United States
                      Environmental Protectio^i
                 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

  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
  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

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).

  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
  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
  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

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
Jap Water
Single-Analyst Precision
Overall Precision
Surface Water
Single-Analyst Precision
Overall Precision
Waste Water 1
Single-Analyst Precision
Overall Precision
Waste Water 2
Single-Analyst Precision
Overall Precision
Waste Water 3
Single-Analyst Precision
Overall Precision
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
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
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

Single-Analyst Precision
Overall Precision
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
  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
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