18
SR=0.28X + 0.27
S = 0.49X + 1.51
X =O.91C-O.99
SR=0.24X+ 1.26
S = 0.55X + 0.45
X =0.990-2.07
SR = 0.22X + 2.27
S = 0.49X + 1.35
X = 0.940 - 0.87
SR = 0.13X + 3.19
S =0.58X+1.11
X =0.810-0.16
SR = 0.19X + 4.99
S = 0.38X + 5.31
X =0.700 + 6.44
(8.00 - 500.00)
SR = 0.13X +0.65
S = 0.27X + 0.40
X = 0.970 - 0.36
SR = 0.14X-0.17
S =0.32X + 0.07
X = 1.060 - 1.86
SR = 0.16X + 0.15
S = 0.33X-0.29
X =1.120-1.59
SR = 0.12X + 1.00
S =0.22X+1.06
X =1.130 - 2.63
SR = 0.12X+ 1.89
S =0.37X-0.10
X = 1.080 - 2.36
SR = 0.09X + 2.04
S = O.21X + 1.36
X =1.140 - 1.05
(8.00 - 500.00)
SR = 0.11X + 1.46
S =0.17X+1.46
X =0.970-0.16
SR = 0.16X + 0.29
S = 0.24X + 0.95
X =0.980-1.02
SR = 0.12X + 0.36
S = 0.21 X + 0.59
X = 1.030 - 0.95
SR = 0.13X + 0.27
S = 0.23X + 0.96
>X = 1.020 - 1.55
SR=0.10X + 1.11
]S = 0.15X + 1.47
X = 1.000 - 0.30
:SR = 0.14X + 1.20
S = 0.28X + 1.21
X = 1.03C - 0.90
-------
Table 1. (Continued)
Water Type
Applicable Cone. Range
Distilled Water
Single-Analyst Precision
Overall Precision
Accuracy
Tap Water
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
1, 1, 1 ' -Trichloroethane
(8.00 - 500.00)
SR = 0. 15X + 0.04
S = 0.2OX + 0.37
X = O.90C -O.16
SR = 0. 14C - 0.33
S =0.27X-0.76
X = 0.92C + 0.02
SR-0.14X -0.17
S = 0.23X - 0.67 i
X = 0.94C - 0.00
SR = O.J5X + 1.65
S = 0.30X + 1.24
X = O.94C - 0.51
SR = O.1OX + 2.01
S = 0.22X + 0.91
X = 0.92C + 0.42
SR = 0. 18X + 2.93
S = 0.37X - 0.50
X =1.110-0.17
Trich/oroetfiene"
(8.00 - 501.00)
SR = 0. 13X - 0.03
S = 0.23X + 0.30
X = 1.32C - 2.52
SR = 0. 13X + 0.23
5 =0.32X-0.57
X = 1.40C - 3.26
SR = 0. 13X - 0.39
S = 0.37X - 0.90
X = 1.46C - 4. 16
SR = 0. 10X + 2.22
S = 0.27X + 1.41
X = 1.35C - 2.49
SR = 0. 16X - 0.41
S = O.25X + 0.50
X =1.41C-3.14
SR = 0. 15X + 0.83
S = 0.2SX + 0.47
X = 1.40C - 2.32
Dibromochloromethane 2-Chloroethylvinyl Ether*
(8.00 - 488.00) (8.00 - 501.00)
SR=0.11X+1.10
S = 0.24X+1.68
X =0.94C + 2.72
SR = 0. 10X + 1.55
S = 0.23X + 0.37
X =0.98C + 2.89
SR = 0. 12X + 1.22
S = 0.25X+1.44
X = O.92C + 1.45
SR= O.05X + 3.74
S = 0.1 4X + 3.68
X =0.920 + 2.44
SR = 0. 1OX + 2.99
S = 0.25X + 2.46
X =0.95C + 3.27
SR = 0. 13X + 0.49
S = 0.28X+1.18
X = O.97C + 3.98
X = Mean Recovery
C = True Value for the Concentration
a = Revised equations presented in Table 2 herein.
Water Type
Tetrachloroethene
1.2-Dichlorobenzene*
, Applicable Cone. Range
Distilled Water
', Single-Analyst Precision
Overall Precision
Accuracy
Tap Water
Single-Analyst Precision
Overall Precision
\ Accuracy
i 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
(8.0O - 5OO.OO;
SR = 0.14X + 0.38
S =0.18X + 2.21
. X = 0.94C + O.O6
SR = 0.17X + 0.96
S = 0.25X + 0.58
X = 0.96C + 0.35
SR = 0.13X + 0.71
S = 0.22X + O.56
X =0.97C-0.66
SR = 0.22X + 2.54
S = 0.35X + 2.33
X = 0.85C + 0.03
SR = 0.18X + O.2O
S = 0.26X + 0.57
X = O.96C - 0.12
SR =0.13X + 1.03
S = 0.26X + 1.13
X = 0.96C + 1.24
(8.OO - 5O1.00)
SR = 0.10X + O.97
S =0.13X + 6.13
X =0.93C+1.7O
SR = 0.12X + 2.02
S =0.17X + 2.26
X =0.91C+1.12
SR =0.09X + 0.11
S =0.19X + 0.38
X =0.90C-0.28
SR = 0.14X + O.66
S =0.19X + 3.3O
X = 0.89C-0.29
SR = 0.13X + 0.65
S =0.18X+1.26
X = 0.91 C-0.47
SR = 0.1OX + 0.72
S =0.17X+1.79
X =0.91C-O.71
, X = Mean Recovery
C = True Value for the Concentration
" Revised equations presented in Table 2 herein.
-------
Tabla 1. (Continued)
Water Type
Applicable Cone, flange
Distilled Water
Single-Analyst Precision
Overall Precision
Accuracy
Tap Water
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
Bromomethaneb
(8.00 - 499.00)
SR = 0.28X + 0.27
S = 0.36X + 0.94
X =0.760-1.27
SR = 0.24X + 0.12
S = 0.65X - 0.82
X =1.030-3.70
SR = 0.23X + 1.37
S = 0.45X+1.29
X =0.910-2.05
SR=0.11X + 1.66
S = 0.40X+1.69
X =0.790+0.03
SR = 0. 13X + 2.57
S = 0.40X + 0.69
X = 0.820 - 1.29
SR = 0.1 2X + 0.62
S =0.26X^2.13
X =0.690 + 0.48
Chloroethane
(8.00 - 498.00)
SR = 0. 14X - 0. 13
S = 0.17X + 0.63
X = 0.990 - 1.53
SR = 0.07X + 0.65
S =0. 19X + 0.39
X = 1.080 - 1.97
SR = 0.18X + 0.17
S =0.22X+1.70
X =1.110-1.61
SR = 0.08X + 0.45
S =0.09X + 5.79
X =1.010 + 0.61
SR = 0.07X + 1. 16
S = 0.22X + 0.87
X =1. 100 - 2.58
SR = 0. 10X + 1.02
S =0.29X + 0.35
X = 1.090 - 1.50
1, 1 -Dichloroethene*
(8.00 - 499.00)
SR = 0.21 X - 0.23
S = 0.29X - 0.40
X = 0.980 - 0.87
SR = 0. 12X + 0. 13
S =0.31X-0.71
X = 1.030 - 1. 16
SR = 0.10X+ 1.46
S =0.21X + 1.24
X = 0.980 + 0.05
SR = 0. 19X - 0.81
S =0.28X + 0.14
X =0.930-0.07
SR = 0.07X + 1.82
S =0.32X + 0.34
X = 1.050 - 1.82
SR = 0. 14X - 0.58
S =0.20X + 0.70
X = 1.020 - 0.82
Chloroform
(8.00 - 501.00)
SR = 0.13X + 0.15
S =0.19X - 0.02
X = 0.930 - 0.39
SR = 0.05X + 5.58
S = 0.09X + 6.2?
X = 0.900 + 3.44
SR = 0.12X + 1.48
S = 0.20X + 0.5.0
X = 0.950 + 0.29
SR = 0.13X +0.47
S = 0.18X+1.06
X = 0.900 + 0.49
SR = 0.1 OX+ 0.75
S = 0.17X + 0.11
X =0.950-0.55
SR = 0.07X + 2.98
S =0.19X + 2.26
X = 0.95C + 0.29
= Mean Recovery
C » True Value for the Concentration
* = Revised equations presented in Table 2 herein.
b = Further comments contained in Section 6 of the full report.
Water Type
Applicable Cone. Range
Distilled Water
Single-Analyst Precision
Overall Precision
Accuracy
Top Water
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
Carbon Tetrachloride
(8.00 - 501.00)
SR = 0. 15X + 0.38
S = 0.20X + 0.39
X = 0.980 - 1.04
SR = 0. 10X + 1.57
S = 0.20X + 1.09
X = 1.00C - 2.20
SR = 0.1 3X- 0.21
S = 0.20X - 0.30
X = 0.950 - 0.39
SR = 0. 10X + 0.90
S = 0.23X + 1.09
X = 0.920 - 2.02
SR = 0.09X + 1.33
S = 0.21 X + 0.47
X =0.950-0.81
SR = 0. 10X + 1. 10
S = 0.22X + 2.82
X = 1.020 - 1.62
Trans- 1,3-Dichloropropenea
(8.00 - 488.00)
SR = 0. 15X + 0. 14
S = 0.40X + 0.26
X =0.740-0.23
SR = 0.1 4X + 0.64
S =0.39X+0.79
X =0.690+0.26
SR=0.17X+ 1.01
S =0.39X + 0.73
X =0.750+1.11
SR = 0.28X + 1. 14
S = 0.64X + 1.60
X =0.720 + 0.25
SR = 0.11X+ 1.28
S = 0.37X + 0.91
X = 0.85C - 0.59
SR = 0.20X - 0.55
S = 0.51 X+ 1.78
X =0.780+ 1.36
1, 1,2- Trichloroethane*
(8.00 - 499.00) ,
SR=0.13X-0.04
S =0.19X + 0.67
X = 0.860 + 0.30 :
SR = 0.06X + 0.99
S =0.19X + 0.69
X = 0.840 + 0.83
SR=0.12X + 0.47
S =0.22X + 0.80
X =0.850 + 0.39 '
SR = 0. 17X + 0.15 :
S = 0.24X + 1.53
X =0.780 + 0.03
SR = 0.09X + 0.83
S =0.19X + 0.79
X = 0.930 - 0.40
SR = 0.08X + 1.52
S =0.22X+1.73
X =0.920-0.15
Bromoform
(8.00 - 500.00)
SR = 0. 12X + 0.58
S = 0.21 X + 2.41
X = 0.960 - 2.05
SR = 0. 10X + 0.20
S = 0.24X + 1.25
.X = 1.020 - 1.81
SR=0.17X + 0.47
S = 0.20X + 1.41
X = 1.030 - 1.81
SR = 0. 18X + 0.27
S = 0.21 X+ 1.81
X =0,910-0.39
SR = 0.08X + 2.79
S = 0.22X + 2.82
X =0.970- 1.54
SR = 0.17X+ 1.77
S =0.22X + 2.50
X = 1.010 - 1.00
X = Mean Recovery
C = True Value for the Concentration
* = Revised equations presented in Table 2 herein.
-------
Table 1. (Continued)
Water Type
Applicable Cone. Range
Distilled Water
Single-Analyst Precision
Overall Precision
Accuracy
Tap Water
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
Chlorobenzene*
(8.00 - 500.00)
SR = 0. 15X - 0.02
S = 0.1 8X+ 1.21
X = J.OOC - 1.23
SR = 0.07X+ 1.71
5=0. rex + 1.43
X = J.OOC - 1.39
SR = 0. 12X + O.99
S = 0.18X + 0.72
X = 0.98C - 0.54
SR = 0.14X + 63.60
S = 0.33X + 79.41
X = 0.93C + 13.00
SR = 0.1 2X + 0.48
S = 0.21 X + 0.99
X = 0.93C - 1.44
SR = 0. 18X + 2.24
S = 0.36X + 1.23
X = 1.04C + 1.45
1. 4-Dichlorobenzene*
(8.00 - 499.00)
SR - 0. 14X - 0.03
S =0.28X + 0.13
X = O.80C + 1.23
SR = 0.16X + O.22
S = 0.20X + 0.74
X = 0.81 C + 0.60
SR = 0.09X + 0.87'
S = 0.23X - 0.54
X = 0.84C + 1.06
SR = 0. 17X + 0.99
S = 0.27X + 0.93
X = 0.82C + 1.57
SR = 0.11X + O.9S
S =O.30X + O.O6
X = 0.80C + 0.34
SR = 0. 16X + 1. 14
S = 0.37X + 0.03
X = 0.94C - 1.26
X = Mean Recovery
'• C = True Value for the Concentration
a = Revised equations presented in Table 2 herein.
Water Type
Applicable Cone. Range
Distilled Water
Single-Analyst Precision
' Overall Precision
Accuracy
Tap Water
; 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
Methylene Chloride
(8.00 - 501.00)
SR = 0.1IX + 0.33
S = 0.21 X + 1.43
X = 0.91C- 0.93
SR = 0.08X + 1.04
S =0.17X + 2.43
X = 0.97C - 1.50
SR = 0.08X + 1.44
S =0.14X + 2.55
X = 0.99C - 2.08
SR = 0.09X + 0.97
S =0.18X + 1.50
X = 1.OOC - 1.76
SR = 0.12X + O.37
S =0.20X+1.11
X = 0.98C - 0.28
SR = 0.14X + 1.41
S =0.19X + 1.91
X = 0.95C - 0.31
1,1 -D/chforoethaneb
,2-Dichtoroethaneh
(8.00 - 499.00)
SR = 0.09X + 0. 17
S =0. 14X + 0.94
X = 0.95C - 1.08
SR = 0.09X + 0.47
S =0.18X+1.13
X = 0.93C - 2.04
SR = 0.06X + 0.68
S =0. 14X + 1.07
X =0.97C - 1.72
(8.OO - 500.00)
SR = 0.11X + O.70
S =0. 15X + 0.94
X = 1.04C - 1.06
SR=0.06X+ 1.69
S =O. 18X + 1.21
X = 1.03C-O.41
SR = 0.08X + 0.73
S =0. 18X + 0.89
X =1.01C-1.70
(8.00 - 501.00)
SR = 0.11 X + 0.04
S = 0.20X+'I.OO
X =1. 12C - 1.02
SR =0. 13X + 1.41
5=0. 18X + 3.06
X = r.OOC + 0.96
SR = 0.09X + O.44
S =0.17X+1.14
X =1.12C-1.63
SR = 0.13X + 0.70
S = O.J6X + 0.90
X- = 0.98C - 1.21
SR = 0.13X + 0.17
S =0.16X + 0.95
X = 0.96C - 0.32
SR = 0.12X + 0.24
S =0.16X + O.2O
X = 0.95C - 0.57
X = Mean Recovery
C = True Value for the Concentration
= Further comments contained in Section 6 of the full report.
SR = 0.18X + 7.48
S = 0.28X + 9.59
X = 0.86C + 11.31
SR = 0.10X + 0.53
S =0.18X + 0.89
X = 0.97C + O.53
SR = 0.25X + 14.54
S =0.71X + 4.18
X = 0.39C + 50.00
SR=0.10X + 1.09
S = 0.21 X +2.32
X = 1.09C + 0.32
SR = 0.09X + 1.20
S =0.22X+1.02
X - 1.09C - 0.47
SR = 0.12X + 2.33
S =O.24X + 1.80
X = 1.04C + 0.86
-------
Table 1. (Continued)
Water Type
Applicable Cone. Range
Distilled Water
Single-Analyst Precision
Overall Precision
Accuracy
Tap Water
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
1, 2-Dichloropropane
(8.00 - 499.00)
SR = 0. 18X + 0.49
S =0.28X+1.17
X = 1.020 - 0.52
SR = 0.1 9X- 0.61
S =0.27X-0.10
X =0.980+1.19
SR = 0.1 2X + 0.67
S = 0.21 X + 0.94
X =0.910-0.42
SR = 0.1 7X + 2.88
S = 0.30X + 6.59
X = 0.87C + 4.67
SR=0.20X+ 1.42
S = 0.30X + 1.63
X = 1.040 - 0.82
SR = 0.21X + 2.19
S = 0.33X + 2.65
X =1.100+1.47
Cis- 1 ,3-Dichloropropene*
(8.00 - 488.00)
SR
S
X
SR
S
X
SR
S
X
SR
S
X
= 0.1 1X + 0.42
= 0.38X - 0.26
= 0.59C - 0.90
= 0.1 7X -0.04
= 0.34X + 0.44
= 0.600 - 1.07
= 0.23X + 0.01
= 0.49X + 0.26
= 0.560-0.13
= 0. 19X + 1.94
= 0.46X + 0.36
= 0.610-0.70
SR = 0.20X + 0.02
S =0.37X+1.77
X = 0.500 + 0.69
SR = 0.18X+ 1.64
S =0.36X+1.08
. X -0.530+1.35
1 ,2,2.2-Tetrachloroethane
(8.00 - 499.00)
SR
S
X
SR
S
X
SR
S
X
SR
S
X
SR
S
X
= 0. 14X + 2.41
= 0.23X + 2.79
= 0.950 + 0. 19
= 0.09X + 1.42
= 0.20X+ 1.65
= 0.920 - 0.60
= 0.11X + 1.03
= 0.26X + 0.44
= 0.970 - 0.82
= 0.19X +9.29
= 0.44X + 3.99
= 0.840 + 7. 12
= 0. 16X + 0.87
= 0.30X + 7.26
= 0.910-0.15
SR = 0. 15X + 2.33
S =0.28X + 2.63
X -1.000 + 0.98
a 1,3-Dlchlorobenzene
(8.00 - 500.00)
SR
S
X
S
X
SR
S
X
SR
S
X
S
X
= 0. 14X + 2.33
= 0.26X + 2.34
= 0.950 + 0.43
= 0.15X + 0.64
= 0.24X+ 1.48
= 0.910-0.13
= 0. 15X + 0.45
= 0.23X + 0.69
= 0.980 - O.33
= 0.21 X + 0.37
= 0.29X+ 1.19
= 0.940 - 0.06
' = 0.14X + 0.64
= 0.20X + 1.60
= 0.920 - 0.65
SR = 0. 13X + 1.98
S =0.23X+ 1.27
' X = 0.93C - 0.89
X = Mean Recovery
C = True Value for the Concentration
* = Revised equations presented in Table 2 herein.
Table 2. Revised Equations for A ccuracy and Precision
Water Type
Applicable Cone. Range
Distilled Water
Single-Analyst Precision
Overall Precision
Accuracy
Tap Water
Single-Analyst Precision
Overall Precision
Accuracy
Surface Water
Single-Analyst Precision
Overall Precision
Accuracy
Waste Water 1
Single-Analyst Precis/on
Overall Precision
Accuracy
Waste Water 2
Single-Analyst Precision
Overall Precision
Accuracy
Waste Water 3
Single-Analyst Precision
Overall Precision
Accuracy
Trichloroethene
nge (8.00 - 501.00)
;slon SR = 0.1 3X- 0.03
S = 0.23X + 0.30
X = 0.870 + 0.48
;sion SR = 0.1 3X + 0.23
S = 0.32X - 0.57
X =0.920-0.10
ision SR = 0. 13X - 0.39
S = 0.37X - 0.90
X = 0.970 - 0.88
•fSion SR = 0.1 OX + 2.22
S = 0.27X + 1.41
X = 0.900 + 0.57
.fsion SR = 0.1 6X- 0.41
S =0.25X + 0.50
X =0.950,0.02
-is/on SR = 0. 15X + 0.83
S = 0.28X + 0.47
X =1.110 + 0.86
2-Chloroethylvinyl Ether
(8.00 - 501.00)
SR = 0. 10X + 0.94
S =0.29X+1.65
X =0.930 + 0.77
SR = 0. 19X - 1.03
S = 0.46X + 0.03
X =0.720+1.00
SR = 0.23X- 1.77
S = 0.43X - 0.33
X = 0.870 - 0.57
SR = 0.1 2X -0.40
S = 0.41 X + 0.03
X =1.010-0.19
SR = 0. 14X + 0.07
S = 0.39X + 0.23
X = 0.840 - 0.09
SR = 0.1 8X + 0.28
S =0.52X-0.79
X =0.880-0.19
1 ,£.-UH*IIHJI UUCUZ.GII*?
1 (8.00 - 501. 00)
SR=0.11X + 0.84
S = 0.1 5X + 5.90
. X =0.920+ 1.80
SR=0.12X + 2.02
. S =0.17X + 2.26
X =0.910+1.12
SR = 0.1 1 'X - 0.03
S = 0.21 X + 0.22
' X =0.890-0.19
SR=0.14X + 0.66
, S =0. 19X + 3.30
\ X =0.890-0.29
SR = 0.13X + 0.65
S =0.18X+1.26
X =0.910-0.47 :
SFt =0.10X + 0.72
: S =0.17X+1.79
X =0.910-0.71
-------
, Table 2. (Continued}
Water Type
Applicable Cone. Range
Distilled Water
Single-Analyst Precision
[Overall Precision
Accuracy
Tap Water
Single-Analyst Precision
, Overall Precision
Accuracy
'Surface Water
i 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
\
1, 1 -Dichloroethene
(8.00 - 499.00}
SR = 0.21 X - 0.23
S =0.29X-0.40
X =0.980-0.87
SR = 0. 12X + 0. 13
S = 0.31 X- 0.71
X = 1.03C - 1. 16
SR = 0. 10X + 1.46
S = 0.21 X+ 1.24
X = 0.93C + 0.05
SR = 0. 19X - 0.80
S =O.32X-0.06
X =0.930-0.06
SR=0.07X+ 1.82
S =0.32X^0.34
X = 1.05C - 1.82
SR = 0. 14X - 0.58
S =0.20X^0.70
X = 1.02C - 0.82
Trans- 1 ,3-Dichloropropene
(8.00 - 488.00)
SR = 0. 15X + 0.83
S = 0.40X + 0.56
X = 0.740+0.02
SR = 0.14X + 0.64
S = 0.39X + 0.79
X =0.690 + 0.26
SR=0.17X + 1.01
S =0.39X^0.73
X =0.750+1.11
SR=0.28X+ 1.14
S = 0.64X+1.60
X =0.720 + 0.25
SR=0.11X+ 1.28
S =0.40X + O.74
X =0.870-0.76
SR = 0.20X - 0.55
S = 0.51 X+ 1.78
X =0.780 + 1.36
1, 1 ,2-Trichloroethane
(8.00 - 499.00)
SR = 0. 13X - 0.04
S =0. 18X + 1. 18
X = 0.870 - 0.00
SR = 0.06X + 0.99
S =0.19X + 0.69
X = 0.840 + 0.83
SR = 0. 12X + 0.47
S =0.22X + 0.80
X = 0.85C + 0.39
SR = 0.17X + 0.15
S- =0.24X+ 1.53
X =0.780 + 0.03
SR = 0.09X + 0.83
S = 0.19X + 0.79
X =0.930-0.40
SR - 0.08X + 1.52
S =0.22X+1.73
X =0.920-0.15
X = Mean Recovery
0 = True Value for the Concentration
Table 2. (Continued)
Water Type
Applicable Cone. Range
Distilled Water
Single-Analyst Precision
Overall Precision
Accuracy
Tap Water
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
Chlorobenzene
(8.00 - 500.00}
SR = 0.15X - 0.02
S =0.18X+1.21
X = 7.00C - 7.23
SR = 0.07X + 1.71
S = 0.1 6X+ 1.43
X = 1.000 - 1.39
SR = 0.12X+ 1.04
S = 8.1 8X + 0.89
X = 0.980 - 0.41
SR = 0. 14X + 63.40
S -=0.33X+ 79.41
X =0.930+13.00
SR = 0.1 2X + 0.48
S = 0.21 X + 0.99
X = 0.93C - 1.44
SR = 0. 18X + 2.24
S = 0.36X + 1.23
X = 1.04C + 1.45
1,4 -Dichlorobenzene
(8.00 - 499.00)
SR = 0.1 OX -0.61
S =0.43X- 1.19
X = 0.960 - 0.28
SR = 0.06X + 0.54
S =O.26X + 0.21
X = 0.980 - 0.97
SR = 0.05X + 0.73
S =0. 19X - 0. 16
X = 0.95C + 0-03
SR = 0. 12X + 0.34
S = 0.39X - 0. 16
X = 0.990 - 0.06
SR = 0.07X + 0.73
S =0.40X-0.69
X = 0.960 - 1. 10
SR = 0.09 X + 0.95
S = 0.37X + 0.03
X = 1.080 - 2.55
Cis- 1 -3-Dichloropropene
(8.00 - 488.00}
SR =0.11X + O.42
S = 0.38X - 0.26
X = 0.590 - 0.90
SR = 0.1 7X -0.04
S = 0.34X + 0.44
X =0.600-1.07
SR = 0.23X + 0.01
S = 0.49X + 0.26
X =0.56C-0.13
SR=0.20X+ 1.90
S = 0.48X + 0.24
X = 0.63C - 0.87
SR = 0.20X + 0.02
S = 0.37X + 1.77
X = O.5OC + 0.69
SR =0. 18X + 1.64
S = 0.36X + 1.08
X = 0.530 + 1.35
1, l,2,Z-ieiracmoroeinane
I'S.OO - 499.00)
SR = 0. 14X + 2.41
S =0.23X + 2.79
X =0.950 + 0.19
SR = 0.09X+ 1.43
S = 0.21 X + 1.53 '
X =0.930-0.71
SR=0.11X+ 1.03
S = 0.26X + 0.44
X = 0.97C - 0.82
SR=O.19X + 9.29
S = 0.30X + 3.99
X = 0.840 + 7. 12
SR = 0. 16X + 0.87
S = 0.30X+1.26
X =0.910-0.15
SR = 0. 15X + 2.33
S = 0.28X + 2.63
X = 1.00C + 0.98
X = Mean Recovery
, C = True Value for the Concentration
*USGPO: 1984-759-102-10652
-------
all cases, as expected, the highest %RSD
(poorest precision) occurred at the lowest
Youden pair concentration. The precision
is acceptable at all levels when the
background interferences are minimal.
The single-analyst standard deviation
indicates the precision associated with a
single laboratory. The percent relative
standard deviation for a single analyst
(%RSD-SA), averaged overall the waters,
ranged from 10% to 22% for the 27
analytes, while the average value of
%RSD-SAfor all analytes in a given water
ranged from 12% to 15%. In all cases, the
highest %RSD-SA (poorest precision)
was associated with the lowest Youden
pair concentration. The precision is
acceptable at all levels where background
interference is minimal.
Statistical comparisons of the effect of
water type were performed on all ana-
lytes. These indicated a practical effect of
water matrix on the accuracy or precision
of Method 601 in the following cases:
Carbon tetrachloride in wastewater 1
Chlorobenzene in wastewater 1
1,4-Dichlorobenzene in wastewater 3,
and
1,2-Dichloroethane in wastewater 3.
Conclusions and
Recommendations
Method 601 is recommended for the
analysis of purgeable halocarbons in
municipal and industrial wastewaters.
The accuracy and precision are accepta-
ble, while the matrix effects are significant
only at low concentration levels.
Care should be taken in the handling or
packing of the chromatographic columns.
Any type of mechanical shock may
damage the fragile packing material and
produce fines which result in plugged
columns, decreased separation efficiency,
and/or a contaminated detector furnace.
Metal columns are not recommended as
they may be adversely affected by
halogen compounds.
The proper size quartz combustion tube
should be flamed prior to installation.
Care must be taken in obtaining
laboratory pure ("organic-free") water.
The use of an activated carbon column to
purify distilled water is recommended. The
waters should be capped tightly to
prevent contamination from solvent
vapors in the laboratory atmosphere.
The analyst should check the analytical
curve for linearity. Several laboratories
reported non-linearity above 200 ppt.
It is recommended that*he purity of cis
and ?rans-1,3-dichloroprlDpene. standard
materials be checked. Some laboratories
have observed impurities of 1,2 dichlorp-
propane as a decomposition product.
Extra care should be observed in the
preparation of gaseous standards due to
potential losses of analyte. It is recom-
mended that at least 10 mg of standard be
weighed for the standard solution to
allow three significant figures in the
calculations. Premixed standards for
gases are not recommended due to
instability.
ithpd 6O1-—Purqeable
4-212 448; Cost:
B. J. Warner, C. S. Friedman, L Metcalfe, T. J. Morrow, A. D. Snyder, and C. R.
McMillin are with Monsanto Company, Dayton, OH 454O7:
R. Wesselman is the EPA Project Officer (see below).
The complete report, entitled "EPA Met!
Halocarbons by the Purge Trap Method,
$22.OO, subject to change) will be avak
National Technical Information .' V/\
5285 Port Royal Road ^
Springfield, VA 221 '61
Telephone: 7O3-487-465O
The EPA Project Officer can be contactet
Environmental Monitoring and ,
U.S. Environmental Protection /
Cincinnati, OH 45268
\
or
ec
UJ
o
sr
«t
3
CO
CO
ru
in
United States
Environmental Protection
Agency
Center for Environmental Research
Information
Cincinnati OH 45268
lit.
BULK RATE
POSTAGE & FEES PAID I
EPA
PERMIT No. G-35
Official Business
Penalty for Private Use $300
------- |