Prcpublication Copy
EPA 600/D-81-060
Comparison of Grob Closed-Loop-Stripping Analysis (CLSA)
to Other Trace Organic Methods
R.G. Melton, W.E. Coleman, R.W. Slater, F.C. Kopfler
W.K. Allen, T.A. Aurand, D.E. Mitchell, and S.J. Voto
U.S. Environmental Protection Agency
Health Effects Research Laboratory
Cincinnati, Ohio 45268
S.V. Lucas and S.C. Watson
Battelle Columbus Laboratories
Columbus, Ohio 43201
Presented at: The Second Chemical Congress of the
North American Continent, August 25, 1980,
Las Vegas, NV.
Submitted for publication: Advances in_ the Identification and Analysis of
Organic Pollutants in Water, II, (L.H. Keith, ed.), Ann Arbor Sci. Pub.
Inc.V Ann Arbor, MI (1981).
February, 1981
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PRE—PUBLICATION COPY
Comparison of Grob Closed—Loop—Stripping Analysis (CLSA)
to Other Trace Organic Methods
by
R.G. Melton, W.E. Coleman, R.W. Slater, F.C. Kopfler,
W.K. Allen, T.A.. Aurand, D.E. Mitchell, and S.J. Voto
U.S. Environmental Protection Agency
Health Effects Research Laboratory
Cincinnati, Ohio 45268
S.V. Lucas and S.C. Watson
Batelle Columbus Laboratories
Columbus, Ohio 43201
ABSTRACT
This paper presents a comparison of experimental results from the
analysis of drinking water before and after water treatment using 1 million
gallon per day (mgpd) granular activated carbon (GAC) contactors at the
Cincinnati Water Works. The following methods of organic analysis were
used:
1) Grob closed—loop scrippiñg analysis (CLSA) using capillary
GC/MS/DS.
2) Bellar purge and trap (P&T) using packed column GC/Hall/DS, ie,
EPA Method 601.
3) Batch Liquid — Liquid Extraction (BLLE) using capillary Gd—
MS/DS, and
4) XAD—2 adsorption — ethyl ether elution (XAD—EEE) capillary
GC/MS/DS.
At least twice as many “consent decree” organics (23) and the “EPA
Office of Drinking Water chemical indicators of industrial contamination”
(18) were measured by Grob CLSA than by Bellar P&T, BLLE, and XAD—EEE
analyses. Furthermore, Grob CLSA produced this superior analysis at a low
cost—per—compound—analyzed figure. Of the 183 different organics which
were measured by the four methods, six organics were detected by Bellar
P&T, 107 by Grob CLSA, 90 by BLLE, and 58 by XAD—EEE analysis. A historical
review of Grob CLSA is presented, as well as a brief review of current U.S.
P&T methods. The design of a superior analytical scheme for the
comprehensive analyses of purgeable organics in drinking water is in-
dicated by the data. The combined use of Bellar P&T (EPA Methods 601 or
502), Grob CLSA, and BLLE analyses provides useful data on the level of
many EPA regulated organics in drinking water.
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PRE-PUBLICATION COPY
Comparison of Grob Closed-Loop-Stripping Analysis (CLSA)
to Other Trace Organic Methods
by
R.G. Melton, W.E. Coleman, R.W. Slater, F.C. Kopfler
W.K. Allen, T.A. Aurand, D.E. Mitchell, and S.J. Voto
U.S. Environmental Protection Agency
Health Effects Research Laboratory
Cincinnati, Ohio 45268
S.V. Lucas and S.C. Watson
Battelle Columbus Laboratories
Columbus, Ohio 43201
The Exposure Evaluation Branch of the Health Effects Research Laboratory,
Cincinnati, Ohio, (HERL-CI) is responsible for validating sensitive and
reproducible organic analysis procedures which are used in our research to
determine the health effects of chemical contaminants of drinking water. The
data presented were obtained in January 1980, when HERL-CI was evaluating
different procedures (lyophilization, reverse osmosis, and XAD-2 adsorption)
for concentrating organics in drinking water. The resulting concentrated
organics are used by HERL-CI for biological toxicity testing. XAD-2 resin was
used in this situation to concentrate organics for biological testing purposes
and not as an analytical procedure.
Since there continues to be a great deal of interest among environmental
chemists concerning the comprehensive analysis of purgeable organics in
drinking water, we decided to present at this symposium some of our January
1980, Grob CLSA data and compare it with data from several more conventional
Reference: Melton, R.G., W.E. Coleman, R.W. Slater, F.C. Kopfler, W.K. Allen,
T. A. Aurand, D.E. Mitchell, S.J. Voto, S.V. Lucas, and S.C. Watson, "Comparison
of Grob Closed-Loop-Stripping Analysis (CLSA) to Other Trace Organic Methods.",
Advances in the Identification and Analysis £f Organic Pollutants in Water, II,
(L.H. Keith, ed.^, Ann Arbor Sci. Pub. Inc., Ann Arbor, MI. (1981).
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methods of organics analysis. For researchers studying the health effects and
use of alternate disinfectants, such as chlorine dioxide, chloramines, and
ozone, or the use of granular activated carbon in the treatment of drinking
water, simple packed—column gas—chromatographic/f lame ionization detector
(GC/FID) chromatograins of organic components over 100 ng/l in concentration do
not provide data upon which decisions can be based. Instead, state—of—the—art
metnods that use internal standards (Is) spiked in water samples, a high degree
of organic concentration, high resolution capillary column separations, repro-
ducible gas chromatography/mass spectrometry (GC/MS) measurements, and sophis-
ticated computerized quantification methods are required.
Since the presentation of our papers 1 ’ 2 in Mexico City at this same
symposium five years ago on the Bellar purge and trap (P&T) gas chromatogra-
phy/mass spectrometry/data system (GC/MS/DS) analysis of drinking water, we
have followed with great interest new developments in the methodology of
purgeable organic analysis. Even though chemists worldwide have learned a great
deal in the past five years about comprehensive analysis of volatile organics in
water, there is no consensus at this time as to the optimum method or methods of
comprehensive analysis of purgeable organics in drinking water. For example,
the literature indicates that most European environmental chemists would
recommend Grob CLSA (a P&T Method) with wall—coated open tubular (WCOT)
capillary GC/MS as the best method, whereas, most environmental chemists in
North America would probably recommend some alternative method. We became
interested in applying comprehensive capillary GC/MS/DS methodology to our
health effects research objectives soon after the development of the CLSA method
by Grob in 1973. Progress in using Grob CLSA was slow in our laboratory between
1975 and 1977 until WCOT capillary column techniques were learned. In the past
two years we have measured approximately 500 unique purgeable organics using
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Grob capillary GC/MS/DS CLSA. We published a preliminary report 3 in December,
1979, detailing some of our CLSA results and applications. The present report
reviews briefly U.S. P&T Methods and presents some comparative analytical data
of surface water samples (Cincinnati tap water before and after granular
activated carbon [ GAC] treatment) using the following four methods of analyses:
Method A Bellar Purge and Trap Analysis (EPA Method 601)
Method B Crob Capillary GC/MS/DS CLSA
Method C Batch Liquid—Liquid Extraction (BLLE) Analysis Using
a Modified Master Analytical Scheme (MAS) Procedure
Method D XAD—2 Adsorption — Ethyl Ether Elution Method (XAD—
EEE)
The authors wish to clearly point out at the outset that even though the
subsequent data indicates the presence of many organics in water from the
Cincinnati Waterworks (CWW), these specific Cincinnati drinking water samples
are less contaminated than most tap water samples that we have analyzed from
other locations. For example, the average concentration of Grob CLSA purgeable
organics (other than trihalomethanes) in water samples from CWW was 9.2 ng/l.
Grob capillary GC/MS/DS CLSA is an extremely sensitive method of trace organic
analysis. In fact, the lower GCIMS detection limit of Grob CLSA for over 200
organics is 1 to 10 ng/l. Therefore, the reader should bear in mind that very
reproducible chemical data of trace levels of volatile organics in relatively
“clean” drinking water samples is being presented. Secondly, not all
laboratories require purgeable organic analytical methods that are as
sensitive and comprehensive as Grob CLSA. Certainly, research laboratories
that are generating chemical data on which important decisions concerning the
choice of drinking water treatment processes, such as research on the use of
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granular activated carbon (GAC), alternate disinfectants, filtration tech-
niques, and the health effects of such water treatment processes should use
state—of—the—art comprehensive analytical methods such as those which are
proposed in EPA’s Master Analytical Scheme 4 °. However, most laboratories are
not equipped with good state—of—the—art capillary GC/MSIDS hardware and
software, and the capital investment of comprehensive capillary GC/MS/DS
methods should be put in perspective with the required objectives of each
laboratory. Environmental scientists also realize that the cost per organic
compound analyzed is constantly decreasing due to major improvements in
analytical methods and laboratory hardware and software. Five years ago 2 we
identified the presence of 60 purgeable organics in Miami tap water using an
“exotic” instrument (CC/MS) and the Bellar P&T method. Today, this same
analysis (EPA Method 624) is no longer considered “exotic”. In fact, it is now
being used by several U.S. waterworks laboratories. Perhaps five years from
now, Grob capillary GC/MS/DS CLSA and other comprehensive trace organic
procedures will be “affordable” to more environmental and drinking water
laboratories. The Crob CLSA data for 292 organics in this paper were produced
by our laboratory group and further illustrate the application of Grob CLSA in
drinking water treatment research and in the determination of the health effects
of drinking water treatment processes.
In a second chapter 11 of this text, W. Emile Coleman of our group, presents
a discussion of the use of GC/MS/DS and internal standards for long—term
quantification studies. In a third chapter’ 2 , Jack DeMarco et al. of the
Municipal Environmental Research Laboratory of U.S. EPA, will present chemical
data obtained over a four—month period on the effect of full scale GAC
contactors (one million gallon per day (mgpd]) at the Cincinnati Waterworks.
The Grob CLSA results presented by DeMarco et al. were conducted by the Exposure
Evaluation Branch of HERL—CI.
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HISTORICAL BACKGROUND OF GROB CLSA
In 1973 in Zurich, Switzerland, Grob 13 reported on CLSA for the measurement
of purgeable, intermediate molecular weight organics in drinking water at the
part—per—trillion (nanogram—per—liter) level. Later, in 1974, Bellar 14 ” 5 re-
ported his P&T method for the analysis of purgeable volatile organics at the
part—per—billion (microgram—per—liter) level. U.S. water analysis laboratories
quickly adopted the Bellar P&T method’’ 2 ” 6 using packed GC columns, whereas
Western European laboratories adopted the Grob CLSA method which uses WCOT
capillary columns. The primary reason for slow adoption of the Grob CLSA in the
U.S. was the slow acceptance of state—of—the—art WCOT glass capillary column
technology and capillary column hardware by U.S. manufacturers. Presently,
U.S. laboratories remain behind our Western European counterparts in the use of
capillary CC for the separation of environmental pollutants. Comprehensive
organic analytical procedures, such as Grob CLSA and .GC procedures in the Master
Analytical Scheme (MAS), require the use of high resolution capillary column
separations. Fortunately, U.S. manufacturers and environmental laboratories
are beginning to catch up with our Western European counterparts. For this
reason, the use of comprehensive trace organic methods in the U.S. can now
realistically be proposed.
Grob CLSA utilizes 1.5 mg of activated carbon as a trapping adsorbent 17 .
Activated carbon has been used in the past to monitor organic pollutants in air.
For example, White etal. of the National Institute for Occupational Safety and
Health (NIOSH), reported 18 a standard method in 1970 to measure selected solvent
vapors in industrial atmospheres. The NIOSH method involves passing a standard
10—liter volume of industrial room air through a standardized adsorption tube
that is packed with activated carbon. After capping the tube and shipping it
back to the laboratory, the activated carbon is removed from the tube and placed
in a clean vial. One ml of carbon disulfide (Cs 2 ) is added, and the resulting
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solution analyzed by GC/FID. All phases of this method have been standardized,
and the equipment is readily available.
Grob has thoroughly discussed the design and development of the CLSA
procedure in his first CLSA paper 13 . Like the NIOS}I air analysis method’ 8 , Crob
uses CS 2 to elute the organics from the activated carbon and gas chromatography
to separate the organics in the eluant. Like the Bellar P&T method 14 , the CLSA
method is a vapor—phase P&T stripping technique in which those compounds with
appreciable vapor pressure over water are removed from the sample by purging it
with a large volume of gas and by passing the stripping gas through an adsorption
tube. Unlike other vapor phase procedures, Grob has achieved nearly a one
millionfold concentration of most low and intermediate molecular weight
organics by using a closed loop design where 0.5 liters of stripping gas is
recycled continuously through the water sample, and the adsorption trap is
extracted with 12 ul of CS 2 . Quantitation is achieved by spiking the initial
water sample with a series of internal standards and reference standards, by
stripping at 30°C for two hours, and by chromatographing the CS 2 extract on a
WCOT capillary column. Grab reported the capillary CC/MS identification of 62
organics in samples of Lake Zurich water and Zurich potable water (ca. 60Z comes
from Lake Zurich) in this initial CLSA paper.
Grab’s second paper 19 on CLSA was dedicated primarily to the application of
GLSA to raw and finished drinking water in the area of Zurich. Using capillary
GC/MS for identification, K. Grob and G. Crab reported the occurrence of 136
organics in area water at the low ng/1 range and demonstrated that automobile
gasoline was the major pollutant in Lake Zurich. In these first two CLSA
papers 13 ” 9 Grab identified 29 unique alkanes and 34 alkyl—substituted benzenes
in Zurich raw and finished drinking water.
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In 1975, K. Grob, K. Grob, Jr., and G. Grob 20 compared CLSA with a new trace
organic analysis technique, rapid liquid extraction. Grob points out the
complementary nature of the two procedures. CLSA is very sensitive for low and
intermediate molecular weight nonpolar organics, whereas, rapid solvent ex-
traction is the method of choice for heavier compounds. He also points out
something that many environmental laboratories have recently rediscovered;
Solvent extracts of water heavily stress capillary GC columns, because nonvola-
tile components in the extracts shorten column life. In contrast, CLSA extracts
contain GC volatile substances so that capillary columns may be used over a very
long period of time without any loss of column performance.
In 1976, Grob and Zurcher 17 improved and standardized the CLSA procedure
when they realized that many water research laboratories (mostly European) were
already using the procedure routinely to study source pollution and drinking
water treatment techniques, such as the use of bank filtration, activated carbon
adsorption, and alternate disinfection. Grob, as he has in previous papers,
clearly points out the major limitations of CLSA, such as the limited
intermediate volatility and molecular weight range of substances that are
readily measured by the method. Most laboratories that are using CLSA to
measure low level organics in water are following this standardized method and
have made only slight modifications of it.
We have recorded a total of 16 additional references from seven different
laboratories (five European) that have used. Grob CLSA to measure 192 unique
organics in water. However, a brief tour of European drinking water labora-
tories will indicate that CLSA is being used daily in many waterworks. Stieg—
litz al. 21 in West Germany published in 1976 an early comprehensive applica-
tions paper. They used capillary CC/MS CLSA exclusively to measure 103 organics
at three different water utilities on the Rhine River. Their data c learly show
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some of the effects on the raw water of different treatment techniques, such as
bank filtration, chlorination, and ozonation. Stieglitz modified the CLSA
method of Grob and Zurcher in order to analyze water from the heavily
contaminated Rhine River. Two—liter samples were stripped at pH 3 in two
different stages.After 15 minutes of stripping, the first activated carbon
filter was removed from the loop and a new filter inserted. Stripping was then
continued for an additional two hours and 45 minutes. Each filter was
extracted separately, and the eluants of filters I and II were combined prior to
capillary CC/MS analysis. Stieglitz reported a relative standard deviation of
10 to 15% for 24 organics at the 100 ng/1 level, and an average GC/MS detection
limit of 0.2 ng/1.
Starting in 1976, Giger in Dubendorf, Switzerland, began publishing the
following series of comprehensive application papers using Grob CLSA. Zurcher
and Giger 22 reported the occurrence of 70 orgartics at different points on the
Glatt River using capillary CC/MS. Giger, Reinhard, Schaffner, and Zurcher 23
reported in Mexico City five years ago the capillary CC/MS analysis of trace
organics using methylene chloride solvent extraction and Grob CLSA. In 1978,
Ciger, Molnar, and Wakeham 24 applied Grob CLSA to trace the source of
chlorinated volatile hydrocarbons in groundwaters and lake waters in the Zurich
area. Tetrachloroethylene, the most dominant chlorinated compound, was shown
to originate from tertiary treated sewage and from ground spills. Giger clearly
demonstrated that Grob CLSA is an excellent method to trace the source of
chlorinated hydrocarbons and substituted aromatic hydrocarbons from industrial
point sources. In 1979, Schwarzenbach, Molnar—Kubica, Giger, and Wakeham 25
used Grob CLSA to determine the distribution of tetrachloroethylene and 1,4—
dichlorobenzene in Lake Zurich at various depths over a 12—month period. One—
liter samples were stripped at 30°C for 90 minutes, and quantitation was done by
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capillary GC/FID peak height measurements. DuDlicate measurements over the one—
year study at the 5 to 70 rig/i range had relative standard deviations of less than
10% except at the therinocline depth of the lake where concentration gradients
were greatest. Using Grob CLSA data, Schwarzenbach was able to conduct an
accurate mass balance for l,4—dichlorobenzene into and out of Lake Zurich.
Sewage treatment plants introduced 62 kg/year of l,4—dichlorobenzene to the
lake, whereas, the Zurich water utilities transferred 1 kg/year out of the lake.
In 1977, Giger proposed 26 the use of Grob CLSA to measure volatile organics in the
marine environment. Ia 1978, Schwarzenbachetai. 27 , at Woods Hole Oceanographic
Institute, along with the late Max Bluxner, conducted an extensive analysis of
volatile organics in coastal seawater using Grob CLSA. Since most volatile
organics in seawater are present below the 10 ng/kg range, Schwarzeribach stripped
5—L samples at 35°C in order to have a higher concentration of organics for GC/MS
analysis. Reproducibility for 20 selected organics in seawater samples was ÷ 15
to 30%.
Reinhard and McCarty at Stanford University have published many papers 2832
using Grob CLSA as one of three analytical methods to assess advanced wastewater
treatment processes and the transport of organics from groundwater injection
wells. As early as 1976, Reinhard chose the following analytical methods due to
the complexity of the organics in biologically treated municipal wastewater at
Water Factory 21 in California. Bellar P&T analysis using a packed column
GC/Hall detector system was used for haloforms and halogenated compounds with one
and two carbons. Grob GC/MS GLSA was used to measure compounds of medium
volatility and low water solubility. Solvent extraction with two different
solvents was used to measure compounds of lower volatility and higher water
solubility. Capillary separations were required except for Bellar P&T samples,
and GC/MS was used to confirm all identifications. Reinhard’s data clearly
indicate the complexity of environmental water samples and the need for high
resolution capillary separations.
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In December 1979, the Exposure Evaluation Branch of HERL—CI published 3 a
brief applications paper by Coleman et al. on Grob capillary GC/MSIDS CLSA of
drinking water samples. Co,leman reported the use of GC/NS computer procedures to
automatically quantify purgeable organics in Grob CLSA data files using internal
standards spiked in water samples, a computer library of 215 reference standards
with narrow relative retention time windows, reverse mass spectrum library
searches, and relative response factors for the 215 standards based upon single
mass spectral ions. This procedure permits a laboratory to quantify three
drinking water samples within a 24—hour period for 215 reference purgeable
organics using twelve person—hours of time. The resulting Grob CLSA data were
reported to have correctly identified 80% of the 215 reported compounds with
quantitative accuracy to within ± 25% for most solvent—type organics in the 50
ng/l range. Coleman reported a CC/MS detection limit of 1 to 10 ng/l for most oJ
the 300 to 400 organics which are identifiable by the method.
HISTORICAL BACKGROUND OF U.S. P&T METHODS
A number of P&T methods have been recently standardized by EPA. The authors
will attempt to illustrate the design differences between Grob CLSA and these
newer EPA P&T methods. On December 3, 1979, the U.S. EPA published in the Federal
Register (FR) a set of proposed chemical methods for the analyses of pollut-
ants 33 . The use of these proposed methods would be required for filing
applications under the National Pollutant Discharge Elimination System, for
State certifications, for compliance monitoring under the Clean Water Act, and
for analyses of 113 organic toxic pollutants (priority pollutants) under a
Settlement Agreement 34 (Natural Resources Defense Council, Inc., et al. versus
Train) and under Section 304(h) of the Clean Water Act of 1977. The December 3,
1979, FR proposed the following analytical methods for the analyses of organic
pollutants in water:
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Method 601 Purgeable Halocarbons using packed GCfHall
602 Purgeable Aromatics using packed GC/Photoionization
603 Acrolein/Acrylonitrile using packed CC/FID
604 Phenols
605 Benzidines
606 Phthalate Esters
607 Nitrosamines
608 Organochiorine Pesticides and PCB’s
609 Nitroaroniatics and Isophorone
610 Polynuclear Aromatic Hydrocarbons
611 Haloethers
612 Chlorinated Hydrocarbons
613 2,3,7 ,8—Tetrachlorodibenzo-p—dioxin
624 Purgeables using packed CC/MS
625 Base/Neutrals, Acids, and Pesticides
using packed CC/MS
The above 15 methods are designed for the analyses of 113 specific “consent
decree” organics. Method 601, 602, 603, and 624 are all Bellar P&T methods. All
four P&T methods require the use of packed CC columns and different CC detectors.
T.A. Bellar of Environmental Monitoring and Support Laboratory, Cincinnati
(EMSL—CI) recently reported 35 ’ 36 the following two additional P&T methods:
Method 502 Purgeable ia1ogenated Chemical Indicators of Indus-
trial Contamination using packed GC/Hall.
Method 503 Purgeable Aromatic Chemical Indicators of Industrial
Contamination using packed CC/Photoionization.
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Methods 502 and 503 are identical to Methods 601 and 602, respectively. The only
difference in Methods 601 and 502, and in Methods 602 and 503 is that Methods 601
and 602 are limited to 113 “consent decree” organics. Methods 502 and 503 were
developed by EMSL—CI for the EPA Office of Drinking Water (Washington, D.C.) to
measure a broad spectrum of purgeable chemical indicators of industrial
contamination of drinking water. EPA Method 601 will measure 29 “consent decree”
organics, whereas Method 502 viii measure 48 halogenated purgeable organics
(chioromethane to l,4—dichlorobenzene) at concentrations between 0.1 and 50
ugh. Like EPA Method 601, Method 502 requires a total analysis time of 1 hour
and uses a packed column CC/Hall instrument system. Method 50336, like Method
602, is designed to measure aromatic purgeabie organics with a packed column
GC/Photoionization instrument system. Method 602 measures seven “consent
decree” aromatics, whereas, Method 503 is capable of measuring 33 purgeable
aromatic organics over a concentration range of 0.05 to 0.5 ugh. The combined
use of Bellar P&T Methods 502 and 503 will measure 81 unique purgeable organics
in drinking water or raw source water with a lower limit of detection of at least
0.1 ugh.
Methods 601 to 625 are designed for the analyses of 113 specific organics.
These methods were not intended to be comprehensive methods for the in—depth
analysis of a broad range of organics in water. In order to develop a
comprehensive master analytical scheme (MAS), U.S. EPA (Environmental Research
Laboratory, Athens, Georgia) awarded a competitive contract to Research Triangle
Institute (R.TI) in 19784—10. This research effort was designed by EPA to insi.ire
the use of a minimum number of organic analysis procedures to analyze a very broad
spectrum of organics in water. Consequently, EPA required the use of high
resolution chromatography separations and broad spectrum chromatography detec-
tors such as state—of—the—art MS/DS hardware and software. The lover detection
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(LD) limits for the analysis of drinking water using MAS procedures is 0.1 ugh. 5
For the analysis of “extractable” organics at the 1 ugh range, the MAS
recommends a BLLE procedure using methylene chloride to stir—bar extract one
liter of water. 7 For the same “extractables” in cleaner water such as drnking
A
water, the MAS recommends passing - -€ou-r liters of water through a XAD—4 resin
sorbent column and elution of adsorbed organics with ethyl ether solvent. 7 XAD—
4 and XAD—2 resins differ only in pore size. Both resins have the same polymeric
chemical composition and have similar sorptive characteristics. The MAS XAD—4
procedure is similar to the procedure described by Junk, et al. 37 and the XAD—EEE
procedure described in this report. These three XAD procedures differ primarily
in volume of drinking water used and the adjusted pH of water that is passed
through the sorbent column.
For the comprehensive analysis of purgeable organics for the MAS, RTI
adopted the use of the P&T capillary GCIMSIDS procedure that was previously
developed by RTI and outlined in Figure 1. This procedure was intended to cover
a spectrum of purgeable organics from the very volatile gases (chioromethane and
vinyl chloride), such as EPA Method 601 measures, to intermediate molecular
weight purgeable organics. The lower limit of detection of the current MAS P&T
procedure is 0.1 ugh for drinking water; 5 thus, according to the designers of
the MAS 8 , “the MAS P&T procedure does not present competition with Grob capillary
GCINS CLSA for the measurement of purgeables in drinking water at the parts per
trillion level”. However, since both P&T methods are intended to provide
comprehensive research information on the level of purgeable organics in
drinking water, the methods should be compared for differences in design and
experimental performance. Such comparative information is important to chemists
who must decide which P&T method (or methods) will provide the best and most cost
effective analytical data. RTI has not reported research or data on the use of
Grob CLSA for low to intermediate molecular weight nonpolar organics, for which
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the CLSA method was designed. Instead, RTI attempted to extend Grob CLSA for the
analysis of water soluble low molecular weight organics (volatile intractables),
such as methanol and acetone. Not surprisingly, the method failed for this group
of organics 5 .
HERL-CI SCHEME FOR TRACE ORGANIC ANALYSIS
During the past two years, HERL—CI used the following three methods for the
organic analysis of drinking water:
Method A - Bellar P&T CC/Hall Detector Analysis (EPA Method 601)
Method B - Grab Capillary GC/MS/DS CLSA
Method C — Liquid—Liquid Extraction (BLLE) of lO—L Samples using
Methylene Chloride and Capillary GC/MS/DS Analysis
The reasons why we chose the combination of Bellar P&T (601) and Grab GC/MS CLSA
to analyze purgeable organics are outlined in Figure 2. Overall, we have found
that the combination of Methods 601 and CLSA provides a comprehensive, broad
spectrt , cost effective, quantitative analysis of trace levels of purgeable
organics in drinking water. Methods 601 (502) and CLSA are simply diagrammed in
Figures 3 and 4. It is clear from these figures that the desorption modes of
Bellar P&T analysis and Grob CLSA are distinctively different. Bellar P&T
depends upon thermal desorption of organics from the trapping material, whereas,
Grob GLSA depends upon CS 2 solvent extraction of organics from the surface of the
activated carbon. It is this basic difference in method of desorption of
organics from the trapping material that makes Bellar P&T Method 601 (502) and
GLSA complementary in the spectrum of organics analyzed. The gaseous—type
purgeable organics, which are covered up by the CS 2 solvent in the Grob CLSA, are
readily quantified by the cost effective Bellar P&T method using a packed column
CC/HALL instrument system. Whereas, the Grob CLSA provides a very cost
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effective, quantitative analysis of purgeable organics, which elute after
benzene and bromoform and which require the use of high resolution capillary
columns. The data presented in this report illustrate this important principle
of complementary analysis. In addition, results obtained by using Method 601,
CLSA, and BLLE, above, will be compared with the XAD—2 adsorption method (XAD—
EEE) of Junk et al. 37 .
EXPERIMENTAL
Source of Water Samples
Drinking water samples were obtained from the Cincinnati Waterworks (CWW)
on January 14, 1980, (GAC Contactor A) and on January 28, 1980, (GAC Contactor D)
at sampling points into (influent) and out of (effluent) one million gallons per
day (mgpd) GAC columns (Contactors) that had been on line for seven weeks and two
weeks, respectively. These same GAC Contactors at CWW are described in more
detail by DeMarco etalJ 2 . Method 601, CLSA, and BLLE were applied to influent
and effluent water samples from GAC Contactor D (as diagrammed in Figure 5).
Analytical results of samples XAD—Inf., XAD—Eff., and XAD—EEE were obtained from
Contactor A GAC—Inf. water on January 14, 1980. All water samples were preserved
at collection with 10 mg/i of mercuric chloride and 20 mg/l of sodium sulfite.
The data, however, indicate a possible problem with the use of mercuric chloride
as a preservative (see RESULTS) . For the XAD-2 concentration experiments, five
gallons of GAC-Inf. water (see Figure 5) were brought back to HERL—CI for concen-
tration. Bellar P&T analyses and CLSA were conducted by HERL—CI. Water samples
and reagent water samples for BLLE were shipped to Battelle—Columbus Labora-
tories (EPA Contract 68—03—2548) for analysis. Battelle also carried out the
capillary GC/MS/DS analysis of XAD—EEE extracts. Reagent water, pre.pared by
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passing distilled water through a Millipore Super Q water purification system
(all three cartridge housing units were filled with activated carbon cartridge
filters), was concurrently analyzed by the same four methods. All analytical
data reported in this paper have been corrected for methodology artifacts.
Bellar P&T Analysis
Purgeable, low molecular weight organohalides were analyzed using Method
601 (Figure 3), except that the purge and trap device described by Bellar and
Lichtenberg 14 in 1974 was used, and the trap was packed with 60/80 mesh Tenax GC.
This packing material is a deviation from the combination of Tenax GC, silica
gel, and activated carbon as is specified in Method 601 and 502. Compounds such
as chloromethane would not have been appreciably trapped by the sole use of Tenax
CC at room temperature. Future Bellar P&T analyses from HERL—CI will be
conducted using the above combination packing material.
Bellar P&T samples were chroma ographed according to the following condi-
tions:
Injector temperature 150°C
Initial column temperature 28°C
Temperature program sequence a) Heat column from 28°C
to 60°C at 40°C/mm
b) Hold for 1 mm.
c) Heat from 60°C to 160°C
at 8°C/mm
d) Hold at 160°C
CC column 0.2 % Carbowax 1500 on
Carbopak C (80/100 mesh)
packed in 9 ft x 2 mm
I.D. glass column
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17
Grob Capillary GC/MS/DS CLSA
The experimental method described by Grob and Zurcher 17 was followed using
the following minor modifications:
1. Water samples were collected in one—gallon screw—capped bottles.
2. Samples were analyzed in the above shipment bottles by decanting
sample water down to the one—gallon mark, adding five internal
standards (52 ng/l each of chlorohexane, chlorooctane, chioro—
dodecane and chlorohexadecane, and 260 ng/l of chiorooctadecane)
dissolved in 0.6 ul of acetone to the sample, and then purging
the sample for two hours at 30°C.
3. The filter holder (trap) was maintained at 40°C and the heat
exchanger at 80°C.
Details of HERL—CI modifications to the Grob and Zurcher CLSA method are given in
another paper by Coleman at al. 11 in these proceedings and the previously
published procedure by Coleman et al. 3 . The schematic in Figure 4 reflects
changes in HERL—CI CLSA since the CWW samples in this publication were analyzed
in January 1980. These August 1, 1980, modifications are designed to promote the
CLSA of a broader and higher molecular weight spectrum of purgeable organics by
maintaining a higher purge temperature and a heated all—glass system from the
sample bottle to the trap. Ultrapure CS 2 from Matheson, Coleman, and Bell
Chemical Company (Cincinnati, Ohio) or from Tedia Chemical Company (Fairfield,
Ohio) was used without additional redistillation or clean—up.
Grob CLSA samples were separated by capillary CC according to conditions
described by Coleman at al. 11 . Briefly, CLSA carbon extracts were injected
(splitless) at 2 °0c with a capillary column flow velocity of 25 cm/sec. When the
CS 2 begins to elute, the SP 2100 capillary column was heated at a rate of 2°C per
minute to a maximum temperature of 25OO Data acquisition on a Finni.gan—.Incos
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18
GC/MS/DS was begun after the CS 2 finished eluting from the capillary column. The
mass spectrometer was scanned at a rate of 14 to 450 a iim per two seconds. Further
GCIMS/DS details are described by Coleman et al ) 1 .
BLLE Capillary GC/MS/DS Analysis
The batch methylene chloride extraction method that is briefly outlined in
the MAS 5 ’ 8 was used. If EPA Method 625 had been used, the GC/MS detection limit
of 10 ugh would have been unacceptable for the measurement of organics in these
drinking water samples from CWW. The BLLE procedure below requires that lO—L
water samples be collected in three sample bottles (one gallon size) and spiked
with a series of deuterated internal standards at a concentration of 0.2 ugh
prior to stir—bar extraction with methylene chloride. The following experi-
mental details are provided because it is extremely difficult to achieve
acceptable sensitivity and artifact levels for the ELLE analysis of trace—level
organics in drinking water:
1. Solvent Preparation . One—gallon batches of Burdick and Jackson
“Distilled in Glass” methylene chloride were redistilled in a five—L
flask equipped with a 60 cm x 1.8 cm ID column packed with medium size
glass helices. The receiver was the original one gallon solvent bottle
which was preflushed with ultra high purity N 2 (Matheson, 99.99 1/6).
A positive pressure of N 2 was maintained throughout the distillation
using a bubbler chamber. Methylene chloride was distilled at a rate of
1.4 to 1.8 ml/min. The first and the last 300 ml of solvent were
discarded. After distillation, methylene chloride was stored under N 2
and used within three days for ELLE.
2. Sample Extraction . Ten liters of drinking water were extracted in the
original one gallon sample bottles by first removing all but 3.3 L of
sample water from each of three sample bottles, then adding 33 ul of
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19
a mixture of deuterated internal standards (0.2 ug/l) 38 , adding a 3—
in. teflon stirring bar, stirring the water sample at maximum stable
speed, and adding concentrated sulfuric acid until the acidity was
lowered to pH 2 to 2.5. Three 40—mm solvent extractions were made
using 250 ml, 100 ml, and 100 ml of redistilled methylene chloride.
Solvent was removed after each extraction using an all glass andteflon
pipet—type device and about 5 in. of Hg vacuum.
3. Solvent Evaporation . The stir—extraction, above, of 10 L of drinking
water in three sample bottles yields approximately 1200 ml of
methylene chloride. Two Kuderna—Danish (KD) apparatuses were used to
concentrate the solvent to a volume of about 4.5 ml which was
fractionated into an acids fraction (derivitized with diazomethane)
and a neutrals fraction according to the procedure described by Lucas
et al. 38 . BLLE samples were chromatographed on a 40-M x 0.25 mm I.D.
SP1000 WCOT capillary column (prepared by Battelle) according to the
following conditions:
Injector temperature 250°C
Initial oven temperature (hold) 50°C (6 mm)
Temperature program rate 2°C/mm
Upper temperature limit 225°C
Injection volume 2 ul sample +
1 ul heptane
Transfer line temperature 250°C
XAD—EEE Capillary GC/MS/DS Analysis
The grab sample method described by Junk et al. 37 was used for the
concentration of organics with the following modifications:
1. XAD—2 resin sufficient for both CWW GAC Contactor A and D experiments
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(see Figure 5) was cleaned up by consecutive 24—hr Soxhiet extractions
with methanol, acetonitrile, ethyl ether, and methanol. Clean resin
was stored wet under methanol until prior to packing columns.
2. Two columns were set up; one column for 10 L of CWW XAD-Inf. water, and
the second for 10 L of Super Q reagent water. Each column was 2.7 cm
in diameter by 6.5 cm in height. A silanized glass wool plug was placed
on the bottom of the empty column.
3. The resin was removed from the methanol storage bath and slurried into
a beaker of Super Q reagent water. The resin was then rinsed four times
with Super Q reagent water. Next the resin (37 c m 3 ) in the beaker was
slurried into the glass column, which was filled with reagent water.
Silanized glass wool was placed on top of the resin which was always
kept wet with reagent water. The column resin was then rinsed with one
L of Super Q reagent water.
4. Ten liters each of CWW sample and reagent water were adjusted to pH 2
with 20 ml of 12 N sulfuric acid.
5. Each acidified sample water and reagent water were passed through each
respective XAD—2 column at a flow rate of approximately 28 ml per mm.
Each column was immediately rinsed with 200 ml of pH 2 reagent water.
Sample water and reagent water that passed through each respective XAD
column were labeled XAD-Eff. and were later analyzed by HERL—CI using
EPA Method 601 and Grob CLSA, and by Battelle—Colunibus Laboratories
using BLLE.
6. Three bed volumes of freshly redistilled ethyl ether were used to elute
the adsorbed organics from the XAD—2 resin. This ethyl ether eluant
was labeled XAD—EEE.
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7. The sodium sulfate drying procedure of Junk et al. 37 was used.
8. The ethyl ether eluant was evaporated to 1 ml (KD) and shipped to
Battelle—Columbus for capillary GC/MSIDS analysis under EPA contract
68—03—2548.
All capillary GC/MS/DS parameters for the analysis of XAD—EEE samples were
the same as previously described for BLLE samples.
RESULTS
Chromatograms using Method 601, Grob CLSA, and BLLE are presented for GAC-
Inf. and GAC—Eff. water only, due to manuscript space limitations. Unfortun-
ately, the XAD—2 ethyl ether eluant (XAD—EEE) samples from CWW GAC Contactor D
were heavily contaminated with chemical artifacts from the XAD—2 resin. Since we
had good samples and data files using all four methods taken at the same points
at GAC Contactor A at the CWW on January 14, 1980 (two weeks prior to CWW
Contactor D samples), we have presented, instead, analytical results on the XAD—
Inf., XAD—Eff., and XAD—EEE samples from Contactor A water. Basically, this
change from Contactor D GAC—Inf. water to Contactor A GAC—Inf. water is simply a
difference in sampling CWW raw Ohio River water on dates differing by two weeks.
Comparison of CWW GAC—Inf. water samples on January 14, 1980, and January 28,
1980, using Grob CLSA and BLLE analyses shows that water samples on these two
dates are quite similar, except that there was a slightly higher level of alkyl—
substituted benzenes in the January 28, 1980, water samples.
Total organic carbon (TOC) measurements of combined volatile and non-
volatile organics were determined on GAC—Inf. and GAC—Eff. water from CWW. On
January 14, 1980, the TOC of GAC—Inf. to Contactor A was 1.9 mg/l and of GAC—Eff.
water was 1.2 mg/l. This represents a removal of 37% total organic carbon by the
GAC (7 weeks old) in Contactor A. The TOC of Contactor D water on January 28,
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22
1980, (GAC was in use for two weeks) showed a corresponding reduction from 1.6
mg/i to 0.2 mg/i, or a removal of 87% TOC.
Results of Bellar P&T analysis (Method 601) are presented in Table 1, and
representative chromatograms in Figure 6. Only six halogenated organics were
detected due to the low level of purgeable organics in GAC—Inf. water. All six
compounds were “consent decree” organics with an average concentration of 16
ugh. No organics were detected in the corresponding GAC—Eff. water. This would
represent a 100% removal by GAC Contactor D at CWW. According to EPA Method 601,
an additional 23 (29—6) organics would have been detected in GAC—Inf. water if
present in concentrations above 0.06 ug/l. EMSL—CI Method 502 would have
detected an additional 42 (48—6) halogenated organics if they had been present
above 0.1 ug/l. Table 1 also shows the effect of the 37—cm 3 XAD—2 analytical
column in removing halogenated purgeable organics from XAD—Inf. water. Overall,
Table 1 indicates that the 1 mgpd GAC Contactor D at CWW was more effective in
removing organics than was the small XAD—2 analytical column.
Results of Grob capillary GC/MS/DS CLSA are presented in Table 2. Grob CLSA
detected 107 purgeable organics in GAC—Inf. water (Contactor D). Quantitative
results of organics listed in Table 2 that have the designation “S” under “Quan.
Method” are based upon actual relative response factors of reference compounds,
as compared to the internal standard, chlorododecane, which was initially spiked
in each water sample at 52 ng/l. A total ion current area relative response
factor of one (chiorododecane, IS) is assumed for the compounds which do not have
the “S” designation in Table 1. As mentioned earlier, the average concentration
of the non—trihalomethane organics in GAC-Inf. water according to CLSA was 9.2
ng/l. The average concentration of these same organics in GAC—Eff. water was 1.8
ng/l. If the MAS P&T procedure had been used on GAC—Inf. water (Contactor D),
probably only five compounds (four trihalomethanes and l,1,l—trichloroethane)
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23
would have been detected. This prediction is based upon the MAS GCIMS lower
detection limit of 0.1 ugh. 5 The 80% removal of the CLSA organics in GAC—Eff.
water by CWW GAC Contactor D shows surprisingly good agreement to the 87% removal
based on TOC cited above. Since most of the TOC material is probably of humic
origin (and therefore not accessible to Grob CLSA), these data seem to indicate
that GAC Contactor D is removing the same percentages of purgeable organics and
humic material. The XAD—tnf. and XAD—Eff. data in Table 2 indicate that the 37—
cm 3 XAD—2 analytical column removed 79% of these same Grob CLSA organics.
Accordingly, CWW GAC Contactor D and the XAD—2 analytical column are doing
similar jobs (80%, 79%) in removing the organics which can be measured by Grob
CLSA in GAC—Inf. and XAD—Inf. water. The ability of Grob CLSA to directly measure
the effect of XAD resin as a unit process is clearly illustrated in Table 2. Grob
CLSA is also an excellent method to determine if XAD—2 resin is adequately
cleaned—up (See Figure 5) for analytical use as an adsorbent by measuring
purgeable organics in reagent water before and after passage through an XAD
column.
The chromatograms in Figure 7 are arranged to illustrate the Grob CLSA
differences between GAC—Inf. and GAC—Eff. water. Note that the levels of
internal standards (is) in Figure 7 are the same. Also, that two of the first
detectable or anics that elute after the CS 2 solvent are isopropyl ether and
chloroform. If more volatile nonpolar organics had been present, such as
chloromethane, vinyl chloride, and methylene chloride, they would have been
covered up by the CS 2 solvent peak. These more volatile organics would have been
detected, however, by the Bellar P&T analysis (Method 601) of these same CWW
samples (see Table 1 and Figure 6) if we had used a trap packed with Tenax, silica
gel, and activated carbon.
Results of BLLE capillary GC/MS/DS analysis of GAC—Inf. and GAC—Eff. water
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24
are presented in Tables 3 and 4, which correlate with the chromatograms shown in
Figures 8 and 9. Fifty—one and 38 organic compounds were identified in the
neutral and methylated acid fractions of GAC—Inf. water. These BLLE samples are
notably low in solvent artifacts due to the elaborate methylene chloride
purification steps employed. Meticulously clean solvents, reagents, and
glassware are necessary for reproducible CC/MS analysis of BLLE samples of trace
organics in drinking water. Figures 8 and 9 clearly illustrate the high level of
artifact free performance which has been achieved. The peaks labeled “IS” are
deuterated internal standards (0.2 ugh level) which were added to the water
before extraction. The peak marked “IS HEB” is hexaethylbenzene, an internal
standard, which was also added at the 0.2 ugh level prior to CC/MS analysis.
Artifacts which are due to aqueous extraction or extract fractionation are
indicated by special symbols in the figures. Divinylmercury (C 4 H 6 Hg) was present
in GAC—Inf. water according to BLLE (methylated acid fraction). Divinylmercury
also appeared in some of the BLLE blanks of reagent water. The presence of
divinylmercury may be due to a chemicai reaction between the preservative,
mercuric chloride, and certain organics in the water samples.
The contamination of the XAD—EEE extract from the Contactor D experiment by
XAD—2 resin was so severe that the resulting CC/MS data files were of no value.
These artifacts are quite typical of what we have seen on a number of occasions
when analyzing XAD—2 generated organic concentrates. Since XAD—2 resin and XAD—
4 resin are widely used for the concentration of organics from water (the MAS
“extractables” method uses a similar resin, XAD—4, to concentrate organics from
4 liters of drinking water), and since e are not aware of literature
documentation of the specific contaminants one generally encounters, the
abbreviated listing in Table 5 may be of some use to the reader. Capillary
GC/MS/DS analysis of the XAD—EEE extract from the Contactor A experiment is
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25
presented in Tables 6 and 7. A total of 58 organic compounds were identified in
the neutral and methylated acid fractions of this XAD—EEE extract.
DISCUSS ION
The data presented above on these and other water samples will help HERL—CI
determine the authenticity of organic concentrates derived from reverse osmosis,
lyophilization, and XAD adsorption such as those which were produced from the
same GAC—Inf. water on January 14, 1980, and January 28, 1980. For our health
effects research, it is clear to us that we will not be successful in producing
representative organic concentrates of water for biological screening tests, if
we do know how to conduct state—of—the—art organic analysis of the “starting
material” — drinking water.
The contamination problem that we encountered with XAD-EEE sample from
Lontactor D water on January 28, 1980, and not from Contactor A water two weeks
earlier has been a consistent problem in our use of XAD—2 resin over the past six
years. The Grob CLSA data of XAD—Eff. water from Contactor A and D experiments
indicate that the XAD—Eff. water was not contaminated by XAD—2 resin (see Table
2). Therefore, we have obviously contaminated the XAD—EEE sample from Contactor
D during the ethyl ether elution step, even though the same procedure w s used for
both January 14 and January 28 experiments. Hopefully the XAD—4 resin adsorption
method described in the !IAS for the measurement of “extractable” orgaaics in
drinking water will be designed to absolutely prevent such contamination from XAD
resin during the ethyl ether elution of adsorbed organics.
Two hundred fifteen organic compounds have been purchased as authentic
standards and analyzed by Grob CLSA. For those compounds listed in Table 8,
experimental response factors and chromatographic behavior have been determined
so that all CLSA data files can be automatically searched for these 215 compounds
using reverse library search software. For the purposes of this manuscript on
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26
the comparison of Crob CLSA with Bellar P&T, BLLE, and XAD—EEE, an attempt
has been made to summarize the comparative differences of the four selected
methods in Tables 9 and 10 using one water sample; GAC—Inf. water from
Contactor D (Contactor A for XAD—EEE). Reverse library computer searching
for the 215 organics was performed automatically on the CLSA CC/MS data
file of GAC—Inf. water, and 64 organics were detected and quantified by the
Incos data system. The method described by Coleman et al. was used. One
hundred seventy—one of the 215 organics were not found. This negative
information is very valuable in that several of the 171 organics not
detected in GAC—Inf. water are toxic. For example, Coleman reports 11 in
this volume that 2,2’ ,4,4’,6,6’—hexachlorobiphenyl (a PCB isomer of
molecular weight 358), one of the 171 organics not detected, can be
measured in drinking water by Grob CC/MS CLSA at a concentration of 2 ng/1.
The standard deviation for the measurement of this PCB isomer at 6.2 ng/l
concentration (16 replicates, 59% recovery efficiency) was + 1.1 ng/l. For
drinking water treatment researchers and toxicologists, this type of
reproducibility and sensitivity is important. However, the drinking water
consumers in Cincinnati are perhaps the most gratified group over the low
CC/MS detection limits of Grob CLSA, since they probably dislike drinking
PCB isomers. If this PCB isomer were detected in GAC—Inf. water at 2 ng/l,
then the combined concentration of all Arochlor PCB isomers in the drinking
water would have been dramatically higher than 2 ng/l. Unfortunately, we
have detected PCB isomers on previous occasions in several drinking water
samples from other major cities using Grob CC/MS CLSA. The analogous
limits of detection pertaining to BLLE and XAD—EEE is not available, since
it is very difficult and time consuming to obtain quantitative data using
BLLE and XAD adsorption.
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TOC measurements indicate that CWW CAC Contactor D was 87% effective in
removal of organics, whereas, CLSA indicates that Contactor D was 80% effective
in removal of purgeable organics. CLSA also indicates that the XAD—2 analytical
column was 79% effective in removal of purgeable organics.
Table 9 provides us with information on overlap between the four methods.
For example, dibromochloromethane and bromoform were detected by all four
methods. However, only Bellar P&T and Crob CLSA provided quantitative
results. 1 ’ 33 Of the 12 carboxylic acids (including 2,4—dichlorophenoxyacetic
acid) that were identified by BLLE and XAD—EEE analyses, none were observed in
Grob CLSA data. BLLE and XAD—EEE analyses detected the presence of 3—
nitrotol’tene and 2,4—dinitrotoluene in CAC—Inf. water, but Grob CLSA did not
detect these important compounds. Surprisingly, BLLE missed four isomers of
ethyldimethylbenzene that Grob CLSA and XAD—EEE analyses detected. Perhaps
these alkylated benzene isomers were lost during the evaporation of 1200 ml of
BLLE methylene chloride down to 0.5—nil volume. BLLE and XAD—EEE analyses
produced similar CC peak heights for most methylated acids and nitrotoluenes.
Table 10 provides a greater depth of comparative physical—chemical inform-
ation than any other table or figure. Overall, 183 different organics were
detected in GAC—Inf. water by all four methods. Six organics were detected by
Bellar P&T, 107 by Grob CLSA, 90 by BLLE, and 58 by XAD—EEE. As compared to 183
total organics, 3% were detected by Bellar P&T, 58% by CLSA, 49% by BLLE, and 32%
by XAD—EEE. Of consent decree 33 ’ 34 organics, Bellar P&T detected 5%, Grob GLSA
detected 20%, BLLE detected 10%, and XAD—EEE detected 5%. The EPA Office of
Drinking Water published 37 a list of “chemical indicators of industrial
pollution” (1978) as a yardstick—measure to determine if a drinking water supply
would be required to use GAC to remove toxic pollutants from potable water. Of
the 62 organics or organic classes on this list, Bellar P&T detected 3%, .Grob CLSA
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detected 27%, BLLE detected 16%, and XAD—EEE detected 8%. tn summary, for these
samples of drinking water, Grob CLSA has resulted in the quantification of a
larger number and higher percentage of the organics that EPA is currently
monitoring than the three other methods. This summary statement would not be
accurate if the concentration of “consent decree” organics and “chemical
indicators of industrial pollution” had been greater than 40 ng/l. At
concentrations greater than 40 ng/l, Method 601 would have detected 28 (26% of
113) “consent decree” organics and EMSL—CI Method 502 would have detected 43 (69%
of 62) “chemical indicators of industrial pollution”. At concentrations greater
than 0.1 ug/l, the MAS P&T and XAD adsorption procedures should have detected a
majority of the “consent decree” organics and “chemical indicators of industrial
pollution”.
The above statistics do not provide an overview of the physical—chemical
differences of the four methods. Table 10 indicates that Grob CLSA quantified
more aliphatic hydrocarbons and aromatic hydrocarbons than the other three
methods combined. However, LSA detected a lower number of nitrogen compounds
and oxygenated compounds than either BLLE or XAD—EEE. Concerning specific
functional groups, Grob CLSA detected a greater number of alkanes, alicyclic
hydrocarbons, alkylated benzenes, indeno hydrocarbons, naptheno hydrocarbons,
aldehydes, quinones, aliphatic esters, ethers, oxygen—containing heterocycles,
halogenated aliphatics, halogenated aromatics, and halogenated ketones. How-
ever, BLLE detected a greater number of water soluble compounds such as alcohols,
glycols, ketones, halogenated ethers, aromatic carboxylic acids, amides, ni—
trues, halogenated phenols, and phosphates. Table 10 also indicates that
a].iphatic carboxylic acids (fatty acids) were equally well detected by BLLE and
XAD-EEE. Overall, XAD—EEE analysis did not perform as well as BLLE analysis. In
suninary, Table 10 indicates that more toxic or potentially toxic species may be
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quantified by Grob CLSA than by the other three methods, but that Bellar P&T, Grob
CLSA, and BLLE have optimal performance for different classes of organics. Thus,
it is clear that Bellar P&T (Method 601), Grob CLSA, and BLLE are important
complementary methods. For this reason, HERL—CI will continue to require the use
of all three methods for health effects research water samples.
The physical—chemical data in Table 10 also provide valuable information
about the optimum choice of liquid phases for the CC separation of organics in
CLSA, BLLE, and XAD—EEE extracts. Satisfactory separation results can be
obtained for the non—polar organics in CLSA extracts using both non—polar (methyl
silicone) and polar GC liquid phases. The predominance of oxygenated polar
organics in BLLE and XAD—EEE extracts require the use of polar liquid GC phases
for optimum separation results. Chemists should not forget that the splitless
injection of solvent extracts on WCOT capillary columns requires the CC liquid
phase be a liquid (not a solid) at the temp rature needed to achieve the correct
solvent effect performance. For example, the use of CS 2 as a CLSA extraction
solvent requires a CC oven temperature of 20°C or less for a satisfactory solvent
effect. Thus, the capillary column liquid phase must also be a liquid at 20°C.
Consequently, the use of SP1000 or Carbowax 20M liquid phases for the capillary
splitless injection of CS 2 extracts would be unsatisfactory because these polar
phases are a semi—solid at 20°C. Unfortunately, the operating temperature range
(minimum and maximum temperatuares) of most commercially available polar
capillary columns is unacceptable for the splitless injection of GLSA, BLLE, and
XAD—EEE extracts. This limitation of too high of a minimum temperature may be
overcome by using a solvent exchange step (with a higher boiling solvent) or by
adding a higher boiling solvent to a CLSA, BLLE, or XAD—EEE extract prior to
splitless injection. Both of these approaches lead to complete masking and/or
partial loss of many early eluting components.
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“Cost versus benefit (number of organics measured)” is an important
consideration when comparing methods. However, we have not been able to devise
a fair way to make this type of comparison for BLLE and XAD—EEE analyses. The
data in this report is not quantitative and the limits of detection are unknown
for these two methods, therefore, it is difficult to determine a fair basis for
comparison with Bellar P&T and Grob CLSA. Precision and accuracy data has been
previously reported for Method 60l and Grob CLSA 11 . However, some cost
information on Bellar P&T and Grob CLSA can be provided. For these calculations,
the apropriate cost for the analysis of GAC—Inf. water by Bellar P&T (Method 601
or 502) is $85 and by Grob CLSA is $460. Even though only six organics were
detected using Beliar P&T analysis, 48 halogenated organics above 0.1 ug/l
according to EMSL—CI Method 502 could have been detected. One hundred and seven
organics were detected by Grob CLSA plus 171 organics (215—64) were not present
above our CLSA limits of detection. Therefore, Grob CLSA could have detected 278
organics in GAC—Inf. water. Following this logic, the average cost to quantify
an organic by EMSL—CI Method 502 and by Grob CLSA is approximately $2. Even
though these figures would indicate that Bellar P&T Method 502 and Grob CLSA have
a similar “cost versus benefit” ratio, the methods are not similar in the
complexity of instruments required to perform an analysis. However, in
considering the complementary nature and “cost versus benefit” figures of Bellar
P&T analysis (Method 601 or 502) and Grob CLSA, both methods are used for
important health effects research water samples, especially for studying a water
treatment unit process such as GAC adsorption or ozone disinfection.
To further illustrate the effectiveness of CLSA to monitor the fate of
purgeable organics in water, the Grob CLSA chromatograms (Figure 10) of a CWW
sample before and after ozone treatment (Ozone—Inf. and Ozone Eff. water,
respectively) are presented. The predominant oxidation of specific, trace—
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31
level, alkyl—substituted and halogen—substituted benzenes in this drinking water
sample would not have been apparent using the other three methods or HAS
procedures. Ozonolysis water treatment experiments conducted by the EPA
Drinking Water Research Divison (Cincinnati, OH) and analytical Grob CLSA
conducted by HERL—CI indicate that the reduction of purgeable organics in Figure
10 is due to chemical oxidation and not gas—phase stripping (ozone—oxygen). The
apparent chemical oxidation of these organics indicates a possible reduction in
toxic organics in ozonated drinking water. However, this is not to imply that the
reduced amounts of purgeable halogenated and aromatic compounds detected in this
ozonated water by Grob CLSA will provide evidence of a reduction in long—term
health effects. Such a determination would also require the comprehensive
measurement of ozone reaction products and the toxicological effects of ozonated
drinking water. Grob capillary GC/MS/DS CLSA, however, does provide highly
reproducible, quantitative information of many unit process effects (GAC,
ozonation, etc.) for one small group of compounds in drinking water — purgeable
organic s.
CONCLUS IONS
Future Comprehensive Analytical Scheme For Purgeable Organics
The analysis of purgeable organics will continue to be important in future
years, because many industrial pollutants are readily measured by P&T proce-
dures. State—of—the—art knowledge of comprehensive purgeable analytical methods
has reached a sufficiently high level that now allows environmental chemists to
design superior analytical schemes for the comprehensive analyses of purgeables
in drinking water. This comprehensive scheme, in our estimation, should consider
the following requirements which are evident in the data presented:
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1. Bellar P&T methods, such as EPA Methods 60l and 502 , provide
adequate sensitivity, GC resolution, detector specificity, and overall
method reproducibility to cost—effectively quantify low molecular
weight halogenated purgeable organics in drinking water. Furthermore,
gaseous—type halogenated organics such as chloromethane and vinyl
chloride are readily measured by the “combination” trap (Tenax —
silica gel — activated carbon) 33 ’ 35 , which is required in Methods 601
and 502. The above advantages and data indicate that EPA Methods 601
and 502 will continue in the future to be widely used by U.S. drinking
water laboratories. In addition, our data indicate that if Grob
closed—loop stripping analysis (CLSA) is used to measure purgeable
organics in water, the Bellar P&T Method 601 (or 502) should also be
used t measure low molecular weight halogenated organics (chlor—
omethane, vinyl chloride, chloroform, etc.) which are not amenable to
Grob CLSA.
2. Iligh resolution capillary columns are required to separate the
hundreds of alkyl—substituted and halogen—substituted aromatic com-
pounds which are often present in drinking water (see Table 2 and
Figure 10). Future data may show that, due to the complexity of
environmental water samples containing substituted aromatic isomers,
it is extremely difficult to measure purgeable substituted aromatics
using packed GC columns and a photoionization detector such as are
required in EPA Methods 602 and 50336. Instead, capillary GC/MS/DS
analysis such as Grob GLSA or the MAS RTI P&T procedure will be
necessary for these substituted aromatic compounds.
3. If future researchers find that statement 1, above,is correct, then
the required capillary GC/MS/DS procedures described in statement 2
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33
should be developed to quantitatively measure a broad spectrum of
purgeable organics from benzene, toluene, and isomers of dichloro—
benzene to as high a molecular weight range as is practical. Higher
purging temperatures and optimized trapping materials should be
developed and used. There seems to be a misconception today in the
thinking of some environmental chemists that batch liquid—liquid
extraction (BLLE) procedures or XAD adsorption procedures (XAD—EEE)
will cost—effectively measure low levels (1 to 100 ng/l) of purgeable
organics such as alkyl— and halogen—substituted indans, tetrahy—
dronaphthalenes, and biphenyls. These organics are difficult to
quantitatively measure in drinking water by BLLE and XAD—EEE due to
interferences from concentrated solvent impurities, losses of these
organics during Kuderna—Danish evaporation, and to the overall in-
sensitivity of BLLE and XAD—EEE. Therefore, the use of BLLE or XAD—EEE
for these purgeable organics is very difficult and costly. A
comprehensive capillary GCIMS P&T procedure, such as Grob CLSA or the
MAS P&T procedure, should be optimized to quantitatively measure trace
amounts of these higher—molecular weight aromatic compounds in drink-
ing water.
4. The MAS RTI P&T method attempts to use one P&T procedure to achieve the
comprehensive, combined results of both Method 601 (or 502) and Grob
capillary GC/MS/DS CLSA. From a design viewpoint, the MAS procedure
may poorly measure highly volatile compounds (such as chioromethane
and vinyl chloride) which Methods 601 and 502 readily measure. This is
due to the use of a removable—type Tenax (only) cartridge at room
temperature. Furthermore, it is not certain that the MAS P&T procedure
will measure the organics listed in statement 3 which are readily
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34
measurable by Grob CLSA. There is a need to systematically compare EPA
Method 601 (502) and Grob capillary GC/MS/DS CLSA to the MAS RTI P&T
procedure and to optimize a capillary GC/MS P&T procedure that meets
the basic requirements of statement 3. Such a comparison should also
include BLLE, EPA Methods 602 and 503 and the MAS XAD—4 procedure. The
cost effectiveness of each method should be computed.
Future Use of Grob CLSA
Even though Grob capillary GC/MS/DS CLSA is one of the first operational and
viable comprehensive purgeable analytical methods for drinking water, the
subsequent large number of purgeable organics measured by CLSA comprise only a
very small weight of the total mass of organic material present in potable water.
The data, however, indicates that the use of Grob capillary GC/MS/DS CLSA and
Bellar P&T analysis (Method 601 or 502) provide a viable and useful approach for
studying trace—level amounts of a surprisingly wide range of purgeable organics
in drinking water. Some of the advantages, disadvantages, and general features
of the CLSA method are listed here:
Advantages:
I. The method is simple, straightforward, and rapid. A water sample can
go from cold storage to CC/MS injection of the CLSA filter extract in
about 2 1/2 hours: Sophisticated, electronic “black boxes” are not
required for CLSA. No alteration of a standard capillary GC/MS/DS
(equipped with a Grob—type splitless injector) is required. Overall,
CLSA equipment costs about $1300.
2. The method is ultra—sensitive. Good mass spectra can be obtained on
most purgeable compounds in the 1 to 10 ng/l range. The GC/MS
detection limit of some PCB isomers is 2 ng/1.
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35
3. Blanks are extremely clean. The sample is extracted from the activated
carbon filter with only 12 ul of carbon disulfide.
4. Glass or fused—silica capillary columns coated with methyl silicone
liquid phases can be used with CLSA carbon filter extracts for a year
or more without developing sample—induced degradation of column
performance. This is in direct contrast to the injection of BLLE and
XAD—EEE extracts on similar capillary columns.
5. The method is relatively trouble free. The most frequent problem
(about once every 3 months at HERL—CI) has been contamination of the
closed—loop with high molecular weight organics from heavily contam-
inated water samples. Muffling the glass and metal components of the
loop at 450°C for 2 hours corrects this problem.
6. On a per—compound—quantified basis, the method is highly cost effec-
tive. Once initiated, sample purging, GC/MS data acquisition, and
automatic computerized quantification methods proceed virtually un-
attended. Solvent extraction of the activated carbon trap requires
approximately 10 minutes. Overall, three drinking water samples can
be automatically quantified for 215 organics in 24 hour period using
12 person—hours of labor.
Disadvantages:
1. The range of compounds effectively measured by Grob CLSA is somewhat
limited:
a) Highly volatile compounds such as chloromethane, vinyl chloride,
methylene chloride, and chloroform are poorly recovered and/or
covered up by the CS 2 extraction solvent. •Therefore, Bellar P&T
Method 601 (or 502) should also be used with CLSA to provide a
comprehensive analysis of purgeable organics.
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36
b) Moderate and highly polar or ionizable organic species are either
poorly purged or not recovered at all.
2. Highly contaminated samples, such as industrial effluents, may over-
load the 1.5 mg activated carbon trap and contaminate the closed—loop.
A larger capacity 5.0 mg trap, however, is now available from Bender
and Holbein Company in Zurich.
3. The method requires the development of new laboratory skills (extrac-
tion of the trap) before the method can be effectively implemented.
This may account for the surprisingly slow acceptance of Grob CLSA in
the U.S. as compared to European countries. While the CLSA procedure
can become highly routine in the hands of competent technicians, the
method is demanding of careful and consistent manipulations.
4. There is currently no U.S. commercial supplier of the Grob—designed
activated carbon filters or filter holders. In addition, there is no
worldwide supplier of an integrated, self—contained CLSA apparatus.
CLSA components must be purchased from a number of suppliers.
5. Grob CLSA has not been comprehensively researched to optimize ana-
lytical conditions and apparatus since Grob and Zurcher - 2 standard-
ized the procedure in 1976. It is suggested that Grob CLSA be
optimized to measure purgeable compounds from benzene, toluene, and
dichlorobenzenes to as high a molecular weight range as is practical.
Additional Features:
1. Grob CLSA is especially suitable for automatic quantification proce-
dures using state-of—the—art GC/MS/DS. The method provides highly
reproducible relative retention time data (+ 0.2%) and clean mass
spectra, which are important for highly successful automatic GC/MS/DS
software procedures.
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37
2. The five internal standards added before sample purging greatly
facilitate the requirement for good quality control and the monitoring
of recovery efficiencies.
This report shows that many compounds which are not amenable to Bellar P&T
and Grob CLSA (due to low stripping efficiencies caused by polarity, ioniza—
bility, and/or non—volatility) can be effectively analyzed using a large sample
volume (10 L), BLLE, and ultra—clean laboratory techniques. The described BLLE
procedure has produced extremely clean blanks and an apparent CC/MS detection
limit of 5 to 50 ng/l for a wide variety of extractable organic compounds.
The described XAD—2 ethyl ether elution (XAD—EEE) procedure (10 L water
sample) did not perform nearly as well as the above BLLE procedure. This XAD
adsorption procedure has also been shown to erratically contaminate extracts
during the ethyl ether elution phase of the procedure. Consequently, the use of
XAD adsorption procedures is not recommended (especially for the measurement of
alkyl—substituted aromatic compounds in drinking water) unless this type of
contamination can be absolutely prevented. The use of XAD—2 or XAD—4 resin to
measure alkyl—substituted benzenes, indanes, tetrahydronapthalenes, and naptha—
lenes is especially difficult due to the documented contamination artifacts from
XAD—2 and XAD—4 resin in this report (see Table 5). A P&T method such as Grob CLSA
is superior for this group of substituted aromatics.
This report presents experimental data which may be useful to the many
research laboratories that are developing and using comprehensive analytical
methods for the measurement of organics in drinking water. The development of
comprehensive analytical methods is expensive. It is especially important in
this coming era of diminishing monetary support for drinking water research that
comprehensive methods of organic analysis be 1) broad spectrum, 2) sensitive, 3)
cost—effective, and 4) scientifically sound. Hopefully, this report will
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38
stimulate renewed thinking along these lines.
The data presented suggests that the combined use of Bellar P&T Method 601
(502) and Grob capillary GC/MS CLSA (two cost—effective P&T methods) measures a
number of organics (at concentrations between 10 and 100 ngIl) that the HAS P&T
method and MAS XAD—4 adsorption method cannot measure. 8 The data also suggests
that the combined use of Bellar P&T Method 601 (502) and the described Grob CLSA
and BLLE procedure will measure a considerably greater number of organics (both
toxic and non—toxic) in drinking water than the combined use of the MAS P&T and
HAS XAD—EEE procedures 4 °.
Experimental data on samples of drinking water from CWW indicates that twice
as many “consent decree” organics 33 and “chemical indicators of industrial
pollution” 39 were detected and quantified by Grob CLSA than by Bellar P&T, BLLE,
and XAD—EEE analysis. Furthermore, Grob CLSA produced this superior analysis at
a low cost—per—compound—analyzed figure. The comparative data presented verify
the words used by Professor K. Grob, M. Reinhard, L. Stieglitz, and G. Piet to
describe Grob CLSA — “The method works”. This is the primary reason why Grob CLSA
continues to increase in worldwide popularity.
This report has attempted to present a brief review of U.S. P&T methods and
to point out design differences of each method. Interested North American
environmental chemists may find the detailed historical review of Grob CLSA
particularly useful. Finally, experimental data from our health effects re-
search has been presented to illustrate some basic differences between Grob CLSA,
Bellar P&T (Method 601), BLLE, and XAD—EEE analyses. Even though the experi-
mental data from these CWW samples does not validate or invalidate any of the four
tested methods, the data demonstrates some important differences in the
analytical performance which one might expect of each of these methods. Overall,
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39
the data indicate that the combined use of Bellar P&T (EPA Methods 601 or 502),
Grob capillary GC/MS/DS CLSA, and capillary GC/MS/DS BLLE analyses provide
useful information on drinking water treatment unit processes such as the
purification of water with one mgpd GAC Contactors.
ACKNOWLEDGEMENT S
We appreciate the outstanding cooperation of Mr. Richard Miller, Director,
and Mr. Dave Hartman, Chemist, of the Cincinnnati Waterworks in providing samples
and physical facilities to conduct health effects research experiments. Their
continuous cooperation over the years has been a service to drinking water
consumers throughout the U.S. The authors wish to thank Professor K. Grob, M.
Reinhard, L. Stieglitz, and C. Piet for their valuable advice on the use of Grob
CLSA, and the many individuals that diligently worked with us between 1975 and
1977 until we could produce superior WCOT capillary CC separations. We
appreciate the valuable assistance over the past six years of Mr. Tom Bellar,
EMSL—CI, for his constant advice and help on the analysis of purgeable organics
in water. We also thank Ms. Verna Tilford, Ms. Melda Hatfield, Ms. Nancy Koopman,
Ms. Deborah Dean, and Mr. Lon Winchester for typing, Mr. Rob Brown, EPA, CERI, for
graphical reproductions and Mrs. Marta Richards, Mrs. Jean Munch, Mrs. Dot
Reynolds for proof—reading, and Mrs. Judi Olsen for editorial assistance. At
Battelle Columbus Labs, Ms. Vanessa Goff, Ms. Denise Contos, Mr. Tim Hayes, and
Mr. Dan Aichele have made significant contributions in this work.
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40
REFERENCE S
1. Kopfler, F.C., R.G. Melton, R.D. Lingg and WE. Coleman. “CC/MS
Determination of Volatiles for the National Organics Reconnaissance
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Organic Pollutants .j Water , (L.H. Keith, ed.), Ann Arbor Sci. Pub.
Inc., Ann Arbor, MI. (1976).
2. Coleman, W.E., R.D. Lingg, R.G. Nelton and F.C. Kopfler. “The
Occurrence of Volatile Organics in Five Drinking Water Supplies
Using Gas Chromatography/Mass Spectronietry,” Identification
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3. Coleman, W.E., R.G. Melton, R.W. Slater, F.C. Kopfler, S.J. Voto,
W.K. Allen and T.A. Aurand. “Determination of Organic Contaminants
By the Grob Closed—Loop—Stripping Technique,” Proceed . of AWWA
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6. Michael, L., et al. “Quality Assurance In The Application of the
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7. Garrison, A.W., E.D. Pellizzari and .J.F. Ryan. “Master Analytcal
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41
10. Ryan, J.F., J.E. Gebhart, L.C. Rando, D.L. Perry, K.E. Tomer, E.D.
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Ann Arbor, MI (1981).
11. Coleman, W.E., W.K. Allen, R.W. Slater, S.J. Voto, R.G. Melton,
F.C. Kopfler and T.A. Aurand. “Automatic Quantitation and Statis-
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Ann Arbor Sci. Pub. Inc., Ann Arbor, MI (1981T
12. De Marco, J., A.A. Stevens, and D.J. Hartman. “Application of
Organic Analyses for Evaluation of Carbon Adsorber Performance in
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13. Grob, K. “Organic Substances in Potable Water and in its Pre-
cursors, Part I, Methods for Their Determination by Gas—Liquid
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14. Bellar, T.A. and J.J. Lichtenberg. “The Determination of Volatile
Organic Compounds at Microgram Per Liter Level in Water by Gas
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15. Bellar, T.A., .3.3. Lichtenberg and R.C. Kroner. “The Occurrence of
Organohalides in Chlorinated Drinking Waters,” Jour. AWWA , 66, 703
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16. Lingg, R.D., R.G. Melton, F.C. Kopfler, W.E. Coleman and D.E. Mit-
chell. “Quantitative Analysis of Volatile Organic Compounds by
GC/MS,” Jour. AWWA , 69, 605 (Nov. 1977).
17. Grob, K and F. Zurcher. “Stripping of Trace Organic Substances
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18. White, L.D., D.C. Taylor, P.A. Mauer and R.E. Kupel. “A Convenient
Optimized Method for the Analysis of Selected Solvent Vapors in the
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70).
19. Grob, K and C. Grob. “Organic Substances in Potable Water and in
its Precursors, Part II, Applications in the Area of Zurich,” J.
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20. Grob, K., K. Grob Jr. and C. Grob. “Organic Substances in Potable
Water and in its Precursors, Part III, The Closed—Loop—Stripping
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21. Stieglitz, L., W. Roth, W. Kuhn and W. Lager. “The Behavior of
Organohalides in the Treatment of Drinking Water,” Vom Wasser , 47,
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22. Zurcher, F. and W. Giger. “The Study of Volatile Organic Compounds
in the Glatt River,” VomWasser, 47, 37 (1976).
23. Giger, W., M. Reinhard, C. Schaffner, and F. Zurcher. “Analysis of
Organic Constituents in Water by High Resolution Gas Chromatography
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24. Giger, W., E. Molnar and S. Wakeham. “Volatile Chlorinated Hydro-
carbons in Ground and Lake Water,” Aquatic Pollutants (o. Hut—
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25. Schwarzenbach, R.P., E. Molnar-Kubica, W. Giger and S.G. Wakeham.
“Distribution, Residence Time, and Fluxes of Tetrachloroethylene
and 1,4—Dichlorobenzene in Lake Zurich, Switzerland,” Envir . Sd.
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26. Giger, W. “Inventory of Organic Gases and Volatiles in the Marine
Environment,” Marine Chem., 5, 429 (1977).
27. Schvarzenbach, R.P., R.H. Bromund, P.M. Gschwend, and O.C. Zafi—
riou. “Volatile Organic Compounds in Coastal Seawater,” Organ.
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28. McCarty, P.L., N. Reinhard, and D.C. Argo. “Organics Removal by
Advanced Wastewater Treatment,” Proc. 97th AWWA Annual Conf., Ana-
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Organics Removal by Advanced Waste Treatment,” Proc. Amer . Soc.
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30. Reinhard, M., J.E. Schneier, T. Everhart, and J. Graydon. “Speci-
fic Compound Analysis by Gas Chromatography and Mass Spectroscopy
in Advanced Treated Waters,” NATO/GCNS Conf. of Practical Applica-
tion of Adsorption Techniques, Reston, VA (May, 1979).
31. McCarty, P.L. and N. Reinhard. “Statistical Evaluation of Trace
Organics Removal by Advanced Wastewater Treatment,” Annual Conf. of
the Water Pollution Control Federation, Anaheim, CA (Oct. 1979).
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32. McCarty, P.L., D. Argo and M. Reinhard. “Operational Experiences
with Activated Carbon Adsorbers at Water Factory 21,” Jour. AWWA ,
71, 683 (Nov. 1979).
33. “Guidelines Establishing Test Procedures for the Analysis of Pol-
lutants,” Federal Register , 44, 69464 (December 3, 1979).
34. Natural Resource Defense Council, Inc., et al versus Train, 8 ERC
2120 (D.D.C. 1976). —
35. “The Analysis of Halogenated Chemical Indicators of Industrial
Contamination in Water by the Purge and Trap Method, Method 502”,
Environmental Monitoring and Support Laboratory, Cincinnati, OH
45268 (December, 1978).
36. “The Analysis of Aromatic Chemical Indicators of Industrial Con-
tamination in Water by the Purge and Trap Method, Method 503”,
Environmental Monitoring and Support Laboratory, Cincinnati, OH
45268 (May, 1980).
37. Junk, G.A., J.J. Richard, J.S. Fritz, and ll.J. Svec. “Resin Sorp-
tion Methods for Monitoring Selected Contaminants in Water,” Iden-
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ed.), Ann Arbor Sci. Pub. Inc., Ann Arbor, MI. (1976).
38. Lin, D.C.K., S.V. Lucas, and R.G. Melton. “Glass Capillary GC/NS
Analysis of Organic Concentrates from Drinking Water and Advanced
Waste Treatment Water,” in Advances in the Identification and Analysis
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5773 (February 9, 1978).
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LIST OF FIGURES
Figure 1 Fundamental Schematic of EPA Master Analytical
Scheme P&T Method (RTI Method)
Figure 2 HERL-CI Approach to Analysis of Purgeable Orga—
nics in Drinking Water
Figure 3 Fundamental Schematic of EPA Method 601 and 502
(Bellar P&T Method)
Figure 4 Fundamental Schematic 0 f Grab CLSA Method as
Modified by HERL-CI on August 1, 1980
Figure 5 Water Samples Used to Compare Four Analytical
Procedures:
a) GAC-Inf. Water was CWW water prior to pas-
sage through a 1 mgpd GAC contactor at CWW
(GAC contactor A water samples were col-
lected on January 14, 1980; GAC contactor D
water samples were collected on January 28,
1980);
b) GAC-Eff. Water was collected after passage
through the 1 mgpd GAC contactor at CWW;
c) XAD—Inf. Water was GAC Inf. water which was
brought back to HERL-CI for subsequent
adsorption on a 37 cm 3 XAD—2 analytical
column;
d) XAD—Eff. Water was collected after passage
of XAD Inf. water through the 37 crn XAD-2
column.
Figure 6 Chromatographic Results of Bellar P&T Analysis
Figure 7 Chromatographic Results of GAC-Inf. and GAC-Eff.
Water Using Grab CLSA
Figure 8 Chromatographic Results of BLLE Analysis of GAC-
Inf. and GAC-EFF. Samples - Neutral Fraction
Figure 9 Chromatographic Results of BLLE Analysis of GAC-
Inf. and GAC-EFF. Samples - Methylated Acid
Fraction
Figure 10 Chromatographic Grab CLSA Results of CWW Raw,
Settled Water (Ozone-Inf.) and Ozone Treated
Water (Ozone-Eff.)
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45
LIST OF TABLES
Table 1 Results of Bellar P&T Analysis
Table 2 Results of Grob Capillary GC/MSIOS CLSA of GAC-Inf.,
GAC-Eff., XAD-Inf., and XAD-EFF. Samples
Table 3 Results of BLLE Analysis of GAC-Inf. and GAC-Eff.
Samples - Neutral Fraction
Table Results of BLLE Analysis of GAC-Inf. and GAC-Eff.
Samples - Methylated Acid Fraction
Table 5 Artifact Contaminants from XAD-2 Resin in XAD-EEE
Sample
Table 6 Results of Analysis of XAD-Inf., XAD, Eff., and XAD-
EEE Samples - Neutral Fraction
Table 7 Results of Analysis of XAD-Inf., XAD—Eff., and XAD-
EEE Samples - Methylated Acid Fraction
Table 8 List of 215 Reference Compounds Which Are Measured
in Each Grob CLSA Sample
Table 9 Organics Detected in GAC-Inf. Sample by More than
One Analytical Method
Table 10 Comparisona of Analysis Results of Four Methods
Using Organic Functional Groups and EPA Lists of
Toxic Compounds
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PURGE MODE DESORPTION
MODE
Trap at
25°C He
He
CHROMATOGRAPHY
MODE
L___j 1__ J
1
pat 50M SE3O
2500 C Capillary
Column
Figure 1 Fundamental Schematic of EPA Master Analytical
Scheme P&T Method (Rh Method)
60g Na2SO4
Added
He
200 ml Water
Sample at 30° C
)
Liquid N2
Trap at -195° C
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47
Method A - Ana’ysis of 5 ml Water Samples using EPA Method 601
(Bellar Purge and Trap Analysis) for Quantification of 23 Halogenated
Low Molecular Weight (Chioromethane through Bromoform) Organics.
ADVANTAGES:
1. Low Cost - Packed GC Columns/Electro-Conductivity Detector
2. Fast - 20 minutes for Bromoform to Elute.
3. Well Researched and Accepted Method.
5 ml Sample 4. Good Quality Control Procedures.
DISADVANTAGES:
1. Very Few, Considering Cost/Organic
Method B - Analysis of 1 -L Water Samples using Grob CISA for MS
Quantification of over 215 Organics and Qualitative Identification of over
400 Organics.
ADVANTAGES:
1. Good MS Sensitivity - Detection Limit of I to 10 ng/l.
2. Good Reproducibihty - Internal Standards are spiked in Water Prior to
Purging; Accuracy of 25% for most Solvent Type Organics at the
50 ng/I Level.
3. Excellent Method for Control of Unit Processes such as;
A) Use of Granular Activated Carbon.
B) Disinfection with Ozone, Chlorine. Chlorine Dioxide, and Chloramines.
C) Source Contamination of Drinking Water Supplies due to Industrial
Spills and/or Discharges.
DISADVANTAGES:
1. Expensive
A) Cost per capillary GC/MS/DS CLSA - $460, or
$460 - - 215 Organics = $2 per Organic.
B) Cost per capillary/FID CLSA - $80
2. Sample Matrix Interferences.
3. Activated Carbon Trap may become Overloaded with Organics
in Industrial Effluents
Figure 2 HERL-CI Approach to Analysis of Purgeable Orga-
nics in Drinking Water
1 Liter Sample
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PURGE MODE
.-Vent
Activated
Carbon
Silica Gel
Ten ax
at Trap at
C 180°C
DESORPTION AND
CHROMATOGRApHy
MODE
Fundamental Schematic of EPA Method 601 and 02
(Bellar P&T Method)
-l
J
ml Water
Sample
He
Hall E.C.
Detector
8 ft. Packed
GC Column
Figure 3
0: ’
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SOLVENT
EXTRACTION MODE
CHROMATOGRAPHY
MODE
12p 1 of CS2 Used
in Extraction
Activated
Carbon
8p1 of CS2 Recovered
in Extraction
L TTi [ i
60M SP2100
Capillary
Colurnn
—l
Figure 4
Fundamental Schematic of Grob CISA Method as
Modified by IIERL-CI on August 1, 1980
PURGE MODE
Con dens er
at 950
TraPf
Sample
Vial
( :I JLl • i) )
1 L of Water
at 400 C
-------
50
Raw River Water
CWW GAC
Contactor
1
1. Coagulation
2. Sand Filtration
3. Chlorination
pH2 -XAD-Inf.
x
A
D
XAD-Eff.
Ethyl
Ether
Water Samples
Procedures:
Used to Compare Four Analytical
a) GAC-Inf. Water was CWW water prior to pas-
sage through a 1 mgpd GAG contactor at CWW
(GAC contactor A water samples were col-
lected on January 14, 1980; GAG
water samples were collected on
1980);
was GAC Inf. water which was
to HERL-CI for subsequent
a 37 cm 3 XAD—2 analytical
d) XAD-Eff. Water was collected after assage
of XAD Inf. water through the 37 cm XAD-2
column.
b) GAC-Eff. Water was
through the 1 mgpd
c) XAO-Inf. Water
brought back
adsorption on
column;
contactor D
January 28,
collected after passage
GAC contactor at CWW;
XAD-EEE
(Ethyl Ether
Eluant)
GAC-Eff.
Figure 5
-------
GAC kit
GAC U.
Ous$ y Coiuvol Si&nda ds
t I
I I
I
I I
8 10 1
2 14
18
18 20
Tim. (iitin
Chromatographic Results of Bellar P&T Analysis
80
I
I
I
8 10 12
I
Figure 6
8 10 12 14 16 18 20
Lit
-------
GAC-Inf.
E
0
0
o a)
-= C t ,
L) -= a)
4- D
S- zr a)
o -
I 0
o a —
- U) U
U N (t,
- a)
I— QD U)
I F—
GAC-Eff.
a)
0
S . - -
U) U
- Ct,
5—
a)
U)
> E I—
o_ s-
00 a)
S. -4-- 0
0 0 G) 0
05 - N4 5 -
c no
•‘-‘-- a)L)
• — a
L)
zr jL-
N-
TI
I ‘
300 400 500 600
10:00 13:20 16:40 20:00
5—
a)
E
0
a) L 1
0
C U)
(U =
0
C C
a) (U
> -, I
- 0 C
+- 5__ U)
i =0
i U I—
co
r’) c’
c’ r
/ (\
a)
C
0
C
CU
a)
(\J
>
a)
U)
5-
o a)
=
(U 0
ci U)
P
a)
I =
a) C\J 0
Ca) I
(t,=
rU 5- -i — ’—
4- = 0 0—
a)4 ) ?—a)a)
0a) 0=0-W
5-E Ua) I 0
00 • -r -.jc - )rt,
—c sc ><
CO H-a)OU)
U. ,- ‘ 05- =
( U0 — ooo
5-5- .,S__,.—s_
(U I ’ C ‘—4 o= o
C a) - r’Ur
(t, I— -s
X U L L)
a) O r I
= z - Lfl LO ‘—4 r—
800 900 SCAN
26:40 30:00 TIME
SCAN
TI lIE
C)
C
a)
r
0
F—
a)
c
V)
a)
_)
a)
C
a)
5—
0
(U
0
0
><
,—
-=
a)
C
-
UC)
(UC
0
5- 0
5.-
+ 4-
-
a)U
-
5 -)
r
co
LC)
tC
O .:
N-
7
1
\
I
r
7
700 800
23:20 26140
Chrornatograpnic Results of GAC- nf. and GAC-
Eff. water Using Grab CLSA, page 1 of 4.
52
r -)
a)
4)
a)
0
5--
0
0
U
0
0
-o
100 • 0
R
431 .0-
RIC
300 400 50 . 0 6.0.0 700
10:00 j3:29 16:46 26:66 23:20
Figure 7
-------
U)
C
U)
GAC-Inf. C
Cc) F C) a)
U )L() Q ) ¶.-O C NJ
C a_)cr Or—. C
C C CC C a)
_o o C -
+-‘ cflG) 4-)1 U) 0
S.-
a) -C C G)NJ o
U) 0 0 (UU) CC
U) 5 - a)C CC (JJC)
C 0 CCC I U) NJO
U
C) U) Q — C N -J CO
CC C U)5-
D C U f da) a) 00
C) CC 4—DO . >0
.— 0 S.- I ‘— >-, C
U) 0 C’) > - U _
- > U) C I I a) -C
-C —- C)r- JO CJC)
C C - _) I NJ I 5-U) (Ca) El
C) (NJ C 0 0 C 5- F r- —ar
C ’ -) F - a)5-’—a) 5- C)
r- - j 0 0 .C NJ C) (NJ I— ‘—I
10 . ‘ —---UC H-
I . — >-,C0aJ I’—
( NJ O U F >-
• . : 0 - 0’— ‘ O
•zz1- L5-S. . >) -> i
F- CC 0 LU . ; I
c CC - CC- 0 0 IN I
CC - Lfl LO v zr Lf) S.
(N C) I
oo I
C)
L LiLL JU
t f )
a) a)
C C
C) U) a)
C NJ NJ
Cd C C
U) a)
UC).O .0
I—
0 (C>) >-,
S.-C .C
O 4 - - - .4 )
‘—a) a) C)
COE F
C) S.-
to-c -o
r- (NJ
U
(C —l -l
>< I
a)
> - , Cr )> -)
C C C
-H -i- -) rC4 -)
(NJ LU CU)
I 0 I
i
C )
I LO
(NJ , —1r- - )
iLl
I
I ‘
I
I
I
900 1000
1100
1200
1300
1400
1500
SCAN
30:00 33:20
36:40
4Ø O0
43:20
46:40
5OtOO
TIME
-1 )
C
a)
N J
C
a)
0
C)
a
C -i )
GAC-Eff.
a)
C
4 J
C)
C) 0
C S.
a) 0
NJ
C C
C) U
(C
S.-
>_) j
0 a)
+ -
a) I
E ( NJ
C) (NJ
( N J
C) _
CC-
c 5
C C C ) CC- CC
L ) L() LO
LO
1L JLJ
a)
C
U)
NJ
a)C
CC )
C) 0
NJ
C >-,
a) 0
‘-- a)
>E
4 ) S.-
C) F-
F I
I czj- CC
(NJ “C
I (NJ C
4 - .)
> )f-1 U
C C)
4-.)
U) Q—4
CC
cC
CC-c)
C\JC ’ -)
a)C) C)
CC C
Wa) a)
NN NJ
CC C
a)Q) a)
.0.0 -.0
>)C>-) >
4 )4 - .) 4 i
a)G) a)
WEE E
Cd -c -c ‘—C
.0 I I rC I
4 ) CC- (NJ (NJ
a). “ C C
0 S—i —1 C ‘-4
S . - I IC ’
0 ‘ —
‘ -—> >
C 0 C) .0
4-.) 4 J ( ) 4-.)
LU LU r-4 LU
I I
I ‘)
100.0-
RIC
159.0-
RIC
C)
C
4 )
U
0
0
S.-
0
(-I)
-4
a)
C
a)a)
NJC
Ca)
C
f-C)
> ) 0
. 0
Ia)
a)c F
C Ir-
a)’— S .-
NJ >±-
0 . 0 I
a) 4 ) L()
0LU
lt ” )
a)
C
a)
a)NJa)
CCC
wwa)
NJ 0 NJ
C — C
a) > ) C)
o -k-’ 0
S . -a) S .-
OF 0
.0 S.. 0
•Uf7•L)
-4 f - 4 -4
a)
C
a)
NJ
C
C)
>
0
S .-
0
0
L/ )
C- —
- 4
1• T — I • I I
900 1000 1100 1200 1300 1400
30:00 33:20 36:40 4000 43:20 46:40
-4
7
SCAN
TIME
Pgure 7
continued, page 2 of 4.
-------
5/.
‘— s__
GAC-Inf.
C C)
a) L I) - CJ-
C CC)
a) a) -
C ‘—C) C) _
C) (tiC Q)C C
NJ Q) CQ) O .C —
C - 4 -ar -- QJN (0
a) (0 MC C
- ci aj
(04-) Q)CO C)
>) C C C C
C 00 CLr) C) 4- 0
4 ) r0 ‘— C) S .-
) 1JC C) C
E > 0 i > a)
( 0 C —1
(0T J C (0
DTI’ U> 0 S. C)
a) C) -C S -C) C) (0 = -
H- 0 ( 0 — C C C) >-
I I C) (0 10 + -
LC) >,4-> ‘zj — C U >, ‘—
c i (0 (0 0) C (0 > - , C
10 4- H- C\i - U 0 J.) C C ro
C)’ •— a ) 0 C) (0 4— ’ “—U
zj- -4 U (I) a)
0. ‘ C) E
- _1 C J C ) (0 LO (\J CO 0
r— . cC n—
LC) - . • -
1500 1600 1700 1800 1900 2000 2100 SCAN
50:00 53:20 56:40 60:00 63:20 66:40 70:00 TIME
a)
C
a)
0) (‘Al’
159 @ C J ’ ’L—II.
a) a)
C) C —N
C a) ( 0C 0.
a) NJ (a
N J C C
a) U’—
a) - a)>-, > - ,
> - , 4-)
> a) C) W
C
.4 . ) C) .-_ -- ‘- C) I
0) E
C u
(a ..C C)
I C
C (a 5 . -
RIC >, - 0 C)
I— (0 Q)
4- ) 0 ( aC
LC) a) Cf O QJ(0
>- , (00
> C 00) > ( 0
_ CU
4-) C) Cr 1 00)
r-4 ,—1 I , ::o — 0
— c\J
LO N- C’ LO O 0
r r - cO - (\J LC - CoC’ i
N- N- CO C C)
‘ ILLLL
1500 1600 1700 1800 1900 2000 SCAN
5Ø:ØØ 53:20 56:40 60:00 63:20 66:40 TIME
Figure 7 continued, page 3 of 4.
-------
55
V)
I I I • I • I
2200 2400 2600 2800 3000 3200 SCAN
73:20 80:00 86:40 93:20 100:00 106:40 TIME
C)
a) r
(NJ C -
( , 4-’
( Q) C
c-c
r >-
U4- ’ C
C)C 4-’
-ow w
S .-
p-co
- LC) U) N U) N
C\J LX) LO N (NJ
C
-o
C
>-,
C
C) S .-
- C)
ci E
I 0
V)
>) a)
- 4-)
_ 4 _j rt
a)
• _C
S_ 4-’a)
I — CC
( -) r )
>)a)
• ; 4 - C
‘-4 _04 - )
c c
a)
C a)
r -
U
a)
- IC
X 4-’
a) -
-= o_
0
S.- >
o 4 )
0
L)
‘-4
cc
cc
(NJ
100.0-
RIC
159.0
RIC
a)
C
U
a)
-c
4- ’
C-)
0
0
S.-
0
a)
GAC-Eff.
c i i
U
c i)
0
-I -i
U
0
0
S.-
0
( )
‘ -4
a)
C
rC a)
U 4-’
a) (C
0
(C (C
>< C
a) -I-’
- _C
o o
o >
‘—4
cc
cc
C\J
2200 2400 2600 2800 3000 3200 SCAN
73;20 80:00 86:40 93;20 100:00 106:40 TIME
Figure 7
continued, page 4 of 4.
-------
GAC Inf.
56
100 200 300 400 500 600
Spectrum Number
.30 .44) .50 .60 .70 .80
Relative Retention Time
(Both Chromatograms)
Figure 8 Chromatographic Results of BLLE Analysis of GAC—Inf. and GAC—
EFF. Samples — Neutral Fraction, (page 1 of 2).
t
100-
80-
60 -
40
20
8
a,
I
a,
C
a,
x
a,
0
U
0
0
U
16
a,
C
a,
(5
a,
a,
> .
a,
E
0
U
>.
1•
IS
IS
HEB
I 1 ••
100 200 300 400 500 600 700 800 900 1000
Spectrum Number
36
/
100
80
60
t = Water extractton artifact
* = Sample processing artifact
IS = Internal standard, 0.2 ppb
IS
GAC Eff. HEB
IS
t
+
IS
t
IS
.10 .20
700 800 900 1000
1.00
-------
CD
CD
> .
C.,
0
42
> .
a,
E
GAC Inf.
57
- J I
1100 1400 1500 1900
Spectrum Number
IS
HEB GAC Eff.
t = Water extraction artifact
* = Sample processing artifact
IS = Internal standard, 0.2 ppb
37
IS
a,
IS
C
CD
> .
C.,
0
7
t
*
1300 1400 1500 1600 1700 1800 1900
1100 1200
Spectrum Number
i.o iio 1.20
1.30 1.40
Relative Retention Time
(Both chromatograms)
1.50 160
1.70 1.80
IS
a,
C
0
C
CD
C
IS +
a,
>.
C
38
a,
0 )
C
CDE
a)
.
E
CD
CD
>
C
a,
-a
2
49
+
IS
01
C
C D
>.
N
C
CD
a.
In
0
-a
41
t
100-
80-
60-
40-
20-
100-
80-
60
40-
20-
1000
a,
C
0
0 )
C
0
.4-
1200 1300
C
0
C
C
4:
1600
1700
1800
Figure 8 Continued, (page 2 of 2).
-------
100-
80
60-
40-
20-
i
GAC Inf.
Spectrum Number
1 GAC
t
IS+14
58
IS
HEB
Is
* IS+14 HEB
(4:?)
t 4: 16
700
100 200 300 400 500 600 800 900 1000 1100
Spectrum Number
.10 .20 .30 .40 .50 .60 .70 .80 .90 1.00
Relative Retention Time
(Both chromatograms)
Figure 9 Chromatographic Results of BLLE Analysis of GAC—Inf. and GAC—
EFF. Samples — Nethylated Acid Fraction, (page 1 of 2).
U
a,
U
0
4:
a,
‘C
a,
> .
-S
6(t)
C.,
a,
C.)
a’
a,
E
> .
4 .
a,
E
D >
a, a
23
18+19
*
4:
I I
100 200 300 400
26
27
500 600 700 800 900 1000
* Water extraction artifact
= Sample processing artifact
IS = Internal standard, 0.2 ppb
80
60
*
-------
59
GAG mt.
U
C S
C.,
C .,
CS
>.
x
0
( 5
0
0
-6
C%1
4: 38
1050 1100 1150 1200 1250 1300 1350 1400 1450 1500 1550
GAC Eff.
HEB t = Water extraction artifact
c = Sample processing artifact
IS = Internal standard, 0.2 ppb
t
1100 1150 1200 1250
___- - - -
1.0 1.1
t
1300 1350 1400 1450 1500 1550 1600 1650
1.2
Relative Retention Time
(Both Chromatograms)
1.4
IS
HEB
U
CS
*
C.)
( 5
U
33
C .,
( 5
U
0
U
U
( 5
U
.0
> .
x
0
.0
100 -
80-
60
40-
20-
100-
80-
60-
40-
20-
C.)
(5
U
(5
i
-a
4:
*
+
(5
C.,
31
t
t
t
1.3
Figure 9 Continued, (page 2 of 2).
-------
43.5-.
RIC_
Figure 10
aD
600
20 00
Q)
a) -
a)LC)
MI 0
=1 -
I
U
4 -
a)
zj-
1
900 1000
30*00 33 :20
c i)
a)
M
a)
c i) C
C
ci) -
N I
C ci)
C) C
C
0
>
C C
U
a) ra
E 5—
a)
a)
C
a)
NI
C
a)
-o
>
0
C
5-
0
0
:d- ( -1)
C )
C
a)
NI
a)
-C
>
C ia)
CE
WI
NI
C I
a)r-
> -
L J
0 I
5- ‘ —I
a-
SCAN
TIME
SCAN
TIME
Chromatographft Gcob CLSA Results of C W Raw,
settled ater (0zone- nf.) ‘ hich was Treated
60
Ozone Inf
a)
C
a)
0
F-
a)
C
a)
N J
C
a)
. 0
0
5-
0
C-)
c i)
C
a)
I N I
C
Ia)
> —
C>)
UJ4-
IC)
—I E
a)
C
C)
0
5--
0
U
0
E
0
5—
a) C
C C . )
a)
a)
0
5-
0
N U
(••_) ra
‘5--
C)
C)
U
>
aD
(\J
Co
a)
C
a)
NI
C)
- C
>
0
0
5-
C-
0
(I )
N-
a)
C
a)
NJ
=
a)
-C
> -,
a-
C
5--
a-
700 800
23:20 26:40
131.
1100
36:40
Ozone Eff.
a)
C
a)
-c
a)
0
5--
C
-c
U
5--
ci)
F-
a)
a) -
C
a) a)
= E
0
0 5--
I— 0
-C
U
0
E
0
5--
C
a)
-C
-C
a)
E
C
-c
r
a)
C
C
C
ra
x
a)
=
a)
C
a)
NI
C
a)
-o
0
5--
C
LO
700
23:20
N-N-
800
26:40
900
30:00
1000
33:20
With Ozone (Ozone-Eff.), page 1 of 2.
-------
Ozone Elf.
C) C)
C)
C) C)C)
r N C)
C CC) NJ
C) C)NJ C
C)
C)
> , >)-C 0
-= C0
0
a) C)0
E
I •‘- C U
( ‘J —L)
> I C\J
C\J
U
N - Q
coco o
)1ikkI
I • I
1200
40:00
1300
43:20
C)
=
C) C)C)
=
C) C)re
NJ
C) C)0..
>-)
C)
C re C) C) > ,
C E E C
re r :
4 ) C -
0 4 )
a) Wa)
H— I--
I I I
c ) Lr) - -
OCO
(\
. 1 .1.:
C)
0
C
0
C
C)
. LO N- LC) N. C
c’ r r ) t zr
_ .1.1 : . . .•
Ii
1400 1500
46:40 50:00
a)
E
0
.Lf
C)
C
C)
NJ
C)
Lr)
Li
-o
C
r
C)
C
C)
0 .
(0
• : r CO C
LC) U) Lf) LO
1600
53:20
61
43
R
131 .6-
RIC
1200 1300 1400 1SOO 1600
40:00 43:20 46:40 5Ø:OØ 53:20
tf)
SCAN
TIME
SCAN
TIME
Figure 10
continued, page 2 of 2.
-------
Table 1. Results of Beliar P&T Analysis
Retention
Ti me
(mm)
d % Removed by GAC in Contactor 0
XAD -
Eff.
(% Reniovede)
N.)
GAC
Contactor 0 Watera
GAC
Contactor A Water 8
GAC .-
GAC-
GAC-
GAC-
XAD-
XAD-
Inf.
Eff.
Eff.
Inf.
Inf.
Eff.
1.
Methylene Chloride
4.8
NOb
ND
ND
ND
ND
2.
Chloroform
8.9
56
ND
100
65
23
3.4
3.
1,2-Dichioroetharie
9.5
ND
ND
ND
ND
ND
4.
i,l,l-Trichloroethane
10.4
0.4
ND
100
1.9
ND
1.1
5.
Tetrachloromethane
10.7
ND
ND
ND
ND
TP
6.
Bromodichioromethane
11.7
18
ND
100
83
10.9
0.6
7.
Trichioroethane
13.3
TDC
ND
TO
0.1
0.1
8.
Chiorodibromomethane
14.4
5.8
ND
100
8.0
5.0
0.4
9.
Brornoform
17.1
0.2
ND
100
ND
ND
10.
Tetrachioroethene
19.1
ND
ND
ND
ND
ND
85
94
0
92
a Water samples described in figure 5
b ND = Not Detected
C ID = Trace Detected
e % Removed by XAD-2 Resin in Analytical Column (see figure 5)
-------
Table 2. Results of Groli Capillary GC/MS/OS CLSI\ of GAC-lnf., GAC-Eff., XAD-Inf., and XAD-Eff. Samples
Contactor 0 Water Contactor A Watere
Quan. GAC_Inf.e GAC_Eff.e % Removal GAC_!nf.e XAD_Inf.e XAD_Eff.e % Removal
Compound RRTC Methodd (ng/l) (oq/l) by GAC (ng/l) (ng/l) (n /l) by XAD
1. 2 Butanonea .134
2. 3 .Methylpentanea .136
3. Diisopropylether .146 141 RAIJ 0 RAU 100 460 RAU 145 RAU 0 RAU 100
4. Chloroform .149 S 10 ug/l .60 ug/l 94 12 ugh 5 ugll .40 ug/l 91
5. Methylcyclopentane .161 NQ NQ
6. 1,I,1-Trichloroethane .167 S 8 1 88 4 2 0 100
7. 1_Chlorobutanea .171
8. 2-Pentanone .175 NQ
9. Benzene .180 S 86 8 91 53 57 4 93
10. Carbon tetrachioride .184 S 14 4 71 8 6 3 50
11. Cyclohexane .186 4 RAU 0 RAU 100 8 RAEJ 7 RAtJ 0 RAIJ 100
12. C7 alkane isomera .198
13. Cyclohexenea .201
14. Methylpropenoicacid, methylester .207 NQ
I somer
15. 1,2-Dichloropropane .208 2 RAU
16. Trichloroethene .215 S 57 3 95 6 7 2 71
17. Bromodichloromethane .220 S 16 ugh .01 ugh 100 13 ig/l 6.2 ug/l .03 ug/l 100
-------
Table 2., Continued, Page 2
Quan.
Compound RRTC Methodd
Contactor 0 Watere
Contactor A Watere
GAC.Inf.e GAC_Eff.e
(ng/l) (ng/l)
X Removal
by GAC
GAC_!nf.e
(ng/l)
xAD_Inf.e
(ng/l)
XAD_Eff.e
(ng/l)
% Removal
by XAI)
18. Methylpropenoicacid,
methyl ester isomer
19. Heptane
20. 1-Bromo-2-chloroethane 8
21. 5,5_Dlmethyl_2_hexenea
22. Methylcyclohexane
23. 4-Methyl-2-pentanone
24. Dichioromethylbutane isomer
25. 4_Octanonea
26. 2,3,4_Trimethylpentanea
27. 2_Bromo_1_chloropropanea
28. Toluene
29. 4_Methyl_2_pentanola
30. 1,3-Dichloropropane 8
31. 2-Methyl thiophene 8
32. Butyl acetate isomer
33. 34Iexanone
34. 2-Ethyl-4-methyl-1,3-dioxolane
.230
.233
.234
.240
.248
.254
.216
.277
.284
.287
.288 S 32
.289
.299
.299
.300
.304
.310
S
2RAIJ ORAU
5 RAil
0 RAil
4RAU ORAIJ
64 RAil 0 RAil
20 RAil 0 RAil
0
4 RAil
5 RAil
9
0
o RAil
o RAil
100
100
100
100
100
2 RAil
16 RAil
72 19
100
100
0
3 RAU
1 RAil
5 RAil
32
0
0 RAil
0 RAil
0 RAil
59
0
100
100
100
-84
a’
-------
Table 2., Continued, Page 3
Contactor D Watere Contactor A Watere
QU I- . GAC_Inf.e GAC_Eff.e Removal GAC_Inf.e XAD_Inf.e x4O_Eff.e %
Compound RRTC Methodd (ng/l) (ng/I) by GAC (ng/1) (ng/l) (nq/1) by XAD
35. Dibromochioromethane .313 S 6.2 ugh 0 100 5.7 ugh 2.9 ugh .01 lg/l 100
36. Hexanal .319 S 6 4 33 0 6 0 100
37. Ethylmethyl-1,3-dioxolane isomer 3 .320
38. Tritnethylcyclopentane isomer 8 .331
39. Tetrachioroethene .338 S 18 3 83 14 20 3 85
40, Dichloroiodomethane .345 S 9 0 100 47 15 0 1.00
41. Octane .345 NQ
42. Butyl acetate isomera .346
43. Diethyltetrahydrofuran isomer 3 .363
44. 1,1,1-Trichloro-2-propanone .369 34 RAU 0 RAU 100 1 RAU 8 RAU 0 RAU 100
45. Chlorobenzene .375 S 14 2 86 10 14 1 93
46. DicHoro-3-pentanone isomer .382 13 RAU 0 RAU 100 5 RAU 0 RAU 100
47. Ethylbentene .398 S 24 4 83 2 4 2 50
48. 1,3-Dimethylbenzene .409 S 8 6 25 7 13 7 46
49. 1,4-Dimethylbenzene .410 S NO NO NQ NQ NQ
50. Bromoform .415 S .51 ugh 0 100 .66 ugh .38 jg/l 0 100
51. 3-Heptanone .428 NQ
C.’
U i
-------
Table 2., Continued, Page 4
Quan.
Compound RRTC Methodd
Contactor 0 Waters
Contactor A Watere
GAç_Inf.e GAC_Eff.e
(ngfl) (ngfI)
% Removal
by GAC
GAC_Inf.e
(ng/l)
xAD 1nf.e
(nq/l)
XAD_Eff.e
(ng/l)
% Removal
by X/IO
5?. Trimethylcyclohexane isomera .430
53. Styrene .430 S 0 1 - 2 2 0 100
54. 1,2-Dimethylbenzene .434 S 5 3 40 4 6 3 50
55. Dibutylether .436 2 RAU 0 RAU 100 NQ 1 RAt? 0 RAt? 100
56. Heptanal .439 2 RAt? 2 RAt? 0 2 RAt? 4 RAt? I RAil 75
57. Ethylmethylcyclohexane isomer .442 NQ NQ
58. Ethylmethylcyclohexane isomer 8 .445
59. Bromochlorolodocnethane + Bromo- .448 S 3 0 100 6 5 0 100
trichioroethene
60. Oimethylpentanal isomera .448
61. 1-Nonene .449 NQ
62. Methylpropylcyclnpentane isomer 8 .450
63. 1,2,3-Trichloropropane 8 .451
64. 1,1,2,2-Tetrachioroethane .453 S 7 7 0 5 7 4 43
65. Methoxybenzene or Phenylhydrazlne 8 .457
66. Trimethylcyclohexane isomer .458 NQ
67. Benzonitrile 8 .461
68. Trimethylcyclohexane isomer 8 .463
-------
Table 2., Continued, Page 5
Quan.
Compound RRTC Methodd
Contactor U Watere
Contactor A Watere
GAC_Inf.e GAC_Eff.e
(ng/l) (ng/1)
% Removal
by GAC
GAC_lnf.e
(ng/1)
XAD_Inf.e
(nq/l)
XAD_Eff.e
(ng/l)
% Removal
by XAI)
69. C 3 cyclohexane isomera .467
70. C 4 -C 5 Tetrahydrofuran isomer .470 NQ
71. Isopropylbenzene .473 S 1 0 100 1 2 0 100
72. Methyloctahydropentalene isomera .474
73. Isopropylcyclohexanea .478
74. Trichloro-2-butanone isomer .479 9 RAU 0 RAU 100
75. Bromochloro-3-pentanone isomer .481 9 RAU 0 RAU 100 3 RAU 9 RAU 0 100
76. Ethylmethylcyclohexane isomera .488
77. Propylcyclohexane .490 NQ NQ
78. Chlorotoluene isomer .498 NQ NQ 1 0 100
79. 2-Ethyihexanal .502 MQ
80. Propylbenzene .506 S 3 2 33 2 4 2 50
81. Octahydroindene .511 NQ NQ
82. 1-Ethyl-4-methylbenzene .515 S 2 3 -50 2 10 5 50
83. 1-Ethyl-3-methylbenzene .517 2 RAU 3 RAU -50 2 RAIJ S RAtJ 2 RAU 60
84. Dimethylcyclooctane or Tetramethyl .519 2 RAU 0 RAU 100
hexene isomer
85. 1,3,5-Trimethylbenzene .524 0 RAIl 3 RAIl - I RAU 7 RAIl 2 RAU 71
-------
Table 2., Continued, Page 6
Quan.
Compound RRTC Methodd
Contactor D Watere
Contactor A Watere
GAC lnf.e GAC_Eff.e
(ng/l) (ng/l)
S Removal
by GAC
GAC_Inf.e
(ng/l)
XAD_lnf.e
(ng/l)
xAD_Eff.e
(ng/l)
S Removal
by XAD
Pent ach loroethane
2,2,4 ,4-Tetramethyl-3-pentanofle
1-Ethyl -2-methythenzene
3-Ethyl -2,4-dimethylpentane
1 ,2,4-Trlmethylbenzene
Octanal
1 ,3-Olchlorobenzene
Dimethylheptanal Isomera
1 ,4-Dlchlorobenzene
Methyl Isopropylcyclohexane isomera
(2_Methylpropyl)benzenea
(1-Methyipropyl )bénzeneà
Decane
1_Methyl -4 -propy l-7-oxabiCYClO
[ 2.2.1]heptane
1,2, 3-Tr lmethylbenzene
Methy’ isopropylbenzene isomer
1 ,2-Dichlorobenzene+Methyl iso-
propylbenzene isomer
.522 S PIQ
.527
.534
.546
.551
.555
S
S
.556 S
.561
NQ
1
3
5 RAU
5
.562 S 18
.566
.567
.571
.576
.577
.580
.583
.585
S
NQ
4 RAIJ
1
S 17
1
NQ
4
7 RAU
0
2
NQ
0 RAU
1
NQ
1
11
0 2
—33 2
-40 NQ
100 23
89 27
100 3 RAIJ
0
1
94 24
13
2
2 RAU
5
0 RAil
36
41
NQ
2 RAil
2
NQ
33
0
1
0 RAil
3
4 RAil
0
2
NQ
100
50
100
40
- a,
100
95
0 RAil 100
1
NQ
1
50
97
86.
87.
88.
89.
90.
91.
92.
93.
94.
95.
96.
97.
98.
99.
100.
101.
102.
03
-------
Table 2., Continued, Page 7
Quan.
Compound RRTC Methodd
Contactor D Watere
Contactor A Watere
GAC_,nf.e GAC_Eff.e
(ng/l) (ng/l)
% Removal
by GAC
GAC_Inf.e
(ng/l)
XAD_Inf.e
(ngIl)
XAD_Eff.e
(ng/l)
% Removal
by XAt)
Trimethylcyclohexanone isomer 8
Indan
1 ,3,3-Trimethyl-2-oxabicyclo
12.2.?Joctane
(1-Methyipropyl )cyclohexane
Methyl isopropylbenzene isomera
Indene
Ethyldimethylbenzene isomer 8
Butylcyc lohexane 8
2,2-Oxybi s [ 1-ch loro]propane 8
Penty 1 cyc lopentanea
1,3-0 iethylbenzene
Methylpropylbenzene isomer
1,4- Oiethylbenzene
n-Butylbenzene
5-Ethyl-I ,3-dimethylbenzene
Decahydronaphthalene
Methylpropylbenzene isomer
.587
.590 S
.593
.595
.599
.599 S
.599
.604
.606
• 609
.611
.614
.618
.618
.621
.622
• 629
NQ
NQ
S 1
3 RAU
S 1
S 0
S 0
2 RAU
NQ
0
NQ
NQ
1
3 RAU
0
1
0 RAtJ
NQ
100
0
0
100
-
-
100
0
NQ
1
1 RAU
NQ
0
1
NQ
1 RAU
1
5 RAU
3
1
2
NQ
0
100
0 RAIJ 100
NQ
0
2 RAU
0
0
1
NQ
100
60
100
100
50
103.
104.
105.
106.
107.
108.
109.
110.
111.
112.
113.
114.
115.
116.
117.
118.
119.
C’
-------
Table 2., Continued, Page 8
Contactor 0 Waters Contactor A Watere
Quan. GAC_lnf.e GAC_Eff.e % Removal 6AC inf.e XAD_Jnf.e xAD Eff.e % Removal
Compound RRTC Methodd (ng/l) (ng/l) by GAC (ng/l) (ng/l) (ng/l) by XAD
120. C 4 Cyclohexane isomera .632
121. Hexachioroethane .634 S 8 1 88 7 5 1 80
122. 2-Ethyl-1,4-dimethylbenzene .640 S 2 1 50 NQ 4 0 100
123. 4-Ethyl-1,3-dimethylbenzene .642 S NQ NQ NQ 2 0 100
124. d_Fenchonea .645 S 0 0 0 0 0
125. Ethyistyrene isomer .646 1 RAU 0 RAU 100 NQ 1 RAU 0 RAU 100
126. 4-Ethyl-1,2-dimethylbenzene .648 S 1 1 0 1 2 1 50
127. 2-Ethyl-1,3-dimethyibenzene .654 S NQ
128. Ethylisopropylbenzene isomera .657
129. 1,1-Dimethylindan+C4 cyclohexane .659 S
isoinera
130. Nonanal .662 8 RAU 24 RA(J -200 1 RAU 23 RAIJ 9 RAU 61
131. 3-Ethyl-1,2-dimethylbenzene .668 S 1 1 0 0 1 0 100
132. C 5 Benzene isomer 8 .669
133. C 5 Benzene isomer 8 .673
134. C 5 Benzene isomer 8 .615
135. Undecane .679 NQ 0 RAU 3 RAU -
136. 1,2,4,5-Tetramethylbenzene .681 4 RAIJ 3 RAU 25 NQ 8 RAU 0 RAIJ 100
-.4
C
-------
Table 2., Continued, Page 9
Quan.
Compound RRTC Methodd
Contactor 0 Water
Contactor 1\ Watere
GAC_lnf.e GAC_Eff.e
(ngIl) (ng/l)
X Removal
by GAC
GAC_Inf.e
(ng/J)
XAD_Inf.e
(ng/l)
xAD_Eff.e
(ng/J)
% Removal
by XA [ )
1, 2, 3, 5-Te trame thylbenzene
(3-Methylbutyl )benzene 8
Dimethyl indan isomer
1,3, 5-Tr ichlorobenzene
C 5 Benzene isomera
2-Methyl decahydronaphthalene
Methyl indan isomer
C 5 Benzene isomer
Dimethylindan isomer
1, 3-Diethyl -5-methylbenzene
Methylindan or C 2 Styrene isomer
C 5 Benzene isomera
1,2,3, 4-Tetramethylbenzene
p-Isobutyltoluene
Tetrahydronaphtha 1 ene
Diethylmethylbenzene isomer
n-Pentylbenzene
.684 S
.687
.689
.691
.696
.698
.699
.702
705
S
.707 S
.709
.710
.714 S
.718
.718
.721
.722
1
0
I RAU
NQ
1
S 40
S
1
0
0 R4U
NQ
NQ
NQ
NQ
0
NQ
0
NQ
0 NQ
NQ
100 1 RAU
NQ
NQ
100 NQ
100 NO
NQ
2
NQ
NQ
3 RAU
5 RAU
NQ
I
NO
I
NQ
0 RIW
0 RAU
0
50
100
100
100
137.
138.
139.
140.
141.
142.
143.
144.
145.
146.
147.
148.
149.
150.
151.
152.
153.
-4
-------
Table 2., Continued, Page 10
Contactor 0 Watere Contactor A Watere
Quan. GI C_1nf.e GAc..Eu.e % Removal GAC_lnf.e XAD_Inf.e XAD_Eff.e % Removal
Compound RRTC Methodd (ng/1) . (ng/l) by GAC (nq/l) (ng/ l) (ng/l) by XAD
154. C 5 Benzene isomera .122
155. (1,1-Dimethylpropyl)benzene .725 NQ
156. C 5 Benzene isonierd .729
157. 1 ,2 ,4-Trlchlorobenzene + C 5 .731 S 2 0 100 NQ 4 0 100
Benzene Isomer
158. Naphthalene .738 S NQ NQ NQ NQ NQ
159. Dlmethylindan or Methylbutenyl- .744
benzene isomera
160. C 2 indan isomer + a Siloxane .748 7 0 100
161. C 2 Indan + C 6 Benzene isomersa 749
162. C 2 indan isomera 753
163. Ethyltrimethylbenzene isomer .156 NQ
164. C 2 Indan isomer .756 1 RAIJ 4 RAU -300 1
165. 3_Ethyl_1,2,4_trimethylbenzenea .760
166. Decanal .762 17 RAIl 73 RAIl -330 8 RAIl 39 RAIl 17 RAIl 56
167. 1,2,3-Trichlorobenzene .763 S iIQ 1 NQ
168. C 3 Indan isomer .764 1 RAIl 0 RAIl 100 1 RAIl NQ
169. C 6 Renzene Isomer .768 NQ
-------
Table 2., Continued, Page 11
Compound
1—Ethyl-2,3,5-trimethylbenzene
C 3 Indan or C 2 THNb isomer
Dodecane
170.
171.
172.
173. C 5 Benzene isomer 8
174. Methyl THN isomer 8
175. Hexachloro-1,3-butadiene
176. C 6 Renzene isomer
177. C 6 Benzene isomer 8
178. Methyl THN isomer 8
179. C 5 Benzene isomer 8
180. C 6 Benzene 4 C 2 THN or
C 3 Indan isomers
181. C 6 Benzene isomer 8
182. C 6 Benzene isomer 8
183. Dimethylindan or Methyl THN isomer
184. C 6 Benzene isomer
185. Methyl THN isomer or
4,7-Dimethyl indan
186. C 6 Renzene isomera
Contactor 0 Watere
Quan. GAC_Inf.e GAC_Eff.e % Removal
RRTC Methodd (rig/i) (ny/i) by GAC
.770 NQ
.772
1
RAU
0
RAU 100
.775
Ii
RAIJ
0
RAt) 100
.778
.780
.780
S
0
0
.786
2
RAt)
0
RAU
.788
.790
.792
.797
2
RAt)
C)
RAt)
.799
.802
.805 NQ
.808
.818 S
.821
Contactor A Water°
GAC-lnf.° XAD_Inf.e XAD_Eff.e % Removal
(ng/l) (ng/l) (ny/i) by XAD
?RAU 3 RA IJ
5 RAt)
0 RA
0 RAt)
0
0
0
100 NQ
100 NQ
NQ
100
100
100
100
NQ
2
NQ
0
1
-4
Li .)
-------
Table 2., Continued, Page 12
Quan.
Compound RRTC Methodd
Contactor 0 Water
Contactor A Watere
GAC_Inf.e GAC_Eff.e
(ng/l) (ng/l)
% Removal
by GAC
GAC_lnf.e
(ng/l)
XAO_Inf.e
(ng/l)
XAD-EfI. 0
(ng/l)
% Removal
by XAD
187. C 6 Benzene isomer .824 NQ
188. C 7 Benzene isomer .828 1 RMJ
189. Cg-C 12 Aldehyde isomer .829 0 RAt) 2 RAt) -
190. C 6 Benzene isomer .833 NQ 1 RAt)
191. Pentamethylbenzene .835 S NQ
192. C 6 Benzene isomer .838 NQ
193. Olmethyl THN Isomer 8 .841
194. 2-Methylnaphthalene .842 S NQ NQ NQ NQ
195. C 3 Indan or C 2 THN isomer .844 NQ 1 RAIJ 0 RAt) 100
196. C 3 Indan or C 2 THN isomer .847 3 RAt) 4 RAt) 0 RAt) 100
197. C 3 Indan or C 2 THN Isomer .849 NQ
198. C 3 Indàn or C 2 THN Isomer 8 .854
199. 1-Methylnaphthalene t)ndecanal .855 S NQ NQ 0 2
(1) RAt) (8) RAt) (-700)
200. Tridecane .866 NQ 3 RAt) 0 RAt) 100
201. Dimethyl THN isomer .868 5 RAIJ 0 RAt) 100
202. C 6 Benzene isomer 8 .871
203. Dimethyl THN isomer .873 5 RAt) 0 RAt) 100
-------
Table 2., Continued, Page 13
Quan.
Compound RRTC Methodd
Contactor D Watere
Contactor A Watere
GAC_inf.e GAC_Eff.e
(ny/i) (ny/i)
% Removal
by GAC
GAC_Inf.e
(ng/i)
xAD_Inf.e
(ny/i)
XAO_Eff.e
(ng/1)
% Removal
by XAD
Trimethyl indan isomer
C 3 THN isomer
Dimethyl 11311 isomer 8
C 7 Benzene isomer
Ethyl THN or Trimethylindan
i somers
Dimethyl THN isomer
Ethyl THN isomer 8
Trimethyl TUN or C 4 Indan isomer
C 7 Benzene isomer 8
C 3 THN isomer + Siloxane
1,1,-B ipheny l 8
Trimethyl 11411 isomer
C 7 Benzene isomer
Dimethyl TFIN isomer
Diphenylether
C 2 Naphthalene isomer
C 7 Benzene isomer
14 RAU 0 RAIJ
NQ
100
4 RAIJ 0 RAIJ 100
6 RAU 0 RAU 100
4 RAIJ 0 RAIJ 100
1 RAIJ
7 RAU
0 RAt) 100
0 RAt) 100
NQ
2 RAt) 0 RAt) 100
1 RAt) 0 RAt) 100
NQ
3 RAt)
NQ
1 RAt)
0 RAt) 100
0 RAt) 100
204.
205.
206.
207.
208.
209.
210.
211.
212.
213.
214.
215.
216.
217.
218.
219.
220.
.875
.887
.890
• 890
.892
.896
.900
.901
.903
.907
.914
.920
.924
.929
.932
.938
.940
U i
-------
Table 2., Continued, Page 14
Quan.
Compound RRTC Methodd
Contactor 0 Watere
Contactor A Watere
GAC_lnf.e GAC_Eff.e
(ngIl) (ng/l)
% Removal
by GAC
GAC_Inf.e
(ng/l)
XAD_inf.e
(ngfl)
XAD_Eff.e
(ng/l)
% Removal
by XAO
221. Dodecanal .943 0 RAU 5 RAIJ - 6 RAU 2 RAU 67
222. C 3 THU Isomer .946 1 RA J 0 RAU 100
223. C 3 THU isomera 950
224. Dimethylnaphthalene isomer .951 NQ
225. Tetradecane .953 0 RAIJ 3 RAtJ - 3 RAIJ 0 RAIJ 100
226. C 3 1MM or C 4 Indan isomera .954
227. C 5 THU or C 6 Indan Isomer .957 1 RAIJ 0 RAil 100
228. C 4 Indan or C3 THU isomer .958 3 RAIJ 0 RAil 100
229. C 4 indan or C3 THU isomera .962
230. C 4 Indan or C 3 THU isomer 8 .966
231. Dimethylnaphthalene isomer 8 .967
232. C 4 Indan or C 3 THU isomer 8 .971
233. C 4 Indan or C 3 TUN isomer .974 1 RAil 0 RAil 100
234. Trimethyl THU isomer .977 4 RAil 0 RAil 100 9 RAil 0 RAil 100
235. 5,9-Undecadien-2-one,6,l0-dimethyl .977 NQ
236. C 3 THN or C 4 Indan isomer 8 .982
237. C 4 Oihydronaphthalene isomer .984 1 RAil 3 RAil 0 RAil 100
-------
Table 2., Continued, Page 15
Contactor D Watere Contactor A Watere
Quan. GAC_Inf.e GAc_Eff.e % Removal GAC_!nf.e XA [ )-Inf. 0 XAP-Eff.° % Removal
Compound RRTC Methodd (ng/l) (ng/l) by GAC (ng/l) (ng/l) (nq/1) by XAD
238. 2,6-bis(1,1-Dimetbylether)2,5- .991 10 RMI 0 RAt) 100 NQ 24 RAt) 0 RAt) 100
cyclohexadiene 1 ,4-dione
239. Trimethyldihydronaphthalene isomer .992 1 RAt) 0 RAt) 100
240. C 3 THN isomer .997
241. 1-Chiorododecane, l.S. 1.000 S 52 52 52 52 52
242. Diphenylmethane 8 1.002
243. C 2 Riphenyl isomera 1.010
244. C 2 Biphenyl isomer 8 1.016
245. C 2 Biphenyl isomer 8 1.020
246. Tridecanal 1.027 NQ NQ NQ
247. Hexylindan isomer 8 1.029
248. Pentadecane 1.034 0 RAt) 5 RAt) - 9 RAU 0 RAt) 100
249. Cg Benzene isomer 1.037
250. Pentachlorobenzene 8 1.037 5 0 0 0 0 0
251. Tetramethylindan isomer 8 1.041
252. Cg Benzene + C 3 THN or C 4 Indan 1.066
isomers 8
253. Trimethylnaphthalene isomer 8 1.066
-------
Table 2., Continued, Page 16
Quan.
Compound RRTC Methodd
Contactor 0 Watere
GAC 1nf.e GAC Eff.e % Remova’
(ng/1) (ng/l) by GAC
Contactor A Watere
GAC 1nf.e
(ng/1)
XAD_lnf.e
(ng/1)
XAD_Eff.e
(ng/1)
% Removal
by XAD
C 2 Biphenyl isomera
0iethy phtha late
C 2 Biphenyl isomerd
C 3 Biphenyl isomer
Dimethylbiphenyl ,mera
C 3 Biphenyl isomer
2,2,4-Trlmethylpenta-1,3-d lo)
di isobutyrate
C 3 Biphenyl isomera
C 3 Biphenyl Isomer
Tetradecanal
1,2-Diphenylhydraz the
flex adec ane
C 3 Biphenyl isomer
C 3 Biphenyl isomer
Diethylbiphenyl Isomera
C 6 Indan isomera
Phthalate isomera
1.079
1.080
1.085
1.089
1.093
1.095
1.097
1.100
1.103
1.106
1.108
1.110
1.113
1.115
1.119
1.125
1. 130
S
1
0 RAil
3 RAil
S NQ
2 RAil
0 RAIJ
0 RAil
0
2 RAil
S RAil
NQ
4 RAil
1 RIUJ
3 RAil
100 1
-
-67
-100
-
0
.20
1 RAil
1 RAil
NQ
1 RAU
1 RA!J
1RAU
1
3 RAil
NQRAU
3 RAil
ORAU
0 RAil
ORAU
NQ
0
ORAIJ
NQRAtJ
0 RAil
100
100
100
100
100
100
254.
255.
256.
257.
258.
259.
260.
261.
262.
263.
264.
265.
266.
267.
268.
269.
270.
-J
-------
Table 2., Continued, Page 17
271. C 3 Biphenyl isomer
272. 2,5-bis(1,1-Dimethylpropyl)-2,5-
cyclohexadiene-1,4--dione
273. C 5 Biphenyl isomer
274. Diethylbiphenyl isomer
275. 1-Chiorotetradecane
276. C 4 Biphenyl isomera
277. 1,1,3-Trimethyl-3-phenylindan
278. Heptadecane
279. DiethyIbipheny isomera
280. Alkane isomer
281. Dibutylphthalate isomer
282. a Siloxanea
283. Octadecane
284. Alkane isomer
285. Phthalate + a Siloxane 8
286. 1,1_bis(Ethylphenyl)ethanea
287. Nonadecane
1.136
1.141 NQ
1.146
1. 150
1.157
1.160
1.181
1.183
1.187
1.191
1.226
1.22 7
1.254
1.263
1.274
1.217
1.321 NQ
NQ
NQ
3 RAt)
NQ NQ
2 RAIJ 6 RAt) -200
2 RAt) 3 RAt) -50
NQ
NQ
NQ NQ
NQ
ORAIJ IRAIJ
6 RAt) 0 RAt) 100
3RAIJ 1R At) 61
Quan.
Compound RRTC Methodd
Contactor D Watere
Contactor A Watere
GAC_Inf.e GAC_Eff.e % Removal
(ng/l) (ny/I) by GAC
GAC_!nf.e
(ng/l)
XAD_Inf.e
(ny/I)
XAD_Eff.e
(ng/1)
% Removal
by XAD
NQ
2 RAt) 0 RAU 100
7 RAt) 0 RAtJ 100
1 RAt)
I RAt)
NQ
NQ
1 RAt) 0 RAU 100
NQ
-.4
-------
Table 2., Continued, Page 18
Compound
RRTC
Quan.
Methodd
Contactor 0 Waters
Contactor A Watere
GAC_lnf.e GAC_Eff.e % Removal
(ny/i) (ny/i) by GAC
GAC 1nf.e
(ny/ I)
XAD_Inf.e
(ny/i)
XAD_Eff.e
(ng/l)
% Removal
by XAD
288.
Dibutyiphthalate isomer
1.335
NQ
NQ
NQ
NQ
NQ
289.
4_Phenyibicyclohexyla
1.366
290.
Eicosaned
1.385
291.
Benzyibutyiphtha late
1.563
S
NQ
NQ
NQ
292.
Dioctyiphthalate
1.683
NQ
NQ
NQ
NQ
alMs compound was detected in CWW Contactor A GAC-Inf. water on February 20, 1980,
but was not detected in any January 14 and 28, 1980 CWW samples. Compound is included in table 2 in order to provide additional relative retention time.
bTHN Tetrahydronapthalene
cRRT Relative retention time, where RRT of chiorododecane = 1.000
dMethod of Quantitation; All quantitation values reported in Table 2 are in ny/I
unless otherwise noted. S” indicates that a standard was purchased and the
corresponding experimental relative response factor to that of chlorododecane, IS, was
determined.
eSee Figure 5 for an explanation of sample origin.
Total Ion Current Area(UNK) 52
FRAU (Relative Area Unit) = 1t 1 ton Cur eiTf7\ iIt [ S) x
where: UNK Unknown Compound
IS = Chlorododecane
9NQ = Organic was detected but was not quantified.
0
-------
81
Table 3. Results of BLLE Analysis of CAC Inf. and CAC Eff.
Samplesd — Neutral Fraction, GAC Contactor D Water
Sequence
Number(a)
Relative
Retention
Timeth) Compound Name
Relative Aij nt
Detected
Formula GAC Inf. GAC Eff.
Percent
Removal
1 0.14 2—ethyl--4—methyl—l,3—dioxlane C 6 H 12 0 2 25 100
2 0.23 4—methyl—3—penten—2—one C 6 R 0 0 8 100
3 0.23 l —chloro--2,4—hexadiene C 6 H 9 C1 36 100
4 0.25 bromodichloromethane C 1BrCl 2 420 100
5 0.26 2,6—dimethyl—4—heptartone C 9 H 18 0 44 100
6 0.30 chlorobenzene C 6 H 5 C1 9 100
7 0.31 l,1—dichlorocyclohexane C 5 H 10 C1 2 26 100
8 0.39 dibromochloromethane CHBr 2 C1 229 100
9 0.40 cycloheptanone C 1 H 0 7 100
10 0.46 2—methyl—2—cyclopenten—1—one C 6 H 8 0 7 100
11 0.47 dlchloroacetonitrile C 2 HNC1 2 2 100
12 0.47 1,l,3—trichloro—l—propene C 3 H 3 C1 3 3 100
13 0.51 m—dichlorobenzene C 6 H 4 C1 2 3 100
14 0.53 hexachloroethane C 2 C1 6 9 100
15 0.54 bromoform C}lBr 3 75 100
16 0.55 1,2—dichiorocyclohexane C 6 H 10 C1 2 168 100
17 0.57 alcohol 14 100
18 0.59 o—dichlorobenzene C 5 H 4 C1 2 19 100
19 0.62 tetralin C 10 11 12 49 100
20 0.63 di(2—chloroethyl) ether C 4 H 8 0C1 2 5 100
21 0.64 3—propylcyclopentene C 8 H 14 4 100
22 0.66 1—bromo--2—chlorocyclohexane C 6 H 10 C1Br 29 100
23 0.68 fenchyl alcohol C 10 H 18 0 5 100
24 0.69 isophorone C 9 H 14 0 18 100
25 0.70 4—hydroxy—4—methylcyclohexanone C 7 H 12 0 2 3 100
26 0.70 benzonitrile C 7 H 5 N 16 100
27 0.76 triethyl phosphate C 5 R 15 O P 6 100
28 0.83 nitrobenzene C 6 H 5 0 2 N 30 100
29 0.83 naphthalene C 10 H 8 8 100
30 0.85 2—phenyl—2—propanol C 9 H 12 0 7 100
31 0.87 o—nitrotoluene C 7 N 7 0 2 N 18 100
32 0.89 tripropylene glycol methyl ether C 10 H 22 0 4 5 100
33 0.89 “ “ “ 9 100
34 0.90 “ 7 100
35 0.90 “ “ “ “ 6 100
36 1.01 benzylcyanide C 8 H 7 N 14 100
37 1.03 benzthiazole C 7 H 5 NS 6 -
38 1.08 indanone plus C 9 H 8 0 100
phenyl ether C 12 H 10 0
39 1.10 dipropylene glycol 2—propenyl ether C 9 H 18 0 3 S 100
40 1.14 3,4—dihydronaphthalenl—Ofle C 10 H 10 0 31 100
-------
Table 3. (Continued)
Sequence
Nuxnber(a)
Relative
Retention
Time 1
Compound Name
Formula
Relative Amou
Detected (C)
nt
Percent
GAC Inf.
GAC
Eff.
Removal
41
1.17
tributyl phosphate
C 12 H 27 0 .P
38
100
42
1.22
trimethyl isocyanurate
C 6 H,0 3 N 3
196
1
99
43
1.23
tetrahydro—l—naphthalenol
C 10 H 12 0
5
100
44
1.24
sulfolane
C 4 H 8 0 2 S
5
100
45
1.29
N—(4—chlorophenyl)acetamide
C 8 H 8 ONC1
9
100
46
1.33
tetrahydro—trimethyl benzofuranone
C 11 H 16 0 2
8
100
47
1.33
phthalide
C 8 R 6 0 2
4
100
48
1.44
2,4—dinitrotoluene
C 7 H 6 0 4 N 2
7
100
49
1.49
N—phenylacetaniide
C 8 H 9 ON
42
100
50
1.66
fluorenone
C 13 H 8 0
1
100
correspond to the CC peaks, as labeled in Figure 8.
(b)geiative to the internal standard, hexaethylbenzene.
(c) pressed as a peak height percentage of the internal standard, hexaethylbenzene, 0.2 ppb.
(d)see Figure 5 for explanation of sample code names.
82
-------
83
Table 4. Results of BLLE Analysis of GAC Inf. and GAC Eff. Samples(e) — Methylated Acid
Fraction CAC Conractor D Water
Relative
Re
lative Amount
Sequence
Number( -)
Retention
Time(b) Compound Name(d) Formula GAC
Detected(t)
Percent
Inf. GAC
Eff.
Removal
1 0.21
2 0.25
3 0.26
4 0.28
5 0.31
6 0.35
7 0.35
8 0.38
9 0.41
10 0.46
11 0.51
12 0.53
13 0.61
14 0.72
15 0.77
16 0.78
17 0.79
18 0.82
19 0.82
20 0.83
21 0.85
22 0.87
23 0.90
24 0.91
25 0.92
26 0.92
27 0.94
28 0.96
29 1.03
30 1.04
31 1.13
32 1.13
33 1.14
34 1.17
35 1.23
36 1.25
37 1.30
38 1.47
neoheptanoic acid, ME
1—butanol
dibutyl sulfite
hexanoic acid, ME
3 —methoxy—3—methyl—2—butanone
2—ethylhexanoic acid, ME
2—methyloctanoic acid, NE
heptanoic acid, ME
divinylmercury (artifact?)
dichioroacetic acid, NE
m—dichlorobenzene
3,6—dimethyloctanojc acid, ME
1,3, 5—trichlorobenzene
benzoic acid, ME
2—chlorophenol, ME
a glycol ether
o—toluic acid, ME
m—toluic acid, ME
2—phenylpropanoic acid, ME
p—toluic acid, ME
phenylacetic acid, ME
dimethyl maleic acid, di—ME
ethylmerhyl maleic acid, di—ME
p—chlorobenzoic acid, ME
3(p—tolyl)propionic acid, ME
hydrocinnamic acid, ME
2,4—dimethylbenzoic acid, ME
3—phenylpentanoic acid, ME
4—methyl—2—acerylbenzoic acid, ME
4—phenylpentanoic acid, ME
p—cresol
a substituted naphthalene carboxylic
acid, ME
anisic acid, ME
clofibric acid, ME
4—butoxybutyric acid, ME
isomer of clofibric acid, ME
phthalic acid, di—ME
2,4—dichiorophenoxyacetic acid, ME
100
3 -00
5 -
100
10 —
100
100
100
100
100
100
100
5 95
100
3.5 -
100
100
100
100
100
100
100
100
100
100
100
100
100
100
2 —
100
100
100
100
100
l 0
100
‘Numbers correspond to the GC peaks, as labeled in Figure 9.
(b)Relative to the internal standard, hexaethylbenzene.
(C)Expressed as a peak height percentage of the internal standard, hexaethylbenzene, 0.2 ppb.
indicates the compound was detected as the methyl ester or ether. The formula shown is that
for the free acid.
C,H 1
C 4 H 10 0 1
C 8 H 1 8 0 3 S 1
C 6 H 1 202
C 6 H 1 202
C 8 H 1 602
C 9 H 18 0 2
C 7 H 14 0 2
C 4 }1 6 8g
C 2 H 2 0 2 C1 2
C 6 H 4 C1 2
C 1 082002
C 6 H 3 C1 3
C 7 H 4 0 2
C 6 H 5 C1
C 8 11 8 0 2
C 88802
C 9 H 10 0 2
C 8 H 8 0 2
C 88802
C 6 H 8 0 4
C 7 H 1 004
C,H 3 0 2 Cl
C 1 H 1202
C 9 H 1 002
C 9 H 1 002
C 11 11 14 0 2
C 1 082003
C 11 H 14 0 2
C,H 8 0 1
C 8 88 03
C 10 H 1 1 0 3 Cl
C 8 8 1 503
C 10 H 1 1 0 3 Cl
C 8 H 6 0 4
C 8 H 5 0 3 C1 3
1
20
40
1.5
5
1
3
2
2
1.5
102
.05
5
2
2
1.5
2.5
24
55
1
4
3.5
3
2
3.5
7
4
3
10
2
2.5
1.5
3
(e\
See Figure 5 for explanation of sample code names.
-------
84
Table 5. Artifact Contaminants from
XAD—2 Resin in the XAD—EZE
Sample (a)
(b)
Compound
Re lativ
c)
Amount
(b)
Compound
Re lativ
c)
Amount
p—xy lene
890
methyl (l—ethylpropyl) benzene
170
m—xy lene
5170
4—ethyl styrene
5160
ct ene
250
3—ethyl styrene
3280
0—xylem.
5600
5—methyl indan
3040
a propyl bnzene isomer
200
a methyl indan isomer
180
p—ethylcoluene
420
a dimethyl indan isomer
450
mesityl.n.
150
a methyl indan isomer
250
scyrene
690
tetralin
360
1,2,4—crimechylb.nzene
130
divinylbeazene isomer
790
m—diethyibenzene
1820
divinylbenzene isomer
630
p—diethy lbenzene
1710
2—pencenylbeazene
240
o—diethylbenz.ae
720
1,1A,6,6A—tetrahydrocycloprop(A indene
170
am ethyl cumene isomer
1000
mechylbeuzoate
1720
t—pencylbenzene
70
acecophenone
90
p—ethyl cumane
390
o—ethylbenzaldehyde
120
a propyi. xylem. isomer
1040
naphtha.lene
1390
3—p henyipentane
350
methyl m—ethylbenzoace
50
a methylindan isomer plus a
C—6 benzene
1560
p—ethylacetophenone
50
a methyl styren . plus a C—S
benzeue
80
2—mechylcaphthalene
70
2—ethyl scyreme
400
l—metbylnaphthalene
40
‘See Figure 5 for an explanation of sample code names.
Listed in GC retention order.
(C) press as the CC peak height percentage of the internal srandar.i, hexaethylbenzene, added at
the 0.2 ppb level.
-------
85
Table 6. Results of Analysis of XAD Inf., XAI) Eff.,
and XA1) ELE Samples(a) —— Neutral Fractiou,
Contactor A Water
#
(b)
BItT
Compound Name
XAD Inf. XAD
Relative Relative
I mount(C) AmOunt(C)
Eff.
XAD
EEE
Percent
Removal(d)
Relative
Amount(C)
Percent
Recovery@)
1
0.15
bromodichloromethane
3
100
0
2
0.34
dibromochioromethane
27
100
14
52
3
0.39
p—methylpropylbenzene
2
4
0.42
l,3—dimethyl—5--ethyl benzene
3
5
0.44
(dichloromethyl)naphthalene
1
100
0
6
0.45
l,4—dimethyl—2—ethylbenzene
2
7
0.45
l,3—diinethyl—4—ethylbenzene
2
8
0.46
1,2—dimethyl—4—ethylbenzene
4
9
0.48
ethyl dichloroacetate
1
10
0.48
m—dichlorobenzene
1
100
0
11
0.52
p—dichlorobenzene
3
100
0
12
0.52
bromoform
12
100
8
75
13
0.57
o—dichlorobenzene
5
100
60
1200
14
0.62
di(2—chloroethyl) ether
1
100
0
15
0.68
1,1,2,3—tetrachioropropane
1
100
0
16
0.69
benzonitrile
3
100
2
66
17
0.72
methyl beuzoate
4
—
233
18
0.76
ethyl benzoate
3
19
0.80
o—ethylbenzaldehyde
13
20
0.80
phenyl ethyl ketone
5
100
0
21
0.82
nitrobenzene
4
100
0
22
0.82
naphthalene
5
3
40
11
220
23
0.86
o—nitrotoluene
8
100
7
88
24
25
26
27
0.90
0.92
0.93
1.01
methyl m—ethylbenzoate
methyl p—ethylbenzoate
p—nitrotoluene
benzyl cyanide
1.5
4
100
100
13
5
0
0
28
1.02
2—chioroaniline
1
100
0
29
1.04
2,4—dichloro---l—nitrobenzene
.5
100
0
30
31
1.08
1.11
diphenyl ether
hexachloropentane
.5
15
.5
100
97
0
0
32
33
34
1.27
1.37
1.44
ethyl palmitate
2,6—dinitrotoluene
2,4—dinitrotoluene
5
9
100
100
2
3
8
60
89
(a) See Figure 5 for an explanation of sample code names.
(b) RRT relative retention time. Relative to the internal standard, hexaethylbenzene.
(C) Expressed as a peak height percentage of the internal standard, hexaethylbenzene, 0.2 ppb.
(d) Percent removal or recovery, relative to the original water: XAD Inf.
-------
86
Table 7. Results of Analysis of XA1) Inf., XAD Eff.,
and XAD EEE Sanlples(a)__Methylated Acid
Fraction, Contactor A Water
7
6
30
30
15
9
100 16 l ’6
9
6
2
4
4
100 0
9
19
100 0
- 200
3
4
100 13 320
100 6 200
50 22 55
74
10
44 96 140
6
13
100 7 175
7
100 0
100 0
5
25 0
100 0
6
11
# RRT(b) Compound Namee
XAD Inf.
Relati e
Amount(C)
XAD
Eff.
XAD
EEE
Relative
Amount(C)
Percent
Removal(d)
Relative
Atnount(C)
—
Percent
Recovery(d)
1 0.19
2 0.19
3 0.27
4 0.30
5 0.38
6 0.41
7 0.46
8 0.48
9 0.58
10 0.61
11 0.65
12 0.65
13 6.66
14 0.67
15 0.69
16 0.70
17 0.72
18 0.82
19 0.82
20 0.85
21 0.86
22 0.87
23 0.89
24 0.90
25 0.90
26 0.91
27 0.92
28 0.92
29 0.94
30 0.94
31 1.02
32 1.02
33 1.04
34 1.04
35 1.09
36 1.10
37 1.10
38 1.11
valeric acid, ME
glycol ether
formate
an ether
a fatty acid, ME
1—chloro—2—propano l
dichloroacetic acid, ME 15
2,2’—bis—l,3—dioxolane
2,3,3—trichloroacrylic acid, ME
an oxo—fatty acid, ME
an oxo-fatty acid, ME
an oxo—fatty acid, ME
levulinic acid, ME 6
a 2,3—dimethyl fatty acid, ME
capric acid, ME
2, 2—dichloroethanol 24
benzoic acid, ME
m—toluic acid, ME
2—phenylpropionic acid, ME
phenylacetic acid, ME 4
salicylic acid, ME 3
dimethylinaleic acid, di—ME 40
lauric acid, ME
m—ethylbenzoic acid, ME
ethylmethylmaleic acid, di—ME 68
tetrachlorobutenoic acid, ME
p—ethylbenzoic acid, ME
hydrocinnamic acid, ME 4
3,5—dimethylbenzoic acid, ME
o—methylphenylacetic acid, ME 3
o—chloroaniline 3
4—methyl—2—acetylbenzoic acid, ME
isomyristic acid, ME 4
a-phenyl—t—butyric acid, ME 2
suberic acid, di—ME
phenoxyacetic acid, ME
3—hydroxybenzisothiazole, ME
4(1, 5—dimethyl—3—oxohexyl—
cyclohexane carboxylic
acid, ME
isopentadecanoic acid, ME
120
20
30
1
5 -
8
39 1.13
14
100 0
-------
87
Table 7. (Continued)
11
RRTO )
XADInf.
Relative
Compound Name(e) Amoumt(’ )
XAD
Eff.
XAD
EEE
Relative
Amount(c)
Percent
Removal(d)
Relative
pmount(C)
Percent
Recovery@)
40
1.14
anisic acid, ME 5
100
8
160
41
1.17
clofibric acid, ME 11
100
9
82
42
1.18
azelaic acid, di—ME
30
43
1.27
N—hydroxy phthalimide
6
44
1.29
phthalic acid, di—} E
8
45
1.31
anteisoheptadecanoic acid, ME 6
100
0
46
1.35
heptadecenoic acid, ME 16
100
0
47
1.46
linoleic acid, ME 28
100
0
48
1.47
2,4—dichlorophenoxyacetic acid, 6
100
5
83
4
1.49
a derivative of N,N—dimethyl urea
2
50
1.48
4—ethoxyethyl aniline
10
—
51
1.49
1,4—benzothiazin-2—one 22
100
0
52
1.49
N—phenylacetamide
3
—
( ) See Figure 5 for an explanation of sample code names.
(b) RRT = relative retention time. Relative to the internal standard, hexaethylbenzene.
(c) Expressed as a peak height percentage of the internal standard, hexaethylbenzene, 0.2 ppb.
(d) Percent removal or recovery, relative to the original water: XAD Inf.
(e) ME = methyl ester or methyl ether.
-------
88
Table 8. List 0 f 215 Reference Compounds t 1hich Are Measured In Each Grob CLSA Sample
Compound Formula RRTb
1. 1,1—Dichioroethane 98 C 2 H 4 C12 0.137
2. Bromochioromethane 128 CH 2 C 1Br 0.153
3. Chloroform 118 CHCL 3 0.155
4. 1,2-Dichioroethane 98 C 2 H 4 C1 2 0.170
5. 1,1,1-Trichioroethane 132 C 2 H 3 C 1 3 0.173
6. Benzene 78 C 6 H 5 0.185
7. Carbon tetrachioride 152 CC1 4 0.188
8. Dibromomethane 172 CH 2 Br 2 0.215
9. Trichioroethene 130 C 2 HC13 0.219
10. Brotnodichloromethafle 162 CHC 1 2 Br 0.223
11. N-Nitrosodimethylamine 74 C 2 H 5 0N 2 0.260
12. Pyridine 79 C 5 H 5 N 0.260
13. Bromotrichioromethane 196 CC1 3 Br 0.284
14. Toluene 92 C 7 H 8 0.288
15. 2-Methyithiophene 98 C 5 H 6 S 0.295
16. Dibroinochloromethafle 206 CHC1BR 2 0.315
17. Hexanal 100 C 6 H 12 0 0.323
18. 1,2,2-Trichloropropane 146 C 3 H 5 C1 3 0.323
19. Tetrachioroethene 164 C 2 C1 4 0.339
20. Oichloroiodomethafle 210 CHC I 2 I 0.349
21. 1,1,2-Trichioropropane 146 C 3 H 5 C1 3 0.367
22. 4-Hydroxy-4-methyl -2-
pentanone 116 C 6 H 12 0 2 0.368
23. Chlorobenzene 112 C 6 H 5 C1 0.379
24. Dibromodichioronlethafle 240 CC 1ZBr2 0.391
25. 1-Chiorohexane 120 C 6 H 13 C1 0.396
26. Ethylbenzene 106 C 8 H 10 0.400
27. m-Xylene 106 C 8 H 10 0.411
28. p-Xylene 106 C 8 H 10 0.411
29. Brornoform 250 CHBr 3 0.417
30. Styrene 104 C 8 H 8 0.425
31. o-Xylene 106 C 8 H 1 0 0.435
32. 1,2,3—Trichioropropane 146 C 3 H 5 C1 3 0.442
33. Bromotrichioroethene 208 C 2 C1 3 Br 0.446
34. 1,1,2,2-Tetrachioroethane 166 C 2 H 2 C14 0.446
35. Isopropylbenzene 120 C 9 H 12 0.475
36. 2-Chiorotoluene 126 C 7 H7C 1 0.499
37 3 .. .Chlorotoluene 126 C 7 H7C1 0.501
38. 4-Chiorotoluene 126 C7H7C1 0.504
39. n-Propylbenzene 120 C 9 H 12 0.507
40. Bromocyclohexane 162 C 6 H 11 8r 0.512
41. 1-Ethyl-4—methylbeflzene 120 C 9 H 12 0.514
42. 1 -Ethyl-3—methylbeflZefle 120 C 9 H 12 0.515
43. Pentachioroethane 200 C 2 HCl 0.517
44. Benzonitrile 103 C 7 H 5 N 0.518
45. 1,3,5-Trimethylbenzene 120 C 9 H 12 0.523
46. bis_(2-Chloroethyl)ether 142 C 4 H 8 0C 1 2 0.525
47. a-Methylstyrene 118 C 9 H 10 0.530
48. 1 -Ethyl-2-methylbeflzefle 120 C 9 H 12 0.533
49. (1,1 -Dimethylethyl)beflZefle 134 C 10 H 14 0.546
50. BromochiorolOdomethafle 254 CHC1BrI 0.550
-------
89
Compound M.W.a Formula RRTb
51. 1,2,4—Trimethylbenzene 120 C 9 H 12 0.550
52. 1,3-Dichlorobenzene 146 C 6 1-I 4 Cl 2 0.556
53. 1,4-Dichlorobenzene 146 C 6 H 4 C1 2 0.560
54. a-Chlorotoluene 126 C 7 H 7 C 1 0.560
55. (2-Methylpropyl)benzene 134 Ci 0 H 14 0.567
56. (1-Methylpropy1)benzene 134 C 10 H 14 0.570
57. 1,2,3-Trimethylbenzene 120 C 9 H 12 0.579
58. 1,2-Dichlorobenzene 146 C 6 H 4 C 1 2 0.585
59. Indan 118 C 9 H 10 0.589
60. Indene 116 C 9 H 8 0.59)
61. 1-Phenylethanone 120 C 8 1- 1 8 0 0.608
62. 1,3-Diethylbenzene 134 C 10 H 14 0.610
63. 1,4-Diethylbenzene 134 C 10 h 14 0.615
64. n-Butylbenzene 134 C 10 H 14 0.617
65. 2-Chloro-p-xylene 140 C I-IgCl 0.617
66. N-Nitroso-di-n-propylamine 130 C 6 H 14 01’4 2 0.618
67. 5-Ethyl-1,3- dimethylbenzene 134 C 10 H 14 0.619
68. 2-Chlorostyrene 138 C 8 H 7 C1 0.621
69. 1,2-Diethylbenzene 134 C l 0 H 14 0.621
70. 1-Chlorooctane 148 C 8 H 17 C 1 0.623
71. 3-Chlorostyrene 138 C 8 H 7 C1 0.624
72. 4-Chlorostyrene 138 C 8 H 7 C1 0.627
73. Phenyl-2-butene 132 C 10 H 12 0.627
74. 2,6-Dimethylstyrene 132 C 10 H 12 0.633
75. Hexachioroethane 234 C 2 C 1 6 0634
76. 2-Ethyl-1,4-dimethylbenzene 134 C 1 0 H 14 0.639
77. 1,1-Dimethylindene 144 C 11 H 12 0.642
78. 4-Ethyl-1,3-dimethylbenzene 134 C 10 H 14 0.642
79. d-Fenchone 152 Ci 0 H 16 O 0.644
80. 4-Chloro-1,2-dimethylbenzene 140 C 8 H 9 C1 0.645
81. 4-Ethyl-1,2-dimethylbenzene 134 C 10 H 14 0.647
82. 2—Ethyl-1,3-dimethylbenzene 134 C 10 H 14 0.651
83. (1,1—Dimethylpropyl)benzene 148 C 11 H 16 0.653
84. 4-Ethylstyrene 132 C 10 1-1 12 0.653
85. 1,1-Dimethylindan 146 C 11 H 14 0.662
86. 3-Ethyl—1,2—dimethylbenzene 134 C 10 H 14 0.666
87. a-Chloro-m-xylene 140 C 8 H 9 C1 0.667
88. Isophorone 138 C 9 H 14 0 0.667
89. a-Chloro-o-xylene 140 C 8 H 9 C 1 0.670
90. a-Chloro-p-xylene 140 C 8 H 9 C1 0.670
91. 2,4-Dichiorotoluene 160 C 7 H 6 C1 2 0.675
92. 2,5-Dichiorotoluene 160 C 7 H 6 C 1 2 0.676
93. 2,6-Dichiorotoluene 160 C 6 H 6 C1 2 0.679
94. 1,1,2,3,3-Pentachloropropane 214 C 3 H 3 C1 5 0.679
95. 5-Isopropyl-1,3-dimethylbenzene 148 C 11 H 16 0.680
96. o-Chloroaniline 127 C 6 H 6 NC1 0.681
97. 1,2,3,5-Tetramethylbenzene 134 C 10 H 14 0.681
98. 1,3,5-Trichlorobenzene 180 C 5 H 3 C1 3 0.688
99. d-Camphor 152 C 10 H 16 0 0.694
100. Isoborneol 154 C 10 H 18 0 0.696
101. p-Methylphenol 108 C7N 8 0 0.699
102. 3,4-Dichiorotoluene 160 C 7 H 6 C 1 2 0 702
-------
90
Compound M.W.a Formula RRTb
103. 1,3-Diethyl-5-methylbenzene 148 C 11 H 16 0.704
104. bis(2-Chloroethoxy)methane 172 C 5 U 10 0 2 C1 2 0.706
105. Menthone 154 C 10 H 18 0 0.706
106. 1,2,3,4-Tetramethylbenzene 134 C 10 H 14 0.713
107. 1,2—Dihydronaphthalene 130 C 10 H 10 0.717
108. 1,3-Diisopropylbenzene 162 C 12 H 18 0.717
109. 1,2,3,4-Tetrahydronaphthalene 132 C 10 }- 1 12 0.718
110. n-Pentylbenzene 148 C 11 H 16 0.720
111. Borneol 154 C 11 H 18 0 0.726
112. 1,2,4-Trichlorobenzene 180 C 6 H 3 C1 3 0.729
113. a,2-Dichlorotoluene 160 C 7 H 6 C1 2 0.730
114. 1,4-Diisopropylbenzene 162 C 12 H 18 0.734
115. Naphthalene 128 C 10 H 8 0.737
116. 1-tert-Butyl-3,5-dimethylbenzene 162 C 12 H 18 0.741
117. a,3-Dichlorotoluene 160 C 7 H 6 C 1 2 0.742
118. a,4-Dichlorotoluene 160 C 7 H 6 C1 2 0.743
119. m-Chloroaniline 127 C 6 H 6 NC1 0.751
120. p-Chloroaniline 127 C 6 H 5 NC1 0.755
121. 1,2,3-Trichlorobenzene 180 C 6 H 3 C1 3 0.761
122. 2-Methylpentylbenzene 162 C 12 H 18 0.766
123. 2,6-Dichiorostyrene 172 C 8 H 6 C1 2 0.769
124. a,a,a-Trichlorotoluene 194 C 7 H 5 C1 3 0.773
125. 2,5-Dichiorostyrene 172 C 8 H 6 C1 2 0.777
126. Hexachloro-1,3-butadiene 258 C 4 C1 6 0.779
127. 1,3,5-Triethylbenzene 162 C 12 H 18 0.782
128. 2,5-Dichloro-p-xylene 174 C 8 H 8 C1 2 0.784
129. 3,4-Dichiorostyrene 172 C 8 H 6 C1 2 0.804
130. 4,7-Dimethylindan 146 C 11 H 14 0.817
131. n-Hexylbenzene 162 C 12 H 18 0.817
132. Pentamethylbenzene 148 C 11 H 16 0.834
133. 2-Methylnaphthalene 142 C 11 H 10 0.839
134. 5-Methyltetrahydronaphthalene 146 C 11 H 14 0.840
135. 2,4,5-Trichiorotoluene 194 C 7 H 5 C1 3 0.841
136. 2,3,6-Trichiorotoluene 194 C 7 H 5 C1 3 0.851
137. 1-Methylnaphthalene 142 C 11 H 10 0.855
138. a,a’-Dichloro—o-xylene 174 C 8 H 8 C1 2 0.859
139. Cyclohexylbenzene 160 C 12 H 16 0.867
140. 2,6-Dimethyltetrahydro- 160 C 12 H 16 0.867
naphthalene
141. 2,5-Dichioroaniline 161 C 6 H 5 NC1 2 0.868
142. 1,2,3,5-Tetrachlorobenzene 214 C 6 H 2 C1 4 0.870
143. 1,2,4,5-Tetrachlorobenzene 214 C 6 H 2 C1 4 0.870
144. a,2,4-Trichlorotoluene 194 C 7 H 5 C1 3 0.877
145. a,2,6-Trichlorotoluene 194 C 7 H 5 C1 3 0.880
146. Hexachloro-1,3-cyclopentadiene 370 C 5 C 1 6 0.884
147. 1,8-Dimethyltetrahydro- 160 C 12 H 16 0.886
naphthalene
148. a,a’-Dichloro—m-xylene 174 C 8 H 8 C1 2 0.896
149. a,&-Dichloro-p-xylene 174 C 8 H 8 C 2 0.904
150. Butylbenzoate 178 C 11 H 14 0 2 0.908
-------
91
Compound MWa -mu1a p pjb
151. 2-Chloronaphthalene 162 C 10 H 7 C1 0.909
152. n—Heptylbenzene 176 C 13 H 20 0.909
153. 1,2,3,4-Tetrachlorobenzene 214 C 5 H 2 C1 4 0.910
154. a,3,4-Trichlorotoluene 194 C 7 H 5 C1 3 0.914
155. 2-Ethylnaphthalene 156 C 12 H 12 0.928
156. 5,7-Dimethyltetrahydro- 160 C 12 H 16 0.929
naphthalene
157. 1-Ethylnaphthalene 156 C 12 H 12 0.929
158. 2-Methylbiphenyl 168 C 13 H 12 0.932
159. 1-Phenyl-1-cyclohexene 158 C 12 h 14 0.933
160. 2,4,6-Trichioroaniline 195 C 6 H 4 NC1 3 0.935
161. 2,6-Dimethylnaphthalene 156 C 12 H 12 0.938
162. 1,3—Dimethylnaphthalene 156 C 12 H 12 0.950
163. 1,6-Dimethylnaphthalene 156 C 12 H 12 0.953
164. Diphenylmethane 168 C 13 H 12 0.955
165. 1,4-Dimethylnaphthalene 156 C 12 H 12 0.965
166. 2,3-Dimethylnaphthalene 156 C 12 H 12 0.966
167. 2-Methoxynaphthalene 158 C 11 H 10 0 0.970
168. 1,2-Dimethylnaphthalene 156 C1 2 H 12 0.977
169. 2-Isopropylnaphthalene 170 C 13 H 14 0.981
170. Hexamethylbenzene 162 C 12 H 18 0.982
171. n-Octylbenzene 190 C 14 H 22 0.996
172. Acenaphthene 154 C 12 H 10 0.999
173. 1-Chlorododecane 204 C 12 H 25 C1 1.000
174. 2,7-Dimethyltetrahydro- 160 C 12 H 16 1.000
naphthalene
175. Pentachioropyridine 249 C 5 NC1 5 1.015
176. 2,4-Dinitrotoluene 182 C 7 H 6 0 4 N 2 1.021
177. Pentachlorobenzene 248 C 6 HC1 5 1.031
178. 2,4,5-Trichioroaniline 195 C 6 H 4 NC1 1.041
179. 2,3,4-Trichioroaniline 195 C 6 M 4 NC1 3 1.064
180. 2,3,5-Trimethy naphtha1ene 170 C 13 H 14 1.067
181. Fluorene 165 C 13 H 10 1.077
182. Diethyl phthalate 222 C 12 H 14 0 4 1.079
183. n-Nonylbenzene 204 C 15 H 24 1.079
184. 4-Chiorophenyl phenyl ether 204 C 12 H 9 OC1 1.084
185. 1,2-Diphenyihydrazine 184 C 12 H 12 N 2 1.104
186. 2,4,5,6-Tetrachloro-m-xylene 242 C 8 H 6 C1 4 1.111
187. 3,4,5-Trichioroaniline 195 C 6 N 4 NC1 3 1.128
188. BE -IC isomer 288 C 5 H 6 c1 6 1.153
189. n-Decylbenzene 218 C 16 H 26 1.158
190. Hexachlorobenzene 282 C 6 C1 6 1.176
191. Lindane 288 C 6 H 6 C1 6 1.180
192. BHC isomer 288 C 5 H 6 C1 6 1.197
193 Phenanthrene 178 C 14 H 10 1.221
194. a,a,a,a,a,&-Hexachloro- 310 C 8 H 4 C1 5 1.223
p-xylene
195. Anthracene 178 C 14 H 10 1.228
195. 2,4,5-Trichiorobiphenyl 256 C 12 F1 7 C1 3 1.268
197. 1-Chiorohexadecane 160 C 16 H 33 C1 1.301
198. Heptachior 370 C 10 1- 1 5 C1 7 1.309
199. Aidrin 362 C 12 H 8 C1 5 1.355
200. 2,3,4,5_TetrachiorobiphenYl 290 C 12 1- 1 6 C1 4 1.370
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Table 9. Organics Detected in GAC-Inf. Sample by More Than One Analytical Method
GAC-Inf. Contactor 0 GAC-lnf. Contactor A
Beflara Grobb BILE XAD-EEE
P&T CISA Neutrals Acids Neutrals Acids
( ugh) (ng/fl (RSd) (RS ) (RS) (RS)
Chloroform 56 10 ugh
I,l,l-Tr lchloroethane 400 8
Trichloroethene 57
Bromoform 0.2 .51 ugh 75 8
2- [ thyl-4-methyl-l,3-dioxo lane 5 RA(J 25
Bromodich loroinethane 18 16 ugIl 420
Ch lorobenzene 14 9
l,3,5-Triniethy lbenzene 0 RAtJ 5
1,2,4-Triinethy lbenzene 3 5
[ )ibroinochloromethane 5.8 6.2 ugh 229 14
1 3-Dichlorobenzene 5 3 2
Flexachioroetliane 8 9
l,2-Dichlorobenzene 17 19 60
TetrahydronaphthaIene 40 49
Naphtha lene NQ 8 11
1 tseny1ether 14 RAU 37
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Table 9. Continued
GAC-Inf.
Contactor D
Bellar
Grob
B L L E
P&T
CLSA
Neutrals
Acids
(ugh)
(ng/l)
(RS)
(RS)
Beozoic acid 102
Phenylpropanoic acid 2
m-Toiuic acid 1.5
Phenylacetic acid 2.5
Dimethylmaleic acid 24
Ethylinethylmaleic acid 55
Ilydrocinnamic acid 3.5
4-Methyl-2-acetylbenzoic acid 3.5
Anisic acid 3
Clofibric acid
Phthalic acid 1.5
2,4-DichlorophenoxyacetiC acid 3
Methylpropylbenzene isomer 3 RALJ
5-Ethyl-1,3-dimethy lbenzene 0
2-Ethyl-) ,4-climethylbenzene 2
4-Ethyl-) ,3-diinethyibenzene NQ
4-Ethyl-i ,2-dimethylbenzene
Beuzoijitrile
GAC-Inf. Contactor A
XAD-EEE
Neutrals Acids
(RS) (Rs)
200
4
3
13
22
96
7
5
8
9
8
5
2
3
2
2
4
16
2
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Table 9. Continued
GAC-Inf. Contactor 0 GAC-Inf. Contactor A
BellarGrobBLLE X A 0 -E E E
P&T CLSA Neutrals Acids Neutrals Acids
( ugh) (ng/1) (RS) (RS ) (RS) (RS)
o-Nitrotoluene 18 7
2,4—Dinitrotoluene 7 8
a Standards were obtained and quantitation is based upon an experimental response factor.
b Standards were obtained and quantitation is based upon an experimental relative response
factor to that of chlorododecane, IS.
C RAU (Relative Area Unit) = Total Ion Current Area(U ) x 52
Total Ion Current Area(IS)
where: UNK = Unknown Compound
IS = Chiorododecane
d RS = Relative Size; GC/MS peak height compared to that of hexaethylbenzene, IS, 0.2 ppb.
e ID = Trace detected.
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95
Table 10. Coniparisona of Analysis Results of Four
Methods Using Organic Functional Groups
and EPA Lists of Toxic Compounds
I.
Broad Categories
Bellar
No.
P&T
%
Grob
No.
CLSA
%
3L
No.
LB
%
XAD
No.
%
Aliphatin Hydrocarbon
Aromatic Hydrocarbon
Halogenated 0r anic
Nitrogen Compound
Oxygen Compound
Sulfur Compound
Phosphorous Compound
Mercury Compound
Total Compounds Detected
6
100.0
26
31
26
1
23
24.3
29.0
24.3
0.9
21.5
6
4
16
8
52
1.
2
1
6.7
4.4
17.8
8.9
57.8
1.1
2.2
1.1
6
10
6
36
10.3
17.2
10.3
62.1
6
100.0
107
100.0
90
100.0
58
100.0
LI.
Specific Categories
No.
Z
No.
%
No.
Z
No.
%
Alkane
Alkene, Alkyne
Alicyclic Hydrocarbon
Benzene Hydrocarbon
Indeno Hydrocarbon
Biphenyl Hydrocarbon
Naphtheno Hydrocarbon
Po lyhydro furan
Aliphatic Mercury
Po lyhydrottaphtha lene
Alcohols
Glyco Is
Amine s
Phenols
Aldehydes
Ke tones
Quinones
Aliphatic Esters
Aroniatic Esters
Ethers
Halogenated Ethers
Aliphatic Carboxylic Acids
Aromatic Carboxylic Acids
Amides
Nitriles
Cyclic Oxygen
Basic Nitrogen
Aromatic Nitro
4 3.7 1 1.1
1 1.1
1 1.1
3 2.8 2 2.2
5 5.6
5 5.6
6 5.6
2 1.9
2 1.9
2 1.9
4 3.7
3 2.8
1 1.1
1 1.1
1 1.1
1 1.0 15 16.7
18 20.0
2 2.2
3 2.8 2 2.2
1 1.0 2 2.2
5 8.6
1 1.7
1 1.7
1 1.7
3 5.2
4 6.9
2 3.4
16 27.6
15 25.9
1 1.7
1 1.7
1 1.7
4 6.9
6 5.6
6 5.6
31 29.0
7 6.5
2 2.2
3 3.3
1 1.1
5 5.6
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96
Thiophenes
Halogenated Aliphatic
Halogenated Aromatic
Ha logenated
Halogena ted
Ha logena ted
Halogenated
Phosphates
Table 10. Continued
a Comparison is based upon GAC—laf. water from Contactor 0.
b XAD—Inf. water from Contactor A was used.
Bellar P&T
No. ¼
Grob CLSA
No. ¼
BLLE
No
XAD—EE& ’
No. %
Ke tones
Phenols
Amide S
PCB & Pesticides
z
6
100.0
15
7
4
14.0
6.5
3.7
10
4
11.1
4.4
2
1
3.4
1.7
1
.1.1
100.0
107
100.0
2
90
2.2
100.0
58
100.0
Total Number of Organics b
Detected
III.
Total Number of Unique Organics
Analyzed by
All Four
Methods
was
183.
Percent of Total
3%
58%
49¼
32%
Number of Unique
Organics
(183 organics)
IV.
Total Number of Consent 6
23
11
6
Decree Organics 28
(113 organics)
Percent of Consent
5Z
20%
10¼
5%
Decree Organics
(113 organics)
V.
Total Number of EPA 2
18
10
5
Chemical Indicators
in Drinking Water
of Industrial Pollution 34
(62 organics)
Percent of EPA Chemical
3%
29%
16%
8%
Indicators in Drinking
Water of Industrial
Pollution (62 organics)
* ILS. 4 VIG OFA 1 1 -Th7-064/0297
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