«>EPA
.United States
Environmental Protection
Agency
"Office of Solid Waste
. and Emergency Response
(5104)
EPA 550-R-98-003
May 1998
www.epa.gbv
-•"5
•A- '"-. .' J
EPA CHEICAL
INVESTIGATION
REPORT ; : . - ' r- ;
Po we 11 D uf f ry n
Terminals, Inc.
Savannah, Georgia
Chemical Emergency Preparedness and Prevention Office
) Printed on recycled paper
-------
-------
The EPA Accident Investigation Program
EPA has a responsibility under section 112(r) of the Clean Air Act Amendments of 1990
for the prevention and mitigation of accidental releases. One of the fundamental ways to prevent
accidents is to understand why accidents occur and to apply the lessons learned to prevent future
incidents. Consequently, EPA has a responsibility to investigate and understand why certain
chemical accidents have occurred. A key objective of the EPA chemical accident investigation
program is to determine and report to the public the facts, conditions, circumstances, and causes
or probable causes of chemical accidents that resulted, or could have resulted, in a fatality, serious
injury, substantial property damage, or serious off-site impact, including a large scale evacuation
of the general public. The ultimate goal of the accident investigation is to determine the root
causes hi order to reduce the likelihood of recurrence, minimize the consequences associated with
accidental releases, and to make chemical production, processing, handling, and storage safer.
This report is a result of an EPA investigation to describe the accident, determine root causes and
contributing factors, and identify findings and recommendations.
In the EPA accident investigation report preparation process, companies mentioned in the
report are provided a draft of only the factual portions (no findings, conclusions or
recommendations) for their review for confidential business information. Federal agencies are
required by provisions of the Freedom of Information Act (FOIA), the Trade Secrets Act, and
Executive Order 12600 to protect confidential business information from public disclosure. As
part of this clearance process, companies often will provide additional factual information that
EPA considers and evaluates for possible inclusion hi the final report.
Chemical accident investigations by EPA Headquarters are conducted by the Chemical
Accident Investigation Team (CAIT) located in the Chemical Emergency Preparedness and
Prevention Office (CEPPO) at 401 M Street SW, Washington, DC 20460, 202-260-8600. More
information about CEPPO and the CAIT may be found at the CEPPO Homepage on the Internet
at "www.epa.gov/swercepp/". —-••
U.S. Chemical Safety and Hazard Investigation Board (CSB)
In 1990, the U.S. Chemical Safety and Hazard Investigation Board (CSB) was created as
an independent board in the amendments to the Clean Air Act. Modeled after the National
Transportation Safety Board (NTSB), the CSB was directed by Congress to conduct
investigations and report on findings regarding the causes of any accidental chemical releases
resulting hi a fatality, serious injury, or substantial property damages. In October 1997, Congress
authorized initial funding for the CSB. The CSB started its operations in January 1998 and has
begun several chemical accident investigations. More information about CSB may be found at the
CSB homepage on the Internet at "www.chemsafety.gov".
For those joint investigations begun by EPA and OSHA and prior to the initial funding of
the CSB, the agencies have committed to completing their ongoing investigations and issuing
public reports. Under their existing authorities, both EPA and OSHA will continue to have roles
-------
-11-
and responsibilities in respondhig to and investigating chemical accidents. The CSB, EPA, and
OSHA (as well as other agencies) are developing approaches for coordinating efforts to support
accident prevention programs and to minimize potential duplication of activities.
Basis of Decision to Investigate and for Involvement of EPA
An explosion and fire took place at the Powell Duffryn Terminals, Inc., Savannah,
Georgia, on April 10, 1995, resulting in extensive public evacuations and significant plant damage.
The accident involved flammable and toxic substances.1'2> 3 EPA and OSHA undertook
investigations of this accident because of the serious consequences and the opportunity for lessons
learned to prevent similar accidents from occurring. The EPA and OSHA coordinated their
investigations and shared their findings. However, OSHA did not take part in writing the report.
-------
-111-
EXECUTWE SUMMARY
On April 10, 1995, at approximately 11:30 p.m., explosions and fire occurred at Powell
Duffryn Terminals, Inc. (PDTI), a commercial bulk liquid chemical storage and transfer facility, in
Savannah, Georgia. Flames and thick black smoke from the fire forced the residents of the
adjacent townhome development to immediately evacuate. The company's office building on-site
was engulfed and destroyed in the fire. It took fire fighters almost three days to finally put out the
fire. The fire centered around a concrete walled enclosure area containing six large storage
tanks. During the fire, part of the enclosure wall was breached releasing contaminated fire water.
The runoff from the fire contaminated an adjacent marsh on the Savannah River resulting in a fish
kiU.
After the fire, chemicals leaking from the storage tanks in the enclosure area reacted and
produced toxic hydrogen sulfide gas. The hydrogen sulfide gas release forced residents within
one-half mile of the facility to evacuate. As many as 2,000 people were involved in the
evacuation. An elementary school nearby was also forced to close. Approximately 300 people
went to hospital emergency rooms complaining of symptoms attributed to hydrogen sulfide
exposure. For many nearby residents, the evacuation lasted more than 30 days because of the
continued evolution of hydrogen sulfide gas from the PDTI site. After the incident, extensive
cleanup of the site and neighboring area was required.
PDTI is fully enclosed by a security fence with locked gates. On April 10, 1995, the last
employee left the site for the day at 5:50 p.m.. The gates were locked, and no employees were
on-site until after the explosions and fire had occurred.
On the day of the fire, contractor employees had been installing a sealed foam chamber on
the storage tanks containing crude sulfate turpentine (CST), a flammable liquid. This closed the
CST tanks to the atmosphere and directed CST vapor to the vapor control (VC) system. The VC
system was designed to control fume and odor from the CST by capturing the CST vapor using
activated carbon in two fifty-gallon drums connected to the CST tanks using PVC piping.
According to PDTI modification plans, each CST storage tank was supposed to be equipped with
a flame arrester at its connection to the PVC piping. These flame arresters had been delivered but
had not yet been installed.. In addition, a fixed-piping foam fire protection system was not
completed at the time of the fire.
The explosions and fire at PDTI involved CST which the facility began to store on January
17, 1995. Prior to 1995, the facility was permitted only for storing non-flammable liquids. The
facility had not completed modifications to accommodate the storage of flammables when the fire
occurred. The CST was stored in three storage tanks (two 237,000 and one 422, 000 gallon
capacity) in a walled enclosure that contained a total of six tanks. The three CST storage tanks
were connected by the partially completed VC system used to remove CST vapor from any
venting that may occur. In the same enclosure were three other storage tanks (one 340,000 and
two 323,000 gallon respectively) containing sodium hydrosulfide solution (pH 10.4 to 11.5);
Briquest, an acidic cleaning solution (pH of 1); and Antiblaze 80, a fire retardant chemical. These
-------
-IV-
tanks and associated pipes were damaged by the explosions and fire and leaked their contents into
the six-tank enclosure area. Reaction of the sodium hydrosulfide with acids present in the
enclosure area produced hydrogen sulfide, a toxic, foul-smelling gas.
The CATT identified the following as root causes and contributing factors in the accident:
• The design for the VC system was inadequate. There is a history of fires in drums
containing activated carbon where the VC system design permitted the backflow of
outside air through the drums. Organic sulfur compounds in CST can produce heat when
they are adsorbed by the activated carbon. Enough heat may be produced in the drums to
raise the temperature above the autoignition temperature of CST. Since there is a limited
amount of oxygen in the drums, a fire usually does not occur. However, if outside air is
permitted to be drawn through the drums containing activated carbon, as when CST is
withdrawn from the storage tank or when ambient temperature drops causing the vapor in
the storage tanks to contract, air can provide oxygen needed for combustion and the CST
vapor in the drums may ignite triggering a fire. (The solution for preventing the backflow
of outside air into the drums is to install a one-way valve between the drums and the
storage tanks that would permit air to enter the storage tanks without going through the
carbon drums.)
• The storage tanks were not equipped with flame arresters. The PVC piping provided a
conduit for the fire to travel from the carbon drums to the CST storage tanks. Flame
arresters were included in the design of the VC system. However, CST storage began
before the modifications were completed. At the time of the fire, the flame arresters were
on-site but had not been installed.
• The foam fire suppression system was not completed on the tanks containing CST. Foam
fire suppression system was included as part of changes to be made for storing
flammables. CST storage had begun before modifications were completed. Fire fighters
were not able to use the foam pumper connection outside the enclosure area. Fire fighters
used water to fight the fire until a connection to the foam pumper could be rigged within
the enclosure area. An operational foam fire suppression system could have reduced the
amount of time required to suppress the fire and reduce the amount of heat damage to the
adjacent storage tanks and limited the amount of runoff from fire water which
contaminated sensitive wetland area along the Savannah River.
• The concrete containment wall was breached as a result of heat from the fire. The
enclosure area had been used to store nonflammables. No modifications were made to the
secondary containment before commencing storage of flammables.
• Incompatible chemicals were stored in the same walled enclosure area. Sodium
hydrosulfide solution was stored in the same enclosure area as acidic cleaning solution
resulting in production of toxic hydrogen Sulfide vapor when the tanks leaked. The toxic
-------
-V-
hydrogen sulfide release caused injuries, forced extended evacuations, and hampered
response and cleanup.
Based on the root causes and contributing factors of this accident described above, the
CATT provides the following recommendations to prevent accidents like this one from occurring
in the future at this and other facilities:
• Facilities designing or adding on environmental control, fire safety, or hazard control
systems, must ensure that these systems do not adversely impact the processes or
equipment where they are to be added and that they are properly designed and installed.
Designs should be reviewed by competent professionals or recognized experts. The
hazards associated with the new systems and the impact of the new system on the
existing systems should be thoroughly assessed. There are many formal hazard
evaluation techniques available (such as HAZOP or What If) that can facilitate this
assessment.
• Facilities using activated carbon systems, in conjunction with vendors or recognized
experts, should conduct tests to determine the potential for formation of hot spots,
runaway reactions, or other consequences associated with adsorption of vapors on
activated carbon and ensure that the hazards associated with the heat of adsorption are
identified, well understood, and addressed through safeguards, procedures, or other
controls. An evaluation of the potential for, and the consequences associated with, air
being drawn into a carbon adsorption system (for example, associated with normal tank
breathing) must also be addressed as necessary through safeguards or other controls.
• Facilities storing flammable and combustible materials must evaluate and ensure that the
storage tanks and venting systems are protected from potential fire or explosion
propagation back into the tank from external fire or ignition sources.
• Facilities must ensure that equipment for use in handling hazardous substances is
equipped with the proper safety devices, and in compliance with national, state, and local
fire and hazardous material safety codes and standards before hazardous materials are
handled in such equipment. The safeguards, safety devices, or emergency systems
designed to prevent or protect the equipment must be in place and fully operational as
intended prior to startup of the equipment.
• Facilities should examine process and storage areas and equipment to ensure that
potentially incompatible substances are kept separated. Leaks or spills of incompatible
substances from equipment should not go into the same containment or other areas as a
result of fire or other incident.
In addition to the root causes and contributing factors of this accident described above,
the CAIT makes the following recommendations based on potential problem areas found during
the investigation.
-------
-VI-
Facilities should evaluate the need for bonding and grounding to prevent the buildup and
discharge of static electrical charges that could provide an ignition source. If used,
ensure that bonding and grounding devices are properly designed, installed, maintained,
inspected, and tested.
Facilities must ensure that electrical devices and equipment in areas where flammable or
explosive materials are handled are properly designed, installed, maintained, tested,
inspected and operated, and meet codes and standards to prevent potential ignition
sources.
-------
-Vll-
Table of Contents
Page
1.0 Background 1
1.1 Facility Information 1
1.2. Physical Layout 1
1.3 Chemical Information 4
1.4 Process Information and Status Before Accident 5
2.0 Description of the Accident 9
3.0 Analysis and Significant Facts 14
3.1 Analysis 14
3.2 Significant Facts 14
4.0 Causes of the Accident 17
4.1 Most Likely Scenario 17
4.2 Other Possible Scenarios 19
4.3 Factors that Contributed to the Consequences 20
4.4 Root Causes and Contributing Factors 21
5.0 Recommendations 23
References 25
Appendices
A EPA personnel Participating in Accident Investigation and Report Development ... A-l
B Material Safety Data Sheets for Chemicals Stored in the Containment Area B-l
C Article on Carbon Drum Systems Applicable to Crude Sulfate Turpentine C-l
D Chemical Safety Alert - Fire Hazard from Carbon Adsorption Deodorizing System . D-l
-------
-viii-
List of Exhibits
Page
1 Powell Duffryn Terminals Site 2
2 Six-Tank Enclosure Area 3
3 Vapor Control System 7
4. Carbon Drums 8
5. Fixed Piping Foam Fire Protection System 10
6. Area of Fire and Firefighting Efforts 12
7 Area of Fire and Oaktree Townhomes 12
8 Area of Fire and Savannah River 13
9 Burned-out Tanks and Pool of Contaminated Water 13
10 Event and Causal Factors Diagram 18
-------
-1-
1.0 BACKGROUND
1.1 Facility Information
Powell Duffryn Terminals, Inc., (PDTI) of Savannah, GA, is a subsidiary of the Powell
Duffryn Company of the United Kingdom. PDTI is a commercial bulk liquid chemical storage
and transfer facility (i.e., a tank farm), primarily for chemicals used in the pulp and paper
industry. The company provides chemical storage as a "third party," serving chemical suppliers
and purchasers of the suppliers' chemicals. PDTI has facilities for shipping and receiving by
truck, rail, and water.4'5
PDTI is located about two miles from the middle of downtown Savannah, just northeast
of the city limits of Savannah. The site covers about six acres and is situated along the banks of
the Savannah River, which is to the north of the site.6
Oaktree Townhomes, a residential development, borders the PDTI property on the south;
the two properties share a common property line. The PDTI property is bordered on the west by
Wahlstrom Road, on the north by a CSX Railroad track, and on the east by marshlands. The
property is surrounded by a chain link fence with concertina wire on top. Numerous commercial
industrial facilities also operate in the general area. In addition, the Eli Whitney Elementary
School is located in the area.6'7
1.2 Physical Layout
The fire and explosion centered around six storage tanks surrounded by a five-foot
concrete wall. These are the only storage tanks on-site enclosed by a containment wall. The six
steel storage tanks in the enclosure area have capacities ranging from approximately 240,000 to
420,000 gallons. Exhibit 1 is a map of the area of PDTI showing the site of the explosion and
fire in relation to the Savannah River, Oaktree Townhomes, and Whitney Elementary School.
(The tanks and walled enclosure area are indicated in the exhibit as six small ckcles enclosed in a
rectangle.)8
The six-tank enclosure area is about 100 by 200 feet (20,000 square feet in area). A
diagram of the enclosure area along with the approximate capacity and contents of each tank is
presented in Exhibit 2. The enclosure area is located slightly north of the midpoint of Powell
Duffryn's southern property line. Five other tanks, much larger than the tanks in the enclosure,
are located to the north and east of the enclosure.8'9 (These other tanks are also shown in Exhibit
1.)
-------
-2-
Exhibit 1
Powell Duffryn Terminal Site
Powell Duffryn
Storage Site
City of Savannah
Whitney Elementary School
Not to Scale
-------
Exhibit 2
Six-Tank Enclosure, Site of Fire
(100 x 200 feet, surrounded by 5-foot Concrete Berm)
TANK 23
» 237,000 gal.
capacity
• contained
210,000 gal. of
Crude Sulfate
Turpentine
TANK 21
• 323,000 gal.
capacity
• contained
240,000 gal. of
Briquest
TANK 19
• 421,000 gal.
capacity
• contained
340,000 gal. of
45% Sodium
Hydrosufide
.solution
TANK 22
• 237,000 gal.
capacity
• contained
210,000 gal. of
Crude Sulfate
Turpentine
TANK 20
• 323,000 gal.
capacity
• contained
260,000 gal. of
Antiblaze-80
TANK 18
• 422,000 gal.
capacity
• contained
210,000 gal. of
Crude Sulfate
Turpentine
-------
-4-
The six tanks in the enclosure were constructed in their present location in April 1992.4
They were constructed in accordance with API-650 standards of the American Petroleum
Institute. Each of the six tanks in the enclosure was built with a weak-seam roof. The walls are
welded on both the inside and the outside, but, as a safety factor, the roof is welded only on one
side, the outside, and is designed to break if over pressurization occurs. In the event of a fire,
these tanks are designed to contain the product and to collapse inward as the product burns off
and the interior product level drops. The tanks were constructed with one-quarter to one-half
inch carbon steel walls.7
1.3 Chemical Information
The chemicals being stored at PDTI inside the enclosure area where the fire occurred are
shown in the table below. The quantities of the chemicals and the tank capacities shown in the
table are approximate.
Chemical7'8'10
Crude sulfate
turpentine (CST)
Sodium
hydrosulfide
(NaSH), 45
percent solution in
water
Briquest, a
cleaning agent (1-
hydroxyethane-
1,1-diphosphonic
acid)
Antiblaze 80, a fire
retardant (tris(l-
chloro-2-
propyl)phosphate)
Location7'8'10
Tanks 18, 22,
&23
Tank 19
Tank 21
Tank 20
Quantity7'10
(gallons)
Tank 18: 210,000
Tank 22: 210,000
Tank 23: 210,000
340,000
270,000
260,000
Tank Capacity12
(gallons)
Tank 18: 422,000
Tank 22: 237,000
Tank 23: 237,000
421,000
323,000
323,000
Hazardous
Properties
Flammable,
volatile13
Alkaline,
corrosive
(pH of 10.4
toll.5)14'15
Acidic,
corrosive
(pH of I)16
Relatively
non-
hazardous17
Crude sulfate turpentine (CST), the substance involved in the fire and explosion, is an
impure form of turpentine produced as a byproduct of the "kraft" pulping process, also known as
the sulfate process. CST is classified as a Class 1C flammable liquid; this class includes liquids
with flash points at or above 73° F (22.8° C) and below 100° F (37.8° C). The flash point of CST
may vary somewhat with composition. It is reported by various sources as 75° - 100° F (24° -
-------
-5-
38° C) or 90° - 115° F (32° - 46° C). The boiling point of CST is 310° - 340° F (154° - 171° C).
Its lower explosive limit (LEL) is 0.8 percent by volume. Turpentine (the primary component of
CST) has an autoignition temperature of 488° F (253° C). CST contains volatile sulfur
contaminants (e.g., sulfides and mercaptans); it is a dermal, eye, and pulmonary irritant; and has a
strong odor.13> 18
Sodium hydrosulfide solution, stored in the same enclosure, is strongly alkaline (pH of
10.4 to 11.5) and corrosive. When sodium hydrosulfide is exposed to heat or mixed with an acid
(e.g., Briquest), hydrogen sulfide, a toxic gas, can be produced. During the fire hydrogen sulfide
was probably produced as a result of the heat from the fire. Since hydrogen sulfide is
combustible, hydrogen sulfide produced from heating was probably consumed in the fire. After
the fire, the reaction between the sodium hydrosulfide solution and acids in the enclosure area is
most likely the source of the hydrogen sulfide released at the PDTI site. As shown in Exhibit 2,
Tank 19, containing sodium hydrosulfide, and Tank 21, containing Briquest, were located next
to each other in the enclosure.15
Briquest is a strong acid (with pH of 1) and, as an acid, it is corrosive. Phosphine (a
toxic gas) potentially can be produced if Briquest is heated to temperatures above 200° C (390°
F). There is no evidence that phosphine was generated at the PDTI site. Phosphine is
combustible; had it been produced, it could have been quickly consumed in the fire.16
Antiblaze 80 is nonflammable and relatively nontoxic and non-reactive. There is no
evidence that any leakage of Antiblaze 80 contributed to the consequences of the fire.17
Appendix B contains Material Safety Data Sheets (MSDS) for the substances stored in
the six-tank enclosure.
1.4 Process Information and Status Before Accident
The Chatham County Department of Inspections and the Savannah Fire Department have
responsibilities for the review and approval or disapproval of operations, construction, structural
modifications, fire protection systems, and electrical systems at facilities in the Savannah area,
including PDTI. The Georgia State Fire Marshal's Office and the Georgia Department of
Natural Resources, Environmental Protection Division, also have various regulatory and
permitting authorities. n-19
In 1994, PDTI requested approval for storage of CST on-site from the Fire Inspector for
the Chatham County Department of Inspections.20'21 The Chatham County Department of
Inspections, with technical assistance from the Savannah Fire Department, evaluated the impact
and required changes in equipment and procedures. The Chatham County Department of
Inspections and the Savannah Fire Department shared this information with PDTT as PDTI was
designing its activated carbon drum VC system.22
-------
-6-
In December 1994, the Chatham County Department of Inspections informed PDTI in
writing that there would be no problems with the storage of CST at PDTI if the following
stipulations were met:22
(1) A fixed foam piping system must be provided;
(2) This system must be installed according to NFPA 11, Standard for Low-
Expansion Foam, and NFPA 30, Flammable and Combustible Liquids Code, and
others, if applicable;
(3) The pumper connection for this system must be outside the enclosure area;
(4) A foam induction system must be built into the piping, and enough of the
recommended foam for this product (i.e., CST) to furnish the recommended
applications for the minimum time must be on site and available to the Fire
Department; and
(5) The piping connections must be compatible with the Fire Department's.
On December 22,1994, PDTI wrote to the Savannah Fire Department that all
requirements would be met and that CST would be stored for about six weeks until the fixed
piping foam fire protection system could be completed.23 On January 17, 1995, PDTI began to
store CST in Tank 22; by February or March, CST was stored in three tanks.4 The fire and
explosions occurred on April 10, 1995, about 16 weeks after the date which PDTI indicated it
would finish its safety system as required by the Savannah Fire Department.
On January 27,1995, PDTI submitted to the Georgia Department of Natural Resources,
Environmental Protection Division, a notification and application for storage and transfer of
turpentine. The notification indicated that PDTI would connect the storage tanks together with
piping and route the vapor through drums of activated carbon to control odor.24
The vapor control (VC) system and fixed piping foam fire protection system, designed by
a PDTI employee, are described below.4'5< 25> 26
Vapor Control (VC) System for Reducing Vapor Emission and Odor
Prior to the accident, contract personnel were in the process of installing a VC system.
(See Exhibits 3 and 4) This system was designed to prevent CST vapor from escaping into the
environment as a result of volumetric expansion due to increasing ambient temperatures or
during tank filling. PDTI installed this system in response to repeated complaints from
neighboring residents of strong odor arising from the facility.
The system consisted of two metal drums (50-gallon size) containing activated carbon
used for absorbing CST vapor, polyvinyl chloride (PVC) piping connecting the drums to the
three flame arresters, and three pressure release vents located on the storage tanks.M It was
intended that vapor from the tanks would travel through the flame arresters to the PVC piping
that was mounted to existing cat walks and enter two drums of activated carbon located at
ground level just outside of the enclosure area. Each tank was supposed to be equipped with a
-------
-7-
Exhibit 3. Vapor Control System
-------
-8-
Exhibit4. Carbon Drums
9s
-------
-9-
flame arrester at its connection to the PVC pipe; however, at the time of the accident, the flame
arresters were not installed. The VC system was in place, with the exception of the flame
arresters, for more than a month before the accident. Piping "spools" (small fixed sections) were
installed in place of the flame arresters. (However, the system was not completely closed to the
atmosphere until the last foamer was installed and sealed at 2 p.m. on the afternoon of the
accident - see below.)
Fixed Piping Foam Fire Protection System
On the day of the accident, contractors were installing a fixed piping foam fire protection
system on the tanks storing CST. (See Exhibit 5) This system consisted of carbon steel piping
separately connected to a foamer unit at the top of each CST tank. The foamers were bolted
over an opening on the side wall of each tank where the side wall meets the roof. The pipes
were supported by brackets anchored to the concrete wall of the enclosure and joined together at
a header approximately 50 feet from Tank 23. At the header, valves were to be provided for
connecting fire department hoses.26 The system was intended to enable the fire department to
apply foam, from outside of the enclosure, directly into the CST tanks, in the event of a fire. At
about 2 p.m., on the day of the accident, the last foamer was installed and sealed closing the
system to the atmosphere.4'41 However, at the time of the fire, the foam system was not fully
installed. The connection to enable the fire department to apply foam from outside the enclosure
was not completed.
2.0 DESCRIPTION OF THE ACCIDENT
On the night of April 10, 1995, no employees were present at the PDTI site.4 At about
11:30 p.m., fire broke out in the enclosure area where CST was stored. Several witnesses
observed a flash of flame on the side of one of the tanks (identified as Tank 23, which contained
CST), followed by an explosion and fireball. Other explosions and fireballs followed as the other
tanks containing CST (Tanks 18 and 22) exploded and burned.3'4-7'8-10
Because of the intensity of the fire, firefighters had difficulty entering the area to
extinguish the blaze. Black smoke was sent billowing into the air, raising fears that toxic
chemicals might reach downtown Savannah.3'27'28 Exhibits 6 and 7 are photographs of the fire
and the firefighting efforts in progress.
Eventually, firefighters were able enter the enclosure area and connect the foam system to
apply foam to the tanks. The fire appeared to be extinguished several times only to reignite
because the CST tanks had become extremely hot as a result of the fire. Water was used to cool
the CST tanks to prevent re-ignition and protect the adjacent tanks within the enclosure area.
However, due to concerns over contamination of marshland and the Savannah River from the
overflow of fire water, the use of cooling water had to be limited until the Coast Guard
constructed a berm to prevent contaminated water from reaching the river. The Savannah
-------
-10-
Exhibit 5. Fixed Piping Foam Fire Protection System
-------
-11-
River in relation to the fire in the six-tank enclosure area can be seen in the photograph in
Exhibit 8. The fire burned on and off for approximately three days before being extinguished late
on April 12, 1995.3-30,31,32 ^ ^^ tankg containmg CST (18j 22, and 23) were destroyed, and
the other three tanks hi the six-tank enclosure were damaged. The company's office building,
located about 100 yards north of the enclosure, was also destroyed in the fire. Some of the
large tanks to the north and east of the enclosure area suffered some degree of radiant heat and
smoke damage, but none of them leaked as a result of the damage.7 Some of these large tanks
are shown in Exhibit 9.
The explosion and fire damaged the storage tanks and associated piping in the enclosure
area and caused the leak of sodium hydrosulfide solution (pH of 10.4 to 11.5) and Briquest (pH
of 1). Their reaction produced hydrogen sulfide, a toxic, foul-smelling gas whose release
required extended evacuation and slowed the cleanup efforts.3'7> 30> 31
The intense fire forced the nearby residents of the Oaktree Townhomes complex to
immediately evacuate. The fire was sufficiently intense to cause damage to some trees and
buildings in the Oaktree complex. The location of the Oaktree Townhomes in relation to the fire
can be seen in the photograph in Exhibit 6.3> 7> 30> 31
At the start of cleanup operations, after the fire was extinguished, all residents within
one-half mile of the facility were evacuated as a precautionary measure because of the generation
of toxic hydrogen sulfide gas. Overall, nearly 2,000 people were involved in the evacuation.
Most of the evacuees were allowed to return after a few days, but the evacuation lasted more
than 30 days for residents closest to the site of the fire. A local school, Whitney Elementary, was
temporarily closed during the cleanup.30'31-32> 33> 34> 35
Eleven people were treated at local hospitals during the fire Monday night.37 Most of
these people were treated for respiratory problems; one person also reported "burning eyes," and
one was treated for anxiety. About 60 people sought treatment during the cleanup operations,
but no one was hospitalized.5'7'8 A fish kill in the Savannah River, at Savannah, Georgia, as a
result of a spill of CST was reported to Georgia Environmental Protection Division (EPD) at
7:51 am, April 11, 1975.36
Follow-up by the Agency for Toxic Substances and Disease Registry (ATSDR) with
three area hospitals found that 171 residents reported to hospital emergency rooms from the time
the incident began on April 10 up to April 18, 1995. The hospitals reported no admissions
related to the incident as of April 18.38 As of April 25, 1995, ATSDR estimated the number of
persons reporting to local area hospitals emergency rooms as 337, with no admissions or follow-
up treatment required.39
The damaged tanks and firefighting effort left approximately 12 million gallons of
contaminated water covering an area of about 25 to 40 acres of marsh. The photograph in
Exhibit 9 shows the area after the fire was extinguished. A large pool of water that overflowed
from the enclosure area can be seen. The contaminated water was determined to be hazardous
-------
-12-
Exhibit 6
Area of Fke and Fkefighting Efforts 29
Exhibit 7
Area of Fke and Oaktree Townhomes 29
-------
-13-
Exhibit 8
Area of Fire and Savannah River 29
Exhibit 9
Burned-out Tanks and Pool of Contaminated Water 29
-------
-14-
because of the high pH and the presence of reactive sulfides that produced hydrogen sulfide.
Hydrogen sulfide is toxic, with an Immediately Dangerous to Life and Health (IDLH) level of
100 parts per million (ppm). (IDLH levels are developed for worker protection by the National
Institute for Occupational Safety and Health (NIOSH).) Hydrogen sulfide is also flammable,
with a flammability range between 4.0 and 44.0 percent. An extensive cleanup of the area was
required.9
3.0 ANALYSIS AND SIGNIFICANT FACTS
3.1 Analysis
After the accident, GAIT investigators toured the site and examined the storage tanks and
piping and interviewed employees and contractors to determine the process and operations
involving the storage tanks and sequence of event leading to the explosion and fire. CAIT
investigators also received information from other federal, state, and local agencies which had
investigated the fire and interviewed witnesses. Since PDTI's office on site was destroyed in the
fire, CATT investigators examined records related to the application of permits and
correspondences with regulating agencies by PDTI to determine the conditions that existed prior
to the fire. Extensive research was also carried out on the properties of crude sulfate turpentine
and activated carbon used for removal of CST vapor.
The CATT used the information collected to develop and Event an Causal Factors Chart.
The Event and Causal Factors Chart combined with factual information collected in addition to
professional and engineering judgement were used to determine the causes of this accident.
Significant facts considered by CATT in its analysis of the causes of the accident are
discussed in Section 3.2 below. Possible scenarios are discussed in Section 4.0.
3.2 Significant Facts
EPA considered the following facts to be particularly significant in determining the causes
of the PDTI accident:
• In the six-tank enclosure area, Tank 19 had been used to stored sodium hydrosulfide
solution since July 1992. Tank 20 had been used to store Briquest since January 1993.4
• Sodium hydrosulfide is incompatible with Briquest. They react to form, among other
things, hydrogen sulfide gas.40
• On December 5, 1994, PDTI requested approval to store CST on-site from the Chatham
County Department of Inspections. On December 8,1994, the Chatham County
Department of Inspections and the Savannah Fire Department stipulated that certain
safety requirements be met for CST storage; however, they did not ensure that PDTI met
these requirements.20'21> 22
-------
-15-
PDTI began storing GST on-site before completing the modifications required by the
Chatham County. On January 17, 1995, PDTI began storing CST in the six-tank
enclosure area in Tank 22. By end of March, PDTI was storing CST in Tanks 18 and 23
as well. At the time of accident on April 10, 1995, PDTI had been storing CST without
completing the required modifications for about three months.4
On January 27,1995, PDTI submitted to the Georgia Environmental Protection Division
a notification of and an application for the storage and transfer of turpentine (CST) in
existing storage tanks and loading lines. This notification indicated that odor would be
controlled by piping the storage tanks together and routing the vapor through drums
containing activated carbon.u
On February 21, 1995, PDTI's contractor started installation of the VC system. The
installation of the VC system was not completed at the time of the fire.41
At the time of the fire, the VC system was being installed on the storage tanks containing
CST. Although the design called for flame arresters, they had not been installed when the
explosion and fire occurred, and pipe spools were temporarily installed hi their place.41
The VC system was designed by a PDTI employee and was not reviewed by a qualified
engineer or recognized expert.4'5
PDTI based the design of the VC system on an existing system in use for the storage tank
containing sodium hydrosulfide solution (Tank 19).4'5
The design of the VC system did not have a bypass valve that would prevent outside air
from being drawn through the drums containing activated carbon.25
Product literature from Calgon, the manufacturer of the activated carbon, highlighted the
hazards of exotherms caused by adsorption of organic sulfur compounds on carbon and
recommended installation of flame arresters and back-flow preventer (a bypass valve),
and pre-wetting and re-wetting of the activated carbon.50
PDTI management stated'that their standard procedure was to pre-wet and re-wet
periodically the activated carbon in the drums in the VC system.5
The design of the VC system did not provide for electrical grounding.25-42
Bureau of Alcohol, Tobacco, and Firearms (ATF) investigators discovered the remains of
an extension cord plugged in on the back side of Tank 5. This cord ran around the north
side of Tank 5 to an area between Tanks 1 (the caustic soda tank), 5, and 8.7 (See
Exhibit 1 for the positions of these tanks.)
-------
Parts of another extension cord were observed lying between Tank 1 (the caustic soda
tank) and the six-tank enclosure wall. This cord ran around the enclosure wall to the area
of the stairs on the enclosure wall.7> 42 (See Exhibit 1.)
At the truck loading and unloading station, ATF discovered an explosion-proof electrical
box that had the cover taken off and a device similar to a CB radio installed inside the
box.7 (See Exhibit 1 for the location of the truck loading and unloading station.)
An additional electrical outlet not on the electrical schematic for the plant was found by
ATF near the electrical panel the workers were using.7'42
The facility had been broken into and vandalized on two occasions — two months prior to
the fire and two weeks prior to the fire.4
On March 3,1995, PDTI's contractor began installing the foam fire protection system.
The installation of the foam fire protection system had not been completed, and the
system was not operational at the time of the fire.41'44
On April 7,1995, the flame arresters for the VC system had arrived on-site and were
uncrated, but they had not been installed on April 10, the day of the accident.45
On the day of the accident, April 10,1995, the third and final sealed foam chamber was
installed on the CST tanks. This closed the CST tanks to the atmosphere and directed
vapor to the VC system.46
PDTI's Terminal Manager stated that after 2:30 p.m. on April 10, 1995, 6,200 gallons of
CST was off-loaded from a tanker truck using in-house pumps.4'42> 43'46
At 5:50 p.m. on April 10,1995, the last PDTI employee left the site for the day.7 The
gates were locked, and no employees were there until after the fires and explosions had
occurred. The facility is fully enclosed by a security fence with locked gates. There are
no other provisions for site security.4'7> 47
The weather conditions at the time of the accident, as reported by the National Weather
Service - Savannah were: temperature 69 degrees Fahrenheit; winds, 110 degrees (S-SE)
at seven miles per hour; relative humidity 92 percent; pressure 32.09 and rising. There
were scattered clouds up to 4,300 feet and thin scattered clouds up to 30,000 feet. There
were no thunder storms reported in the area.7
Records show that there was no lightning activity on the day of the accident within a 20-
mile radius of the PDTI faculty.48
-------
-17-
• A resident of Oaktree Townhouses reported that on the evening of April 10,1995, he
saw what he described as a bright ball glowing red and orange near the base of Tank 23.
As he tried to focus his eyes on the object, Tank 23 blew up. Other witnesses
corroborated this account.7'49
4.0 CAUSES OF THE ACCIDENT
An Event and Causal Factors Diagram for the PDTI accident is presented in Exhibit 10.
This diagram presents the sequence of events and causal factors that may have contributed to the
occurrence of each of the events. Possible scenarios for immediate cause of the accident, and
contributing factors are discussed below. They are included hi the Events and Causal Factors
Diagram.
4.1 Most Likely Scenario
Ignition of CST Vapor witMn the Drums Containing Activated Carbon
On the day of the accident, the final sealed foam chamber was installed on the CST tanks.
It had the effect of closing the CST storage tanks to the atmosphere and making the path through
the VC system as the only opening to the outside. Also, on the day of the accident, after the
foam chamber was installed, 6,200 gallons of CST was off-loaded into the tanks. The displaced
vapor inside the storage tanks was forced through the activated carbon drums where the CST
vapor is removed by adsorption.
Product literature from Calgon, the manufacturer of the activated carbon, highlighted the
hazards of exotherms (high temperatures) caused by adsorption of organic sulfur compounds,
present in CST, onto activated carbon. Heat generated from the adsorption of CST vapor on the
activated carbon can raise the temperature in the drums above the autoignition temperature of
the CST vapor.
Although the temperature of the activated carbon may have become hot when CST vapor
was vented from the storage tanks to the carbon drums, the low level of oxygen present in the
drums probably averted a fire. However, the VC system did not have a bypass for preventing
outside air from being drawn into the drums when cool outside temperatures caused vapor in the
storage tanks to contract. The introduction of air provided the needed oxygen to trigger a fire.
An article written by SCM Corporation personnel (see Appendix C) describes a history of
fires in the drums containing activated carbon where the VC system design permitted outside au-
to be drawn into the drums. The article specifically mentions that typically the fires have
occurred late at night following a hot sunny day, as did the PDTI accident, when the nighttime
cooling of the storage tanks cause vapor to contract and draw outside air into the drums
containing activated carbon. The article recommends installing a vacuum breaker (a bypass)
between the storage tanks and the drums that would allow air to enter without being drawn
through the activated carbon bed.51
-------
Prior to accident:
• CST stored for three months.
• Vapor recovery system, including drums of activated
carbon, in place for one month.
• Fixed (oam fire protection system partially installed on
day of accident,
« Seals installed on foamers on day of accident.
Exhibit 10
Powell Duffryn Terminals, Inc. - Savannah, GA
4/10/95 Explosion and Fire
Event and Causal Factors Diagram
ff Flammable""*
/vapor autoignitem
tin carbon drum by/"
V reaction with /
"-—&-''
/''FlammableX
/ vapor escapes \
i from vapor '
\ recovery /
' Flammable \
i vapor escapes \
i from (oam /"
\spiping system/
/' Vapor ignited v
_j by arc from '
> electrical i
^^^ system_,••
/ Vapor ignited \
-i by vandalism or i
\ sabotage /
/ Vapor ignited\
-i by static |
\ discharge '
Ignition
of Vapor
Fire
through
PVC pipe
/Fires and N
explosion
\3CSTtanks,
Enclosure
wall
breached
Chemicals
leaked
Hydrogen
sulfide
generated
x* \ X" "\ x"" —
/Fh-flrfsmsrA / Other tanks\ /. Sodii
eno|osure 4 mbermed J
\area damaged/
00
hydrosullide
and acid
react
KEY
CST - Crude sulfate turpentine
Event triggering investigation (
Known events I I
Known causal factors O
Possible causal factors CT)
-------
-19-
The eyewitness' accounts of the accident are consistent with this scenario.
Calgon Carbon Corporation, the manufacture of the activated carbon, recommended a
procedure of wetting the carbon in the drums with water and of re-wetting it periodically
thereafter. The evaporation of the water in the drums would prevent the activated carbon from
becoming too hot. PDTI reportedly followed this procedure during initial installation. The VC
system had been in place for over a month before the accident. However, it was not functioning
as designed during this time, since part of the system was open to the atmosphere. During this
time, the carbon in the drums could have dried out, even if it had been wetted initially. It is not
known if the carbon was rewetted at anytime after initial installation.
Other possible scenarios for initiation of this fire were considered and are described
below.
4.2 Other Possible Scenarios
Ignition of CST Vapor in the Ambient Air
This scenario involves possible external ignition sources which ignited CST vapor that
may have leaked out from the storage tanks. The fire then flashed back and ignited the CST in
the storage tanks. There are several possible sources from which CST vapor may have leaked.
The CST vapor might have escaped from the VC system through the drums containing
activated carbon. Any residual CST vapor not adsorbed by the activated carbon would be
released to the atmosphere where it could be ignited if an ignition source were present.
The CST vapor might also have leaked from the pressure release vents. The pressure
release vents are designed to release excess pressure in the storage tanks. If these vents were
faulty, were improperly installed, or if there was too much backpressure from the VC system, the
vapor could have leaked out. The fire then could have flashed back through the vents.
Another possible source of CST vapor is the foam fire protection system. If the foam fire
protection system under construction were inadequately sealed, broken, or cracked, flammable
CST vapor could have escaped from this system, reached a source of ignition, and flashed back
to the tanks.
Finally, a breach in any of the CST storage tanks could result in release of CST vapor.
The CST vapor, being 4.8 times denser than air, may not have diffused quickly in air. It
may possibly collect within the enclosure area.13 The lower flammability limit of the CST vapor,
0.8 percent, would enable it to ignite at relatively low concentrations.13
Supporting these scenarios is the fact that there were several possible ignition sources.
One might be arcing from electrical systems at the facility. Some of the electrical equipment at
-------
-20-
the facility was not explosion-proof. Investigators found a conventional extension cord plugged
in near the six-tank enclosure and parts of what is believed to be an extension cord near an
electrical outlet. They also found an explosion-proof electrical box with the cover taken off
(thus nullifying its safety feature) at the truck loading and unloading station. (See Exhibit 1.)
Such equipment could have provided a source of ignition for the CST vapor. Other potential
ignition sources include any flame as a result of vandalism or sabotage. (ATF investigated the
scene and reported that the fire was not the result of vandalism or sabotage.)
These scenarios are much more apt to take place during filling of the storage tanks or
during the day when vapor may be displaced as a result of thermal expansion. The timing of the
accident make these less likely scenarios.
Ignition of Vapor by Static Charge Buildup on Carbon Drum
The VC system was designed without electrical grounding for the drums containing
activated carbon. The metal drums were connected to the storage tanks by non-conducting PVC
pipes. This permitted possible development of differences in electric potential between the
drums containing activated carbon and the CST storage tanks. A spark in the PVC pipe resulting
from static discharge could possibly ignite the CST vapor and trigger a vapor explosion and fire.
However, the weather conditions at the time of the fire, low wind speed and high humidity, make
this an unlikely possibility.
Ignition of Vapor by Lightning
Lightning was examined as a possible ignition source. However, no lightning was
detected in the area of the PDTI site at the time of the incident or for a number of hours before
and after the incident.
4.3 Factors that Contributed to the Consequences
Although there is a history of fires hi the drums containing activated carbon, vast majority
of these fires have been of minor consequences. The conditions that existed at PDTI contributed
to the serious consequences.
• The CST storage tanks did not have flame arresters. Flame arresters are devices
permeable to gas flow but impermeable to any flame it may encounter by quenching the
flame and cool the products to prevent reignition of hot gases exiting the arrester. They
are used to prevent a flame propagating into a system from outside or other parts of the
system. The fire spread to the CST storage tanks through the PVC piping system that
connected all three tanks to the carbon drums.
• The pumper connection located outside the enclosure area for the fixed foam fire
protection system, as required by Chatham County Department of Inspections, had not
been completed at the time of the fire. The foam system was only activated after the fire
-------
-21-
department was able to reach the foam pumper connection within the enclosure area.
Since the storage tanks had gotten extremely hot during the initial fire, the CST in the
storage tanks reignited several times after being doused with foam. The fire burned on
and off for three days before it was completely put out, causing extensive damage to
other tanks and associated piping located in the same enclosure area as the CST. The
other tanks and piping leaked chemicals, leading to the generation of toxic hydrogen
sulfide.
• The concrete wall of the enclosure area failed during the fire, resulting in the release of
contaminated water from the firefighting efforts. This contributed to damage to the
environment and slowed the fire fighting effort.
• Incompatible chemicals were stored next to one another resulting in release of toxic
hydrogen sulfide gas. Hydrogen sulfide gas was produced when sodium hydrosulfide
solution was heated during the fire (most of the hydrogen sulfide release during the fire
would likely have been consumed in the fire since it is combustible) and later leaked from
its storage tank and associated piping into the enclosure area and reacted with the acid
present. The hydrogen sulfide release caused injuries, forced extended evacuations, and
hampered response and cleanup. Storage of incompatible chemicals in the same
enclosure area created the potential for the release of a hazardous gas in the event of a
fire or damage to the tanks. Proper storage of these chemicals in separate locations
would have prevented the hydrogen sulfide release. Without the release of hydrogen
sulfide, the evacuations would have involved a smaller area and for shorter duration, and
cleanup of the site would have been quicker and easier.
4.4 Root Causes and Contributing Factors
The CATT concludes that the most likely cause of the incident at the PDTI facility was
ignition of CST vapors in the carbon adsorption drums due to the inadvertent addition of
atmospheric air. The fire then traveled back to the storage tanks through the vent piping, igniting
the contents triggering explosions and fire.
Below are the root causes and contributing factors associated with this incident. Root
causes are the underlying prime reasons, such as failure of particular management systems, that
allow faulty design, inadequate training, or deficiencies in maintenance to exist. These, in turn,
lead to unsafe acts or conditions which can result in an accident. Contributing factors are reasons
that, by themselves, do not lead to the conditions that ultimately caused the event; however, these
factors facilitate the occurrence of the event or increase its severity. The root causes and
contributing factors of this event have broad application to a variety of situations and should be
considered lessons for industries that conduct similar operations.
The GAIT uses a variety of analytical techniques to determine the root causes and
contributing factors of accidents, and to generate recommendations to prevent a recurrence. The
techniques used in this case included Events and Causal Factors charting, engineering and
-------
-22-
operations management experience and professional judgement. A number of factors involving
equipment, facility layout, and procedures may have contributed to this incident, as discussed
below. Based upon the facts and circumstances described above, the CATT identified the
following root causes and contributing factors in this incident:
• The design for the VC system was inadequate. There is a history of fires hi drums
containing activated carbon where the VC system design permitted the backflow of
outside air through the drums. Organic sulfur compounds in CST can produce heat when
they are adsorbed by the activated carbon. Enough heat may be produced hi the drums to
raise the temperature above the autoignition temperature of CST. Since there is a limited
amount of oxygen hi the drums, a fire usually does not occur. However, if outside air is
permitted to be drawn through the drums containing activated carbon, as when CST is
withdrawn from the storage tank or when ambient temperature drops causing the vapor hi
the storage tanks to contract, air can provide oxygen needed for combustion and the CST
vapor in the drums may ignite triggering a fire. (The solution for preventing the backflow
of outside air into the drums is to install a one-way valve between the drums and the
storage tanks that would permit air to enter the storage tanks without going through the
carbon drums.)
• The storage tanks were not equipped with flame arresters. The PVC piping provided a
conduit for the fire to travel from the carbon drums to the CST storage tanks. Flame
arresters were included hi the design of the VC system. However, CST storage began
before the modifications were completed. At the time of the fire, the flame arresters were
on-site but had not been installed.
• The foam fire suppression system was not completed on the tanks containing CST. Foam
fire suppression system was included as part of changes to be made for storing
flammables. CST storage had begun before modifications were completed. Fire fighters
were not able to use the foam pumper connection outside the enclosure area. Fire fighters
used water to fight the fire until a connection to the foam pumper could be rigged within
the enclosure area. An operational foam fire suppression system could have reduced the
amount of time required to suppress the fire and reduce the amount of heat damage to the
adjacent storage tanks and limited the amount of runoff from fire water which
contaminated sensitive wetland area along the Savannah River.
• The concrete containment wall was breached as a result of heat from the fire. The
enclosure area had been used to store nonflammables. No modifications were made to the
secondary containment before commencing storage of flammables.
• Incompatible chemicals were stored in the same walled enclosure area. Sodium
hydrosulfide solution was stored hi the same enclosure area as acidic cleaning solution
resulting hi production of toxic hydrogen sulfide vapor when the tanks leaked. The toxic
hydrogen sulfide release caused injuries, forced extended evacuations, and hampered
response and cleanup.
-------
-23-
5.0 RECOMMENDATIONS
Based on the root causes and contributing factors of this accident described above, the
CAIT provides the following recommendations to prevent accidents like this one from occurring
in the future at this and other facilities:
• Facilities designing or adding on environmental control, fire safety, or hazard control
systems, must ensure that these systems do not adversely impact the processes or
equipment where they are to be added and that they are properly designed and installed.
Designs should be reviewed by competent professionals or recognized experts. The
hazards associated with the new systems and the impact of the new system on the
existing systems should be thoroughly assessed. There are many formal hazard
evaluation techniques available (such as HAZOP or What If) that can facilitate this
assessment.
• Facilities using activated carbon systems, hi conjunction with vendors or recognized
experts, should conduct tests to determine the potential for formation of hot spots,
runaway reactions, or other consequences associated with adsorption of vapors on
activated carbon and ensure that the hazards associated with the heat of adsorption are
identified, well understood, and addressed through safeguards, procedures, or other
controls. An evaluation of the potential for, and the consequences associated with, air
being drawn into a carbon adsorption system (for example, associated with normal tank
breathing) must also be addressed as necessary through safeguards or other controls.
• Facilities storing flammable and combustible materials must evaluate and ensure that the
vessel and its venting system are protected from potential fire or explosion propagation
back into the tank from external fire or ignition sources.
• Facilities must ensure that equipment for use in handling hazardous substances is
equipped with the proper safety devices, and in compliance with national, state, and local
fire and hazardous material safety codes and standards before hazardous materials are
handled in such equipment. The safeguards, safety devices, or emergency systems
designed to prevent or protect the equipment must be in place and fully operational as
intended prior to startup of the equipment.
• Facilities should examine process and storage areas and equipment to ensure that
potentially incompatible substances are kept separated. Leaks or spills of incompatible
substances from equipment should not go into the same containment or other areas as a
result of fire or other incident.
In addition to the root causes and contributing factors of this accident described above,
the CAIT makes the following recommendations based on potential problem areas found during
the investigation.
-------
-24-
Facilities should evaluate the need for bonding and grounding to prevent the buildup and
discharge of static electrical charges that could provide an ignition source. If used,
ensure that bonding and grounding devices are properly designed, installed, maintained,
inspected, and tested.
Facilities must ensure that electrical devices and equipment hi areas where flammable or
explosive materials are handled are properly designed, installed, maintained, tested,
inspected and operated, and meet codes and standards to prevent potential ignition
sources.
-------
-25-
REFERENCES
1. Incident Report #296522, National Response Center, USCG HQ, Washington, D.C.; April
11, 1995.
2. DDO Form, Report #04/11/95-:01, Georgia Environmental Protection Division, April 11,
1995.
3. Viele, Elisabeth L., "Tanks explode: Area blocked, residents evacuated," Savannah
Morning News, Tuesday, April 11,1995, p. 1.
4. Powell Duffryn Terminal Manager. Interview held during accident investigation.
Savannah, Georgia. April 20, 1995.
5. Powell Duffryn Company, Vice President for Operations. Interview held during
investigation. April 27,1995.
6. LandView™ H. Mapping of Selected EPA-Regulated Sites, TIGER/Line ® 1992, and 1990
Census of Population and Housing.
7. "Statement of ATF Certified Fire Investigator," Department of Treasury: Bureau of
Alcohol Tobacco and Firearms: Office of Criminal EnforcementSavannah, Georgia. April
26, 1995.
8. OSHA Investigators. Interview at OSHA Savannah Area Office, Savannah, Georgia. April
19, 1995.
9. Powell Duffryn Incident Report: Observations and Chemistry, Report HMRAD 95-9
National Oceanic and Atmospheric Administration, Hazardous Materials Response and
Assessment Division, Seattle, Washington. October 1995. p. 1.
10. "Investigation Report, Fire and Explosion-Powell Duffryn Terminals, Inc.," Hazardous
Materials Section, Safety Fire Division, Office of Commissioner of Insurance, State of
Georgia, April 28, 1995.
11. Hazardous Materials Inspection Report for PDTI, State of Georgia, Office of
Commissioner or Insurance, Safety Fire Division, Savannah, Georgia. October 19,1994.
12. Powell Duffryn Terminal, Inc., "Savannah Daily Terminal Inventory Activity Report;
Shipyard Terminal," December 9,1993
13. "Material Safety Data Sheet, Crude Sulfate Turpentine," ITT Rayonier Forest Products,
Stanford, Connecticut. November 2, 1994.
-------
-26-
14. "CAMEO Response Information, Chemical Report, Sodium Hydro sulfide, [Solution],"
NOAA, 7600 Sand Point Way, NE, Seattle, Washington. April 18,1995.
15. "Material Safety Data Sheet, Sodium Hydro sulfide, Solution," Jupiter Chemicals Inc.,
Westlake, Louisiana, June 1, 1994.
16. "Albright and Wilson Americas, Inc., Material Safety Data Sheet, Briquest ADPA
60AW," Albright and Wilson Americas, Inc., Richmond, Virginia. January 12,1993.
17. "Albright and Wilson Americas, Inc., Material Safety Data Sheet, Antiblaze 80," Albright
and Wilson Americas, Inc., Richmond, Virginia. November 20,1991.
18. John Drew, James Russell, and Henry W. Bajak, eds., Sulfate Turpentine Recovery. Pulp
Chemicals Association, New York, 1971
19. Director, Chatham County Department of Inspection. Interviews held during accident
investigation. Savannah, Georgia. September 10 and 11,1996.
20. Faxed letter from PDTI to Fire Marshall, Chatham County Department of Inspections,
asking for comments regarding request for storage of CST on-site. January 31, 1994
21. Letter from PDTI to Fire Marshall, Chatham County Department of Inspections, asking
for comments and recommendations regarding PDTI's request for approval to store CST
on-site. December 5,1994.
22. Letter from Fire Chief, Savannah Fire Department, to Fire Marshall, Chatham County
Department of Inspections stating stipulations to be met prior to storage of CST at PDTI,
December 8,1994.
23. Letter from PDTT to Fire Chief, Savannah Fire Department requesting approval for
temporary storage of CST on-site, and committing to meet all of the requirements of Fire
Chiefs letter dated December 8, 1994. December 22, 1994.
24. Georgia Department of Natural Resources, Environmental Protection Division, Air
Protection Branch, Memorandum Subject "Powell Duffryn Terminals, Savannah, Georgia
Permitting and Complaint History." April 18, 1995. p. 9.
25. "Scope of Work, Item #2, Tank #18, 22, 23 Vapor Control System," PDTI, Savannah,
Georgia, January 13, 1995. 2 pp.
26. "Scope of Work, Tk #18, 22, 23 Foam Piping," PDTI, Savannah, Georgia, February 7,
1995. 7 pp.
-------
-27-
27. Soloman, LoyaU, and Zoellner, Tom., "Company: Cost May Reach $8M," Savannah
Morning News, Tuesday, April 12, 1995.
28. Wilbert, Tony, and Williams, Jenel, "Slow Burn in Savannah; Area residents vent
frustrations; some left temporarily homeless," Savannah Morning News, Tuesday April
12, 1995.
29. Official U.S. Coast Guard photographs of the PDTI incident in April 1995. U.S. Coast
Guard, Marine Safety Office, 222 West Oglethorpe, Savannah, Georgia.
30. U.S. Coast Guard, Captain of the Port of Savannah, Georgia. Interviews held during
accident investigation. Savannah, Georgia. April 20, 21 and 27. 1995.
31. Swann, Amy and Donald, David "Slow Burn in Savannah; Here's chronology of the
incident," Savannah Morning News, Tuesday, April 12,1995.
32. Williams, Jenel, Orr, Tony Lee, and Zoellner, Tom., "Slow Burn in Savannah; Fire
doused; now we wait; Special foam — and lots of it ~ appears successful," Savannah
Morning News, Tuesday, April 13,1995.
33. Fuller, Njeri, "Neighbors file class-action suit against Powell Duffryn," Savannah News
Press, Tuesday, April 15, 1995.
34. Donald, David, and Orr, Tony, "Evacuees exit homes when told," Savannah News Press,
Tuesday, April 15, 1995.
35. Zoellner, Tom, "Neighborhood off-limits as fumes linger; 'We're just going to sit here and
pray,'" Savannah Morning News and Savannah Evening Press, April 16, 1995.
36. EOC Operator, Fish Kill Investigation Form, Report EPD #01195-01, April 11, 1995.
37. "Situation Report (SITREP) One, Powell Deuffryn (sic) Warehouse Fire, Savannah, GA,"
Agency for Toxic Substances and Disease Registry, April 12, 1995.
38. "Situation Report (SITREP) Six, PoweU Duffryn Chemical Storage Fire, Savannah, GA,"
Agency for Toxic Substances and Disease Registry, April 18, 1995.
39. "Situation Report (SITREP) Nine, PoweU Duffryn Terminals, Inc., Chemical Fire,
Savannah, GA," Agency for Toxic Substances and Disease Registry, April 21, 1995.
40. "Material Safety Data Sheet, Sodium Hydro sulfide Solution," Jupiter Chemicals, Inc.,
Westlake, LA, March 21, 1990.
41. President of US Mechanical Contractor. Interview held during accident investigation.
Savannah, GA, April 24, 1995.
-------
-28-
42. Operator, PDTT, Interview held during accident investigation, Savannah, GA, April 28,
1995.
43. "Investigation Report, Fire and Explosion-Powell Duffryn Terminals, Inc.," Hazardous
Materials Section, Safety Fire Division, Office of Commissioner of Insurance, State of
Georgia, April 28, 1995. Attachment #5, Foye Howell Rockett, Pipe Fitter, US
Mechanical Contractors, Inc., ATF interview during accident investigation on April 15,
1995.
44. Fire Marshall, Chatham County Department of Inspections. Telephone interview held
during accident investigation, Savannah, GA, April 28,1995.
45. "Investigation Report, Fire and Explosion-Powell Duffryn Terminals, Inc.," Hazardous
Materials Section, Safety Fire Division, Office of Commissioner of Insurance, State of
Georgia, April 28,1995. Attachment #4, Owner, US Mechanical Contractors Inc., ATF
interview during accident investigation on April 16,1995.
46. "Investigation Report, Fire and Explosion-Powell Duffryn Terminals, Inc.," Hazardous
Materials Section, Safety Fire Division, Office of Commissioner of Insurance, State of
Georgia, April 28, 1995. Attachment #6, Pipefitter, US Mechanical Contractors, Inc.,
ATF interview during accident investigation on April 15,1995.
47. "Investigation Report, Fire and Explosion-Powell Duffryn Terminals, Inc.," Hazardous
Materials Section, Safety Fire Division, Office of Commissioner of Insurance, State of
Georgia, April 28,1995. Attachment #13, Project Manager, Powell Duffryn Terminals,
Inc., ATF interview during accident investigation on April 13,1995.
48. Letter dated April 4,1997, from Global Atmospherics, Inc., Tucson, AZ, to Henry T.
Hudson, EPA Region 4, Atlanta, GA. Transmitting a copy of a Lightning Verification
Report for the area around Powell Duffryn Terminal, Savannah, GA for the 24-hour
period 11a.m. April 10 to 11a.m. April 11,1995.
49. Resident of Oaktree Town homes. "Report of Interview," interview held during accident
investigation by Officer Simpkins, Chatham County Police Department, Savannah, GA,
April 12, 1995.
50. Calgon Carbon Corporation, "Ventsorb Equipment Bulletin," Pittsburgh, PA, March
1993.
51. R.W. Harrell, J.O. Sewell, and T.J. Walsh, SCM Corporation, Cleveland, Ohio. "Control
of Malodorous Compounds by Carbon Absorption," AIChE Loss Prevention Journal, v.
12, pp. 124-7,1979.
-------
A-l
Appendix A
Personnel Participating in Accident Investigation and Report Development
EPA personnel who participated in the accident investigation and development of the
accident report include:
David Speights
Craig Matthiessen
Henry T. Hudson, Environmental Engineer
David Chung, Chemical Engineer
Charlie Cartwright, Chemical Engineer
Eric Simmons, Environmental Engineer
EPA Headquarters
EPA Headquarters
EPA Region IV
EPA Headquarters
EPA Region IV
8(a) Technical Assistance
Applications, Inc.,
Team, Resource
Burke, VA
OSHA personnel involved hi the investigation include:
John Vos, Safety Specialist
James White, Industrial Hygienist
OSHA Savannah Area Office
OSHA Savannah Area Office
-------
B-l
Appendix B
Material Safety Data Sheets for Chemicals Stored in Six-Tank Enclosure
This appendix contains Material Safety Data Sheets (MSDS) for the chemicals stored in
the six-tank enclosure area that was the site of the initial explosion and fire at PDTI. MSDS are
included for:
• Crude sulfate turpentine;
• Briquest;
• Sodium hydrosulfide solution; and
• Antiblaze 80.
-------
MATERIAL SAFETY DATA SHEET
CRUDE SULFATE TURPENTINE-
Page: 1
Date Prepared: November 2,1994
MSDS No.: 0004
1. CHEMICAL PRODUCT AND COMPANY IDENTIFICATION
Product Identifier: Crude sulfate turpentine
Product Description: Mixture of terpenes and other volatile
degradation products obtained during the
kraft pulping process.
Synonyms: Sulfate turpentine, wood turpentine, turpentine
Chemical Family: Terpenes
Chemical Formula: Mixture; primarily C10Hie isomers
MANUFACTURER: EMERGENCY TELEPHONE NUMBERS
Rayonierlnc. Health and (912)427-5560
Specialty Puip Products Transportation
JesupMill CHEMTREC* (800)424-9300
4470 Savannah Highway
Jesup, GA 31545 'Transportation Emergencies only
(912) 427-5000
2. COMPOSITION/INFORMATION ON INGREDIENTS
„ J ^ - CAS Registry Mn
Crude Sulfate Turpentine 100 8006-64-2
Alpha pinene 60-62 80-56-8
Betapinene 19-21 127-91-3
Limonene 7-9 138-86-3
Beta pneiiandrene 6-8 555-10-2
Pine oil. 2-3 8002-09-3
-------
Page: 2
Data Prepared: November 2, 1934
MSDS No.: 0004
3. HAZARDS IDENTIFICATION
EMERGENCY OVERVIEW:
Crude sulfate turpentine (CST) is a flammable
liquid; it is toxic (LDso for humans is estimated to be
between 1,100 and 2,400 mg/kg) and is a dermal,
eye and pulmonary irritant. Acute renal injury may
follow exposure to turpentine either by the dermal,
oral, or inhalation routes, but there appears to be no
evidence of kidney damage in nonfatal cases. A
very dangerous fire hazard when exposed to heat or
fiame.
POTENTIAL HEALTH EFFECTS:
INHALATION:
EYE CONTACT:
SKIN CONTACT:
INGESTION:
CHRONIC:
EXPOSURE LIMITS:
Inhalation can be irritating to mucous membranes,
produce headache, dizziness, pulmonary edema,
bronchitis, rapid heart beat, cyanosis, and may
resuitin acute renai injury.
Vapors are irritating. Liquid turpentine causes
immediate severe pain and eyelid spasm.
Direct skin contact causes irritation. May result
in acute renal injury.
Ingestion can cause burning of the mouth and throat,
nausea and abdominal pain. May result in acute
—Tenal injury. Initially causes CNS stimulation. This
may be followed by CNS depression leading to
progressive stupor and coma.
Chronic exposure may cause kidney and liver
damage. May produce dermatitis and allergenic
sensitization.
ACGfH TLV- 100 ppm (Turpentine)
OSHA PEL -100 ppm (Turpentine)
OSHA TWA -100 ppm (Turpentine)
-------
CRUDE SULFATE
Page: 3
Date Prepared: November 2,1994
MSDS No.: 0004
4. FIRST AID MEASURES
INHALATION:
EYE CONTACT:
SKIN CONTACT:
INGESTION:
Remove patient to fresh air. If breathing is
difficult, give oxygen. Refer to physician if
patient shows any ill effects or if irritation persists.
Rush thoroughly with large quantities of warm
water. Hold eyelids apart to ensure thorough
irrigation. Refer to physician.
Wash exposed skin with mild soap and water.
Remove contaminated clothing. Refer to
physician if irritation persists.
Poisonous (mean lethal dose for adults is 4-6 oz.).
Do not induce vomiting. Get medical help promptly.
Stomach pumping and lavage may be required.
5. FIRE FIGHTING MEASURES
PHYSICAL PROPERTIES
GENERAL HAZARD:
FIRE FIGHTING
INSTRUCTIONS:
FIRE FIGHTING
EQUIPMENT:
HAZARDOUS
COMBUSTION
PRODUCTS:
Flash point 90 - 115°F (CC) (32 - 46°
Flammable limits: LEL - 0.8%
UEL - unk.
C)
Turpentine is a flammable liquid. Avoid heat,
sparks and open flames. A very dangerous fire
hazard when exposed to heat orfiame. Moderate
explosion hazard in the form of .vapor when
exposed to flame.
Extinguish with foam, CO2 or dry chemical.
If water must be used, use as a spray only. Water
can be used to cool fire-exposed surroundings.
Use firefighters protective clothing (bunker gear)
with SCBA.
Emits acrid smoke and fumes when heated to
decomposition. Forms heavy black smoke and
soot when burning. Carbon dioxide and carbon
monoxide are among combustion products.
-------
-r.ifil
<5?*UDE SULFATE TURPENTINE
Page: 4
Data Prepared: Novembers, 1934
MSDSNo.: 0004
6. ACCIDENTAL RELEASE MEASURES
LAND SPILL: Evacuate the area. Eliminate ignition sources.
Vapor is heavy and may travel to ignition sources.
An explosion hazard exists ff vapor enters a
confined area such as a sewer. Provide explosion-
proof ventilation to remove vapors from spill area.
Protect personnel from breathing vapors or contact
with liquid. Air-line respirator or self contained
breathing apparatus may be required. Contain
spiff and pick up with absorbent material and put
in a labeled, closed metal container.
WATER SPILL: Notify appropriate authorities if spill enters water-
ways or municipal sewers. Material is a listed
marine pollutant under 49 CFR 172.101, Appendix
B.
7. HANDLING AND STORAGE
Store in cool, dry, well-ventilated location away from
sources of heat and ignition. Storage drums should
be air-tight Store away from oxidizing agents. No
smoking.
No open flames or ignition sources in handling or
storage areas. Use explosion-proof electrical equip-
ment Surfaces covered with crude sulfate turpentine
may be slippery.
CST vapor is highly corrosive to mild steel.
8. EXPOSURE CONTROLS/PERSONAL PROTECTION
Use chemical goggles or full face shield with safety
glasses.
Use Viton/neoprene, Won, chloroprene or PVA
gloves and apron (to protect against splashing).
-------
SULFATE TURP TINE
P*fl«: 9
BatePniMnKf: Auguct 9,1194
MSD3NO.: 0004
Maintain eyewash facilities and safety showers in
handling areas.
Provide adequate general ventilation to meet PEL
requirements.
Avoid inhalation of mist and vapor. Avoid contact
with skin and eyes. No smoking in storage or use
areas. Take special care when opening pumps and
pipe lines.
9. PHYSICAL AND CHEMICAL PROPERTIES
Vapor Pressure: 5 mm (Hg, 77'F, 25* C)
Vapor density: 4.8 (air * 1)
Specific Gravity: 0.86
Boiling Point 310-340*F(154-171'C)
PH: Not applicable
Odor Pungent, offensive, sutfurous
Appearance: Pale yellow liquid
10. STABILITY AND REACTIVITY
GENERAL CST is flammable. Spontaneous heating is
passible. Avoid impregnating combustibles with
CST.
INCOMPATIBLE Avoid contact with strong oxidizing agents such as
MATERIALS AND chlorine dioxida and chlorine. Avoid sparks and
CONDITIONS TO open flames. Mi!d steel is susceptible to severe
AVOID: vapor-phase corrosion by some components of CST.
HAZARDOUS Emits acrid smoke and fumes when heated.
DECOMPOSITION:
-------
SWJDE SULFATE TURPENTINE
Page: 6
Data Prepared: November 2,1394
MSDS No.: 0004
11. TOX1COLOGICAL INFORMATION
CARCINOGENICITY: No reports of carcinogenictty were found.
MUTAGENICITY: Several of the CST constituents were not found to
be mutagenic in the Ames test
TERATOGENICITY: Possible teratogenlc effect exists for pregnant
women.
TOXICITY: LDso for humans is estimated at 1,100 - 2,400
mg/kg.
SENSITIZER: The major constituents are non-sensitizing. Chronic
exposure may produce aliergenic sensttkation.
IRRITANT: CST is a skin, eye and mucous membrane irritant
12. ECOLOGICAL INFORMATION
No data available.
13. DISPOSAL CONSIDERATIONS
Material meets the Federal definition of an
ignitable hazardous waste. Disposal should be only
in accordance with applicable regulations.
14. TRANSPORT INFORMATION
Shipments of this product are regulated by the
Department of Transportation (DOT). The proper
shipping name is Turpentine. The correct bill of
lading description is:
Turpentine, (Crude Sulfate Turpentine).
3, UN 1299 , PG Hi" Placard - Flammable
-------
CRUDE SULFATE TURf'^NTINE
Page: 7
Date Prepared: November 2, 1994
MSDS No.: 0004
Special provisions B1 and T1 should be noted
according to 40 CFR 172.101. Therefore, bulk
packing according to 40 CFR 173.241 applies.
Emergency Response Guidebook No. 27
15. REGULATORY INFORMATION
TSCA (Toxic Substance This product is listed on the TSCA inventory.
Control Act):
RCRA:
CERCLA (Comprehensive
Emergency Response
Compensation, and Liability
Act):
DOT Hazmat:
OSHA:
Discarded material would be a hazardous
waste under 40 CFR 261.21.
Reportable under 40 CFR 302.4(b) for releases
greater than 100 pounds [40 CFR 302.5(b)]
-in-l Listed as
FR 172.101,
Turpentine is a 29 CFR 1910 SubpartZ
compound. TWA 100ppm(560 mg/m3).
marine pollutant under
SARA TITLE it! (Super-311/312 Hazard Categories: Immediate health,
fund Amendments and Re- delayed health, fire
authorization Act): 313 Reportable Ingredients: None
OTHER
We recommend you contact local authorities to
determine if there may be other local reporting
requirements.
-------
SULFATE TURPENTlfll:
Page: 8
Ozt« Prepared: November 2.1994
MSDSNo.: 0004
CALIFORNIA
PROPOSITION 65:
This product Is derived as a co-product of cellulose
production from trees. As a consequence, some
chemical compounds'listed by the State of California
under Proposition 65 may naturally be present
Rayonier does not know of any universal analytical
scheme that enables us to analyze this product for
the absence or presence of all chemical compounds
listed by the State of California. No testing has
been done for Proposition 65 listed chemical
compounds.
16. OTHER INFORMATION
For more information about this product, please call Rayonier Inc., Jesup Mill,
Jesup, GA at (912) 427-5000 or the Savannah office at (912) 651-8056.
THE INFORMATION RELATES TO THIS SPECIFIC MATERIAL. IT MAY NOT
BE VALID FOR THIS MATERIAL JF USED JN COMBINATION WITH ANY
OTHER MATERIALS OR IN ANY PROCESS. IT IS THE USERS'
RESPONSIBILITY TO SATISFY THEMSELVES AS TO THE SUITABILITY
AND COMPLETENESS OF THIS INFORMATION FOR THEIR OWN
PARTICULAR USE,
-------
71K PAGE I
ALBRIGHT S, WILSON AMERICAS INC. MATERIAL SAFETY DATA SHEET'
ALBRIGHT fc WILSON AMERICAS INC. P. 0. BOX 26S8*
ENVIRONMENTAL SERVICES RICHMOND, VA. £3260-6329
»»*»**»*****»«««*****»* PRODUCT IDENTIFICATION *»*»»*«****«««*«»»**»*»
BRIQUEST ADPA 60AW
SUPPLIER* HEALTH EMERGENCY TELEPHONE:
ALBRIGHT i WILSON INC. (803)554-1289
CHEMICAL NAMES AND SYNONYMS* TRANSPORT EMERGENCY TELEPHONS,
l-HYDRCXYETHANE-i,1-DIFHOSPHONIC ACID <800>4a4-93OO(CHEMTRSO
USE Oft DESCRIPTION: OTHER DESIGNATION:".
CLEANING AGENT 71K
************** TYPICAL CHEMICAL AND PHYSICAL PROPERTIES •»*»»**»*»****
APPEARANCE* VISCOSITY* AT 100 F, SUS AT SO C, CS
CLEAR-PALE YELLOW LIQUID NE 64
ODORj VISCOSITY: AT 210 f. SUS AT 100 C, CS
ODORLESS NE NE
RELATIVE DENSITY: 13/4 C SOLUBILITY IN WATER: PH:
l.*6 MISCXBLE i
MELTING POINT: FCC) POUR POINT: F FLASH POINT: F(C) (METHOD)
> 212F NOT FLAMMABLE
VAPOR PRESSURE:MM HG SOC
< 17 MM HG a 68F
NA-NOT APPLICABLE N£»NOT ESTABLISHED D-DECOMPOSES
»********«««**«***»»*****»*» INGREDIENTS *******«»***«*»****«»«**»**»*
P€L TLV
WT PCT M6/M3 PPM MG/M3 PPK
(APPROX >
HAZARDOUS INGREDIENTS:
1-MYOROXVETHANE- 60 NE N£ NE NE
1,1-DIPHOSPHONIC ACID
NOTES TLVS SHOWN FOR GUIDANCE ONLY. FOLLOW APPLICABLE REGULATIONS.
INFORMATION GIVEN HEREIN IS OFFERED IN GOOD FAITH AS ACCURATE, BUT
WITHOUT GUARANTEE. CONDITIONS OF USE AND SUITABILITY OF THE PRODUCT FOR
PARTICULAR USES ARE BEYOND OUR CONTROL? ALL RISKS OF USE OF THE PRODUCT
ARE THEREFORE ASSUMED BY THE USER AND V£ EXPRESSLY DISCLAIM ALL
WARRANTIES 0£ EVERY KIND AND NATURE. INCLUDING WARRANTIES 0£
MERCHANTABILITY AND FITNESS FOR, A PARTICULAR PURPOSE IN RESPECT TO THE
UJ£. 0£ SUITABILITY 0£ JJ£ PRODUCT. NOTHING IS INTENDED AS A
RECOMMENDATION FOR USES WHICH INFRINGE VALID PATENTS OR AS EXTENDING
LICENSE UNDER VALID PATENTS. APPROPRIATE WARNINGS AND SAFE HANDLING
PPnrEDURES SHOULD BE PROVIDED TO HANDLERS AND USERS.
-------
&RIQUEST ADPA 60AW 71K PAGE 2
**««««****«**«***** FIRE AND EXPLOSION HAZARD DATA ****«*****«»**«»****
FLAMMABLE LIMITS: LEL
NA
UEL
NA
FLASH POINTJ F(C) (METHOD)
NA
EXTINGUISHING MEDIA:
GOVERNED BY OTHER MATERIALS PRESENT
SPECIAL FIRE FIGHTING PROCEDURES!
AS IN ANY FIRE SITUATION, THE USE OF SELF-CONTAINED BREATHING APPARATUS
IS RECOMMENDED.
UNUSUAL FIRE AND EXPLOSION HAZARDS]
PRODUCT CAN FORM FLAMMABLE PHOSPHINE 6AS WHEN HEATED ABOVE SOOC.
***««•*«***««»*«« EMERGENCY AND FIRST AID PROCEDURES «**«*«*«**#•«#««»»
EYE CONTACTS
FLUSH THOROUGHLY WITH WATER FOR AT LEAST 15 MINUTES. GET IMMEDIATE
MEDICAL ASSISTANCE. IF MEDICAL ASSISTANCE IS NOT IMMEDIATELY AVAILABLE,
FLUSH FOR AN ADDITIONAL 15 MINUTES WITH WATER.
SKIN CONTACT:
IF WIDESPREAD CONTACT, IMMEDIATELY REMOVE CONTAMINATED CLOTHING UNDER
SAFETY SHOWER AND WASH EXPOSED AREA WITH SOAP AND LARGE AMOUNTS OF WATER.
GET MEDICAL ASSISTANCE. FOR LESSER CONTACT, WASH CONTACT AREAS WITH SOAP
AND WATER. REMOVE CONTAMINATED CLOTHING AND LAUNDER BEFORE REUSE.
INHALATION:
REMOVE FROM FURTHER EXPOSURE. IF UNCONSCIOUSNESS OCCURS, CALL A
PHYSICIAN. IF BREATHING HAS STOPPED, USE MOUTH-TO-MOUTH RESUSCITATION,
INGESTIQNi
DO NOT INDUCE VOMITING. GIVE LARGE QUANTITIES OF MILK OR WATER. GET
MEDICAL ASSISTANCE AND CALL A PHYSICIAN. DO NOT GIVE ANYTHING BY MOUTH
TO AN UNCONSCIOUS PERSON.
•««««*********»«*«*«**««*** REACTIVITY DATA ***************************
STABILITY! (THERMAL, LIGHT, ETC.) CONDITIONS TO AVOID!
STABLE TEMPERATURES GREATER THAN SOOC
INCOMPATIBILITY! (MATERIALS TO AVOID)
STRONG OXIDIZING AGENTS AND SUBSTANCES WHICH REACT WITH ACIDS.
HAZARDOUS DECOMPOSITION PRODUCTS!
PHOSPHINE
HAZARDOUS POLYMERIZATIONS CONDITIONS TO AVOIDi
-------
ERIGUEST ADPfi 60AW 71K
*»***»*«*«*«*****»***»* SPILL OR LEAK PROCEDURE **#*»*****»****«»»*»**,
ENVIRONMENTAL IMPACT:
REPORT SPILLS AS REQUIRED TO APPROPRIATE AUTHORITIES. REGULATIONS
REQUIRE IMMEDIATE REPORTING OP SPILLS THAT COULD REACH ANY WATERWAY
INCLUDING INTERMITTENT DRY CREEKS. REPORT SPILL TO NATIONAL RESPONSE
CENTER TOLL FREE NUMBER 800-4S4-8805. IN CASE OF ACCIDENT OR ROAD SPILL.
NOTIFY CHEMTREC (800) *2<»-9300.
PROCEDURES IF MATERIAL IS RELEASED OR SPILLEDi
ABSORB ON FIRE RETARDANT TREATED SAWDUST, OIATOMACEOUS EARTH, ETC.
SCRAPE UP AND REMOVE. DEPOSE OF AT AN APPROPRIATE WASTE DISPOSAL FACILITY
IN ACCORDANCE WITH CURRENT APPLICABLE LAWS AND REGULATIONS, 'AND PRODUCT
CHARACTERISTICS AT TIME OF DISPOSAL.
WASTE MANAGEMENT:
DISPOSE OF WASTE BY SUPERVISED INCINERATION IN COMPLIANCE WITH
APPLICABLE LAWS AND REGULATIONS. DISPOSE OF WASTE AT AN APPROPRIATE WASTE
DISPOSAL FACILITY IN ACCORDANCE WITH CURRENT APPLICABLE LAWS AND RE6ULATIONS
AND PRODUCT CHARACTERISTICS AT TIME OF DISPOSAL.
******************* SPECIAL PROTECTION INFORMATION »**«»*»*»**»#*#»**»»
EYE PROTECTION:
CHEMICAL TYPE GOGGLES WITH FACE SHIELD SHOULD BE WORN.
SKIN PROTECTION*
IMPERVIOUS GLOVES SHOULD BE WORN. PROTECTIVE CLOTHING SUCH AS UNIFORMS,
OVERALLS, AND LAB COATS SHOULD BE WORN. WHEN HANDLINS LARGE QUANTITIES,
IMPERVIOUS SUITS AND BOOTS MUST BE WORN.
RESPIRATORY PROTECTION!
NO SPECIAL REQUIREMENTS UNDER ORDINARY CONDITIONS OF USE AND WITH
ADEQUATE VENTILATION. APPROVED RESPIRATORY PROTECTIVE EQUIPMENT MUST BE USED
WHEN VAPOR OR MIST CONCENTRATIONS EXCEED APPLICABLE STANDARDS.
VENTILATION:
NO SPECIAL REQUIREMENTS UNDER ORDINARY CONDITIONS OP USE AND WITH
ADEQUATE VENTAT I ON. AVOID USING IN CONFINED SPACES.
OTHER »_
PRIMARY ROUTE OF ENTRY - SKIN CONTACT,
ft************************ SPECIAL PRECAUTIONS *******»»**»*««****»**»»
HANDLIN3*
PRODUCT IS A CORROSIVE MATERIAL WHICH CAN CAUSE EYE AND SKIN BURNS.
AVOID ALL PERSONAL CONTACT.
STORAGE:
STORE PRODUCT IN SEALED CONTAINERS IN A COOL DRY PLACE.
STORED MATERIALS MUST BE LABELED ASl BRIQUEST ADPA 60AW.
-------
BRIQUEST ADPA 60AW ' 71K PAGE <
HEALTH HAZARD DATA ****************************
ACUTE HEALTH HAZARDS!
STRONG IRRITANTj MAY CAUSE SKIN, EYE OR MUCOUS MEMBRANE BURNING.
CARCINOGENICITYi
LISTED: NTP? NO
IARC MONOGRAPHS? NO OSHA REGULATED? NO
SIGNS AND SYMPTOMS OF EXPOSUREI
IRRITATION OF EYE, SKIN OR MUCOUS MEMBRANE.
MEDICAL CONDITIONS AGGRAVATED BY EXPOSURE:
MAY AGGRAVATE ANEMIA.
SUBACUTE AND MUTASENICITY (SUMMARY)
NONE KNOWN.
CHRONIC Oft SPECIALIZED (SUMMARY)
POSSIBLE SKELETAL EFFECTS* MAY DECREASE THE AFFINITY OF HEMQ8LOBIN FOR
OXYGEN.
TARGET OR6AN EFFECTS
SKIN, EYE, RESPIRATORY TRACT(IRRITATION);
TOXIC TO BONE AND BLOOD.
OTHER DATA
FETAL ANOMALIES HAVE BEEN REPORTED IN MICE.
ENVIRONMENTAL SERVICES
PHONEl
REVISED!
01-12-93
-------
BRIOUEST ADPA 60AW
****«*********»*»»»*««* WARNING STATEMENTS *««**«*t«****«»*«*#***«»»*
CALIFORNIA:
"WARNING: THIS PRODUCT MAY CONTAIN A CHEMICAL KNOWN TO THE STATE OF
CALIFORNIA TO CAUSE CANCER, OR BIRTH DEFECTS OR OTHER REPRODUCTIVE HARM".
ALL PHOSPHORUS COMPOUNDS MAY BE REASONABLY EXPECTED TO CONTAIN ARSENIC
.AND POSSIBLY CADMIUM AND/OR LEAD IN CONCENTRATIONS RANGING FROM A FEW
PARTS PER BILLION TO A FEW PARTS PER MILLION.
HAZARD WARNING: THERE IS A POSSIBILITY BICYCLIC PHOSPHATES OR PHOSPHITES
CAN BE PRODUCED AS A RESULT OF THE THERMAL DECOMPOSITION OF THIS PRODUCT
• IN COMBINATION WITH TRIMETHYLOL PROPANE, 'TRIMETHYLOL PROPANE DERIVED
PRODUCTS OR THEIR CORRESPONDING TRIMETHYLOL ALKANE HOMOLOGS. BICYCLIC
PHOSPHATES AND PHOSPHITES ARE A CLASS OF MATERIALS WITH ACUTE NEUROTOXIC
PROPERTIES WHICH PRODUCE CHARACTERISTIC CONVULSIVE SEIZURES IN TEST ANIMALS.
THEREFORE, THIS PRODUCT SHOULD NOT BE USED IN CONJUNCTION WITH TRIMETHYLOL
PROPANE OR TRIMETHYLOL PROPANE DERIVED PRODUCTS.
-------
MATERIAL SAFE^ DATA SHEET
P.O. BOX 789 WESUAKE, LA 70448
MSDS NUMBER 080-6J
PAGE 1 OF 4
'RODUCT
Sodium Hydrosulfide Solution
CHEMICAL/
SYNONYMS
FAM!LY°AL
Inorganic Satt Solution
C.A.S. NUMBER 16721-80-5
24 HOUR EMERGENCY ASSISTANCE
JUPITER 800077-1737
CHEUTREC WXM24-9300
HAZARD RATING
LEAST w SLIGHT
MODERATE. HIGH . EXTREME
a a
HEALTH
F.RE
REACTIVtTY
iriorttiLll EN I o
COMPOSITION
TOX1CITY DATA
Sodium Hydrosulfide
Water
(typical)
20-45
4
55-80
ipr-rat LD5fl: QQmg/Kg
ipr-mus LD_ : 20mg/Kg
* NIOSH RTECS (1983 Supplement)
HEALTH INFORMATION
Solutions of sodium hydrosulfide are strongly alkaline (pH 10.4-11.5) and should be handled with
all of the precautions which are generally used for handSng strong alkalies. The solutions are
highly corrosive to the eyes or any human tissue. Liquid contact causes marked eye irritation and
could result in severe cornea) injury. Liquid contacTwiBnhe skin causes irritation and corrosion of
the skin. Ingestion causes severe burning and corrosion in all portions of the gastrointestinal
tract. Avoid the inhalation of fumes. Be particularly careful of fumes near open tank truck domes
or open covers on storage vessels.
When heated or on coming into contact with adds or acidic materials, highly toxic hydrogen
sulfide gas may be evolved in large quantities. Exposure to this gas causes headache, dizziness,
nausea and vomiting. Continued exposure can lead to loss of consciousness and death.
Not listed as a carcinogen by NTP, IARC or OSHA.
Proper personal protection (See Section IX) is required in the handling of this product.
SECTION IV
OCCUPATIONAL EXPOSURE UMTS
Not established 1or this product. ACGIH and OSHA Bmtts tor hydrogen suffide are TWA 10 ppm and STEL 15
ppm. The OSHA acceptable ceilng for hydogen sulfide Is 20 ppm.
-------
MATERIAL SATETY DATA SHEET
MSDS NUMBER 080-60
PAGE 2 OF <•
SECTION V
EMERGENCY AND FIRST AID PROCEDURES
Inhalation: Remove victim from contaminated area. Wear protective respiratory equipment. If breathing is
labored, administer oxygen. If breathing has ceased, clear airway and start mouth to mouth
resuscitation. If heart has stopped beating, external heart massage should be applied. Obtain
immediate medical attention.
Eye Contact: Immediately flush with targe quantities of water for 15 minutes. Moid eyelids apart during irrigation
to insure thorough flushing of the entire area of the eye and lids with water. Obtain immediate
medical attention.
Skin Contact: Immediately flush with large quantities of water for 15 minutes. Remove contaminated clothing
under shower. Obtain medical attention if irritation persists.
Ingestion: Do not induce vomiting. If victim is conscious, immediately give large quantities of water. If
vomiting does occur, repeat fluid administration. Obtain immediate medical attention.
SECTION VI PHYSICAL DATA
BOtUNGPOiNT k 253.25g
SPECIFIC v
1^ > 1-152-1.303
SOLUBIUTYIN k ort__i-,a
WATER Y Complete
MELTING POINT k co c
CP) T 62-6
% VOLATILE BY V 55 . OQ
VOLUME » g^aa
Not determined
VAPOR .
PRESSURE k Not determined
(rnmHg) r
VAPOR .
9,F,Ssn^ r Not determined
(AIM m if *
Freeze R: 20%-0°F. 45%-56°F
pH: 10.4-11.5
A PPEA RANGE AND OOOR
Yellow to red solutions with a strong hydrogen suifide odor.
SECTION Vlt
FIRE AND EXPLOSION HAZARDS
FLASH POINT AND METHOD USED
Not applicable
FLAMWABLE LIMITS/% VOLUME INAIB k LOWER UPPER
Hydrogen Suifide ^ 4.3 46.0
EXTINGUISHING MEDIA
As appropriate for materials involved in the lire.
SPECIAL FIRE FIGHTING PROCEDURES AND PRECAUTIONS
Sodium hydrosulfide solutions are non-flammable. However, if these solutions are exposed to
heat or acids, the hydrogen sutfide gas which is released will form explosive mixtures with air
(see above). Personnel fighting a fire in any area where sodium hydrosulfide solution is stored
should be equipped with NIOSH approved self-contained breathing apparatus.
UNUSUAL FIRE AND EXPLOSION HAZARDS
Storage vessels in the area of a fire should be thoroughly cooled by water spray or foam. If
hydrogen suifide venting from a vessel in a fire area is burning, it should be perrmitted to
continue to burn until source of ignition has been extinguished
-------
SECTION VIII REACTIVITY
MSOS NUMBER *. Q80-6J
PAGE 3 Of
STABILITY . Q UNSTABLE [g STABLE
NOMATERIALSTOWlUlLl1
HAZARDOUS POLYMERIZATION Q MAY OCCUR (3 WILL NOT OCCUR
Avoid any exposure to significant heat or any contact with acids or acidic materials (evolution of
hydrogen suftide). Avoid the storage ot combustibles near containers or storage vessels of
sodium hydrosuiflde solutions.
Sodium hydrosulfide solutions are not compatible with copper, zinc, aluminum and their alloys.
See also Section XI.
HAZARDOUS DECOMPOSITION PRODUCTS
In tire conditions, hydrogen suffide gas will evolve. Combustion oi this gas will produce sulfur dioxide.
SECTION IX EMPLOYEE PROTECTION
RESPIRATORY PROTECTION
Good ventilation must be provided. Feed the product below the surface of water to minimize the
formation of product vapors. NIOSH approved self-contained breathing apparatus should be
readily available in case of a spill or other emergency.
pftcrrecTWE CLOTHING
Neoprena apron, gloves and protective boots. Safety goggles or preferably a full face shield is required. Do not
wear contact lenses.
ADDITIONAL PftOTECTNE MEASURES
Contaminated clothing should be removed immediatly and iaunderd prior to reuse. Contaminated leather shoes
cannot be cleaned and should be Discarded.
SECTION X ENVIRONMENTAL. PROTECTION
SPU. OR LEAK PROCEDURES
Use all proper protective equipment.
Absorb smalt spills with sand, earth, sweeping compound or other inert absorbent. Treat spill with dilute
hydrogen peroxide to oxidize sutfides to sulfates. Place contaminated material in approved container for
disposal.
Large spills should be diked to prevent entry into sewers or drains. Recover as much of the solution as
possible. Carefully treat remaining material with dilute hydrogen peroxide to oxidize sulfides to sutfates.
CAUTION, there wilt be an evolution of heat and some release of hydrogen sulfide. Neutralize remaining
material, if necessary and place contaminated material in approved containers for disposal.
WASTE DISPOSAL
Dispose of contaminated material in an approved chemical waste landfill in accordance
with all governmental regulations.
ENVIHONMEHTALHAZAPOS
Avoid discharge of significant quantities of the product to surface waterways because of potential aquatic toxfctty.
-------
a
FETY DATA SHEET USOSNUVBEB
_PAGE4 OF 4
SECTION XI
SPECIAL PRECAUTIONS
Transfer Operations:
Before transfer, carefully inspect all points using seals, gaskets or packings, as well as any hoses to be used to
be certain that they are in place and in good condition. Replace any defective units before transfer. Operators
must wear protective equipment.
SECTION XII TRANSPORTATION REQUIRMENTS
DEPARTMENT D FLAMMABLE LIQUID D COMBUSTIBLE LIQUID EH OXIDIZING MATERIAL
OF
TRANSPORTATION (_j FLAMMABLE SOUD D POISON, CLASS A LXl CORROSIVE MATERIAL
CLASSIFICATION
D FLAMMABLE GAS D POISON. CLASS B Q IRRITATING MATERIAL
O.O.T. PROPER SHIPPING NAME ' "
Corrosive liquids, poisonous, n.o.s., 8, UN2922, PG II (sodium hydrosulfide solution)
D NON-FLAMMABLE
GAS
D NOT HAZARDOUS BY
O.O.T. REGULATIONS
LJ OTHER- Sp.dlyb.iow
•MER REQUIREMENTS
Corrosive placards are required on containers greater than 450 L (119 gal)
I Corrosive and poison labels required on smaller containers.
SECTION xin
OTHER REGULATORY CONTROLS
Reportable Quantity (RQ) is 5.000 Ibs (100% basis).
AH chemicals contained in this product are listed on the Toxic Substance Control Act (TSCA) inventory.
The information contained herein is based on data which is
believed to be accurate. However, no warranty of
mareanlabiCty, fitness for use or any other warranty is
expressed or is to be implied concerning the accuracy of
*ese data, (he results to be obtained from the use of the
.ateriaJ. or the hazards connected with such use. This
information is furnished on the conation that the person
receiving it shall make his own determination as to the
suitability of the material for his particular purpose and on
the condition that he assume (he risk o( his use thereof.
JUPITER CHEMICALS, INC.
P.O. Box 789
Westlaka, LA 70669
James E. Oviatt
Environmental Engineer
FORM* 6012 B
DATE PR EMBED
8- 1 -1994
-------
•sassn ONV saaiaNW 01 osaiAoad as ennoHS
3dvs MJL 13d
***************************** SIN3IG3a9NI ****************************
(33 HSVTdViSS) d
(0)d UNIOd HSVId
3N
(3>d
J.HSITS
NI Aimenios
S3 (3 001 IV
e*es
S3 *3 0« IV
»»******»****«
T* >
305 OH viw'sanssaad
d UNIOd
3N
(3>d UNIDd 9NI113W
63'!
SA1ISN3C1
'd 013 iV »A1IS03SIA JHOQO
6*TIT ainon avsis
SflS 'd OOT 4.V «A1ISQ3SIA (33NVaV3ddV
lyaiSAHd ONV TV31U3HD IfDIdAl **************
(33aiM3H3) OOe6-*5<7( 008)
o asn
-T) siai
ISWANDNAS ONti S3WN 1V3IH3KD
•3Ni
••3NOHd3131 ADN33a3W3 H11V3H
08
**»***»*»»»*»*»»»**»*»* NOlJ.V3!dIlN3Ql 13000ad ft**********************
(VSR) 6S29-092E2 VVA *QNOWH3ia
63393 XOS *D *d
S33IAH3S !VlN3WNOaiAN3
•3Ni svoiaswv
I33HS viva
*3Ni swiaswy MOST in
-------
ANTIBLAZE 80 947 PAG£
********««««**»«*«*• FIRE AND SXPLOSION HA2ARQ DATA
FLASH POlNTj F
-------
ANTIBLAZE 80
947
PAGE 3
»#*»»#***#*****»*«**«** SPILL OR LEAK PROCEDURE »**»«*»*•*****•#»»***«*
ENVIRONMENTAL IMPACTi
REPORT SPILLS AS REQUIRED TO APPROPRIATE AUTHORITIES. RE5UALTIQNS
REQUIRE IMMEDIATE REPORTING OF SPILLS THAT COULD REACH ANY WATERWAY,
INCLUDING INTERMITTENT DRY CREEKS. REPORT SPILL TO NATIONAL RESPONSE
CENTER TOLL FREE NUMBER BOO-424~B80a. IN CASE OF ACCIDENT OR ROAD
SPILL NOTIFY CHEMTREC (80*)) 484-9300,
PROCEDURES IF MATERIAL IS RELEASED OR SPILLED!
ABSORB ON FIRE RETARDANT TREATED SAWDUST, DIATQMACEOUS EARTH, ETC.
SCRAPE UP AND REMOVE. DISPOSE OF AT AN APPROPRIATE WASTE DISPOSAL
FACILITY IN ACCORDANCE WITH CURRENT APPLICABLE LAMS AND REGULATIONS, AND
PRODUCT CHARACTERISTICS AT TIME OF DISPOSAL.
WASTE MANAGEMENTS
DISPOSE OF WASTE BY SUPERVISED INCINERATION IN COMPLIANCE WITH
APPLICABLE LAWS AND REGULATIONS. DISPOSE OF WASTE AT AN APPROPRIATE
WASTE DISPOSAL FACILITY IN ACCORDANCE WITH CURRENT APPLICABLE LAWS AND
REGULATIONS, AND PRODUCT CHARACTERISTICS AT TIME OF DISPOSAL.
**««»«»»»***««»*«** SPECIAL PROTECTION INFORMATION «*«*»«****»»•«***+*»
EYE PROTECTION:
NO SPECIAL EQUIPMENT REQUIRED.
SKIN PROTECTION*
NO SPECIAL EQUIPMENT REQUIRED. HOWEVER, GOOD PERSONAL HYGIENE
'PRACTICES SHOULD ALWAYS BE FOLLOWED.
RESPIRATORY PROTECTIONj
•NO SPECIAL REQUIREMENTS UNDER ORDINARY CONDITIONS OF USE AND WITH
ADEQUATE VENTILATION.
VENTILATION!
. NO SPECIAL REQUIREMENTS UNDER ORDINARY CONDITIONS OF USE AND WITH
ADEQUATE VENTILATION.
OTHER! PRIMARY ROUTE OF ENTRY- SKIN CONTACT
***»*«**«*»****«*«***4**« SPECIAL PRECAUTIONS *»******«*#*#*»*««**#**«*
HANDLINGS NO SPECIAL PRECAUTIONS REQUIRES.
STORAGE I NO SPECIAL REQUIREMENTS. AVOID EXPOSURE TO TEMPERATURES ABOVE aSOF,
STORED MATERIALS MUST BE LABELED A8t ANTIBLAZE BO.
THIS PRODUCT IS CLASSIFIED AS NOT RESTRICTED BY DOT.
-------
ANTT8LAZE 80 947 FflGE
ft********************* HEALTH HAZARD DATA **«««**»«*««*«***««*«f»«*»*
ACUTE HEALTH HAZARDS
POSSIBLE MILD IRRITATION OP THE EYES AND SKIN.
CARCINOGENICITY
LISTED! NTP NO IARC MONOSRAPfW NO 08HA RCSULATEO NO
SIGNS AND SYMPTOMS OF EXPOSURE!
POSSIBLE MILD IRRITATION Of THE EY1 SKIN.
MEDICAL CONDITIONS AGGRAVATED BY EXPOSURE!
NONE KNOWN
SUBACUTE AND MUTAGENICITY
-------
ANTIBLAZE 80 947 PAGE 5
****«**»**«***««**«*«*» WARNING -STATEMENTS «****«***#******»*******•*
CALIFORNIA:
"WARNING! THIS PRODUCT MAY CONTAIN A CHEMICAL KNOWN TO THE STATE OF
CALIFORNIA TQ CAUSE CANCER, OR BIRTH DEFECTS OR OTHER REPRODUCTIVE HARM".
ALL PHOSPHORUS COMPOUNDS MAY BE REASONABLY EXPECTED TO CONTAIN ARSENIC
AND POSSIBLY CADMIUM AND/OR LEAD IN CONCENTRATIONS RANGING FROM A FEW
PARTS PER BILLION TO A FEW PARTS PER MILLION.
HAZARD WARNINGS THERE IS A POSSIBILITY BICYCLIC PHOSPHATES OR PHOSPHITES
CAN BE PRODUCED AS A RESULT OF THE THERMAL DECOMPOSITION OF THIS PRODUCT
IN COMBINATION WITH TRIMETHYLOL PROPANE, TRIMETHYLOL PROPANE DERIVED
PRODUCTS OR THEIR CORRESPONDING TRIMETHYLOL ALKANE HOMOLGGS. BICYCLIC
PHOSPHATES AND PHOSPHITES ARE. A CLASS OF MATERIALS WITH ACUTE NEUROTOXIC
PROPERTIES WHICH PRODUCE CHARACTERISTIC CONVULSIVE SEIZURES IN TEST ANIMALS.
THEREFORE, THIS PRODUCT SHOULD NOT BE USED IN CONJUNCTION WITH TRIMETHYLOL
PROPANE OR TRIMETHYLOL PROPANE DERIVED PRODUCTS.
-------
C-l
Appendix C
Article on Carbon Drum Systems Applicable to Crude Sulfate Turpentine
This appendix presents an article, "Control of Malodorous Compounds by Carbon
Adsorption," that describes systems of the type used at the PDTI facility which include drums of
activated carbon. The article discusses fires that have occurred in such systems in the past and
their causes.
-------
Control of
Malodorous
Compounds by
Carbon Adsorption
Here is a simple, straightforward design for a carbon adsorber with wide
applications, based on a successful unit controlling odors from a fine
chemicafs-from crude sulfate turpentine plant.
R. W. Harrell, J. O. Sewell, and T. J. Walsh,
SCM Corp., Cleveland, Ohio
The Organic Chemicals Division of SCM Corp. operates
a plant in Jacksonville, Fla., that produces fine chemicals
from crude sulfate turpentine. When this plant was first
built in 1910, it was so far out of Jacksonville that houses
had to be built for employees. Today, it is located well
within the city limits, and neighbors have built homes
right next to the property line.
Crude sulfate turpentine is an excellent source of ter-
penes1 which are the base chemicals for many flavors and
odors. Such products as pine oil, lemon-grass oil. synthe-
tic spearmint, and related essences are produced, but
crude sulfate turpentine might be called the skunk of the
organic chemical world. Due to certain impurities such as
methyl mercaptan and dimethyl sulfide, it has an objec-
tionable odor. In our operation these impurities are re-
moved and destroyed. Before they are thus handled, the
vapors from "crude" storage tanks and certain other
points in the plant must have odor controls to prevent our
being a source of neighborhood odor.
The only solution we have found for keeping odor
under control is adsorption of the vapor on activated car-
bon. The first carbon adsorbers were installed in the
Jacksonville plant in 1967 on various storage tanks con-
taining crude sulfate turpentine and terpene derivitives.
The performance over the last 10 years has shown that
carbon is effective as an adsorber for general' use on ter-
pcnes. Retention is typically 15 wt.-% of the carbon. The
Pittsburgh Activated Carbon Division of the Calgon Corp.
has supplied IVP and BLP carbon for use in this plant.
Over 50 adsorbers are in active use. The life of a bed var-
ies from 2 to 6 months. Consumption of carbon exceeds
30,000 Ib./yr.
The beds are checked daily. 5 days per week, by a
qualified technician who checks for emissions and for
condensate in the base of the bed. When he detects an
emission, the adsorber is replaced with a fresh adsorber
which has been previously prepared. The carbon is re-
moved for disposal. The adsorber is repacked: with fresh
carbon for use when required.
This adsorption is an exothermic reaction capable of
liberating, enough heat to raise the temperature of the sys-
tem to the ignition point. This must be stressed. Most of
the problems encountered with fires in carbon adsorption
have occurred with oxygenated hydrocarbon molecules.
This article is reporting a similar reaction with com-
pounds that do not contain oxygen. We recognize that
sulfur is below oxygen in the same column of the
periodic table. Thus, there is a relation between dimethyl
sulfide and dimethyl ether that is evident in the alternate
name dimethyl thioether. But. we stress that chemicals
other than oxygenated hydrocarbons can burn on activated
carbon.
The adsorption of sulfurated organics on carbon is ac-
companied by an exotherm. Several fires have occurred in
the adsorbers. Details are difficult to obtain as the design
of the adsorber and the system has been such as to isolate
and minimize the damage. My recollections of a typical
fire are as follows:
This incident was reported to me on a Monday morning
during a phone call on another subject.
"Oh yes, we had another fire last night."
"You did? Where, when.'what, how much damage?"
"You know, one of the carbon adsorbers on the crude
sulfate (turpentine) tank caught about. 10:45."
Now. this is typical-. ""10:45" was 10:45 p.m. The day
had been hot. 95° or more, and the tank was exposed to
full sunlight. We expect that within the crude sulfate tank
the temperature rose to 135°F or more, the liquid ex-
panded and vaporized, forcing vapor-ladened air out
through the tank vent. It is now evening, and cooling has
-------
/^SwgTPi?e>
V .saaSSL-^r:
figure 1. Details of carbon bed adsorber.
begun. Initially, vapor condenses creating a slight vacuum
in the tank. Air is drawn in with.oxygen to oxidize the
hot adsorbed organic molecules spread in a thin layer on
the carbon particles.
I further pursued the issue:
"How did you handle it?"
"The operator saw the drum glowing. He disconnected
it, picked it up with a fork lift and put it where it could
burn itself out. Then, he got another drum and hooked it
up."
Two problems
There have been two problems in using carbon adsor-
bers in this plant. The first occurred when the beds get
saturated with water vapor. A unit installed on a waste
water neutralization tank operating at 50°C failed within
36 hours. The second problem occurs when we adsorb the
forecut from crude sulfate turpentine fractionation. This
cut contains the thioethers (dimethyl sulfide, dimethyl
disulfide), mercaptans (methyl mercaptan) and methyl sul-
'foxide.
If the above conversation sounds casual; it is, in a con-
trolled way. The design of the equipment permits rapid
disconnect and removal of the hot drum. All drums are
located where they can be easily reached for removal or
replacement. Drums are situated with space between them
and major pieces of equipment or tanks. Access is free
and open land is near by. The operators are checking on
schedule, and they have been trained (in most cases by
experience) to handle an incident.
-------
Figure 2. Typical single-drum adsorber connections to
tank.
Construction of adsorber
The adsorbers at Organic Chemicals are home-made
from 55-gal. drums. Figure I shows the details of a typi-
cal drum. The carbon is confined between screens in a
circular bed about 2 ft. deep. About 200 Ib. of carbon are
used in a bed. Flow through the bed is along the long
axis of the drum. Flow is very slow. Where flow seems
to be excessive two or four units are used in parallel.
There are many advantages to this construction
technique. Units are relatively inexpensive and are aban-
doned when exhausted. Raw material for a new adsorber
is readily available. The maintenance crew, makes up new
adsorbers at leisure and a number are readily available
when needed.
Installation of adsorbers
The typical installation of adsorbers, shown in Figure
2, indicates several important points:
1. The adsorbers are physically isolated from the tank
they are protecting.
2. The adsorbers are located at ground level. They can
be easily seen,.connected, and removed.
3. Emissions are readily followed by the human nose.
4. Hot spots are isolated and noticeable.
5. Drums, are disposable in their entirety, or they may
be carried by fork lifts to open spots for burning.
At this point, we should note that the Jacksonville plant
is not enclosed. The installation is typically "outdoors."
The design of both the adsorber and the installation il-
lustrate several concepts.
Simplicity. Although the drawings appear to represent
almost casual assembly, the design has been well thought
through and tested by time in service.
Convenience. Units are assembled in modular form.
Each module is easy to assemble, to store, and to handle
when needed. Where necessary, modules in parallel offer
control of greater gas flow. The quick-disconnect fittings
permit very rapid, installation or removal by one man of a
module or group of modules. All .parts are standard, such
as are found in our plant shop at all times.
Economy. No special materials or controls have been
provided. Units are built and connected as required.
Safety. The limited size of the module, the location of
the installations, isolation of adsorbers from the source of
odor that they control, and accessibility of the units are
all factors that have protected the plant from fires and the
-------
environment from pollution in an effective manner.
The designs are not proprietary with us. Any plant
operator is welcome to adapt them, at his own risk, to his
own situation. The use of carbon adsorption has been
most helpful in controlling transient odors from our opera-
tion. The problems have occurred when excessive mois-
ture resulted in failure to adsorb organics, or when certain
molecules were adsorbed with a great exotherm. By
isolating the adsorbers, such fires that have occurred were
limited to minimal damage. By simple construction using
readily available materials, cost of replacement is control-
led.
WALSH, T.J.
SEWELL, J.O. HARRELL, R.W.
DISCUSSION
ROBERT AKELL, DuPont: I thought you indicated that
there were a number of different fire occurrences. You
then put this alternate air inlet to account for air coming
back into the system, but did you say then that that
eliminated ail of your problems, or were there still others
remaining?
WALSH: I am of the impression that after the change,
the number of fires greatly decreased, but I won't say
that it absolutely stopped.
JAMES SEWELL: We never have had any fires as far
as open flames in these units. They have been detected
when the drums had paint peal or began to glow a little
bit, and they were removed at that time. As far as what
changes we made - we put a vacuum breaker on the
storage tanks so that instead of breathing air in at night
or at other times when you are pumping out, we simply
brought the air in in another direction - didn't bring air
over that carbon bed.
And our problem we found came from having the
turpene organics on the carbon bed and then Wowing air
across. After we did this, i don't know that we've had
more than maybe one or two drums that we've had to
remove for overtemperature.
AKELL: How do you account for those one or two -
since then?
SEWELL: Possibility that the vacuum breaker wasn't
working as it should have. We did some breathing
anyhow.
RICHARD DERLACK, Anchor Continental: A final
question for the gentleman from Jacksonville. How do
you dispose of 30,000 Ibs. of contaminated carbon per
year?
WALSH: We have not found it to be economical to put in
any facilities at the present time to regenerate the
carbon. We have been, and this may be temporary, but
we have been disposing of it with a landf/H operation.
-------
D-l
Appendix D
Chemical Safely Alert — Fire Hazard from Carbon AdsorptionDeodorizing Systems
-------
United States
Environmental Protection
Agency
Office of Solid Waste
and Emergency Response
(5104)
EPA550-F-97-OQ2e
May 1997
»EPA
FIRE HAZARD FROM CARBON
ADSORPTION DEODORIZING
SYSTEMS
The Environmental Protection Agency (EPA) is issuing this Alert as part of its ongoing effort to
protect human health and the environment by preventing chemical accidents. Under CERCLA,
section 104(e) and Clean Air Act (CAA), EPA has authority to conduct chemical accident
investigations. Additionally, in January 1995, the Administration asked the Occupational Safety
and Health Administration (OSHA) and EPA to jointly undertake investigations to determine
the root cause(s) of chemical accidents and to issue public reports containing recommendations
to prevent similar accidents. EPA has created a chemical accident investigation team to work
jointly with OSHA in these efforts. Prior to the release of a full report, EPA intends to publish
Alerts as promptly as possible to increase awareness of possible hazards. Alerts may also be
issued when EPA becomes aware of a significant hazard. It is important that facilities, SERCs,
LEPCs, emergency responders and others review this information and take appropriate steps
to minimize risk.
PROBLEM
Activated carbon systems used to
adsorb vapors for control of
offensive odors may pose a fire
hazard when used for certain types of
substances, if proper procedures are not
followed. In particular, crude sulfate
turpentine, commonly produced in the
pulp and paper industry, can pose a fire
hazard if the adsorption system is not
properly designed and proper
procedures are not implemented.
Facilities should take precautions to
avoid or mitigate these fire hazards.
ACCIDENTS
In a 1995 accident at a chemical
terminal facility, a fire and explosion
occurred involving three tanks of
crude sulfate turpentine. The tanks
were connected to drums of activated
carbon for deodorizing. The fire and
explosion damaged other storage tanks,
resulting in the release of toxic gases and
forcing a large-scale evacuation of area
residents.
Fires have occurred in the past in
activated carbon systems used for
deodorizing crude sulfate turpentine. In
general, such fires have not had effects
as serious as those reported in the 1995
fire. Serious effects would not be
expected if fires are confined to the
activated carbon containers and do not
spread to tanks containing flammable or
combustible substances.
HAZARD AWARENESS
Activated carbon is widely used to
adsorb vapors to prevent their
release to the air. For certain
classes of chemicals, reaction or
adsorption on the carbon surface is
accompanied by release of a large
amount of heat that may cause hot spots
in the carbon bed. Such chemicals
include organic sulfur compounds (e.g.,
mercaptans), which may be found as
impurities in crude sulfate turpentine
and other materials. Other classes of
chemicals that may cause large thermal
releases are ketones, aldehydes, and
some organic acids. Adsorption of high
vapor concentrations of organic
compounds also can create hot spots. If
flammable vapors are present, the heat
released by adsorption or reaction on the
surface of the carbon may create a fire
hazard (e.g., a fire may start if the
temperature reaches the autoignition
temperature of the vapor and oxygen is
present to support ignition).
Chemical Emergency Preparedness and Prevention Office
Printed on recycled paper
-------
Fire Hazard from Carbon Adsorption Deodorizing Systems
May 1997
The fire hazards of carbon adsorption
deodorizing systems may increase at night. At
certain times (typically during the day), high
temperatures may lead to the expansion of vapor
in the system, and vapor is likely to exit to the
atmosphere. When temperatures drop (typically
at night), a slight vacuum may be created,
causing air to be drawn into the system. If the
carbon surface is very hot, because of the heat
generated by adsorption, air drawn in over the
carbon may provide the oxygen to start a fire.
HAZARD REDUCTION
If the potential exists for fires in the acti-
vated carbon system, be sure the carbon
containers are separated from containers of
flammable or combustible substances and
can be easily and rapidly removed in case
the container becomes hot or catches fire.
If high concentrations of organic com-
pounds may cause development of high
temperatures, take steps to control the
heating. Such steps may include diluting
inlet air, time weighting the inlet concentra-
tion to allow heat to dissipate, and pre-
wetting the carbon.
Facilities should be aware of the potential
fire hazards of activated carbon systems for
absorbing flammable vapors and take
steps to minimize these hazards. Actions that
may help to prevent fires include:
+ Follow the manufacturer's instructions for
design and operation of activated carbon
adsorption systems.
+ Ensure that a qualified engineer or technician
supervises the design, construction, and
operation of the carbon adsorption system.
+ Evaluate the composition of the vapors that
will contact the carbon and heed the
manufacturer's warnings about potential
hazardous interactions with the carbon. If
the vapor may contain organic sulfur
compounds (e.g., vapor from crude sulfate
turpentine), ketones, aldehydes, or organic
acids, or if the vapor contains high concen-
trations of organic compounds, consider the
potential for development of hot spots on
the carbon.
•* Test the action of the vapors on carbon for
potential heat release before putting the
carbon adsorption system into service, if
possible reactions are not known.
*• If test results or known reactions with
carbon indicate the potential for fires in the
activated carbon system, design the system
so that air does not enter the system over
the carbon bed (e.g., install vacuum break-
ers on the storage tanks).
Visually inspect activated carbon adsorp-
tion systems frequently for hot spots and
fires.
Before using an activated carbon adsorption
system, ensure that safety systems are in
place for fire prevention and mitigation,
including flame arrestors to prevent the
spread of fire from the carbon containers to
the flammable chemical containers.
Ensure that flammable and combustible
chemicals connected to activated carbon
adsorption systems are handled in accor-
dance with applicable regulations, codes,
and standards.
INFORMATION RESOURCES
Some references that may contain
information about the fire hazards of
activated carbon adsorption systems and
methods of minimizing them are listed below.
Regulations applicable to such systems, and
codes and standards that may be relevant, are
also listed.
For more information consult the following:
General References
Information on carbon adsorption systems for
crude sulfate turpentine can be found in W.A.
Harrell, J.O. Sewall, and T.J. Walsh, "Control of
Malodorous Compounds by Carbon Adsorption,"
American Institute of Chemical Engineers, Loss
Prevention, Volume 12,1979, pp 124-127.
-------
Fire Hazard from Carbon Adsorption Deodorizing Systems
May 1997
Manufacturers of activated carbon can provide
product literature with information on properties, safe
handling, and use.
flammable and combustible substances are included,
in DOT's Hazardous Materials Table [49 CFR
172.102].
Statutes and Regulations
Section 112(r) of the Clean Air Act focuses on
prevention of chemical accidents. It imposes on
facilities with regulated substances or other extremely
hazardous substances a general duty to prevent and
mitigate accidental releases. Accident prevention
activities include identifying hazards and operating
a safe facility.
EPA's Risk Management Program (RMP) Rule [40
CFR 68] is intended to prevent and mitigate
accidental releases of listed toxic and flammable
substances. Requirements under the RMP rule
include development of a hazard assessment, a
prevention program, and an emergency response
program.
Processes containing flammable gases and liquids
may be covered under the Occupational Safety and
Health Administration's (OSHA) Process Safety
Management Standard, which establishes procedures
intended to protect employees by preventing or
minimizing the consequences of chemical accidents
involving highly hazardous chemicals [29 CFR
1910.119].
OSHA also has a Standard for Flammable and
Combustible Liquids [29 CFR 1910.106].
Occupational Safety and Health Administration
Phone: (202) 219-8151 - Public Information
Web site: http://www.osha.gov
The Department of Transportation (DOT) regulates
transportation of activated carbon and other
flammable and combustible substances under its
Hazardous Materials Regulations. Activated carbon
and many combustible and flammable substances are
listed individually, and several categories of
Department of Transportation
Phone: (202) 366-5580 - Public Information
Web site: http://www.dot.gov
Codes and Standards
The NationalFire Protection Association (NFPA) has
a code for flammable and combustible liquids thatmay
be adopted into law at the state or local level. NFPA
30 — Flammable and Combustible Liquids Code.
1996.
National Fire Protection Association
1 Batterymarch Park
P.O. Box 9101
Quincy, MA 02269-9101
Phone: (617) 770-3000
Customer Service: 1 (800) 344-3555
Web site: http://www.nfpa.org
FOR MORE INFORMATION.
CONTACT THE EMERGENCE PLANNING AND
COMMUNITY RIGHT-TO-KNOW HOTLINE
(800) 424-9346 OR (703) 412-9810
TDD (800) 553-7672
MONDAY-FRIDAY, 9 AM TO 6 PM, EASTERN TIME
VISIT THE CEPPO HOME PAGE ON THE WORLD
WIDE WEB AT:
http://www.epa.gov/swercepp/
NOTICE
The statements in this document are intended solely as guidance. This document does not substitute for EPA's or other
agency regulations, nor is it a regulation itself. Site-specific application of the guidance may vary depending on process
activities, and may not apply to a given situation. EPA may revoke, modify, or suspend this guidance in the future, as
appropriate.
-------
------- |