PB85-188837
Assessment of PCDDs (Polychlorinated
Dibenzodioxins) and PCDFs (Poiychlorinated
Dibenzofurans) from PCB (Polychlorinated
BiphenyTs) Transformer and Capacitor Fires
Technical Resources, Inc., Bethesda, MD
Prepared for
Environmental Protection Agency, Cincinnati, OH
Apr 85
ffifr^^rey$?CTgftakt^
&to^^^l&tt&*tti]L&uuvjv-\iw*fAKjni_vwn*
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PB85-1868J7
EPA/600/2-85/036
April 1985
ASSESSMENT OF PCDDs AND PCDFc PROM PCB
TRANSFORMER ANT) CAPACITOR FIRES
by
Anthony Lee
Technical Resources, Inc.
3202 Monroe Street, Suite 300
Rockville, Maryland 20852
Contract No. 68-03-3212
Project Officer
Brian A. Westfall
Alternative Technologies Division
Hazardous Waste Engineering Research Laboratory
Cincinnati, Ohio 45268
HAZARDOUS WASTE ENGINEERING RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
mmnturtti •«
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1 REPORT NO 2
EPA/oOO/2-S5/ 036
3 REd AC ( 3 S Nr NP
YDD j8ooi I
• TI ll_ I AND SU$ TL6
Assessment of PCDDs and PCDFs from PCB Transformer
nd Capacitor Fires
5 REPOR1 DATE
6 ERFORuIpdG ORGANIZATION CODE
7 AUTNCiRIS?
Anthony Lee
I PERFORMING ORGANIZATION REPORT NO
PERFORMING ORGANIzATION NAME AND ADDRESS
Technical Resources, Inc.
3202 Monroe Street, Suite 3C0
Rockville, Maryland 20852
10 PROGRAM ELEMENT NO
11 cO dTpACTIGRANTMO
68—03—3212
12 SPONSORING AGENCY NAME AND ADDRESS
HAZARDOUS WSTE ENC1NEERING RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIROX ENTAJ. PROTLCTI0N AGENCY
C1NCINNATI, OH 45268
‘. TYPE OF REPORT AND PEP 100 COVERED
14 SPONSORING AGENCY CODE
EPAI600-12
15 5UPPLEMENIA Y NOTES
16 ABSTRACT
The EPA, under the Toxic Substances Control Act, has been mandated to develop appr
priate regulations for the control of exposure to oolvchlorinated biphenyls (PCBs). In
light of this responsibility the EPA Office of Toxic Substances recently issued an Ad-
vance Notice of Propc ed Rulemakinrj (ANPR) intended to define the nrobleri of releases o
PCBs and other toxic compounds during fires involvina transformers and capacitors con—
tair inq PCBs.
The EPA Office of esearch and Development CORD) has also been mandated under the
recently released Diox:n Strateq document to evaluate fire accidents involving PCB
:ransforners and caDacifors as ootential new sources of polvchlorinated ‘iibenzodioxins
(PCDDs) and polychiorinated dibinzofurans (PCDFs) in the environment. To di veloo the
•nformation to supoort the two nandated programs, the EPA/ORD undertook this study to
issess the problems associated with fires involvinn askarels, to catalog thu contamina—
ior. experience s and to review potential decontamination methods as well as disposal of
:ontaminated material.
This study assesses the chemistry
he generation of PCDDs and PCDFs. It
f PCBs and their toxic contaminants.
educe exposure are also ‘ iscussed.
p KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS b IDENTIFIE!1S/OPEN ENDED TERMS C COSAT! I leld/Gloup
*8 DISTRIBUTION STATEMENT
Release Unlimited
19 SECURITY CLASS (ThuRepor;f
Unclassified
21 NO OF PAGES
129
20 SECURITY CLASS (Thu page,
Unchssifjed
22 PRICE
TECHNICAL REPORT DATA
(Pteaxe i odInnr enonz on the ,e c e before complenngl
of PCBs under thermal conditions and ev iluates
reviews technoloqies for destruction and disnosal
Methodolooies to assess potential hazards and
EPA 2220—I (Re ,,. 4—77 1 P (v.OuI CD ,YtO ,. II ODIOLCYt
1
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NOT! CF
This document has been reviewed in accordance with U.S. Environmental
Protection Agency policy and approved for publicatior . Mention of trade
names or commercial product2 does not constitute endorsement or
recommendation for use.
ii
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Today’s rapidly developing and changing technologies and industrial
products and practices frequently carry with them thc increased generation
of solid and hazardous wastes. These materials, if improperly dealt with,
can threaten both public health and the environment. Abandoned waste Sites
and arcidental releases of toxic and hazardous substanLes to the environment
also have important environmental and public health irnplicati ns. The
Hazar’;ous Waste Engineering Research Laboratory assists in providing an
authoritative and defensible engineering basis for assessing and solving
these problems. Its products support the policies, programs and regulation’;
of the Environmental Protection Agency, the permitting and other respon-
sibilities of State and local governments and the needs of both large and
small business in handling their wastes responsibly and economically.
This report describes the occurrence of toxic chlorinatr- organic
Compounds resulting from combustion or pyrolysis of transforrer and capaci-
tor dielectric fluids containing polyc ’ilorinatec biphenyls (PCBs). Results
from accidental fires in buildings as sell as from the scientific iterature
a ’e presented. The report will be use il to the ei rtric utility industry,
the fire fighting profession and the heiardous wcst’ res arcri ani reguatory
communities. For further information, please corn. t the Alternative
Technologies Division of the Hazardous Waste Engineering Research Laboatory.
David G. Stephan, Director
Hazardous Waste Engir’eering Research Labo-atory
ii i
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LBSTRACT
The discovery of toxic contamin . nts such as polychlorinated dibenzofurans
(PCDFs) in PCBs and askarel fluids has elevated the environmental a d health
concerns associated with PCB transformers and cepacitors. Th F A Office of
Research and Development (ORD) is mandated under EPAs iecently—released
Dioxin Strategy document to evaluate fire accidents involving PCB
tranrforrners and capacitors as potential new sources of PCDDS and PCDFs in
the environment. To develop the recessary information, the EPA/ORD unc ertook
this study to assess the problems associated with fires involving oskarels,
to catalog the contamination experiences and to reviev emergency response
measures and decontamination protocols. This study assesses the chemistry of
PCBs under thermal conditions and evaluates the generation of PCDDs and
PCDFs. It thaws upon the present knowledge on the thermodynamic equilibria
of chlorinated substances and the more common experiences gained from
decontamination and detoxification of PCBs in non—fire accident situations.
It documents the emergency response and decontamination protocols and
summarizes technologies for destruction and disposal of PCBs and their toxic
contaminants.
This report was submitted in fulfillment of Contract No. 68—03—3212 by
Technical Resources, Inc., Rockville, Hary]and, under the sponsorship of the
U.S. Environmental Protection Agency. This report covers e ricd from
February 1984 to July 1984, and aa completed as of August 31, 1984.
iv
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CONTENTS
Notice
Foreword
Abstract iv
Tables
Figures
Abbreviations
I. Introduction 1
2. Conclusions and Recommendations 5
3. PCB Transformers and Capacitors 8
4. The Chemistry of PCBs Combustion 23
5. PCBs Fire Incidents 50
6. Prcvention and Management of ?CBs Fires 75
7. Decontamination of Buildings and Final Disposal of PCBs —
Contaminated Material 90
V
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TABLES
Number
1 U.S. Transformer Manufacturing Industry Using PCBs in 1975 . 9
2 U.S. Capacitor Manufacturing Industry Using PCBs in 1975 13
3 Volume of Fluid Contained in Askarel Transformers 17
4 Distribution of PCBs Concentrations for Mineral Oil
Transformers 19
5 NumLer of Mineral Oil Transformers in the Utility Industry by
PCBs Concentration Level 19
6 PCBs Concentrations by Transformer Size 20
7 Percent of Transformers Conta ning less than 50 ppm PCBs 20
8 Volume of Fluid Contained in Mineral Oil Transformers in the
Utility Industry 20
9 Isomers of PCBs and their Chlorine Content 25
10 Isomers of Chlorobenzenes and their Chlorine Content 25
11 Composition of General Electrica Dielectric Grade
Trichlorobenzene 25
12 Carbon/Hydrogen Ratio and Chlorine Content for PCBs 27
13 Percent of PCBs Remaining After Exposure at Different
Temperatures 28
14 Percent PCBs Remaining After Ireatment at 704°C 28
15 Pyrolysia of Aroclot 1254 in Quartz Mini—Ampoules 33
16 Formation of PCDFs from the Pyrolysis of Chlorobenzenes 39
17 Formation of PCDDs from the Pyrolysis of Chlorobenzenes 39
18 Formation of PCDDs and PCD1 s from the Pyrolysis of
Chlorobenzenes 41
19 Amounts of PCDD& Found in Burning Experiments of Commercial
Chiorophenates 44
20 Amounts of PCDDs Found in Burning Experiments of Purified
Chiorophenates . 45
21 Levels of PCDDS and PCDFS from Burning of Pentachiorophenol
Contaminated Waste 47
22 PCB and PCDF Levels in Capacitors and in Environmental
Samples 51
23 Analysis of PCBs in Air Samples from School in Ohio 54
24 Summary of PCBo Wipe Sample Results from School in Ohio 54
25 Amounts of PCBs, PCDDB, PCDFS Found at Binghamton State Office
Building Prior to Clean—up 56
vi
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TABLES (Continued)
Number Page
26 Levels of PCDFS and PCDDs In Soot from Accidental Burning of
PCBs- ContainIng Electrical Equipment at Binghamton 57
27 Concentration of PCDFs in Soot Samples Taken frorn the
Binghamton State Office Building 59
28 Amounts of PCDFS in Samples from Accidental PCB Fire,
Stockholm, Sweden 62
29 Levels of PCDFO and PCDDS from Accidental Burning of PCBs—
Containing Electrical Equipment at Boston, Massachusetts 63
30 Levels of PCDFS for Samples from the Skovde Fire 65
31 PCBs Residue from a Tr rn8former Vault Fire, Collected 4/16/82
in Miami, Florida 65
32 Results of Analyses for PCDDs and PCDFs in Bulk Samples of
Residue from Miami Transformer Fire 67
33 Analyses of PCBs (Reported as Aroclor 1260) In Wipe Samples
from the Hill—Murray School 68
34 Area Concentrations of PCBs *Reported as Aroclor 1260)
and Chlorinated Benzenes 68
PCDFs Found at Surahamzaar, Sweden 71
36 PCDF Levels in PCBs Fires 72
37 Personnel Protective Equipment 82
vii
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FIGURES
umber Page
I Askarel Transformer — Gallons vs. Rating 18
2 Mineral Oil Transformer — Gallons vs. Rating 18
3 Decomposition of PCBs at 704°C 30
4 The Most Toxic PCDD and PCDF Isomers 34
S Pyrolysis of Aroclor 1254 35
6 Pyrolysis of Commercial PCEs (Aroclor 1254, 1260) 35
7 Reaction Routes in the Pyrolysis of Infividual PCBs 37
& Pyrolysis of Aroclor 1254 and PCDF Fcrtr.ation 38
9 Formation of PCDFS and PCDDS from Polychi rinated Benzenes 40
10 Proposed Reaction Mechanism for Dioxin Fcrr.ation in the
Production of 2,5—Dichiorophenol 40
11 PCDDS Formed Under Laboratory Pyrolysis of a Mixture of Common
Commercial Chiorophenates 42
viii
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ABBREViATIONS
AC alternating current
ACG IH American Conference of Governmental Industrial Hygienists
AFFF nqueous film formLng foam
ANPR advance nctice of proposed rulemaking
APCS a r pollution control system
C centigtade
COD chlorodib nzodioxin
CDF chlorodibenzofuran
cm 2 centimeter(s)
cm square centimeter(s)
d day(s)
DCD!J dichlorodibenzodioxin
09 New York State Department of £nviionmental Conservation
square decimetei(s)
DOll New York State Department of Health
United States Environmental Protection Agency
F Fahrenheit
F?LC Florida Power and Light Company
ft foot or feet
g gram(s)
gal gallon(s)
CC/FIRMS gas chrornatograph/high resolution mass spectrometer
CC/MS gas chromatograph/mass cpectrometer
RCDD hexachlorodibenzodioxin
hr hour(s)
HRCCIMS high resolution gas chromatograph/mass spectrometer
IIVAC heating, ventilation and sir conditioning
Hz hertz or cyc1 (s) per second
IAFF International Association of Fire Fighters
l.D. inside diameter
IERL-Ci Industrial Environmer tal Research Laboratory—Cincinnati
kg kilogrart(s)
kv ki1oiolt( )
kVA kilovolt — ampere(s)
L liter
lbs pounds
LC liquid cbromatograph
ix
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meter(s)
m 3 Square meter(s)
m cubic meter(s)
M molar
mcg inictogram(s)
mci microiiter(a)
mcm micrometer(c)
ml milliliter(s)
m.p. melting point
m.d. not detected or none detected
ND not detected or none detected
NEC National Electrical Code
ng nanogram(s)
NIOSH National Institute for Occupational Safety and Health
OCDD octachlorodibenzodioxin
OCS New York State Office of General Services
ORD Office of Research and Development
OSHA Occupational Safety and Health Adr inistration
PCB polychiorinated biphenyi
PCBP polychiorinated biphenylene
I CCY polychlorinated chrynene
PCDD polychlorinated dibenzodioxin
PCDE polychiorinated diphenylether
PCDF polychiorinated dibenzofuran
PCN polychiorinaced naphthalene
PCP pentachiorophenol
PCPY polychiorinated pyrene
pg picogram(s)
PG&E Pacific Gas and Electric Company
PlC product of incomplete combustion
ppb parts per billion
ppm parts per million
ppt parts per trillion
PVC polyvinyl chloride
RFP request for proposal
SCHA self—contained breathing apparatus
sec second(s)
TCDD tetrachlorod benzodioxin
TCDF tetrschlorodibenzofuran
TSCA Toxic Substances Control Act
TWA time—weighted average
ug microgram(s)
weight
x
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SECTION 1
INTRODUCTION
Polych lorimated biphenyls (PCBs) are a class of compounds that have
various combinations of chlorine atoms attached to the birhenyl molecule.
Since commercial introduction in the late l92Os, over 1.25 btllion pounds of
PCBs have been manufactured and used in the U.S., primsrily in mixtures with
chlorobeuzenes known as askarels which are used au dielectric fluids for
electrical transformer& and capacitors, heat transfer systems, and hydraulic
systems. A large amount of FCBs sold in the USA is still in use as
dielectric fluid in capacitors and transformers (1).
Federal regulation of PCBs took several years to develop. Beginning in
the late 19611s, ecientiffc evidence began to accumulate on PCBs’ various
toxic effects and con entration in many biological species. Because oi these
concerns, in 1971, t he I4onsanto Industrial Chemical Co., the sole United
States producer, terminated sales of PCBs for all but closed electrical
systems uses (I). In 1976, Congress enacted the Toxic Substences Control Act
(TSCA) and included special provisions for the regulstion of PCBs. Accord-
ingly, in 1979, EPA banned all production and sales of PCBs. Follow—on regu-
lations enacted under the Toxic Substances Control Act now govern the
disposal of PCBs and PCBs—containing equipment (2).
Recently, there have been additional concerns brought on by the finding
of other toxic contaminants in PCBs and askarel fluids including polychl r—
mated dibensofurans (PCDFs), chlorinated benzenes and other chicrinated
substances. PCDFa and the other chlorinated substances are formed as contam-
inants in the manufacturing and formulation processes for FCBs and askarel
fluids. Polychiorinaced dibensodioxins (PCDDs) can be formed from the
reaction of chlorinated benzenes when askarel fluids are heated to a very
high temperature (3). The finding of PCDFS and the potential generation of
PCDDS under thermal conditions has major implications for the recently—adopted
EP& strategy in nitigating and controlling chlorinated dioxins in the nation’s
environment. Findings of such toxic chemicals will also further complicate
1
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emergency response and clean—up procedures for fires involving PCBs—
containing transforners and cap citore.
Several such fires have been reported. The most famous is the fire
involving a transformer that occurred in an 18—story office building in
Bi.ghanton, New York on Februaty 5, 1981. The transformer contained 652
Aroclor 1254 (a Mo.isanto PCBs product trade name) and 35% chlorinated ben—
zenes together with some other additives. Analyses of soot sampies taken
from the building showed high levels of PCBs, and the presence of 2,3,7,8—
tetrachlorodibenzo(p)dioxin (213,7 ,8—TCDD) and 2,3 ,7,8—tetrachloro—
dibeazofuran (2,3,7 ,8—TCDF) (4). The estimated clean—up cost for the
building is $24 million and almost $1 billion in liability claims have been
filed against the state in law suits filed primarily by the fire fighters
(5).
Similar cases have been reported in other par:s of the country as well as
in foreign countries such as Sweden and Finland. Li.°se accidents have led to
the need for assessing potential enviror mental loading of PCDDs and PCDFS and
human exposure risk from this new a urce category. Additionally, because
such fire accidents have occurred randomly in office buildings, schools,
etc., and not only in industrial plants, there is a high public awareness of
this issue. Thus, there is a genuine public concern over potential exposure
to highly toxic substances (i.e., dioxins and furana) from such fire
incidents.
Fire fighters, electric utility companies and insurance companies are
particularly concerned that fire emergency procedures and fire site clean—up
protocols may not be adequate in light of these new findings. Present fire
fighting methods were developed when the hazards of exposure to highly toxic
chemicals were not as veil understood. In an already dangerous profession,
f ire fighting personnel must now recognize the danger of exposure to hazard-
ous cbemcals with potential long term health inpli’ ations.
2
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The EPA, under the Toxic Substances Control Act, has been mandated to
develop appropriate regulations for the control of exposure to PCBs. In
light of this responsibility the EPA Office of Tovic Substances recently
issued an Advance Notice of Proposed Rulemaking (AI PR) intended to further
define the problem (6). The ANPR is intended to cover the following areas:
• Risks associated with PCB transformer and capacitor fires
• Number and distribution of PCB transformers and capacitors
• Location of equipment
• Frequency of fires
• Furan/dioxin formation
• Regulatory options.
The EPA Office of Research and Development (ORD) has also been mandated
und er EPAs recently—rele red ioxin Strategy document to evaluate fire acci-
dents involving PCB transformers and capacitors as potential new sources of
PCDDS and PCDFs in the environment (7). To develop the information to
support the two mands ed programs, the EPA/ORD undertook this study to assess
the problems associated with fires involving askarels, to catalog the
contamination experiences and to review potential decontamination methods as
well as disposal of contaminated material. The study recognized t ;e
limitation of available data. It has drawn upon the body of scientific
knowledge available on tbert odynamic equilibria of chlorinated substances and
the more common experiences gained from decont. 3 jnination and detoxification of
PCBs in non—fire accident situations. This study assesses the chemistry of
PCBa under thermal conditions and evaluates the generation of PCDDs and
PCDF . It reviews technologies for deBtruction and disposal of PCBs and xtb
toxic contaminants. Methodologies to assess potential hazards and reduc€
exposure are also discussed.
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REFERENCES
1. EPA. PCBs in the United States: Industrial Use .ind Environmental
Distribution Task 1. Final Report. EPA 560/6—76—005. Prepared by
Versar, Inc. February 25, 1976.
2. Federal Register. Rules and Regulations, 40 CFR Part 761,
Polychiorinated Biphenyls (PCBs) Manufacturing, Processing, Distribution
in Commerce, and Use Prohibitions. Vol. 44. No. 106, May 31, 1979.
3. H. Buser and C. Rappe. Formation and Degradation of Polychiorinated
Dibenzo—p —Djoxjns (PCDDS) a d Dibenzofurans (PCDFs) by Thermal
Processes. Paper presented a 178th National American Chemical Society
Meeting. Washington, D.C., S . iiber 9—14, 1979.
4. R.M. Smith, D.R. Bilker, P.W. OKeefe, S. Kumar and R.M. Aldous.
Determination of Polychlorjcated Dibenzofurans in Soot Samples from a
Contaminated Office Bui.ldiag, New York State Department of Health, March
1982.
5. R. Lyons. Amid Debate and Doubt, Tower Cleanup Goes On. The New York
Times. May 4, 1982.
6. Federal Register. Advance Notice of Proposed Rulemaking (ANPR), 40 CFR
Part 761, Polychlot inated Bipnenyls; Manufacture, Processing, Distri-
bution in Commerce and Use Prohibitions; Use in Electrical Transformers;
Advanced Notice of Proposed Rulemaking. Vol. 49 No. 58, March 23, 1984.
7. EPA. Dioxin Strategy. November 28, 1983.
4
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SECTION 2
CONCLUSIONS AND RECOI*IENDATIONS
Approximately 130,000 transformers and 2.8 million Capacitors Currently
in service contain PCB or a mixture of PCB and tri h1orobenzenes which ia
also called askarels. There have been a number of fire accidents involving
PCB& transformers and capacitors throughout the world. The two most infamous
involve the two office building complexes in Binghamton, New York and San
Francisco, California where widespread contamination occurred.
Analysis of soot samples from PCBs transformer aud capacitor fire
incidents indicate that a number of highly t..xic chlorinated products are
formed including polychiorinated dibeuzofurans (PCDFa) nd polychiorinated
dibenzodioxins (PCDD ). Laboratory combustion studies on PCBs have
identified a variety of other chlorinated products such as polychiorinated
naphthalenes, pyrenes, biphenylenes and chrysenes.
The types of chlorinated products that are formed depend on the
compocition of the fluid in the transformer or capacitor. In the Binghamton
incident, both PCDDS and PCDFS were identified whereas in San Francisco, only
PCDFS were found. The Binghamton transformer contained a mixture o PCBs
(Aroclor 1254) and trichlorobenzenes and the San Francisco transformer
contained only PC s. The finding of PCDDS in the Binghamton incident is
attributed to chemical reactions involvng trichlorobenzenes present in the
transformer fluid.
The presence of highly toxic substances such as PCDFs and PCDDs in PCBs
fire incidents has elevated concerns for the safety of emergency response
personnel and complicated clean—up and remedial measures. There is an
obvious need for the development of a generally accepted protocol for
fighting and extinguishing fires involving PCBs electrical equipment.
Electrical utilities can assist local fire fighting de ’mrtments with
better information on the problems associated with PC 8 fires. Fire
departments should know the number and location of PC transformers and
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capacitors within their jt.risdictions. Righly visible labels or si&ns should
be placed on all PCBs—containing electrical equipment and in other nearby
areas to indicate the presence or PCBs—containing electrical equipment.
Electrical utilities, owners and/or operators of the equipment should
retrofit the equipment to assure that electrical power could be rapidly
disconnected in the event tne transformer enters a failure mode. The primary
load breaker air switch on the high—voltage side of the transformer should be
located outside of the equipment vault to alloy rapid disconnect without
t Lering the vault contait’ing high concentrations of PCBs and associated
pyrolys s products.
Re ponse operations during the initial phase of a fire incident involving
PCfls—contajning transformers and capacitors requires familiarity with
response organization and management, the uses and limits of equipment and
apparatus, site entry, control, and decortamination procedures. In order to
contrcl and handle PCB fire situations, adequate protective clothing,
equipment and fire extinguishing chemicals are necessary to ensure personnel
safety.
PCBs transformer/capacitor fires are unique because of the toxic residues
generated and the resultant long—lasting contamination. Every effort should
be made to put out the fire as quickly as possible in oLder to minimize the
production of highly toxic pyrolysis producta. After the fire, access to
areas possibly contaminaLed by the fire niust be limited until the exient of
contamination can be determined. Wipe and bulk soot sampling are used to
identify PCBs contaminated areas, and to delineate the extent of both
vertical and horizontal contamination.
There are no Federal guidelines to define acceptable clean—up for PCBs
releases due to fires. NIOSH has found background levels in urban areas up
to 0.5 mcg PCBsIIOO cm 2 of surface area. In the absence of certain PCDF and
PCDD isomers, the mitigation effort could be directed at clean—up of the PCBs
contamination to 0.5 wcg per 100 cm 2 of ‘ffected area. In terms of airborne
exposure the NTDSH recommended guideline or the workplace is 1.0 mcg PCBs
per in 3 of air.
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The presence of PCDF and PCDD isomers will affect surface and ai: clean-
up guidelines accor iing to the biological and toxicological activity of the
specific iLomers. Reoccupancy criteria have been established by the State of
New York and the State of California following the Binghamton and the San
Francisco fires. The State of New York proposed an average daily intake of 2
pg/kg/d for 2,3,7,8—TCDD, resulting in an air/inhalation exposure limit of 10
pg/rn 3 for 2,3,7,8—TCDD. A Limit of 39 pg/rn 3 for 2 ,3,7,8—TCDF was proposed.
The State of California lroposed air exl’oaure guidelines of 10 pg/rn 3 for
2 ,3,7,8—PCDDs/pcDFs, 1.0 mcg/m 3 for PCBs. The criteria for surface exposure
are 3 ng/m 2 for 2,3,7,8—PCDDs/pcnFs and 100 mcg/m 2 for PCB . In addition to
these values for decontapinatecj areas outside of the transforner vault, the
State of California proposed reentry guid.!lines or the area inside the
vault. These consist of an air exposure of SO pg/ma for 2 ,3,7,8—PCDDS/PCDFB
and 1.0 Incg/m 3 for PCBs and a surface exposure of 24 ng/m 2 for 2,3,7,8—
FCDDs/PCDF and 1.0 mg/rn 2 for FCBs. Sweden and Finland have also established
reoccupancy criteria after the occurrence of PCBs fire incidents.
7
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SECTION 3
PCB TRANSFORMERS AND CAPACITORS
TYPES OF TRANSFORMERS
Transfor’ ers are used to raise or lover electric voltage and general3y
consist of a core an’J a coil immersed in a dielectric fluid. A list of tie
13 companies which manufactured oskarel transformers in 1975 is given in
Table 1 (1, 2). Lt electric generating utility facilities, large trans-
formers are used to raise voltage. As the e1ectric i1 power is sent throi.gh
the transmission and distribuiion system(s) the voltage may be raised or
lowered a number of times to meet the technical configuration of Lhe system
and the voltage requirenents of the customer.
A large transformer may be several times larger than an automobile and
‘ ntain hundrec s co thousands of gallons of oil and dielectric fluid. Such
transfe—mers are typically located in generating facilities or substations.
Most transformers re considerably 8maller and are often mounted on utility
poles located throughout the distribution systems. These overhead trans-
formers are used to lower voltage to a level usable by private re3idences or
small businesses, and typically contain an average of 20 gallons of fijid.
Between the large transformers used to transmit power and th small
overhead transformers used to bring power into homes, there are a nt.mber of
transformers of assorted sizes and voltage ratings designed to rLeet the
requirements of various commercial, industrial, and resale customers.. Where
these transformers are located indoors, local fire codes often specify the
use of PCBs as the insulating fluid, since PC is are less combustible than
mineral oil.
According to the National Electrical Manufacturers Association, all
transformers can be classified into five categories:
8
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Table 1. U.S. TRANSFORMER MANUFACTURING INDUSTRY USING PCBs IN 1975 (1 2).
Company Name
Locaticn of Plant
PCBs Trade Name
Westinghouse Electric Corp.
South Boston, VA
Sharon, PA
inerteen
General Electric Company
Rome, CA
Pittsfield, MA
Pyranol
Research—Cottre l l
Pinderne, NJ
Niagara Transformer Corp.
Buffalo, NY
EEC—lB
Standard Traijsformer Co.
War en , OB
Medford, OR
Helena Corp.
Helena, AL
Hevi—Duty Electric
Goldaboro, NC
uhlman Electric Co.
Crystal Springs,
MS
Saf—T—Kuhl
Electro Engineering Works
San Leandro, CA
rnvirotech Buell
Lebanon 1 PA
R.E. Uptegt. ff Mfg. Co.
Scottsdale, PA
H.K. Porter
Belmont, CA
Lynchburg, VA
Van TrLn Electric Co.
Vandalia, IL
Waco, TX
9
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o Large Power Transformers
Small Power Transformers
• Distribution Transformers
• Network Transformers
• Instrument and Special Purpose Transformers.
Large Power Transformers
Large Power Transformers are liquid—immersed with a capacity range
greater than 10,001 kVA. There are two subcategories:
O Conventional Transformers and Autotransformers
• Primary and Secondary Unit Subst tion Transformers.
Small Power Transformers
Small c,ver Transformers are basically the sane as the Large Power Tran8—
formers except their ratings range from 501 to 10,000 kVA. There are three
subcate orjes:
• Conventional Trsnsformers £nd Autotransformers
• Secondary Unit Substation Transformers and Single Circuit Substations
o Primary Unit Substation Transformers.
Distribution Transformers
Distribution Transformers are liquid immersed ranging froci 500 kVA and
smaller. Based on their installation, there are three types:
10
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a) Overhead
They are usually located on the top of office buileinge, schools,
hotels and highly populated structures where fire 8afety is an
important consideration.
b) Pad—mounted
They are installed on a concrete pad outside the area they serve and
are usually found in less populated locations.
c) Sub—surface
They are ir.staflri! underground such as in subways and the basements
of buildings.
Network Transfo:msrs
Network Trenformers are a special arrangement of transformers to distci—
bute the electrical load to form a network system. There cie t jo types:
a) Grid type secondary network system
These systems are most commonly employed in a high density load
location such as in the metropolitan areas. This grid system pre-
vents cerv 4 ce interruption to any load on the system because if the
power supply to any load is lost, that load will be serviced by the
other power sources in the system.
b) Spot network system
Spot network uses two or more transformers. Fuch networks provide
service reliability and operating fle ib’)ity in downtown, high—
density areas anu are beir.g applied frequenily in outlying areas for
large commercial services where the supply feeders can be made
available.
Instrument and p çial Purpose Transformers
There ate special purpose trRnsfortnerc to serve specific functions and
they include:
• Reactors
• Furnace Transformers
11
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• Rectifier Transformers
o Locomotive Transformers
o Grounding Tranafo’ mers
• Ground Fault iTeutraljzers
• Mobile Iransformers
o Mobile Unit Substations
• L- egra1 Single Circuit Unit Substation.
TYPES OF CAPAC TORS
Through the use of trdnsformers, power System engineers raise or lower
voltages to meet consumers ’ requirements. However, much more precise c. ntrol
of electric powe: is required. Capacitors are commonly used to improve
distribution voltage Levels by improving the system power factor. This 1-as
the net effet.t of zcduciug load on certain power aystem components, such s
transfermers, cables, and generators.
CapacLtors are located throughout a utility system network, both in
substations and mounted on poles in the distribution system. Fifty—six
percent of utility capacitors are located in substations or generating
facilities and the remainder are located in distribution systems. Their
precise number and location in a system is purely a function of how the
system is designed to meet the requirements of i s customers.
The physical size of capacitors does not vary as much as that of trans-
formers. Most are a?proximately two feet by one foot by aic and
contain approximately 2—3 gallons of fluid.
Virtually all capacitors manufactured prior to 1978 were filled with
PCBs. The lcentration of PCBs in a PCB capacitor is known to approximate
100%. Those manufactured sir.ce 1978 contain a variety of flu d , excluding
mineral oil. Table is a list of 17 companies manufacturing k’(.E capacitors
in 1975 (1, 2).
12
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Table 2. U.S. CAPACITOR MANUFACTW it’ G INDUSTRY USING PCBs IN 1975 (1, 2).
General Electric Company
Westinghouse Electric Corp.
Aerovox
Universal Manufacturing Corp.
Cornell Dubilier
P.R. Mallory & Co., Inc.
Sangamo Electric Co.
Sprague Electric Co.
Electric Utility Co.
Capacitor Specialists, Inc.
JARD Corp.
York Electronics
McGraw—Edison
RI Interonic8
Axel Electronic, Iv.c.
Tobe Deutschmann Labs.
Cine—Chrome Lab, Inc.
Hudson Falls, NY
Ft. Edward, NY
Bloomington, IN
Neu Bedford, MA
Bridgeport, CT
Totova, NJ
New Bedrord, MA
Waynesboro, TN
Pickens, SC
North Adams, MA
LaSalle, IL
Eocondido, CA
Bennington, VT
Brooklyn, NY
Greenwood, SC
Bayshore, NY
Jamaica, FY
Canton, MA
Palo Alto, CA
Pyranol
Inerteen
Hyvol
Dykano 1
Aroclor B
Diaclor
Chiorinol
Eucarel
Clorphen
Company Name
(In Order of PCBs Usage) Location of the Plant PCB Trade Name
El emex
13
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The number of PCB capacitors currently in service is esfimated to be
approximately 2.8 million units (3), and approximately 400,000 non—PCB units
(i.e., large capacitors generally :ontaining less than 50 ppm of PCBs) have
been ecquired since 1978.
Two important types of capacitors are phabe correctors on power lines and
ballast capacitora for fluorescent lighting. The principal types of PCBs
impregnated capacitors are (1):
o sigh Voltage Power Cepacitors
o Low Voltage Power Capacitors
o Lighting Cdpacitors
o Air Conditioning Capacitors
o Industrial Electronics Capacifors.
High Voltage Power
Generally AC capacitors are used to improve the power factor of a
circuit. The power factor is the ratio of true power in watts to the
apparent ?ouer as obtained by multiplying the current flowing to the load by
the circuit voltage. The power factor correction can be made dire t1y at the
load or at utility substations. In the latter case, high voltage units will
be designed for 4,800 to 13,800 volt service.
Low Voltage Power
Capacitors installed in industrial plants at the demand site (typically
large motors and welders) are designed for 230— to 575—volt service.
Capacitors installed near the loads are the most efficient way to supply the
electrical current which is converted to magnetizing current, to produce the
fJux necessary for the oçeration of inductive devices. Rates for the sale of
power are generally structured to encoerage power factor orre.tion at the
site, eliminating tFe need for the electric utility to transmit both power—
14
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producing current and .sagnetizing current all the way from the generator o
ti&e plant site.
The same considerations apply to induction heating applications, the
principal difference being that capacitors for this application are designed
for op’ raticn at 960 to 9600 Ha. These low voltage power factor capacitors
operate wobt efficiently at a voltage of 400 volts/mu (1).
Ligj t n
Capacitors improve the efficiency of lighting systems. A fluore.cent or
mercury vapor Lamp can be ballasted without the use of a capacitor, but the
p wer factor of the lighting systerl would then be in the range of 50 to 60%.
For commercial or industrial lighting with either fluorescent or high inten-
sity discharge lanpa, the use of a capacitor in the circuit provides part of
the lamp ballast ing and brings system power factor into the range of 90 to
95%.
Air Conditionin9 .
As in the lighting applications, the capacitor improves syrtem effi-
ciency. Air conditioners could be wade to operate without capscitorF, a do
boise refrigerators, but because of the higher capacity required for sir
conditioners, the resultant line current would virtually e minate home
“p Lug—ins” and would still further overburden a seriously threatened national
power network. Almost all air conditioner pump motors are of the split—
winding type on which the capacitor provides phase differential for the so—
called start winding, thus delivering good starting torque. The proper size
capacitor permits a high (90%) power factor after start—up.
Industrial Electronics
This market category is a catch—all overing many varLed applications)
two important ones being motor run and power Bupply applications. Motor run
ap licaLions are for pumps, fans, and farm feed equipment, and do not differ
-------
significantly from air conditioning applications. The power upp1y market
uses capa itor8 principally to provide a high power factor, but through
careful design a capacitor an also provide wave shaping where desired.
TYPES OF TRANSF DRNER FLUID
There are two commonly used transfoLiner fluids:
• Mixtures of PCBs and Trichlorobenzene
• Mineral Oil.
PCBsjTrjchlc’robenzene Transformers
The mixtures of PCBs and trichiorobeuzenes are commonly known by the
generic term askarels . Aekarels arc usually mixtures of —70 percent PCBs and
30 to 40 percent tri hlorobenzenes. Further information about the chemica)
composition of ask rels can be found in Sections 4 and 6.
The volume oi _ ‘3re1 us d in various transformers ranges from 40 to l5CO
gallons (440 to 17,000 ibs), with an average of about 230 gallons (2500
Ibs). It is estimated that the total number of askarel—filled transformers
still in service in the United States is 130,000. The typical lifetime of a
transformer is often greater than 30 years, and units that do fail are
usually rebuilt and returned to service. The production of askarel—filled
units was stopped in 1979 after thc ban of PCBs production by the EPA. Table
3 provides the average number of gallons per transformer for each size range.
A graph of the average number of gallons versus transformer size using
the data of Table 3 is in Figure 1. This graph can be used to estimate the
volume of askarel fl:jid in the transformer for a given kVA rating.
16
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Table 3. VOLUME OF FLUID CONTAINED IN ASKAREL ThANSFORMERS (3).
Transformer Size
(kVh Rating)
Average Number
of Gallon8 per
Transformer
Total
Number of
Gallons of Fluid
lO0
101—500
501—1,000
1,001—5,000
,oOi— 10 o,o 00
43
183
330
490
1,700
570,000
2,113,000
3,240,000
2,336,000
266,000
TOTAL
8,525,000
Mineral Oil Transformers
PCBs are also present in mineral oil transformers at variouo concentra-
tions but usually at less than 10 ppm. A substantial portion of the PCBs is
present at concentrations of 100 to 500 ppm and mainly located in small
transformers. Tables 4 and 5 show the distribution of PCBs concentrations
for mineral oil transformers.
As can be seen, 10 percent of the transformers are contaminated at levels
of 50 ppm or greater. As illustrated i Table 6, contamination levels do not
appear to be significantly related to the size of the equipment. The age of
the equipmert was also analyzed in relation to contamination levels, and no
significant correlation was found.
Table 7 indicates the percentage of transformers containing PCBs at a
concentration of less than 50 ppm. Table 8 provides data regarding the total
volume of mineral oil contained in mineral oil transformers owned by the
utility industry, as well as the average zumber of gallons per transformer
reported for each size range.
Thirty—nine percent of this oil is contained in transformers located in
substations or generating facilities. A graph of the average number of
gallons versus transformer size was plotted in Figure 2. The data are taken
from Table 8. This graph can be used to estimate the number of gallons of
fluid in the mineral oil transfotmer for a given kVA rating. -
17
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17
Tranaformer Size (kVA Rating)
Figure 1. Askarel Transformer — Gallons vs Rating
Figure 2. ifineral I1 Tr3 ,, oi-, r — a1lons vs Rating
. 1oo
i I
101 .50030—1000 1001—5000 sooi—ioo.
Transformer Sir. (kVA Rating)
I
.4
S
I
100 101—300 501—1000 1001—5000 5001—100,000
5000
3000
2000
0
.4
1000
18
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Table 4. DISTRIBUTION OF PCBs CONCENTRATIONS FOR NINEFAL OIL TRANSFORMERS (3).
PCBs Concentration Percent of Transformers
(ppm)
<1 46.1Z
1—9.9 27.8
10—15.9 6.8
20—29.9 4.3
30—39.9 2.1
40—49.9 1.1
50—99.9 4.8
100—499.9 5.9
50O Li
ioo.oz
Table 5. NUMBER OF MINERAL OIL TRANSFORJjER IN THE UTILITY INDUSTRY BY PCBs CONCENTRATION LEVEL (3).
Transformer Total Mineral Number of Transformers by
Size (KVA Oil PCBs Concentration in ppm
rating) Transformers
________________ C 1 1—9.9 10—49.9 50—99.9 100—499.9 500
. 100 19,046,654 8,770,232 3,395.599 2,688,266 915,134 1,086,746 190,637
101—500 928,556 429,493 161,407 170,684 43,598 96,473 26,901
501—1.000 96,327 46,410 17,262 18,017 3,093 6,791 754
1,001—5,000 80,645 37,933 18,243 14,867 3 ,29j 4,6 i 1,446
5,0O1—1O0,0 )3 53,488 22.466 18,240 8,344 1,818 2,460 160
) 100,000 5,883 3,360 1,700 753 47 23 0
TOTAL 20,209,353 9 .3O9,89 5,612,451 2,900,931 969,005 1,197,154 219,918
-------
Table 6. PCBs CONCENTRATIONS BY TRANSFORMER SIZE (3).
Trarsformer Percen
Size
(kVA Rating) <1 1—9.9
tage of Equipment Contaminated at
PCBs Concentration (ppm)
10—49.9 50—99.9 100—499.9 50O
<100 46.1% 28.3%
14.1% 4.82 5.7% 1.0%
101—500 46.2 17.4
18.4 4.7 10.4
501—1,000 49.2 18.3
19.1 5.4 7.2 0.8
1,001—5,000 47.1 22.7
18.5 4.1 5.8 1.8
5,001—100,000 42.0 34.1
15.6 3.4 4.6 0.3
>100,000 57.1 28.9
12.8 0.8 0.4 0.0
Tab1 7. PERCENT OF TRANSFORMERS
CONTAINING LESS THAN 50 PPM PCBs (3).
Transformer Size
2 of Transformers
(kVA rating)
with <50 ppm
88.4%
<100
101—500
82.1
501—1,000
86.6
1,001—5,000
88.4
5,001—100,000
91.7
>100,000
98.8
Table 8. VOLUME OF FLUID CONTAINED
IN MINERAL OIL TRANSFORMERS IN ThE UTILITY
INDUSTRY (3).
Transformer Size
Average Number Total
(kVA Rating)
of Gallons per Number of C 11ons
Transformer of Mineral Oil
100
20 384,174,000
101—500
120 108,083,000
501—1,00e
400 37,519,000
1,001—5,000
1,100 88,326,000
5,001—100,000
4,700 251,990,000
>100,000
15,000 88,273,000
958,365 ,000
20
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The concentrations of PCBs in askarels vary from transformer to trans-
former. EPA ha8 classified PCB transformers as follows:
1) > 500 ppm: includes all askarel—filled transformers and about 1.2%
of all mineral oil transformers.
2) .‘ 50 ppm but < 500 ppm: includes 8.8% of all mineral oil trans—
formcrs.
3) < 50 ppm: includes 90% of all minqral oil transformers.
INSTALLATION AND POSSIBLE LOCATION OF TRANSFORMERS
The National Electrical Code (NEC) requires that mineral oil transformers
located in or near buildings must be enclosed in “quits. Ask rel trans-
formers insta ied in similar locations must be enclosed it vaults only if
they are rated at more than 35,000 volts. The NEC further provides specific
construction requi: ments for vault valls, roof, floor, and doors. Vaults
are typically construc.ted of concrete four to six inches thick.
If the transformer is to be vaulted, special provision muSt be made to
ensure adequate heat release and cooling.
Possible locations of the transformer vary with many factors such as
population of the building and the distribution network of the electric load.
It is desirable to have the transformer away from crowded population to mini-
mize fire hazard. The building design and the preference of the design
engineer also weigh heavily in the location of the transformer. Mo&t trans-
formers can be found on the roof or in the pa ements of buildings, although
some can be found outside or adj& cent to the building on a pad or under-
ground. A number are also found moun’ed on poles outside the buildings.
21
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REFERENCES
1. EPA. PCBs in the United States: Industrial Use and Environmental
Distribu jon Task 1. Final Report. PA 560/6—76—005. Prepared by
Versar, Inc. February 25, 1976.
2. EPA, Office of Toxic Substances. Polychiorinated Biphenyls: An Alert
for Food and Feed. Revised June 1980.
3. Resources Planning Corporation. Comments and Studies on the Use of
Polycblorjnated Bipheny1 in Response to an Order of the United States
Court of Appeals for the District of Columbia Circuit, Volume III,
Report of the Study of PCEs in Equipment Owned by the Electric Utility
Industry. Submitted to the EPA Ftbruary 12, 1982.
22
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SECTION 4
ThE CHEMISTRY OF PCBs COMBUSTION
CBEMICAL CONSTITUENTS OF ASKARELS
Available information on the composition of askarels offers a rather
hazy picture of the chemical constituents. In the last 60 year& of commer-
cial use, the formulation of askarels has undergone various changec dud few
manufacturers have made or kept records of the type and quality of PCBs and
other chemical substances used in the formulating process. There is no
evidence to itdicate that in the early days, the PCBs and the dilus.’ts used
to formulate askarels were required to meet particular chemical . uality
specifications. Performance specifications in terms of heat transfer pro-
perties were probably the only major requirements associated with the
formulation process.
Askarel fluids are normally mixtures of 60% to 702 PCB& and 40% to 30%
trichlorobenzenes. Chlorinated benzenes were added as solvents or diluents
to improve the viscosity of PCBs for transformer fluids. Monsanto, the sole
producer in the U.S., sold PC’Ss under the trade names of Aroclor 1242 (422
chlorine content), Aroclor 1254 (542 chlorine content) and Aroclor 1260 (60%
chlorine content). The Aroclor mixture is referred to by a four digit number
where the first two digits (i.e., 12) indicate the compound chlorobiphenyl
and the last two digits represent the weight percent chlorine present in the
mixture. Aroclor mixtures which General Electric has used in transformers
have contained anywhere from 13% to 60% trichlorobenzene , with the remainder
being pentachlorobiphenyl or hexach1orobi henyl or mixtures of either tn—,
penta—, or hexachlorobiphenyl and tetrachlorobenzene. The most common
formulations of askarels used in the U.S. were Inerteen and Pyranol. Inerteen
was used by Westinghouse and tiad at times contained 60% PCBs and 402
trichiorobeuzenes. Pyranol was used by General Electric and contained 70%
PCBs and 30% trichlorobenzenes. The exact compositions of both Inerteen and
Pyrariol were changed from tine to time. Various isomers of PCBs and
trichiorobenrenes along with other impurities were mixed in askarel fluids.
23
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PCBs in Askarels
Theoretically, there are 209 possible PCB i8omers, although not all are
found in manufactured products. Table 9 illustrates the possible isomers and
the chlorine content of the PCBs class of chemicals.
Chlorobenzenes in Askarels
Chlorobenzenes are added to PCBs to alter the viscosity of the trans-
former fluid. Table 10 presents the isomers and their chlorine content. The
trichloro— and tetrachlorobenzenes are the most common chlorobenzenes for
askarels. The trichlorobenzenes n askarels are usually of a commercial
grade and contain a mixture of isomers and other impurities. Tne trichloro—
benzenes used by General Electric in dielectric fluid have the compositic n
shown in Table 11.
Contaminants of Askarels
Small amounts of polychiorinated dibenzofurar.s (PCDFs) and polychiori—
nated naphthalenes (PCNs) have also been detected in PCBs mixtures. The
quantities vary from batch to batch, reflecting production process varia-
tions. Bowes and coworkers (1) analyzed several samples of PCBs mixtures and
found tetra—, penta—, and h xa—PCDFs at levels from 0.8 to 2 ppm, with levels
up to 10 ppm for some European samples. They also detected 3 to 4 ppm of
each hexa— and heptachloro—naphthalenes in Aroclor 1254. Miyata and
Kashiiaoto (2) found 2 to 9 ppm PCDFs in Aroclor 1242 and 1260. No PCDDS are
found in PCBs and askarel fluids. The finding of PCPDs at fire accident
sites is mostly attributed to chemical reactions involving contaminants in
askarel mixtures under thermal conditions.
PCBs COMBUSTION PROCESS CHARACTERISTICS
The major combustion products of PCBs are carbon dioxide, water and
hydrochloric acid. Small amounts of other products known as Products of
Incomplete Combue - (PICo) are alec found in the combusticn emissions.
24
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Table 9. ISOMERS OF PCBs AND THEIR CHLORINE CONTENT.
Molecular Possible no. Molecular Weight 7
Chiorobiphenvi formula of isomers wei ht chlorine
mono — C 12 8 9 C1 3 188.65 18.79
di — C 12 11 8 C1 2 12 223.10 31.78
tn — C 12 H 7 C1 3 24 257.55 41.30
tetra — C 12 H 6 C1 6 42 291.99 48.57
penta — C 1 ,H 5 C1 5 46 326.44 54.30
hexa — C 12 H 4 C1 6 42 360.88 58.94
hepta — C 12 11 3 C1 7 24 395.33 62.78
octa — C 12 H 2 C1 8 12 429.77 65.99
mona — C 12 liC1 9 3 464.22 68.73
deca — C 12 C1 10 1 498.66 71.10
Table 10. ISOMERS OF CHLOROBENZENES AND THEIR CHLORINE CONTENT.
Molecular Weight Number of
Ch’ robenzene Formula Weight ChiorAne Isomers
mono— C 6 H 5 C1 112.56 31.50 1
di— C 6 H 4 C1 2 147.00 48.24 3
tn— C 6 H 3 C 1 3 181.45 58.62 3
tetra— C 5 H Cl 4 215.89 65.69 3
penta— C 6 H 1 5 250.34 70.81 1
hexa— C 6 C1 6 284.78 74.70 1
Table 11. COMPOSITION OF GENEKAL ELECTRICS DIELECTRIC GRADE
TRICRLOROBENZENE.
l, 2 , 4 —Tnicb lorobenzene > 707
1 ,2,3—Trichloroben7efle and 1 , 3 ,5—Trichlorobenzene ‘ 207
Dichlorobenzene ca
Tetrach lorobenzene Ca .17
Pentachiorobeuzene trace
25
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These PICs include the PCDFS, PCDDs and other toxic contaminants discussed
earlier.
PICs are formed from the incomplete combusticn of the reacting nioleculeb
in the incineration process. For instance, if 1000 gallons per hour of PCBs
are being burned, 9x10 27 moJecules per hour of PCBs are undergoing react on.
u_the probability of forming a particular incomlete combustion product was
one in a trillion, then about 5 mcg per hour of that PlC would be produced.
Characteristics of the feed that influence the formation of PICs include:
(1) the carbon—to—hydrogen ratio,
(2) the chlorine content, and
(3) the nature of the contaminants.
In general, the higher the carbon—to—hydrogen ratio, the greater the
probability of forming PICs. Aromatic compounds have high carbon—to—hydrogen
ra .ios and have a high probability for forming PICs when burned. The
L.n aturated ring is a stable building block and undergoes additional inter-
molecular reactions in a combustion zone to form more complex condensed ring
Structures.
Chlorine content of the PCBb is another important factor in the formation
of PICa. Thermochemical calculations presented later ahoy that the higher
the chlorine content, the higher the concentrations of chlorinated PICs in
the combustion products. The carbon—to—hydrogen ratio and the chlorine
content for each PCB are listed in Table 12.
Process parameters a]so influence the formation of PICs in the combustion
of PCBs. Theso parameters include:
(1) reaction (fire) temperature;
(2) residence time of reactants (air and fuel) and products in the high
temperature zone;
26
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(3) turbulence or mixing efficiency of fuel and air;
(4) air/fuel ratio including the effects of operating cycles on combus-
tion air supply;
(5) fuel feed rate.
Table 12. CARBON/HYDROGEN RATIO AND CHLORINE CONTENT FOR PCBs.
Compound C/H ratio (wt/wt) Cl Content (v ii)
C 12 11 10 14.3
(biphenyl,
parent compound)
C 12 H 9 C 1 15.9 18.8
C 12 II 8 C1 2 17.9 31.8
C 12 1 1 7 C1 3 20.4 41.3
C 12 11 6 C1 4 23.8 48.6
C 12 P 5 C 1 5 28.6 54.3
C 12 H 4 C1 6 35.8 58.9
C 12 H 3 C1? 47.7 62.8
C 12 H 2 C1 8 71.5 66.0
C 12 HC1 9 143.0 68.7
C 12 C1 10 — 71.1
Laboratory studies have in icated that with adequate reaction time and
efficient mixing betwe’ n air and fuel, I’eBs are completely decomposed into
1120, C0 2 , and BC1 at a temperature range of 800—1000°C. Pyrolytic condi-
tions, however, allow the formation of PCDFs..\ Duvall and Rubey(3 , 4)
investigated combustion efficiency under varying temperature conditions.
They gradually vaporized PCBs samples into a flowing carrier gas,, which were
subsequently subjected to a controlled high temperature exposure in a quartz
tube reactor. Compounds exiting from the high temperature zone were
separated and analyzed by an in—line CC/MS. The results are shown in Tabieu
13 and 14
27
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Table 13. PERCENT OF PCBs REMAINING AFTER EXPOSURE AT DIFFERENT
TEMPERATURES (3)
Compounds Exposure Temperature (°C)*
550 650 67 700 725 )750
2 , 2 ’,S,5—Tetrach loro— 100 92 74 57 21 0.14
biphenyl
775
——
2 , 2 ’, 4 ,S,5—Penta— 100 98 80 53 9.3 0.05
chlorobiphenyi.
0.007
2 , 2 , 4 , 4 ’,5,5—Hexa— 100 100 73 26 — —
chiorobiphenyl
0.005
* 2 —second residence time, flowing air.
Table 14. PERCENT PCBs REMAINING AFTER TREATMENT AT 704° c (4).
Com ’ound Residence Time (Sec in flowing
0.27 0.95
air)
Biphenyl 8.1 0.7
3.84
0.07
78.5 14.0
biphenyl
2.6
2 , 2 , 4 1 5,5’—Pentachlo—o— 81.1 18.5
bipheLly 1
3.4
Decachiorobiphenyl
2 .
-------
The data in Table 13 show that at a selected residence time, the decom-
position efficiency of PCJ3s increases with exposure temperature. No deconi—
position of PG s takes place below 550°C and PCBs only th compose moderately
at temperatures between 650°—725°C. The data in Table 14 sLow that increased
residence tine results in increased decomposition of PCBs.
Using the data from Table 14, the decomposition rate of PCMs at 704°C is
charted as shown in Figure 3. Extrapolation of data such as that presented
in tbis section was utilized in developing the temperature and residence time
guidelines for land—based incineration. PCBs burn tests at ENSCO facilities
at El Dorado, Arkansas and at Rollins in Dcer Park, Texas have confirmed PCBs
destruction at the desired destruction efficiency when conducted within the
specific guidelines.
ThERMOCHEMICAL EQUILIBRIUM ANALYSIS OF PCDDs AND PCDFs FORMATION
The potential formation of polychiorinated dibentofuraña (PC’)Fs) and
dibenzo—p—dioxinc (PCDD8) during the combustion of PCBs can be preRcted by
thermochemical equilibrium calculations. However, accurate thermodynamic
data are not anilable for PCDFs and PCDDs, and their formation potential may
be examined only indirectly through review of combustion conditions aud waste
types that favor the fornation of intermediates, such as chlorobenzenes and
chiorophenols.
Shih, et al. , calculated equilibrium products for several chlorinated
wastes under pyrolytic cenditions (5). These were theoretical equilibrium
calculations and do not take reaction kinetics into account. The pyrolysis
cases assumed the absence or near absence of oxygen and, hence, of oxidizing
species. Such conditions may be encountered in a real combustion system in
several ways:
• Malfunctions of cyclic operation leading to excessively lean
air/fuel ratios,
• Poor mixing of fuel and air leading to localized oxygen deficient
conditions,
29
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90
P1
C
• — 8iphenyl
£ —
• —
O — Decachiorobiphenyl
6C
30
0
3 2 3
Residence Time (arc)
Figure 3. Decomposition of PCBs at 704°C
30
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a Thermal quenching of portions of the burning mixture at the walls
and carrying of the quenched mixture into the hot post—flame region
where pyrolysis can occur, and
a Pro—combustion reactions on the fuel side of the flame.
Shihs calculations cover a temperature range of 540°C (1000°F) to 1100°C
(2000°F) for seven hypothetical VaBte8 of varying carbon, hydrogen, and
chlorine content. The program used was ca?able of simultaneously considering
a maximum of 200 gaseous species, including alkenes, chlorinated benzenes,
and chlorinated phenols. Calculaticns for the first three cases where the
chlorine content is up to 10% led to the following bservazions (5):
• Under pyiolytic conditions, the major equilibrium products are:
ethylene, acetylene, methane, benzene, styrene, monochlorobenzene,
hydrogen, and hydrogen chlorLde.
• Concentrations of hydrocbloric acid and monochlorobenzene increase
with increasing chlorine content.
• Formation of ethylene, acetylene, and styrene is favored by
increasing reaction temperatures.
• Formation of methane and toluene is favored by decreasing
temperature.
• In the range studied, temperature appears to have a negligible
effect on the formation of benzene, monocblorobenzene, and hydio—
chioric acid.
Calculations for mixtures containing from 502 to 732 chlorine led to the
follow ing observations:
• Major equilibriun products from pyrolysis of the highly chlorinated
mixtures are: acetylene; benzene; styreue mono—, di—, tn—,
tetra—, penta—, and hexachlorobenzenes; hydrochloric acid in most
cases; and carbon monoxide when small amounts of oxygen are present.
• Depending on the ratio of carbon—to—hydrogen—to-chlorine, hydro-
chloric acid is not necessarily favored by pyrolysis of highly
chlorinated mixtures.
• Chlorobeuzei* s are more favored thermodynamically than chlorinated
Aliphatic and phenolic compounds.
31
-------
o The relative equilibrium concentrations of polychlorinated benzenes
generally increase with Lcreasing chlorine content of the mixture.
• Reaction temperature in the range examined appears to have a negli-
gible effect on the formation of hydrochloric acid and ch loro—
benzenes.
o The presence of small amounts of oxygen does not appear to have a
major imp ct on the equilibrium product distribution except for the
formation of carbon r onoxide.
The second set of calculations indicated that, under pyrolytic condi-
tions, formation of chlorobenzenes was thermodynamically feasible. Because
chlorobenzenes are known precursors of FCDDa, PCDFs, and PCSs, these calcu-
lations under pyrolysis conditions implied that:
• PCDFs and PCDDs may form during the thermal destrt.ction of PCBs
carried out under pyrolytic conditions.
o PCDFs and PCDOs may form during thernal PCBs destruction carried out
under oxidizing conditions n an incinerator if inadequate design
and/or operation allow the existence of pyrolytic zones in the
system.
The formation of PCDDs and PCDFs in PCBs have been attributed to the
range of chemical reactions that occur in:
1) pyrolysis of PCBs,
2) condensation of chlorobenzenes, and
3) condensation of cblorophenols.
Both PCBs and chlorobenzenea are major components of PCB transformer fluid,
whereat the cblorophenols are intermediates formed in tke pyrolysia of
chlorobenzenes. PCBs are also known to be contaminated with traces of PCDFs
and polychlorinated naphthalenes (PCNs). These compounds are formed in the
range of 550 to 700°C. The amounts of these compounds formed during the
combustion process vary with temperature and concentration.
32
-------
PCDDs A} ’D PCDFs FROM PYROLYSIS OF PCBs
The pyrolysis of commeicial PCE’s yields about 30 major PCOFs and more
than 30 minor ?CDFs. One of the main constitnents is 2 ,3 7 8 —TCDF, poten-
tially the most toxic of the PCDFS (7). The most toxic species are shown in
Figure 4.
In a study by, et al.(8) , Aroclor 1254 was pyrotyzed at temper—
atures of 550°—7,50°C in q rtz inini—anpoules . CC/MS analysis showed PCDF&
were formed in the process. The results are presented in Table 15.
At 550—650°C, the decomposition at the 100 ncg—level ranged from 12% to
90%, at the. lO mcg—level it ranged from 80% to 98%. Aroc lot 1254 was com-
pletely destroyed (> 99.9%) at temperatures of 700°C and above (see Figure
5).
Table 15. PYROLYSIS OF AROCLOR 1254 IN QUARTZ }1INI-A}1POULE (8).
Temp.
(°C)
Mt.
(mcg)
Decotap.
(Z) mono—
PCDFa
di— tn—
formedt
tetra—
(%)
peota— Total
- 55O 1OO ‘12. 0.25 0.65 0.90 0,75 0.20 2.75
10 hO 0.02 0.40 0.70 0.70 0.15 1.97
100 45 0.10 0.40 0.70 0.60 0.12 1.92
10 90 <0.01 0.10 0.25 0.35 0.05 <0.76
100 90 < .01 0.02 0.18 0.25 0.12 (0.58
10 98 0.01 0.12 0.25 0.12 <0.02 <0.52
100 >99.9 <0.01 <0.01 <0.01 <0.02 <0.02 <0.07
10 >99.9 <0.01 <0.01 (0.01 <0.02 <0.02 <0.0?
750 100 >99.9 <0.01 <0.01 <0.01 <0.02 <0.02 <0.07
* Combined values of all isomers c f aPCDF.
)ouo— to penta—CDFs were found at temperatures of 550—650°C at levels
ranging from < 0.01—0.90%. The maximum amounts found were at 550°C. Takir’g
into consideration the amount of PCSs recovered after pyrolysis, the total
yield of PCVFs ranged front 3—25% (see Figure 6).
33
-------
1. 2,3,7 , 8 —Tetrachlorodjbenzodjoxjn
2. 1 , 2 , 3 1 7 .8Pentachlorodjbenzodioxjn
3. 2, 3,7 ,8-Tetrachlorodjbenzofuran
4. 2,3,4 ,7,8—Pentachlorodjbenzofuran
5. 1 , 2 1 3,4,7,8—Hexach1orodjben od1o jn
6. l,2,3,7,8,9—Hexachlorodjbenzodjoxjn
7. 1 , 2 , 3 ,7,8—Pentachlorodjbenzofuran
8. l,2,3,6,7,8—Hexachlorodjbenzodjoxjn
CIy O o
cI
CI1 yX u
c,- o, ,-cI
C,
::çx:x c:
Figure 4. The Most Toxic PCDD and PCDF Isomers
34
-------
100
Em
S
-4
e4
. 4
S
0
• 50
100 pg
25
0 I I I
330 600 630 700 750
Temperature (‘C)
Figure 5. Pyrolysis of Aroclor 1254
PCB.
600°C
1 8 y • 1 — 6 (yield 3—25Z)
30 1io ere ‘ 60 1soi ers
Figure 6. Pyrolysis of Comniercial PCBs (Aroclor 1254, 1260)
35
-------
It was found that the cyclizatjon process which yields PCDFS from PCBs
was intermolecular and followed 6everal competing reaction pathways (see
Figure 7) (9, 10). In addition to PCDFS, polychlorjnated biphenylols as
possible precursors, were identified at levels of approximately one—fifth of
the amount F PCDFB present.
Plots of the Aroclor 1254 decomposition rates and PCDFS formatfon vs.
temperature ranges in the experiment are presented in Figure 5 and Figuze 8.
Because theae values varied with the quantity of Aroclor 1254 used in the
experiment, average values were also indicated.
There is no experimental evidence for PCDDS formation from pyroly8is of
PCBs and theoretical considerations indicate that this conversion does not
occuc.
FROM PYROLYSIS OF POLYCHLORINATED BENZENES
PCDDs and PCDFS are also produced from the pyrolysis of polychiorinated
benzenes but the yields ar lover than that from the pyrolysis of PCBs. In
Buser’s experiments using scaleJ quartz mini—ampoules (8), tetra— to octa—
CDF and also tetra— o octa—CDD were identified in the pyrolysis of tn—,
tetra— and pentachlorobenzenes. In addition to PCDFs and PCDDS, chioro—
phenols and a series of other chlorinated compounds were also formed.
Significant quantities of PCDFs ama PCDDS were found in most of the
pyrolyzed samples (see Tables 16 and 17). The formation of these tricyclic
aromatic compounds is bimolecular; the likelihood of this f ’rmation is highly
dependent on the concentration of chlorob€nzenes ir the reaction system (see
Figure 9) (11). Figure 10 shows a possible reaction mechanism for dioxin
formation froi a trichiorobeuzene (12).
A Been in Table 16, significant quantities of P DFs were formed from the
tn— and tetrachlorobenzenes and from the combined chlcrobennenes sample.
Tetra—, penta— and hexa—CDF were formed from trichiorobeazenes, and hexa—,
hepta— and octa—CDF were formed from tetrachlorobenzeres. The combined
36
-------
Reaction Route 1: — C l 2
(loss of ortho — Cl 2 )
Cl Cl Cl
Reaction Route 2:
—HCI
(loss of HC1 involving a CI CIY
2,3— hlorine shift)
— HCI
Reacr.ion Route 3:
(loss of ortho — RC1)
Reaction Route 4: H 2
(loss of ortho — 112)
H Cl c i
Figure 7. Reaction Rout. s in the Pyrolysis of Individual PCBs (9)
37
-------
Figure 8. Pyrolysis of Aroclor 1254 and PCDF Formation
g
8
100 ug
Temperature (C)
38
-------
Tab.e 16. FORMATION OF PCDFs FROM TRE PYROLYSIS OF CHLOROBENZENES (11).
Compound(s)
PCDFS formed (ag/sample)
tet &i—
penta—
hexa—
1 epta—
octa—
Trjch lorobenzenesa
Tetrachlorobenzenes
b
400
“
< 2
1100
5
550
160
50
450
< 5
200
PentacblorobenzeneC
Combined chlorobenzenesd
< 2
80
< 5
600
< 5
1100
5
600
30
60
a: 200 vc?g total witi equal amounts of 1,2,3—, 1,2,4— and 1,3,5—
trichlorobenzene
b: 200 mcg total with equal amounts of l,2,., ’—. 1,2,3,5— and 1,2,4,5—
tetrach lorobenzene
c: 200 mcg pentachlorobenzene
d: 500 mcg total with equal amounts of all tn—, tetr6— and
pentach1orobenz. nes (7 compounds).
c) 77)
/
Table 17. FORMATION OF PCiDs FROM THE PYROLYSIS OF CHLOROBENZENES (11).
Compound(s)
PCDDS formed
(ag/sample)
tetra—
penta—
hexa—
hepta—
octa—
Trichlorobenzenes 8
30
20
< 5
< 5
< 5
Tetrachlorobenzenesb
( 2
5
140
160
30
Pentacb lorobenzeaeC
< 2
< 5
< 5
< 5
5
Combined chiorobeozenead
50
220
220
70
5
a,b,c,d: for explarations see Table X6.
7 Q ) K / -
2- x O ’
io x/
— -
39
-------
2L ±!o0 flJ
CIJI CI V
CI ,
Figure 9. Formation of PCDFS and PCDDs from Polychiorinated Benzenes (10)
I, 2 ,4—Trichlorobenzene
I
2, 7—DcDD
Figure 10. Proposed Reaction Mechanism for Dioxin Formation in thr’
l’roduction of 2 ,S—Dichlorophenol (11)
2
Cirn
• r 2m
CI
CI
2, 5 Dic 1orobenzene
“p
C,
o
Is—
CI
CI
I
2,8—DCDD
40
-------
sample formed PCDFS ranging from the tetra— to the octachioro compounds. In
general, the PCDFs formed had chlorine numbers of 2m—2, 2m—l and 2m, where n
represents the chlorine number of the chlorobeurene et pLoyed. With the
trichlorobenzenes, some higher chlorinated dibenrofurans (hepta—CDF) were
also observed; presumably, they are formed from higher thlorinated benzenes
produced during pyrolysia.
The optitsal temperature for the co’iversion to PCDDa and PCDFS seems to be
5O00_6OO0C >j At temperatures ex eedi fg 600° 70 j the degradation of PCDDS
and FCDFs takes place at a faster rate tEai the rate of formation. In addi-
tion to the temperature, the retention time is an important parameter.
The experimental results are summarized in Table 18. PCDDs and PCDFS
ii omers were present, but not as main components.
PCDDS AND PCDFs R0M PYROLYSIS OF CHLO OPBENOLS
Most of the commercial chiorophenola are contaminated with traces of
PCDDa and PCDFs. Chiorophenols produced in chlorobenzenea pyrolysis form
both PCDDS and PCDFs. Examples of PCDDS formation can be seen in Figure 11.
Table 18. FORMAT1IOf OF PCDDS AND PCDFS FROM ThE PYROLYSIS OF
CHLOROBENZENES (9).
1,2,3—, 1,2,4— and
1,3,5—trichloroben ene
PCDDS
PCDFS
0.025%
1Z
1,2,3,4—, 1,2,3,5—
and l,2,4,5—tetrachlorobenzene
0.15%
O.42t*
Pentachiorobensene
0.002%
0.022
* tetra—CDFs
0.2%
bexa—CDFs
0.1%
penta—CDFs
0.5%
hepta—CDFs
0.2%
hexa—CDFs
0.3%
octa—CDF
0.22
41
-------
I . 2 , 4 , 6 ,7,8—hez CDD
1
l,3.6,8—tet aCDD
l,3,7,9—tetraCDD l,Z,3,7,8,9—hGzaCDD octaCDD
ft ft
ci. 5 ci
l. 2 1 3 ,8—tetraCDD 1 . 2 . 3 ,4,7—peøtscDD I . 2 I 4 , 7 ,9—POUtCCDD l, 2 , 3 ,4,6.8.hOZaCDD 1,2,3,4 ,6,7 ,8—b pt*CDD
l ’ l, 3 ,6,8—Pt tICDD
I .2,3,6 .$—pentaCDfl
i are 11. PCDDS Formed Under Laboratory Pyrolysis of a Mixture of Ccmmon Coercjal Chiorophenates (8)
-------
Rappe, et al. (13), reported PCDDs and PCDFS formation from the burning
of chlorophenols. Two of the most commonly used chlorophenol formulations on
the Scandinavian market, Servarex Teknish (Gullviks Fabrinks AB, Malmo,
Sweden, lot Npur 524) and Kymmene £ 99 were prepareG by multiple recrystallizations. The results
from the burning of these purified 2 , 4 ,&—tri— and pentachiorophenate are
given in Table 20. In these . xperiments, only birch leaves and charcoal
filter trapping of the smoke gases were used. In the case of ‘he 2,4,6—
tricbloropheoate, the dominatin 1 FCDDs were tetra—CD’)s. In the case of the
peutachiorophenate the highest level was found for the octa—CDD, but the
amounts of hexa— and hepta—CDDs were found to exceed 50 mcg/g pentachioro—
phenate (13).
43
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Table 19. AMOUNTS OF PCDD FOUND IN BURNING EXPERIMENTS
CF COMMERCIAL CELOROPHENATES (13).
(mcg PCDDs/g chiorophenate)
SERVAREX KY—5
birch leavea wood wool brch leaves
original original
sample charcoal sah XAD—2 charcoal XAD—2 sample charcoal
I I I I I I
1
Tetra—CDDs 0.7 35 17 26 96 210 I 0.4 30
Pants—CODs 5.2 90 58 59 120 357 I 3.5 84
litXR—CDD S 9.5 80 74 57 110 347 5.3 82
Hepta—CDDs 5.6 8 18 8 65 29 2.1 8.2
Octa—COD 0.7 0.3 6.4 0.2 1.2 1.2 I 0.3 0.4
TOTAL 21.7 213.3 173.4 150.2 392.2 944.2 11.6 204.6
I I I I I I
-------
Table 20. AMOUNTS OF PCDDS FOUND IN BURNING EXPERIMENTS
OF PURIFIED CULOROPHEWATES (13).
(mcg PCDDs/g chlorophenate)
2,4 ,6—Trichlorophenate Pentachiorophenate
birch leaves birch leaves
original original
sample charcoal sample charcoal
Tetra-CDDs
<
0.02
2100
<
0.02
5.2
Penta—CDDa
(
0.03
5.0
I <
0.03
14
Rexa—CDDg
(
0.03
1.0
I <
0.03
56
Hepta—CDDs
Octa—CDD
TOTAL
(
<
<
0.1
0.1
0.28
3.0
6.0
2115
I
I
I
0.3
0.9
1.28
172
710
957.2
-------
PCDFs in Starting Materials and Burnj! Extracts
Using the same techniiiue as previcLsly described fc’r the PCDDs, PCDFs in
the starting materials and burning extracts were found. The main PCDFS in
the starting materials were the hexa— and hepta—CDF8 present at levels of 6C—
70 mcg/g each, and the amounts found for the tetra—, penta— and octa—CDFs
were about 10 mcg/g. The sane l . vels and the same isomers were fcund in the
two formulations studied.
After burning, the levels of most PCDF& were generally lover (as opposed
to PCDDs), but the levels of a few inc i idual PCDFs nevertheless increased
(e.g., the major tetra—CDF, an unknown isomer, increased during burning more
than 100—fold from 0.04 to 5 zncg/g). Two PCDF isomers which increased upon
burning had never been found in the starting material. 2,3,7,8—TCDF, which s
considered to be the most toxic of all PCDFs, was only a minor component in
all these samples and was less than 0.1% of the total tetra—CDF& in the
starting meterial (7). The same PCDFs were formed in the Servarex micro—
pyrolysis as in the burning experiments. However, no PCDFS could be found
after the burning or micropyrolysis of the purified chiorophenates. There-
fore, the PCDFs were formed from impurities in the chemical formulation,
probably in reactions with higher absolute yields than those leading to PCDDs
(13).
Test burns of pe itachloropheno1 (PCP) waste were performed in an
industrial boi’er in the U.S. Samples of baghouse ash and bottom ash were
analyzed and results are reflected in Table 21. In the baghouse ash the
total level of PCDDs was found to be 5.3 mcg/g. Lower chlorinated PCDD
predominates. In the bottom ash, the higher chlorinated PCDDs wcre found in
greater amounts. PCDFS were found in the baghouse sish (14).
46
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Table 21. LEVELS OF PCDDB AND PCDFS FROM BURNING OF PENTACULOROPHENOL
CONTANIMATED WASTE (iucg/g) (14).
Contami cant Baghouse
Bottom
Tetra—CDDs 0.96 0.01
2,3,7 8—Tetra—CDD <0.005 <0.001
Penta—CDD8 1.4 0.02
Ilexa—CDDs 2.0 0.04
H pta—CDDs 0.7 0.10
Octa—CDD 0.2 0.14
Tetra—CDFs 0.90
2,3,7,8—Tetra—CDF 0.10
Penta—CDFs 1.5
1,2b3,7,8—Perlta—CDF 0.05
2 1 3,4,7,8—Penta—CDF 0.10
Hexa—CDFs 0.15
l)2,3,4,7,8—Uexa—CDF 0.02
Repta—CDFs 0.06
Octa—CDF 0.006
47
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REFERENCES
1. C.W. Bayes, M.J. Mulvihill, B.R.T. Sinioneit, A.L. Burlingame and R.W.
Risebrough. Identification of Chlorinated Dibenzofurans in American
Polychiorinated Eipheuyls, Nature (London), 256, pp. 305—307 (1975).
2. 11. Miyata and T. Kashimoto. The Finding of Polychlorodibenzofurans in
Commercial PCBs (Aroclor-, Phenoclor and Clophen), Food Hyg. Soc. Japan,
17, pp. 434—437 (1976).
3. D.S. Duvall, V.A. Rubey and J.A. Mescher. High Temperature Decoin—
position of Organic Hazardous Waste, in: Treatment of Hazardous Waste——
Proceedings of the Sixth Annual Symposium, D. Schultz, ed., EPA—600/9—
80—011, March 1980.
4. D.S. Duvall and V.A. Rubey. Laboratory Evaluation of High Temperature
Destruction of Polychiorinated Biphenyls, EPA—600/2—77—228, December
1977.
5. C.C. Shih, R.F. Tobias, J.F. Clausen and R.J. Johnson. Thermal
Degradation of Military Standa’d Pesticide Formulations for U.S. Army
Medical Research and Development Command, TRW Report No. 24768—6019—RU—
00, March 1975.
6. G. Langendijk and B. Kransberg. Askarels at Noogovens, Ijmuideia, The
Netherlands, June 21, 1982.
7. Y.M. Ioannou, L.S. Birnbaum and H.B. Matthews. Toxicity and Distri-
bution of 2 , 3 ,l,S—Tetrachlorodibenzofuran in Male Guinea Pigs. Journal
of Toxicology and Environmental Health, 12, pp. 541—553 (1983).
8. H.R. Buser, 11.—P. Bosshardt md C. Rappe. Formation of Polychiorinated
Dibenzofurans (PCDFS) from the Pyrolycis of PCBs, Chemosphere 7(1), pp.
109—119 (1978).
9. C. Rappe and H.R. Buser. Formation and Degradation of Polychiorinated
Dibenzo—p—Dioxinc (PCDDs) and Dibenzofurans (PCDFs) by Thermal
Processes, Paper Presented at 178th National American Chemical Society
Meeting, Washington, D.C., September 9—14, 1979.
10. 11.R. Bucer and C. Rappe. Formation of Polychiorinated Dibenzofurans
(PCDFS) from the Pyrolysis of Individual PCB Isomers, Chemosphere 3, pp.
157—174 (1979).
11. H.R. Buser, Formation of Polychiorinated Dibenzofurans (PCDFs) and
Dibenzo—p—Dioxins (PCDDa) from the Pyrolysis of Chlorobenzenes, Chemo—
sphere 6, pp. 415—424 (1979).
12. M.P. Eapo8itu, T.O. Tiernan and F.E. Dryden. Dioxins, EPA—60O/2—80—i 7,
November 1980.
48
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13. C. Rappe, S. Markiund, H.R. Buser and 11.—P. Bosshardt. Forration of
Polychiorinated D benzo—p—Djoxjns (Pcnns) and Dibenzofurans (i’CDF ) by
Burning or Heating Chiorophenates, Chemosphere 3, pp. 269—281 (1978).
14. C. Rappe, S. Markiund, P.—A. Bergqvist, and M. Hanseon. Polychlorjnated
Dioxjn , Dibenzofurans and Other Polychiorinated Polynuclear Aroniatics
Formed During Incineration and PCBs Fires, Department of Organic
Chemistry, University of Utnea, 5—901 87 Umea, Sweden (1983).
49
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SECTION 5
PCBs FIRE INCIDENTS
ANALYSIS FOR PCBs, PCDDs AND PCDFs AT FIRE ACCiDENT SITES
The analysis of soOt sbmple8 from actual PCBs incidents has led to con-
cern for the safety of fire fighter personnel and the importance of clean—up
measures.
In this section the results of sample analyBis for PCBs, PCDDs and PCDFS
are presented from tI e following fires:
• Norrtal e, Sweden
• Cincinnati, Ohio
o Binghamton, New York
• Stockholm, Sweden
• Boston, Massachusetts
o Skovde, Sweden
o Miami, Florida
• St. Paul, Miitneso
• San Francisco, Calif,raia
o Other Fires.
Norrtalje Sweden
On September 25, 1978 there was an intense fire in a capacitor battery
north of Norrtalje, Sweden. The fire could not be extinguished for over
thirty minutes while high voltages were turned off. Eighteen PCBs—containing
capacitors (100 kVA each) were involved in the fire. When the capacitors
were demounted, some showed no signs of damage while others had exploded with
the contents exposed. B. Jansson and G. Sundstrom (1) at the Special
Analytical Laboratory, National Swedish Environmental Protection Board
50
-------
located at the University of Stockholm were contacted a fv weeks after the
accident and asked to perform sample analysis for PCDF formatjc ,n. Up to 300
mg samples together with 100 ng [ 2,3,7,8_ 37 C1]_tetrachloro_ [ 1469_2H]_
dibenzo—p—dioxin as internal standard dissolved in 1 ml n—hexane were chroma—
tographed on aluminum oxide. The first fraction containing most of the PCBs
was eluted with 90 ml 5 dichioromethane in n—hexane. The second fraction
which was eluLed with 60 ml dichioromethane contained all PCDF references,
the internal standard and at least two PCBs.
Results of the analysis are given in Table 22. An Aroclor 1242 standard
was used as a reference. Samples were taken from intact and exploded
capacitors, from the wire fence surrounding the capacitors (fence was washed
with acetone to obtain sample), and from pinetree needles which were located
about 10 m downwind from the fire.
Table 22. PCB AND PCDF LEVELS IN Ct PACIT0RS AND
IN ENVIRONMENTAL SAMPLES (I).
Sample
PCB 8
g/g sample
mono—CDF
- PCDF
di—CDF
tncg/
tri—CDF
sample
tetra—CDF
PCDF
PCDF/PCB
mcg/g
Liquid in intact
0.83—0.86
0.2—0.5
0.2
0.2—0.3
capacitor
0.2—0.3
0.9—1.1
1.1—1.3
Liquid j explo—
0.93
24
38
11
ded capacitor
3
75
81
Liquid explo—
0.49—0.60
12—21
9—21
3—7
ded capacitor
2
27—52
45—107
Extract from
0.3x10 3
<0.03
wire fence
<0.03
<0.04
<0.3
—
Pine needles
O.3x10 6
n.d.
m .d.
n.d.
n.d.
s.d.
—
a 88 Aroclor 1242
The wire fence was found to contain unexpectedly low PCB concentrations.
The extractable part contained only 0.3 mg PCB per g extractables. As a
51
-------
result of this low PCBs level the upper limit of the PCDF/PCB ratio for the
fence extract becomes high. While no presence of PCDF was found in the fence
sample, if the extremely high detection limit for the dichiorinated compounds
is excluded, the aighest possible concentration should be about 300 mcg per g
PCBs.
In addition to these environmental samples, blood samples were taken from
6 firemen who were exposed to the fire. The samples were not taken until a
few weeks after the fire incident. At that time the PCB levels in the blood
samples were within the same range 2.3 to 3.6 mg PCBs/g as those for
unexposed Swedes (1).
Cincinnati. Ohio
On December 3, 1980, a capacitor containing PCBs for an electric motor in
a unit heater overheated in a basement storage room of Our Lady of Visitation
Elementary School in Cincinnati, Ohio (2). The capacitor was used for a one—
half horsepower electric motor in the unit heater. The motors capacitor
contained a design specification dielectric fluid volume of 22 ml, of which
99.6% by volume (or 21.91 ml) was a biodegradable fluid and 0.4% by volume
(or 0.088 ml) was PCBs (Aroclor 1254). On March 18, 1981, NIOSH was
requested by the Hamilton County Health Department to determine the extent of
PCBs contamination of the school. Air and surface wipe samples were obtained
throughout the school building on March 19 and 26 to determine the presence
of PCBs.
Airborne PCBs were collected on Florisil packed in approximately 7 cm
long 4 mm I.D. glass tubes. The Florisil was packed into two sections
separated by a polyurethane plug: the front section contained 100 nig and the
backup section (used as the blank) contained 50 ing of Florisil. The samples
were collected using calibrated constant flow vacuum pumps operating at 0.20
liters per minute. The PCBs were desorbed from the Florisil with toluene and
analyzed using a gas chromatograph equipped with an electron capture
detector. Air ccncentrations were reported as micrograms (meg) of PCBs per
cubic meter ( n 3 ) of air sampled. As seen in Table 23, PCBs were not detected
52
-------
in air samples obtained in the basement storage room nor in another room
tested. These results were as expected based on the extremely low vapori-
zation rate (0.000052 glcm 2 /hr at 100°C) of Aroclor 1254.
Wipe samples of surfaces were obtained by wiping an area of approximately
100 cm 2 using a Whatman smear tab moistened with pesticide quality cyclo—
hexane. The samples were extracted using toluene and analyzed using the
procedure used for the air samples. The presence of PCBs wa reported as meg
per 100 cm 2 of surface area. As seen in Table 24, samples obtained from the
floor, ceiling, desk and bookshelves in the basement storage room (Room 27)
shoved a surfaLe presence of < 0.05 to 7200 mcg PCBs/100 cm 2 (5— ’2,000
meg/rn 2 ). Background levels of PCBs on surfaces in the school showed a
presence of < 0.05 to 0.45 rncg PCBs/100 cm 2 . Surfaces tested in buildinRs in
eastern, central and western Cincinnati showed a background presence of
< 0.05 to 0.13 rncgIlOO cm 2 (( 5—13 meg/rn 2 ).
The two wipe samples with the highest concentration of PCBs were also
analyzed for PCDDs and PCDFs with special emphasis on the 2 , 3 , 7 ,8—isomers.
No dibenzodioxins or dibenzofurans were detected in either of the samples.
The lower limits of analytical detection using this method were 0.10 and 0.09
mcg/100 cm 2 sample, respectively.
The Health Commissioner of Hamilton County offered the following recom-
mendations to the school:
1. The concenlrjtjon of PCBs on surfaces (i.e., floor, desks, book-
shelves) in Room 27 should b 2 e reduced to backgroun I levels, i.e.,
less than 0.5 meg PCBs/100 cm surface area (50 meg/rn ‘.
2. Other than Room 27 no rooms require decontamination.
The school was reopened in all areas except the wing containing the
contaminated storage Room 27 and nearby classrooms 24, 25 and 26 (2).
53
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Table 73. ANALYSIS OF PCBs IN AIR SAMPLES FROM SCHOOL IN OHIO (2).
Air
Sample
Sample
Location
Volume Q j
Levels
Inside
heating
unit on floor
(Room
27)
45.2
N.D.*
Center
of room
on be kshe1f
43.3
N.D.
Principal s office
34.7
N.D.
* N.D. or None Detected means that the PCBs were not detected at the lowest
level ( < 0.05 mcg/sample) capable of being measured by the analytica’
method equivalent to an airborne concentration of approximately < 1 mcgfm
for these samples.
Table 24. SUMMARY OF PCBb* WIPE SAMPLE RESULTS FROM SCHOOL IN OHIO (2).
PCBs Level (mcg/100 cm 2 )
Sample Location 11 Mean Ran&e
Room 27 (Basement location) 20 771 < 0.05—7200 **
Room 25 4 0.08 < 0.05—0.14
Room 24 3 0.05 < 0.05—0.06
Room 26 3 < 0.05 < 0.05 ****
Hallway between rooms 24—27 4 0.05 < 0.05—0.07
Room 8 4 0.06 < 0.05—0.08
Room 22 6 0.11 < 0.05-0.29
Room 9 2 0.11 < 0.05—0.16
Room 10 4 0.12 < 0.05—0.20
Room 11 2 0.09 < 0.07—0.11
Room 12 2 0.08 < 0.06—C .09
A.V. room 4 < 0.05 < 0.O!3
Principals office 3 0.21 0.05—0.45
Mobile classroom 2 0.06 0.06
Background level (3 locations) 10 0.07 < 0.05—0.13
* Reported as Aroclor 1254.
** A < value means PCBs were not detected at detection limit.
*** Excludes &l 2 e taken c n capacitor surface showing Pi Bs presence of
4.9 mcg/100 cm
Exc1ude sample 2 taken on capacitor surface shoving PCBs presence
of 2.3 mcgIlOO cm
n number of samples
Rooms 27, 25, 26 and 24 were all in the basement.
54
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B HR
fIST TY ’ING GUIDE SHEET
r
1 -XT
HER: Binghamton . New’York—-—-
On February,5, 1981, a fire broke out in the basement of the State Office
Building in Binghamton, New York. In this fire, electrical arcing from a
iiearby switchgear ignited insulation around a basement transformer. A number
power could be switched off, it was obvious that the fire had affected the
transformer. Approximately 180 gallons of Pyranol (65% Aroclor 1254 and 35%
polychiorinated benzenes) had been lost from the transformer. The floor of
the machine room was covered with an oily substance with a strong smell. The
electric company informed the Assistant Fire Chief that the transformer con-
tained PCBs. After additional calls by the Assistant Fire Chief to CEEMTREC
and EPA, information was gained on how to protect fire fighting personnt 1
-f torn- further- exposure. The- initial- exposure-to- the Pyranol- and- heavy- s noke
had already caused reactions in a number of fire fighting personnel ranging
from . cute nausea to skin rashes, high liver enzymes, high cholesterol and
triglyceride levels, to respiratoryproblerns. Over 1 billion dollars i
lawsuits have been filed in the names of 23 individuals and groups against
the state. Most of the claims have been filed by the fire fighters. Some
500 people who believe they were exposed are being monitored (3, 4).
The New York Office cf General S rvices began an immediate clean—up of
the building. Members of the clean—upcrew also developed skin rashes and on
1 February 26, clean—up was halted when the actual levels of PCDFS and PCDDS
were discovered. Ten different pentachiorinated dibenzofurans were iden-
tified. PCF.s, 2,3,7,8—TCDD, and 2,3,7,8—TCDF were found throughout the
building. Resjlts are summarized in Tables 25 and 26. The total PCDF con—
centrations in tX e soot were initially found to be as high as 2163 rncg/g,
PCDDs 10—20 mcg/g, and PCBs lOO,O’)O—200,000 mcg/g (3, 5, 6, 7, 8).
Table 27 listb the levels of PCDFS in the soot samples collected from
each of the 17 floors of the State Office Building. The samples were taken
by wiping one half (2 ft x 2 it) of a ceiling panel with dry cellulosic
filter pa .er. The particled were extracted with benzene antI oncentra :ed. - ,— -
samples were spiked with ‘ 3 C 2,3,7 ,8—TCiiD, 37 C1 TCDF and 37 C1 0Cb . Each,
) I , ____ ____________
r T 3
( )
L’ U’i :U
3 -lN
[ C 1C
I [ RE
i :/ , c
w
[ A ibl IC
-------
Table 25. AMOUNTS OF PCBs, PCDDS, ?CD} FOUND AT BINGHAMTON STATP OFFICE
BUILDING PRIOR TO CLEAN—UP (5, 7).
Sample Location Type of Sample Chemical Amount (Average)
comç site (thr ughcaut Air
building)
Composite Air
Composite Air
Composite Soot
Composite Soot
4th and 7th floor Soot
4th and 7th ficor Soot
Air ducts Soot
Interstitial space
above ceiling levels Soot
Exposed horizontal surfaces
(desk tops, floors, sills) Soot
Exposed vertic3l surfaces
(walls, desk sides) Soot
Unexposed horizontal
surfaces (inside closed
file cabinets and desk
drawers) Soot
Unexposed vertical surfaces
(inside closed cabinets
and drawers) Soot
Garage and sub—basement
floors and surface areas Soot (swab)
PCBs 1.48 mcg/ra 3
2,3,7 ,8—TCDD
2,3,7,8--TCbp
2,3,7,8—TCDD
2,3,7,8—TCDF
2,3,7, 3—TCDD
2,3,7,8—TCDF
PCBs
0.3 ppm
21 ppm
3.5 ppm
200 ppm
2—5 mcg/g
300 mcgfg
156—1200 rncg/m 2
PCBs 1995 mcg/m 2
PCBs 162.18 mcgfm 2
PCBs 6.76 mcg/m 2
PCBs 74.47 mcg/mL
PCBs 4.62 mcg/m 2
PCBs 0.61 rncg/m 2
56
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Table 26. LEVELS OF PCDFS AND PCDDS IN SOOT FROM ACCIDENTAL BURNING OF PCBs—
CONTAINING ELECTRICAL EQUIPMENT AT BINGliANTON (6, 8).
Isomerb Amount (mcg/g)
Total PCDFS 2163
Total Trj—CDFs
Total Tetra—CDF’s 28
2 , 3 ,7,8—Tetra—CDF 12
Other Tetra-CDF Isomers (6) 16
Total Penta—CDFs 670
l,3,4,7,8—Penta—CDF 65
1 , 2 , 4 ,7,8—Penta—CDF 25
l,2,4,7,9—Penta—CDF 22
l,2 ,3,7,8—Pen ’—CDF 310
l, 2 1 3,6 ,7—Penta—CDF 60
1,2,6,7 ,8—Penta—CDF 25
2 ,3,4,7,8—Penta—CD F 48
2,3 ,4,6 ,7—Penta—CDF 12
Other Penta—CDF Isomers (12) 110
Total flexa—CDFs 965
1,2,3,4,6 ,8—Rexa—CDF 50
l, 3 , 4 ,6,7,8_He?a_CDF 125
l, 2 ,4,6,7,8—Hexa—CDF 50
l, 2 ,3,4,7,8—Eexa—CDF 510
l, 2 , 3 ,6,7,8—Hexa—CDF 150
l, 2 , 3 ,6,8,9—llexa—CDF 58
2 ,3,4,6,7,8—He a—CDF 10
Other HeKa—CDF Isomers 250
Total Hepta-CDFe 460
l, 2 1 3 , 4 ,6,7,8—Hepta—CDF 230
l, 2 , 3 , 4 ,6,7,9—Repta—CDF 120
l, 2 ,3,4,6,8,9—H pt —CDF 55
l , 2 , 3 , 4 , 7 ,8,9—Repta—CDF 55
Octa—CDF 40
Total PCDDs 20
Total Tri—CDDs
Total Tetra—CDD3 1.2
2,3,7,8—Tetra—CDD 0.6
Other Tetra—CDD Isomers (4) 0.6
57
-------
Table 26. (Continued)
Isomers Amount (incg/g)
Total Penta—CDDs 5.0
1,2,3,7,8—Penta--CDD 2.5
Other Penta—CDD Isomers (7) 2.5
Total eca—CDDs 4.7
1,2,3 ,4,6 ,8—}lexa—CDD 1.2
l,2,4,6,8,9—Hexa—CDD 1.2
1,2,3,4,7,8—Hexa—CDD 0.7
l,2,3,6,8,9—Hexa--CDD 0.6
1 ,2,3,7,8 ,9—Hexa—CDD 0.4
1,2,3,4,6,7—llexa-CDD 0.5
Total Hepta—CDDs 7
1,2,3,4,6,7 ,9—llepta—CDD 4
1 ,2,3,4,6,7,8—Hepta—COD 3
Octa—CDD 2
58
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Table 27. CORC ’ThATtO! (tc s) OP PCDFs II SOOT SAMPLES TAXES IRON THE SI hAicroB STATE OFFICE SOILDING (9).
Ihoor I 1
2 3
4
5
6
7
9
10
11
12
13
14
IS
16
17
&
Tetra—CD7 0.06
1.8
2.3
40
3.1
77
33
3 C 1 T.tr.—CDF(n ) 1 10.7og
3.Bo
7.Zn;
4.4n
B.6o
14.2ii
9.Scg
160
1.9og
47
6.3og
150
0.7
.97
*9
54
(2)
139
Pa rts—CDT (0.06
(2.0
3.2
35
0.0
73
40
220
55
210
O.15c
S.8o
12.he
O.Sii;
2 5.S i i;
Seis—CDF (0.07
‘2.4
2.0
36
3.0
14
16
140
28
21
5.
9.7
58
149
139
B.ptsCDF (0.08
‘2.8
0.2
12
0.6
1.5
7.1
51
2.1
160
42
4.3
—
16
69
06
Octa—CD T ‘0.09
‘ 2 ..
(0.2
4.2
<0.2
—
1.4
37
12
‘2.0
1.8
30
34
20
4 8 5c 0v.r7 29
22
16
20
22
41
50
17
49
0.56
33 •
18
59
3.6
<1
‘2.0
7
0.86
31
4.7
25
11
9.3
52
1 I ter —.i.ul •tardi d ount r,eo,ered (me)
2 D.ta lost diii to icstnuasnt slfuiictjoa
3 11.t. urcorr.ct,4 for r.co,ery
4 1.cor.r, basud on 37 C 1 T.I.a-CD? liI.ros l Stuadird
-------
sample was diluted with acetone to 20% benzene, applied to a low pressure LC
system (PX—21 adsorptive carbon/celite), and washed with 40 ml 20%
benzene/acetone. Flow through the column was reversed and the PCDD&/PCDFs
fraction was eluted with 30 ml toluene. This fraction was condensed and
redissolved in dodecane, applied to a 2% deactivated silica gel column and
eluted with bexane. The eluted sample was then applied to an activated
Florisjl column and washed with 20 ml benzene to remove PCBs. PCDDs/PCDFs
were eluted with 20 ml of 3% cyanomethane 47% dichioromethane and 50% hexane.
The sample was concentrated in benzene before GCIERrIS analysis (9).
The entire 18 story building has been abandoned awaiting clean—up.
Clean—up is expected to cost 2 or 3 times the buildings original cost.
Clean—up efforts have begun at a slow pace. On the advice of expert con—
sultant , 3 contracts have been issued. These include:
1) Air Poll’ .ion Control Systems Contract
— purchase and installation of e- pollution control equipment on the
roof including fans, chemicb ad particulate filters and necessary
duct work.
2) Entry Module Contract
— purchase of a partially outfitted mobile structure which was expanded
and modified to include temporary entry facilities and locker areas,
rest rooms, and s urity offices soth r complete control of entry
could be maintained.
3) Preliminary Clean—up Contract
— intended to acco.nplish removal of soot. This operation includes high
effi.iency vacuum cleaning, wiping and washing of exposed surfaces
and readily accessible hidden areas, removal of files, records,
furniture and iersonal effects.
The site is expected to remain vacant for several years while undergoing
decontamination procedures. Ongoing activities related to the site, program
and overall management of current activities include:
1. Program organization
2. Security
60
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3. Contaminant control
4. Emergency response
5. Support of community resources
6. Control of water discharged from site
7. Control of ai: movements
8. Planning for solid waste disposal
9. Disposal of contaminated documents
10. Collection of soot samples
11. Air sampling in the garage of site complex.
Stockholm Sweden
In Augu8t 1981, an explosion (electrical arc) took place in a 10 kv
capacitor battery in an electrical power station in Stockholm, Sweden.
Kleenex tissue wipe tests (assumably 1 dm 2 ) were taken about 1 m from the
capacitor and were tested for PCDF and PCDD levels. Extraction and measure—
ment was accomplished by spiking the wipe tests with 1—5 ng of labeled CDD.
The sample was treated with 10 ml of 1M HC1 for 1 hr. The slurry was filtered
and dried, extracted with toluene and dried with N 2 . The residues were
redissolved in 2 ml of n—hexane, added to a silica gel column and eluted with
5 ml of n—hexane. The hexane was evaporated with N 2 until 10 mcI remained.
PCDDs and PCDFs were separated from other polychiorinated impurities using an
Alox—columo. The first fraction, 10 ml n—he ane:methy1ene chloride (98:2)
was discharged. The second fraction, 10 ml n—hexane:metbylene chloride (1:1)
was collected and dried in N 2 . This residue was used in the CC/MS analyses.
Individual MS—response factors were used to calculate levels given in Table
28. Roughly 25—30 incg/m 2 polychiorinated biphenylener. (PCBPs) were also
found (8, !0). Polychiorinated pyrenes (P(.PYs) were also detected but riot
quar.tified.
61
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Table 28. AMOUNTS OF PCDFS FOUND IN SAMPLES FROM ACCIDENTAL E’CB FIRE,
STOCKHOLM, SWEDEt (8, 10).
PCDF - Amount (nglm 2 )
2,3,7,8—Tetra—CDF 150
1,2,7 ,8—Tetra—CDF 150
2,3,6 ,8—Tetra--CDF 125
1 14,6 ,9—Tetra—CDF 75
2,4,6 ,7—Tetra—CDF 37
3 ,4,5,7—Tetra—CDF 7.5
1,3,6,7— and 1,3,6,9—Tetra—CDF 300
Other Tetra—CDFs 750
Total Tetra—CDFs 1200
2 ,3 ,4,7 ,8—Penta—CDF 45
1 ,2,4,7,8—Penta—CDF 38
1,2,3,6,7—Penta--CDF 15
1 ,3,4,7,8—Penta—CDF 11
2,3,4,6,7—Penta—CDF 7.5
1,2 ,4 ,6,8—Penta—CDF 3.8
1,2,4,7 ,8—Penta—CDF 3.8
I ,2 ,3,6 ,7—Penta—CDF 3.8
1,2,4 ,8,9—Penta—CDF 3.8
2,3,4,6 ,8—Penta—CDF 2
1,2,3,7,8— and 1,2,3,4,8-Penta—CtaF 15
Other Penta—CDFs 19
Total Penta—CDFs 175
Total Hexa—CDFs < 0.5
Bo ’ton Massachusetts
In January 1982, an electrical fire involving a transformer containing
&roclor 1254 occurred in a Region I OSI1A Department of Labor facility in
Boston, Massachusetts. One bulk soot sample was analyzed fcr the presence
of PCDDs and PCDFS. The bulk soot sample was spiked with 200 ng d 12 —chrysene
nd was then Soxhiet extracted for 24 hours with hot toluene. This eitract
was decar’teci and labelled fraction 1. More hot toluene was added to the
&3ample for an additional 24 hours. The extract was labelled frjction 2. Both
extracts were analyzed. 70% of the d 12 —chrysene was recovered in fraction 1.
The two extracts were concentrated. Fraction I. required multiple RRCC—MS
analysis because of its complex components. PCDFs were confirmed in
fraction 1. These results are shown in Table 29 (11).
62
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Table 29. LEVELS OF PCDFS AND PCDD FROM ACCIDENTAL BURNING OF PCBS—CQNTAINING
ELECTRICAL EQUIPMENT AT BOSTON, MASSACHUSETIS (ii).
Concentration
Isomers iucglg Soot
Total PCDFS 165
Total Tri—CDFs 50
Total Tetra—CDFs 60
2,3,7 ,8—Tetra—CDF 3
Total Penta—CDFs 35
Total Hexa-CDFs 15
Total Hepta—CDFs 2
Octa—CDF n.d.
Total PCDDS m.d.
Total Tri-CDDs m.d.
Total Tetra—CDDs m.d.
2 ,3,7 ,8-Tetra—CDD m.d.
Total Penta—CDDg m.d.
Total Hexa—CDDs n.d.
l , 2 , 3 , 4 1 6 ,7,9—Mepta—CDD m.d.
l , 2 . 3 , 4 1 6 ,7,8—Hepta—CDD m.d.
Octa—CDD m.d.
*Detection limit: 100 ng/g 0.1 mcglg 0.1 ppm
63
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Skovde Sweden
In March 1982, a fire broke out in a capacitor battery Serving a hig! —
frequency oven in a metal treatment factory in Skovde, Sweden. Both mineral
oil and PCBs types of capacitors were in use. There were no chlorinated
benzene additives in the oil. The fire started in a mineral oil copacitor
and 2 hours elapsed until the fire was extinguished. The smoke spread to an
extent of 60 m x 30 m. Copper bars for electricity in the capacitor room
ceiling partially melted (m.p. 1080°C). The capacitor battery contained 21
capacitors filled with PCBs (5 kg each). After the fire, 12 of these
capacitors had been opened, 9 remained sealed.
Wipe tests (tissue 1 dna) were used to take samples from a) floor of
capacitor battery, b) floor close to battery, c) the vail of the capacitor
room, 2 m from tne battery, 3 m above the floor, and d) bench 10 m from the
oven (1 floor above the capacitor). Table 30 shove the results. High levels
of PCDFS could only be found close to the fire. No PCDDS or polychiorinated
biphenylenes (PCBPs) could be identified in the samples from this fire (8,
10).
Miami, Florida
On April 13, 1982, a fire involving an underground electrical transformer
vault occurred in Miami, Florida (12). The International Association of Fire
Fighters (I.A.F.F.) requested NIOSH to perform analyses o 6urface samplc in
order to determine if fire fighters had been exposed to PCBs or other aore
toxic decomposition products such as PCDDS and PCDFs. The fire fighters were
also concerned about the possible contamination of fire equipment and pro-
tective clothing used during the fire.
In these an .1yses, samples were collected by NIOSH in two ways. Swipe
samples were collected using sterile cotton pads saturated with n—hexane from
sample areas with an approximate size of 100 cm 2 . Surfaces thought to be
less heavily contaminated were wiped with dry Whatman 9 ’Iear tabs.
64
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Table 30. LEVELS OF PCDFS (ng/m 2 ) FOR SAMPLES FROM ThE SKOVDE FIRE (8, 10).
Sample N
a b
umber
c d
2 , 3 ,7,8—Tetra—CDF 20 100
< 1 m.d.
Total Tetra—CDFs 100 600
< 1 1O*
Total Penta—CDFs 40 100
s.d. m.d.
Total Eexa—CDFs 40 60
—“— —“--
Total Hepta—CDFs 8 8
—“—
Octa—CDF 5 5
—t,-.
m.d. not detected
* different isomers than those found in samples a and
b
Table 31. PCBs RESIDUE FKOM A TRANSFORMER VAULT FIRE,
COLLECTED
MIAMI, FLORIDA (12).
4/16/82 IN
Sample Location/Description Type Sample
PCBs * 2
(mcg/100 cm )
Inside Transformer Vault:
wall behind removed transformer (soot) swipe
-.-.
top of primary cable above fire (soot) swipe
primary cable support bracket (soot) swipe
389
floor near base of isolating switch (dirt) swipe
ceiling near fire location (soot) swipe
secondary bus near vault ceiling (dirt) swipe
860
wall next to exit ladder (dust)
smear
rung of exit ladder (dust) smear tub
2
79
Above Transformer tault:
sidewalk grating smear tab
2
sta.ding water at curb near vault swipe
3
Fire Personnels .i ’thing and Equipment:
sleeves of tt.ruout coat
smear
top of boot smear tab
< 0.1
<
inside helmet smear tab
front of turnout coat
tab
0.1
smear
inside helmet face shield
tab
< 0.1
smear
outside facepiece smear tab
< 0.1
<
smoke ejector fan smear tab
) 31
* As Aroclor 1260 (used as standard for q.iantitation of samples).
As mixture of Aroclor 1254 (231 mcg) and Aroclor 1260 (203 incg).
65
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Table 31 represents the results of the surface sample analyses for PCBs
contamination. Samples taken within the vault shoved the heaviest contami—
nijtion. Turnout coats and other persunal protective equipment were cot found
to be contaminated (probably due to the decision to allow the fire to self—
extinguish). - The only contaminated equipment at the station was found to be
the smoke ejector fan. Results showed PCBs contaminat ton of > 31 mcgIlOO
c m 2 . Previous NIOSH investigations indicate normal background levels for
PCBs on non—contaminated surfaces should be less than 0.5 m g/10O cm 2 .
Table 32 presents the results of the analyses of 6 bulk samples of soot
and other fire residues for the presence of isomers of PCDDS and PCDFS. No
PCDDs were detected in these samples, but PCDFs from trichioro— to
hexachioro— isomers were detected in samples Bi to B6. The samples also
exhibited high levels of PCBs through Cl 10 and polychlorinated diphenylethers
(PCDES) through Cl 8 . The highly toxic 2 1 3 1 7 ,8—tetrachloro— isomer was not
detected in at y of these samples.
Gas chronmatograph/mass spectrometer (CC/MS) analyses of soot samples
collected from the vault ceiling directly above the fire scene was also
performed. Peaks identified included penta—, hexa—, and heptachiorohiphenyls
and numerous alkanes mostly larger tLan C 20 (12).
St. Paul, Minnesota
On June 22, 1982, a PCBs fire occurred at the Bill—Murray High School in
St. Paul, Minnesota (13). NIOSH samples of surface wipes and air were
obtained on June 23, 1982, and results can be seen in Table 33. Samples were
again obtained on July 7, and results are presented in Table 34.
San Francisco California
On the morning of Sunday, May 15, an electrical fire of unknown origin
occurred in an underground transformer vault located at One Market Plaza in
San Francisco adjacent to a 28 story high—rise. The vault, located beneath a
66
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Table 32. RESDLT OF ANALYSES FOR PCDDe AND PCDFa IN BULK SANPLES OF RESIDUE FROM MIAMI AMsvoaMza F7.RZ (12).
Icomere
Number
Poae i .ble
Number
Detected
Concect
In Sample
ratio
(nglg
a
or ppb)
Samples:
31
82
83
84
85
86
B!
32
83
84
35
36
Mono CD I)
2
0
0
0
0
0
0
ND
ND
ED
ND
ND
ND
Di CDD
10
0
0
0
0
0
0
ND
NI)
ND
ND
ND
ND
Tr j CDD
14
0
0
0
0
0
0
ND
ND
ND
ND
ND
ED
Tetra CDD
22
0
0
0
0
0
0
ND
ND
ND
ND
MD
MD
Penta CDD
14
0
0
0
0
0
0
ND
ND
ND
ND
ND
Rexa CDD
10
0
0
0
0
0
0
ND
ND
ND
ND
ND
ND
Repta CDD
2
0
0
0
0
0
0
ND
ND
ND
ND
ND
ND
Oc ta CDD
1
0
0
0
0
0
0
ND
ED
ND
MD
ND
ND
2 ,3,7 ,8-T CDD
1
0
0
0
0
0
0
M I )
ND
ND
N I )
ND
ED
Mono Cl ) !
4
0
0
0
0
0
0
MD
l TD
ND
ND
ND
ED
D i. CD!
16
0
0
0
0
0
0
ND
MD
ND
ND
ND
ED
l x i CD!
Terra CD!
28
38
6
6
0
0
0
0
0
0
0
0
6
7
180
530
ND
ND
ND
ND
ND
NI)
ND
ND
110
280
Pence CDF
28
7
0
0
0
0
5
1000
ND
ND
MD
ND
2 50
Raze CDF
16
3
(
0
0
0
4
180
MD
III)
MD
MD
100
Bepta CD!
4
0
0
0
0
0
0
MD
ND
lTD
MD
ND
ND
Octa CD!
1
0
0
0
0
0
0
M D
ND
ND
ND
ND
MD
2,3,7,8—lCD!
1
0
0
0
0
0
0
ND
ND
ND
RD
ND
ED
Detection Limit — For PCDDe: 10 eg/g for samples 81, B5, nd EG; 100 ngfg for sample 32, 83, and 84.
Detection Limit — For PCDFe: 10 ng/g for anpLee 81, 82, B5, and 86; 50 08/8 for sample 84; 100 ng/g for sample 83.
SampLe Deocripton/Location: 81 Soot, dust, cad dirt from top of primary cable support bracket, circutt #2.
82 Residue from floor under isolating switch near burned transformer.
83 Scrapingo from ceiling above transformer.
84 Scrapings from secondary bus.
85 Vault wall, near exit ladder.
86 Scrapings of soot and dirt from smoke ejector fan used to exhaust smoke from icult
during fire.
ND — Not Detected
-------
Table 33. ANALYSES OF PCBa (REPORTED AS AROCLOR 1260) IN WIPE SAMPLES FROM
THE HILL—MURRAY SCHOOL (13).
Sample Location ________
Vault room 100—5000
Vault door < 5
Corridor outside vault room ( 5
Room 048 20
Boiler Room < 5
Cafeteria 0.22—0.24
Corrij4’r leading to fieldhouae < 0.05
Corridor vail across from room 109 0.26
Corridor vail adjacent to music suite 0.27
Corridor vail leading to office 1.6
Outside room 106 5.8
Room 106 0.61—0.95
Room 138 1.4—2.1
Cymnasium 0.29
Athletic building lobby 0.16
Priory C 0.05
*
PCBs (ncgIlOO cm 2 )
on 6/23/ 82
PCB& (mcg/lOO cm 2 )
Q 7/7/82
2—120
3
C 0.05
C 0.05
C 0.05
< 0.05
0.8
0.2—0.5
Table 34. AREA
CHLORINATED
CONCENTRATIONS OF PCBs
BENZENES (13).
(REPORTED AS AROCLOR 1260) AND
Sample
Sample
Airborne
Concentration
(mg/1n 3 ) .
Total
Total
Sample Vicinity
Duration
Volume
Trichloro—
Tetrachloro—
by Date
(Hours)
(Liters)
PCBa*
Benzene**
Benzene **
June 2k i!
Transformer Vault
2.54
137
0.05
22.6
18.2
Transformer Vault
2.52
136
0.09
17.6
25.7
Vault Doors
2.37
123
0.02
10.2
11.7
ROOD 018
306
165
0.004
0.73
1.21
Outside Room 109
2.6
144
C 0.001
0.12
0.26
Cafeteria
2.98
161
C 0.001
0.35
0.27
1 HiZ2 Li
Transformer Vault
2.82
169
0.007
0.331
Ô.651
Vault Doors
2.83
170
C 0.001
0.048
0.229
Outside Room 018
2.82
169
C 0.001
0.020
0.089
OuLside Room 109
2.92
175
C 0.001
0.011
0.037
Cafeteria
2.92
175
C 0.031
0.010
0.032
N105H recommended permissible exposure limit for
weighted average (TWA) exposure criteri is 0.001 mg/n
** ACCIS threshold limit value is 40 mg/m for 8—hour TWA.
nor OSHA have exposure criteria.
No 8—hour TWA exposure criteria.
8—hour time—
Neither NIOSH
68
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sidewalk manhole grate, contained three Pacific tas and Electric Company
(PG&E) owned transformers and associated network protection equipment. Each
of the three transformers was filled with approximately 515 gallons of PCB
fluid.
During the course of the fire, a cooling fin on one of the transformers
was damaged, resulting in the release of approximately 50 gallons of PCB
fluid. The fire burned and smoldered for approximately eight hours after
discovery. Subsequent sampling of the building and surrounding area indi-
cated that PCBs and by—products of PCB combustion had been released through
the sidewalk grate, through conduits into the buildings awitchgear room, and
through diacontinuities in the vault wall into at. adjac nt basement garage.
The ventilation system serving floors 5—2 through 6, whtch draws air from a
point near the switchgear room, was also shown to have surface contamination
of PCBs and combustion by—products.
Samples taken and analyzed after the incident revealed that the trans-
former oil involved was 100 percent Aroclor 1242. The dielectric fluid
itself contaminated the vault, while smoke from the vault contaminated the
vault, portions of basement B—l and basement 3—2, the exterior wall of the
Steuart Street tower near the vault, the brick sidewalk near the vault, and
portions of the air handling system that supplies floors 32 through 6.
Sampling for PCBs and TCDPs in the vault after the fire, prior to clean-
up, revealed the following (highest recorded) contatiination levels:
Sample TCDFs
Soot from manhole cover 110,000 ppm
Wipe sample from floor 910,000 mcg/lOO c m 2
Soot from vault wail 15.6 ppm
Extensive air sampling was conducted during the clean—up operations.
Approximately 4000 air samples were taken in various locations inside and
outside the high—rise tower to monitor decontamination efforts. The highest
69
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air conceotrations were measured in the vault; the second highest concen-
trations were found in the svitchgear room, adjacent to the vault. Prior to
cleaning, air sau.ples in the vault revealed PCBs levels up to 1,500 mcg/ i 3
and air samples from the svitchgear room shoved PCBs levels up to 98.6
meg/rn 3 . The highest level outside the vaLit and svitchgear room was found in
a storage room, where a level of 12 incg/m 3 was measured.
Other Fires
There have been a host of other fires associated s.ith PCB transformers
and capacitors. )lauy in the U.S. probably go unreported. The following are
some of the fires reported in the Scandin vian countries:
Location Category Date
Aruika (Sweden) Explosion in PCB filled May 1982
capacitor
Irnatra (Finland) Explosion in PCB filled Aug 2, 1982
capacitor
Helsinki (Finland) Expl,ç sionin PCB filled Aug 1982
capacitor
Surahanrnar (Sweden) PCB fires with mineral oil Sept 23, 1982
as the external energy source
Rallstahaminar (Sweden) Explosion in PCB filled Nov 8, 1982
capacitor
Railway locomotive Explosion in PCB filled Winter 1982/83
(Sweden) capacitor
Kias (Sueaen) Explosion in PCB filled Apr 25, 1983
capacitor
Ralcistad (Sweden) Explosion in PCB filled Aug 15, 1983
capacitor
In September 1982, a 500—unit capacitor battery at a steel mid’
Surahammar, Sweden, was ignited by 10 tons (9090 kg) of molten steel. The
capacitors were filled witb PCBs [ 2 tons (1820 kg)) and mineral oil [ 3 tons
(2730 kg)]. The fire burned for 2 to 3 hours, and filled the entire building
with smoke. Table 35 presents the results of analyses of wipe t anp1es.
70
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Table 35. PCDFs FOUND AT SUPAEAIIMAR, SWEDEN (ngIm 2 )*.
2,3,7,8—
Sample Location TCDFs TCDF Cl 5 Cl 6 Cl 7 Cl 8
Capacitor Room (Sample 1) 4000 875 3300 1800 1500 30C
Capacitor Room (Sample 2) 1100 365 1250 940 625 145
N.E. Corner 1 10 m height 1250 300 355 150 65 13
S.E. Corner, 10 in height 480 120 210 140 60 30
N.E. Corner, floor 100 25 27 15 5 2
S.E. Corner, floor 90 22 25 17 17
10 in Outside, downwind (250 (25 (25 <60 58 17**
300 in Outside, downwind <250 <25 (25 <60 <30 <12
After Cleaning (Sample 1) <20 <4 <10 <12 <15 2
After Cleaning (Sample 2) <40 <3 <20 <20 <30
* Wipe tests.
- •- Possibly due to Cl 9 or Cl 10 PCBs in casting sand.
There have been several other capacitor fires after which PCDFS were
found, su:h as those at a paper mill ii’. T natra, Finland (August 1982), and
Volvo in Skovde, Sweden. Table 36 presents n comDaris n of the gro.3s PCDF
levels from several incidents.
71
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Table 36. PCDF LEVELS 1K PCBs FIRES.
Site
PCDF Levels
P BP Levels*
Skovde (foundry,
well—ventilated)
2
0.01 mcglm
None
Skovde (basement
capacitor room)
Danniken, Sweden
Surahammar, Sweden
Imatra, Finland
0.8 uicg/m 2
1.5 mcgfm 2
1—10 mcglm 2
1—3 mc ,fin 2
1.5
Less
Less
None
mcglm 2
than
than
PCDFS
PCDFs
Imatra, Finland
1.5 ppm
Binghamton, New York
2160 ppm
Less
than
PCDF&
* Quantification not possible due to the lack of standards.
72
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REFERENCES
1. B. Jansson and G. Sundstrom. Formation of Polychlorjnated Dibenzofurans
(PCDFs) During a Fire Accident in Capacitors Containing Polychlorinated
Biphenyl (PCB), in: Chlorinated Dioxins and Related Compounds—Impact on
the Environment , (0. Butzinger, R.W. Frei, E. Merian, and F. Pocchiari,
ed.), pp. 201—207, Pergamon, Oxford (1982).
2. J.R. Kominsky and J.P. Flesch. Hedlth Hazard Evaluation Report——Our
Lady of Visitation £lementar School, Cincinnati, Ohio, NIOSH Report No.
HETA 81—237, July 1981.
3. G. Langendijk and B. Kransberg. Askarels at Hoogovens, Ijmuiden, The
Netherlands, 5/21/82, June 21, 1982.
4. E.F. Fitzgerald and S.J. Standfast. Summary of Binghamton State Office
Building Medical Surveillance Program: Design and Implementation, New
York State Department of Health (1982).
5. A. Schecter. Contataination of an Office Building in Binghamton, N.Y. by
PCBs, Dioxin, Furans and Biphenylenes after an Electrical Panel and
Electrical Tranformer Incident. Chemosphere 12(4/5):669—680, 1982.
6. C. Rappe and S. Markiund. Thermal Degradation of Pesticides and Xeno—
biotics: Formation of Polychlorinated Dioxins and Dibenzofurans,
Department of Organic Chemistry, University of Umea, S—901 87 Umea,
Sweden (1982).
7. New York State Department of Health. Health Questions and Answers
Related to Chemical Contamination of the Binghamton State Office
Building, (1982).
8. C. Rappe, S. Marklund, P.—A. Bergqvist, and N. Hansaon. Polychiorinated
Dioxins, Dibenzofurgns and Other Polychiorinated Polynuclear Aromatics
Formed During Incineration and PCB Fires, Department of Organic
Chemistry, University of Unea, S—9O1 87 Umea, Sweden (1983).
9. R.M. Smith, D.R. Bilker, P.W. OKeefe, S. Kumar and K.M. Aldous. Deter-
mination of Polychiorinated Dibenzofurans in Soot Samples from a
Contaminated Office Building, Toxicology Institute, Center for
Laboratories and Research, New York State Department of Health, March
1982.
10. C. Rappe, S. Marklund, P.—A. Bergqvist, and N. Uansson. Polychlorinatcd
Dioxins (PCDDs), Dibenzofurans (PCDFs) and Other Polynuclear Aromatics
(FCPNAS) Formed During PCB Fires, Chemica Scripta . Vol. 20, pp. 56—61,
1982.
11. Memorandum from C. Choudhary and J.C. Posner to K. McManus (Regional
Program Consultant). Results of the Analysis of Chlorinated Dioxins and
Diben2.ofurans in Bulk Soot Sample Sequence p3314, Department of Health
and Human Services, Received October 1, 1982.
73
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12. Personal Communication from S.A. Salisbury (Regional Industrial
Hygienist) to R. Duffy (I.A.F.F.), Department of Health and Human Ser-
vices, Division of Preventive Health Service. Document 0409 g, HETA 82—
224, October 22, 1982.
13. Personal Communication from J.R. Kominsky (Supervisor Industrial
Hygienist) to D.E. Anderson (Industrial Hygiene Engineer, Hinnesota
Department of Health). BETA 82—310, July 26, 1982.
14. Letter from LM. Howe (Chief Engineer, Pacific Gas and Electric Company)
to C.A. White (Regional Administrator, California Department of Health
Services), December 9, 1983.
74
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SECTION 6
PREVENTION AND MANAGEMENT OF PCBs FIRES
Fires and catastrophic failures involving PCBs transformers, capacitors
and other PCBs—containing electrical equipment have occurred in many
countries in a variety of buildings and facilities. Such incidents will
undoubtedly recur. This section essentially presents the current thinking of
people within government, the electrical utilities, fire fighters and
academics who have been involved with PCBs transformer and capacitor fires.
The lack of carefully evaluated scientific data and empirical evidence does
not lessen the validity of the thinking, su :gestions and approaches discussed
in this section. PCBs fires do not represent carefully conducted scientific
experiments.
EARLY PREVENTIVE MEASURES
Phase—out of PCBs—Containinp Electrical Eguipment
The removal of all PCB—containing elactrical equipment may appear to be
the ideal solution, but there are a number of practical considerations whica
currently limit this approach. First, there is the question of the cost.
Because PCBs electrical equipment still forms a major core of the electrical
equipment still in service, there would be substantial cost to the utilities,
building owners and ultimately the consumers if all the equipment is replaced
immediately. The second consideration deals with available substitutes.
PCBs usage as the dominant heat exchange fluid for transformers and
capacitors over the years is due to the fire safety properties offered by
PCBs low flammability. Eliminating PCBs at this time would mean a reversal
to the use of mineral oil which is substantially more flammable. A number
of new heat exchange fluids ere now offered as PCBs substitutes. In addition
to the higher cost, very little is known about the toxicities of these new
materials and their use could create an even higher ri8k to thu environment.
Finally, there is also the problem of responsibility and liability.
Ownersh .p of PCBs—containing electrical equipment is mixed. In some
75
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instances, the equipment is owned by the utilities and in others it is the
property of the building owners.
Following the PCB transformer fire at One Market Plaza in San Francisco,
Pacific Gas and Electric (PG&E) has adopted a policy of gradeal phase—out of
its PCBs transformers and capacitors. Undex a consent decree with the city
government, PC&E agreed to phase—out over a two—year period, more than 400
PCBs—containing transformers. These 400 transformers were selected on the
basis of their location in high population oensity areas such as office
buildings and metro stations. Similarly, Florida Power and Light Company
(FPLC) has announced plans to replace 458 PCE—transformers over a five—year
period.
Better Information Exchange and Coordination with the Local Fire g jin
Departments
Electrical utilities can assist local fire fighting departments with
better information on the problems associated with PCBs fires. Fire
departments should know the number and location of PCBs transformers and
capacitors within their jurisdictions. In the Nay, 1983, PCBs transformer
incident at One Market Plaza in San Francisco, the fire fighters who
initially responded to the fire were not aware that a PCBs traasforiner was
involved. Filmed accounts of the fire indicate that when a tremendous amount
of black smoke poured out of the underground sidewalk vault housing the PCBs
transformers, no respiratory protection was used by the fire fighters present
above the transformer vault during their response to the fire. PG&E now
provides the San Francisco fire department and other fire jurisdictions,
listings of the locations of PCBs transformers and capacitur8.
Improvements in Labeling of PCBs Electrical Fr uipine
All PCB—containing electrical equipment is now r quired to be labeled
under EPA regulation. However, this labeling may not be readily visible or
apparent in the case of a fire. Highly visible la - 1s ‘r signs should also
76
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be placed in other areas near the transformer to indicate that a PCBs.-
containing transformer(s) is in the building. Ex imp1es of areas include
p:imary entrance points to the building likely to be used by emergency
response personnel and outtide the vault on the door. These labels should be
on the transformer vault doors at heights of 2— and 5—feet above the floor.
Th label at the 2—foot height would likely be visible to a fire fighter
crawling in a smoke filled room.
De—energizjn and Power Disconnect
Electrical utilities, owners and/or operators of the equipment should
retrofit the equipment to assure that electrical power could be rapidly
disconnected in the event the transformer enters a failure mode. The primary
load breaker air switch on the high—voltage side of the transformer should be
located outside of the equipment vault. This would allow a rapid disconnect
of the elecvrical power and also remove the need to enter the vault
containing high concentrations of PCBs and associated pyrolysis products.
The gang operated futed air switch on the utility pole should be considered
as the secondary procedure because it requires a service person from the
utility company to disconnect the power. Such a person may not be available
immediately.
RESPONDING TO PCBS—CONTAINING ELECTRICAL EQUIPMENT FIRE DfERGENCIES
Fire fighting has long been recognized as a dangerous profession. Over
the years, many successful steps have been taken to reduce the intensive
hazards and to increase the safety of fire fighting personnel. Better
training and advances in protective equipment have substantially improved
safety for fire fighting personnel. Yet, none of the existing protective
measures completely eliminate exposure to very low level concentrations of
highly toxic materials, such as PCBs and their pyrolysis products.
77
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When fire emergencies involving PCBs c:cur, the responding fire officers
must make some very difficult decisions. Thc fire off.cers decisions can be
facilitated the more informed they are with rega.d to the size and locution
of the equipment. No specific protocols tor fighting PCBs fires have been
developed by the fire fi bting departments or the electric utilities.
Response operations during the initial phase of a fire incident
involving PCBs—containing transformers or capacitors requires familiarity
with response organization and manage eut, the uses and limits of equipment
and apparatus, site entry 1 control, and decontamination orocedures. Fire
officers in command of such fire emergencies should examine all issues and
make decisions using the three—step process of recognition 1 evaluation, and
control.
Recognition
Recognition consists ot determining the hazard and its degree c 4 isk.
When an emergency involves a fare) a fire officer’s first decision is .f ether
it is safe to attempt to fight it. Sometimes the best approach may be to let
the fire burn, eBpeCially if it is in an isolated storage area. If fire
fighters are likely to be exposed to PCBs in the emergency situation, the
following elements should ie recognized and considered:
1. What is the situation?
What is involved? Is it a transformer? At vhat location or within what
area? What is the ma imuia potential danger? Is life safety threatened;
if so, to what extent? What other damage can occur?
2. What are the hazards?
What is the PCBs concentration in the transformer or capacitor? What is
the capacity of the electrical equipment? What is the total amount of
PCBs involved?
78
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3. What are the safety measures?
How much area will be needed for control operations? How much time is
available? Is it necessary ‘o evacuate nonemergency personnel from the
dangerous zone? What extent of evacuation is necessary? What protection
will be needed for fire fighters and others working at the scene? What
are the influences of wind, terrain, wat r supply, vehicular traffic, and
thoroughfares?
4. What are the capabilities available?
flow many emergency personnel are available and are they trained for the
situatLon? Are reserve .orces ready for immediate response? What appa-
ratus, equipment, and extinguishing agent8 are available? Row close to
the scene can you operate? WhEt are the be8t locations for placing and
moving apparatus and personnel?
Eva luat ion
Evaluation provides judgment based or the information obtained in the
recognition phase and gives response personnel an understanding of the
hazards.
Once a decision is wade to fight the fire in the presence of PCBs—
containing electrical equipment, the following precautions should be
observed:
• Approach the fire from upwind, wearing self—contained breathing
apparatus.
• Evacuate occupants of building which ma-j be downwind of toxic gases
and smoke.
o Be careful to avoid touching PCBs with bare hands. Keep hands which
may have contacted PCBs away from eyes and mouth.
79
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• Keep cooling streams of water on drums as well as on cylinders that
are exposed to heat, so as to .it. nt flame impingement, fusing of
the safety devices, or rupture of the cylinders which have no safety
devices.
• Use water spray streams to flush pathways, disperse vapors, and to
protect men attempting to shut off a valve to stop the flow, or who
are trying to plug a leak.
• Foam can also be used. A more detailed description will be
discussed later.
• Wear full protective clothing (in add tior to respiratory protec-
tion), including boots and gloves, during fire fighting and over-
hauling operations.
The fire fighter may attempt to stop leakage in thi PCBs—containing elec-
trical equipment which is not on fire by closing valves or plugging holes.
However, full protective clothing is required for handling PCBs. Fire
fighters must also be careful riot to splash PCBs on themselves. Another
alternative is to transfer the contents of or to relocate a drum or tank car
away from an exposed area to a safer location before trying to stop the leak.
Control
The control step addresses all potentially feasible controls. It is
based upon the inforu ation obtained from the previous steps of recognition
and evaluation, and is used to determine the most feasible mitigation pro-
cess. In order to control cud handle PCBs fire situations, adequate protec-
tive clothing, equipment and fire extinguishing chemicals are necessary to
ensure personnel safety.
Protection of Fire Fighters and Other Emergency Response Workers
The highest priority in responding to a PCBs transformer incident is to
prevent exposures to the emergency response workers such as fire fighters and
paramedics. Early prevention measures discussed previously can substantially
prevent fire fighters’ exposures. First, correct labeling of PCBs—containjng
transformers will allow early recognition of the hazard in the event of a
80
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fire. Seco’.id, the location of primary load breakers should be known to
permit rapid power disconnect by authorized personnel. In any case, the
number of fire fighters exposed to the smoke from the burning transformer
should be limited. The smoke from such a fire must be considered cztremely
hazardous as it may contain PCBs and their highly toxic pyrolysis products
PCDFS ann PCDDa.
In general, three levels of protective equipment are needed. Table 37
contains the different levels of equipment that are currentLy available and
utilized in hazardous chemical emergencies response.
The first category, Level 1, is the maximum level of protection provided
to the personnel for the normal operations. Level 1 protective equipment is
designed to be worn by workers and technicians when working on the spill site
when there is a reasonable potential for direct contact with the PCBs
mdterial. Level 2 safety equipment is worn by all other on—site personnel.
In a PCBs fire situation, Le:el 3 protective equipment should be used.
To ensure the adequacy of the protective equipment, a personnel and envi-
ronmental monitoring program should be developed. Air samples should be
continuously collected from the breathing zone of all workers to check for
contaminated particulate matter such as PCDDS and PCDFs. All personnel
involved in PCB fire fighting should also be required to participate in some
follow—up health and safety program which includes medical monitoring and
safety training.
Fire fighters who are expected to be exposed to the smoke should wear a
self—contained breathing apparatus (SCBA) operated in the lositive pressure
mode and standard turn—out gear (Level 2). Although the neoprene vapor
barrier commonly used in fire fighter protective clothing may not prevent
penetration by vaporous PCBs and other compounds, practical alternatives are
not readily available. When possible, flame resistant disposable protective
clothing should be worn over the usual primary protective turn—out gear.
This use of disposable protective clothing will serve as a barrier against
combustion particul tes and ultimately reduce the problem of decontamination
81
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Table 37. PERSONNEL PROTECTIVE EQUIP} T
Level Equipment
Cap with air—line respirator
PVC chemical suit
Chemical gloves taped to suit, leather gloves as needed
Work boots with neoprene overshoes taped to chemical suit
Cotton overalla/underclothjng/socks (washed daily)
Cotton glove liners
Walkie—talkjes for conmlunjcatjon
Safety glasses or face shield
‘2 Positive pressure self—contained breathing apparatus
PVC chemical suit
Chemical gloves, leather gloves as needed
Neoprene safety boots
Cotton overalls/underclothing/socks (washed daily)
Walkie—talki ,s for conanut.icatjon
Safety glasses or face shield
3 Hard hat
Air purifying respirator with chemical cartridges
PVC chemical suit artd chemical gloves
Work boots with neoprene overshoes taped to chemical suit
Cotton overalls/underclothing/socks (washed daily)
Cotton glove liners
Walkin—talkjes for communication
Safety glasses or face shield
82
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of the turn—out gear. Similarly, all fire equipment such as air ejection
fans, hoses, non—dibposable protective equipment, etc., exposed to the smoke
should be properly decontaminated using an alkaline or nonionic synthetic
detergent. To assure that all materials have been adequately decontaminated
may require laboratory analysis or the disposal of the materials.
Fikhting PCBs Fires
One of the greatest needs at this time is the developmt’nt of a generally
accepted protocol for fighting and putting out fires involving PCBs
electrical equipment. Neither the fire fighters nor the electric utilitiea
have reachet any consensus on what are the best v. ys to respond to a PCBs
transformer/capacitor fire situation. There are substantial differences as
evidenced in recent negotiations between the fire fighting unic n of a major
West Coast city and the electric utility. The electric utility believes that
the PCBs fires should be treated like any other iire and fought with water
after power disconnect and de—ener izj.ng. The fire fightr r union believes
that PCBs fires are unique and in many instances no attempt shculd be made to
fight it and the fires should be allowed to burn out with the aide of ince.i—
diary halides. The unions also wanted the electric utility to provide
special CO 2 cylinders and training to tb fire fighter to combat PCBs fires.
Technical weaknesseB can be identified on both sides on the issue. PCBs
transformers/capacitors fires are not similar to any other fire because of
the toxic residues that they generate and their long lasting contamination.
Every effort should be mad• to put out the fire as quickly as possible in
order to minimize the amouLt of highly toxic pyrolysis products that are
generated. Allowing a fire to burn itself out may result in the in—situ
thermal production and dispersion of a large number of highly toxic PCDFS,
PCDIJs, PCBPS, PCPYS, PCCYS, PCNs, etc.
In addition to water, special chemical agents ha’e been utilized to fight
fires involving hazardous chemicals. The most common agents are criemical
foams. These foams can be divided into the following categories:
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• Protein loam
• Aqueous Film Forming Foams
• Fluoroprotein Foam
• Synthetic Foam
• Chemical Foam.
Protein—based foam is formed from the decomposition of vegetable or
animal proteins, with a etal1ic salts added for strength. There ar two basic
concentrations, 6% and 3% in water (i.e., 94% and 97% vat r is ddda4), Air
is added to the mixture to expand the solution into the fini hed foam
product.
The expansion ratio of protein foams varies between the manufacturers
from 1:7 to 1:12. Foams with this type of air ratio are known as low—
expansion foams.
Aqueous film forming foam (AFFF) uses several chemicals called fluoro-
carbon surfactants to function. Tnese groups of chemicals operate by
altering the vhysical properties of voter (reducing the surface tension) sc
that they are able to spread and float acrofs the surface of a hydrocarbon
fuel even though they are more devce. Because of this property the foam has
been called “light water.” Like protein foam, AFFF is available in 3% and 6%
concentrations.
A further refinement of AFFF is the combining of the fluorocarbon surface
acti” agents with protein foam. This cojibination is called fluoroprotein
foam. Variable physicnl properties can be achieved by varying the pro-
portions of the two products.
The low expansion foama, protein, AFFF, and fluoroprotein extin&uish
fires involving flammable liquids by.
1. Excluding air from the flammable vapors.
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2. Eliminating vapor release from the fuel surface.
3. Separating the flames from the fuel surface.
Another class of fire fighting foanis is the synthetic detergent type.
These are sometimes referted to as high expansion foams because of their
expansion ratios in the order of 1:15 and 1:20. They use ordinary, air—
aspirating equipment.
These foams flow veil, are capable of rapid flame breakciown, and can gain
control of hydrocarbon fires at low .o moderate solution application
dt.nsitics. Ultra—high—expansion foam is produced in specialized equipment by
driving a high—volume air stream, by means of a fan, through a metal or
cloth grid which is continuously sprayed with a synthetic foam solution at a
predetermiaed rate and conrentration. Expansion ratios of 1:800 have been
achieved, depending upon the type and chemical composition of the foam as
well as its stabilizers.
Chemical foam is formed by the reaction of an alkaline material with an
acid in the presence of a stabilizer, The two products to mix come in either
powder form or a liquid solution. The acid solution is aluminum sulfate and
the alkaloid material is sodium bicarbonate. This foam is infrequent’_y used
due to the inconvenience of mixing plus the time delay required for
application. In addition, getting the foam on the fire requires special
application tools, which adds another delay factor.
hSSESSMENT
After the fire, access to areas possibly contamin ted by the fire must be
limited until the extent of contamination can be determined. This is
important to prevent further exposure to humans and to avoid transferring
contaminants to clean areas. Next step is to determine the extent and
relative degrees of contamin9tion of the area. The intent is to develop
4 uantitative information as input for the decisions in defining the nature
and extec .t of the decontamination and clean—up effort. Areas of
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contamination can be identified and boundarirs of the areas defined by visual
observation acd analytical deteruiiuation6. Whils combustion SOOt
characterized as a black. friable carbonaceous material nay be visible on
surfaces contaminated by a transformcr fire, the full extent of coataminatlon
will not be known until extensive wipe sampling has been com?leted. This
iuit al wipe sampling should focus or PCBs spread by the fire. PCEs—
contaminated areas can best be identified by collecting aufficient wi e
samples to delineate the extent of both vtrtical and horizontal contamination
in terms of mass per unit area of surface such as incg/l( O cm 2 or incg/v1 2 .
Sufficient wipe samples aldo must be obtained to determine background levels
for an area unaffected by the incident. These samples are necessary to
derive the relative degree of contamination by comparing the sample analyses
from the contaminated areas to the b ickgrouud level values.
While PCBs surface wipe samples are vseful in establishing the extent auU
degree of contamination, sampling for FCDFs and PCDDB is necessary to
establish an unequivocal as8essme it c Z the contaminat o ’. Bulk soot samples
obtained by vacuuming a unit area of surface are preferred for this analysis.
but wipe samples as described above may also be used. The sample should be
initielly submitted fo- a PCDF and PCDD isomer—group (mon.— through
octachioro compou.ids) analyois. If this analysis shows that the tetra— or
pentachloro isomer—gi ups are represeflted, them an isomer specific analysiB
should be conducted for 2,3,7,8-TCDD, hh2,3,7,8—PCDD, 1 ,2,3,7,8,9—HCDD,
2,3,7,8-TCDF and l,2,3,7,8—PCDF. The collection of air satnpl s for PCBs and
PCDFs or PCDDs may be necessary to define :he level of personnel protective
equipment used by clean—up workers.
REOCCUPANCY CRITERiA
There are no Federal guidelines to define acceptable clean—up levels for
toxic releases from PCB transformer fires. TSCA regulations do state,
however, that all spilla and leaks of PCBs should be cleaned up to pre—
ezisting background levels whenever there is a threat of contamination of
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water, food, feed or humau beings. NIOSH has found background levels in
urban areas up to 0.5 rncg PCBa per 100 cm 2 of surface area. In the absence
of certain PCDF and PCDD isomcr, the r.itlgation effort could be directed at
cleanup of the PCBs contarninatior to 0.5 mcg per 100 crn 2 of affected a:ea.
In terms of airborfle exposure, the NIOSH recommended guideline for the
work ’la e is 1.0 rnc PCEs per cubic meter of air.
The State of Hew York has proposed the follot .ing guideliceb for reentry
( ):
a Average Daily Intake (ADI) 2 pglkgld for 2,3,7,8—TCDD
• Air
— InhalaLio.t Lzposure 10 pg/rn 3 of 2,3,7,8—TCDD
9 pg/rn 3 of 2 ,3 ,) ,8—TCDF
a Surfaca
— Ingestion from Derm 1 Exrosure 3 ng/n (minirnum) — 28 ng/r 2
(ntaximu ) or 2,3,7 ,8—TCDb
12 ng/ n 2 (minimum) — llfl r ig/rn 2
(maximum) of 2,3,7,8—TCDF
In response to the One Market Plaza fire jucident clean—up, the San
rrancisco Health Department and the California State DepaLtme t of Health
Services issued the foIlovin guidelines for safe reentry levels;
a) for decontaminated areas (4):
o Air Exposure 10 pg/rn 3 f 2,3,7,8_PCDD/PCDF*
1.0 mcg,’rn of PCBa
• Surface Exposure 3 ng/m 2 o 2,3,7,8—PCDDs/PCDFs’
100 wc /m cf PCBs
b) for the area inside the PG E vault:
o Air exposure 80 pg/rn of 2,3,7,8—PCDDs/PCDFs
1 rncg/m’ of PCBs
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O ur ace ex [ esure 24 ngI i 2 of 2,3 ,7,8—PCDDs/PCDF&
1 ing/ of PCBs
* Above Dackground levels. All PCDD and PCDF levels excluding oct3—
CDDs/CDFs.
Reoccupancy criteria have also been evaluated ir Sweden and Finland. In
Sweden, the accepted surface guideline value was 50 ng,’m 2 of 2,3,7,8—TCDF.
Finlands reoccupancy criteria are still being diccusb d, but the suggested
surface guidelines are (5):
• 5 ngIra of 2,3 ,7 ,8—TCDF
• 50 ng/ 2 of total TCDF
• 5 ng/vi of 2,3 ,7,8—TCD!.
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REFERENCES
1. U.N. Cuv, G.R. Simpson and D.S. Siyali. Use and Health Effect8 of
Arocl.r 1242) a Polychiorinated Biphenyl, in an Electrical Industry.
Arch. Environ. Health, 31, pp. 189—194, (1976).
2. National I 8titute for Occupational Safety and iealth. Criteria for a
Recomn.eaded Standard: Occupational Exposure to Polychiorinateci
Bip!.enyis. Cj cj 3 j, Ohio: National Institu:c for Oceupetior.al Safety
and Health (1917). (DREW publication no. (N1O H) 77—225).
3. N.H. Kim and J. Hawley. Revised Risk Assessmeut Binghamton State Office
Building, New York State Department of Health, Albany, New York. June 7,
1983. (Draft)
4. M.F. Silverman, Director of Health of City and County of San Francisco.
Letter to V. Rose, District upet intendent Pacific C s & Electric
Company. November 17, 1983.
5. C. Reppe, University of t’mea. Letter to R.R. Huffaker, N w York State
Department of Health. October 19, 1983.
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SECTION 7
DE(:ONTAMIN/ TION OF BUILDING AND FINAL DISPOSAL
OF PCBs-CONTAIIINATED MATERIAL
BUILDING DECOLZTAMINATION
General Consideration
When a buildirg is being decontaminated follo ing an accident involving
toxic waterial such as PCBs, precaution must be takan before work ommenc.eq
to ensure that the presence of a toxic chemical will not cause pr3b]ems. The
decontarninz.tion must be carefully planned if it is to be safely carried out.
In comparing options fnr decontaminating and possibly dismantling a building
and its interior, it i important to consider 1111 the possible routes of
exposure to the tcxic chemical. These include:
o handling contaminated fixtures, materiaJa and contents of trie building,
• handling contaminated material during dismantlLng and decontamination
• transfer oi contaminated material
• preparing the t aterialc for transport
• transport of material
o handl og materials at the .n.sposal site
o final disposal
Three overall strategies are usually considered for the “clean—up” of 8
contaminated building (1). These are:
• construct3.on of a monolith
• comprehensive decontam!nation of the building, follc’wed by dismantling
and disposal I the contaminated wastes removed from the building
• containment of The contaminated 3olid materials as far as possible,
within the site
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Construction of a Monolith
The first option which needs to be considereo ic to leave the
contamiiated material in its present location, by turning the buJdir g into a
concrete momolith. Conbtructillg such a monolith involves:
• clean up loose debris and dismantle old ixtures and furniture and
place in containers
• coat all surfaces with polymeric coating material to prevent migration
of contamination during working
• coat the highly contaminated transforme:Icopacitor and other equipment
with a thick layer of resinous material in order to provide an addi
tional protection agairt 1 t aubs quent release
• reinforce outside wall ,; of the builoing, or that part of the building
which it is planned to retain
• fill the • uilding with concrete, taking care to fill all spaces
betv er pipes, etc.
• if desired, demolish those parts of the building ‘hich are both not
contaminated and not essential to the integrity of the monolith
• seal the monolith to prevent, as far as possible, the ingress of water
• landscape the nionoliti’.
The principal advantage of this apptoach is that it reduces cuntact of
the workers with the :ontaciinatcd area, once the loose debris has been
cleared and the surfaces coated. The disadvantages are many. It is impos-
sible to gnarantee that the mnolith will remain intact indefinitely. The
effects of weathering and/or flooding might lead to fissuring of the concrete
and water ingress, with a chance of leaching out. Socially, the monolith
will be aesthetically unattractive, nd vil . serve as an unwelcome reminder
of the accident.
Comprehensive Decontamination
Comprehensive decontamination of the building would have as its objective
the restoratiol of the building to its original use condition. Various
techuiçues are available for the decontamination of extern,.i surfaces, but
they are either difficult to apply to complex surfaces (e.g., mechanical
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meth ds, vac ’ iming), or they offer a l .igh riak of contarni.’atiug the workers
or the’ .Emviror.ment (e.g., solvent or steam cleaning).
Decontaminstion of the interior of the building and iti ducts, wirings
and plumbing pores even greater problems. Sc,me of the ducts con.ain tarry
deposits whic’ could be difficult to r’emov . Even if the conterts could be
safely removed, the internaj surfaces would still have to be decontaminated.
The success of s’ich an operation could no be adequately monitored, as it
would be impcsaib e to check all inte.nal surfaces for frcedom from PCBs,
PCDFs and PCDDs. rhus, even if comprehensive deconti,minatjon could be
achieved, it would still he necessary to dispose of the equipment as if it
contained some resid ,a coutariinatjon. Any decisijn to decon aminate ‘tz.xi—
mizea expoaure of the workers to the higi iest levels oi coctaminat ion and
generates larger quantities of highly contamina..ed liquid wastes fo’
disposal.
Direct Disposal
The third option is that of “direct disposal”. In this, no specific
attempt is made to remove contaminated material from the ducts and pipework.
The building is dismantled as directly as possible, the majority of the
contaminated materials being sevled into the origiTial ducts and pipes:
obviously any li” uids or loose soids encountered during dismantling are
removed and disposed of separately.
Couiparing direct disposal with the previous option of comprehensive
decontamination, the main advantage is that ‘iandling of the most highly
contaminated materials is minimized. The problems of dismantling are largely
common to both options. Transport and direct disposal yields mainly eq aip—
ment with contaminants sealed inside, while decontimination yields both
i.ominally cleam equipment and highly coutan’inated, mainly liquid, wastes.
Operations in PCBs transformer vaults have the potential to spread
contamination and put tue work force at tisk. The control techniques are
very similar to thoae used for disnantling plants contaminated with
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radioactivity, aebestos, mercury, etc. All these operations t some tine
involve taking contaminated items from a highly contaminated rone into a
clean zone in a safe manner.
Combustion soot from a transforuer fire is a black, friable carbonaceous
material tbit dc s not adhe—e strongly to surfa. es unless it has beert ground
in by pressure. Iaitiaj clean—up of the soot should be achieved by dry
vacuuming of both horizontal and vertical surfaces. Subacquently, the degree
of residual contem nation should ‘ ‘e determined by how much additional
ciean ng needs to bc’ done to comply with the established reoccupancy
criteria. During the initial clean—up phase, control zones arid p-ocedures
should be established and implemented to preveot redistribution of the soot
to other areas. For inatance, if the transformer incident involves a multi-
level building, high efficiency particulate filters should be installed in
the air circula. .jon system to prevent movement of soot from one floor to
another through the ,entilation ducts.
Nonionic and alkaline synthetic detergents have been used to effectively
decontaminate moat surfaces. The synthetic detergents have the advantages of
not having a flash or fire point, arid can be appied manually through power
acrubbera, power sprayers and steam cleaners. In addition, the detergent and
rinse (aormaJly water) solutions are easily picked up by vet vacuum cleaners
and treated to remove all toxic materials before being released to the sani-
tary BewOrs.
Ultimate cleen—up methods may involve washing surfaces with organic
solvents highl’ compatiL le with PCBs ouch as deodorized kerosene, methyl ene
chloride, or a mixture of l,l,l—trichloroethane and trichiorobeozenes.
Although these solvents may effectively decontaminate certain porous and non-
porous surfaces, they are not routinely used for t o reasons. First, the
Froblems as nciated with r u.oval and disposal of the spent decontaininant
material. Second, the generation of potentially high cond’entratioas of an
c rganic vapor that viii reduce the aervice life of the carbon cartridge
respirators used by clean—up workers.
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The use of an organic z olvent may even be inadequate to reduce the le e1
of surface contamination below the reoccupancy criteria. Concrete floora and
walls in transformer v ulta and switch gear rooms may occasionally be one
such example. In these situations, an elastoLleric , abrasion and flame
resistant sealant should be applied to the sdrfnces. Consideration also
should be given to applying such a secondary containment system to surfaces
in vaults and PCBs—equipmeot rooms prior to a failure incident. A secondary
containment system would facilitate both efficient recovery due to the de—
creased pcrosity of the surface and rapid clean—un.
Clean—up at the Binghamton State Office Building PCBs Transformer Fire Site
The Binghamton State Office Building forms a prominent central tower
within a goverumeutal building complex shared by the State of New Yerk, the
County of Broome 1 and the City of Binghamton. The State Office Building,
completed in the spring of 1973, rises 18 stories (260 feet) above street
level and has two sub—surface levels. Thirty—three State agencies normally
occupy Lhe State Office Building, with approximately 700 employees. The
following provides an overview in a chronological manner, the r.a3or efforts
undertaken and scheduled to resolve r.hc problems resulting from the fire.
Material was adopted from a progress report filed by the Office of General
Services of the St’te of New York in January 1983.
Cn Thursday 1 February 5, 1981, the Office of General Services (OG ) in
Aihany, was notified that there had been an electrica] fire and subsequent
power failure at the Binghamton State Office Building The fire occurred at
approximately 5 3O a.n., and the building was unoccupied with the exception
of a Security Guard and a Stationary Engineer.
Since the markings on ‘he tranuformer indicated that the oil contained
polychlc inated biphenyls (PCBa), the DOS engineering staff initiated
necessary action in accordance with the applicable regulations of the federal
Envirounental Protection Agency (EPA) and the New York State Department of
Emvirormeutal Conservation (DEC). New England Pollution Control (NEPCO)
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arrived mid—afternoon and, outfitted with protective fuita and r apiratorc,
began to clean the firor of the transformer room.
Workers eatablis)(•d a tenpora y electrical system, cleaning of the
meca.. . icsl equipment room proceeoed, and DEC Was contacted • to the proper
disposal of the hazardous materials. A complete Inspection of the building
revealed that a fine soot had been distributed throughout all areas of the
upper floors. Tbe estimated time required for cleon—uv was eztended from
several days to several weeks. I was also determined that the New York
State Department of Health would arrange to more fully charactcrl7.e the
chemical contents of Boot and air sauples. Sampling began ou Friday the 6th
and continued on a near daily basic through Februaiy 27th.
Early Saturday morning, the County Health Commissioner received the ce t
rest.lts. The samples contained 6—62 mcg/m” c.f PCBa and the so J
registered PCBa levels of from 10 to 20 percent. The County Iesith
Commissioner concluded that the air wao elativeIy clean in light of the fact
that levels were below the al2ow bIt. otandor ’ls promulgated by the
Occupational Safety and HeaPtb Mminietrijtion (OSHA). The tett resuLts were
relayed to OGS in Albhny along with samples to be tested further by the State
Health Department. Blood sampLes were taken. Personnel workLng sithin the
building continL.ed to wear respirators and air samples for testing were
collected on a regular basis.
On Sunday, February 8th, t ev Englsnd Pollution Control began the clean—up
of the overhead areas in the mechanical equipment rcom, 90 that the area
could again be used to house the power dir.tribut ion system. Teat results
indicated that the levels of PCBa contamination in the air samples were still
well within OSRA stondard .
Early during the week of the 9th, Department of Health staff iflBpected
the building, and arranged for the collection of additional soot and air
sazn .les. The DOll team also preseutci OCS with a Safety Plan which van
approved by the Occupational Safety and Health Act (29CFR) pro’;iding the
basic safety progrem for the operation. The Pla, 1dre&sed security, showers
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and change &reos , safety equipment, respiratory protection, and sampling
schemes. All surfacer. conta u,ated by soot and smoke partlcles ve’e to be
cleaned initially by a high—efficiency vacuum and washed with water and
detergent. Fzpo9ed aurfac.s no emi’ ’ cleaned; such as papers, carpets,
drapes, etc., were p.st in i1a tic bags and temoved to a storage area in the
sub—basement. Cleaned areas wtre sampled (or PCBa by i e testing. The
State issued icatructious to have all water discharged from the buildicg
during the cleaning deposited into 55-gallon barrels to await treatment and
final disposal.
By mid—week, in accordance wit i the Safety Pica, the collection of blood
samples rom all personnel who were working in or had entered i ’ .e building
c,as initiated.
It was during this week albO that the cleaning of the mechanical—
equipmenr room was completed and necessary temporary -:iectrical connections
cccompliAhed. The temporary power dietrit uti n system was ready for instal-
lation. Representatives from the Department of !nviroi u rntal Conser ation
(DEC) also arrived to provide technical assistance.
i y Friday, the P p rtment of Health iepor ec finding PCBs ir all soot
samples tested, indicating that the contamination was wide pread in the
building.
Based upon the findic , s of the Health e?artment teats, soot samples from
the basement and parking a:eos ve e taken. DEC took water samples for
testing Ir n the nearby Susquehenr.a Rivev and also supervised the preparation
of the 55-g*llon drums that were to be used fcr the shipment of debriB.
The State decided, during the ,,eek of February 16th, that based on the
test results from both the Depi .rtment of Health and Calson Technical
Services, the basement parktn a:ea t ould also be treated as a contaminated
areR. While waiting fe.. the definitive :eculta of the tests of the samples
caker from the parking gerage, precautionary nca urcv were t kcn. Revisions
to the Safety Plan were made ro that personnel would no longer enter and e t
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at the parking garage level. By that week, CECOS International, Inc., a
licensed waste disposal firm that had been hired by the State, had removed
220 barreh. of toxic waste from the buildi g for disposition i a secure and
certified landfill.
Repeat medical examinations were peri orwed u cleaning personnel and
others who were deternihed to have been exposed to any contaminated material.
furthermore, DEC commenced sa lir .g of ambient air to determine current PCB
levels.
On Thursday, Febru ary 19th, Nati’ nal Inatitute of Occupational Safety and
Uealth (NIOSH) representatives reviewed and approved the health and Safety
Plan and trained two OGS personnel to act as safety observers throughout the
clean—up effort.
Since the duTation of the clean—up etfort was not able to be definitively
determined, OGS began considering long—ten!J alternative office space in which
to continue b einess of governm nt.
On ‘ebruary 20th, DOll released its first at a1ytical report regarding
samples taken from the buildings, and on the week—end of February 21st,
Department of Health testing confirmed that PCBs contamination had been found
in samples taken from the parking garage area. DOll recommended that the area
be cleaned.
The next iay, clean—up of the parking garage began. After consultation
with 1 Zi and Hew En lacd Pollution Control, a treatment system for the water
discharged froa the building was constructed. since large volumes of water
would be generated b7 the cleaning procedures, a earnent plant was built, in
the sub—basement level of the parking garage. This treatment plant con-
sisted, at the tine, of two above ground swimming pooi initially having a
capaciLy of approximately 13,000 gallons each. The water was collected in
one pooi and pumped through two high rae sand filters to remove any large
particulate matter which might exi t. The water was then pumped into a
column of activated carbon and allowed o run through, by gravity, into the
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second pool. This water was then tested and, when acceptable chemical levels
were reached, was discharged into the sanitary sever system of the city in
accordance with the terms of the permit issued by the City of Binghamton.
This system has now been expanded to 3 pools.
On Wedaesday, Febiuary 25th, the State Health Department inforuied OCS
that their (DOE) analysis indicated that in addition to the previously
detected levels of PCBs, the soot also contained lesser amounts of dioxin and
diber zofuren. Upon being apprised of this information, it was determined
that a request for proposal (REP) to clean the b tilding would be developed by
the Office of General Services working in cooperation with the State Health
Department, Labor Department, and the Department of Enviroomental Conser-
vation, as well as appropriate Federal agencies and acknowledged experts.
Photodo.jmentation of the building’s condition began and, at the request
ot OGS, the Dep itment of Health began to assemble a panel of internationally
renowned chemists and physicians, to meet in early April in New York City, to
focus on medical issues related to the event.
DOll began taking samples of air on the buildings 7th floor from March
12th through March 18th.
During the week of March 16th, DEC tests of samples of air taken from
outside the building resulted in no measureable levels of PCBs. By that
time, DOll had circulated information on tox ology protocol for approval by
appropriate parties.
In that same week, the ‘ mbership of the expert panel was finalized. Its
members included physi . isns, chemists, toxicologists, epidemiologists, engi-
neers, and representatives from various federal and state agencies, as well
as Canada. The panel met at New Yorks Laguardia airport on April 3rd. Th
results of the expert panel meeting were used as the basis for a request or
proposal (RFP) from independent firms specializing 1.j the development of
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plans and the supervision of the execution of such plans regarding toxic
chemical decontamination projects.
On Wednesday) April 1, 1981, the Office of General Services hired Versar,
Inc., a Virginia—based engineering and research firm, specializing in working
with toxic and industrial chemicals, to advise and develop clean—up proce-
dures, air pollution control plans, and primary clean—up plans.
Events during the first week in April included Versar’s representative,
as well as members of the expert panel, arriving to tour the building. Their
recommendation was that further biological and ches.ical testing be done. At
the States reçuest, the National Institute of Occupational SafeLy and Health
agreed to act as lead agency in the implementation of the Medical
Surveillance Plan. On Wednesday, April 8th, Versar scientists arrived to
further assess the situation and discussed plans for the primary phase.
Two days later, State and local officials formed an Intergovernmenta l
Coordinating Group. The purpone of the group was to bring together, in a
formal setting, key personnel so there could be direct and effective exchange
of ideas and information.
063 began accepting bids on the Air Peliution Control System (APCS) on
July 23rd. The State expected to award the contract within a month’s tine.
The plans for the APCS were developed by Versar, Inc., for the Office of
General Services. This system was designed to control the flow of air in the
building by drawing it through a series of filters to remove pollutants and
toxic substances including dioxins and PCBs in both particulate and vapor
phases.
The second Intergovernmental Coordinating Group meeting was held on
August 10th iu Binghamton. The meeting was presided over by the Executive
Deputy Commissioner of OGS, and representatives from the Departments of
Health, Environmental Conservation, Labor 1 the Office of General Services,
Broome County and the City of Binghanton were present. Both the public and
the press were invited to the meeting. Topics on the meeting agenda included
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medical surveillance program, the air pollution control system and the
biobgical and chenital tests conducted by DOB.
The week of August 10th, as part of th’ Health 6 Safety Plan, OGS awarded
the contract for the construction of a trailer (entrance module) which would
control all passage into and out oi the b’iilding. The trailer would be
equipped with showers, decontamination areas, appropriate receptacles for the
disposal of contaminated protective clothing and laundry facilities.
On Tuesday evening, August 18th, fl81, a public meeting was held in
Bing1 amton to answer citizenC questions regarding any aspect of the States
plans or activities relating to the State Office Building. The meeting vas
presided over by the Commissioner of the Office of General Services. The
Commissioner of Environmental Conservation was also in attendance alcng with
Health Department staff and physicians. The Health & Sefety Plan and the Air
Pollution Control Plan were prescnted and discussed. The following week, the
Department of Health Commissioner held a meeting with the editorial board of
the local newspapers to inform them of the state activities and to clarify
any pertinent matters.
Toward the end of the month of August, th Office ‘if General Services
completed an Environmental Quality Review Act. The assesste’tt concluded that
the primary clean—up phase of the Binghamtnn State Office Building wculd not
have any significant adverse effect upon the environment.
The construction of an access corridor to connect the trailer to the
building, began on the week—end of August 29th. Workers readied the rooftop
for the Tuesday ins’ allat ion of the air filtration system. At this same
time, a medical surveillance program was initiated for all personnel who
would enter tha building for proposed activities outlned in the Hcalth and
Safety Plan.
On Tuesday, September 8th, a helicopter made four trips to the roof of
the State Office Building lifting two 2500 pound filtration units and two
pallets of asscciated equipment.
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Later in tnat month, equipment was moved inte the building for tests of
he filtration system. In accordance with t)’e Bealth and Safety Plan, six
engineers cnt red the building to monitor the testing and a Health and Safety
Officer va’ present. By the end of the month, the completed trailer arrived
and was :onnected to the building at the point of the corridor which had
previously been constructed.
The RFP for primary clean—up of the building was developed, put to bid
and awarded. Alluash, Inc. of Syracuse, N.Y. was the successful low bidder.
The primary clean—up ccnsists of three activities: the first, completing the
initj8l clean—up within the building; the second, removing soot from ceiling
panels and s’jrface s above those panels; and third, cleaning elevator shafts
avd mechanical chases.
By month’s end, a DOll physician had begun to hold regular Thursday and
Friday office hours in Binghamton f or the purpose of counseling and advising
any person having health—related questionS or any inquiry concerning the
Department of Health’s medical surveillance program.
In early December, tests performed on areas of the basement parking
garage were analyzed. The area was detennined to be clean and parking was
allowed in those areas.
The on—going testing of the venting efficiency of the Air Filtration
Pollution Control System was completed. Results of the extensive testing
shoved that the system worked effectively.
In discussions with the County consultant, additional monitoring proce-
dures weze developed. After review of all data and a general announcement,
the venting of the building through the Air Pollution Control System (APCS)
commenced February 1, 1982. The primary clean—up phase commenced and is
following the procedures outlined in the applicable plans.
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Safety of Personnel
The entry uodule provides for the safe entry and exit of those who must
enter the building and is constructed to inciude entry facilities, locker
areas, showers, rest rooms and security offices. The trailer is located at
the oasement level loading dock. The APCS creates a negative pressure
throughout the building and entry uodule innuring that the flow of air is
from the outside of the building, through the building, and finally filtered
through the APCS on the roof.
All personnel entering the building must wear protective clothing and a
full face respirator. The special clothing compribes socks, underwear,
sneakers and rubbers, coveralls, an outer “Tyvek” protective suit and both
cotton and rubber gloves. The respirator weighs approximately four pounds
and features both activated carbon and high efficiency particulate filters.
As personnel exit the building through the module, all protective clothing i
removed and thorough showers are taken. Respirators are cleaned and their
filters are replaced for future use. The outer suit, gloves and respirator
fil.tera are disposed of after each use.
Security
To insure maximum control of movement into, within and out of the struc—
ture, 24—hour a day security is maintained. Not only does the security staff
regulate personnel mcvement, bu’ also issues and inventories proper safety
clothing and equipment.
All secur ty systerns are tested twice weekly and are mc’nitored by
personnel in the central security office. The fire and smoke alarm system
will be autot etically activated in the event of any fire or smoke energency
in the building. Five doors in the building are designeted as emergency
exits and are wired for an alarm to sound should they be tampered with or
opened for any reason.
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Pressure gauges monitor the operetion of the APCSs. The apparatus is
checked daily and, it fc,r any reason the APCS should ralfunction, the moni-
toring devices wot.ld automatically notify the security office of de problem
and shut the APC3 down. In the event of a sjstem malfunction, a magnetic
door, located i i the entry module, would be released and shut autonatically,
to prevent any backlow of sir from the building to the outside.
Testi g fr Contamination
Ovor 265 small bottles and 30 large containers of boot from the buil ing
have been collected and delivered t the State Department of Hea’th for use
in the testing process. Additional soot samples are being collected on a
regular basis from above ceilings and other areas.
The APCSs are constantly cleaning the buildinf’s air as it filters
through both carbon and high efficiency particulate filters for purification
before its release to the atmosphere. Periodic testing of the air moving
through the system is performed and the system ’s falters are checked and
replaced as required.
Since considerable volumes of wastc ‘iater are generated by the cleaning
procedures, a water treutzaent system is in opernt ion at the sub—basement
level of the parking garage. This system consists of three above—ground
swimming pools 1 each having a capacity 01 13,000 gallons. The water is
collected in oae tank and runs to the second tank through high rate sand
filters which remove large particulates. The water then travels Lhrough a
series of activated carbon filters that remove dissolved contaminants. The
filtered water is dischar ed into the zanitary sewer system of the city after
it is found to be purified in accordance with the terms of the permit issued
by the City of Singhamtoa.
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Pestordtion and 2 ration of Building Sjstem
Electrical power was psrti ’Jy restored soon after the fire in February
of 1981. Fince that timer full electrical power wiLh tevaporary equipment ha
been restored and is being maintained.
The heat’ ng, ventilating and air conditioi ing system (IIVAC), which is
crucial to the clean—up, has been successfully restored to service. At
present, the building temperature is being maintained at between 50 and 60
degrees to allow cleaning personnel dressed in several layers of non—porous
and therefore hot clothing to efficiently pioceed with the clean—up.
The elevator system has been restored in phase a over the past few months
so that the systc’m is currently providing service that fulfills the require-•
ments of cleaning personnel.
All building systems are operating at levels that are satisfactory to the
overall ch aning operation.
0peratJ dures
Maintenance and operations personnel test and ready the building systems
each day before trie initial entry to the structure. Five cleaning “teams”,
each consisting o 11 personnel, including one foreman, ther begin their
work. Since no personnel are allowed to remain inside the building for
longer than 4 hours at ‘ ne time, the clearing crews work in shifts of
approximately hours and 50 minutes each. In addition to the cleaning
persounel, there are 5 State inspectors in the building during each shift.
They insure that the work already completed and the work in progiess is in
acc ,rdance with the clean—up standards.
As a means of both basic cleaning and preparing the building for more
intensive cleaning, all furniture has been vacuumed and remo ed from all
floors and placed in the sub—basement area. The following account of the
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amount of furniture and equipment vacuumed and relocated shows the magnitude
of the preliminary work:
930 desks 1.950 chairs 200 typewrjt—rs
2 tables 325 bookcases 15 pOstage m .chines
850 file cabinets 310 storage cabinets 15 copters
116 map files 190 stools 90 :e orders
100 luckers 52 benches 20 postage scales
120 racks 50 couches 40 adding machines
microfiche readera 15 computer terminals 400 miscellaneous items
Many other small items have been compacted and are destined for disposal.
Removal of draperies, carpets and blank ceiling panels ha been accom-
plished to provide for the most meticulous clean—up. These materials, as
well as loose paper and desktop items, have been removed to a secure landfill
at Niagara Falls. As of 0c..ob r 28, 19e2, 1,327 fifty—five a1lon drums and
approximately 1,200 cubic yarda of material had been remtved.
Since the building is not perfe:tly square, the ceiling pieces had been
customized for each floor. As piecea are removed and cleaned, each is coded
iii a way that will allow for jrs pctential reuse.
Many o’ the cleaning act .vitiea are intricate. For example, the cleaniug
of the light fixtures and air conditioning terminals, by workers dressed in
protective clothing, including two pairs of gloves, is an arduous and time
consvming task.
A vitally necessary project was and the positive identification of all
areas within the buLlding. Sin e it is cruciai that all persorn .l speak
pre isely and in common terms .hen speaking oe the building, all offices and
spaces within the building have been identified in a systematic, and certain
manner. The scheme for location identification has resulted in the highest
degree of control of information regardirg clean—up accomplishments.
There are two areas of the clean—up operation that rr’present maic tasks
in their own right. Thø fir st is the cleaning of intricate heating/cooling
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terminal boxes which includes the opening of the box, removal of insulation,
cleaniflg of the box and it8 c1c sing. Given the restrictions placed upon
clean—up personnel by both fhe required protective clothing and the vc iou8
smafl parts of the terminal boxes, the cleaning of such boxes t kes a rela-
tively long time. There are a total of 820 perimeter boxes with another 220
installed in the ceiling.
The second is the cleaning of light fixtures which number • pproximately
285 on each of the 18 floors. It takes nearly 90 minLte& to prepare one
fixture for cleanLng — that is to take it down, open it. and take out the
lighting element. It then takes over 2 hours to thoroughly clean the fixture
and tie tracks in the ceiling that hold the fixture. The time consumcd then
eq ials roughly 5,100 fixtures times an average 4 hours per fixture, or 20,600
man hours for this activity alone.
Preparation, cleaning and inspection represent a work day time span Srom
approximately 6 em, through 5:15 p.m.
Furthermore, the State’s constant demand for the highest quality work
requires — in every respect — a methodical and meticu1ou i process that cannot
be rusheu.
Records Destruction
Since the contamination within the building had affected the recoids and
other work papers kept i the building, the State Department of Health
advised that it would not be feasible to attempt to clean the documents.
Accordingly, the decision was made to destroy all paper records.
All documents scheduled for deotruction have been shredded or Ijled and,
if they are of a confiden:ial nature, their destruction by shredding has been
confirmed by witneoses. AL the request of the State Attorney General, a
limited number of documents have been located, segregated and temporarily
stored in the sub—l’asement due to their importance with regard to pending
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litigation. All contaminated materials — in whatever form they take — will
be transported to and disposed of at a secure disposal site.
9th and 16th Floors Used ar Sample Areas
Both the 9th and 16th f toots of the building have been completely cleaned
and serve at sample areas, while also providing personneL w’th the oppor—
tunity to experiment with different testing and cleaiing tectiniques. Vatious
experimental cleaning nethods have been employed o the sample floors and
those that pzo e succetsful will be used on the buildings other floors.
The followi..g is a listing of several activities and acconplishnents
which help illustrate the amount of work being performed insid2 the building
as of the week ending January 31, 1983:
o inveastory of all equipment and records in building
• removal of all furniture and office equipment to sub—basement
• opening of duct shafts to allow for cleaning
o shredding and baling of all paper materials
• removal of all carpet
• rcmoval of ..ll bathroom and corridor accessories
• installation of temporary core lighting on floors 3 through 18
• access and removal of exhaust ducts from rest rooms
o preliminary vaci .uming of exhaust duct shafts on menC room side
• removal of secondary duct bork in basement
o removal of insulation from terminal boxes in basecient
• removal of records and shelving from DOT storage room in
basement.
In the concluding atages of the preliminary clean—up operntion,
activities and actions were initiated to restore the Binghamton State Office
Building to a nornal operating mode. Activities undertaken can be classified
into two major groups:
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1. Mechanical/Operational activities
2. Medical/Scientific activities
The following items represent some of the activities which need to be
completed to ready the building for reoccupancy from a Mecttanical/Operational
perspective:
1. The current primary cleaning activity consists of the washing
and vacuuming of all office areas of the building to achieve a high
level of cleanliness. This activity included the removal of all
furniture from the floors as well as the removal of carpeting,
draperies, and other appointments. Additionally, lighting fixtures
and terminal boxes were removed from their normal stations, cc.m—
plctely cleaned and returned to their proper location. The existing
vinyl and ceramic tile flooring will also be removed.
2. As the primary cleaning program draws to conclusion, the
Binghamton State Office Building is than divided into basic work
areas as follows:
1. Upper Area — floors 2—18
2. Lower Area — below the secoad floor
The establishment of these areas enable the workmen to wore expedi-
tiously function in the Upper Area while mare exteasive cleaning
activities take place in the lower area.
3, Upon establishint that the air in the Upper Area meets the pre—
established standard for cleanliness, the need to continue air
filtration in that area will bc unr 1 es_essacy. This will permit the
reconfiguration of the APCS to reestablish normal building voqti—
lation in the Upper Area. The LPCS units on the roof will, be
relocated adjacent to the basement area to provide ongoisg effective
sir pollution control for the Lower Area of the building as they
have for the entire buiLding in the past.
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At the same time, ork. en viii no lc’ni er be required to wear the
full range of protective equipment n the Upper Area.
4. On.e the Upper ‘.red is eot. ibiishpd as above described, vor wen
nay begin their activiti c at a regular pace exped!ting the rate at
which build icg work may roniLnue.
Service projects to be comple:ed in this phase are related primarily
to the restoratioo of mechanical areas which were opened for
cleaning to insure against the exfiltration of any foreign materiala
which moy be left as a result of previoun a tivitie9.
It is anhicipated that all of I ese restoration act ivities viii take
approxiciate y 18 months to 24 months to conpiet’ from the dote on
which they are begun.
5. While the upper Area projects ore being completed as described
above, the Lower Area wil’ receive a thorough cltaning in accordance
with the provisions of the Health and Safety Plan which had pre-
viously been in existence for the entire facility. Workmen will
continue to wcai protective clothing and utilize the entry module to
insure maximum safe’ v and the APCS viii function as in the past.
While the workmen are active in this phase, they will be c. 1 .eantng
valid, ceilings and all other surfaces in the Lover ftrea.
Upon completion of Liis cleaning r ase, a new electrical tra. sforner
and related building mechanical and electrical equips ent will be
installed.
Waste material shall be concurrently removed to appropriate
Iandfii s.
It is anticipated that this Lower Area activity will take about 18
to 21. months fcr completion.
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While the ongoing work continues at the Binghamton State Office Building,
there will be bignhlicant additional activity) on an integrated basis, in the
?(edicai/Sc,eutific areas related to the u1t ate restorotioQ of the faciiity
to U6€ 85 o1lovi:
1. Ai sampling which was completed iste in l S2 f r dioxin nd
dibenz ofuran viii be repeated v3th the air handling systems of the
buiidin . in operation. Air sampling will be conducted .n the normal
operating zones of the ht oting , venting and air conditioning syStemB
to insure that ccmprehensive results are available for revic . All
rasulta viii be transmitted to the ExperL Panel fom. their commentS
and critique.
The first round of samples indicated that the fur n levels were
bracketing the levels established for reentry and that dioxin was
not detectable at the limits wL ch were the capacity of the testing
machinery. Repetition of the eamplen with the air handling systems
in operat ion and the taking of grea er air volumes viii allow for
ana1 sis an’I determinations which are representative of the air in
the facilit y as a vhoe. Results of these tests viii guide the
State in the final rehabiLtation of the faciIit .
2. Si. ilcr1y. C.ie ongoing tests consucted on the operation of the
APCS will continue for the entire period during which the APCS is
utilized.
3. The development of a new .ipe aample test is being coctinued to
mast closely duplicate the ae uai condition of everyday work life.
Similarly, the continuous monitoring of waste water and the saumpUng
of water utilized in the ciea, ing and held for purification and
disposal will continue throughoit tac utilization of the waste water
treatment o;’aten.
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4. The Ned .ca! Surveillance Program for workers will continue to
operat in sccordance with the Health and Safety Plz.n, thereby
requiring bimonthly physicals for tbos entering the lower ares. of
the builling and subsequent final and follow—up physical exami-
nations u n completion of a vorkers assignment within the
Binghain on State Office Building.
5. Purther, the monthly industri . l hygiene samples which now show
the PCBs levels below all previously established standards (at 0.2—
0.3 mcg/m 3 ) will be continued as work in the bt ilding novos forward.
Finnncial Data
The restoration of the Binghemtom StaLe Office Building is expected to
cost approximately $24 inilliou. This sum reflects payments for the Health
and Safety ProgramS building security, field operations, engLneering consul-
tations, investigations and risk analyses, waste removal plauning, APCS,
design fabrication, water treatment and sampling and analyses; testing, the
purchase and installation of the building entry moaule and support
facilities; installation of special security and alarm systems; boiler re—
pairc, chiller repairs and elevator equipment cooling; emergency electrical
work, rennvaticns and repairs at the Christophor Columbus School to provide
alternate office space; the primary clean—up contract, equipment, materials,
and staff; waste disposal, etc.
Clean—ui at the San Francisco One Market Plaza Office Building PCBs Tr,ns—
former Fire Site
Clean—up of the site cou.menced on May 16, 1983. Pacific Gas & Electric’s
(PG&E) clean—up contractor for the project is I.T. Corporation. The building
owners retained B.M.S. Catastrop ie, In ”., to conduct a clean—up of Floors 2
through 6 and stored tenant materials, to photocopy stored documents, and to
direct restoration of the air handling system.
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The building was evacuated and sealed off d!iring the fire. Ar ns exhi-
biting surface contanination outside the bui1 ing, were al&o cordoned off
pending clean—up. After extensive air and surface testing indicated no
contamination, most ground—floor areas and all of Floors 7 through 28 were
opened to normal ..ccupancy on May 25, 1963. Portions of Floor B—i were also
opened at that time. Floors 2 throii h 6 rew...in cosed pending restoration of
the air handling cystem. Floor B—2 anJ portioLu3 of Floor —l remain cloBed
pend±ng the results of the sampling after clean—up.
The methods of c ean—up or decontamination emp1oy d epcnaed on tue sur-
face involved and the level of contamination. Vacuuming was the first method
useG on surfaces such as concrete floors and walls, metal ducts, switch gear,
and a eetroc vjll&. Fuither cleaning included wiping these surfaces with
L.0.C. (Amway), Penetone Po ier Cl aner 155, or freon when vacuumiog wa not
sufficient.
The clean—up of the 250,000 square feet of Floors 2 through 6 by B.M.S.
Catastrophe, Inc .., took seven months and cost $10 million. Complicated items
to clean, such as cooling coils, electrical switch gear and electronic con-
trol panels were cleaned using a high pressure freon spray. Concrete floors
were further citaned when necessary, by coating with a peelable ad rbant
which was peelea off to remove any remaining cot.tainination. Concrete sur-
faces in pro4cimity to the vault were painted with r sealant as a post—
rleaning measure. The vault itself was virtually rebuilt due to the high
contamination levels. Reinforced concrete s- faces in the vault were sand—
blasted, jackhammered nd scabbled to remove contamiL.a ion. Concrete block
walls weie torn down and replaced.
Three charcoal air cleaning systems were used to remove airborne contami-
nation, and to filter ai rele’sed to the a moephere. RemovaJ efficiencies
of these systems were generally greater than 99.9 percent for air rele ed to
the outside.
For final disposal of hazardous waste solid and low—level wastes, the
waste was transported by registered hazardous waste hauler to the Kettleman
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Hills Disposal Facility near Kettlen an City, Ca!.ifornia operated by Chem—
WISt9 Mana ,cc ent or to the Casmalia Disposal site near Santa Barbara,
California. } igh—level liquid wastes were .3hipped for incineration t EPA—
approved sitor.
A BRIEF REVIEW OF DISPOSAL ThCBNOLOCY FOR PCBs-CONTA}fIKATED MATERIAL
As regulations g’verning the dis osa1 of PCBs and PCBs—contaninated
equ pcient grow more stringent, a number of technologies end methods hava been
developed to destroy and dispc,se of PCts. They include:
(1) Chemical Waste 1i ndf ills
(2) Chemicaj ethods
(3) Land—Based Incineration
(4) High Efficiency Boilers and Cement Kilos
(5) At—Sea Incineration.
Chemical Waste Landfills
From a practical point of view, the mo:,t effective method currently
available by which a PCDDs- and FCDFa—contaminated waste could be secured is
disposal in approved hazardous waste landfills. For instance, solid and lo t—
leve’ contaminated • astes from the One larket Plaza San Francisco clean-up
operation were dis2osed in the Kettleiian Hills Disposal Facility near
Kettleinan City. The integrity of the l ndfill is influen d by the type of
materiel used to line the la dfiJl. Clayey, silty, and alJuvial soils have a
strong affinity ‘ r TCDD. This affinity has bc”n demonstrated in areas where
TCDD contamination has become w2ll known, s ch as Seveso, Italy (ICHESA), and
Aurora, Missouri (Denney Farm Site). The appropriate liner material woul
thus function as an adsorbent as well as a flow barrier for contaminants
which escape from their original containers. Waste containing oils and
solvents which might increase the mobility of PCBs, PCDDS, and PCDFG in soil
should not be disposed of in the section of the landfill containing
contaminated material from transformer/capacitor fires.
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Chemical Methods
Alk 1ine dehydrochiorination is a generic term for several new chemical
processes for treatir.g hazardous chlorinated hydrocarbon liquid wasten, in-
cluding PCBs. Of the many processes, only the Vertac Chemical Company of
lemphia, Tennessee, process has been tested on TCDD nnd other cF lorinated
dioxins. The other pro.esses are designed to treat PCBs.
The Vert ic process i.nvolves the dehalogenation of chlorinated dioxins
with anhydrous alkali metal salts of polyhydroxy alcohols at atmospheric
pressure. Deh alogenatjon may also be accomplished by reacting a mixture of
chlorinated dioxins, an alc.ohol, and a water solution of an alkali metal
hydroxide. Vertac claims that 2,3,7,8—TCDD and chlorinated diozins concen—
tratione are reduced to essentially zero (2).
The Gc odyear Tire and Rubber Con pany has invented a process to remove
PCBs from heat transfer fluids and claims that it reduces PCB levels to less
than 10 ppm from a high level of more than 500 ppm (3). It ppeirs t be
based on research conducted earlier by Oku, et al. (4), where sodium naph—
thalenate as found to be a remarkable dechlorination agent for PCBs.
The Franklin Institute has developed a similar process for alkaline
dehydrochiorination of PCBs (5). The process first makes sodium glycolate
(NaPEG) from molten sodium and polyethylene glycol. NaPEG acts as a super—
base and reacts with chlorine atoms in PCBs. l aPEG—containing PCBs go to a
separate vessel and are exposed to air; and oxygen completes the PCBs break-
down. Any remaining chlorine is replaced ) y oxygenated compounds ‘ hich form
oxygenated biphenyls; sodium chloride is the by—product. In tests with
soils, NaPEG has reduced PCB concentrations from 1.000 ppm to 481 ppm after
53 days. One drawback with NaPEG is its inability to function effectively in
soils containing more than ?Z moisture (6).
Sunohio has also developed a reagent process for treating PCBb and has
developed units that can be mounted on tractor trailers and moved to a waste
site. Sunohio claims that its process reduced PCBs levels in transformer oil
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from 1,000 ppm to 1 ppm and from a high of 10,000 ppr to 50 ppm——all in one
pass (3). The Sunohio PCBX process has received EPA approval as a nears of
removing PCBs from transformer oils.
Ontario ilydro has developed a process where PCBs c4estruction is achieved
by reaction with mo1te’ sodium. In this proces8 water content of askarel—
contaminated oil is reduced to less than 100 mg/kg. PCBs and other chlori-
nated cumpounde are then destroye’ over a period of 15—60 minutes by reactng
them with finely dispersed woltea metallic sodium at temperatures in the
range of 120—140°C. The mixture is then centrifuged to remove excess sodium,
insoluble reaction products and s]udge.
Wescinghouse research has found that PCSs can be dechlorinated by using
sodium hydride and alkylamine. This process (if found feasible) hab a rapid
reaction rate under relatively mild conditions. It is inexpensive with
common and available reagents and does not require special pressure vessels
(7).
Acurex Waste Technologies, Inc., and SED, Inc., have developed sodium—
based reagents to treat PCBa. Acurex is building a portable 250 gal/hr
demonstration unit to be mounted on a 35—foot lcng trailer; SED is building a
waste treatment plBnt in Greensboro, North Carolina (4, 8).
Finally, professore at the University of Georgia have re;orted that there
are over 20 different bacteria capable of breaking down PCBs irto water and
carbon dioxide in 90—130 days (9). They are presefltly looking at ways to
speed up the process. ‘eneral Electric has already patented a bacteria that
consusies oil (10). Another firm, Polybac Corporation, as several organic
spill control producto on the market that employ the use of microorgan 8ms to
degrade oil. The products contain stabilized microbial organisms in
suspended amiv ti n. The organisms when hydrated on spills of oil reactivate
and metabolize spilled materials (10).
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Land—Based Inr n ration
Uighly contaminated we tes can be destroyed in incinerators. Th ’
incineration process is quite complex acid the destruction efficiency depends
on the physical and checnical characteristics of the waste, the combustion
temperature, reaLdesce time and feed conditions. Sir.cc the design features
and rapabilities of the majtJr types of incinerators differ widely, no single
incinerator can be used for all wastes. For each type of waste, the right
incinerator nuat be used under the correct temperature and residence time
conditions in order to achif’ve complete ‘waste destruction.
At leant two commercial iu:inerators have been authorized by the USEPA
for PCBs destruction — one at Deer Pork, Texas, and the other at El Dc’tado,
Arkuneas. Teat burns at he El Dorado site showed that 99.99992 ef PCBs and
their toxic by—products were destroyed, and dioxins and furans were detected
at the very Low ppb levels.
ii .zJi Efficien Boilers Cement iUM
The disposal alternative of using high efficiency boilers is restricted
to PCB—contaaiiaated mineral oil of low PCBs concentration (50—500 ppw) and
offers a substantial r&luction in disposal costs.
Accordiig ro the USEPAs final r 1ing on the disposAl of PCBs, waste oils
that contain PCBs in the rang of 50—500 ppm can be fired with fuel oil and
burned in a high eficien -j icidustr,al boiler (11). In May 1980, waste oil
containing approximately 500 ppm PCBe was co—fired in accordance with the
applicable state and federal regulations. This combustion took place in a
high efficiency boiler owned by Geneal tfotors Corporation in Bay City,
Michigan (12). PCB destruction efficiency was detercin’ d to be > 99.992
during the evaluation. toiler residue PCB lt vel was ( 1 ppm. No TCDD or
TCDF was detected in stacy samples at tn? iiclte of detection.
The USEPA is also conductirii tests for incineration of vantes using
cement kline, If thene tests prove successful, cement kilne may also be
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employed in the f iture for the destruction of PCBs—coitamina ted material.
Limited duration trials with PCB wastes have takei place outside the U.S.
Besides the obvious economic reasons for a cement plant to engage in PCB—
va5te disposal, a number of complications are associated with the procedure.
These include:
• confidence in staff industrial hygiene safety
• control of variable quality of the second fuel
• potential for rings and plt ggin due to excessive chlorine
• need for extensive contingency plans
• control of vast transportation traffic
• management of analysis requirements and inventories
o impact of public controversy on basic business.
At—Sea Incineration
At—sea incineration of comhust b1e cblori ,ated waste has been carried out
for many years in Euro [ e aboard incinerator ships, most notably the K/B
VESTA. Incineration—at—sea of chlorinated dioxins—containjriated materials was
first performed in 1977, aboard the vessel MIT Vulcanus , This ship was
utilized to incinerate three shiploads of Agent Orange, totalling 10,400
metric tons, in the Pacific Ocear. west of the Johnston Atolls. More
recently, the M/T Vulcanus has been employed for the incineration of PCBs.
The MIT Vu .canus is the only incineration vessel that has been employed
to incinerate PCBs and chlorinated dioxins-contamjnated materials. Addi-
tional ships are expected. At—Sea Incineration, Inc. of New Jersey,
supported in part by the U.S. Maritime Administration, has announced plans
fcr the construction of ships specifically designed for chlorinated hazardous
waste.
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