EPA-600/4-81-062
July 1981
DETERMINATION OF HALOETHERS
IN INDUSTRIAL AND MUNICIPAL WASTEWATERS
by
Paul L. Sherman, Joseph M. Kyne, Roger C. Gable,
John V. Pustinger, and Carl R. McMillin
Monsanto Research Corporation
Dayton, Ohio 45407
Contract No. 68-03-2633
Project Officer
James Longbottom
Physical and Chemical Methods Branch
Environmental Monitoring and Support Laboratory
Cincinnati, Ohio 45268
U.S. Environmental Protection Agency
Region V, Libr?ry
2 JO South Dearborn Street
Chicago, Illinois 60604
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
NATIONAL TECHNICAL
INFORMATION SERVICE
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DISCLAIMER
This report has been reviewed by the Environmental Monitoring
and Support Laboratory, U.S. Environmental Protection Agency/
and approved for publication. Approval does not signify that
the contents necessarily reflect the views and policies of the
U.S. Environmental Protection Agency, nor does mention of trade
names or commercial products constitute endorsement or recom-
mendation for use.
11
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FOREWORD
Environmental measurements are required to determine the quality
of ambient waters and the character of waste effluents. The
Environmental Monitoring and Support Laboratory-Cincinnati con-
ducts research to:
• Develop and evaluate techniques to measure the presence
and concentration of physical, chemical, and radiological
pollutants in water, wastewater, bottom sediments, and
solid waste.
• Investigate methods for the concentration, recovery, and
identification of viruses, bacteria, and other microbio-
logical organisms in water. Conduct studies to determine
the responses of aquatic organisms to water quality.
• Conduct an Agency-wide quality assurance program to assure
standardization and quality control of systems for monitor-
ing water and wastewater.
Under provisions of the Clean Water Act, the Environmental Pro-
tection Agency is required to promulgate 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 pollut-
ants to be toxic under Section 307(a) of the Act. This report
is one of a series that investigate the analytical behavior of
selected priority pollutants and suggests a suitable test pro-
cedure for their measurement.
Dwight G. Ballinger
Director
Environmental Monitoring and Support Laboratory
111
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ABSTRACT
This document describes an analytical method, not based on
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-chloroisopropyl) ether, bis (2-
chloroethyl) ether, bis(2-chloroethoxy) methane, 4-chlorophenyl
phenyl ether, 4-bromophenyl phenyl ether, and (bischloromethyl)
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 informa-
tion on the hydrolytic stability of the haloehters, methods for
the detection of haloethers in water, and methods for the
isolation, concentration, and analysis of haloethers. Gas
chromatography studies were completed to compare different pack-
ings for use with haloethers and to compare the results obtained
using a Hall electrolytic conductivity detection with those
obtained using an electron capture detector. Various solvents
were evaluated for use in extracting haloethers from wastewater.
Sample preservation was studied at various pH and residual chlo-
rine levels and different temperatures. The stability of halo-
ethers stored in acetone and in methanol was observed. Chroma-
tographic 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 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 chro-
matography using an electrolytic conductivity detector.
This report was submitted in partial fulfillment of Contract No.
68-03-2033 by Monsanto Research Corporation under the sponsor-
ship of the U.S. Environmental Protection Agency. This report
covers the period 25 October 1977 through 31 December 1978.
IV
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CONTENTS
Foreword ill
Abstract iv
Figures vi
Tables vii
1. Introduction 1
2. Summary 2
3. Haloethers literature review 4
Introduction 4
Hydrolytic stability ..... 5
Detection of haloethers in water 10
Methods for the isolation, concentration,
and analysis of haloethers 11
4. Gas Chromatography Studies 18
Columns and conditions 18
Initial detector studies 23
5. Extraction Studies 29
Extraction at pH 2 29
Extraction at pH 7 30
Extraction at pH 10 30
6. Preservation Studies 34
Preparation 34
Results 34
7. Solvent Stability Studies 37
8. Resin Studies 44
9. Column Chromatography Studies 47
Column packed with Florisil 47
Column packed with silica gel 48
10. Application of Method to Wastewater Samples. ... 53
References 59
Appendices
A. Method for Sampling and Analysis 63
B. Standardization of Florisil 69
v
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FIGURES
Number Page
1 Chromatogram of haloethers on column packed with
SP-1000 on Supelcoport and using flame ioniza-
tion detector 20
2 Chromatogram of haloethers on column packed with
SP-100 on Supelcoport and using Hall electrolytic
conductivity detector 20
3 Chromatogram of haloethers on column packed with
Tenax-GC and using flame ionization detector ... 21
4 Chromatogram of haloethers on column packed with
Tenax-GC and using Hall electrolyte conductivity
detector 21
5 Chromatogram of haloethers with new conditions ... 23
6 Calibration curve for CPPE 24
7 Chromatogram of BCIPE on column packed with SP-1000
and detected simultaneously using FID and electron
capture detectors, showing electron-capture
impurities 25
8 Chromatogram of haloethers on column packed with
SP-1000 and detected using an electron capture
detector 25
9 Chromatogram of haloethers on the modified Hall
Model 700 detector 27
10 Chromatogram showing the response of BCME in
comparison to three other haloethers on column
packed with SP-1000 on Supelcoport 28
11 Typical Chromatogram for CEVE with purge and
trap system 33
VI
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TABLES
Number
1 Haloethers in this Study 4
2 Amount of BCME Formed at 40% Relative Humidity and
26°C at Various CH20/HC1 Concentrations in Air. . 7
3 Amount of BCME Formed at Various Relative Humidities
and Room Temperature at Various CH20/HC1 Concen-
trations in Air 8
4 Hydrolysis Half-Life of BCME in Humid Air 8
5 Hydrolysis of Bis(chloromethy) Ether in Water
and Aqueous HCl and NaOH 10
6 Haloethers Detected in Water 12
7 Analysis of Haloethers in Air with Porous Polymer
Absorber/Gas Chromatography/Mass Spectrometry . . 14
8 Derivative Formation for Analysis of BCME in Air. . 16
9 Analysis of Haloethers in Water 17
10 Haloether Chromatographic Conditions for Columns
Packed with SP-1000 or Tenax-GC 19
11 Retention Times of Haloethers on Two GC Columns
Relative to Aldrin 19
12 New Haloether Chromatographic Conditions for
Column Packed with SP-1000 22
13 Haloether Chromatographic Conditions for Column
Packed with SP-1000 and Using Electron Capture
Detector 24
14 Sensitivity for Haloethers 26
15 Reproducibility Data 27
16 Results of Extraction Studies 31
17 Results of Anova for Solvent Extraction Studies . . 31
18 Conditions for GC/MS Analysis of CEVE 32
19 Percent Recovery for CEVE 32
20 Preservation Study Results 35
21 Results of Anova Analysis of Preservation
Study Results 36
22 Average Recovery (%) of Haloethers from Preservation
Study Samples at Neutral and Basic pH 36
23 Concentrations of Solvent Solutions 37
24 Concentrations of Standards 38
25 Haloether Chromatographic Conditions with Electron
Capture Detector 38
26 Concentration of Initial Methanol Solution Used for
Solvent Stability Study 38
VII
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TABLES (continued)
Number Page
27 Concentration of Initial Acetone Solution Used for
Solvent Stability Study 39
28 Results of Analysis of Methanol Solution After
Storage for 30 Days 39
29 Results of Analysis of Acetone Solution After
Storage for 30 Days 40
30 Results of Analysis of Methanol Solution After
Storage for 60 Days 40
31 Results of Analysis of Acetone Solution After
Storage for 60 Days 41
32 Results of Analysis of Methanol Solution After
Storage for 90 Days 41
33 Results of Analysis for Acetone Solution After
Storage for 90 Days 42
34 Comparison of All Storage Times. . 42
35 Statistical Data for XAD-2 Resin at pH 2 44
36 Statistical Data for XAD-2 Resin at pH 7 45
37 Statistical Data for XAD-2 at pH 10 45
38 Average Recovery Percent (Three Detectors) of
Haloethers on Chromatographic Column Packed
with Florisil and Eluted with 200 mL 6% Ethyl
Ether in Petroleum Ether 47
39 Recovery of Haloethers on Chromatographic Column
Packed with Silica Gel and Eluted with Methylene
Chloride in Hexane - First FID Analysis 49
40 Recovery of Haloethers on Chromatographic Column
Packed with Silica Gel and Eluted with Methylene
Chloride in Hexane - Second FID Analysis 50
41 Recovery of Haloethers on Chromatographic Column
Packed with Silica Gel and Eluted with Methylene
Chloride in Hexane - Third FID Analysis. ..... 51
42 Recovery of Haloethers on Chromatographic Column
Packed with Silica Gel and Eluted with Methylene
Chloride in Hexane - (Hall Model 700) 52
43 Distribution of Wastewater Sample Portions 53
44 Concentration of Haloethers in Spiking Solution. . . 53
45 Recovery of Haloethers from Wastewater from
Municipal Secondary Waste Treatment Plant Using
Column Packed with SP-1000 and Hall Electrolytic
Conductivity Detector 54
46 Average Results for Five Analyses of Haloether
Standard Analyzed on Column Packed with SP-1000
and Using Hall Electrolytic Conductivity Detector. 55
47 Percent Recoveries of Haloethers from Industrial and
Municipal Wastewater (Determined by Peak Amplitude)
Using Column Packed with SP-1000 and Hall Electro-
lytic Detector (Average of Three Samples) 56
48 "t" Values for Three Sets of Wastewater Samples. . . 57
viii
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SECTION 1
INTRODUCTION
This report describes work completed on EPA contract 68-03-2633,
"Development and Application of Test Procedures for Specific
Toxic Substances in Wastewater, Category 2: Haloethers." The
objective of this program is to develop a method for the analysis
of haloehters in water and wastewater which does not involve mass
spectrometry.
The following haloethers were included in this study: 2-chloro-
ethyl vinyl ether (CEVE), bis(2-chloroisopropyl) ether (BCIPE),
bi(2-chloroethyl) ether (BCEE), bis(2-chloroethoxy) methane
(BCEXM), 4-chlorophenyl phenyl ether (CPPE), and 4-bromophenyl
phenyl ether (BPPE). Bis(chloromethyl) ether (BCME) was origi-
nally included in this category; however, due to its hydrolytic
instability, BCME was removed from this study, but its chroma-
tographic retention time was determined under the same conditions
as the other six haloethers.
The following studies were included in this project: a litera-
ture review, gas chromatography, solvent stability, sample
extraction and preservation, column chromatography, resin per-
formance, and the application of the analytical technique to
actual wastewater samples. Accomplishments are summarized in
Section 2. Detailed description of all studies are provided in
Sections 3 through 10 of this report.
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SECTION 2
SUMMARY
The objective of this study is to develop a method for the
analysis of haloethers in water and wastewater that does not in-
volve mass spectrometry (GC/MS). The method developed involves
sample extraction, cleanup, and analysis by gas chromatography
with an electrolytic conductivity detector. This category
originally included seven compounds: chloroethyl vinyl ether
(CEVE), bis (2-chloroisopropyl) ether (BCIPE), bis(2-chloroethyl)
ether (BCEE), bis(2-chloroethoxy) methane (BCEXM), bis(chloro-
methyl) ether (BCME), 4-chlorophenyl phenyl ether (CPPE), and
4-bromophenyl phenyl ether (BPPE). BCME and CEVE were subse-
quently removed from the list, the former because of its hydro-
lytic instability in water, and the latter because of its
extreme volatility.
Two gas chromatographic packings were compared for best results
with these haloethers. The 3% SP-1000 on Supelcoport was found
to be superior to Tenax-GC because of better peak shape and
resolution. Comparison of the Hall electrolytic conductivity
detector with the electron capture detector showed the Hall
detector to be the better choice because of its specificity. The
Hall detector also has better reproducibility and lower detection
limits for the haloethers.
Studies were completed to determine the best methods for sample-
extraction and preservation, including resin sampling. A solvent
stability study was also conducted. The following solvents
were evaluated for the extraction of haloethers from wastewater:
methylene chloride, 15% ethyl ether in hexane, and pentane. For
this liquid/liquid extraction, methylene chloride proved to be
the best extracting solvent.
The possible use of Ambersorb XE-340 and XAD-2 resins for sample
collection was also studied. Very little difference was found
between the liquid/liquid extraction and the resin sorption
methods. The average percent recovery for the four haloethers
(BCIPE, BCEE, BCEXM, and BPPE) was 67% using resin sorption and
68.3% using liquid/liquid extraction. While there seemed to be
little difference between the direct sampling parameters (pH,
temperature, and residual chlorine), the XAD-2 was definitely
the better choice of sampling resin because the haloethers could
not be stripped from the Ambersorb XE-340 resin.
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Sample preservation was determined at three different pH levels
(2, 7, and 10) and with residual chlorine levels of 0 ppm and
2 ppm using temperatures of 0°C and 25°C. A study was also com-
pleted to compare the storage stability of the haloethers in
acetone and methanol. Samples of the haloethers in these water
miscible solvents were stored in flame-sealed glass ampules under
normal laboratory conditions for periods of 30, 60, and 90 days.
CEVE was found to be very unstable in methanol, but the other
five haloethers were very stable in both solvents.
Two chromatographic cleanup procedures involving silica gel and
Florisil were investigated for the removal of potential inter-
ferences in actual wastewater samples. Column chromatography on
silica gel yielded very erratic and irreproducible results, but
the Florisil cleanup procedure produced very stable and accept-
able results.
A study was performed to determine the validity of the analytical
method developed for application to actual wastewaters. Four
samples were obtained, one from a municipal source and three from
industrial sources. The samples were spiked, extracted, evap-
orated, column chromatographed, and evaporated again before
analysis by gas chromatography with an electrolytic conductivity
detector. One of the industrial effluent extracts was too com-
plex for analysis using extraction and column chromatographic
methods developed during this project. A "t" test was performed
on the data from these four sets of samples. The only signifi-
cant difference in recovery occurred between samples extracted
and those processed by resin sorption; resin sorption yielded
better recovery for the two industrial samples.
All of the aforementioned studies led to the development of an
actual workable method for the analysis of wastewater. This
method involved a liquid/liquid extraction using methylene chlo-
ride, an evaporation step using Kuderna-Danish (K-D) evaporators,
a column chromatographic cleanup procedure using Florisil,
another K-D evaporation of the fraction from the Florisil column,
and subsequent analysis by gas chromatography using an electro-
lytic conductivity detector.
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SECTION 3
HALOETHERS LITERATURE REVIEW
INTRODUCTION
A review of literature pertinent to the seven haloethers included
in this program was conducted during November 1977, prior to the
preliminary contract meeting. The seven haloethers of interest
and their abbreviations are listed in Table 1. Information in
this report was gathered from a literature search performed by
MRC in 1976 on EPA contract 68-01-1980, a literature review of
haloethers conducted by Syracuse University in 1975 (1), and a
computerized literature search of three commercial search ser-
vices, the National Library of Medicine, System Development Cor-
poration, and Lockheed Information Systems. These information
sources provided coverage of all scientific literature in this
report through approximately 15 November 1977. The main topics
discussed in the following sections are hydrolytic stability
of haloethers, reports of detection of haloethers in water, and
methods for the isolation, concentration and analysis of
haloethers.
TABLE 1. HALOETHERS IN THIS STUDY
Compound Abbreviation'
Bis(chloromethyl) ether BCME
2-Chloroethyl vinyl ether CEVE
Bis(2-chloroethyl) ether BCEE
Bis (2-chloroisopropyl) ether BCIPE
Bis (2-chloroethoxy) methane BCEXM
4-Chlorophenyl phenyl ether CPPE
4-Bromophenyl phenyl ether BPPE
(1) Durkin, P. R., P. H. Howard, and J. Saxena. Investigation
of Selected Potential Environmental Contaminants: Halo-
ethers. EPA 560/2-75-006, U.S. Environmental Protection
Agency, Washington, D.C., September 1975. 178 pp.
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HYDROLYTIC STABILITY
Literature related to the hydrolytic stability of chloroethers
can be divided into two types: 1) information related to all of
the ethers except BCME, and 2) data related to BCME. These types
are discussed separately below.
Haloethers Other Than BCME
Bohme and Sell (2) measured the hydrolysis rate of BCEE in a
dioxane-water mixture (20M water in dioxane) at 100°C.- The half-
life for BCEE under these conditions was 12.8 days. Van Duuren
and co-workers (3) measured the kinetics of the hydrolysis of
microliter quantities of six chloroethers in 10 mL of a water-
formaldehyde (3:1) solution. The hydrochloric acid formed was
titrated with an automatic recording titrator. The half-life of
all ethers with alpha-chloro substituents was found to be less
than 2 minutes, and the half-life of ethers with no alpha-chloro
substitution was greater than 23 hours. The half-life of BCME
was listed in this study as less than 2 minutes and that of BCEE
as greater than 23 hours. Salomaa and associates (4) have stud-
ied the hydrolysis of chlorovinyl eithers and chloro-substituted
acetals under acid conditions . They found that chlorovinyl
ethers, such as chloroethyl vinyl ether, are readily hydrolyzed
to an aldehyde and alcohol as shown in Equation 1.
C1CH2CH2-0-CH=CH2 3 • C1CH2CH2OH + CH3-C-H (1)
Their equations for two hydrolysis pathways for chloro-
substituted acetals are shown below:
H+ +
C1CH2CH2OCH2 OCH2CH3 — - — »-ClCH2CH2O=CH2 + HOCH2CH3 (2)
H+
C1CH2CH2 OCH2OCH2CH3 — -— +• C1CH2CH2OH + CH2=OCK2CH3 (3)
(2) Bohme, H. and K. Sell. The Hydrolysis of Halogenated Ethers
and Thio Ethers in Water-Dioxane Mixtures. Chem. Ber.,
81:123-130, 1973.
(3) Van Duuren, B. L., C. Katz, B. M. Goldschmidt, K. Frenkel,
and A. Sivak. Carcinogenicity of Halo-ethers. II. Struc-
ture - Activity Relation of Analogs of Bis(chloromethyl)
ether. J. Nat. Cancer Inst., 48:1431-1439, 1972.
(4) Salomaa, P., A. Kankaanpera, and M. Lajuneh. Protolytic
Cleavage of Vinyl Ethers. General Acid Catalysis, Struc-
tural Effects and Deuterium Solvent Isotope Effects. Acta.
Chem. Scand., 20 (7):1790-1801, 1966.
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As part of a hazard priority ranking program for the National
Science Foundation, Stanford Research Institute (5) predicted a
half-life of 38.2 days for BCEE in water at a pH of 7. One other
process for the catalytic cleavage of BCIPE, based on a patent by
Dow Chemical Company, is shown below (6):
HCl
(C1CH2CH[CH3])20 7 ~T ** CH3-CH-CH2C1 and CH3-CH-CH2C1 (4)
6m,J.2 I |
Cl OH
Bis(chloromethyl) Ether
The hydrolysis of BCME has been studied very extensively during
the past ten years. Because BCME had been found to be a very
potent carcinogen, the hydrolysis mechanism has been studied as
a possible pathway for the destruction of the compound. Van
Duuren, et al, (7, 8) reported that BCME reaches an equilibrium
with its hydrolysis products, formaldehyde (CH20) and hydrogen
chloride (HCl), in aqueous solutions as shown in Equation 5.
H20 0
C1CH2OCH2C1-* HCH + HCl (5)
Where this hydrolysis was studied in heavy water (D2O) (7),
approximately 70% of the BCME was hydrolyzed in 2 minutes, and
80% after 18 hours according to the Van Duuren study. A number
of other subsequent studies have explored the formation of BCME
from HCl and formaldehyde in air or water and the hydrolysis of
BCME in moist air or water. The status of hydrolysis studies in
air are discussed below, followed by a discussion of hydrolysis
studies in aqueous environments.
(5) Brown, S. L., F. Y. Chan, J. L. Jones, D. H. Liu,
K. E. McCaleb, T. Mill, K. N. Sapios, and D. E. Schendal.
Research Program on Hazard Priority Ranking of Manufactured
Chemicals (Chemicals 61-79). NSF-RA-E-75-190D, National
Science Foundation, Washington, D.C., April 1975. 198 pp.
(6) Roberts, R. F., Jr. Catalytically Cleaving Dichloro-
isopropyl Ether. U.S. Patent 3,723,544 (to Dow Chemical
Co.), 27 March 1973.
(7) Van Duuren, B. L., A. Sivak, B. M. Goldschmidt, C. Katz, and
S. Melchionne. Carcinogenicity of Halo-ethers. J. Nat.
Cancer Inst., 43:481, 1969.
(8) Van Duuren, B. L. Carcinogenic Epoxides, Lactones and
Halo-ethers and Their Mode of Action. Ann. New YOrk Acad.
Sci. 163:633-651, 1969.
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The results of Van Duuren, et al, essentially went unnoticed with
regard to their potential for the formation of BCME from HCl and
formaldehyde or their potential for the incomplete hydrolysis of
BCME (as indicated by only 80% hydrolysis after 18 hours). In
1973, Rohm and Haas Company (9) preliminarily announced that
part-per-billion (ppb) levels of BCME may be formed in humid air
from low levels of HCl and formaldehyde (5 ppm and 2 ppm, respec-
tively) . Subsequent studies by Frankel, et al., of Rohm and Haas
(10) and by Kallos and Solomon of Dow Chemical Company (11) found
that the potential was not as great as had been initially be-
lieved. Results of the Frankel Study are shown in Table 2.
TABLE 2. AMOUNT OF BCME FORMED AT 40% RELATIVE
HUMIDITY AND 26°C AT VARIOUS CH2O/HC1
CONCENTRATIONS IN AIR (10)
CH20/HC1,
ppm/ppm BCME, ppb
4,000/40,000 5,000
1,000/10,000 730
1,000/1,000 130
300/300 23
100/100 3
20/20 <0.5 (limit of
detection)
In the Kallos and Solomon study, BCME was found to be formed in
five of 18 sample mixtures of HCl and CH20 as shown in Table 3.
The reactant concentrations in both studies in which detectable
BCME was formed were greater than can be tolerated by humans.
One reason for the concern about the formulation of BCME from
CH2O and HCl in air is the relatively long half-life of BCME in
(9) Bis(chloromethyl) Ether Can Form Spontaneously. Chem. Eng,
News, 51(2) :13, 8 January 1973.
(10) Frankel, L. S., K. S. McCallum, and L. Collier. Formation
of Bis(chloromethyl) Ether from Formaldehyde and Hydrogen
Chloride. Environ. Sci. Technol., 8(4):356-359, 1974.
(11) Kallow, G. J. and R. A. Solomon. Formation of Bis(chloro-
methyl) Ether in Simulated Hydrogen Chloride-Formaldehyde
Atmospheric Environments. Amer. Ind. Hyg. Assoc. J.,
34:469-473, November 1973.
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TABLE 3. AMOUNT OF BCME FORMED AT VARIOUS RELATIVE
HUMIDITIES AND ROOM TEMPERATURE AT VARIOUS
CH2O/HC1 CONCENTRATIONS IN AIR (11)
CH20/HC1 ,
ppm/ppm
3,000/10,000
750/10,000
1,000/500
500/1,000
500/1,000
BCME,
ppb
48
2
0.6
0.3
0.3
humid air. The results of Tou (12) show the half-life of BCME
to be as long as 25 hours in air. The results of their study of
the hydrolysis of BCME in air in various reaction vessels are
shown in Table 4. These results for the formation and hydrolysis
of BCME in air have been included in this report because any BCME
formed in air can enter the aquatic system through washout or
absorption.
TABLE 4. HYDROLYSIS HALF-LIFE OF BCME
IN HUMID AIR (12)
ReactorRelativeHalf-life,
material T, °C humidity, % hr
Glass 25 67 20
Fused ground
glass 25 81 25
Fe203-powder 23 42 9.0
Coated saran 23 81 7.2
(12) Tou, J. C. and G. J. Kallos. Kinetic Study of the Stabili-
ties of Chloromethyl Methyl Ether and Bis(chloromethyl)
Ether in Humid Air. Anal. Chem., 46(12):1866-1869, 1974.
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In aqueous systems typically, BCME is rapidly hydrolyzed as
reported by Tou and associates (13-15). However, there is
potential for the formation of BCME in fairly significant con-
centrations in acidic formalin solutions in contact with mate-
rial containing chloride ions. The potential for the formation
of BCME in such formalin solutions is discussed below followed
by a review of the hydrolytio rates of BCME in more normal
aqueous solutions.
Frankel, et al., (10) have monitored the vapors above formalin
slurries of Friedel-Crafts chloride salts and detected BCME in
concentrations from 210 ppb with FeCl3 to 1,500 ppb with AlCla.
Marceleno, et al., (16) also found BCME in solutions containing
MgCl2 catalysts. BCME was found to form in the chloromethylating
medium (HCl-CH20-ZnCla) (17). These results indicate that fairly
significant amounts of BCME could be present in any formalin
solution which contains chloride ion. This result would present
a problem in wastewater samples if high concentrations of for-
malin solution and chloride ion were present.
Recent publications by Tou and associates provide details of
studies of the hydrolysis of BCME in aqueous media. In one
study, hydrolysis rates were measured for a 1-ppm concentration
of BCME in acidic, basic, and neutral aqueous solutions. Results
(13) Tou, J. C., L. B. Westover, and L. F. Sonnabend. Kinetic
Study of Bis(chloromethyl) Ether Hydrolysis by Mass Spec-
trometry. J. Phys. Chem., 78(11):1096-1098, 1974.
(14) Tou, J. C. and G. J. Kallow. Study of Aqueous HC1 and
Formaldehyde Mixtures for Formation of Bis(chloromethyl)
Ether. Amer. Ind. Hyg. Assoc. J., 35:419-422, July 1974.
(15) Tou, J. C., L. B. Westover, and L. F. Sonnabend. Analysis
of a Non-Crosslinked, Water Soluble Anion Exhange REsin
for the Possible Presence of Parts Per Billion Level of
Bis(chloromethyl) Ether. Amer. Ind. Hyg. Assoc. J.,
36:374-378, May 1975.
(16) Marceleno, T. and P. J. Bierbaum. A Preliminary Report on
the Formation and Detection of Bis-Chloromethyl Ether in
the Industrial and Medical Environment. Presented at
American Industrial Hygiene Association Conference, Miami,
Florida, 12-17 May 1974.
(17) Alvarez, M. and R. T. Rosen. Formation and Decomposition
of Bis(chloromethyl) Ether in Aqueous Media. Int. J.
Environ. Anal. Chem., 4:241-246, 1976.
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of this study, presented in Table 5 (13), indicate that under
the conditions listed BCME will not survive long enough to per-
mit analysis using the techniques to be studied in this program.
TABLE 5. HYDROLYSIS OP BIS(CHLOROMETHYL)
ETHER IN WATER AND AQUEOUS
HC1 AND NaOH (13)
Half-life, s
Solution
2N NaOH
IN NaOH
H2O
IN HC1
2N HC1
At
0°C
88
108
277
365
630
At
20°C
29
22
38
38
63
At
40°C
11
5
7
6
8
A second study by Tou and associates showed that the hydrolysis
rate of BCME is 14 seconds when equal concentrations of hydro-
chloric acid and formaldehyde (at 1, 10, 100, 250, and 1,000 ppm)
are added to water (14). A third study by the same workers
investigated whether the hydrolysis rate of BCME in water would
be changed by the presence of a final product (a non-crosslinked,
water-soluble, anion exchange resin) produced from BCME (15).
Results of the study showed that no BCME existed in the product.
In a spiked mixture of BCME with the resin and water, BCME was
still hydrolyzed very rapidly. From these studies, it is
apparent that the only possible way for BCME to remain in waste-
water solution is in a very rapidly agitated water solution con-
taining a non-water-soluble organic phase in which BCME has a
favorable distribution coefficient compared to water. Even in
this situation, BCME would be continually partitioning back into
the aqueous phase due to the hydrolysis of the BCME fraction in
the aqueous phase.
DETECTION OF HALOETHERS IN WATER
Since Rosen, et al., (18) discovered the presence of bis(2-chloro-
ethyl) ether in the Kanawaha River in West Virginia in 1964, a
number of other government workers have reported the detection
of haloethers in industrial wastewater, river water, and drinking
(18) Rosen, A. A., R. T. Skeel, and M. B. Ettinger. Relation-
ship of River Water Odor to Specific Organic Contaminants.
J. Water Pollut. Contr. Fedr., 35 (6) :777-782, 1963.
10
-------
water. Table 6 summarizes the compounds found, concentration if
determined, and location; references are also provided (18-25).
METHODS FOR THE ISOLATION, CONCENTRATION, AND ANALYSIS OF
HALOETHERS
The isolation, concentration, and analysis methods described in
the literature have been directed primarily toward four of the
haloethers (BCME, BCEE, BCIPE, and BCEXM) of interest in this
program. The reported methods are described separately below for
haloethers in air and in water. The air methods are included
primarily to describe the gas chromatographic columns which have
been utilized to date for the haloethers.
Haloethers in Air
The primary focus of methods for haloethers in air has been
directed toward collection and analysis of BCME; few other
references cover methods for other haloethers in air. Three
main types of methods have been employed for collection and con-
centration of haloethers: direct analysis, absorbers, and deri-
vatives. These three methods are discussed in the subsequent
(19) Frilous, J. Petrochemical Wastes as a Pollution Problem in
the Lower Mississippi River. Paper submitted to Senate
Subcommittee on Air and Water Pollution, 5 April 1971.
(20) Industrial Pollution of the Lower Mississippi River in
Louisiana. PB 229 814, U.S. Environmental Protection Agency,
Region VI, Dallas, Texas. April 1972. 154 pp.
(21) Kleopfer, R. D, and B. J. Fairless. Characterization of
Organic Components in a Municipal Water Supply. Environ.
Sci. Technol., 6(12):1036-1037, 1972.
(22) Analytical Report New Orleans Area Water Supply Study.
EPA 909/9-75-003, 1975. 90 pp. U.S. Environmental Protec-
tion Agency, Region VI, Dallas, Texas.
(23) Webb, R. G., A. W. Garrison, L. H. Keith, and J. M. McGuire.
Current Practice in GC-MS Analysis of Organics in Water.
EPA-R-73-277, U.S. Environmental Protection Agency, Athens,
Georgia, August 1973. 94 pp.
(24) Manwaring, J. F., W. M. Blankenship, L. Miller, and F. Voigt.
Bis(chloroethyl) Ether in Drinking Water - Its Detection and
Removal. J. Amer. Water Works Assoc., 69:210-213, April
1977.
(25) Dressman, R. C., J. Fair, and E. F. McFarreh. Determinative
Method for Analysis of Aqueous Sample Extracts for Bis(2-
Chloro)Ethers and Dichlorobenzenes. Environ. Sci. Technol.,
11(7) :719-721, 1977.
11
-------
TABLE 6. HALOETHERS DETECTED IN WATER
Concentration,
Location
Reference
Bis(2-chloroethyl) ether
Bromophenyl phenyl ether
Bromophenyl phenyl ether
Bis(2-chloroethyl) ether
Bis (2-chloroisopropyl) ether
Bis(2-chloroethyl) ether
Bis (2-chloroisopropyl) ether
r -"
_a
a
_a
_a
a
_a
0.5 to 5.0
2.0
Kanawha River, West Virginia
New Orleans drinking water
Jefferson Parish No. 2
Jefferson Parish No. 2
Jefferson Parish No. 2
Evansville, Indiana drinking water
Evansville, Indiana
Ohio River, Evansville
18
19
20
20
20
21
21
Bis(2-chloroethyl) ether
Bish(.2-chloroisopropyl) ether
Bis(2-chloroethoxy) methane
Bis(2-chloroethyl) ether
Bis(2-chloroisopropyl) ether
Bis(2-chloroethyl) ether
Bis(2-chloroethyl) ether
Bis(2-chloroethyl) ether
Bis(2-chloroisopropyl) ether
0.07
0.16
0.12
0.18
0.05
0.03
140,000
160
_a
10
0.4
0.01 to 0.36
0.02 to 0.55
Carrollton
Jefferson Parish No. 1
Jefferson Parish No. 2
Carrollton
Jefferson Parish No. 1
Jefferson Parish No. 2
Synthetic rubber plant
Synthetic rubber plant
Glycol plant
thickening and sediment pond
Philadelphia Northeast
water treatment plant
Delaware River, Philadelphia
Various cities during NOMS .
Various cities during NOMS
22
22
22
22
22
22
23
23
23
24
24
25
25
Detected but not quantified.
-------
paragraphs; where appropriate, the gas chromatographic column
and type of detector are described.
Direct Analysis—
A number of laboratory studies, primarily involving the formation
or hydrolysis of BCME, have utilized the direct analysis of air
and water samples (12-15). In these studies, a semi-membrane
silicone fiber probe was used and connected directly to a high-
resolution mass spectrometer.
Direct analysis for fumigant gases was performed by Berck (26)
using a (1.8 m x 4 mm) stainless-steel column packed with 10%
SE-30 on Diatoport S. The gases were analyzed for BCEE, and a
thermal conductivity detector was used.
Absorbers—
A variety of absorbers have been used to collect haloethers
(primarily BCME ) from air. The absorbers were subsequently
thermally desorbed onto a gas chromatographic column connected
to a low- or high-resolution mass spectrometer. Table 7 cites
the haloethers collected, the abosrber used for collection, the
gas chromatographic column employed, and the literature refer-
ence from which these data were taken (10, 11, 27-35).
(26) Berck, B. Determination of Fumigant Gases by Gas Chromato-
graphy. J. Agr. Food Chem., 113:373-377, 1965.
(27) Collier, L. Determination of Bischloromethyl Ether in the
ppb Level in Air Samples by High Resolution Mass Spectro-
scopy. Environ. Sci. Technol., 6 (10) :930-932, 1972.
(28) Shadoff, L. A., G. J. Kallos, and J. S. Woods. Determina-
tion of Bis(chloromethyl) Ether in Air by Gas Chromato-
graphy - Mass Spectrometry. Analytical Chemistry, (45(14):
2341-2344, 1973.
(29) Ellgehausen, D. Determination of Volatile Toxic Substances
in the Air by Means of a Coupled Gas Chromatograph - Mass
Spectrometer System. Analytical Letters, 8(l):ll-23, 1975.
(30) Sawicki, E. Bis(chloromethyl) Ether (Bis-CME) in Air
Analytical Method. Health Lab Sci., 12:403-406, 1975.
(31) Pellizzari, E. D., B. H. Carpenter, J. E. Bunch, and
E. Sawicki. Collection and Analysis of Trace Organic Pol-
lutants in Ambient Atmospheres - Techniques for Evaluating
Concentration of Vapors by Sorbent Media. Environ. Sci.
Technol., 9(6):552-555, 1975.
(32) Pellizzari, E. D., B. H. Carpenter, and J. E. Bunch. Col-
lection and Analysis of Trace Organic Vapor Pollutants in
Ambient Atmospheres, Thermal Desorption of Organic Vapors
(Continued)
13
-------
TABLE 7. ANALYSIS OF HALOETHERS IN AIR WITH POROUS POLYMER
ABSORBER/GAS CHROMATOGRAPHY/MASS SPECTROMETRY
Haloether
Absorber
Gas chromatographic column
Reference
BCME Porapak Q
BCME Ascarite/
Chromosorb 101
BCME Chromosorb 101
BCME Porapak Q
BCME Porapak Q
BCME Chromosorb 101
BCME, BCEE Chromosorb 101
Chromosorb 104
Tenax-GC
Porapak Q
Activated carbons
20% Carbowax 600
on Chromosorb W
Carbowax 400/Porasil C
Oxypropionitrile/
Porasil C
25% Dldecylphthalate
on Chromosorb P
20% Tricresyl phos-
phate on Chromo-
sorb W
BCME Porapak Q
Tenax
Chromosorb 101
Chromosorb 104
BCME, BCEE Tenax-GC
BCME
Porapak Q
Chromosorb 101
Chromosorb 11
(1.22 m x 2 mm or 4 mm)
OV-225
3% OV-225 on Chromosorb W
80/100 mesh, 3 m x 2 mm
2% DECS on Chromosorb W
(HP) 80/100 mesh, 3.6 m x 2.5 mm
27
11
28
10
29
30
31
32
Porapak Q (1.8 m, 50/80 mesh)
Chrosorb 101 (1.8 m,
80/100 mesh)
15% Polyterg B-300 on
Chromosorb P
(3.6 m, 60/80 mesh)
7% OV-225 on Gas Chrom Q
(3.6 m, 80/100 mesh)
20% Carbowax 20M-TPA on
Chromosorb W (4.6 m, 60/80 mesh)
10% DC-200 (3.1 m)
7% OV-225 (4.6 m)
OF-1(1.95%)/OV-17(1.5%)(6.1 m)
1% SP-1000(6.1 mm)
33
Tenax GC (3.6 m x 2.5 nun)
2% DECS on Supelcoport
(80/100 mesh)(3.6 m x 2.5
30% Polyethylene glycol
adipate on 100/120 mesh
Celite (2.7 m x 4 mm)
mm)
34
35
14
-------
Two methods based on the use of absorbers for collection utilize
solvent for desorption. The National Institute of Occupational
Safety and Health (NIOSH) traps BCEE from workplace environ-
ments on charcoal. The BCEE is desorbed with carbon disulfide
and analyzed using gas chromatography on 10% FFAP on 80/100 mesh,
acid-worked, DMCS-treated Chromosorb W (36).
An approach developed by MRC for the EPA's Office of Toxic Sub-
stances (37) under contract for the analysis of 3-chloroethers
(chloroethyl ethyl ether, CEVE, BCEE, BCIPE, BCEXM, and
1,2 bis[2-chloroethoxy] ethane) in air involves the use of Tenax-
GC as an absorber. The Tenax-GC tube is then desorbed with
methanol and analyzed using gas chromatography/mass spectrometry.
The gas chromatographic colmn is Tenax-GC, and the mass spectro-
meter is operated in the selected-ion mode.
Derivative—
The third procedure used to collect and analyze BCME in air is
based on derivative formation followed by gas chromatography
with an electron capture detector. The derivatives are formed
via the reaction in methanol solution between BCME being scrubbed
from the air and the sodium salt of 2,4,6-trichlorophenol. Other
sodium salts of alkyl or aryl oxides have been used by other
(Continued)
from Solid Media. Environ. Sci. Technol., 9(6)556-560,
1975.
(33) Frankel, L. S. and R. F. Black. Automatic Gas Chromato-
graphic Monitor for the Determination of Parts-Per-Billion
Levels of Bis(chloromethyl) Ether. Anal. Chem., 48(4):
732-737, 1976.
(34) Pellizzari, E. D., J. E. Bunch, R. E. Berkley, and J. McRa-e.
Collection and Analysis of Trace Organic Vapor Pollutants
in Ambient Atmospheres, The Performance of a Tenax-GC
Cartridge Samples for Hazardous Vapors. Analytical Letters,
9(1):45-63, 1976.
(35) Evans, K. P., A. Mathias, N. Mellar, and R. Selvester.
Detection and Estimation of Bis(chloromethyl) Ether in Air
by Gas Chromatography - High Resolution Mass Spectrometry.
Anal. Chem., 47 (6) :821-824, 1975.
(36) NIOSH Analytical Methods for Set V. NIOSH-SCP V, National
Institute for Occupational Safety and Health, Cincinnati,
Ohio, December 1976. 43 pp.
(37) Sherman, P. L., A. M. Kemmer, L. Metcalf, and H. D. Toy.
Environmental Monitoring Near Industrial Sites:
3-Chloroethers. EPA 56/6-78-003, U.S. Environmental Pro-
tection Agency, Washington, D.C., 1978. 271 pp.
15
-------
workers. The materials used to form derivatives, the gas
chromatographic colmn used for analysis, and the literature
reference are listed in Table 8 (38-40).
TABLE 8. DERIVATIVE FORMATION FOR
ANALYSIS OF BCME IN AIR
Derivative reagent
Gas
chromatographic
column
-Reference
Sodium 2,4,6-trichlorophenate
Sodium phenate
Sodium methoxide
Sodium ethoxide
Sodium thiophenate
Sodium 2,4,6-trichlorophenate
Sodium 2,4,6-trichlorophenate
0.1% QF-1 and 0.1%
OV-17 on 100/200
mesh textured
glass beads (GLC
100)(1.8 m x 4 mm)
LAC-2R446 + 2% H3P04
38
39
40
The major methods for the isolation and concentration of halo-
ethers from water have centered around sorption on charcoal or
solvent extraction. Methods of analysis are primarily gas
chromatography with different detectors.
(38) Solomon, R. A. and G. J. Kallos. Determination of Chloro-
methyl Methyl Ether and Bis Chloromethyl Ether in Air at
the Parts Per Billion Level by Gas-Liquid Chromatography.
Anal. Chem., 47(6)955-957, 1975.
(39) Solomon, R. A. Detection of Chloromethyl Methyl Ether or
Bischloromethyl Ether, U.S. Patent 3,944,389 (to Dow Chem-
ical Co.), 16 March 1976.
(40) Sawicki, E. Analytical Method for Chloromethyl Methyl Ether
(CMME) and Bischloromethyl Ether (BCME). Health Lab Sci.,
13:78-81, 1976.
16
-------
Table 9 lists the method of isolation and concentration, the gas
chromatography detector, and the literature reference for halo-
ethers in water (18, 21, 23, 41). In addition to these standard
techniques, Deinzer, et al., tested the use of a cellulose ace-
tate reverse-osmosis membrane for concentrating BCEE and BCIPE
from water (42). They were not successful in increasing the con-
centration of these two compounds in the reject water using that
specific membrane.
TABLE 9. ANALYSIS OF HALOETHERS IN WATER
Haloether
Isolation
concentration
technique
Gas
chromatograph
column
Detector
Reference
BCEE, BCIPE
BCEE, BCIPE,
BCEXM
BCEE, BCIPE
BCEE, BCIPE
Carbon chloroform
extraction
Solvent
Carbon chloroform
extraction
Extraction with 5%
ethyl ether in hexane
Extraction with 15%
ethyl ether in hexane
BCEM, CEVE Purge and trap
BCIPE, BCEE,
BPPE
BCIPE, BCEE
Hethylene chloride
extraction
4% FFAP on
Chromosorb W
(1.8 m x 2.1 mm or
4 mm)
5% SE-30 on
Chromosorb W
60/80 mesh
(1.8 m x 2 mm)
5% OV-17 on
Chromosorb W
60/80 mesh
(1.8 m x 2 mm)
4% SE-30 + 6%
OV-210 on Gas
Chrom. Q (1.8 m x
2.1 mm)
3% SP-1000 on
Supelcoport
100/120 mesh
(1.8 m x 2.1 mm)
0.2% Carbowax
1500 on Carbopak
C (60/80 mesh)
(2.4 m x 2.1 mm)
+ Carbowax 1500
on Chromosorb W
(0.3 m x 2.1 mm)
1% SP-2250 on
Supelcoport
(100/120 mesh)
(1.8 m x 2 mm)
OV-17 SCOT
column
IR
FID, mass
spectrometry
FID, mass
spectrometry
18
23
21
Microcoulometric,
electrolytic
conductivity
25
Mass spectrometry
41
Mass spectrometry
Mass spectrometry
41
41
(41) Sampling and Analysis Procedures for Screening of Industrial
Effluents for Priority Pollutants, U.S. Environmental Pro-
tection Agency, Cincinnati, Ohio, April 1977.
(42) Deinzer, M., R. Melton, and D. Mitchell. Trace Organic Con-
taminants in Drinking Water; Their Concentration by Reverse
Osmosis. Water Res., 9:799-805, 1975.
17
-------
SECTION 4
GAS CHROMATOGRAPHY STUDIES
Gas chromatography studies were conducted to determine the opti-
mum 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. The results of these studies are
described in the following subsections.
In summary, initial studies of the gas chromatography of the halo-
ethers 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. Unfortu-
nately, bis(2-chloroisopropyl) ether was found to contain a large
number of electron-capturing impurities, while showing no signif-
icant impurities with either the electrolytic conductivity de-
tector or the flame ionization detector. Because of the BCIPE
electron-capturing impurities, work was continued on the electro-
lytic conductivity detector and the resulting improvements made
possible the use of this detector. With the modified electro-
lytic conductivity detector, sensitivity was approximately equal
to electron capture and flame ionization detectors but with much
greater specificity. The retention time was determined for
bis(chloromethyl) ether on the SP-1000 column under the same
conditions as those used for the other haloethers. Details
regarding this work are provided below.
COLUMNS AND CONDITIONS
Previous work with similar compounds indicated two columns worthy
of more detailed study. The columns were packed with SP-1000 on
Supelcoport or with Tenax-GC. Both yielded adequate separations.
Conditions found to be optimum for both columns are listed in
Table 10. Figures 1 and 2 consist of the chromatograms obtained
with SP-1000, and Figures 3 and 4 were obtained with Tenax-GC.
Table 11 lists the retention time of the six haloethers on the
two columns relative to Aldrin. The superior peak shapes for
the haloethers when chromatographed on the column packed with
SP-1000 make this the column of choice. An important fact
learned during this study concerning SP-1000 was the need to use
ultra-high-purity (UHP) grade helium as carrier gas. When
regular-grade helium, nitrogen, or argon/methane (95/5) are used
18
-------
TABLE 10. HALOETHER CHROMATOGRAPHIC CONDITIONS FOR
COLUMNS PACKED WITH SP-1000 OR TENAX-GC
Item Description/value
Chromatograph Hewlett-Packard Model 5700
Injection port temperature 250°C
Column gas flow 40 nL/min helium
Column 1.8 m x 2.1 mm, glass packed with 3*
SP-1000 on supelcoport (100/120 mesh)
or Tenax-GC (60/80 mesh)
Column program SP-1000 - 60°C for 2 min, programmed at
8°C/min to 230°C
Tenax - 150"C for 4 min, programmed at
16"C/min to 310°C
Detector conditions for Figures 1 through 4
Hall 700 furnace 850"C
Hall-electrolyte flow 3.0 mL/min, 40/60 isopropyl alcohol/
water
FID temperature 300"C
Gases
Column effluent 40 mL/min helium split with 26 mL/min
to Hall and 14 mL/min to FID
Hall 24 mL/min helium makeup; 50 mL/min
hydrogen
FID 30 mL/min hydrogen; 240 mL/min air
Sample: 1 uL of hexane containing:
Compound Concentration, ng/yiL
CEVE 262
BCEE 305
BCIPE 275
BCEXM 300
CPPE 250
BPPE 355
Aldrin 275
TABLE 11. RETENTION TIMES OF HALOETHERS ON
TWO GC COLUMNS RELATIVE TO ALDRIN
Column packed
with SP-1000 on Column packed
Compound Supelcoport with Tenax-GC
CEVE
BCEE
BCIPE
BCEXM
CPPE
BPPE
Aldrin
0.12
0.41
0.37
0.58
0.86
0.94
1.00
0.25
0.50
0.53
0.60
0.81
0.88
1.00
19
-------
K)
O
TITU-
SWf>LE> NIX
INJECTED AT
METHOD= FID
£HJ*GE- IBB
9<10<43 ON JAN 31. 1978
RAM- HFK9>JK, f*C> Pf9'JK
a TO 25 NINC1 OIO 3 NIH)
2i.ee
BFPE
BCEXM
,i3.ee
CPPE
A"
12 15
Time, min
18
21
24
Figure 1,
Chromatogram of haloethers on
column packed with SP-1000 on
Supelcoport and using flame
ionization detector (see
Table 10 for conditions).
TITLE-
SAMPLE' NIX
INJECTED AT 9'19'43 OH JAN 31. 1978
METHOD* HALL RAH> RHeW'JK, PRC- JKH9-JK
EHUWGE- 1 TIME- e TO 23 HINC1 OIO 3 NIN)
BCEE
CEVE
Hexane
.83
»
9.32
Aldrin
BCIPE
1
I 1
BPPE
.21
I
41 1
BCEXM fl
«.ee
I 1 CPPEll
I tL •«]<
V— JV ILJvJ
22.96
15
s
0 3 69 12 15 1» 21 24
Time, min
Figure 2. Chromatogram of haloethers on
column packed with SP-1000 on
Supelcoport and using Hall
electrolytic conductivity
detector (see Table 10 for
conditions).
-------
TITLE-
SAMPLE- HIX-1/1
INJECTED AT 12'11'89 ON FEB 6, 1978
METHOD. FID (MM- RflW'JK PRC' PFIW'JK
ENLARGE- 208. TIME' 8 TO 21 NINCt 010- 3 MIN)
BPPE
6.0
Aldrin
.16.27
TITLE- SNO RTS*
SftnPtE- HIX-1/1
INJECTED AT 13'33'W ON FEB 6. 1978
METHOD' HALL RAM> RH189-JK PRC- FH12
ENLARGE- 48 TIME- 8 TO 25 HIHO 010- 3 «IH>
12
15
18
21
12 15
Time, min
18
21
24
Figure 3. Chromatogram of haloethers on
column packed with Tenax-GC
and using flame ionization
detector (see Table 11 for
conditions).
Figure 4. Chromatogram of haloethers on
column packed with Tenax-GC and
using Hall electrolytic conduc-
tivity detector (see Table 11
for conditions).
-------
as carrier, the peak shape of the haloethers degrades with time.
With the use of UHP-grade helium, no peak shape degradation was
observed for the SP-1000 column when used continuously for
thirty days.
After the initial column and conditions study was completed,
additional work refined the chromatographic conditions using the
SP-1000 column. The new conditions reduced the chromatographic
run time from over 21 minutes to less than thirteen minutes.
There was no sacrifice in peak separation in spite of a 40%
savings in time. The neW chromatographic conditions are listed
in Table 12, with the resulting chromatogram in Figure 5.
TABLE 12. NEW HALOETHER CHROMATOGRAPHIC CONDITIONS
FOR COLUMN PACKED WITH SP-1000
Item Description/value
Chromatograph Hewlett-Packard Model 5710 A
Injection port temperature 250°C
Auxiliary transfer line 250°C
Column gas flow 30 mL/min UHP-grade helium
Column 1.8 m x 2.1 mm, glass, packed with 3%
SP-1000 on Supelcoport (100/120 mesh)
Column program 100°C for 4 min, programmed at 16°C/min
to 230°C
Detector conditions for Figure 5
Hall 310 furnace 850°C
Hall-electrolyte flow 0.5 mL/min, 50/50 ethyl alcohol/water
Hydrogen flow 70 mL/min
Sample: 1 yL of acetone containing:
Compound Concentration, ng/yL
BCIPE 50
BCEE 62
BCEXM 53
CPPE 50
BPPE 52
22
-------
0.39
HEXANE
BCBXH
7.80
BPPE
CPPK 12.54
11.57 -
JL_IL_
8 10 12
Tine, min
14 16
Figure 5. Chromatogram of haloethers with new conditions
(see Table 12 for conditions).
INITIAL DETECTOR STUDIES
In the early stages of this study, the electron capture detector
seemed to be the best candidate for final selection as the method
for haloether detection. Linearity was very good for all com-
pounds being studied. Figure 6 shows an example of this linear-
ity for CPPE. Although the sensitivity and reproducibility data
(see Tables 14 and 15 near the end of this section) are not
impressive, it was felt that refinement in technique and condi-
tions could improve results to the desired level. The greatest
problem with the electron capture detector was created by one of
the haloethers. Even the "purest" sample of BCIPE that we could
obtain contained over 20 electron-capturing impurities. These -
impurities created peaks which interfered with other haloethers.
Based on the desire to keep BCIPE in the study, it was decided
to investigate other detectors. Data and sample chromatograms
from these early studies are shown in Table 13 and Figures 7
and 8.
The flame ionization detector (FID) was used routinely during the
selection of optimum conditions and columns. This detector gave
very good results in sensitivity, linearity and reproducibility
for our pure haloether standards (see Tables 14 and 15). However;
knowing wastewaters contain many compounds which would be ex-
tracted and detected along with the haloethers, we did not con-
sider the FID as our final detector choice because it is so
non-specific.
23
-------
250
200
a 150
100
50
456789
CONCENTRATION, mg/ml
10 11 12
Figure 6. Calibration curve for CPPE.
TABLE 13. HALOETHER CHROMATOGRAPHIC CONDITIONS FOR
COLUMN PACKED WITH SP-1000 AND USING
ELECTRON CAPTURE DETECTOR
Item
Description/value
Chromatograph
Hewlett-Packard Model 5713
Injection port temperature 250°C
Electron capture
detector temperature
Column
Column program
Gases
Column
300 "C
1.8 m x 2.1 mm, glass packed with 3%
SP-1000 on supelcoport (100/120 mesh)
60"C for 2 min, then programmed at 8°C/
min to 230"C
Electron capture makeup
Sample: 2 yL of hexane containing:
Ether Concentration,
40 mL/min ultra-high-purity helium
20 mL/min, 5% methane in argon
CEVE
BCEE
BCEXM
CPPE
BPPE
205
138
133
50
8
24
-------
M
Ul
s
a
a
o
24
Figure 7. Chromatogram of BCIPE on
column packed with SP-1000
and detected simultaneously
using FID and electron
capture detectors, showing
electron-capture impurities.
TITLE STORAGE $TABILITV-H»Y
SAMPLE HEXANE tNUL
INJECTED AT 9 48 W ON AP* «. 19T»
METHOD EXT1 ft* t«ei7«-IK ft?
EKJ^GE- 1 TIME' 0 TO Zl.9 HIKI OIO 3 MM)
BPPE
21.20
BCEXM
13.26
CPPE
19.45
12 15
Time, rain
IS
21
24
Figure 8.
Chromatogram of haloethers on
column packed with SP-1000
and detected using an elec-
tron capture detector.
-------
The early work with the model 700 Hall electrolytic conductivity
detector was not very promising. If this detector were to be
used, sensitivity and reproducibility would have to be improved
(see Tables 14 and 15). It was difficult to stabilize the unit
each day, and linearity of results over a wide range of concen-
trations was not possible. In spite of these problems, it was
decided to be worthwhile to develop the system because of the
Hall's specificity.
A number of changes were made on the model 700 Hall detector
which significantly improved the sensitivity and the reproduci-
bility of the detector (see Tables 14 and 15). The major changes
were:
• The addition of a glass-lined, heated (^275°C) collection
port at the exit of the chromatograph as well as the heat-
ing of the transfer line.
• The use of ethanol/water or absolute ethanol as the electro-
lyte solution instead of isopropanol/water.
• Modifications on the exit end of the quartz tube, such as
the use of Teflon instead of stainless steel and the
insertion of the tube from the detector cell up into the
end of the quartz tube.
The Hall detector still does not give linear results over a wide
range of concentrations, but careful calibration will give re-
liable values for the haloethers. The greatest advantage of this
system is the specificity for the compounds of this study. Fig-
ure 9 shows a sample chromatogram from the modified model 700
Hall detector.
TABLE 14. SENSITIVITY FOR HALOTHERS
5 x noise,
Electron
Haloether
CEVE
BCIPE
BCEE
BCEXM
CPPE
BPPE
capture
40
9.
28
26
12
1.
0
6
FID
1
0
1
1
0
0
.5
.65
.25
.75
.25
.15
Hall
8.
46
8.
240
5.
28
ng
Modified
700
4
6
8
Hall
0.
0.
0.
0.
1.
0.
700
5
45
25
20
1
55
26
-------
TABLE 15. REPRODUCIBILITY DATA
Standard manual injection -
• 1 yL solution containing: CEVE
BCIPE
BCEE
BCEXM
CPPE
BPPE
105 ng
100 ng
98 ng
96 ng
100 ng
99 ng
Relative standard deviation/ percent
Haloether
Electron
capture
FID
Hall 700
Modified
Hall 700
CEVE
BCIPE
BCEE
BCEXM
BPPE
10.4
6.3
11.1
15.5
7.0
42.5
1.2
1.2
0.8
1.2
23.1
11.2
22.1
37.7
28.7
6.4
4.5
3.4
3.7
3.9
Hall 310
1.9
2.4
4.6
2.4
1.3
Caused by the venting of the solvent peak.
u
B*
u
8:
12 15 18
Time (min)
21
24
27
Figure 9. Chromatogram of haloethers on the
modified Hall Model 700 detector.
27
-------
The final detector used was the model 310 Hall electrolytic con-
ductivity detector. As with the model 700 Hall, many alterations
were needed before good results were possible. Results from the
model 310 are comparable to those from the modified model 700
(see chromatogram in Figure 5).
Detector Summary and Recommendation
Each of the detectors discussed in this section has its own limi-
tations; EC - interference peaks from BCIPE, FID - nonspecific,
both Hall models - nonlinear over a wide range. The final
selection of a detector must be based on the quality of results
needed and the type of sample being analyzed. We have no control
over the number or types of compounds in the wastewaters to be
analyzed. Therefore, we feel it is essential to select a detec-
tor that is as specific as possible for our compounds. The Hall
detector models are the most specific detectors discussed. The
Hall's major problem (nonlinearity over wide ranges) can be
overcome with careful calibration techniques, while the problems
of the other detectors have no obvious solutions. We feel the
electrolytic conductivity detector is the best choice for halo-
ether detection.
Bis(chloromethyl) Ether
Bis(chloromethyl) ether was analyzed by gas chromatography using
a column containing 3% SP-1000 on Supelcoport (100/120 mesh).
The BCME elutes at approximately 2.7 minutes under the conditions
normally employed for the haloethers (60°C for 2 minutes, then
programmed at 8°C/min to 230°C and held at that temperature for
8 minutes). There was no problem in separating the BCME from the
CEVE, as shown in Figure 10.
2.K
z.r
Figure 10.
Chromatogram showing the response
of BCME in comparison to three
other haloethers on column packed
with SP-1000 on Supelcoport.
28
-------
SECTION 5
EXTRACTION STUDIES
Extraction studies for the six haloethers using spiked laboratory
samples were conducted at three pH's (2, 7, and 10) with three
solvents (methylene chloride, 15% ethyl ether in hexane, and pen-
tane). Due to problems caused by the presence of a large number
of electron-capturing impurities in BCIPE, it was necessary to
perform a separate extraction study for the compound. The pro-
cedures used for the studies are described in detail for the
pH 2 studies. The pH 7 and pH 10 extractions were conducted in
exactly the same manner except for the composition of the buf-
fers, which are described below.
Extraction at pH 2
Three one-liter buffered deionized water solutions were spiked
with 10 yL of a standard solution of five of the haloethers (CEVE,
BCEE, BCEXM, CPPE, and BPPE) in acetone. The deionized water was
prepared by adding 0.82 mL of concentrated hydrochloric acid to
one liter of water (0.01M). The concentrations of the five halo-
ethers in the acetone spiking solution were 8.2 mg/mL of CEVE,
5.5 mg/mL of BCEE, 5.3 mg/mL of BCEXM, 0.32 mg/mL of BPPE, and
and 2.0 mg/mL of CPPE. Three additional one-liter solutions of
deionized water were spiked with 100 yL of an acetone solution
containing 9.24 mg/mL of BCIPE.
The solutions were extracted immediately after spiking with three
60-mL portions of pentane. These extracts were combined and
passed through a 2-gram bed of sodium sulfate which was held in
a glass funnel by glass wool. The dried extracts were' then
evaporated using Kuderna-Danish evaporators to a volume of %4 mL.
These concentrates were then transferred to tared, Viton, septum-
capped vials and reweighed. The final volume of the concentrates
was determined by dividing the net weight of the concentrates by
the density of pentane.
The three extraction concentrates from the solutions spiked with
the five haloethers (CEVE, BCEE, BCEXM, CPPE, and BPPE) were
analyzed onal.8mx2.lmm glass column packed with 3% SP-1000
on (100/200 mesh) Supelcoport, with an electron capture detector.
The three remaining concentrates from solutions spiked with BCIPE
were analyzed onal.8mx2.lmm glass column packed with
29
-------
(60/80 mesh) Tenax-GC, with a flame ionization detector. In both
analyses, the areas of the peaks were integrated and the percent
recovery determined by comparing the areas of the concentrates
with those of standard samples. Calibration curves were deter-
mined for all six haloethers with the appropriate detector, and
the curves were found to be linear in the concentration range
used.
The extraction study was repeated for two other solvents (15%
ethyl ether in hexane, and methylene chloride) using the same
procedure as that described above for pentane. However, for
these other solvents, the hexane was solvent exchanged for
methylene chloride during the Kuderna-Danish evaporation. This
solvent exchange was acomplished by allowing the methylene chlo-
ride to evaporate to ^6 mL, adding 20 mL of hexane and evapora-
ting to 6 inL, and finally adding 10 mL of hexane and allowing the
solvent to evaporate to M' mL.
Extraction at pH 7
Extraction studies at pH 7 were performed in the same manner as
those studies at pH 2 except for the buffered deionized water.
The buffered deionized water for the pH 7 studies was prepared by
mixing 500 mL of 0.1M potassium dihydrogen phosphate with 291 mL
of 0.1M sodium hydroxide and diluting to one liter.
Extraction at pH 10
Extraction studies at pH 10 were also performed in the same
manner as those at pH 2 and pH 7 except for the buffered deion-
ized water composition. The buffered solutions for the pH 10
studies were prepared by mixing 500 mL of 0.025M borax (sodium
tetraborate) with 183 mL of 0.1M sodium hydroxide and diluting
to one liter.
Results
The analytical results of the extraction studies are presented
in Table 16. Each value listed for "percent recovered" repre-
sents an average of three different extractions at a given pH
and for a given solvent. These results were analyzed using anal-
ysis of variance (ANOVA), and the resulting F values for each
haloether and the average are listed in Table 17. 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 haloethers,
only the solvent contributed to the variance. These ANOVA
results, together with the data presented in Table 16, indicate
that the best average recoveries of the haloethers are achieved
using methylene chloride as solvent.
30
-------
TABLE 16. RESULTS OF EXTRACTION STUDIES
Solvent
15% Ethyl
ether in hexane
PH
7.
7
10
Haloether
CEVE
BCIPE
BCEE
8CEXM
CPPE
BPPE
CEVE
BCIPE
BCEE
BCEXM
CPPE
BPPE
CEVE
BCIPE
BCEE
BCEXM
CPPE
BPPE
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. 7C
59.9
54.5
54.4
52.7
RSD,3 %
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,3 %
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. 8L
22. lb
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,3 %
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.
°Average of two extractions.
TABLE 17. RESULTS OF ANOVA FOR SOLVENT EXTRACTION STUDIES
Degrees
Variable of freedom
Solvent j
PH 1
Replicates
2
2
2
T values
3
3
3
.55
.55
.55
CEVE
0.69
9.64
1.22
BCEE
72.05
3.10
1.49
BCEXM
34.8
2.68
1.11
F
values
CPPE
20
0
0
.65
.01
.005
BPPE
16.6
1.97
0.61
BCIPE
18.1
10.1
0.73
Average
27.1
4.6
0.86
-------
The average recoveries for all six haloethers combined using
methylene chloride as a solvent were 64.5%, 81.0%, and 83.4% at
pH 2, pH 7, and pH 10, respectively. A t-test was employed to
determine whether these means are statistically different from
each other at the 95% confidence interval. The t-test indicated
that there is a statistically significant difference in the mean
values obtained at pH 2 and pH 7, and also at pH 2 and pH 10.
There is, however, no difference in the mean values obtained at
pH 7 and pH 10.
These statistical analyses indicate that when the six -ethers are
extracted by a group, the average variance due to the solvent
used, the pH, and the reproducibility constituted approximately
60%, 10%, and 1%, respectively, of the total variance.
Chloroethyl Vinyl Ether
Because of the general inability to recover CEVE from the samples
due to its volatility, it was decided to test CEVE for percent
recovery as a purgeable. Hence, 50 yL of a solution containing
1.2 mg/mL of CEVE was injected into 5 mL of organic-free water.
The sample was then sparged for 12 minutes with helium at a flow
of 40 mL/min. The trapping device was a stainless-steel tube
(0.3 m long, 3.2 mm OD) packed with ^0.2 m of Tenax-GC and ^50 mm
of silica gel. After sparging, the tube was thermally desorbed
onto a Carbowax column held at -40°C. The sample was then an-
alyzed by GC/MS using a Hewlett-Packard 5981 GC/MS with a H-P
5934 data system. The conditions for the GC/MS analysis are
listed in Table 18. The data for the percent recovery of CEVE
by this method are listed in Table 19. A typical chromatogram
is shown in Figure 11.
TABLE 18. CONDITIONS FOR GC/MS ANALYSIS OF CEVE
Item
Value/description
Carrier gas
Temperature program
Column and packing
Injection port temperature
Helium at 30 ml/min
-40°C to 180°C/min
1.8 m x 3.2 ram, stainless steel,
packed with Carbowax 1500 on
Carbopak C; 0.3 m x 3.2 urn,
stainless steel, precolumn
packed with Carbowax 1500 on
Supelcoport
250°C
32
-------
TABLE 19. PERCENT RECOVERY FOR CEVE
Area
average,
Major three
masses runs
Std. dev.
Rel. std.
dev., %
Std.
area
Recovery, %
63
106
41906
23974
6592
2980
15.7
12.4
12072
7889
34.7
30.4
IXS'79
FRN 5559 .
1ST SCxPG: 331
X' 1.00 V 1.00
'06.
63. <
GAIN 5
B56S
TX
Figure 11. Typical chromatogram for CEVE
with purge and trap system.
33
-------
SECTION 6
PRESERVATION STUDIES
Preservation studies were conducted by spiking one-liter solu-
tions of buffered deionized water at pH 2, pH 7, and pH 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 ppm and 2 ppm and storage tempera-
tures of 4°C and 25°C; storage time was seven days. Extraction
of the stored solutions was performed using methylene chloride.
In the following two sections/ the composition of each sample is
described and results are provided for the preservation study.
The analytical portion of this study was done using the electron
capture detector, therefore BCIPE was excluded because of the
number of electron-capturing impurities.
Preparation
The preservation samples containing 0 ppm residual chlorine were
prepared in the same manner as described in the extraction stu-
dies (Section 5). Once prepared, each solution was stored in a
separate amber glass jug at 4°C or 25°C. Three sample solutions
were stored at each set of conditions. The matrix of samples
containing 2 ppm of residual chlorine were also prepared in the
same manner except that 10 mL of a 432 mg/liter solution of cal-
cium hypochlorite was added to each solution before dilution to
one liter. This hypochlorite concentration generates a residual
chlorine level of 2 ppm. After preparation, these solutions were
stored in amber glass jugs as described above.
After storage, the solutions were extracted with methylene chlo-
ride. The methylene chloride extracts were combined, dried with
sodium sulfate, concentrated, solvent exchanged with hexane, and
analyzed as described for the extraction studies.
Results
The analytical results of the preservation studies are presented
in Table 20. The "average percent recovered" values listed
represent an average of three separate extractions.
These data were subjected to ANOVA testing and the results are
shown in Table 21. These results are expressed in gross terms
with "+" denoting significant contributions of the variable to
34
-------
the variance and "-" showing no significant contribution. The
effect of the pH-chlorine level interaction is as important as
the main factors, chlorine level and pH. Temperature had no
statistical effect on the variability. The pH-temperature inter-
action was significant for BCEE and BPPE.
TABLE 20. PRESERVATION STUDY RESULTS
Chlorine ,
pH ppm
2 0
2 2
7 0
7 2
10 0
10 2
Haloether
CEVE
BCEE
BCEXM
CPPE
BPPE
CEVE
BCEE
BCEXM
CPPE
BPPE
CEVE
BCEE
BCEXM
CPPE
BPPE
CEVE
BCEE
BCEXM
CPPE
BPPE
CEVE
BCEE
BCEXM
CPPE
BPPE
CEVE
BCEE
BCEXM
CPPE
BPPE
At 4
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
°C
RSD,3 %
*
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,3 %
*
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
a
RSD = relative standard deviation.
* = none detected.
35
-------
TABLE 21. RESULTS OF ANOVA ANALYSIS OF
PRESERVATION STUDY RESULTS
Variable
C12 pH-Cla
Compound Temperature level pH level Temperature-pH
CEVE - + + +
BCEE - - +
BCEXM - - ' -
CPPE - + + +
BPPE - + + + +
+ = Caused significant variation.
- = Caused no significant variation.
The data in Tables 20 and 21 show that the only precaution needed
for sample preservation is an adjustment of the pH to at least 7
because of the sensitivity of CEVE to acid hydrolysis and the
reaction between residual chlorine and BPPE and CPPE at acid pH.
Closer examination of Table 20 shows that there is very little
difference, if any, between preservation at pH 7 or pH 10. Also,
the table shows little difference between preservation at 4°C or
25°C. Since preserving samples in ice for shipping is more time
consuming, more expensive, and requires more care; it is fortu-
nate that cold storage is not needed.
The data for CEVE appears to be most erratic. Much of this vari-
ance can be attributed to the extreme volatility of this compound,
Recovery of the haloethers increases significantly with the re-
moval of CEVE from the list as shown in Table 22.
TABLE 22. AVERAGE RECOVERY (%) OF HALOETHERS FROM PRESERVATION
STUDY SAMPLES AT NEUTRAL AND BASIC pH
At 4°CAt 25°C
Chlorine Five Four Five Four
pH level, ppm haloethers haloethers haloethers haloethers
7
7
10
10
0
2
0
2
65.2
56.0
63.3
67.6
75.1
70.0
69.6
65.8
62.4
54.6
51.0
74.6
70.8
66.6
57.0
76.1
36
-------
SECTION 7
SOLVENT STABILITY STUDIES
Five haloethers were included in the solvent stability study:
CEVE, BCIPE, BCEE, BCEXM, and BPPE. CPPE was not included in
this study because of its cost ($2/mg or $1,250 for the study).
The concentrations used in this study were determined using the
data generated in the sensitivity studies for the two detectors
(electron capture and electrolytic conductivity). The concen-
trations used were equal to 1,000 times the baseline noise for
the least sensitive detector. The concentration of the BCEXM
was changed to 12.0 mg/mL because sufficient material was not
on hand to use the concentration of 48.0 mg/mL in each solvent.
Acetone and methanol were the two water-miscible solvents used
in this study. These materials were high-purity, "distilled in
glass" solvents purchased from Burdick and Jackson. Each solu-
tion was made up in a 250-mL glass volumetric flask. Using a
5-mL syringe with 0.05-mL gradations, the compounds were added
in the amounts shown in Table 23. Twelve 4-mL aliquots of each
solution were quantitatively transferred, using a 4-mL glass
pipet, into 5-mL prescored sealable-glass ampules. The ampules
were placed in dry ice for cooling and then flame sealed.
Immediately after sealing and after storage times of 30, 60,
and 90 days, three ampules were opened, placed in septum-capped
vials, and analyzed against fresh standards (Table 24) by gas
chromatographic conditions are listed in Table 25. Data from the
analyses of the solutions are shown in Tables 26 - 33; data from
all four storage times are summarized in Table 34.
TABLE 23. CONCENTRATIONS OF SOLVENT SOLUTIONS
(250 mL)
Amount
added, Concentration,
Compound mL mg/mL
CEVE 1.95 8.2
BCIPE 2.10 9.2
BCEE 1.15 5.6
BCEXM 2.50 12.0
BPPE 1.0 5.7
37
-------
TABLE 24. CONCENTRATIONS OF STANDARDS
(1 itlL)
Compound
CEVE
BCIPE
BCEE
BCEXM
CPPE
Amount
added,
UL
7.8
8.4
4.2
8.6
4.0
Concentration ,
mg/roL
8.2
9.2
5.6
10.3
5.7
TABLE 25. HALOETHER CHROMATOGRAPHIC CONDITIONS
WITH ELECTRON CAPTURE DETECTOR
Item
Description/valug
Chromatograph
Injection port temperature
Electron capture
detector temperature
Column
Column program
Gases
Column:
Electron capture makeup:
Hewlett-Parkard Model 5713
250"C
300°C
1.8 m x 2.1 mm, glass,
packed with 3% SP-1000
on Supelcoport (100/120
mesh)
60°C for 2 min, then pro-
grammed at 8°C/min to
230°C
40 mL /min ultra-high-
purity helium
20 mL/min, 5% methane
in argon
TABLE 26. CONCENTRATION OF INITIAL METHANOL SOLUTION
USED FOR SOLVENT STABILITY STUDY
Concentration
Haloether
CEVE
BCIPE
BCEE
BCEXM
BPPE
Concentration
added ,
8
9
5
12
5
.2
.2
.6
.7
found (avg.
of 3 runs) ,
yg/mL
9.
5.
14
5.
2
7
4
Avg.
std.
5
4
4
0
rel.
dev. ,
%
.1
.4
.7
.91
38
-------
TABLE 27. CONCENTRATION OF INITIAL ACETONE SOLUTION
USED FOR SOLVENT STABILITY STUDY
Concentration
Concentration found (avg. Avg. rel.
added, of 3 runs), std. dev.,
Haloether yg/mL yg/mL %
CEVE
BCIPE
BCEE
BCEXM
BPPE
8.2
9.2
5.6
12
5.7
9.9
9.9
6.0
16
5.4
4.9
2.4
3.4
3.8
0.48
TABLE 28. RESULTS OF ANALYSIS OF METHANOL SOLUTION
AFTER STORAGE FOR 30 DAYS
ConcentrationAvg.rel.
Sample (avg. of 3 runs), std. dev., Percent
number Haloether ug/mL % change
30 M-l CEVE 0 -a -a
BCIPE 9.6 8.0 +4.3
BCEE 5.6 3.4 -1.8
BCEXM 14 2.9 0.0
BPPE 6.3 14 +17
30 M-2 CEVE 0 -a -a
BCIPE 9.6 .7.2 +4.3
BCEE 5.6 1.6 -1.8
BCEXM 14 1.4 0.0
BPPE 5.7 9.2 +6.0
30 M-3 CEVE -0 -a -a
BCIPE 9.8 4.6 +6.5
BCEE 5.6 1.9 -1.8
BCEXM 15 1.9 +7.1
BPPE 5.9 14 +9.3
aNot determined.
39
-------
TABLE 29. RESULTS OF ANALYSIS OF ACETONE SOLUTION
AFTER STORAGE FOR 30 DAYS
Sample
number
30 A-l
30 A-2
30 A-3
Haloether
CEVE
BCIPE
BCEE
BCEXM
BPPE
CEVE
BCIPE
BCEE
BCEXM
BPPE
CEVE
BCIPE
BCEE
BCEXM
BPPE
Concentration
(avg. of 3 runs) ,
vg/mL
11
9.7
6.0
16
6.1
10.1
9.9
6.0
16
6.3
10
10
6.1
16
5.9
Avg. rel.
std. dev.,
%
2.5
2.4
3.7
2.0
12
3.7
0.92
0.3
1.0
13
3.8
1.1
1.8
1.7
14
Percent
change
+11.1
-2.1
0.0
0.0
+13 .
+2.0
0.0
0.0
0.0
+17
+1.0
+1.0
+1.7
0.0
+9.3
TABLE 30. RESULTS OF ANALYSIS OF METHANOL SOLUTION
AFTER STORAGE FOR 60 DAYS
Sample
number
60 M-l
60 M-2
60 M-3
Haloether
CEVE
BCIPE
BCEE
BCEXM
BPPE
CEVE
BCIPE
BCEE
BCEXM
BPPE
CEVE
BCIPE
BCEE
BCEXM
BPPE
Concentration
(avg. of 3 runs) ,
yg/mL
0
9.0
5.5
14
5.2
0
9.1
5.4
14
5.2
0
9.3
5.5
15
5.2
Avg. rel.
std. dev.,
%
_a
3.2
4. a
4.0
0.4
a
1.2
1.2
1.4
1.3
_a
2.9
2.9
2.6
11
Percent
change
a
-2.2
-3.6
0.0
-3.8
_a
-1.1
-5.6
0.0
-3.8
_a
+1.1
-3.6
+6.6
-3.8
aNot determined.
40
-------
TABLE 31. RESULTS OF ANALYSIS OF ACETONE SOLUTION
AFTER STORAGE FOR 60 DAYS
Sample
number
60 A-l
60 A-2
60 A-3
Haloether
CEVE
BCIPE
BCEE
BCEXM
BPPE
CEVE
BCIPE
BCEE
BCEXM
BPPE
CEVE
BCIPE
BCEE
BCEXM
BPPE
Concentration
(avg. of 3 runs) ,
yg/mL
11
11
6.3
17
4.7
11
10
6.2
17
5.0
9.9
9.5
5.7
15
4.4
Avg. rel.
std. dev.,
%
3.0
0.5
0.9
0.7
0.6
5.9
4.8
5.4
7.7
9.7
1.8
1.6
1.6
1.6
0.5
Percent
change
+10
+10
+4.8
+5.9
-15.
+10
+10
+3.3
+5.9
-8.0
0.0
-4.2
-5.2
-6.7
-23
TABLE 32. RESULTS OF ANALYSIS OF METHANOL SOLUTION
AFTER STORAGE FOR 90 DAYS
Sample
number
90 M-l
90 M-2
90 M-3
Concentration Avg.
(avg. of 3 runs), std.
Haloether yg/mL
CEVE
BCIPE
BCEE
BCEXM
BPPE
CEVE
BCIPE
BCEE
BCEXM
BPPE
CEVE
BCIPE
BCEE
BCEXM
BPPE
0
11
6.
12
5.
0
12
6.
13
5.
0
12
6.
13
5.
3
8
5
9
6
9
1
1
1
0
_
3
3
3
1
*•»
0
1
0
0
rel.
dev. ,
%
a
.4
.5
.9
.6
a
.4
.5
.9
.8
a
.9
.6
.7
.1
Percent
change
_a
+ 20
+11
-14
+ 7.4
_a
+30
+14
-7.2
+9.3
a
+30
+16
-7.2
+9.3
aNot determined.
41
-------
TABLE 33. RESULTS OF ANALYSIS FOR ACETONE SOLUTION
AFTER STORAGE FOR 90 DAYS
Sample
number
90 A-l
90 A-2
90 A-3
Haloether
CEVE
BCIPE
BCEE
BCEXM
BPPE
CEVE
BCIPE
BCEE
BCEXM
BPPE
CEVE
BCIPE
BCEE
BCEXM
BPPE
Concentration
(avg. of 3 runs) ,
pg/mL
19
12
5.8
15
6.0
17
11
5.4
13
5.9
15
10
5.6
12
5.7
Avg. rel.
std. dev. ,
%
13
8.7
9.4
11
2.3
6.2
4.1
4.9
4.6
1.4
6.7
4.7
5.4
6.5
3.4
Percent
change
+92a
+21
-3.4
-7.3
+11
+72a
+11
-10
-19
+9.3
+52a
+1.0
-6.7
-25
+5.6
An unresolved impurity peak eluted as a hump on the trailing
edge of the CEVE peak. This caused the computer to inte-
grate both peaks together - giving very high values. The
hump may be a degradation product of electron capturing
impurities.
TABLE 34. COMPARISON OF ALL STORAGE TIMES
Haloether
Initial analysis
(avg 3 runs),
yg/mL
Percent recovery (avg 3 samples)
30 days, 60 days, 90 days,
percent percent percent
Acetone solution
CEVE
BCIPE
BCEE
BCEXM
BPPE
9.9 ± 0.5
9.9 ± 0.2
6.0 ± 0.2
16.0 ± 0.6
5.4 ± 0.1
105 ± 3
100 ± 2
100 ± 2
100 ± 2
113 ± 15
107 ± 4
103 ± 3
102 ± 3
102 ± 3
94 ± 3
172 ± 15
111 ± 6
93 ± 6
83 ± 6
109 ± 3
Methanol solution
CEVE
BCIPE
BCEE
BCEXM
BPPE
9.
5.
14.
5.
2 ±
7 ±
0 ±
4 ±
0.
0.
0.
0.
5
2
6
1
105 ±
98 ±
100 ±
111 ±
7
2
2
14
99
96
100
96
± 2
± 3
± 3
± 4
130
114
93
109
+
+
+
+
2
2
2
3
42
-------
These statistics show that CEVE is very unstable in methanol.
In the initial analysis of the methanol solution, we were unable
to arrive at an acceptable concentration for CEVE. The concen-
tration of CEVE in methanol was a steadily decreasing value with
time. This is due largely to the rapid hydrolysis of CEVE in
methanol. By the time the 30 day samples were analyzed, the
CEVE had hydrolyzed completely and we were unable to detect any
CEVE. Inspection of the data in Table 34 seems to indicate that,
except for CEVE, which has since been dropped from the study be-
cause of its volatility, the compounds are stable in both acetone
and methanol.
There is some fluctuation in data of the samples over the varying
time periods. This is attributed largely to the impurities in
BCIPE and their decomposition and interference. The purest
sample of BCIPE that could be obtained still contained over 30
electron-capturing impurities, many of which had retention times
near those of the other haloethers. These impurities made the
analysis very difficult. Because of these impurity interfer-
ences, we were unable to obtain any data regarding the growth
of degradation peaks from the original haloether compounds. A
sample chromatogram showing the elctron-capturing impurities in
BCIPE is shown in Figure 7 (see page 25).
43
-------
SECTION 8
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 acetontrile overnight; then Soxhlet
extracted with methanol overnight. The resin was then stored
in methanol. They were packed into columns (10 mm ID) to a
depth of 6 cm. Buffered solutions (of pH 2, pH 7, and pH 10)
were prepared in the manner described for the extraction studies
(Section 5). One-liter portions of the buffers were then spiked
with 100 uL of the concentrated haloether solutions and passed
through the resin beds. The beds were then eluted using 150 mL
of ethyl ether for the XAD-2 and 150 mL of acetone for the
Ambersorb XE-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 worked well on both counts, and the recovery data are
presented in Tables 35-37 for pH values of 2, 7, and 10. Due
to the high volatility of CEVE, we were unable to recover any
appreciable amounts of the compound. Analysis of the data using
the F test showed no significant variation in the percent re-
covery at any of the three pH values used.
TABLE 35. STATISTICAL DATA FOR XAD-2 RESIN AT pH 2
Ether
CEVE a
BCIPE #1
#2
#3
BCEE # 1
12
#3
BCEXM #1
#2
#3
BPPE fl
#2
#3
Perc
reoov
62.
71.
79.
40.
47.
47.
59.
67.
77.
69.
81.
81.
Average
:ent percent
•ered recovered
2
7 71.2
7
4
4 45.0
2
3
3 67.9
3
9
7 77.7
6
Rel. std.
Std. dev. dev. , %
8.8 12.3
4.0 8.9
9.0 13.3
6.8 8.7
Insufficient data for statistics.
44
-------
TABLE 36. STATISTICAL DATA FOR XAD-2 RESIN AT pH 7
Ether
CEVEa
BCIPE #1
#2
#3
BCEE # 1
#2
#3
BCEXM #1
#2
#3
BPPE #1
#2
#3
Percent
recovered
58.0
76.2
77.8
43.8
56.1
54.3
59.0
69.8
77.9
65.6
67.2
82.7
Average
percent Rel. std.
recovered Std. dev. dev. , %
70.7 11.0 15.5
51.4 6.7 12.9
68.9 9.5 13.7
71.8 9.4 13.1
Insufficient data for
TABLE
statistics.
37. STATISTICAL DATA FOR XAD-2 AT pH 10
Ether
CEVEa
BCIPE #1
#2
#3
BCEE tl
#2
#3
BCEXM #1
#2
#3
BPPE #1
#2
#3
Percent
recovered
80.9
68.7
83.6
54.8
52.8
65.7
84.8
66.9
81.6
78.0
69.2
78.0
Average
percent Rel. std.
recovered Std. dev. dev. , %
77.8 7.9 10.2
57.8 7.0 12.0
77.8 9.6 12.3
75.1 5.1 6.7
Insufficient data for statistics.
45
-------
In comparing the resin sorption method of sampling and analysis
with the grab and extraction method, we see that each has its
own advantages and disadvantages. Grab sampling requires only
an adjustment to neutral pH and is therefore very simple in com-
parison with pumping an exact amount of sample through the resin
tube. Neither method requires refrigeration. The resin method
requires considerable preparation i.e., Soxhlet extraction and
tube packing. The grab sampling, on the other hand, requires
only a one gallon bottle. The resin tubes are smaller and would
be easier and cheaper to ship than the gallon bottles which
weigh about 9 pounds each.
The resin method seems to give recovery data equal to the grab
and extraction method. Serious consideration should be given
to this method as an alternative.
46
-------
SECTION 9
COLUMN CHROMATOGRAPHY STUDIES
Column chromatography studies were conducted to find a chromato-
graphic medium sufficient for the removal of potential interfer-
ences that may be encountered in actual industrial wastewaters.
Column Packed with Florisil
Four columns were packed with Florisil and eluted with 200 mL of
varying concentrations of ethyl ether in petroleum ether accord-
ing to the Method for Organochlorine Pesticides in Industrial
Effluents (43).
Data for the recovery of the six haloethers from the Florisil
columns are listed in Table 38. The samples were run simulta-
neously using a Hall Model 700 detector and a FID, as well as a
Hall Model 310 detector. Table 38 provides the average recovery
for the three detectors.
TABLE 38. AVERAGE RECOVERY PERCENT (THREE DETECTORS)
OF HALOETHERS ON CHROMATOGRAPHIC COLUMN
PACKED WITH FLORISIL AND ELUTED WITH
200 mL 6% ETHYL ETHER IN PETROLEUM ETHER
Ether
CEVE
BCIPE
BCEE
BCEXM
CPPE
BPPE
Average
percent
recovered
(3 detectors)
6.8
82.1
79.0
71.6
78.5
80.9
Average
standard
deviation
4.2
2.7
2.6
8.6
4.7
5.2
Relative
standard
deviation,
percent
61. 8a
3.3
3.3
12.0
6.0
6.4
aTwo detectors (not detected on FID due to
solvent venting).
(43) Determination of Organochlorine Pesticides in Industrial
Effluents. Federal Register, 38(125):17319, Part II,
Appendix II, 29 June 1975.
47
-------
Most of the haloethers elute in the 6% ethyl ether fraction, as
shown in Table 38, with only a slight amount (10%) of BCEXM
eluting in the second or 15% ethyl ether fraction. None of the
haloethers were detected in the 50% ethyl ether fraction. Fur-
ther studies showed that 300 inL of 6% ethyl ether in petroleum
ether was sufficient to remove all (including BCEXM) of the
haloethers from the column.
Column Packed with Silica Gel
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 concentrations (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
are shown in Table 39. Since the data were so erratic, the
analyses were repeated. These results are shown in Table 40.
Faced with another set of erratic data, it was decided to start
again with a repeat experiment. The resulting fractions were
analyzed with the FID (Table 41) and the Hall Model 700 detector
(Table 42). The recovery of the six haloethers was very erratic
and did not reproduce from one replicate to the other. There-
fore, Florisil appeared to be the packing of choice for the
sample cleanup. Because of the erratic data shown in Tables
39-42, the use of silica gel was not explored further as a column
cleanup media. It was further concluded that 300 mL eluate of
6% ethyl ether in petroleum ether is needed to get complete
release of all the haloethers from the Florisil.
48
-------
TABLE 39. RECOVERY OF HALOETHERS ON CHROMATOGRAPH1C COLUMN
PACKED WITH SILICA GEL AND ELUTED WITH METHYLENE
CHLORIDE IN HEXANE - FIRST FID ANALYSIS
Percent recovered
Haloether
Using 5% MeCla in Hexane
CEVE
BCIPE
BCEE
BCEXM
CPPEa
BPPE
Using 10% MeCla in Hexane
CEVE
BCIPE
BCEE
BCEXM
CPPEa
BPPE
Using 20% MeCla in Hexane
CEVE
BCIPE
BCEE
BCEXM
CPPEa
BPPE
Using 30% MeCla in Hexane
CEVE
BCIPE
BCEE
BCEXM
CPPEa
BPPE
Using 50% MeCla in Hexane
CEVE
BCIPE
BCEE
BCEXM
CPPEa
BPPE
Total Elution
CEVE
BCIPE
BCEE
BCEXM
CPPEa
BPPE
No. 1
w
-
3.4
0.4
100.7
_
4.9
4.5
0.7
~
_
71.3
53.7
—
~
_
1.9
22.5
0.2
—
_
0.2
—
43.3
—
•»
78.3
84.1
44.6
100^.7
No. 2
_
0.6
8.4
-
101.1
_
2.9
4.8
-
~
_
90.8
80.4
—
~
_
1.8
40.3
68.7
~
-
0.2
—
27.6
—
_
96.3
133.9
96.3
101.1
No. 3
_
1.0
14.5
5.4
100.3
-
7.4
4.9
-
— *
-
99.7
107.8
—
™
-
5.4
50.7
0.8
"™
-
-
—
8.6
™
_
113.5
177.9
1 14.8
100.3
No. 4
-
1.1
-
5.3
100.5
-
19.0
4.9
2.7
"
-
87.1
79.5
~
~
-
2.5
59.5
46.5
"
-
0.2
_
19.9
"
_
109.9
143.9
74.4
100.5
included.
49
-------
TABLE 40. RECOVERY OF HALOETHERS ON CHROMATOGRAPHIC COLUMN
PACKED WITH SILICA GEL AND ELUTED WITH METHYLENE
CHLORIDE IN HEXANE - SECOND FID ANALYSIS
Haloether
Using 5% MeCla in Hexane
CEVE
BCIPE
BCEE
BCEXM
CPPEa
BPPE
Using 10% MeCl2 in Hexane
CEVE
BCIPE v
BCEE
BCEXM
CPPEa
BPPE
Using 20% MeCl2 in Hexane
CEVE
BCIPE
BCEE
BCEXM
CPPEa
BPPE
Using 30% MeCla in Hexane
CEVE
BCIPE
BCEE
BCEXM
CPPEa
BPPE
Using 50% MeCla in Hexane
CEVE
BCIPE
BCEE
BCEXM
CPPEa
BPPE
Total Elution
CEVE
BCIPE
BCEE
BCEXM
CPPEa
BPPE
Percent
No. 1
^
-
4.2
7.9
107.9
_,
4.7
4.2
_
-
_
68.4
51.9
.
-
_
2.1
22.7
_
-
_
0.2
-
60.2
-
_
75.4
83.0
68.1
107.9
No. 2
—
0.5
8.2
—
105.7
_
2.9
4.7
_
-
_
88.9
80.4
_
-
_
1.7
40.0
73.2
-
_
0.3
-
29.3
-
_
94.3
133.3
102.5
105.7
recovered
No. 3
—
1.0
-
5.7
101.0
_
7.1
4.7
_
-
_
96.5
104.8
-
-
_
5.8
51.6
0.8
-
_
-
-
8.8
-
_
110.4
161.1
15.3
101.0
No. 4
^
1.0
—
5.6
100.7
—
18.8
4.8
_
-
_
86.6
79.9
_
-
_
2.5
61.0
50.6
-
_
_
-
26.6
-
_
108.9
145.7
82.8
100.7
aNot included.
50
-------
TABLE 41. RECOVERY OF HALOETHERS ON CHROMATOGRAPHIC COLUMN
PACKED WITH SILICA GEL AND ELUTED WITH METHYLENE
CHLORIDE IN HEXANE - THIRD FID ANALYSIS
Baloether
Using 5% MeCla in Hexane
CEVE
BCIPE
BCEE
BCEXM
CPPE
BPPE
Using 10% MeCla in Hexane
CEVE
BCIPE
BCEE
BCEXM
• CPPE
BPPE
Using 20% MeCla in Hexane
CEVE
BCIPE
BCEE
BCEXM
CPPE
BPPE
Using 30% MeCla in Hexane
CEVE
BCIPE
BCEE
BCEXM
CPPE
BPPE
Using 50% MeCla in Hexane
CEVE
BCIPE
BCEE
BCEXM
CPPE
BPPE
Total Elution
CEVE
BCIPE
BCEE
BCEXM
CPPE
BPPE
Percent recovered
No. 1 No. 2 No. 3 No.
_ .. _
- -
_
_ _ -
10.7 40.3 7.7 10
6.4 39.6 5.5 7
3.5
27
- 100
_ -. _
65.7 36.2 46.5
66.9 35.0 45.2 1
— — —
4.1
_
_ _ _
44.0
44.5 1.4
— - —
80.8 58.6 66
29.5 2
_
_ _ _
1.3
_ _ _
41.3 13.9 6.1 20
65.7 36.8 74
_ _ _
_ _ _
1.6 0.7
3.5
41.3 94.7 68.8 114
65.7 66.3 177
_ _ _
120.4 76.5 54.2 10
120.7 76.7 50.7 8
4
_
-
-
-
.3
.0
.
.2
.1
-
-
.0
_
-
-
-
-
-
_
.6
.3
-
-
—
_
.7
.8
-
-
—
—
.5
.2
-
.3
.'0
51
-------
TABLE 42. RECOVERY OF HALOETHERS ON CHROMATOGRAPHIC COLUMN
PACKED WITH SILICA GEL AND ELUTED WITH METHYLENE
CHLORIDE IN HEXANE - (HALL MODEL 700)
Haloether
Percent recoverea
No. 1No. 2No. 3No. 4
Using 5% MeCla in Hexane
CEVE
BCIPE
BCEE
BCEXM
CPPE
BPPE
Using 10% MeCla in Hexane
CEVE
BCIPE
BCEE
BCEXM
CPPE
BPPE
Using 20% MeCl2 in Hexane
0.1 0.1
6.9 41.3
4.1 31.9
8.5
5.4
4.3
0.3
0.1
59.6
33.2 48.8
64.1 27.9 35.4
0.1
8.6
4.9
27.2
94.5
1.0
1.0
CEVE
BCIPE
BCEE
BCEXM
CPPE
BPPE
Using 30% MeCla in Hexane
CEVE
BCIPE
BCEE
BCEXM
CPPE
BPPE
Using 50% MeCl2 in Hexane
CEVE
BCIPE
BCEE
BCEXM
CPPE
BPPE
Total Elution
CEVE
BCIPE
BCEE
BCEXM
CPPE
BPPE
-
-
-
0.1
38.9
38.9
1.7
-
0.1
0.2
0.4
0.4
_
43.1
2.5
0.1
0.2
0.7
1.7
43.1
2.6
0.6
106.0
108.2
-
-
-
-
0.5
1.1
0.3
82.9
-
-
0.7
-
_
14.5
65.1
0.1
-
0.6
8.8
97.4
65.1
0.2
75.7
61.5
1.6
4.3
0.1
0.1
1.3
0.4
_a
_a
_a
_a
_a
_a
_
6.3
35.9
-
0.2
0.2
1.9
10.6
36.0
0.1
55.7
40.3
1.7
-
-
-
-
—
_
68.1
4.1
-
-
-
-
21.9
76.2
-
0.4
0.2
1.7
117.2
174.8
0.1
10.0
6.1
aMissing.
52
-------
SECTION 10
APPLICATION OF METHOD TO WASTEWATER SAMPLES
Wastewater samples were obtained from a municipal secondary waste
treatment plant and three industrial sites. Each of these four
samples was divided into seventeen one-liter portions as shown
in Table 43. The spiked samples were one-liter portions of
wastewater spiked with 100 uL of a solution containing the con-
centrations of the six haloethers listed in Table 44. These
concentrations are equal to 1,000 times the baseline noise for
either the Hall electrolytic conductivity detector or the flame
ionization detector, depending which was least sensitive for
that particular haloether.
TABLE 43. DISTRIBUTION OF WASTEWATER SAMPLE PORTIONS
No< of
1-liter
Sample portions
Blank 1
Spiked as received for extraction 3
Spiked as received for XAD 3
Blank for XAD 1
Spiked storage 7 days at 4°C, for extraction 3
Spiked storage 7 days at 25°C, for extraction 3
Spiked storage 7 days at 4°C, for XAD 3
TABLE 44. CONCENTRATION OF HALOETHERS
IN SPIKING SOLUTION
Concentration,
Haloether mg/mL
CEVE
BCEE
BCIPE
BCEXM
CPPE
BPPE
1.17
0.97
0.54
1.38
0.3
0.14
53
-------
The samples were extracted with three 60 mL portions of methylene
chloride. These three portions were combined, dried with sodium
sulfate, concentrated with hexane, and eluted from Florisil using
300 mL of a solution containing 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 43 shows that the XAD resin sorption method
was also used to prepare samples fr analysis. In this procedure
the wastewater samples were spiked and run through the resin
procedure as described in Section 8. The samples were then
either stripped and analyzed immediately or stored for 7 days
at 4°C and then stripped and analyzed.
All of the analyses were done using the Hall electrolytic con-
ductivity detector with a column packed with 3% SP-1000. The
municipal wastewater was the first to be analyzed. The results
of these analyses are shown in Table 45. This table shows
results based on both peak area and peak amplitude as determined
by a Hewlett-Packard computer integrator.
TABLE 45. RECOVERY OF HALOETHERS FROM WASTEWATER FROM
MUNICIPAL SECONDARY WASTE TREATMENT PLANT
USING COLUMN PACKED WITH SP-1000 AND HALL
ELECTROLYTIC CONDUCTIVITY DETECTOR
Sample condition
Spiked, as received,
extracted (3 samples)
Spiked, as received,
XAD- 2 (3 samples)
Spiked, storage at
25°C, extracted
( 3 samples )
Spiked, storage at 4°C,
(3 samples)
Haloether
CEVE
BCIPE
BCEE
BCEXM
CPPE
BPPE
CEVE
BCIPE
BCEE
BCEXM
CPPE
BPPE
CEVE
BCIPE
BCEE
BCEXM
CPPE
BPPE
CEVE
BCIPE
BCEE
BCEXM
CPPE
BPPE
Based on
Percent
recovered
9.28
72.17
70.67
75.36
80.93
92.28
8.59
65.33
51.58
64.58
63.30
89.60
21.43
85.00
83.91
85.06
97.50
159.85
11.94
74.61
71.17
73.35
78.22
85.49
peak area
Rel. std.
dev . , %
32.5
2.9
7.7
4.4
11.6
55.7
35.6
12.0
11.5
13.6
20.1
51.6
22.5
6.4
11.1
8.2
14.4
60.9
16.1
10.1
10.0
6.4
14.4
9.7
Based on
peak amplitude
Percent
recovered
16.66
67.86
64.59
68.36
73.17
81.26
13.31
58.6
47.33
55.95
64.39
. 73.81
21.57
60.77
58.29
59.58
64.59
71.95
20.32
73.73
71.32
74.25
76.72
75.62
Rel. std.
dev. , %
4.3
14.3
17.5
19.2
16.2
8.8
10.5 '
4.6
5.6
4.1
0.3
5.5
9.3
7.6
7.1
9.3
7.1
7.3
2.8
1.2
1.9 '
1.3
2.0
1.2
54
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No final conclusions could be drawn from Table 45 because of
the unresolved question of peak areas versus amplitudes. There-
fore, an experiment was devised to determine which method of
measurement gave more consistent results. The average results
for five analyses of a standard sample with the Hall detector
are listed in Table 46. An improvement of the relative standard
deviation was noted in almost all cases for the results cal-
culated using amplitudes as compared to those calculated using
areas. Therefore, it was decided to use peak amplitude in the
rest of the analyses.
TABLE 46. AVERAGE RESULTS FOR FIVE ANALYSES OF
HALOETHER STANDARD ANALYZED ON COLUMN
PACKED WITH SP-1000 AND USING HALL
ELECTROLYTIC CONDUCTIVITY DETECTOR
Relative standard
deviation, %
Haloether
CEVE
BCIPE
BCEE
BCEXM
CPPE
BPPE
Concentration ,
yg/mL
23.4
10.8
19.4
27.6
6.0
2.8
Based on
peak area
10.5
3.9
3.2
4.4
7.8
17.8
Based on
peak amplitude
4.0
2.2
1.4
2.4
2.2
3.6
After the decision was made to use peak amplitude, the rest of
the wastewater analyses were completed. The blank samples
(except for 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 overshadowed all
compounds near them. The data for recovery of the haloethers
from the wastewaters are shown in Table 47. A "t" test was
conducted on the data from the three sites; the values for these
sets are listed in Table 48. The "t" values were generated by
the following comparison.
The mathematical formula used in calculating the "t" values was:
- Xa|
S2
55
-------
Ul
TABLE 47. PERCENT RECOVERIES OF HALOETHERS FROM INDUSTRIAL AND MUNICIPAL WASTEWATER
(DETERMINED BY PEAK AMPLITUDE) USING COLUMN PACKED WITH SP-1000 AND
HALL ELECTROLYTIC DETECTOR (AVERAGE OF THREE SAMPLES)
As received
Percent Percent
Sample recovered RSD
Industrial tl
BCIPE
BCEE
BCEXM
CPPE
BPPE
Industrial 12
BCIPE
BCEE
BCEXM
CPPE
BPPE
Industrial #3a
Municipal fl
BCIPE
BCEE
BCEXM
CPPE
BPPE
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
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
58.6
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.S
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
Unable to obtain recovery data because of interferences.
-------
TABLE 48. "t" VALUES FOR THREE SETS OF WASTEWATER SAMPLES
Sample
Industrial
Industrial
Municipal
Haloether
#1 BCIPE
BCEE
BCEXM
CPPE
BPPE
#2 BCIPE
BCEE
BCEXM
CPPE
BPPE
BCIPE
BCEE
BCEXM
CPPE
BPPE
A/B B/C
1.52 0.23
5.08 2.52
3.90 0.92
0.46 1.71
1.57 3.68
1.43 0.41
0.99 0.14
2.15 0.75
2.16 1.33
0.98 2.01
1.14 4.42
0.91 5.17
1.07 4.22
1.16 4.69
1.81 1.17
A/C
2.39
1.63
3.30
2.22
2.33
1.76
1.08
2.38
3.91
2.23
1.03
1.03
0.65
0.51
1.36
A/D
13.85
8.06
7.41
2.88
2.23
11.53
19.77
4.84
4.57
8.22
1.60
2.60
2.39
1.28
1.57
D/E
3.41
2.82
2.46
1.58
2.20
0.89
0.76
0.97
0
1.72
2.93
4.90
0.57
0.50
0.34
Note: A/B:
A/C:
B/C:
A/D:
D/E:
Initial (A)
Initial (A)
25°C (B) to
Initial (A)
XAD-2 (D) to
to 25°C (B)
to 4°C (C)
4°C (C)
to XAD-2 (D)
XAD-2/week (E)
where Xi and X2 are the values of the two samples being compared
and Si and S2 are the standard deviation of each. If the "t"
value is >2.776, then there is a 95% probability that the two
data points are not from the same population. If the "t" value
is >8.610, the probability of the two data points being from
different populations is 99.9%. Observation of the data from
Table 48 seems to indicate that, on the whole, there is not much
difference in the samples extracted initially or stored at 25°C
and 4°C. There is, however, a statistical 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.
The method application study determined the effectiveness of the
elements in the Phase I research. Experience indicates that most
elements of the study have been resolved. The 3% SP-1000 on
Supelcoport performed without failure. The Hall detector proved
to be a reliable system when proper precuations were observed,
and the current GC temperature program gives well defined results
within an efficient time frame. Interferences, however, may
prove to be a significant limitation to the application of the
57
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method. Many non-halogenated compounds were identified in waste-
water samples by GC/MS which gave significant peaks on the Hall
detector spectra. Wastewater #3 of this study, in particular,
confirmed potential interference problems with the extraction-
cleanup procedure/detector system used. Since both liquid/
liquid extraction and XAD resin sorption give good recovery
data, further research could determine if XAD resins could
reduce the interferences which were observed in various waste-
water types.
It has been shown that the haloethers have no special "storage
problems. However, special storage is indicated for biologically
active wastewaters because of possible composition changes which
may interfere with haloether detection.
58
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23. Webb, R. G., A. W. Garrison, L. H. Keith, and J. M. McGuire.
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Appendix II, 29 June 1975.
62
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APPENDIX A
METHOD FOR SAMPLING AND ANALYSIS
During the first year of this contract, a complete method was
developed for the sampling and analysis of haloether in water and
wastewater. The method involves a liquid-liquid extraction using
methylene chloride, a solvent exchange with hexane, a Florisil-
column chromatographic cleanup procedure, and subsequent analysis
by gas chromatography using an electrolytic conductivity detector.
A detailed description of this method is provided below.
Scope and Application
This method covers the determination of the following halogenated
ethers in wastewaters:
• 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)
Summary
This method offers an alternative to the high cost and technical
expertise required for the analysis of haloethers by gas chroma-
tography/mass spectrometry. The procedure involves a liquid-
liquid extraction using methylene chloride and a column chromato-
graphic cleanup procedure to remove potential interferences. The
samples are then analyzed by gas chromatography using an electro-
lytic conductivity detector.
Apparatus and Reagents Required
For sample extraction, the following are required:
• 2,000-mL separatory funnel with Teflon stopcock
• 8-ounce Boston round bottle (glass)
• 4-dram vials (glass) and caps with conical polyethylene
liners
63
-------
• Funnel (60-mm diameter)
• Glass beads (2-mm diameter)
• Aluminum foil
• Kuderna-Danish (K-D) glassware with three-ball (micro)
Sny'der column, 500-mL evaporation flask, and 10-mL
receiver ampule
• Extracting solvent - methylene chloride, "distilled in glass"
• Sodium sulfate - (ACS) granular, anhydrous (400°C for
4 hours
For chromatographic cleanup, the following are required:
• Florisil - 60/100 mesh
• Chromatographic columns - 11 mm ID x 300 mm long with
250-ml reservoir (KIMAX) with removal Teflon stopcocks
• Glass wool
• Kuderna-Danish evaporators with three-ball (macro) Snyder
column, 500-mL evaporation flask, and 10-mL receiver ampule
• 4-dram vials (glass) and caps with conical polyethylene
liners
• Septum-capped, glass, sample vials
• Sodium sulfate - (ACS) granular, anhydrous (400°C for
4 hours)
• Petroleum ether - "distilled in glass"
• Ethyl ether - (ACS) reagent grade
• Hexane - "distilled in glass"
• Laurie acid - reagent grade
• Sodium hydroxide - (ACS) reagent grade
For sample analysis, the following are required:
• Gas chromatograph - temperature programmable
• Detector - electrolytic conductivity
• Glass column - 2.1 mm ID x 1.8 m long
• Column packing - 3% SP-1000 on 100/120-mesh Supelcoport
• 10-yl syringe
• Carrier and auxilliary gases - helium and hydrogen, pure
grades, to preserve column life and avoid interferences
• Haloethers standards - Commercial sources of haloether
are listed below:
64
-------
Compound Commercial source
BCIPE Monsanto Research Corporation,
Dayton, Ohio 45407
BCEE RFR Corp., Hope, Rhode Island 02831
BCEXM Pfaltz & Bauer, Stamford, Conn. 06902
CPPE RFR Corp., Hope, Rhode Island 02831
BPPE Pflatz & Bauer, Stamford, Conn. 06.902
• Ethanol - absolute (95%)
• Deionized water
Sampling and Preservation Procedure
Collect samples in one-liter glass containers having an inert
liner (Teflon) incorporated in the cap. Prewash and solvent
rinse the containers prior to sampling to prevent interferences.
Follow conventional sampling practices.
Preserve the samples by sealing the bottle lids with a plastic
tape and icing for shipment.
Sample Extraction Procedure
(I) Transfer a measured 1,000 mL of sample from the container
to a two-liter separatory funnel. Discard the balance of
the water from the container.
(2) Add 60 mL of the extracting solvent (methylene chloride) to
the sample container and shake vigorously to rinse the bottle
thoroughly. Transfer the solvent to the separatory funnel
and shake the separatory funnel vigorously for 2 minutes.
(3) Allow the two phases to separate and draw the bottom (methy-
lene chloride) layer into an 8-ounce Boston round bottle.
(4) Repeat Steps (2) and (3) two more times.
(5) Plug a standard laboratory funnel with glass wool and fill
with approximately 40 mm of anhydrous, granular sodium
sulfate.
(6) Pass the collected fractions through the sodium sulfate and
collect in a 500-mL K-D flask.
(7) Rinse the 8-ounce Boston round bottle with approximately
50 mL of methylene chloride, pass it through the sodium sul-
fate, and collect in the 500-mL K-D flask.
65
-------
(8) Place two glass beads into the flask, attach the three-ball
Synder column to the flask, and place the lower half of the
ampule in a steam bath.
(9) Insulate the K-D flask with aluminum foil to complete the
evaporation in approximately 10-15 minutes.
(10) When the volume of the methylene chloride in the flask
reaches approximately 10 mL, pour 50 mL of hexane in the
top of the Snyder column. Be sure that there is a good
washing of the walls of the Snyder column when the hexane
passes down to the flask.
(11) Evaporate until the ampule is nearly dry. Drain the con-
densed vapors from the column into the cooled flask to
obtain a final volume of approximately 6 mL.
(12) Rinse the Snyder column and walls of the K-D flask with an
additional 1 mL of hexane.
(13) Remove the Snyder column and flask from the ampule.
(14) Transfer the concentrate to a 4-dram vial. Rinse the ampule
with 1 mL of hexane and also transfer to the vial. Cap and
seal the vial, and store in a cool, dark place to await
column chromatography (volume at this point will equal
^8 mL).
Quantitation Procedure
Complete the quantitative measurements using gas chromatography
with an electrolytic conductivity detector at the conditions
listed below:
Item Value/description
Carrier gas Helium at 40 mL/min
Temperature program 60°C with 2 min post-script, then 8°C/min to
230°C with a 4-min hold
Column and packing 1.8 m x 2.1 mm ID glass packed with 3% SP-1000
on 100/200 mesh Supelcoport
Injection port temperature 250°C
Detector conditions Tracor Model 700 Hall electrolytic conductivity
detector or equivalent halogen selective de-
tector. Furnace temperature at 900°C; trans-
fer line temperature at 250°C. Absolute
ethanol (95%) electrolyte at 0.3 mL/min.
66
-------
Take the vials containing the samples and transfer the contents
of each to a 10-mL volumetric flask. Rinse each vial with a
total of 1 mL of hexane, transfer to flask and rinse again
(rinses should equal ^1 mL). Dilute each sample to exactly 10 mL
using more hexane. Transfer the contents to each flask into
septum-capped vials for gas chromatography and possible column
chromatography.
Dilute the standard solutions containing haloethers in the con-
centrations shown below, by injecting 80 yL into 4 mL of hexane.
The dilute solution is the gas chromatography standard and is 20
times baseline noise.
Haloether Concentration/ ug/mL
BCIPE 120
BCEE 70
BCEXM 50
CPPE 300
BPPE 150
The above concentrations are equal to 1,000 times the baseling
noise for each compound on the Tracer Model 700 Hall electrolytic
conductivity detector.
Procedure for Removal of Interference
Remove interference by Florisil column adsorption chromatography
using the following procedure which has been taken from the
"Method for Organochlorine Pesticides in Industrial Effluents"
(43) .
Place a charge of activated Florisil (weight determined by lauric
acid value as described in Appendix B) in a glass chromatography
column. After settling the Florisil by tapping the column, add
about 15 mm of granular, anhydrous sodium sulfate to the top of
the Florisil.
Pre-elute the column, after cooling, with 50-60 mL of petroleum
ether. Discard the eluate. Just prior to exposure of the sul-
fate layer to air, quantitatively transfer the sample exact
(either the contents of the 4-dram vial or the contents of the
10-mL volumetric flask) onto the column by decantation and sub-
sequent petroleum ether washings. Charge eluate to 300 mL of 6%
ethyl ether in petroleum ether. Adjust the elution rate to 5 mL/
rain and collect the eluate in a 500-mL K-D flask equipped with a
10-mL ampule.
Concentrate the eluate to approximately 6 mL in a K-D evaporation
system using a steam bath, transfer to a 10-mL volumetric flask
with subsequent rinsings, and dilute to exactly 10 mL.
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Transfer to a septum-capped vial, and analyze by gas
chromatography.
Quality Assurance Practice
Use standard quality assurance practices with this method.
Collect field replicates to validate the precision of the samp
ling technique. Analyze laboratory replicates to validate the
precision of the analysis. Analyze fortified samples to vali-
date the accurracy of the analysis.
Calculations and Reporting
Determine the concentration in the sample according to the
following formula:
microgram/liter =
where A = ng standard/standard area, integrator counts or cm2
B = sample aliquot area, integrator counts or cm2
Vt = volume of total extract, mL
Vi = volume of extract injected, y.
Vs = volume of water extracted, £
Report results in micrograms per liter without corrections for
recovery data. When duplicate and spiked samples are analyzed,
report all data obtained.
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APPENDIX B
STANDARDIZATION OF FLORISIL
This rapid method for determining the adsorptive capacity of
Florisil is based on the adsorption of lauric acid from hexane
solution. An excess of lauric acid is used and the amount not
adsorbed is measured by alkali tritration. The weight of lauric
acid adsorbed is used to calculate, by simple proportion, the
equivalent quantities of Florisil for batches having different
adsorptive capacities.
Apparatus Required
(1) 25-mL buret with 1/10 mL graduations
(2) Erlenmeyer flasks - 125 mL narrow mouth and 25 mL
glass stoppered
(3) Pipette - 10 mL and 20 mL transfer type
(4) 500-mL volumetric flasks
Reagents and Solvents Required
(1) Ethyl alcohol - USP or absolute, neutralized to
phenolphthalein
(2) Hexane - "distilled in glass"
(3) Lauric acid - purified, CP
(4) Lauric acid solution prepared by transferring, 10,000 gram
lauric acid to a 500-mL volumetric flask, dissolving in
hexane, and diluting to 500 mL (1 mL = 20 mg)
(5) Phenolphthalein Indicator - dissolve 1 gram in alcohol and
dilute to 100 mL
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(6) Sodium hydroxide - dissolve 20 grains of NaOH (pellets,
reagent grade) in water and dilute to 500 m: (IN). Dilute
25 mL of IN NaOH to 500 mL with water (0.05N). Standardize
as follows: Weigh 100-200 mg lauric acid into 125 mL
Erlenmeyer flask; add 50 mL of neutralized ethyl alcohol and
3 drops phenolphthalein indicator; titrate to permanent end
point; calculate mg lauric acid/mL of 0.05N NaOH (about
10 mg/mL).
Procedure
(1) Transfer 2.000 gram Florisil to 25-mL glass-stoppered
Erlenmeyer flasks. Cover loosely with aluminum foil and
heat overnight at 130°C. Stopper, cool to room temperature,
add 20.0 mL lauric acid solution (400 mg), stopper, and
shake occasionally for 15 minutes. Let absorbant settle and
pipette 10.0 mL of supernatant into 125-mL Erlenmeyer flask.
Avoid inclusion of any Florisil.
(2) Add 50 mL of neutral alcohol and 3 drops indicator solution;
titrate with o.OSN to a permanent end point.
Calculation of Lauric Acid Value and Adjustment of Column Weight
(1) Calculate the amount of lauric acid adsorbed on Florisil as
follows:
lauric acid value = mg lauric acid/gram of Florisil
= 200 - [(mL required for titration)
x (mg lauric acid/,1 O.OSN NaOH)]
(2) To obtain an equivalent quantity of any batch of Florisil,
divide 110 by lauric acid value for that bath and multiply by
20 g.
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