United States
Environmental Protectio^i
Agency
Environmental Monitoring and
Support Laboratory
Cincinnati OH 45268
Research and Development
EPA-600/S4-84-052 July 1984
&EPA Project Summary
EPA Met
hiod Study 21,
Method 611 — Haloethers
Carl R. McMillin, Roger C. Gable, Joseph M. Kyne, Richard P. Quill, Arthur
D. Snyder, and James A. Thomas
This report describes the interlabo-
ratory study of an analytical method
which detects haloethe'rs in water. EPA
Method 611 — Haloethers, consists of
a liquid/liquid extraction using methy-
lene chloride, an evaporation step using
Kuderna-Danish (K-D) evaporators, a
cleanup procedure using Florisil sorbent,
another K-D evaporation of the fraction
from the Florisil column! and subsequent
analysis by gas chronjatography (GC)
using a halide-specific detector. The six
concentrations (three Vouden pairs) of
spiking solutions usejd in this study
contained BCIPE, BCEE, and BCEXM,
CPEE, and BPPE. Six v rater types were
used in the study: distil! ed, tap, surface,
and three different industrial waste-
waters. Statistical anal'
sions in this report
rses and conclu-
are based on
analytical data obtained by 20 collabo-
rating laboratories.
Participating laboratories were se-
lected based upon technical evaluation
of proposals and upon the analytical
results of prestudy samples. The data
obtained from the interjaboratory study
were analyzed employing EPA's series
of computer programs known as the
Interlaboratory Method Validation
Study (IMVS) system, which basically
implements ASTM Standard D 2777.
The statistical analyses included tests
for the rejection of outliers, estimation
of mean recovery (accuracy), estimation
of single-analyst and overall precision,
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 EPA's analytical laboratories
gather water quality data to provide
information on water resources, to assist
research activities, and to evaluate
pollution abatement activities. The
success of the Agency's pollution control
activities, 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 promulgates guidelines
establishing test procedures for the
analysis of pollutants. The Clean Water
Act Amendments of 1977 emphasize the
control of toxic pollutants 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
and suggests a suitable test procedure for
their measurement. The priority pollutants
analyzed by Method 611 in this report are
the study haloethers: 6/s(2-chloroisop'ro-
pyl)ether (BCIPE), 6/s(2-chloroethyl)ether
(BCEE), 6/s(2-chloroethoxy)methane
(BCEXM), 4-chlorophenyl phenyl ether
(CPPE), and 4-bromophenyl phenyl ether
(BPPE).
EMSL-Cincinnati develops analytical
methods and conducts a quality assurance
program for water laboratories to maxi-
mize the reliability and legal defensibility
of water quality information collected by
EPA laboratories. This responsibility is
assigned to the Quality Assurance Branch
(QAB) which conducts interlaboratory
studies on the methods in order to
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generate precision and accuracy data.
This report presents the results of
interlaboratory study 21, conducted for
the USEPA by the prime contractor;
Monsanto Company (MC).
Procedure
Monsanto Company conducted the
study in three phases. Phase I involved
the analysis of the prestudy samples by
20 participating laboratories. Two samples
were analyzed for each of the five
haloethers. A medium concentration
sample was analyzed in distilled water
supplied by the participating laboratories
and a low level sample was analyzed in a
wastewater sample supplied by MC. The
objective of Phase I was to familiarize
laboratories with Method 611 and to
identify potential problems associated
with the analytical methodology. A short
report, including the data obtained and
any potential problems encountered, was
received from each subcontracting
laboratory by MC at the completion of
Phase I.
Phase II consisted of a prestudy
conference held at EMSL-Cincinnati, on
May 16,1979 to which each subcontract-
ing laboratory sent at least one participant.
The prestudy conference was designed to
examine the results of Phase I and to
discuss any problems encountered in the
methodology.
Phase III was the formal interlaboratory
study. Five haloethers were analyzed at
six concentrations (three Youden pairs) in
six different water matrices. Each partici-
pating laboratory supplied its own
reagent grade water, tap water and
surface water. MC supplied the three
industrial wastewaters. In addition, the
participating laboratories performed
analyses of all water blanks with no
spiked compounds. Each participating
laboratory then issued a report to
Monsanto Company containing all data
obtained, copies of all chromatograms,
and comments.
The final step in the study was a
statistical analysis of data by Battelle
Columbus Laboratories, Columbus, Ohio,
under contract 68-03-2624 employing
U.S. EPA's IMVS computer programs.
Results and Discussion
The object of this study was to
characterize the performance of Method
611 in terms of accuracy, overall precision,
single-analyst precision and the effect of
water types on accuracy and precision.
Through statistical analyses of 3,600
analytical values, estimates of accuracy
and precision were made and expressed
as regression equations, which are
shown in Table 1. One measure of the
performance of the method is that 16.3%
of the analytical values were rejected as
outliers. Of these, 6.1% were rejected
through application of Youden's laboratory
ranking procedure and 10.2% were
rejected employing the Thompson-T-test.
The accuracy of the method is obtained
by comparing the mean recovery to the
true values of the concentration. It is
expressed as percent recovery and
ranges from 56% to 85% for all five
analytes in all six waters. A detailed
examination of the data indicated a
background interference problem for
waste water 2. Table 2 presents revised
linear regression equations'for BCEE and
4-CPEE in this wastewater after omitting
the low Youden'pair data:
The overall standard deviation indicates
the precision associated with measure-
ments generated by a group of laboratories.
The percent relative standard deviation
(% BSD) ranges from 32% to 53%.
The single-analyst standard deviation
indicates the precision associated within
a single laboratory. The percent relative
standard deviation for a single analyst {%
RSD-SA) ranges from 15% to 31%.
A statistical comparison of the effect of
water type was performed indicating a
statistically significant difference for six
of the analyte/water matrix combtnations.
Of these six cases, a practical significant
difference was established only for 4-
chlorophenyl phenyl ether in wastewater
2. This combination also exhibited the
lowest accuracy and highest precision
(lowest % RSD and RSD-SA) values of all
30 analyte/water pairs.
Conclusions and
Recommendations
Method 611 is recommended for the
analysis of haloethers in municipal and
industrial wastewatersr The matrix
effects are significant only at low
concentration levels.
Care should be taken in the Florisil
cleanup and K-D concentration steps.
Analyst care and experience is required
to conduct the concentration step in a
reproducible manner.
Special care should be taken to break
the emulsions developing in the extraction
step of the analysis to prevent loss of
analyte.
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Table 1. Regression Equations for Accuracy and Precision
Water Type Bisf2-ChloroisopropyHether Bisl2-Chloroethyl!Ether
Applicable Cone. Range
Distilled Water
Single-Analyst Precision
Overall Precision
Accuracy
Jap 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
I2AO- 624.001
SR=0.20X + 1.05
S = O,3eX + 0.79
X -0.85C-H.67
SR = 0. 16X 4- O.03
S = 036X + 0.55
X -0.78C+O.99
SR = 0.29X^0.77
S =0.47X^0.23
X =0.770+0.42
SR = 024X+ O.1B
S = 0.40X^1.93
X =0.730 + 2.00
SR = O.29X + O.09
S = 0.52X t J.OO
X =O.83C+1.66
SR = O.28X 4- O.22
S =0.42X + O.33
X = 0.80C + 0.39
11.40 - 6O2.OO)
SR = 0. 19X +• 0.28
S =O.35X + O.36
X =0.810+0.54
Sfl=0, 18X + O.25
S = O.4OX + 0. 18
X =O,72C + 0.4S
SR-0.27X- O.O6
S = O.SOX +0.09
X =0.670 + 0.39
SR -- 0.26X + O.O7
S =04JX + O.OB
X =0.69C + 0.25
SR = O.15X+ 226
S =0.35X+4.12
X =O.72C+ 7.77
SR=O.23X + O.O4
S =0.41X + 0.06
X =0.720 + 0.14
Bi
'11
SI
S
X
s/
s
X
st
s
X
st
s
X
SI
s
X
SI
s
X
sfZ-.CJlloroft/ioxylMethane
00 - S28.QPf
! = 0.20X + 0. IS
= O.33X + O.11
= O.71C + 0.13
! =O.21X + O,21
= O.38X 4 O.69
= 0.67C+0.69
! = 0.29X-0.08
= 0.53X + 0.47
= 0.600+0.74
' = 0.23X+O.43
= 0.48X + 0.54
--- 0.690 + 0.69
',-0.22X^1.37 '
= 0.34X + 2. 10
= 0.710 + 2.33
= O.26X + O.18
.= 0.36X + 0.70
= 0.670 + 0.97
4-Chlorophenyl Phenyl Ether
I6.6O-4S9.00)
SR = 0. 18X + 2. 13
S =0.4tX + O.SS
X =0.820 + 1.97
SR=0.17X+ 1.22
S =0.39X + O,78
X =O.75C + 0.63
SR = 0.22X + 0. 83
S =0.42X + 0.14
X =0.670+1.14
SR = 0.25X + 0.78
S =0.43X+0.40
X =0.650+0.97
' SR = 0. 15X + 15.99
S =0.32X+ 17.01 ,_
X = 0.560 + 20.40
SR = O.28X + 0.89
S =0.38X + 0.97
X =0.690+1.51
4-Bromophenyl Phenyl Ether
(2.80 - 626.00)
SR = O.25X + 021
S =O.47X+0.37
X =0.85C + 2.S5
SR = 0.22X + 0.33
S =0.47X + O.S2
X =0.820+1.87
SR = 0.27X + O.59
S =0.49X + O.47
X =0. 780 + 2. 10
SR = 0.30X + 0.33
S =0.48X+0.61
X =0.770 + 2.16
' SR = O.29X+ 1.26
S =0.51X + 0.45
X =0.810 + 2.30
SR = 0.31X + 0, 13
S -0.47X+0.22
X =0.790+ 1.68
A = Mean Recover*/
C = True Value for the Concentration
Table 2. Revised Linear Regression Equations for Waste Water 2
BCEE
4-CPPE
Single-Analyst Precision
Overall Precision
Accuracy
SR = 0. WX - 3.47
S_ =0.39X-2.26
X =0:720 + 8.61
t = Q.1TX+6.00
S = O.49X - 8.98
X =0.690 + 9.75
Carl R. McMillin, Roger C. Gable, Joseph M. Kyne, ft/chard P. Qufff, Arthur D.
Snyder, and James A. Thomas are with Monsanto Company, Dayton, OH
454O7.
Raymond Wesselman is the EPA Project Officer (see below).
The complete report, entitled"EPA Method Study 21, Method611—Hatoethers,"
(Order No. PB 84-2O5 939; Cost: $J3.0O, 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 Officer can be contacted at:
Environmental Monitoring and Support Laboratory
U.S. Environmental Protection Agency
Cincinnati, OH 45268
U.S. GOVERNMENT PRINTING OFFICE; 1984 — 759-015/7756
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Environmental Protection
Agency
Center for Environmental Research
Information
Cincinnati OH 45268
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