EPA-600/2-78-059
March 1978
Environmental Protection Technology Series
EVALUATION OF CHLORINATED
HYDROCARBON CATALYTIC
REDACTION TECHNOLOGY
industrial Environmental Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the ENVIRONMENTAL PROTECTION TECH-
NOLOGY series. This series describes research performed to develop and dem-
onstrate instrumentation, equipment, and methodology to repair or prevent en-
vironmental degradation from point and non-point sources of pollution. This work
provides the new or improved technology required for the control and treatment
of pollution sources to meet environmental quality standards.
EPA REVIEW NOTICE
This report has been reviewed by the U.S. Environmental Protection Agency, and
approved for publication. Approval does not signify that the contents necessarily
reflect the views and policy of the Agency, nor does mention of trade names or
commercial products constitute endorsement or recommendation for use.
This document is available to the public through the National Technical Informa-
tion Service. Springfield, Virginia 22161.
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EPA-600/2-78-059
March 1978
EVALUATION OF CHLORINATED
HYDROCARBON CATALYTIC
REDUCTION TECHNOLOGY
by
Mitchell D. Erickson and Eva D. Estes
Research Triangle Institute
P. 0. Box 12194
Research Triangle Park, N. C. 27709
Contract No. 68-02-2612
Tasks 17 and 28
Program Element No. 1BB610
EPA Project Officer: David K. Oestreich
Industrial Environmental Research Laboratory
Office of Energy, Minerals, and Industry
Research Triangle Park, North Carolina 27711
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, D.C. 20460
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EVALUATION OF CHLORINATED HYDROCARBON
CATALYTIC REDUCTION TECHNOLOGY
by
Mitchell D. Erickson
Eva D. Estes
John M, Harden
Research Triangle Institute
Research Triangle Park, North Carolina 27709
EPA Contract No. 68^02-2612
RTI/1430 - 01 .F
D. K. Oestreich
U.S. Environmental Protection Agency U.S. Environmental Protection Agency
Industrial Environmental Research Lab Industrial Environmental Research Lab
Research Triangle Park, NC 27711 Research Triangle Park, NC 27711
RESEARCH TRIANGLE INSTITUTE
P. 0. BOX 12194
RESEARCH TRIANGLE PARK, NORTH CAROLINA 27709
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DISCLAIMER
This report has been reviewed by the Industrial Environmental Research
Laboratory, U.S. Environmental Protection Agency, and approved for publication.
Approval does not signify that the contents necessarily reflect the views
and policies of the U.S. Environmental Protection Agency, nor does mention
of trade names or commercial products constitute endorsement or recommendation
for use.
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ABSTRACT
A control technique developed for the Environmental Protection Agency for
the catalytic reduction of chlorinated hydrocarbons (specifically polychlori-
nated biphenyls [PCBs] and chlorinated pesticides such as heptachlor and
endrin) was evaluated under laboratory conditions. The technique involves
elution of polluted water at ambient temperature and at neutral pH through a
column containing a mixture of sand and copper/iron catalyst. The evalua-
tion found that PCBs are not detectably reduced, but are chromatographi-
cally eluted from the column in order of increasing chlorination. Thus,
early column eluate fractions were found to contain only the lower chlori-
nated PCBs, giving the illusion that partial reduction had occurred.
The catalyst was found to partially reduce heptachlor and endrin. The
carbon skeleton remained intact and chlorines were successively replaced by
hydrogens. In a stirred flask of the catalytic mixture and pesticide-
spiked water at 60°, the reaction was found to be only partially successful
with most of the products accounted for as the parent compounds or the analogs
representing loss of one chlorine.
The possibility of chromatographic elution of endrin and/or heptachlor
was briefly investigated using miniature columns and found to be insignificant.
A degradation product of heptachlor upon standing in water was found to be
not heptachlor epoxide, but rather C10HgClc02 (tentative)—apparently a dihy-
droxy derivative of heptachlor.
An additional on-site demonstration of the catalytic reduction technology
was observed by an RTI and an EPA representative. This program included obser-
vation of the test procedure, gas chromatography with electron capture detection
and subsequent GC/MS analysis of transported samples at the RTI laboratory.
An evaluation of the reports generated during the development of the
catalytic reduction technique is presented. It discusses errors and
omissions in the developmental experimental protocol that led to the
erroneous conclusions that the technique was applicable to PCBs.
ii
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CONTENTS
Disclaimer ±
Abstract , ±±
Figures iv
Tables v
Abbreviations vi
Acknowledgments vii
I. Introduction 1
II. Summary and Conclusions 2
III. Recommendations 3
IV. Materials and Methods ..... 4
Column Preparation 4
Extraction 4
Analysis 4
V. Evaluation of PCB Reduction Technology 6
VI. Evaluation of Endrin/Heptachlor Reduction 11
Stirred Flask Experiments 11
Miniature Column Experiments 18
Summary Evaluation of Endrin and Heptachlor Reduction .... 18
VII. Critique of Monthly Reports of Contract No. 68-03-2364 20
References • 22
Appendix 23
iii
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FIGURES
Number Page
1 Chromatograms (GC/ECD) of extracts of copper/iron/sand
column eluate fractions: (A) Fraction 2 (1.35&), (B)
Fraction 5 (2.9£), (C) Fraction 20 (14.3£), (D) Fraction
37 (17.9&), (E) Fraction 39 (21.9£), (F) Fraction 41
(28£). A-1016 standard (B) is shown as reference 3
2 Chromatograms (GC/ECD) of extract of sand column eluate
(A) Fraction 3 (1.4£), (B) Fraction 15 (10.9£) and (C)
Fraction 19 (23.9£). A-1016 standard (D) is shown as
reference 9
Chromatograms (GC/ECD) of endrin/heptachlor reduction.
Experiment No. 1 in a stirred flask: (A) copper/iron/sand
plus endrin and heptachlor aqueous solution (B) sand plus
endrin and heptachlor aqueous solution (C) endrin and
heptachlor aqueous solution only
Chromatograms (GC/ECD) of endrin/heptachlor reduction.
Experiment No. 2 in a stirred flask: (A) Mixture
reacted at 60° in presence of copper/iron/sand (B)
Mixture reacted at 25° in presence of copper/iron/
sand ................. . . ........ 14
Total ion current chromatogram of chemical ionization
GC/MS analysis of products from catalytic reduction of
endrin (Experiment 4) ................... 16
Gas chromatograms of endrin/heptachlor reduction
experiments using miniature copper/iron/sand column.
(A) Column effluent after 3300 m£ — typical of all
fractions. (B) Column effluent after 3500 m& — after
standing in column for 65 hours. Compound identification
a) heptachlor, b) heptachlor epoxide isomer ........ 19
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TABLES
Number Page
1 Elution of PCBs on Copper/Iron/Sand Column 6
2 Compounds Identified in Electron Impace GC/MS Analyses
of Endrin/Heptachlor Reduction (Experiment 3) 15
3 Compounds Identified in Chemical lonization GC/MS
Analysis of Endrin Reduction (Experiment 4) 17
v
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ABBREVIATIONS
A-1016 — Aroclor^-1016
ESC — Envirogenics Systems Company, El Monte, California
GC/ECD — Gas Chromatography/Electron Capture Detection
GC/MS — Gas Chromatography/Mass Spectrometry
PCB — Polychlorinated Biphenyl
TCB — 2,3',4',5-tetrachlorobiphenyl
CIS ••— Copper/Iron/Sand
VI
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ACKNOWLEDGMENTS
We wish to thank Drs. Edo Pellizzari and Denny Wagoner of Research
Triangle Institute (RTI) for their assistance in the planning and
execution of this project. Major credit for the successful completion
of this project is due to Messrs. Russel P. Cepko, Bobby J. Parker,
Peter Grohse (RTI), and Dr. K. Tomer who assisted with the laboratory
experimentation. Finally, we wish to thank Mr. David Oestreich of IERL,
EPA, RTP, NC for his helpful discussions and advice.
vii
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SECTION I
INTRODUCTION
In an effort to assist industry in compliance with legislation concerning
the permissible levels of toxic substances in industrial water effluents,
the EPA has undertaken to develop various control technologies which may be
applied by industry. An example of this research is the catalytic reduction
of chlorinated hydrocarbons (specifically PCBs and chlorinated pesticides
such as heptachlor and endrin). Under a contract to Envirogenics Systems
Company (ESC), El Monte, CA (EPA Contract No. 68-03-2364), a technique for
the chemical removal of PCBs from water was investigated whereby the aqueous
PCB solution is passed through a column containing sand and a copper/iron
catalyst at ambient temperature and pressure.
Experiments by Envirogenics indicated successful removal of PCBs from
water; however, a test at the Gulfbreeze, FL, EPA laboratories discovered the
column effluent was toxic to fish. Analysis of effluents of the process by
Gulfbreeze-EPA and Bionomics detected little or no changes in the concentra-
tion of PCBs as compared to the feed solutions.
The purpose of this project was to chemically evaluate the technique.
Aqueous solutions of PCBs and chlorinated pesticides were analyzed before and
after treatment with the copper/iron catalyst and examined for changes in
their composition. The main analytical technique used in this study was electron
capture gas chromatography (GC/EC), which showed whether or not changes had
occurred in the chlorinated compounds. When a species change was noted, the
more sophisticated technique of gas chromatography-mass spectroscopy (GC/MS)
was used to identify the species. Samples were analyzed for iron and copper
in solution, and as a check for evidence of catalytic dechlorination, samples
were analyzed for ionic chloride.
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SECTION II
SUMMARY AND CONCLUSIONS
The catalytic reduction technology was evaluated (according to the
procedures provided by the developing laboratory) for PCBs and found totally
ineffective. In essence, the column (160 cm x 37 mm i.d.) behaves as a
large chromatographic column, requiring on the order of 40 bed volumes
(30£) to elute all components of the Aroclor™ -1016 feed solution. No
evidence of catalytic reduction of PCBs was observed.
The reduction technique was also briefly evaluated for endrin and
heptachlor. To facilitate the evaluation, the reductions were carried out
in stirred round bottom flasks at elevated temperature (~60°) for extended
times (4-6 hours). Partial reduction was observed at these elevated temp-
eratures. GC/MS analysis of highly concentrated batches indicated that the
endrin and heptachlor were being reduced by successive replacement of
chlorine by hydrogen. No evidence for changes in the carbon skeleton were
observed. The extent of dechlorination, even under these highly favorably
conditions, was slight. Although all of the C 2H Cl 0 analogs were found,
including the tentative identification of some C^H^O and related hydr°-
carbons, C10H0C1,0 (endrin) and various isomers of C -H-drO accounted for
J.Z O O -L^ " J
greater than 80% of the total ion current response in the GC/MS. The evalua-
tion of the reduction of heptachlor and endrin thus showed that the technique
worked, although apparently not well enough to efficiently reduce the
pesticide to hydrocarbons and mono- and dichlorinated species which may be
biodegradable.
The progress reports generated by the development laboratory were
evaluated to determine the errors and omissions in the experimental protocol
which led the investigators to erroneous conclusions about their results.
A list of the points of criticism is presented.
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SECTION III
RECOMMENDATIONS
Based on the findings of the research presented herein, it is
recommended that no further effort be made to develop and/or implement
on a pilot scale the technology for catalytically reducing PCBs. The
brief evaluation of the reduction of heptachlor and endrin by this
technique also indicated that the technique is insufficient for genera-
ting low- or non-chlorinated organics which are bio-degradable. Thus,
it must be conclusively shown that reduction is complete before any
attempts at commercial application are undertaken.
Any further research and development of the chemical reduction of
chlorinated hydrocarbons in water utilizing copper/iron catalyst must
first address the chemistry of the reactions. Basic research should be
carried out to understand the mechanism(s) and kinetics involved before
any work at optimizing the conditions can be undertaken. Once the chemistry
is well defined, the types of compounds for which the catalyst would be
effective, and thus reaction conditions, may be predicted.
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SECTION IV
MATERIALS AND METHODS
COLUMN PREPARATION
The columns for the PCS work were constructed of Fisher and Porter
Lab-Crest 37 mm i.d. Pyrex tubing with a stopcock at the bottom and 0.5 cm
bed of glass wool. The column packing was prepared by blending the copper
catalyzed iron powder and sand supplied by Envirogenics Systems Company in
a ratio of 1:3.6. The packing was poured into the column to a depth of
160 cm and the intersticies filled with water. The void volume (or bed
volume) of the column was determined to be 750 m . This column will here-
after be referred to as the copper/iron/sand (CIS) column. A duplicate
column was prepared in a similar way using sand without the copper/iron
powder.
EXTRACTION
Previous experience in these laboratories (1) has shown that PCBs
are much more soluble in toluene than in hexane and thus are more readily
extracted from a variety of media, including water, using toluene. Accord-
ingly, aliquots of the column effluent and influent were extracted using
toluene as follows: a 100 raH aqueous aliquot was extracted three times with
20 mH portions of toluene in a separatory funnel. The combined toluene
extracts were dried over sodium sulfate and concentrated on a hot plate in
a flat bottom boiling flask with a Snyder column, followed by blow-down
under a nitrogen stream at 25°. This recovery procedure has been demonstrated
in our laboratory to be quantitative.
ANALYSIS
All gas chromatography-electron capture detection (GC/ECD) analyses
were performed on a Fisher Victoreen 4400 gas chromatograph with a Ni
electron capture detector. GC/MS analyses were obtained.using a Finnigan
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3300 quadrupole GC/MS with a PDP/12 computer. The determination of Cu and
Fe was carried out on a Perkin Elmer 603 Atomic Absorption Spectrophoto-
meter equipped with deuterium background correction. Chloride ion determi-
nations were accomplished using a chloride ion^-specific electrode on an
Orion 801A Digital lonalyzer.
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SECTION V
EVALUATION OF PCB REDUCTION TECHNOLOGY
Solutions of PCB mixtures (ArocloiR-1016 and 2,3',4',5-tetrachloro-
biphenyl [TCB]) were passed through two columns in parallel experiments.
One column held the CIS mixture, while the second held only sand. A
condensed sampling schedule is shown in Table 1.
TABLE 1
Fraction
0
2
5
20
31
37
39
40
41
# Feedstock
A-1016
A-1016
A-1016
A-1016
TCB
TCB
TCB
Distilled water
Distilled water
Volume (£)
0.75
0.1
0.1
0.1
0.3
0.4
2.0
2-0
0.1
Cumulative
0.75
1.35
2.9
14.3
16.8
17.9
21.9
23.9
24.0
Volume Description
Void volume
Change of feedstock
Attempt to flush
column
After 14.6£ (20 bed volumes) of Aroclor solution had been passed through
the column, subsequent chromatograms of the eluate fractions were essentially
identical to one another. At that point, the feedstock was changed to TCB
because it is a single polychlorinated species and thus easier to trace than
the complex Aroclor mixture.
After 5.4£ (7 bed volumes) of TCB solution had been passed through the
column and no TCB could be found in the eluate, the column was flushed with
2£ (2.7 bed volumes) of distilled water. Next, a 0.1 portion of distilled
water was passed through and analyzed.
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The results of this experiment, summarized in Figure 1, indicate clearly
that chromatographic elution is taking place on the CIS column. The lower
chlorinated isomers (which have shorter GC retention times) eluted more
quickly than the higher isomers. The lower chlorinated isomers are more
water soluble than the higher chlorinated molecules, and this would account
for their passing through the column more quickly. After passing 28$,
(37 bed volumes) through the column, all isomers present in the A-1016
were observed, although the last major peak (RT «10.2 min) had just begun
to elute and was present only as a shoulder on the adjacent peak (RT «9.4 min).
The isomers which eluted between 4^8 minutes were present in higher concentra-
tion since they were not as easily stripped from the column during feed of
water and TCB solutions. The identification of the major peaks in Fraction 41
(the distilled water fraction) was confirmed by GC/MS using multiple ion
detection. The TCB, which was first applied to the column about 15£ before
the experiment was terminated, was never observed in the column eluate.
This is to be expected in light of the chromatographic behavior of the higher
isomers (also tetrachlorobiphenyls) in Arochlor •<• 1016.
(S)
In the parallel experiment, Aroclor - 1016 and TCB solutions were
eluted through a column containing sand only. The results of this experiment
were similar to those observed for the CIS column, although the elution
appeared to be slightly faster. Typical gas chromatograms illustrating the
chromatographic elution of successive components of A-1016 are shown in
Figure 2.
To determine the significance of long contact time within the column,
two successive fractions were collected from the CIS column 65 hours apart.
No significant reduction had taken place after this lengthy interruption
of flow.
The above experiments clearly illustrate that both the CIS column and
the sand column act as crude liquid chromatographic columns. Because of their
greater aqueous solubility, the lower chlorinated isomers in the PCB mixture
pass through first. The disproportionate amount of lower chlorinated species
in the initial eluates from the CIS column could lead to the erroneous con-
clusion that the higher chlorinated species are• being dechlorinated.
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cc
a
g
TIME (min)
(A) fraction 2 (1.35A)
(B) fraction 5 (2.9£)
(C) fraction 20 (14.
(D) fraction 37 (17.9£)
(E) fraction 39 (21.9£)
(F) fraction 41 (23£)
(G) A-1016 standard -shoim for reference
10 12
Figure 1. GC/ECD chroiuatogratas of CIS column eluates.
8
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in
1
(B) fraction 15 (10.95,)
(A) fraction 3 (l.U)
(C) fraction 19 (23.95,)
(D) Ar-1016 standards-shown for
reference
2468
TIME (min)
Figure 2. GC/ECD chromatograms of sand column eluates.
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Only the 2,3',4',5-tetrachlorobiphenyl (TCB) fed onto the column remained
unaccounted for. It was suspected that this material and A-1016 were adsorbed
on the column packing. At the conclusion of the elution experiments, 50 g of
column packing was collected from the top of each column, vacuum filtered to
remove the aqueous portion, and extracted with toluene. The results of this
experiment show clearly in both cases, large amounts of TCB in the gas chroma-
togram, although large volumes of non-TCB-containing water had passed through
the column (8.15, or 11 bed volumes in the case of the CIS columns and 17.l£
in the case of the sand column) and several days had elapsed. This presents
further evidence that reductive degradation is not occurring to any appre-
ciable extent.
The concentrations of chloride, as measured using a chloride ion-selective
electrode, were below the detection limit C~5 ppm) in all samples analyzed.
Since this measurement yielded no useful information, it was discontinued.
In all fractions analyzed by atomic absorption, the iron concentrations were
found to be less than 0.3 ppm and the copper concentrations less than 0.01
ppm. The consistently low concentrations of iron and copper in the effluent
do not support a reductive mechanism in which iron is an indicator of
reduction.
10
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SECTION VI
EVALUATION OF ENDRIN/HEPTACHLOR REDUCTION
STIRRED FLASK EXPERIMENTS
The catalytic reduction performance of the copper/iron/sand mixture
was also evaluated for endrin and heptachlor. At the request of the project
officer, the reduction effects were first evaluated by the stirred flask
technique.
An experiment was performed with three parallel solutions of endrin and
heptachlor in: (a) a flask containing the copper/iron/sand mixture (50g);
(b) a flask containing sand; and (c) a flask which contained the endrin/
heptachlor solution only. All three flasks were heated to 60° and stirred
for not less than 4 hours. GC/ECD analysis of the reaction mixtures after
several hours indicated that some degradation of endrin and heptachlor may
have taken place (Figure 3). Since the loss of heptachlor and concurrent
appearance of another peak at RT ~ 7 min* was observed in both the flask
containing sand and the flask containing solution only, this reaction cannot
be attributed to catalytic reduction by the copper/iron/sand mixture.
This peak was, in fact, observed in extracts of the stock solution after
storage at 5° for two days. Analysis of this extract by GC/MS indicated
heptachlor (RT ~ 7 min*) and endrin (RT ~ 11 min*). The mass spectrum of the
unknown peak at RT = 8 min* led to a tentative structural assignment of
C H_C1 0_. The lack of a parent ion precludes a definitive assignment. This
compound would be a product of addition of two water molecules and loss of
two chlorines, an unusual reaction, especially under these mild conditions.
The presence of this compound has been reported numerous times in the
literature (3-5) as a degradation product of heptachlor in water. The
compound has been identified in these reports as 1-hydroxychlordene
(C C1,H,0, m/e = 352). Further analytical characterization, beyond the scope
10 66 ' .
of his project, is needed to resolve the apparent discrepancies and assign
a structure to this compound.
*
Retention times were different in the GC/ECD and GC/MS analyses because of
differences in the column temperatures.
11
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A
ro
CD
M
o
a.
EC
O
o
o
CC
0
Figure 3.
Chromatograms (GC/ECD) of endrin/heptachlor reduction.
Experiment No. 1 in a stirred flask.
Top: A—copper/iron/sand + endrin and heptachlor aqueous
solution
Center: B—sand + endrin and heptachlor aqueous solution
Bottom: C—endrin and heptachlor aqueous solution only
1: heptachlor
2: C-LQHgCLjC^ (tentative—see text)
3: endrin
12
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In a second experiment the effects of temperature were investigated and
it^was found (Figure 4) that the degradation was substantially more marked at
60° than at 25°. Thus, degradation of heptachlor and endrin was established
as being related to the presence of the copper/iron mixture, although the
degradation products were unknown. A third flask, containing distilled water
and the copper/iron/sand mixture, was used as a blank in this experiment. The
GC/ECD analysis of an extract showed no contamination of the blank, as expected.
To establish the identity of the degradation products, a reaction was
carried out with much larger amounts of endrin and heptachlor to yield enough
of the reaction products for GC/MS analysis. The solubility limit of endrin and
heptachlor was exceeded during this experiment. The results of this experi-
ment (Table 2) demonstrated that several dechlorinated heptachlor and endrin
species as well as some oxygenated analogs were present. There was no evidence
of complete (or even nearly complete) dechlorination or of a reverse Diels-Alder
type reaction to form chloro-cyclopentadienes.
Experiment 3 indicated the complexity of the reaction products, so a further
experiment with endrin alone was conducted to elucidate the reduction products
of this single starting material. A large batch (19 mg) of endrin was reacted
at 60° in a stirred flask and analyzed by chemical ionization mass spectrometry.
The results, shown in Figure 5, and Table 3, indicate that endrin is catalytically
degraded (i.e., replacement of chlorine by hydrogen) to some extent, although
the vast majority of the reaction product is found as C ^HgClgO (endrin) and
Dechlorinated endrin (G12H14°) was tentatively identified although
the amount found is minor compared to the higher chlorinated analogs.
Thus, even under much more severe reaction conditions than recommended, the
catalytic reduction is far from complete.
The results of the stirred flask experiments show that endrin and hepta-
chlor were catalytically reduced by the successive replacements of chlorine
by hydrogen in the presence of the copper/iron/sand catalyst. However, the
evidence indicated that, even at 60° for 4 hours, this process was far from
13
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ra
eu
u>
O
Q.
vs
O>
tr
x.
ID
•o
O
o
0)
CC.
Time (min.)
Figure 4. Chromatograins (GC/ECD) of endrin heptachlor reduction.
Experiment No. 2 in a stirred flask:
A. Mixture reacted at 60° in presence of copper/iron/sand
B. Mixture reacted at 25° in presence of copper/iron/sand,
See figure 3 for peak assignments.
14
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TABLE 2
CO»CUm,S IBENHFIKD a ELECTRON IMPACT GC/MS ANALYSIS OF ENDRIN/HEPTACHLO*
REDUCTION (Experiment 3)
Compound
— — • _
C10H7C15
C10H6C16
C10H7C150 (tent)3
and
C10H5C17 (heptachlor)
C10H6C16°
C10HgCl502 (tent)°
C12H10C14°
C12H9C150
C.,H0C1,0 (endrin)
J.Z O D
C12H8C16°C
Retention
Time (min)
— .
4.0
4.9
6.4
7.3
7.7
8.8
9.4
9.8
10.8
- 4.4
- 5.6
- 7.3
- 7.7
- 8.6
- 9.4
- 9.8
-10.8
-13
Integrated ,
Response (%)
—————— — — —_ . _^_ — _^__ _ —__»«_»„_ .^^__
0.2
1.2
4.6
•
1.8
25.9
0.3
1.9
17.2
47.0
ilass spectral quality was too poor for definitive assignments.
b
Response values are listed as a percent of the summed integrated areas
for each peak in the chromatogram.. These values mav correspond approxi-
mately to relative concentration although no molar response factors are
available.
Differences in fragmentation and chromatographic retention times indi-
cate at least two isomers with this molecular formula are present in
addition to endrin.
15
-------
100.0
80.0
4-)
•H
w
01
4-1
fi
l-l
4J
C
(1)
u
GO.O
40.0
20.0
.0
10
Time (min.)
15
Figure 5.
Total ion current chromatogram of chemical ionization GC/MS
analysis of products from catalytic reduction of endrin
(Experiment 4). See Table 3 for identification.
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TABLE 3
COMPOUNDS IDENTIFIED IN CHEMICAL IONIZATION GC/MS ANALYSTS OF ENDRIN
REDUCTION (Experiment 4)
Integrated
Response (%)b
C12H160 (tent.)
C12H13C10
C12H12C12°
C12H11C13°
C12H1QC140
C12H9C150
C10HQC1C0 (endrin)
1 £. O D
C12HgCl50
d 1.3
3.0
4.4
6.2
7.7
9.6
10.8
12.4
- 2.8
- 3.9
- 5.9
- 7.0
- 9.5
- 10.7
- 11.7
- 13.3
4.4
1.1
2.0
0.8
6.1
32.7
45.6
7.4
Retention times represent boundaries of the integration. Some compounds
represent two or more isomers, as evidenced by multiple peaks in the
chroma togram..
Response values are listed as a percent of the summed integrated areas for
each peak in the chroma togram. These values may correspond approximately
to relative concentration although no molar response factors are available.
17
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complete. These results indicate that a column reduction at room temperature
with a much shorter contact time would have produced even less dechlorination
of endrin and heptachlor. This hypothesis was tested as described below.
MINIATURE COLUMN EXPERIMENTS
The reduction of heptachlor and endrin by the copper/iron/sand mixture
was tested using 18 cm x 1.0 cm i.d. (14.1 ml) columns. Two columns were prepared
in parallel: one of the copper/iron/sand mixture and one of the sand only.
The void volume of the columns was determined to be 7 m & .A mixture of
heptachlor and endrin (200yg/£ of each) was prepared in pH=7 water and
eluted through the columns.
The sand column was found to be inert. The column effluent contained
endrin, heptachlor, and the compound tentatively identified as C-^B.gCl.0
(vide supra).
The copper/iron/sand column exhibited some reduction as shown in
Figure 6. The extent of reduction, however, is minor in comparison with the
stirred flask reactions. Even upon sitting in the column for about 65 hours,
endrin and heptachlor are clearly visible and the predominant peak in the
chromatogram corresponds to the compound previously tentatively identified
as CinHQCl,-0,-. Thus, even with extremely long contact time, the reduction is
incomplete and merely represents partial substitution of the chlorines.
SUMMARY EVALUATION OF ENDRIN AND HEPTACHLOR REDUCTION
Both the stirred flask and miniature column experiments demonstrated
some catalytic reduction of heptachlor and endrin. The extent of reduction,
however, is slight even when experimental conditions are much more severe
(higher temperature and/or longer times) than those used in the developing
lab.
18
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»
'5
=J
o
Q.
cn
1U
cs
UJ
a
cc
o
o
UJ
cc
Figure 6-
TIME (min)
Gas chromatograms of endrin/heptachlor reduction experiments
using miniature copper/iron/sand column.
A. Column effluent after 3300 m£—typical of all fractions
B. Column effluent after 3500 m£—after standing in column
for 65 hrs.
Compound identification: a) heptachlor, b) C-^HgCl^,
c) endrin.
19
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SECTION VII
CRITIQUE OF MONTHLY REPORTS OF CONTRACT NO. 68-03-2364
The reports generated during the development of the catalytic reduction
technology have been evaluated. A list of errors and omissions which led to
the erroneous conclusion that the technique was applicable to PCBs follows:
1) No preliminary feasibility studies (kinetics, thermodynamics,
mechanisms, etc.) were carried out to determine whether the
catalytic reduction could take place at ambient temperature and
pressure.
2) It is disturbing that this technology was found to be unsuccessful
in batch (stirred flask) reactions (see January 1976 report). One
would expect the same type of reaction in a flask unless the process
is a function of chromatography on the column. No attempt was
made by the development laboratory to explain this observation.
3) The suggested increased efficiency of the column as a function
of the mesh size (and therefore surface area) of the sand supports
the theory that adsorption is the process rather than reduction.
However, there was no extraction of the solid bed material to
investigate this possibility.
4) Observations of the chromatograins of the inlet (feed) and outlet
sample from the March, Gulf Breeze (Bionomics) study yielded
the conclusion that both chromatograms were essentially identi-
cal. No significant reduction was achieved. This was proved
subsequently by toxicity data and the high concentration of PCBs
in Bionomics1 Control samples.
5) There was no identification of reaction products (although a
GC/MS study was mentioned in the reports) , and no attempt was made
to do a complete mass balance across the column. Mass balances for
chloride were conducted in several cases by turbidity. Chloride
ion balances at these concentration levels (at or near the limit of
detectability) by a turbidometric procedure are difficult at best.
6) A carefully designed experiment should have included blanks, controls
(for example, a column packed with sand only) and internal standards.
These were lacking in the work done by the development laboratory.
7) Based on the size of the columns and the possibility of a chromato-
graphic mechanism, the number of void volumes (water) passed through
the column were insufficient. Extended runs should have been made
in order to mimic plant conditions.
20
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Evaluation and justification of catalytic technology in the developmental
portion of the program was primarily based on gas chromatography/electron
capture detection. Interpretation of gas chromatograms on inlet and outlet
samples (Gulfbreeze, Florida) demonstrated the difficulties and problems
associated with the lack of GC/MS confirmation. A stricter control of the
development phase with supporting documentation of the degree of dechlorination
by GC/MS would have controlled boundary conditions of the experimental program.
21
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REFERENCES
1. M.D. Erickson, R. A. Zweidinger, L. C. Michael and E. D. Pellizzari,
"Environmental Monitoring Near Industrial Sites: Polychloronaphthalenes,"
EPA-560/6-77-019, July 1977.
2. Personal Communication, K... H. Sweeney, Envirogenics Systems Company,
El Monte, California, April, 1977.
3. A. S. Y. Chan, J. D. Rosen, and W. P. Cochrane, Bull. Environ.
Contamin. Toxicol. , Jo, 225-230 (1971).
4. A. Demayo, Bull. Environ. Contamin. Toxicol., 8_, 234-237 (1972).
5. J. J. Eichelberger and J. J. Lichtenberg, Environ.. Sci. Technol,, 5_,
541 (1971).
22
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APPENDIX
On-site Demonstration by Envirogenics of a Catalytic Reduction Process for
Endrin/Heptachlor.
INTRODUCTION
This appendix describes the on-site test procedures, and the analytical
results of a catalytic reduction process of endrin/heptachlor. AnRTI and EPA
representative observed the demonstration by Envirogenics of the technology,
on-site sampling and analysis by GC/EC, and returned concentrated aliquots
of the feed materials, blanks and eluates to RTI laboratories for GC/MS
analysis.
The "Test Procedure" section of this appendix was copied verbatum from
an Envirogenics Systems Company experimental procedures manual.
23
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TEST PROCEDURE
ENDRIN AND HEPTACHLOR REDUCTION
ENVIROGENICS DEMONSTRATION TESTS
COLUMN REDUCTION
Two aqueous .solutions will be used, one containing approximately 100 PPb
of endrin, and the second approximately 30 ppb of heptachlor. Each solution
will be passed through separate copper-catalyzed iron columns at approximately
35 m£/min using freshly-prepared columns (37 mm by 1600 mm bed), each containing
600 g of copper-catalyzed iron powder and 2150 g of sand. Samples of the
catalyzed iron and sand will be provided EPA or RTI if desired. The runs will
be for a sufficient period to provide material for GC/MS analysis. Both the
endrin and heptachlor solutions will also be passed through sand columns and
eluate samples will be collected and analyzed.
ANALYSIS
Envirogenics intends to analyze the samples for endrin and heptachlor by
electron capture and flame ionization detection gas chromatography, for
chloride by turbidity, and iron and copper by atomic absorption spectrometry.
For purposes of the chloride analysis, it will be necessary to wash all
columns with water before use. It may be advisable to establish a chloride
blank from the eluates of the endrin and heptachlor solutions passed through
the sand columns. In order to avoid losses of organic material from the
dilute aqueous phases by sorption on the container walls, the samples will be
extracted with hexane immediately. The extractions will be made with Burdick
and Jackson glass-distilled hexane of a single lot. The extracts will be
analyzed by EC-GC, composited (unless the result is an obvious sport, in
which case an additional sample would be drawn), and concentrated for GC/MS
and FID/GC in Kuderna-Danish evaporators. The extracted aqueous samples would
be retained for concentration and chloride analysis.
24
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Small samples of the extracted effluent will be taken also for iron and
copper analyses. These samples would acidified and analyzed for iron and
copper by atomic absorption spectroscopy,
DETAILED PROCEDURE
Columns
The 37 mm dia x 1800 mm long glass tubes will be thoroughly cleaned and
the glass wool mat put in place. For the reduction tests, 2150 g of type
30 sand and 600 g Fe/Cu will be blended and placed in the glass tube. The
bed will then be washed with 1 £ acetone, drained, and filled with water by
bottom feed. Deionized water (2 £) will then be passed through the column.
The sand column to be operated in parallel with the reductant column will
be prepared by placing 2150 g sand in the same sized, similarly prepared
column. The beds will be examined and suitably treated to remove air
bubbles before starting flow.
Column Feeding
The endrin feed would be sampled at the beginning of the test, after
6-8 H flow, and after 12 £ flow. Each sample would be 500 m$L, and would be
extracted with 3-50 m£ portions of hexane. In making the extractions, it
is important that no aqueous phase be carried over into the organic phase,
so that if phase separation is difficult, 5 m£ of 2% aqueous Na^SO, may be
added to promote separation of the layers. One m£ portions of the extract
will be reserved for EC/GC analysis, and the remainder composited and con-
centrated to 1.5 m£ in the Kuderna^Dani-sh evaporator. The 1,5 mil concentrate
will be divided with EPA/RTI taking 1.0 m& and Envirogenics 0.5 m£. In
addition, 1.3 & portions would be sampled for chloride (and the 3^1/3 S,
samples combined), and 25 mi samples would be taken for AA, The heptachlor
feed would be sampled similarly.
25
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COLUMN RUNS
General
The columns will be started and adjusted to a flow of 30-40 mi/min. Both
the reductive column and sand column are to be running simultaneously. The
flow valves will be adjusted to give a static head of -15 cm. It is important
that the column be kept covered with water at all times.
The first 2-1/2 I of flow will be required to replace the water in the
column at the start, and will not be extracted. However, a sample will be
taken for chloride analysis.
Endrin and Heptachlor
A total of 15 £ of endrin solution will be run through the reduction column
and the sand column. Each 3 £ of effluent will be collected, extracted with
three 200 m£ portions of hexane, and 1 ml of the extract taken for EC/GC. If
the result is not a sport, the extracts will be combined and concentrated
in the Kuderna-Danish to 1.5 m£ (from the total 3 £ of hexane extracts). If
any sample is obviously out of line (gross contamination, etc.), then an
additional 100 m£ will be drawn, extracted with three 10 m£ portions of hexane,
and reanalyzed as a check. The sample would then either be composited or
rejected by mutual agreement. If rejected, the test would be continued for
an additional 3 £. The 3 £ sample after extraction will have a 1 £ sample
retained for chloride analysis. In addition, a 25 m£ sample will be taken
for AA. The AA samples will be acidified with 1 m£ cone HC1.
At the conclusion of the test (15 £), a 2-1/2 £ portion of deionized
water (post wash) is passed through the column, and the column allowed to
drain. A 1 £ portion of glass-distilled acetone is then passed through the
column, drained, and analyzed by EC/GC. The 1 £ acetone washes are continued
until the effluent analysis is clear.
The heptachlor test will be carried out similarly, except that a total
of 50 £ will be passed through the reduction column and the sand column.
26
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ON-SITE GAS CHROMATOGRAPHY
All feed solutions for endrin and heptachlor were analyzed three times
during the experimental phase to document the integrity of the stock (Figures
C-1A and C-1B) . The on-site demonstration of the technology for endrin and
heptachlor used one common feed solution to feed both the sand and Fe/Cu columns.
In addition, the concentration of the feed solution was determined by comparison
to standard endrin solution to within 4% of the theoretical feed solution.
Aliquots were analyzed from the effluent Fe/Cu and sand columns periodically
during the tests to follow the extent of reaction. Six samples were concen-
trated following GC/EC analysis for later GC/MS analysis. These included
endrin feed, endrin Fe/Cu effluent, endrin sand effluent, heptachlor feed,
heptachlor Fe/Cu effluent, and heptachlor sand effluent. All gas chromatographic
analyses were performed on a Perkin Elmer gas chromatograph with an electron
capture detector. Data reduction was via a Hewlett Packard data system. Two
gas chromatographic columns (OV-17 and DC-200) were utilized for analysis.
The results of the on-site gas chromatography analyses are as follows:
1) Both endrin and heptachlor feeds compare with stock standards in
purity. The gas chromatographic retention times of the stock endrin
(6.50 minutes) and heptachlor (2.15 minutes) are the same for the
feed solutions (Figures C-1A and C-1B).
2) No conversion or reaction was observed in either sand column (without
Fe/Cu catalyst) for endrin (Figure C-2A) or heptachlor (Figure C-3A),
i.e., the major peak observed was parent endrin (Figure C-1A) or
heptachlor (Figure C-1B).
3) Immediate changes in the eluate GC/EC chromatograms for both endrin
(Figure C-2B) and heptachlor (Figure C-3B) were observed for the
Fe/Cu catalyst containing columns.
4) Effluent from the Fe/Cu endrin column experiment was shown not to
contain parent endrin. This was demonstrated by injections of endrin
(sand column effluent, Figure C-4A) and effluent from the Fe/Cu column
(Figure C-4B) on an additional gas chromatographic column (DC ZOO).
An equal volume injection of the sand and Fe/Cu effluent (Figure C-5)
on DC-200 is included to show the difference in retention time.
Presence of parent is not eliminated based on the retention times of
the margin peaks on the OV-17 gas chromatographic column (Figures C-2A
and C~2B). The absence of parent compounds was confirmed later by
GC/MS analysis.
27
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5) Following the addition of endrin and heptachlor feed to two separate
Fe/Cu columns, the columns were washed with water and stripped with
acetone. GC/EC chromatograms of the acetone wash indicated the
presence of additional electron capturing species.
23
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31
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GC/MS ANALYSIS
INSTRUMENTATION AND ANALYSIS TECHNIQUE
GC/MS analyses were obtained using a 180 cm x 0.2 cm i.d. glass column
packed with 2% OV-101 on Chromosorb W-HP maintained at 120°C for 3 minutes,
then programmed at 12°C/min to 230° and held there for the duration of the 'run.
The flow rate was 20 m£/min helium. GC/MS chromatograms were obtained using
a Finnigan 3300 quadrupole GC/MS with a PDP/12 computer.
SUMMARY OF RESULTS
The results of the GC/MS investigation of six samples obtained during
the on-site demonstration are as follows:
1) Heptachlor feed - The only species and only major substance found
was heptachlor (see Figure C-r-6) .
2) Heptachlor sand column - The only chlorinated species found was
heptachlor (see Figure C-7). However, the sample was heavily
contaminated with C „ and greater hydrocarbons.
3) Heptachlor Fe/Cu eluants - The chlorinated species observed are
listed below.
Figure C-9. Heptachlor eluate concentrated to 1.0 ml.
Retention Time (min) Tentative I.D. Characteristic Ions
7.91 C10H7C15 236,238,240,302,304,306
8.33 C1()H7C15 236,238,240,302,304,306
9.66 CHCl 283,285,287
9.91 CiOHxC14+n 236,238,240
32
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Figure C-8. Heptachlor eluate concentrated to 100 ul.
Retention Time (min) Tentative I.D. Characteristic Ions
4.73 C1()H9C13 168,170,172,234,236
6.41 CHCl 168,170,172
6.66 C H Cl 236,238,240,201,203,205,
1U ' * 301 to 310
7.00 G-mH7C1< 236,238,240,201,203,205,
1U ' 3 201 to 310
7.41
8.16
8.33
8.41
8.60
? 218,220,222
? 283,285,287,215,217,219,
221,183,185
C1()H7C15 236,238,240
Mixture 283,285,287,183,185
Mixture 236,238,240,318 to 322,
283 to 287
5) The predominant species are the higher chlorinated ones with the Cl,
species being observed only in the very concentrated species (see
Figure C-8). The major component has a minimum of 4 Cl's (see
Figure C-9). No parent heptachlor was detected. This confirms
earlier onr-site GC/EC findings.
6) Endrin feed - The chlorinated (and significant) species observed
were endrin and two isomers (see Figure C^IO). The other isomers
were not dieldrin.
7) Endrin sand column eluents - The only chlorinated species observed
were endrin and two isomers (see Figure C-ll).
8) Endrin Fe/Cu column eluent - The chlorinated species observed as
follows:
33
-------
60.9-
u
V*
o
a-
Tino (nin)
Figure C-6. local ion current chronogram of electron impact GC/MS analysis of
heptachlor feed solution extract (sample no. 3, 1.0 ml).
Time (nin)
Figure C-7. Total ion current chromatogram of electron impact GC/MS analysis of
eluate from sand column with heptachlor feed (sample no. 1, 1.0 ml).
Tioe (min)
Figure C-8. Total ion current chromatogram of electron impact GC/MS analysis of
concentrated eluate from copper/iron column with heptachlor feed
(sample no. 2, 0.1 ml).
Time (min)
Figure C-9- Total ion current chromatograo of electron impact GC/MS analysis of
eluate from copper/iron column with heptachlor feed (sample no. 2,
1.0 ml).
3 4
-------
Time (rain)
Figure C-10. Total ion current chromatogram of electron impact GC/MS analysis of
endrin feed solution extract (sample no. 5, 1.0 ml).
Time (min)
Figure OH. Total ion current chronatogram of electron impact GC/MS analysis of
eluate from sand column with endrin feed (sample no. 4, 1.0 ml).
Time (min)
Figure C-12. Total ion current chrooatogran of electron impact GC/MS analysis of
eluate from copper/iron column with endrin feed (sample no. 6, 1.0 ml).
2
S M.-J
Time (min)
Figure C-13. Total ion current chromatogram of electron impact GC/MS analysis of
concentrated eluate from copper/iron column with endrin feed (sample
no. 6, 0.1 ml).
35
-------
Figure C-12. Endrin eluate concentrated to 1.0 ml.
Retention Time (min)
= =
10.49
11.49
11.83
13.33
Tentative I.D.
C12H10C14°
Characteristic Ions
^
310,312,314,275,277,247,
249,211,213
344,346,348,309,311,313,
281,283,285,245,247,209,211
344,346,348,309,311,313,
281,283,285,245,247,209,211
245,247,281,283,285,309,
311,313
Figure C-13. Endrin eluate concentrated to 100 ul.
Retention Time (min)
9.66
9.74
10.66
11.08
11.74
12.00
13.66
Tentative I.D.
C12H11C13°
C12H11C13°
C12H10C14°
C12H10C14°
C12H9C15°
Characteristic Ions
207,209
241,243
276,278,241,243
275,277,279,240,242,310,
312,314
275,277,279,310,312,314
309,311,313
245,247,281,283,309,311,313
The major chlorinated species again are the higher chlorinated ones (see Figure
C-12). The major peaks in the. dilute sample are the ones at 11.49 and 11.83 where
only one chlorine has been lost. No endrin was observed again confirming _
earlier GC/EC analysis. The identifications for the lower chlorinated species
in the concentrated samples are extremely tentative due to high background
(see Figure C-13).
36
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CONCLUSIONS
• No conversion or reactions were observed on either sand column (no catalyst
present) for endrin or heptachlor, i.e., the major component remaining was
parent endrin or heptachlor.
• An immediate change in the parent endrin and heptachlor was observed in the
Fe/Cu columns.
• Effluent from the Fe/Cu endrin experiment was shown by on-site gas chroma-
tography not to contain parent endrin. This absence of parent endrin was
later confirmed by GC/MS analysis at RTI.
• The evaluation of the reduction of heptachlor and endrin showed the
test procedure worked, although apparently not well enough to efficiently
reduce the pesticides to hydrocarbons and mono-and dichlorinated species.
• The biodegradability and toxicity of chlorinated compounds is a function of
the degree of chlorination. The extent of biodegradability is predicated
on reduction to mono- or di-chlorinated compounds. Based on the above
requirements and the results of various controlled experiments, the effluents
generated by this technology would not be environmentally acceptable.
37
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REPORT NO.
EPA-600/2-78-059
4. TITLE AND SUBTITLE —
Evaluation of Chlorinated Hydrocarbon Catalytic
Reduction Technology
... TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
3. RECIPIENT'S ACCESSION NO.
5. REPORT DATE
March 1978
6. PERFORMING ORGANIZATION CODE
Mitchell D. Erickson and Eva D. Estes
8. PERFORMING ORGANIZATION REPORT NO
RTI-1430/F1
ADDRESS
Research Triangle Institute
P.O. Box 12194
Research Triangle Park, North Carolina 27709
10. PROGRAM ELEMENT NO.
1BB610
. CONTRACT/GRANT NO.
68-02-2612, Tasks 17 and 28
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
14. SPONSORING AGENCY CODE
EPA/600/13
15. SUPPLEMENTARY NOTES IERL_RTP project officer is David K. Oestreich, Man Drop 62,
919/541-2547.
16. ABSTRACT
The report gives results of a laboratory evaluation of a control technique
developed for the EPA for the catalytic reduction of chlorinated hydrocarbons
(specifically PCBs and chlorinated pesticides such as heptachlor and endrin). The
technique involves elution of polluted water at ambient temperature and at neutral
pH through a column containing a mixture of sand and copper iron catalyst. The
evaluation found that PCBs are not detectably reduced, but are chromatographically
eluted from the column in order of increasing chlorination. The catalyst was found
to partially reduce heptachlor and endrin. The possibility of chromatographic
elution by endrin and/or heptachlor was briefly investigated using miniature columns
and found to be insignificant. The report also describes the observation of an
additional on-site demonstration of the catalytic reduction technology, including
observation of the test procedure, gas chromatography with electron capture
detection, and subsequent laboratory GC/MS analysis of transported samples. An
evaluation of the reports generated during the development of the catalytic reduction
technique is presented. It discusses errors and omissions in the developmental
experimental protocol which led to the erroneous conclusions that the technique was
applicable to PCBs.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
n Field/Group
Pollution
Chlorohydrocarbons
Pesticides
Reduction
Catalysis
Gas Chromatography
3. DISTRIBUTION STATEMENT
Unlimited
EPA Form 2220-1 (9-73)
Biphenyl
Heptachlor
Endrin
Water Pollution
Pollution Control
Stationary Sources
Polychlorinated Biphe-
nyls
19. SECURITY CLASS (This Report}
Unclassified
13B
07C
07B
07D
21. NO. OF PAGES
45
20. SECURITY CLASS (This page>
Unclassified
22. PRICE
38
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