NCD980602163_19810930_Warren County PCB Landfill_SERB C_Franklin Institute Research Library brochure on chemical PCB destruction-OCR

~nklin Institute Research Laboratory, Inc.
A Subsidiary of The Franklin Institute
Dr. Heisings, Office of the Governor
State of North Carolina
Suite 810 Capital Club Building
Raleigh, NC 27610
Dear Dr. Heisings:
September 30, 1981
Attached is a preview copy of the preliminary descriptive brochure on the
chemical PCB destruction system developed here at the Franklin Research Center.
Finished copies will be forwarded to you as soon as they are ready by Dr.
L.A. Lee, Director of the Franklin Institute Research Laboratory, Inc., the
marketing agency for this project.
I have discussed your inter.est with our EPA Project Officer, Mr. Charles
Rogers, EPA-IERL (Cincinnati) because it is with EPA support that a
substantial portion of the experimental development has been conducted. He,
or someone from Region IV, may be in contact with you directly to discuss the
possibility of our participation in demonstration tests. At this point it
would seem desirable to us to coordinate a testing program through the EPA.
Should the results warrant a full scale treatment program, we expect to be in
a position to participate in that kind of effort on a contractual basis as
well.
If you have questions or comments please feel free to contact either
myself or Dr. Lee. Thank you for your interest.
SWO/jhc
Enclosure
Very truly yours,
s. w. Osborn, Manager
Chemistry and Chemical
Engineering Laboratories
The Benjamin Franklin Parkway, Philadelphia, Pa. 19103 [phone] nVX-710 670 1889
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THE NaPEG™ SYSTEM
THE FRANKLIN INSTITUTE'S
CHEMICAL METHOD FOR DETOXIFYING
POLYCHLORINATED BIPHENYLS (PCBs)
AND OTHER TOXIC WASTES
~~ Franklin Institute Research Laboratory, Inc.
A Subsidiary of The Franklin Institute• The Benjamin Franklin Parkway, Philadelphia, Pa. I 9103 • 215/448-1218
THE FRANKLIN INSTITUTE RESEARCH LABORATORY, INC.
The Franklin Institute Research Laboratory, Inc. (FIRL), is a wholly
owned for-profit subsidiary of The Franklin Institute, a not-for-profit
organization created in 1824. Long a leader in the development of
science and technology, the Institute continues its scientific work today
through its major divisions--the Franklin Research Center (FRC); the
Bartol Research Foundation; and the Science Museum and Planetarium.
FIRL and FRC are headquartered in a modern research building in
midtown Philadelphia. FRC also maintains other offices around the world.
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TABLE OF CONTENTS
SYNOPSIS
TOXIC WASTES
A Disposal Problem
The NaPEG™ System--A Solution
THE NaPEG™ SYSTEM
Definition
Status
SUMMARY
ADDENDA
Brief Chemical Description
NaPEG'" Reagents
NaPEG'" Process
Action
Current Uses
Future Uses
Advantages
Cost Considerations
Addendum A: News Release, 8/21/81
Addendum B: Miscellaneous Ne~s Clips
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SYNOPSIS
Researchers at The Franklin Institute have developed a chemical method
for destroying certain classes of toxic chemicals, including the chlorinated
organic materials. They have had particular success in the decomposition of
polychlorinated biphenyls (PCBs) and are conducting EPA-sponsored field trials
of this technology for the clean-up of PCB spills. They are currently
awaiting EPA authorization before testing their process to remove PCBs from
contaminated transformer oil for an electric utility company.
The chemical reagents and related method employed to dechlorinate PCBs
are known as the NaPEG™ System, named for the principal constituents of the
reagents: specially modified sodium (Na) salts of nontoxic polyethylene
glycol (PEG). NaPEG™ Reagents will dechlorinate PCBs in any concentration,
either in fluids or on solids, under moderate reaction conditions. The
products of dechlorination are disposable water-soluble oxygenated compounds
and common salts. The NaPEG™ Process is particularly cost-effective when
the dehalogenation process produces recoverable dielectric fluids or oils.
In addition to the dechlorination of PCBs, NaPEG™ Reagents are expected
to have wide-ranging uses for dehalogenating or decontaminating chemical plant
effluents, pesticide and herbicide residues, toxic spills, and chemical warfare
materials.
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TOXIC WASTES
Wastes--chemicals, residues, byproducts--have become a fact of life in
our industrialized society, and technological advances are often accompanied
by technological leftovers. Frequently these wastes are toxic. Scientists
strive to keep pace with the problem, but sophisticated substances requir~
sophisticated disposal techniques. This is particularly true of the
organohalides.
A Disposal Problem
The halogens have long been a valued family of chemicals. They combine
readily with many materials, including the organics, forming compounds of
great stability and high resistance to combustion. As a result, the
organohalides have been used for thousands of products that are now an
integral part of daily life. It is impossible to get through a day in any
civilized country without encountering manufactured halogen compounds in
electrical or railroad transformers, hydraulic pumps, fluorescent lights,
carbonless copy paper, inks, paints, caulking compounds, insect sprays, or
weed killers.
The stability and ubiquity of the organohalides present a major problem.
Scientists have learned that some of the chemicals once hailed for their
effectiveness also carry a considerable potential for harm and, in some cases,
it appears that the dangers outweigh the benefits. The stability that once
made these products so useful serves as an impediment to their destruction.
Disposal has become a major problem. 1
Among the stable organohalides are pesticides such as Kepone and DDT,
herbicides, various alicyclic and aromatic compounds, and especially the
polychlorinated biphenyls (PCBs). PCBs create one of the largest disposal
problems simply because so many pounds of these materials were used. More
than 750 million pounds were manufactured2 between 1929 and 1977.3 Initially,
PCBs were recognized for their superb dielectric properties and their
inertness, and no acute toxic properties were observed. Consequently they
were used extensively as electrical insulating fluids. About 300 million
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pounds were installed in electric utility and railroad transformers, and some
450 million pounds were used to manufacture capacitors, electrical equipment,
plasticizers, and printing inks.~
Worn-out or leaking electrical equipment presented an unforeseen problem
when scientists determined that ordinary disposal methods created the
potential for human health problems. The PCBs released into the environment
failed to break down, Stable compounds could be passed from plants, animals,
and fish through the food chain to humans, with magnification of their effects
along the way as they became ever more concentrated in fatty tissues.5 The
documented adverse health effects include reproductive failures, gastric
disorders, skin lesions, and tumors in laboratory animals. Workers exposed to
PCBs have experienced chloracne and other epidermal disorders, digestive
disturbances, jaundice, impotence, severe headaches, and throat and
respiratory irritations,6
Until now, there has been no satisfactory method to render these
chemicals harmless, according to EPA standards. The options have been limited
by regulation7 to burning or burying, but neither method is completely
satisfactory. Both methods require packaging and shipping to the disposal
sites, with all the problems incident to the transportation of hazardous
wastes.
Combustion of PCBs requires capital-intensive incinerators and costly
energy sources to maintain the high temperatures that are mandated. The
method also incurs objections from neighbors, may give off undesirable
byproducts, and precludes recovery of materials.
Burying involves extensive packaging to prevent future leakage, the use
of expensive real estate for landfill sites, provisions for security and
supervision for years to come, and loss of ability to recover materials.
Furthermore, the use of burying is limited by regulation to substances having
only low levels of PCB contamination.
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The NaPEG™ System--A Solution
Faced with the general problem of toxic waste disposal, researchers at
The Franklin Institute set out to find solutions, working initially under
Institute sponsorship with a small endowment fund for support. They
concentrated first on the organohalides because these chemicals presented a
major and immediate problem with far-reaching consequences.
Chemistry created the halogen-disposal problem. Therefore, it seemed
logical that chemistry might also provide the basis for a solution. Because
stability in the organohalides results from their strong carbon-halogen bond,
researchers sought a chemical means to break that bond and remove the
halogen. They expected that such a process would allow the remainder of th e
compound to be decomposed or disposed of by established chemical and
biological methods. After several years of research and testing, they
concluded that the NaPEG™ System produced the desired results.
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THE NaPEG™ SYSTEM
Definition
NaPEG'", which is named for its principal ingredients--specially modified
sodium (Na) salts of nontoxic polyethylene glycol (PEG)--is the trademarked
designation for both a new family of chemical reagents and the process
that employs them. Invented at The Franklin Institute by Dr. Louis Pytlewski and
coworkers, the reagents and the process for using them are the property of
the Institute, protected by pending patent applications filed in the U.S. and
other nations.
Status
The Institute presently prepares the nonhazardous NaPEG'" Reagents in a
specially designed facility in suburban Philadelphia. Developmental work is
also continuing on other, broader uses for the NaPEG™ System. However,
most of the discussion in this brochure will focus on two specific uses:
o decontaminating PCB-impregnated soil and equipment;
o decomposing PCBs in dielectric and hydraulic fluids.
Franklin is conducting a yearlong test of NaPEG™ Reagents to detoxify
PBC-contaminated soil at the Piccillo Farm waste site in Coventry, Rhode
Island, with funds granted by the EPA. The Institute has also submitted a
proposal, prepared jointly with Philadelphia Electric Company, to test the
NaPEG™ Reagents and Process for destroying PCBs in dielectric fluids. This
test, to be conducted at a PECO facility, is awaiting EPA authorization.
Brief Chemical Description
NaPEG™ Reagents--The NaPEG™ Reagents are polymeric complexes consisting
basically of modified sodium polyethylene glycolates. These reagents,
available in several strengths and compositions, are viscous, deeply colored
liquids or semisolids that flow readily at temperatures above 50°C. They are
completely miscible in polar solvents such as PEG, PEG ethers, and water.
Aqueous solutions are strongly alkaline. The reagents are stable in storage
and nonexplosive. They contain no metallic sodium compounds, produce no
hydrogen in storage or in use, and are biodegradable in conventional waste
treatment facilities.
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The NaPEG™ Reagents are available in several formulations, partially
determined by the specific polyethylene glycol used in their preparation and
in the amount of modification used during preparation. For example, NaPEG'"
200 is made with a PEG 200 mixture, while PEG 400 yields a NaPEG™ 400
reagent. The degree of modification affects polarity and stability of the
reagents.
NaPEG™ Process--In the NaPEG™ Process, a NaPEG'" Reagent is used to treat
a substance contaminated with a toxic waste. In the case of PCB contami-
nation, the NaPEG™ treatment results in complete dechlorination of the
polychlorinated biphenyl molecules.
The NaPEG™ Reagent is mixed with the contaminated substance and the
reaction proceeds under mild conditions, at temperatures below 125°C. The
process is so flexible that this reaction can occur with any concentration of
contaminants, ranging from trace levels to 100%.
DECHLORINATION REACTION
NaPEG + PCB ___ A_1_·r ___ _,C> COMPLETE DECOMPOSITION
Action
The action of the various NaPEG™ Reagents differs mainly in degree of
rapidity, depending on the strength of the formula used and its compatibility
with the contaminated substrate.
The NaPEG™ Reagents used in the treatment of contaminated oils are not
adversely affected by oxygenation. In fact, present evidence indicates that
autoxidation products and intermediates present in these NaPEG™ Reagents
strongly enhance the reactivity of the glycolate complex for dechlorination of
PCBs.
Similarly, the reagent is not adversely affected by the presence of
moisture, either in air or in contaminated substances.
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NaPEG™ Reagents, then, can be used under ambient conditions without
the need for an inert atmosphere.
ADVANTAGES OF NaPEG™ REAGENTS
o OPERATE EFFECTIVELY IN PRESENCE OF MOISTURE
o OPERATE EFFECTIVELY IN PRESENCE OF AIR
o OPERATE EFFECTIVELY AT MODERATE TEMPERATURES
Current Uses
NaPEG™ Reagents are currently being used on a trial basis for:
o dehalogenation of dielectric fluids and oils contaminated with
organochlorides (transformers, capacitors, hydraulic pumps, etc.)
o reclamation of oils after decontamination
o decontamination of spills on porous and nonporous surfaces. Because
the NaPEGm Reagents are not sensitive to air and water, they can be
sprayed on spill areas and allowed to react over time. Eventually the
excess can be taken up by soil components or neutralized; products
of the reaction can be decomposed by normal bacterial action.
o reclamation of contaminated condensates after decontamination.
Future Uses
Continuing examination of the reaction's scope indicates the NaPEG™
system may be effective for:
o destruction of pesticide and herbicide residues
o destruction of certain chemical warfare agents containing chlorine or
phosphorus
o desulfurization of coal and petroleum products
o purification of effluents from chemical plants.
Advantages
The advantages listed below have been observed when the NaPEG'" Reagents
and Process have been employed to treat contaminated oils and dielectric
fluids.
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o Effectiveness--In a series of laboratory tests, the NaPEG™ Reagents
have reduced PCBs to zero detectable. This has been done in a matter
of hours, depending on the degree of contamination and the material to
be decontaminated, Field testing has recently been initiated,
o Simplicity--Users can usually process their own oils for clean-up and
reclamation onsite, using relatively simple equipment. A batch plant
can be constructed from components that are normally available (e.g.,
steel tanks, piping, heaters, and chemical process pumps). Although
some equipment--a stirrer, a controller, OL a specific-duty pump--may
have to be purchased, an outside vendor probably is not required
either to build or to operate the equipment.
o Stability--NaPEG™ Reagents are shipped to users as a one-component
system that remains stable for at least two years when stored at room
temperature.
o Insensitivity to air and moisture--Chemically, the NaPEG™ Reagents are
insensitive to moisture and air, operating at a temperature that can
range from ambient to well above the boiling point of water. These
features contrast with other recently announced chemical decomposition
methods which require extreme dryness and the absence of oxygen.
Accordingly, the NaPEG™ System should provide a distinct
advantage in decontaminating oils and cleaning up outdoor spills.
o Adaptability--The NaPEG™ Process can be adapted easily and
inexpensively to the requirements of either a portable or stationary
batch plant. Although the size of the batch is flexible, many utility
company representatives consider 1000 gallons as optimum. It should
be possible to process two batches of this size in one shift, and the
addition of another reaction vessel--possibly with a heat exchanger--
could double the throughput, lowering processing costs.
o Compatibility--Several utility companies are considering combining the
NaPEG™ Process with an oil reclamation unit (clay filtration plus
vacuum drying). For this application, both treatments could be done
together so the reclamation unit would never receive PCB-contaminated
oil. The NaPEG™ treatment would be carried out first. Then the oil
would be routed to the reclamation unit, where reheating would be
unnecessary. The single drying step at the end, serving both units,
would present another savings opportunity and, under normal NaPEG™
Process conditions, might not even be required, By selecting batch
sizes carefully, the two processes could be combined rather easily.
o Universality--The NaPEG™ Process will handle PCB-contaminated oils
and other dielectric fluids at all concentrations up to 100%.
o Availability--Franklin has constructed a process demonstration unit in
the Philadelphia area to manufacture and supply NaPEG™ Reagents in
developmental quantities. The raw materials--primarily sodium and
polyethylene glycol--are inexpensive and readily available and the
reagent preparation is simple.
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o Safety--Neither the NaPEG™ Reagents nor the NaPEG™ Process is expected
to require extraordinary safety measures. The reagents are mildly
alkaline and normal chemical handling procedures should be employed.
The reagent-preparation process eliminates the presence of any sodium
metal or hydrogen in the reagents. The NaPEG™ decomposition process
itself releases no undesirable byproducts into the atmosphere. Instead,
it destroys the PCBs and produces reaction products--nontoxic organic
compounds and inorganic salt--that are disposable by normal water-
treatment methods or adsorption onto solids.
o Recycling potential--Since dielectric fluids, oils, and other
substances treated by the NaPEG™ Process are neither incinerated nor
buried, they can usually be reclaimed after the chlorine or other
halogen atoms have been removed.
o Cost-effectiveness--The cost of using the NaPEG'" System is expected to
be lower than that of other methods which may require shipping,
energy, processing, or landfill expenses. If sufficient oil is
reclaimed after decontamination with the NaPEG™ Reagents, use of this
procedure may actually generate a positive cash flow.
I FEATURES OF THE NaPEG'" PROCESS
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o PROCESS IS NOT SENSITIVE TO AIR OR WATER
o REACTION SYSTEM DOES NOT CONTAIN SODIUM METAL
o REAGENT IS PREPACKAGED IN A SINGLE, STABLE MIXTURE, READY FOR USE
o REACTION CONDITIONS ARE MILD AND SIMPLE
o PROCESS PLANTS CAN BE STATIONARY OR PORTABLE
o REACTION PRODUCTS CONSIST OF REUSABLE FLUIDS, WATER-SOLUBLE OXYGENATED
COMPOUNDS, AND SALT
Cost Considerations
The cost of the NaPEG™ Process depends on the type of process, size of
the process unit, technical assistance provided, and equipment costs. In
general, there are three cost components:
o license fee (which includes professional and technical support);
o plant construction and operations costs;
o cost of NaPEG™ Reagents purchased.
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The value of recovered products may counterbalance these expenses. Thus the
total cost of using the NaPEG'" Reagents and Process can range from less than a
half-dollar per gallon treated to a positive return, depending on the intended
reuse.
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SUMMARY
There can be little doubt that toxic chemical disposal and clean-up are
major problems not only in the United States but throughout the world.
Moreover, they are high-priority problems. Although businesses and govern-
mental agencies may be faced with the need to make budget cuts in selected
areas, few can delay dealing with chemical wastes. The risks--especially for
health and the environment--are too great.
The problem of chemical waste disposal is innnediate, and t he need for a
practical solution is vast. The Franklin Institute has found such a solution
in its development of the NaPEG™ System for decomposing toxic chemicals.
STATUS AND OUTLOOK OF NaPEG™ SYSTEM
o RIGHTS OFFERED FOR COMMERCIAL USE
o DEVELOPMENTAL QUANTITIES OF REAGENTS AVAILABLE
o PROGRAM SUPPORTED BY TECHNICAL STAFF OF THE FRANKLIN INSTITUTE
o PROCESS UNDERGOING CONTINUING DEVELOPMENT STUDIES
o SYSTEM LOW-COST BECAUSE OF INEXPENSIVE MATERIALS AND PROCESS
o METHOD USEFUL FOR CHEMICAL PLANT EFFLUENTS, PESTICIDE AND HERBICIDE
RESIDUES, SPILLS, LEAKS, CHEMICAL WARFARE MATERIALS.
The NaPEG~ System is straighforward, flexible, and versatil e. It employs
chemical reagents that are easily manufactured from available, inexpensive raw
materials. These reagents can be mixed with toxic wastes or con taminated
substances, using simple processing equipment and standard chemical procedures.
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FOOTNOTES
lsee, for example, Wilkinson, R.R., Kelso, G,L., Hopkins, F,C.
State-of-the-Art Report: Pesticide Disposal Research. Kansas City, MO:
Midwest Research Institute; 1978; EPA-600/2-78/183, No. 64110.
2 11Polychlorinated Biphenyls; Criteria Modification; Hearings." Federal
Register, Part VI: Environmental Protection Agency, May 31, 1979; Section III,
Table 2, p. 31515.
3EPA's Final PCB Ban Rule: Over 100 Questions & Answers to Help You
Meet These Requirements, Washington, D,C,: U.S. EPA, Office of Toxic
Substances, Industry Assistance Office, TS-799, June 1980, p, 3.
4Federal Register, loc. cit.
5EPA's Federal PCB Ban Rule, p.3.
7Federal Register, op.cit., pp. 31518-31521.
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I ADDENDA
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THE
FRANKLIN
INSTITUTE
ADDENDUM A I
FOR RELEASE : IMMEDIATELY
BENJAMIN FRANKLIN PARKWAY AT 20TH STREET, PHILADELPHIA, PENNSYLVANIA 19103 (215) 448 -1000
CONTACT: Jo Carmosky (215/448-1287), Jane Grinspan (215/448-1129)
FRANKLIN INSTITUTE'S CHEMICAL DETOXIFICATION PROCESS BEGINS FIELD TRIALS
PHILADELPHIA,PA--A nonhazardous method to make polychlorinated biphenyls (PCBs)
harmless has been developed by Franklin Institute Research Laboratory, Inc. (FIRL),
a subsidiary of Philadelphia's Franklin Institute.
. TM The technical breakthrough is call ed the "~aPEG System." The name is taken
from abbreviations for the principal ingredients--specially modified sodium (Na) salts
of nontoxic polyethylene glycol (PEG). The new system involves a chemical reaction
at moderate temperatures, results in safe biodegradable products, and can be performed
at the site of contamination.
When NaPEGTM reagents are mixed with substances containing PCBs, the strong
carbon-chlorine bonds that make PCBs so stable are broken. Then the sodium from
NaPEG™ combines with the chlorine from PCBs to form ordinary salt, which is disposed
of along with other products of this chemical action (nontoxic organic compounds) by
normal water-treatment methods or adsorption onto solids.
The NaPEG™ reagents and process, invented at Franklin by Dr. Louis Pytlewski
and coworkers, have been undergoing research and testing for several years.
The NaPEG™ System received nationwide attention .in July when Franklin began
a yearlong test, with EPA approval and funding, to detoxify PCB-contaminated soil
at the Piccillo Farm waste site in Coventry, Rhode Island. According to Dr. Steve
Osborn, technical manager of the NaPEG™ program for FIRL, the laboratory portion
of this work has been proceeding satisfactorily and field trials will begin shortly.
Because PCBs and related halogenated chemicals are very stable and highly
resistant to combustion, they have been used for thousands of products that are now
an integral part of daily life. It is impossible to get through a day in any
civilized country without encountering manufactured halogen compounds in electrical
or railroad transformers, hydraulic pumps, fluorescent lights, carbonless copy
paper, inks, paints, caulking compounds, insect sprays, or weed killers.
Recently, however, PCBs have been identified as a potential risk to human
health and the environment, and two years ago the EPA banned their manufacture and
import, setting a timetable for phasing out most uses of the substance by July 1984.
more
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I Because they are so stable and do not degrade naturally , disposal of PCBs has
become a major problem.
Osborn noted that PCB disposal has generally been restric ted by EPA regula-1 tions to incineration or landfilling . Both methods have significant drawbacks,
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and chemical destruction of PCBs is seen as a desirable alternate method. Burning
requires specially designed high-temperature incinerators, while landfilling , which
is limited to items with very low levels of PCBs, always presents the problem of
future leaking. In addition, both methods require packaging and shipping of the
toxic wastes, and both preclude the recovery of precious natural resources such as
TM oil. Franklin's NaPEG process, however, can be performed wherever a contamination
TM problem exists. Moreover, Osborn said, the NaPEG System permits recovery of
materials such as transformer oils from electrical equipment.
The use of NaPEG™ to decontaminate transformer oils is scheduled for
testing in the near future, pending approval by EPA and other governmental bodies.
Philadelphia Electric Company has a greed to permit test-batch processing of
PCB-contaminated oils, in 25O-gallon batches, to yield clean oil and readily
TM disposable, water-soluble byproducts. Osborn said he expects the NaPEG process
to work as effectively in these field trials as it has in repeated laboratory tests,
converting all PCBs present to safe substances.
The process will be carried out at PE's oil-processing facility at Delaware
and Oregon avenues, where the electric company has routinely shipped and stored oils
for more than a generation. Implementing the NaPEGTM process at this facility will
gradually diminish and eventually eliminate PE's need for storing PCB-contaminated
oil, according to Osborn.
Although Franklin's initial tests have focused on decontaminating PCB-
impregnated soil and equipment and on decomposing PCBs in dielectric and hydraulic
TM fluids, Osborn points out that NaPEG probably will be effective in treating a
number of other toxic chemicals. Other potential uses include destruction of
pesticide and herbicide residues, destruction of certain chemical warfare agents
containing chlorine or phosphorus, desulfurization of coal and petroleum products,
and purification of effluents from chemical plants.
TM "We are very pleased with the behavior of our NaPEG System," said Osborn.
"It has performed as expected, and we believe it will play a significant part in
cleaning up the toxic chemicals that concern us all."
The Franklin Institute Research Laboratory, Inc., is the for-profit sub-
sidiary of The Franklin Institute, a not-for-profit organization which has been
engaged in scientific and technological research since 1824. The Center, head-
quartered in Philadelphia, has branches in Little Rock, AR, Silver Spring , MD,
and Oak Ridge, TN.
30
8/21/81
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ADDENDUM B
MISCELLANEOUS NEWS CLIPS
16C COURIER-POIT,FrldaJ,No,,emberl,tffl . ,· •, . · · . t . ·
F ear·ed. PCB cheIIlical may he lnad[e
' \ . ,. , ' ... \, >· ·.··.;:· .
lhe·egp of chickens lhat ate conta-' •·ufacture of PCBs· .:.. · which havl
mlnated ll!ed had to be be destroyed. caused cancer In laboratory anl•
The feed was contaminated from : · mats and•~ suspected ol causing it.-
By THERESA A, GLAB Of the Courier-Post
PHILADELPHIA. -'-A local PCBs lhat leaked from an electrical · . In humans a,-but · the problem
chemistry _professor ls trying. to , · transformer. ' remains of how to dispose of any of
prove1 that polychlorlnated .. •LJ)e so many things' In chem.is-'. · the clear,' syrupy liquids lhat have ·
bipbenyll (PCBI) cin be.turned Into , :_ try, -PCBs once se"ed a ~I pur• been drairied from _electrical equlp-
usefal 111bstances, ,ta~.i than ''pose." Pytlewski said:•. . ,' · ·_rnentalldkeptlnslorage.
mtrely be laiclnerated at high COSL ' , f · . , . , · , "They were used as :a substitute ', , · · "The EP.\ has put a (ol o money
. ~ of the proposed lnclneratlo~ . .' .lot normal hydrocarbon oils iii ~igh• _: _into .lncinera~on _.studies an~ has
sites Is In Soulh Jene:,, at the Roi-, power electrical systems because, .. , . _come up wilh Indications lhal 1t can
:Jins Environmental &!nlces plan~ : they-are resistant to lire. .. · '.' . be done,safel~, but no one wants it
.In Loctan Township. , ·, _ . , . "But we now realize lhat PCBs are. , , done at an . incinerator near h1S
Dr. ~~ii L. Pytlewsk1, ~n usocl• .• ·. very soluble In . lats, so ·lhe body , ·,home," he said •. · · . ·.
ate professor at Drexel University,, • , stores them up, rather than ge~llng '. ~-The reaction In Logan Township ,
,· Philadelphia, who has spent •, sab-· . ' ri~ ot them," he said. . _ . : .' has been typica_l, w!lh res!dents pro-
ballcal leave al the Franklin,. ,_· Chlorinated malenals of•, ~ll ,· testing that .. lnc1nerallon could
Research Center-bas succeeded lh : · kinds do not degrade and are bound, release the toxic substances Into the
converting PCBs'lnto j,o1ybydroxy• ',lo be picked ~P. by fish, low)-and· · air. • . . ..
lated biphenyls, . CC?mpowids. -that , Qlher anlmal5-lf leaked, Into waler-·. : . A permit !or such incineration has
have been used harml~I:, •.s !odd ,' , ways or Into the ~oil, Pytlewski ·; · i not yet been granted lo Rollins or to pr~~~~v=~ dlrecil·, ~~la~'ed, .,sa!~Bs get In.to hul"an belngs·1. any other plant, said Richard Ser•
f'CBs with · i p_roblem In human .' mostly by belng·ln the ~o-system, 1 ,nyak, regional sales manager.
beings, bat they have liet!nshown to • In lhe food people eat!· · • , · '· Thereareonlythreeor'fourpossi• ·
be ~ ... le _In animal stlldles,_. ~--~,uld._ •. . ·: THE. ENVIRONMENTAL ,.__ ,.·.
1
ble sites In the country that could ,....,.. 'handle the high-temperature·incin-
IN'BIIJ\.INGS; MONT.; recettUY ', · tectlonA.genc~ha1banlled the man-eratlon·(2,200 d~_grees F. or ~,200
· · · .. · · ,, · · :, -0.), Pytlewski said.
.:_. THE-EPA ··has' provided a one-
. '.year grant of. lcsst1!3n U00,000 for
. the PCB research at the center,·
• which Is a dlYlsion of lhe Franklin
· Institute. '· ;... · ' \
SCRAttTON, PA •
POL-AM JOURNAL
MON TIil Y
OEC 12 \979~
0-· ,J",4 -r--,s;:·--.... --..
· Dr. Louis' L. Pytlewski. an
assoc. professor at Drexel U in
Philadelphia. while on sabbatical
leave at the Franklin Research
Center; has succeeaea,. im:·--con-
verting polychlorinated biphe-
nyls CPSBs) into polyhydroxy-
lated biphenyls, compounds-that
have been used harmlessly as
food preservatives. PCB present-
ly-incinerated at high cost, is
also causing an environmental problem. .. • __ _._.....;__...-; ~--.,1·: ... ....---~
Sl!..<t~u.. Ne...J-. iJ;r.-1~~-JJ. \
Detoxifying PCB's:
A promising start
waler-soluble and relativelv harmless
polyhydroxylated bipt,enyl, lie e,plains.
similar to a clas,i of antioxidants (includ-
ing 'IHT) used in packaging materi:,ls as a
food preservative.
, . ·. • Pytlewski estimated that it would
cost between 10centsand40centsa .. .
po~nd to convert PCBs into wale~-' ,. ~-.
. soluble substances.. . I ' •~s•· ' ·;-,r'lt ·,
, "This Is in the range.of indnera-· _,,/ ,-." :' ': '\ lion costs, which could be as high as · "'ij· r:t
$600 a ton." . . • ,
Drexel University chemist Louis L Pyt-Pytlewski. an analytical chemist with
lewslti bu developed wha1 m.1y be the tint more than 10 yP.an· e.perience in chemi•
chemic.al breakdown. or detoxification. of r.al detoxification, says that his finding,
polychlorinated bi phenyl• l ,-<:s's l. It's an while still prelimimu y, mav havl! g!?.al po-
important accomplishment because like tential. Since thl! chemical can bl! r~n-
the pesticide DDT, Pea's are insoluble in dered water soluble, ways might be found ·
water. are thermally stable up 10 862"C to flush it out ol the body. Al pres~nt, Pyt-
and resist biological and chemical break-lewski's process only works on pure peas
down. As a result; once they enter the or PCll's mixed with oil.
biosphere-and 750 million pounds pro-Aslocialed with decreased fertility in
duced between 1930 and 1971 are thought higher mammals (SN: 7/8/79. p. 28) and
to have been discharged into the envi-· with numerous neurological and epider•
ronment-rc,'stendtoaccwnulateinthe mal disorders in humans. ro·s were
body fat of animals, including humans. banned from production and most uses in
Initially engaged in developing new the United States last May by the Environ-
methods to detect POi's in the tnviron-mental Protection Agency.
ment, Pytlewski says he first became con-Although POi's can be destroyed by
cerned with POi's when he realized that coetly incineration (SN: 6/17/78, p. 392),
eYell II one can identify and isolate them, most are merely relegated to landfill burial
"how do you gel rid of them?" A1tacking where they do not degrade. Chemical de• ·
the problem required abandoning the pre-toxilication could prove preferable to
conceived notion that pea's were too sta-both, Pytlewski says. Unlike incineration,
ble ever to break down. And while on saJ>. it does not add to the dangerous buildup of
batical doing research at the Franklin In-carbon· dioxide in the atmosphere. And
stitute in Philadelphia last year, Pytlewski even though it may prove about as costly
happened on a scheme that uses as burning, Pytlewski hopes that chemi•
polyethylene glycol 400 to transler the cally transforming pea's will also yield a
chemical reactivity of metallic scdium to salable byproduct.
POi's. ~ working under an EPA grant back at
"We were lucky, really: he ,ays, By , tl-.U.t"V1 lewski has turned his altenlion
spreading out the "extreme chemical reac• to identifying the fundamental chemical
tivity• of sodiwn, he was able to pull out processes al work in his detoxification
tightly bound chlorine anC: replac:e it with process. With luck. he says. in five years or
hydroxyl groups. Chlorine bound with so ii may be ~sible to design and build a
sodlwn lo form salt. What remained was a piiot-sc.ale detoxification reactor. D .
· The developmenl<>l,a commer-
cially applicable conversion pro-
cess could take about three years, he
said. .
' ' -~·P~I phOlography by Ron Kati
Dr. Louis L. Pytlewski, shown yesterday in his laboratory at Franklin Resea,:ch Cente
1 Is attempting to show that toxic PCBs'can be converted to harmless and useful chem
cals Instead of having to be incinerated, a process opposed by fearful residents <
Logan Township, site of Rollins Environmental Services. ' ·' · '
1
--N .. --- ---.. ~-nt~I~ Sun.,AUOU&f31,1080 CC -'f __ ,:......_~---'--. ~ .. )" Spotllg11~-i""= -·!\.• ·•~ -~;·: .. :,'.:. ;?r \ . \,,. ,. .......... ~-----..... :.. ft, ... .-. ····• -, .• -, • . ,.. 1 /f'TY-'~ . ~-~ >·1·. 1'._ ft•:j• .. ... ,. ----{'«:..4··✓' ~-· • ' 7 ~-•·. t ,?,,,: , .. .,., ,..:!.,J __ , :.--·;, .. ' . ., . ~-\-. ' •• ~. '. f :'it. _jj'.··, •:, . ---,,, • --• . .·, -! • • . . • -............... n.... -1'---deuedPcafnmPaledlorflt.DNrAdudelat,-rafltrMINWlnmal.-iy~. Scientists. Waging war -on a tough_ foe: PCBs .· 1tJ WilUN flOEUCH. 0(11.llulutut&la/f "' blr1li,· 1t -lialleol .. a ..... dMl!lle&I tiat . 'INmedtoclaf)rutun, · -Virtually IDIMltrudillle, It ~ be lllbllltTIN ta.leflllltety la water .-ttlwlut drowt!in1, wu allle to . deflect lllpilJ ID-llunll al electrtdty, aaol-. wtu..taad temperanan. lbat wwlcl bne laelMrat-ed leuer malecllles. Today, Ille chemleat -~ lllpllenyl « PCl-la U 4!ll\'lralmente outlaw. · ··.\lid clletnlatl, w11o creete4 t11t -. m,.. Ill& tlleir teleftti to dellrvy IL ► SdeaU,ti lib lboee M Pllllldtlpllla'i Pruklla la,tltule ud Galldyeu TlN • lubw ~-ill AJl. rcm, Olli&, believe Ibey beff fawd a way to 11:111 lbe lafldloua culprit Willi cbtmltaJ autJ)oti-acttac u uetutlGnen, . _ "It loab pnttJ Nmarbblt,'' uJ4 Dr. JOiia V. kllmiU. Prutlla Imtllllta'I Tice preeideat of pbysleat ud life~. rqanllJII bis --p, 1111. "We'w,ata,utbopefarlt."· "G&adyur'I lecblllque ~ to reduc:e dn-malic&IIY Iba rtu. 11--fhtandal •---prepwit -. twll ,av■ lllrtb ie ltlllbtlnl clilJ. dree, anil faur otlia' illfanta had blrtll defects. lfeaawtille, ldtntllts. around the ~ _... llndin1 Iba dlemlcaJ ill anlmall, flab ud lll.nla tbrouat,out tlle IIIYtranment. It WU cmtuninatlq lakee, rivers and--. It wu evea tuimd ID low CCIIICmtnlloaa amoq Ille I~ caps ot AntarctlCL The aJann wu eounded. Cmgreu put 1111 1ep1 clamp an PCla, placlD& limitations m· lta -wbile INlnnlna lta manufacture In lffl. But the battle wu far from over.~ police-clearly wen OUIIIUlllbered. ' lly 1172 1111 Momant& i:«111 -tlll wwld'1 i... lq IIIJ)lllilll' ol Ille cbemlcal :1... bad manufactured at,aut 1.4 b!Wan pounda Ill the lllbetance, aCCXlr'dlnl -16 Federal Gevermneet reports. About UO million pounda bad been exported cweneu and-. 51 million pounda cleetroyecl. l1le rest rwmalDed la Ille United States, wttb abaul 7'I million pounds ltlll ID .. mc:e. ~ 41111 mUlloa pounds bad been dumped la laaclftJla and Ille natloa'I waterways. A few of these drums an ltond leplly, wttll EPAl~ID..,.,,_tllroupouttbecoun-try, l1le Wlulmmln111..-i.-o1 min Pl1lla.W. ---.. ----"9UIIIIJ'-.,.-'• ~,........__ID~...... -· -~-..--••---------•---matlcally the rUk, time and.finanClal ~t-.• . try. l1le Wla'-lilq llt•ll-of llx In PbllacleJ. fflllllnd to ufely dlspole Of'PCBs;" Kid Dr. "Carl . plda fuHl1lbia Ille llatuUlly ~-for PCB E. Snydlu-, the cmepuy•• 'ficil! praldmt f1lr ~ ' ..._.. NUCII:-' --• A-, dloN requiftmeati II. a '-lndl-llllh Pederal fllYl,-t Mtlclall -t1ae eMrae4 ~ dlD amand a cantainmet ■na lbat mmt wttb tncklq down aJld destnytna PCaa -.... lie bold at .... tWlol the "1)1ume Ill Pell IUll'ed men cauttou&. · t1iere. 1'beff could be no drains or ntvee or otJlff "Tbe IDlon'aatloa we baft u f!IICIDUrallnl, but It · -openillp tbat -W allow the c:llemlcal 16 lealt b&-la premature t6 18Y mucb about tt 1111t11 we ba,,. Jond Ille curbed ....._ Material must be atored im-lllOft 1Dtonnat1c,n,'' Ill.Id aw Gunter, leader of tiie -~-• leak-reai.taat root. · · · -· · Pell re,ulaUOD branch 6f the U.S. l!'.nvlr'alllnetal . . TIie dlamlcal wwkl be boUled In IUCh lltee 1111111 Protectlan AafflCY (£PA) and die natloa'I clllef -11ffl11Ut111 dllpoaal methods a.reJound. eaf-1 llfficer for PCl1. "ID cin1er ID~ · One medlod II llurtal In clay-llned lllldflll. 11111 --Ill Joela yau,-,S EPA approval and at tllepn,el!lit tbe-p:ter d a --inaIY lmpemous llnlll& IUd-Ume no-bu appUed for appro.al.". . , -iy lnullli·c,pea a,ncema many~-ID --11$, realdellta of Ille 1VlalnOllulll · -tallata. . -· -lectiOII el Plllladrlphla dbeevered tbat the dlelllJ. · A110tber dlapaaJ tedlaiqlle ta lndneratloa. a. -cal quietly U11111 ~ residence ill t11e1r eel&bbertillad. -ol Ill IDeredlble ttablllty, temperaUINia -of · In a warahcue lealed 16-tbe ~ Electr1c Co. at S21a £. Oimly 11. la a lt6nll}' -.ton wt WNk ill die efflce ol dty Manqlq Direct« Wlllan Goode, Ibey left 80 doubt tbat Ibey wanted the IIJably·tmlc: dlemlcal drtval aut at towa. · "Tbe botlDlll line II we want It aut Uld we•'ftllt It aut now,•• 181d Eric Mantm, a retldent af tbe area. Federal, ttate and dty affldall Kid they'd Ilka • IO obllae. llut Ibey-added tbeft were 116 lites In Ille ccuntry ltplly NI up to dupaM ol die buarllOul . ,material. · · To tbe re&ldentl' dllmay, -cifflCW Kid IDUIJ al the 2,1110 berrela ll6red at tbe warehaule mlpt llave to remain tbtre fOr aJmoat uotbar year, _pendlna appraval al tbe na:ton'1 tint lepl dllpoaaJ lite ID Eld&rado, An.. · The lalpuM aaclerte&red wbat mu, talllder a -,-1mpota1ble wt -bc1w to set rid of wllat"lllllt llealme the world'I -perllltant pollutallt .. - -· II WUll't alwaya thil way. WIien flnt produeed · In 1121 to llelp reflDe lullrlcatlq OU., PC1la wwe . -lialled as III Ideal cbemlcal. , . P~Bs storage .sites'· Plllladelpbla attes where PCB, ~ leplly • IIOred: t tmnll Yant. B • vmanao m. -about Ill pll-of PCBI,_. 2. Wayne Junction Electric car Shop. 4500 Germantown ave.-tbout UIO gallonl. 3. -WeltiJlpoUle, 1211 5. 30 st. -about 2,200 p)kml, . . . -· 4. G.2. tleetrtc ArJpuatus Shop, llMO E. .Erie ave. -•bOut 100,000 gallons. :S. Electrical Apparatus a: Repair Co., H21_. Sc:lwylldU ave. -~allc,m. '_ t. G.E. wareboule, 5218,E.• Comly st.-:..._-· .J~;oooaau-.,: » ,...S ,at out about Ila i=que r,n,pertlel, die _ _ cbemlcal -called upen 1& pert-a Wide~ _.. 111aa 2,000 clepeei ,. are-~ t& bum tyllftulll. ., . PCB1 · It helped jleOple ill die mer&Y lluaiDelS to bar-_ ~ Jand-bued -,i-a.re 11e1q n,adled aad -eleetr1clty ID transformers and capsdlM'I. It an.It EPA apprtWJI. 11,e one In Eld&rado, Ark., llraugllt die plullcs lndllllry out Of Ila illfanq, 111d wUJ be at,le Iii burn llOO pounc11 ol liquid and 1 GOO was relp(Jllllble for die "cart,mleN" car11an pa-' pounc11 a, IDlld PC1la every baur. TIie other: ID . par. · · · . · . / -· -beer Park, Teaaa, II deslped 16 bum 5,000 pouncll lt-wu used u • name retard&1lt ill yun. a eoat--· .. a, 114u1c1 PCJII an baur. _ Ina 1or lrOlllna board CDYen, and became. an II>-. • --· nluable lqred,enl In caulldJII CIOlllpaunda putty . An«ber poellblUty II burrilnC at -In an lnclll-" wivua, eavelope1, paints and vanlilbes, pr1nuni entor llblp called Vulcanua, owned by Oceaa Com--platee and flow'es0ent llabts. · 'llullloa Semcel. If there were any accidental lmic Tbe molecule WU.IO pervulvl .iiiat It llelan to · releuee, at least then -W be.no populatlen om-blnl up accidentally, u a byproduct o1 paper ncyJ! ten -rt,y lo be _Injured. 1q. creema, ataa, wues, lnduatltal ~ llut trullp0r1m, tbe c:bemlcal to port -W itlll ■ad -In -s-and compounds used to uw.t wa-poae • problan. . ·' 1111'. _ , • Poe tbla ,.-, • mMbod tllat WOUJcl 18fely,. ·1u1 ID an ~ clualc -,let 1or a bc1mir iM>vel, duce PCla t6 bannlNI Cffllpouncll wltboUt die tM man-made-~ tunled upGn lta tnwntor. It· 'need 16 tnmp0rt to reinl!Ce llttl tbnlll&baUt tha 4UJe(ly Invaded tbe waten be drank, the air ·11e mmtrJ 11-belq viewed as an ldeel 10lutlon. bnatlled. Ille 11111111 ata,-and evaatuilly bll fletll,-lninlcally1 tbat IOlutlon appean to be.a~ tbreatenlnl bll bealtb. . _ -· .,,__ . SdenUflc Studies u early u 1~...,.. reporUa, . _ Two weelll qo. ·Go&dyear ann<,unced a way u, · that worlten exposed to blab COlla!lltntiolll at convert PCl1 Int& ,alt aalq e aodlum compound to l'Cls cleYeloped aCD&-llke bleinllbes -fll tr,tt tllelr tpllt 'the molecule . .bc,diee, ello loalna tbelr awetites and au drtva. . · coeipany Mfldlla laid If patenll on tbe procea Liter, IClenUsta dilcoveffl! the . chemical -were ·aruted,. they -.Id be placed ill .public wllen fed to anlma1I ID IIIUllve doad -caused domain wttb no company pin. . · liver cancer and produced lllldeniJllld -oftlpr1n& · lut cllemllti aald Ille teclmlque, tbou&b promll-. ; wttll leernlq cll18bllltlea. · ID&, bu dr-awbadts. Pint, iarae quanlltles Of Ille la !NI about 1,000 Japaneee were 11ckened after -aodlllOI compau,id -id be IIMded 16 pt rid at• •t1n1 rice contaminated with PCl1. ~ II 111e· 11111811 -al PCB. Purtber, the aodlwn c:om-~ "YusbO" IDdclent ,bowed llkln rubelaad pound ID f111e111o11 li._ble, and reecta to moll-. daralled plamentatloa and ltfnllllll llmbl. Of U tun and aan-, lllillllq It difficult to atore. • I . • ... t -
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Research advances in
chemical 'disposal' of PCB's
Electric Light and Power, 58(11)53; Uov. 1980
Two recent developments in the
chemical treatment of polychlori-
nated byphenyles are now holding out
the promise of large-scale, low cost de-
toxification of transformer and heat-✓
transfer fluid contaminants.
Work done at the Chemistry and
1 Biosciences Lab o! the franklin Re-
garch Center has shown that PCB's
can be rapidly and completely decom-
posed by the use o! molten sodium
metal disperaed in polyethylene gly-
colL
And a mid-August announcement
from the Goodyear Tire & Rubber
Company reveals that it has demon-
■trated that it can transform PCB's to
common table salt by reactions with a
chemical mixture containing sodium
napthalide.
Two potential advantages of the
chemical "disposal" become apparent
when compared to the alternative
method of high temperature incinera-
tion. First, it appears from lab-scale
teats that the by-products of the
chemical processes are relatively in-
nocuous. Second, the process, which
reportedly can be done wi_thout elabo-
rate and sophisticated hardware,
eliminates the need to transport
PCB'• from the utility site to a dis-
poeal facility. Industry observers re-
port that the PCB transportation
iuue ia becoming increasingly worri•
some.
"Incineration is not only extremely
enercY intensive, and becoming in-
creasingly so each . day, but the
effluents are very corrosive and costly
to remove," a Franklin researcher
told attendees at a recent symposium
on the treatment and disposal of
hazardous wastes.
Franklin pracea■ explained
The Franklin researcher, Dr. Louis
L. Pytlewski also said, "We have dis-
covered that molten sodium metal in
the appropriate solvent medium can
function as a broad-based chemical
reactant."
The actual process involve" a mix-
ture of sodium metal in polyethylene
glycol "It can be added directly to the
dielectric fluid and forms a true solu-
tion," Franklin research scientist
Edward J. ~ said. So far, fie
added, the chemistry of the process
has been validated on a laboratory
scale where a quart of fluid has been
heated to 70" C for half an hour with a
chemical reagent. This converts the
PCB's to other materials, which can
then be separated by extraction. The
entire process, including the extrac-
tion, takes about two hours.
Thorne said advantages of the
100
90
80
70 2!50 ml._ T,_., OU (83 ppm PC8°1I
E · Tr-2 hrs. 60"C wid> 2. 5, 10. 20 o, 30 ml Q. Q. . -Mly of 0.73 M Sodium Napn-lde solution
~ 60
s 50
ta u 40 ...
30
20
10
0o 2 50 75 100 125 150
· Sodium Naphthalide-to-Chlorine proportions (molecular weight ratio}
Saun:e: Goodv-
Franklin process included the fact
that the reaction could be conducted
with standard equipment in open air,
and that the reagent appeared to be
nrr stable.
Because commercial PCB's are a
mixture of so many elements, it is dif-
ficult to identify precisely the nature
of all the reaction products, Thome
said. He noted that there are as many
as 30 or 40 PCB isomers and all yield
different reaction products. Tests to
date reportedly have shown that none
of these ia harmful.
In addition to scaling up the chemi-
cal process from laboratory to pilot
plant size, Franklin Research Center
scientists will be working to get the
reagent to be effective at ambient
temperatures. Thorne thought it
-uld be several months before that
is accomplished. Since a "fundamen-
tal rule of chemical kinitics" is the in-
verse relationship between tempera-
ture and time, having the process
work at room temperature would
mean that reaction times would be ex-
tended. Just where the optimum-bal-
ance exists is yet to be determined. he ·
said.
Good-,.ar conversion proceu
In mid-August, The Goodyear Tire
& Rubber Company announced that it
had developed a process that uses a
sodium compound that strips chlorine
from toxic PCB's, rendering them en-
vironmentally safe while producing
common table salt (sodium chloride)
as a by-product. The fluids, purged of
of their contaminants, can be reuaed.
In confronting the problem of con•
verting toxic PCB's to lesa than the
current regulatory requirement of 50
ppm, Goodyear said it defined four
main criteria.
• The process should allow for
complete, yet selective conversion to a
non-toxic state of the chlorinated
species and it should result in reaction
products that can be easily and safely
disposed.
• The process should be capable of
being performed on-site, preferably
with presently available equipment.
• The process should be adaptable
to both large and small quantities of
material.
• The process should be relatively
low in cost.
After experimentation, it became
clear to researchers that reactions
with sodium metal rwr •• were slow
and required high temperatures.
Scale-up of this reaction seemed.only
to intensify the problem.
On the other hand, reactions with
sodium napthalide on laboratory
scale were found to proceed on the
order of five minutes under an inert
atmosphere at ambient temperatures
in either glass or steel vessels.
Nitrogen or a similar inert gas is
used to prevent the generation of po-
PCB inspections: What to expect
Utility instruction programs aimed at
showing electric company employees
the difference between the real and
perceived dan1ters of polychlorinated
biphenyls (PCB's) is one important
way to reduce the potential of facility
inspections by the Environmental
Protection Agency, a senior electrical
engineer at a major midwest utility
has advi~ed.
Speaking to attendees at a recent
engineering conference, Otis L.
Barchers of Missouri Public Service
Company said, ''The EPA may very
MoPub: Speaking from experience
Missouri Public Service can speak
with some authority on what is in-
volved when the Environmental
Protection Agency visits a com-
pany for a foll-blown PCB inspec-
tion. The EPA, moved by a report in
August, 1979, that a transformer
had exploded at the utility's Sibley
generating station conducted four
inspections at three of the compa-
ny's facilities.
3
On August 8, 1980, EPA Region
VII issued a complaint against
Missouri Public Service, charging
the utility had violated the Toxic
Substance Control Act on seven
counts. For the alleged violations,
the EPA slapped the utility with a
civil penalty of $41,250 (see EL&P.
September issue, page 1). The util-
ity, claiming there was no exposure
to the public, said it would appeal.
tentially explosive mixtures involv-
ing hydrogen and oxygen during thE
conversion process.
Further experimentation showec
the capability of producing the re-
agent on either a small or large scale.
Once produced, it can be added in
either a normal or inverse manner to
~arg'II amount of additional contami-
uatad. heat-transfer fluid.
After'the reaction occurs at room
temperature, .the excess reagent i5
quenched with water, the quenched
fluid is vacuum stripped to recover
chemicals for possible recycling and
the residue ia subjected to further dis•
tillation. The residues from this sec•
ond distillation consist of sodium
chloride and types ofpolyphenyls that
can be safely burned.
Typically, PCB's with concen-
. trations of the order of 100 ppm can be
converted to less than 10 ppm -one
fifth .of the EPA's maximum "safe"
limit. This is reported to be true even
when Goodyear adopted the proce-
dure for use on a commercial scale.
Goodyear says that the four criteria
set up for process conversion have
been fulfilled by its new technique.
The proceaa is selective, the company
says, can be performed on-site with
available equipment, and is adaptable
to either small or larp operations.
That the conversion can be accom-
plished for "only pennies per pound"
makes it relatively low-in cost. Spe-
cific coats are pegged to the changing
coats of sodium, plus coats of the other
necessary chemic:ala. (The Franklin
proceaa can also be implemented for a
few cents per pound of PCB, the Re-
search Center reported.)
Goodyear has applied for patents on
its process, and the company says
these patents, if granted, will be dedi-
cated to the public with no commercial
gain accruing to itself.
The EPA has been informed of the
process in detail with the federal
agency reportedly investigating it for
widespread applications. Descriptions
of the process also have been mane
available to inquiring organizations.
Laboratory efforts have reduced
the PCB content of transformer oil to
less than 50 ppm, the safe level stan-
dard set by the Environmental Pro-
tection Agency. Thorne said work has
begun on scaling up the process to
pilot plant scale, although it would be
several months before results would
be available from these processes. He
said-reagent production could be in-
creased to 100 gallons per day, but
"how much transformer fluid can be
converted with this quantity is not yet
known."
well be contacted by one of your own
employees. This contact may be made
if an employee does not fully under-
stand how the regulations affect him
or as a result of his questions on how
dangerous PCB's really are."
Barchers noted that the EPA also
may be contacted by members of the
general public who observe PCB signs
on plant equipment and become
fearful. "It is an observation," he said.
"that the EPA will investigate all
cases regarded by the public as a
possible hazard."
To reduce this possibility, Missouri
Public Service Co. now monitors how
PCB signs are placed on company
continued on page 54
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D2 THB NBW YORK TIMBS. THURSDAY, JUNB 18, 1981
T echnologylBamabyJ.Feder
I
Treating PCB's AtyplcalPCBmolecule
vVith Chemicals
r'.":"lM. IIESE days, there are frequently several ways
In th~ry to solve a technical problem, but only a select few that ha,·c won approval from the
relevant rer,ulntory agency. T~ke, for example, the
problem of how to hnndle PCD's, the ha.r.ardous
chemical compounds thnt have shown up every-
where from rl,er beds to chickens.
· PCl!'s, polychlorlnated blphcnyls, have cnused
cancer and birth delects In animals and skin diseases
In humur.s. By the time further production of them •u b:um~ In Im, mllllon.1 of round., hnd leaked
Into the environment, and mnny limes that nmount
continue to be used as a liquid coolant and Insulator
In power :rnnslorm~rs and as an Insulator or heat
transfer liquid In Industrial equipment.
Burial and Incineration under heavily regulatP.d
con11lll•n3 eru the two methods currently used to dls-
)"JSe ol these compounds. Last m~nth the Environ-
mental Protection Agency announced that hence-
forth onotl1er woy, or ~cttln~ rid ol PCB's -destruc-
tion by uth~r cheijiicnls -would be avnllnble under
certain condlibns.
Becnuse t~, blphr.nyls are closely relr.ted to
numerous other hazardous chemicals, lndudlnr, sub-
stances such as DDT and Kepone, the announcement
raised hope!! that the day was approaching when
chemicals would become a mature weapon In the
waste-management arsenal.
• • •
The approved proce,s wns developed by Sunohlo, a
partnership forn1ed by the Sun Company and the
Ohio Transformer Corporntlon and based In Canton,
Ohio. Sunohlo set out In 1976 to clenn and recycle oil
used In transformers, but quickly found th•t such oil
w~s usu:illy so laced with PCB's that an eflective
method of disposing of the blphenyls was of primary
lmpom.nce.
The trick Is to ;trip the PCB molecule of Its chlo-
rine atoms. Sw.oblo doet II by raising the tempera-·
. . '
Carbon atom Chlorine atom
ture and pressure of the oil/PCB mixture and then
adding a chemical to which the chlorine wlll be
strongly attrncted. Sunohlo will not disclose the
chemical nature of the renr,ent, the substance added
to react with the chlorine In the blphenyl, but because
the chlorine emerges alter several minutes of reac-
tion as part of a salt molecule, the reagent must In-
clude sodium or a close chemical relatlve such as a
salt that lacks chlorine.
The other product of the reaction, occordlng to Olis
Jordon, Sunohlo's vice president for research and
development, Is a polymel' that Is chemlca!ly similar
to the plastic In a telr.phc,ne receiver, lor example.
When It Is dry, II looks like a tan powder. At the end of
Sunohlo's process, It resembles a paste because It
hangs on to some of the oil. However, alter llltenng
through various ag~nt,, su.:h as the clay called Full-
er's earth, most of the oil Is clean enough to be put
back In a tnnslormer, Sunohlo says.
• • •
Sunohlo's processing unit Is mounted on a truck to
make It portable. Its use Is contingent on approval
from regional E.P.A. ofllces. So far, approval has
been received from olllce!! In New England, Kansu
City, Mo. (!l'rvlng Kansas, Missouri, Nebraska and
Iowa), and Atlanta (for four test sites). Approvall
from tbe MYell otherolfices are expected shortly.
P2ge 8 Hazardous Materials ln<eitigence Report 26 June 1981 © 1981 WIS
• Franklin Institute plans to test new PCB detoxicant at Piccillo waste site.
Nor Is It likely to be long belore Sunohlo hns com-
petitors. On~ company, Acurex Wnste Technoloelcs
Inc. of Mountain View, Calli., hos already applied for
npprovol ol a sodium-based process It plnns to
demonstrate at a yet-to-be named site near Clncln-
nnll later this summer.
Doth ol these processes are aimed at w;iste-oll pl"'>-
ccsslng because this sector represents 1hr most con-
centrated PCB problem and thus the first obvious ,
mnrket. William Gunter, the E.P.A.'s rcp1latlor.s
team leader for the biphenyls·, estimates that 35 mil-
lion ~lcctrlcal transformers use oil and that one-third
of them may be contnmlnated by PCD's.
l'he broader problem of cleaning up the biphenyls
In the general environment Is being attncked bj•
E.P.A.-financed research under the direction of the
Franklin Research Institute. On the basis ol l~born-
tory tests, Franklin's upproach could wor~ on con-
taminated soils and sludges. Unlike the others, It re-
quires exposure to oxygen.
• • •
Franklin's reagent Is described hy Charles Rocers,
E.P.A.'s monitor of the project, as a sO<lium atom
surrounded by a rinr, of polyethylene glycol, which Is
similar to antllrce1.e. The rcngent Is sprayer! on th•l
contaminated material. The polyethylene, clycol ·
reacts with oxyr,cn In the air to form an ox yr.en mole-
cule that nttacks the PCD. The bi phenyl Is strlppe,J ol
Its chlorine, which thca combines with the , r.!ium In
the re~gcnt to lorm salt. The rest or the l'Cn 1,i0Je-
c11le forms a compoun1 thnt, unlike th" blpheuyl, cnn
be broken doin by bncterln In ii°l;rndllll.
The lab tests Indicated that the process would de-
stroy nbout GO percent of the PCD's In rontaminnte<i
soil In 5.1 rlnys If the air :empcroture was 5J 1k1;recs.
A yearlong test at a site In Coventry, R. I., Is to ~gin
this summer.
One big name th~t could enter the fie lei Is the Good-
year Tire ~nd Rubber Company. 1.nst summer,
Goodyear announced that It had developed and
demonstrated on a commercial scale a sodium-based
PCB destruction process while working on wnys to
recycle heat transfer liquids. The company's Rsscss-
ment of whether it will enter the waste-management
busln= will reach at.least a preliminary conclusion 1
by the end of the year; according to Allen Kovalchik,
manager of proJecta and ipaterlal1 coordination.
Under a $78,000 grant from the U.S. EPA in Cincinnati, Ohio, scientists from the Franklin Institute
in Philadelphia, Pennsylvania, will begin field testing this week of a new chemical reagent designed to
detoxify polychlorinated biphenyls (PCBs) in contaminated soil. Scientists will conduct the testing on
PCB-contaminated soil located at the Piccillo Farm waste site in Coventry, Rhode Island. (HMIR,
17 Apr. 1981, p.4.) Charles Rogers, EPA project manager, told HMIR that, unlike other chemical
detoxification techniques which require the absence of moisture and oxygen to be effective, the Franklin
Institute reagent is activated by oxygen and is therefore ideal for treating PCBs in situ. EPA and the
Franklin Institute decided to perform the test in summer because the activity of the reagent increases ...s the
ambient temperature rises. In order to test the possible applicability of the process to soils in other regions,
project crews will use a variety of spray application techniques and solvent systems to apply the reagent to
the soil. The project will run for up to one year, during which time the Franklin Institute will monitor the
soil for PCB degradation. John Schmitz, director of physical and life sciences for the Franklin Institute,
told HMIR that the reagent consists of an activated complex of sodium and polyethylene glycol. In the
presence of air, the reagent strips chlorine from the PCB molecule, replacing it with oxygen-containing
groups such as hydroxyls, ~thers, or quinones. Schmitz said that at least pan of this reaction involves the
formation of the superoxide ion. He emphasized that the reagent is prepared from inexpensive substrates
and that it can be shipped in a stable, nonreactive condition. At temperatures of over l0(l°C, the PCB
degradation reaction will be completed in hours instead of months, but Schmitz stressed that the Franklin
Institute process is most valuable because of its ability to continuously reduce PCB concentrations in soil
with the aid of ambient microorganisms, and without the need for high temperatures or for moisture-free
and oxygen-free conditions. For further information, contact: Jo Carrnosky, Franklin Institute, 20th
Street and Benjamin Franklin Parkway, Philadelphia, PA 19103; Tel: [phone].
Hazardous M:it~rials lntclii~cni.:c Report is rubliJhcd weekly by World Information S~·stcms, P .0. Box 535. Harva:d Squ3rc Station,
Cambridge. ~:lib-sa~hu~ o:.:38, U.S.A. Publi'.'ihcr and E.,ecutivc Editor: Rit.:hard S. Golob: Editor: Adam M. Finkel; As.iodate Editor: Roben
Kunzig; Contributinp; Editors: Eric Brus, Daniel W. McShea: Circulation Manager: Anne Loug ... ~; Marketing ~1anascr: C. Lisa ~1onrose.
Subs.::;~~tior. r~:~s en rc:q:..cs~ at Td: 6:7-.•;i-3100; Tv.·x: 7iU-3~J..i628 ·w·oR.LDii..:FO; CaO,c: \\·1.)RLOtNt-U. Copyrignt ..!;11981 by World
Information Systems. All rights r:-s.crvcd, Reproduction in any form whatsoever fort.iJdcn without cxprej,S pcrinission of the copyright owner.
ISSN 0272-9628
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..:t-\ :f( .;· : ··:.\·
Providence Journal, June 18, 1981
New process to remove PCBs
to get first field test at R.I. site
By MICHAEL A. HII.T7.IK
, .............. , • .!.t(lltf "'rtt«
,\ promisin1 new process that could
·d lbt ecological lhrtat of PCB,, • da.ss
' environmentally dUnble and cancer•
1asin1 pollutants. will get its llrst field
•st this month on a moull'! of contami•
.ated ,oil at the Warren V. Picillo
, hemlcal dllfflp in Coventry under an
,nvlronmental Pn:Jtection Acency gnnt.
The proceu, developed by the non•
. 1.ofit Franklin Research Center of Phila•
!elpbia. strips chlorine atoms from PCB
· .nolecul-. yilldln1 two innocuous pro-
ductl: tablt salt · and a biodegradable
llydropD-aad-oxypa compound. Chlo-
rine la wbat lendl PCBs botb their
toxidty IJld their utnordlnary persis-
tence In the envlronmenL PCBI are
parUcularly d.1111e111111 becallle they do
not· naturally brtall down.
Wbat NII this proc:eu &paR from
others develol)ed to datroy PClla.
Charlel J. Ro1us. the projer.t'a EPA
supervllor, laid yesllrday, la tlW it can
be •pplled at the contamir.atto,. site. The
otben. including one pr~ in>ented
by Goodyear Coi;,. re9eaK!len; function
oaJy. under laboratory conditions.
Bued OD small-scale laboratory stad•
le!. llogrrs said from his Cincinnati offl~. "we are pretty mud! convinced
that this process holds promise." :r the tests art successful, he said. "we
hope to cevelop tecllni~ues ·,, treat
sediments in water." Among the ob,ious
applications of that would be purifyln9
the Acushnet River and New Bedford
Harbor, where tons of PCBs discharged
bv two Acushnet manufacturers de-stroyed the lobster fishery ye.._..s. ago.
"This rtally looks like a nice process,"
said Thomas Wright, chief of the hazard,
ous materials division of the state De-
panment of Environmental Manage-
ment. The process. he said, can also
detoxify other hazardous chlorinated compounds that are commonly found in
illeaal chemical dumps. "Tbis is not
&oing to remove everything," he said,
"but what'1 left wUI lend Itself to otber
trutmtnts."
* * * The tests. due to sW't Jun• 29 and nin
throu1b the summer at the Plclllo site.
:11',~l1·e about !0,"'.JO cubic yards of soil
contaminated with oil, 1nuastri1l sol·
vents. and a soup of hi~bly toxic chlorin• ated compound.•. rte s~il was apparent•
5
ly contaminated while Picillo r311 an IIUclt chemical dump In I 976 and I 977 at
his remote, hilltop pi1 farm in Coventry.
PCBs. or polychlorinated biphenyls.
were invent,d ~y Mon<>nto Co. re-
searchers in 1930 and applied to an ever•
expanding inventory of industrial uses
before thev wer, banned bv the federal
gove!'llment and their manufacture was
halted in the early 1970s. By then, scientists h•d concl~ded that !he com•
;,ound,. round in carbon pa~r. electrical
tranS!ormers. and dozens of other com-
mon items. could callie cancer. miscar-
riaaes, and a host of otber serious,·
ailments. The Pictllo dump was selected for the
coming expertmenta, said spokesmen for. ·
EPA and the Franklin center. in part
becallSf such a large quantity of raw.
material wu available at an isolated site:
Under EPA's plan, ,-archel'I will lepa•·
rate the SOIi into a num ber Jf pi'.es and
spray them with varying concentratlona
and volumes o: tl:e c~.lcrinl'-rtripping
compound. Some of the soil will be left
untreated to orovide a measure for the
process's efficiency, said R01ers.
John Schmitz. dl"1:tor of the physical·
anci life sciences br1111ch of Frankl\n
R-b Center, said the proce.s was .
dls~ry,•f"N! b)' Louis Pytlewski. a Frank•
Un ~cientist seeking io· apply simple
chemical p~ to the problem uf
PClls pollutJng sensitive areas.
He discoYered that a mixture of mol•
ten socllum 111d polyethylene &lycol -a
nontoxic compound related to antifreeze
111d ,ometlme. used as a food additive -
would strip the chlorine atoma from the
PCB molecule. The cblorine combines
with ,odium to produ~ sodium chloride,
or table salt, and th• residue is a
nontoxic hydroxyl compound (three hy•
drogen atoms linked to a sln&Je ozyaen atom) th:t breaks down naturally !11 the
environment into other hydrogen and
oxygen com!)Otlllds, .
The reaction takes weeks or months
and produces a small amount of heat.
Under normal circwnswces the reac•
tl011 produces no visible m&llilestllloo
such u firt or smoke.
The discovery hu ~ tested on
contamiaated soil on the Frlltklln Cen·
ter's own rooftop, Scllmitz 111d. and
otbar laboratory tests Indicate that it
will won well In the o;,en,