United States
Environmental Protection
Agency
Environmental Monitoring and Su
Laboratory
Cincinnati OH 45268
Research and Development
EPA-600/S4-81-062 Dec 1981
Project Summary
Determination of
Haloethers in Industrial and
Municipal Wastewaters
Paul L. Sherman, Joseph M. Kyne, Roger C. Gable, John V. Pustinger, and
Carl R. McMillin
This document describes an analy-
tical method, not based on gas
chromatography/mass spectrometry.
for the analysis of haloethers in water
and wastewater.
The following haloethers were
originally included in this study: 2-
chloroethyl vinyl ether, bis(2-chloro-
isopropyl) ether, bis(2-chloroethyl)
ether, bis(2-chloroethoxy) methane,
4-chlorophenyl phenyl ether, 4-bromo-
phenyl phenyl ether, and (bischloro-
methyl) ether. The 2-chloroethyl vinyl
ether and the bis(chloromethyl) ether
were later deleted from the project
because of extreme volatility and
hydrolytic instability, respectively.
A literature search was conducted
to acquire published information on
the hydrolytic stability of the halo-
ethers, methods for the detection of
haloethers in water, and methods for
the isolation, concentration, and
analysis of haloethers. Gas chroma-
tography studies were completed to
compare different packings for use
with haloethers and to compare the
results obtained using a Hall electro-
lytic conductivity detection with those
obtained using an electron capture
detector. Various solvents were eval-
uated for use in extracting haloethers
from wastewater. Sample preservation
was studied at various pH and residual
chlorine levels and different tempera-
tures. The stability of haloethers
stored in acetone and in methanol was
observed. Chromatographic cleanup
procedures were investigated for the
removal of potential interferences.
The workable method developed in
this program for the analysis of
haloethers in wastewater consisted of
a liquid/liquid extraction using meth-
ylene chloride, an evaporation step
using Kuderna-Oanish (K-D) evapora-
tors, a column Chromatographic clean-
up procedure using Florisil, another K-
D evaporation of the fraction from the
Florisil column, and subsequent anal-
ysis by gas chromatography using an
electrolytic conductivity detector.
This report was submitted in partial
fulfillment of Contract No. 68-03-
2033 by Monsanto Research Corpo-
ration under the sponsorship of the
U.S. Environmental Protection Agency.
This report covers the period 25
October 1977 through 31 December
1978.
This Project Summary was devel-
oped by EPA's Environmental Moni-
toring and Support Laboratory, Cin-
cinnati, 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
Under provisions of the Clean Water
Act, the Environmental Protection
Agency is required to promulgate
guidelines establishing test procedures
for the analysis of pollutants. The Clean
Water Act Amendments of 1977 em-
-------
phasize the control of toxic pollutants as
well as 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 following haloethers were origi-
nally in this study: 2-chloroethyl vinyl
ether (CEVE), bis(2-chloroisopropyl
ether (BCIPE), bis (2-chloroethyl) ether
(BCEE), bis(2-chloroethoxy) methane
(BCEXM), 4-chlorophenyl phenyl ether
(CPPE), 4-bromophenyl phenyl ether
(BPPE), and bis(chloromethyl) ether. The
2-chloroethyl vinyl ether and the
bis(chloromethyl) ether were later
deleted from the project because of
extreme volatility and hydrolytic insta-
bility, respectively.
A literature search was conducted to
acquire published information on the
hydrolytic stability of the haloethers,
methods for the detection of haloethers
in water, and methods for the isolation,
concentration, and analysis of halo-
ethers. Gas chromatography studies
were completed to compare different
packings for use with haloethers and to
compare the results obtained using a
Hall electrolytic conductivity detector
with those obtained using an electron
capture detector. Various solvents were
evaluated for use in extracting halo-
ethers from wastewater. Sample pres-
ervation was studied at various pH and
residual chlorine levels and different
temperatures. The stability of halo-
ethers stored in acetone and in methanol
was observed. Chromatographic cleanup
procedures were investigated for the
removal of potential interferences.
The workable method developed in
this program for the analysis of halo-
ethers in wastewater consisted of a
liquid/liquid extraction using methylene
chloride, an evaporation step using
Kuderna-Danish (K-D) evaporators, a
column chromatographic cleanup pro-
cedure using Florisil, another K-D
evaporation of the fraction from the
Florisil column, and subsequent analysis
by gas chromatography using an elec-
trolytic conductivity detector. This
research served as the basis for the
development of EPA Method 611 as
proposed under 40 CFR 136 on Decem-
ber 3, 1979.
Gas Chromatography Studies
Gas chromatography studies were
conducted to determine the optimum
column and conditions for use with
haloethers. In addition, electron capture
and electrolytic conductivity detectors
were studied to determine the most
selective and sensitive detector for use
with the haloethers.
Initial studies of the gas chromatog-
raphy of the haloethers resulted in the
selection of SP-1000 on Supelcoport
over Tenax-GC as the column of choice.
Early studies of detector sensitivity
showed that the electron capture
detector was more sensitive than the
electrolytic conductivity detector. Un-
fortunately, bis(2-chloroisopropyl) ether
was found to contain a large number of
electron capturing impurities, while
showing no significant impurities with
either the electrolytic conductivity
detector or the flame ionization detector.
Because of the BCIPE electron capturing
impurities, work was continued on the
electrolytic conductivity detector. With
this modified detector, sensitivity was
approximately equal to electron capture
and flame ionization detectors, but with
much greater specificity.
Figure 1 illustrates the results achieved
with the SP-1000 column. Column
conditions and retention times for both
columns are described in Table 1.
Extraction Studies
Extraction studies for the six halo-
ethers using spiked laboratory samples
were conducted at pH 2,7, and 10 using
three solvents: methylene chloride,
15% ethyl ether in hexane, and pentane.
The analytical results of the extraction
studies are presented in Table 2. Each
value listed for "percent recovered,"
represents an average of three different
extractions at a given pH and for a given
solvent. These results were analyzed
using analysis of variance (ANOVA). For
CEVE, pH was the only variable which
contributed significantly to the total
variance. For BCIPE, both pH and
solvent were significant contributors to
the variance. For the four other halo-
ethers, only the solvent contributed to
the variance. These ANOVA results, in
addition to the data presented in Table 2,
indicate the best average recoveries of
the haloethers are achieved by using
methylene chloride as a solvent.
Column: 3% SP-1000 on Supelcoport
Program: 60°C-2 minutes 8°/minute to 230°C.
Detector: Hall electrolytic conductivity
.c
02 4 6 8 10 12 14 16
Retention Time-Minutes
Figure 1. Gas chromatogram of haloethers.
18 20 22 24
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'reservation Studies
Preservation studies were conducted
by spiking one liter solutions of buffered
deionized water at pH 2, 7, and 10 with
the standard solution of five haloethers,
CEVE, BCEE, BCEXM, CPPE, and BPPE,
in acetone. The studies were conducted
at residual chlorine levels of 0 parts per
million and 2 parts per million and
storage temperatures of 4°C and 25°C.
Table 1. Chromatographic Conditions
Parameter
Storage time was seven days. Extraction
of the stored solutions was performed
using methylene chloride.
The analytical results of the preserva-
tion studies are presented in Table 3.
The "average percent recovered"
values listed represent an average of
three separate extractions.
The data in Table 3 and ANOVA
analysis show the only precaution
Retention Time
(min.)
Column 1 Column 2
Bis(2-chloroisopropyl) ether
Bis(2-chloroethyl) ether
Bis(2-chloroethoxy) methane
4-Chlorophenyl phenyl ether
4-Bromophenyl phenyl ether
8.4
9.3
13.1
19.4
21.2
9.7
9.1
10.0
15.0
16.2
Column 1 conditions: Supelcoport (100/120 mesh) coated with 3% SP-1000
packed in 1.8 m long x 2 mm ID glass column with helium carrier gas at a flow rate
of 40 mL/min. Column temperature: 60°C for 2 minutes after injection then
program at 8°C/min to 230°C and hold for 4 minutes. Under these conditions the
retention time for Aldrin is 22.6 minutes.
Column 2 conditions: Tenex- GC (60/80 mesh) packed in a 1.8m long x 2 mm ID glass
column with helium carrier gas as 40 mL/min flow rate. Column temperature:
150°C for 4 minutes after injection then program at 16°C/min to 310°C. Under
ithese conditions the retention time for Aldrin is 18.4 minutes.
needed for sample preservation is an
adjustment of the pH to at least 7, due to
the sensitivity of CEVE to acid hydrolysis
and the reaction between residual
chlorine and BPPE and CPPE at acid pH.
Closer examination of Table 3 shows
very little difference, if any, between
preservation at pH 7 or pH 10. The table
shows little difference between pres-
ervation at 4°C or 25°C, although the
buffer solutions analyzed were not
biologically active.
The stability of acetone and methanol
solutions of CEVE, BCIPE, BCEE,
BCEXM, and BPPE were also studied.
The results showed that while CEVE is
very unstable in methanol, the other
four haloethers were stable for at least
90 days in either solvent.
Resin Studies
Studies were completed to evaluate
the Ambersorb XE-340 and XAD-2
resins for use as concentrators. The two
resins were Soxhlet extracted with
acetonitrile overnight, and again with
methanol overnight. They were packed
into 10 mm ID columns to a depth of 6
cm. One liter portions of buffer solutions
at pH 2, 7 and 10 were then spiked with
the haloethers and passed through the
resin beds. The beds were then eluted
Table 2. Results of Extraction Studies
Solvent
pH Haloether
2 CEVE
BCIPE
BCEE
BCEXM
CPPE
BPPE
7 CEVE
BCIPE
BCEE
BCEXM
CPPE
BPPE
10 CEVE
BCIPE
BCEE
BCEXM
CPPE
BPPE
15%
ether in
Percent
recovered
(average)
29.6
66.4
66.9
55.9
67.3
57.4
65.9
88.5
63.7
68.0
65.1
57.1
44.2
61. r
59.9
54.5
54.4
52.7
Ethyl
hexane
RSD*%
32.4
21.8
16.3
15.0
9.8
8.7
16.5
7.6
3.1
14.5
12.5
12.7
29.8
—
20.8
24.7
30.8
30.4
Methylene
Percent
recovered
(average)
31.3
51.2
69.7
83.2
82.9
68.9
70.7
61.6
93.2
88.0
85.6
81.3
55.0
92.1
101.6
75.3
93.2
82.9
chloride
RSD,*%
9.5
21.5
20. 3
11.2
12.7
14.6
31.5
8.2
1.6
7.3
6.8
6.3
41.2
5.2
8.1
8.5
4.3
1.9
Pentane
Percent
recovered
(average)
37.8
22.1*
43.4
50.5
62.8
55.8
61.7
76.2
46.1
43.3
61.1
63.1
30.7
63.0
42.7
38.4
66.1
67.3
RSD,a%
32.1
—
9.8
13.9
20.0
21.3
47.3
10.7
8.7
27.8
12.5
6.5
13.8
10.8
5.3
6.4
2.3
0.56
"RSD = relative standard deviation.
"Value for one extraction.
cAverage of two extractions.
-------
Table 3. Preservation Study Results
1
pH
2
2
7
7
10
10
Chlorine,
ppm Haloether
o CEVE
BCEE
BCEXM
CPPE
BPPE
2 CEVE
BCEE
BCEXM
CPPE
BPPE
0 CEVE
BCEE
BCEXM
CPPE
BPPE
2 CEVE
BCEE
BCEXM
CPPE
BPPE
0 CEVE
BCEE
BCEXM
CPPE
BPPE
2 CEVE
BCEE
BCEXM
CPPE
BPPE
At
Percent
recovered
(average)
*
61.7
75.7
78.7
90.6
10.4
78.3
66.2
20.2
18.7
25.3
66.9
65.3
80.3
87.9
*
59.4
68.1
73.2
79.3
37.7
69.8
63.8
66.6
78.4
74.6
55.5
78.8
68.2
60.8
4°C
RSD*%
*
23.2
22.0
9.5
7.6
32.3
6.9
22.3
60.5
70.2
31.1
13.0
24.0
10.3
8.8
*
26.5
10.1
5.4
9.8
17.8
26.0
26.0
22.3
18.2
10.5
15.7
4.0
8.2
42.0
At 25°
Percent
recovered
(average)
*
76.6
71.0
86.9
91.9
12.5
66.0
89.0
16.4
11.5
28.7
61.4
71.4
74.0
76.5
*
68.7
54.9
70.3
72.5
26.8
53.4
54.0
63.3
57.3
68.6
80.2
70.2
76.9
77.1
C
RSD*%
*
2.6
3.5
3.8
4.6
20.4
12.4
9.7
61.0
25.2
25.3
8.1
5.7
8.0
2.6
*
17.5
20.8
7.6
6.6
19.3
10.1
20.3
1.5
8.0
13.7
6.5
16.9
9.2
0.76
*RSD - relative standard deviation.
* = none detected.
using 150 mL of ethyl ether for the XAD-
2 and 150 mL of acetone for the
Ambersorb SE-340.
Both resins showed the ability to
remove the haloethers from water.
However, we were unable to strip the
haloethers from the Ambersorb XE-340
using either acetone or methanol. The
XAD-2 resin, though, worked well on
both counts. At pH 7, the following
average percent recoveries and standard
deviations were obtained: BDIPE, 71 +
11; BCEE, 51 ± 7; BCEXM, 69 ± 9;
BPPE, 72 ± 9. Due to the high volatility
of CEVE, no appreciable amount of this
compound was recovered. Analysis of
the data showed no significant variation
in the percent recovery at any of the
three pH values used.
Column Chromatography
Studies
Column Chromatography studies
were conducted to find a chromato-
graphic medium sufficient for the removal
of potential interferences that may be
encountered in actual industrial waste-
waters.
Four columns were packed with
Florisil and eluted with 200 mL of 6%
ethyl ether in petroleum ether followed
by 200 mL 15% ethyl ether in petroleum
ether. Most of the haloethers eluted in
the 6% ethyl ether fraction, with only
10% of BCEXM eluting in the 15% ethyl
ether fraction. Further studies showed
at 300 mL of 6% ethyl ether in petroleum
ether was sufficient to remove all the
haloethers from the column, including
BCEXM.
Other columns with 2 cm ID were
slurry packed with 20 grams of 60-200
mesh silica gel. The haloether samples
were then charged on the head of the
column and eluted with varying concen-
trations of 5, 10, 20, 30, and 50% of
methylene chloride in hexane. An
experiment was conducted with four
identical samples charged on four
columns. The FID analyses of the
resulting fractions were so erratic, the
analyses were repeated. These results
and a third attempt were also very
erratic. Therefore, Florisil appeared to
be the preferred packing for the sample
cleanup. The use of silica gel was not
explored further as a column cleanup
media.
Application of Method to
Wastewater Samples
Wastewater samples were obtained
from a municipal secondary waste
treatment plant and three industrial
sites. Each of the four samples was
divided into one liter portions and
analyzed as received, or spiked with six
haloethers. After problems with a
computer integrater were encountered
during the analysis of the first sample,
all results were calculated using peak
heights. The experimental design
served as a check on the liquid extraction
procedure, the XAD resin extraction
technique, and sample stability for
seven days at 4°C and 25°C. Three
replicates of each sample were analyzed
under each of five conditions as described
in Table 4. ^
The samples described in the first m
three conditions were extracted with
three 60 mL portions of methylene
chloride. These portions were combined,
dried with sodium sulfate, concentrated
with hexane, and eluted from Florisil
using 300 mL of 6% ethyl ether in
petroleum ether. Then, the samples
were again concentrated using K-D
evaporator, the volume adjusted to 10
mL, and the samples were ready for
analysis. Table 4 shows that the XAD
resin sorption method was also used to
prepare samples for analysis. In this
procedure, the wastewater samples
were spiked and run through the resin
procedure described earlier. The sam-
ples were then either stripped and
analyzed immediately, or stored for
seven days at 4°C and then stripped and
analyzed. All the analyses were done
using the Hall electrolytic conductivity
detector with a column packed with 3%
SP-1000.
The blank samples, with the exception
of industrial source #3, had no response
on the Hall detector at retention times
which interfered with the haloethers.
Source #3 had several interferences
which could not be removed with the
Florisil cleanup. These interferences
were so large and eluted so close to
some of the haloethers that they
4
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Table 4. Percent Recoveries of Haloethers from Industrial and Municipal Wastewater
As received
Sample
Industrial # 1
BCIPE
BCEE
BCEXM
CPPE
BPPE
Industrial #2
BCIPE
BCEE
BCEXM
CPPE
BPPE
Industrial #3a
Municipal # /
BCIPE
BCEE
BCEXM
CPPE
BPPE
Percent
recovered
68.0
56.5
60.2
73.3
82.9
62.9
51.2
51.4
70.1
71.7
67.9
64.6
68.4
73.2
81.3
Percent
RSD
0.4
0.6
2.0
2.8
3.2
1.2
1.7
1.6
0.4
1.0
14.3
17.3
19.2
16.2
8.8
Stored at
25° C for 1 week
Percent
recovered
70.9
67.1
70.7
74.1
79.8
64.6
53.0
54.3
71.4
72.1
60.8
58.3
59.6
64.6
72.0
Percent
RSD
4.6
5.3
6.3
3.0
2.6
3.0
5.6
4.1
1.4
0.2
7.6
7.1
9.3
7.1
7.3
Stored at
4°C for 1 week
Percent
recovered
71.2
59.8
67.6
77.1
89.4
65.3
52.7
56.0
72.5
73.3
73.7
71.3
74.3
76.7
75.6
Percent
RSD
3.2
5.8
5.5
2.7
4.5
3.4
4.2
5.8
1.4
1.4
1.2
1.9
1.3
2.0
1.2
XAD-2
Percent
recovered
76.9
66.4
69.1
77.5
79.2
76.2
64.8
69.3
77.3
76.3
58.2
47.3
56.0
64.4
73.8
Percent
RSD
1.4
3.1
2.5
1.8
1.2
2.4
1.2
3.0
3.5
1.7
4.6
5.6
4.1
0.3
5.5
XAD-2
stored for 1 week
Percent
recovered
72.6
61.3
63.8
75.4
84.4
77.7
66.5
70.7
77.3
77.8
63.8
60.6
61.1
68.8
74.9
Percent
RSD
2.6
3.8
5.2
2.6
4.7
2.9
2.1
2.0
1.7
1.5
2.3
6.4
4.3
4.1
5.1
aUnable to obtain recovery data because of interferences.
overshadowed all compounds near
them. The data for recovery of the
haloethers from the wastewaters are
shown in Table 4.
Observation of the data from Table 4
seems to indicate that on the whole,
there is not much difference in the
samples extracted initially and those
stored at 25°C and 4°C. There is,
however, a difference in the samples
analyzed using extraction as opposed to
those using the XAD-2 resin. For the
two industrial waters, the data indicate
XAD concentration results in better
recoveries than methylene chloride
extraction for most of the haloethers.
Paul L. Sherman, Joseph M. Kyne, Roger C. Gable, John V. Pustinger, and Carl
R. McMillin are with Monsanto Research Corporation, Dayton, OH 45407.
James Longbottom is the EPA Project Officer (see below).
The complete report, entitled "Determination of Haloethers in Industrial and
Municipal Wastewaters," (Order No. PB 81-232 290; Cost: $9.50, 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: 198I/559-092/3348
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