EPA-430/9-75-014
DISPOSAL OF
ORGANOCHLORINE WASTES
BY INCINERATION AT SEA
Office of Water and Hazardous Materials
U.S. ENVIRONMENTAL PROTECTION AGENCY
Washington, D. C. 20460
/
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DISCLAIMER
This report has been reviewed by the Office of Water and
Hazardous Materials, EPA, and approved for publication.
Mention of trade names or commercial products does not
constitute endorsement or recommendation for use.
DISTRIBUTION STATEMENT
Document is available in limited quantities through the
U. S. Environmental Protection Agency, Forms and Publication
Center, Route 8, Box 116, Raleigh, North Carolina 27607.
It is also available to the public through the National Technical
Information Service, Springfield, Virginia 22151.
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EPA-430/9-75-014
DISPOSAL OF
ORGANOCHLORINE WASTES
BY INCINERATION AT SEA
BY:
T. A. Wastler
Carolyn K. Offutt
Charles K. Fitzsimmons
Paul E. Des Rosiers
Ul
0
JULY 1975
Division of Oil and Special Materials Control
Office of Water and Hazardous Materials
U.S. ENVIRONMENTAL PROTECTION AGENCY
Washington, D. C. 20460
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ABSTRACT
The first officially sanctioned incident of ocean incineration
in the United States occurred aboard the M/T Vulcanus in the
Gulf of Mexico from October 1974 through January 1975 under
an ocean dumping permit issued by the U. S. Environmental
Protection Agency under the authority of the Marine Protection,
Research, and Sanctuaries Act of 1972, as amended, to the Shell
Chemical Company in Deer Park, Texas, for ocean incineration
of organochlorine wastes.
This report describes the monitoring activities undertaken
to evaluate ocean incineration as a disposal method. A total of
16, 800 metric tons of waste were incinerated at a maximum rate
of 25 metric tons per hour with a 1200°C minimum and a 1350°C
average flame temperature. Stack gas emissions were monitored
for plume dispersion characteristics and to determine combustion
efficiency. The findings indicate that more than 99. 9 percent of
the wastes were oxidized. Marine monitoring surveys indicate
that there were no measurable increases in concentrations of
trace metals and organochlorides in the water and marine life.
Results of the project indicate that ocean incineration could
be a viable alternative of waste disposal which should be considered
along with other disposal methods including direct ocean disposal,
land disposal, and land incineration.
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Foreword
The controlled oxidation by incineration of combustible waste
products on land and from certain offshore mining facilities has
been a world-wide practice for many years. The incineration of
highly toxic chemical wastes on board specially designed vessels
has been practiced off European coasts only within the past few
years. This technology was demonstrated off U. S. coasts, for
the first time during October 1974 through January 1975,
sanctioned by an ocean dumping permit issued-by the U. S.
Environmental Protection Agency under the authority of the Marine
Protection, Research, and Sanctuaries Act of 1972, as amended.
A review was made of the European monitoring procedures
for stack gas emissions and possible impacts by the emissions on
both the air and marine environment in the immediate vicinity of
the operating incineration vessel. These procedures were not
totally adequate for the purpose of assessing conformity with this
country's ocean dumping criteria. Consequently, a major
monitoring and surveillance program was implemented by the
Oil and Special Materials Control Division (OSMCD), Office of
Water and Hazardous Materials, in connection with the first and
second "burns" of the chemical waste in the Gulf of Mexico by the
M/T Vulcanus.
Assisting in the program's conceptual design, analyses, and
interpretation of results from the two research burns were the
following agencies:
U. S. Environmental Protection Agency:
Office of the Director, OSMCD, Hdqtrs.
Marine Protection Branch, OSMCD, Hdqtrs.
Spill Prevention and Control Branch, OSMCD, Hdqtrs.
Office of General Counsel, Hdqtrs.
Office of Research and Development, Hdqtrs.
National Environmental Center, Research Triangle Park,
North Carolina
National Environmental Research Center, Las Vegas, Nevada
National Environmental Research Center, Cincinnati, Ohio
Gulf Breeze Environmental Research Laboratory,
Gulf Breeze, Florida
National Field Investigation Center, Denver, Colorado
Region II, Edison Laboratory, Edison, New Jersey
Region HI, Annapolis Field Station, Annapolis, Maryland
Region IV, Athens Laboratory, Athens, Georgia
111
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Region VI: Regional Office, Dallas, Texas; Lower Mississippi
River Project, Slidell, Louisiana; and Houston Facility,
Houston, Texas
National Aeronautics and Space Administration:
Langley Research Center, Hampton, Virginia
Goddard Space Flight Center, Greenbelt, Maryland
U. S. Coast Guard, Hdqtrs.
U. S. Coast Guard, District VIII, Air Station, Corpus
Christi, Texas
National Oceanic and Atmospheric Administration, National
Ocean Survey, Pascagoula, Mississippi
U. S. Department of the Interior, Patuxent Wildlife Research
Center, Patuxent, Maryland
State environmental agencies:
Louisiana, Florida, Alabama, and Texas
National Wildlife Federation, Washington, D. C.
American University, Washington, D. C.
Raytheon Company, Portsmouth, Rhode Island
TerEco Corporation, College Station, Texas
Shell Chemical Co., Houston, Texas
Participation of all these agencies is acknowledged, with
particular appreciation to the Coast Guard Air Station in Corpus
Christi, Texas, for aerial surveillance and navigational assistance
for EPA aircraft, and to the Shell Chemical Company for its
cooperation and commitment of resources on all aspects of this
project and for its permission to include, as Appendix A of
this report, the April 1975 Shell report "At Sea Incineration of
Shell Chemical Organic Chloride Waste: Stack Monitoring Aboard
the M/T Vulcanus. "
Special appreciation is extended to Irene Keefer for her editorial
services and the secretarial staff of the Oil and Special Materials
Control Division for their efforts in typing many drafts and revisions
to this report.
3nneth E. * Biglane, ^Director
Oil & Special Materialg^Cbntrol Division
Office of Water & Hazardous Materials
Environmental Protection Agency
Washington, D. C. 20460
IV
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TABLE OF CONTENTS
I. Summary, Conclusions, and Recommendations 1
Summary 1
Conclusions 3
Recommendations 5
Incineration Design and Operation 5
Monitoring 6
Communication and Navigation Aids 8
n. Introduction 9
HI. Description of Vulcanus 17
Tanks and Pumps 17
Incinerators 20
Recording and Control E uipment 21
IV. Permit Requirements During Vulcanus Missions 23
V. Results of Research Permit Burns 29
Feed Rates and Combustion Temperatures 29
Efficiency of Incineration 38
Stack Sampling Problems 39
Results from Burn I 42
Results from Burn II 43
Plume Characteristics 47
Oregon n Cruises - Burn I 47
Aerial Monitoring - Burn II 52
Chemical and Biological Impact on Marine Environment 59
Short-Term Effects 60
Long-Term Effects 71
Effects on Birds 74
VI. Results of Interim Permit Burns Monitoring Activities 75
Feed Rates and Combustion Termperature 75
Monitoring Activities 77
Appendix A. At-Sea Incineration of Shell Chemical Organic 81
Chloride Waste
Appendix B. Loss of Organochlorides in Teflon Bags 173
Appendix C. Equipment, Calibration Procedures, and Aircraft 179
Data From Aerial Monitoring of Research Burn n
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Page
Appendix D. Equipment and Procedures From Sea-Level 197
Monitoring of Effects on Marine Environment
Appendix E. Additional Data From Oregon II Monitoring of 211
Marine Environment
Appendix F. Log Sheets From Interim Permit Burns 219
Bibliography 225
Technical Report Data 227
VI
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FIGURES
Page
Figure III-l M/T Vulcanus Incinerating Organochlorine 18
Wastes of the Shell Chemical Company
in the Gulf of Mexico
*
Figure IV-1 Incineration Site for Vulcanus Missions 24
Figure V-l Sampling Train for Stack Gas Analysis, 41
Research Burn I
Figure V-2 Sampling Train for Stack Gas Analysis, 45
Research Burn II
Figure V-3 Environmental Protection Agency NERC 53
Las Vegas Aircraft With Sampling Probes
and Monitoring Instruments
Figure V-4 Plume of Ammonium Chloride From M/T 56
Vulcanus Induced by Addition of Ammonia
to Stack Emissions
Figure V-5 Vulcanus Plume Elevation, December 4, 1974 58
Figure V-6 Illustration of Transit Sampling Pattern Run 64
by Orca, Research Burn I
Figure V-7 Illustration of Axial Sampling and Axial 65
Control Sampling Patterns Run by Orca,
Research Burn I
Figure V-8 Sampling Pattern Run by the Orca To 68
Determine Immediate Effects, Research
Burn H
Figure VI-1 Natural Plume of Stack Emissions Due to 78
Meteorological Conditions
VII
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TABLES
Page
Table II-1
Table HI-1
Table V-l
Table V-2
Table V-3
Table V-4
Table V-5
Table V-6
Table V-7
Table V-8
Table V-9
Table V-10
Table V-ll
Table V-12
Table VI-1
Chronology of Ocean Incineration of Shell
Organochlorine Wastes on Gulf of Mexico,
August 1973-January 7, 1975
Specifications of M/T Vulcanus Incineration
Vessel
Chronology of Research Permit Burns,
October 19, 1974 - December 12, 1974
Elemental Analysis of Waste Feeds in Research
Burns
Major Components of Waste Feeds in Research
Burns
Incinerator Temperatures During Research Burns
Overall Efficiency of Combustion of Hydrocarbons
Analysis of Stack Gas Emissions in Research
Burn H
Monitoring of Vulcanus Plume in Research Burn II
Short-Term Effects From Incineration, First
Cruise of Oregon During Research Burn I
Short-Term Effects From Incineration, Second
Cruise of Oregon During Research Burn I
Short-Term Effects From Incineration, Orca
Cruise During Research Burn I
Analysis of Trace Metals in Sea Water, Orca
Cruise During Research Burn II
Analysis of Trace Metals and Organochlorides in
Plankton, Orca Cruise During Research Burn II
Chronology of Interim Permit Burns,
December 18, 1974-January 9, 1975
11
19
30
32
34
35
43
44
51
61
63
67
70
73
76
Vlll
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I. SUMMARY, CONCLUSIONS, AND RECOMMENDATIONS
SUMMARY
On September 27, 1974, the U. S. Environmental Protection
Agency (EPA) determined that ocean incineration of wastes is under
the purview of the Marine, Protection, Research, and Sanctuaries
Act of 1972, as amended. On October 10, 1974, EPA issued a
research permit for incineration at sea of 4, 200 metric tons (MT)
of organochlorine wastes from Shell Chemical Company's Deer
Park, Tex., plant. The wastes--a mixture of chlorinated hydro-
carbons with trichloropropane, trichloroethane, and dichloroethane
predominating--result from the plant's production of glycerin, vinyl
chloride, epichlorohydrin, and epoxy resins.
The incineration took place during October 20-28, 1974, in the
Gulf of Mexico at a new dumping site approximately 241 kilometers
(130nautical miles) from the nearest land. The wastes were in-
cinerated aboard the M/T Vulcanus, which is owned by Ocean
Combustion Services, B.V., of The Netherlands. For 2 years,
the vessel had incinerated similar wastes in the North Sea for
companies in The Netherlands, Great Britain, and Scandinavia.
The two high-temperature incinerators aboard the Vulcanus
are designed to oxidize upwards of 99. 9 percent of organochlorine
wastes. The resulting emissions consisted primarily of hydrogen
chloride, carbon dioxide, and water; they were discharged directly
into the atmosphere without scrubbing.
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In accordance with conditions of the permit, a substantial
monitoring effort was undertaken to determine the feasibility
of this waste disposal technique and the impact of the emissions
on the marine environment. A large amount of data was gathered
during the incineration. Following review of the results, EPA
concluded that the conditions and criteria of the initial research
permit had been met, although there were some shortcomings in
the monitoring efforts, and that the incineration resulted in no
significant adverse impact on the environment. On November 27,
1974, EPA granted a second research permit to incinerate another
shipload (4, 200 MT); the conditions were slightly different from
those of the first shipload. The monitoring requirements were
modified to correct some gaps in the information gathered on the
first incineration.
The second research burn took place December 2-9, 1974.
The following day EPA scientists and representatives of Alabama,
Florida, Louisiana, and Texas met and unanimously concluded
that incineration by the Vulcanus of Shell's remaining organo-
chlorine wastes, under the conditions imposed by the two research
permits, was an environmentally compatible means of disposing of
the wastes. On December 12, EPA issued an interim permit
for incineration of the remaining 8,400 MT. The wastes were
incinerated in two loads, on December 19-26, 1974, and on
December 31, 1974-January 7, 1975.
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CONCLUSIONS
1. The design and operation of the Vulcanus incinerator
were adequate for controlled oxidation of organochlorine
wastes of the type produced by Shell Chemical Company.
2. The ship's design did not include provisions for moni-
toring stack emissions, wind speed, and excess air flow
to the incinerators. In addition, the Vulcanus was not
equipped with sufficient navigation aids and communication
systems. Appropriate systems were subsequently provided.
3. The waste feed rates did not exceed the permit limit of
25 metric tons per hour, and the flame temperatures
complied with the 1, 200° C minimum and 1, 350° C average
temperature requirements.
4. Stack gas emissions were monitored for oxygen, carbon
monoxide, carbon dioxide, chlorine, hydrogen chloride,
and unburned organochlorine compounds. The findings
indicate that more than 99. 9 percent of the wastes were
oxidized.
5. Plume dispersion characteristics were difficult to
determine since the natural plume was not visible except
during surveillance overflights made on the last interim
permit burn. A specially equipped EPA aircraft determined
the configuration of the invisible plume by collecting emis-
sions data at cross-sectional and longitudinal points downwind
from the vessel.
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6. The natural plume trailed back from the Vulcanus stack
at an angle of about 20° from the horizontal, reaching a maxi-
mum altitude of 850 meters, mean sea level. The plume
fanned out horizontally to a width of about 1, 200 meters,
at a distance of 2, 400 meters downwind from the stack.
Maximum hydrogen chloride concentrations measured
by the aircraft occurred between 100 to 240 meters altitude
and zero to 400 meters downwind, with a maximum value
of 3 parts per million (ppm). Sea-surface monitoring indi-
cated a maximum concentration of 7 ppm at 6 meters above
sea level.
7. Ammonia was added to the gaseous emissions above the
stack, and the ammonium chloride cloud generated showed
a comparable configuration to that determined by the aerial
monitoring of the natural plume.
8. Four marine monitoring surveys indicate that there were
no measurable increases in concentrations of trace metals
and organochlorides in the water and marine life. Addition-
ally, no adverse effects on migratory birds were observed.
9. The monitoring requirements imposed by EPA were
appropriate to determine the impact on the marine environ-
ment, the characteristics of the plume, and the degree of
waste oxidation by incineration of the Shell wastes.
10. Results of the project indicate that at-sea incineration of
the Shell wastes was compatible with the intent of the Marine
k
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Protection, Research, and Sanctuaries Act, and that
ocean incineration could be a viable alternative which
should be considered along with other disposal methods,
including direct ocean disposal, land disposal, and land
incineration.
RECOMMENDATIONS
As a result of the information acquired during the two
research permit burns, a number of deficiencies, as well as
desirable features, were noted in the design and operation of the
Vulcanus. Anticipating that other applications will be submitted
for incineration of liquid waste by the Vulcanus or other incinerator
ships, EPA is at this time delineating preliminary recommendations
relating to incinerator design and operation, monitoring, and
communication and navigation aids. These recommendations do
not include requirements that might be imposed for an applicant
to provide additional monitoring of the marine environment, plume,
and waste characteristics, as well as other information. Final
requirements will not be established until additional investigations
and studies are completed.
The following recommendations address those areas of major
interest to EPA. They do not include ship design and operation
requirements that may be imposed by the U. S. Coast Guard.
Incinerator Design and Operation
1. The incinerator shall be designed to operate at a temper-
ature range of 1, 300° to 1, 500° C, with a dwell time
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range of 0. 5 to 1. 5 seconds. Dwell time is to be deter-
mined from incinerator volume and volumetric flow rate
at the specified temperature.
2. Special incinerator tests to determine profiles of stack
gas emissions and temperature within the incinerator may
be required for all new designs. Testing requirements
for existing incinerators will be considered on a case by
case basis.
3. Automatic controls shall be installed to prevent inciner-
ator operation at temperatures below 1, 200° C.
4. Equipment may need to be installed to control excess air
feed rates,if wastes with high chlorine levels are to be
incinerated.
5. Tankage, pumping systems, and piping shall be incorpor-
ated into the design of the vessel to permit addition of fuel
oil for incineration of wastes with low heat values. The
method of fuel addition must ensure complete mixing of
fuel and wastes.
6. Feed rates, fuel requirements, and excess air shall be
determined for each waste before incineration and before
permit conditions are set.
Monitoring
1. Thermocouples shall be installed in the incinerator
stack at two levels and calibrated to determine flame
temperature and exit gas temperatures. Sufficient
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thermocouples are to be installed to ensure monitoring
of the temperatures throughout the burn period.
2. Sampling ports shall be provided in each stack to permit
collection of the gaseous emissions for analysis. -The
system shall include the sample probes and equipment
needed to withdraw samples from various points within the
stack.
3. Appropriate conduits, cooling lines, and heating systems
shall be provided from the sampling ports to the ship's
laboratory. Provisions shall be incorporated in the design
to permit easy removal and replacement of the sample
transfer lines.
4. Laboratory space shall be available on the ship for
devices to determine oxygen, chlorine, and carbon monoxide.
In designing the laboratory, consideration should be given
to special requirements such as ventilation, power supply,
sample storage, and quarters for laboratory personnel.
5. Meters or equivalent methods to determine waste feed
rates shall be installed.
6. Wind speed and direction monitoring devices shall be
installed at an appropriate location on the ship to minimize
interference with true readings, and all data shall be trans-
mitted to a continuous recorder.
7. All data on temperature, feed rate, pump status (on-off),
time, date, location (if possible), and wind speed and
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direction shall be automatically recorded in an enclosed
chamber which can be sealed by government officials.
In addition, all data transmitted to the sealed chamber
shall also be transmitted to a secondary readout point
where they can be recorded by the ship's crew.
8. Equipment and piping shall be provided to permit release
of ammonia into the gaseous emissions at a point above
the incinerator stack.
Communication and Navigation Aids
1. The ship shall be equipped with a LORAN system to
determine its position at any time.
2. Equipment shall be installed to permit radio telephone
communications with commercial marine radio systems
and the U. S. Coast Guard. The system shall be capable
of ship-to-shore and ship-to-ship voice communications.
8
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II. INTRODUCTION
About 9 million metric tons (MT) of toxic chemical wastes are
generated annually in the United States. (1) Their tonnages have
steadily increased over the years, generally paralleling increased
industrial production. At the same time, growing concern in
protecting public health and the environment has made disposal more
difficult.
For industrial plants located near coastlines--the Shell Chemical
Company plant in Deer Park, Tex., for example--ocean dumping
has been a long-standing practice. Since 1954, the Shell plant,
which manufactures glycerin, vinyl chloride, epichlorohydrin, and
epoxy resins, had dumped wastes directly into the Gulf of Mexico.
At first, the dumping was with the qualified approval of the U. S.
Army Corps of Engineers and the U. S. Coast Guard. Following
passage of the Marine Protection, Research, and Sanctuaries Act
of 1972, as amended, the wastes were dumped under a permit granted
by the U.S. Environmental Protection Agency (EPA). That permit
expired in November 1973.
Shell applied for a permit to continue dumping, and, following
a public hearing in Houston, Tex., on December 14, 1973, received
a permit for dumping spent caustic and biological sludge.
1. ReporFto Congress on Hazardous Waste Disposal. U.S.
Environmental Protection Agency, Office of Solid Waste Manage-
ment Programs, Washington, D. C. June 30, 1973.
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(For a chronology of disposal of the Shell wastes, see Table II-l.)
However, EPA held in abeyance the permit for dumping the 1, 900
metric tons (MT) of organochlorine wastes the Deer Park facility
generates every month, pending detailed studies of the waste compo-
sition and continued investigation of alternative means of disposal.
The wastes are a mixture of chlorinated hydrocarbons with trichloro-
propane, trichloroethane, and dichloroethane predominating. They
do not contain vinyl chloride. (2) The emission of organochlorine
compounds into the environment is generally undesirable because
such compounds are extremely stable and persistent. They can enter
the food chain and accumulate in some organisms. Even small
quantities of some compounds can be acutely toxic.
In April 1974, Shell submitted additional information and renewed
its application for a permit for ocean disposal. Shell pointed out
that the wastes at Deer Park were being stored in above-ground
tanks. Long-term storage of large amounts in these tanks carried
the potential for leaks from corrosion, accidental ignition, and spills
from natural disasters. Disposal on land was wholly unsuitable.
There was no current market for the material. However, in 1975
Shell plans to upgrade as much as 20 percent of the wastes into useful
products.
2. Miller, Taylor O. Report of the Presiding Officer. Public hearing
held Oct. 4, 1974, in Houston, Tex., concerning Shell Chemical
Co. application for Permit No. 730D008C to dispose of organo-
chlorine wastes. U.S. Environmental Protection Agency, Oil and
Special Materials Control Division, Washington, D. C. Oct. 9,
1974.
10
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TABLE II-1
CHRONOLOGY OF OCEAN INCINERATION OF SHELL
ORGANOCHLORINE WASTES IN GULF OF MEXICO,
AUGUST 1973-JANUARY 7, 1975
August 30, 1973
December 14, 1973
January 23, 1974
April 1, 1974
July 16, 1974
September 27, 1974
September 27, 1974
October 4, 1974
October 10, 1974
October 20-28, 1974
November 14, 1974
November 27, 1974
December 2-9, 1974
December 10, 1974
December 12, 1974
December 19-26, 1974
Dec. 31, 1974-Jan. 7,
1975
Shell Chemical Co. applies for dumpirig permit
Public hearing; EPA holds permit in abeyance
EPA declares ocean incineration does not re-
quire dumping permit
Shell submits additional information and renews
application
Shell contracts for incineration of wastes
aboard Vulcanus
EPA modifies its decision, declaring ocean
incineration does require dumping permit
Shell amends application
Public hearing on Shell's amended application
EPA grants research permit authorizing
incineration of 4,200 metric tons
Research Burn I takes place
Results of Research Burn I reviewed at
technical meeting
EPA grants research permit authorizing
incineration of 4, 200 metric tons
Research Burn II takes place
EPA technical staff and State representatives
conclude ocean incineration of remaining wastes
is environmentally sound
EPA grants permit for incineration of remaining
8, 400 metric tons of wastes
Remaining wastes incinerated
Source: Records in EPA Headquarters, Oil and Special Materials
Control Division, Washington, D. C.
11
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Incineration was another approach to disposal, and Shell plans
to have a high-temperature land-based incinerator in operation in
1977. Incineration on a temporary basis with waste disposal con-
tractors was considered only a limited solution--not enough capacity
was available to handle the tonnages Shell produces. A more
promising approach appeared to be incineration on the high seas.
At least three incinerator vessels are now in use in Europe.
In July 1974, Shell contracted with Ocean Combustion Services,
B. V. (OCS) of The Netherlands, a wholly owned subsidiary of the
Hansa Lines,for the services of the M/T Vulcanus. For 2 years,
the vessel had incinerated similar wastes in the North Sea for
companies in The Netherlands, Great Britain, and Scandinavia.
The high-temperature incinerators aboard the Vulcanus are
designed to oxidize upwards of 99. 9 percent of organochlorine
wastes. The resulting emissions consist primarily of hydrogen
chloride, carbon dioxide and water; they are discharged directly
into the atmosphere with no scrubbing.
Anticipating operating the Vulcanus in the United States, OCS
requested, through an American representative, an opinion from
EPA as to whether the Marine Protection Act applied to ocean
incineration. In response to the request, which did not detail spe-
cifics, EPA's Office of General Counsel, on January 23, 1974,
rendered the opinion that the Act did not apply. Subsequently, in
response to questions raised by the National Wildlife Federation
12
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and the Committee on Merchant Marine and Fisheries of the House
of Representatives, and in view of certain new information that came
to its attention, EPA modified its previous opinion. Shortly before
September 27, 1974, when the Vulcanus was scheduled to arrive
at the Port of Houston, EPA declared that ocean incineration does
require a permit under the Act. On September 27, Shell amended
its earlier application, requesting permission to burn 16,800 MT
of organochlorine wastes at sea.
EPA scheduled a public hearing on the amended application in
Houston on October 4, and at the same time (as required by Federal
regulation) published its tentative determination to grant a research
permit for incineration of 4, 200 MT (one shipload). At the hearing,
the presiding officer and a panel of five EPA technical personnel
heard testimony and questioned 18 witnesses concerning the nature
of the proposed incineration and the likely effects on the environment.
The recommendations in summary form (2) of the presiding officer
and the panel were to:
+ Issue a research permit for incineration of 4, 200 MT of organo-
chlorine wastes at a new site in the Gulf of Mexico.
+ Require detailed monitoring of the initial research burn, includ-
ing monitoring of the efficiency of combustion (which must
be greater than 99. 9 percent), the dispersion characteristics
of the gaseous emissions, and the effects of incineration on
the environment.
13
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+ Provide for a review by EPA of the data obtained and make
the data available to,t.he.'public.
+ Form a special EPA team of experts to oversee the moni-
toring requirements imposed under the permit to enable
complete and rapid investigation of the effects of incineration.
+ Issue an interim permit for incineration of the remaining
12,600 MT of organochlorine wastes, if the basic conditions
specified in the research permit were met.
+ Conduct a continuing review of monitoring requirements
during the term of the research permit (and, if issued, the
interim permit) to design the best possible monitoring scheme
to determine the effects on the environment of high-temperature
incineration of organochlorine wastes at sea.
On October 10, 1974, EPA granted a research permit in
accordance with these recommendations. (3) The permit constitutes
the first official sanction the United States has given to high-tempera-
ture ocean incineration. EPA also designated a new site previously
unused for dumping (approximately 130 nautical miles or 241 kilo-
meters from the nearest land) where the incineration was to take
place. (4)
3. U.S. Environmental Protection Agency Research Permit No.
730D008C. Issued under Marine Protection, Research, and Sanc-
tuaries Act (Ocean Dumping), Washington, B.C., Oct. 10, 1974.
4. Federal Register, Vol. 39, No 202, p 37057-8, Oct. 17, 1974.
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The first 4, 200 MT were burned during October 20-28. A great
deal of data was gathered during Research Burn I, and the results
were reviewed at a technical meeting in Houston on Novermber 14.
Dissatisfaction was expressed with some aspects of the first burn,
with the major criticisms coming from the Gulf Coast States.
Principally, they objected to the short time they were given to
consider issuance of the first permit, their limited participation
in the monitoring activities, and the adequacy of the data gathered
in monitoring. (5,6)
EPA concluded, nevertheless, that the conditions and criteria
of the initial research permit had been met, and that no information
gathered in Research Burn I in any way changed or called into
question the findings and conclusions of the original hearing panel.
Although there were some shortcomings in the monitoring efforts,
the incineration resulted in no significant adverse impact on the
environment. Therefore, the EPA staff at the technical meeting
recommended granting a second research permit for Shell to burn
an additional 4,200 MT under conditions slightly different from
F! Frick, G. William. Report of the Presiding Officer.Technical
mee ting held Nov. 14, 1974, in Houston, Tex., regarding
application of Shell Chemical Company Permit No. 730D008C pur-
suant to the Marine Protection, Research, and Sanctuaries Act
of 1972. U. S. Environmental Protection Agency, Oil and Special
Materials Control Division, Washington, D. C., Nov. 27, 1974.
6. Train, Russell E. Supplementary decision of the Administrator
regarding application of Shell Chemical Company for Marine Pro-
tection, Research, and Sanctuaries Act Permit No. 730D008C.
U. S. Environmental Protection Agency, Oil and Special Materials
Control Division, Washington, D.C., Nov. 27, 1974.
15
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those in the first burn. The monitoring requirements were modified,
and a working group, which included State representatives, was
established to review potential alternative monitoring approaches. (5)
On November 27, EPA granted a research permit for incineration
of an additional 4, 200 MT.
Research Burn II took place December 2-9. On December 10,
EPA scientists and representatives of Alabama, Florida, Louisiana,
and Texas met in Dallas to consider the results. Their unanimous
conclusion was that incineration by the Vulcanus of Shell's remaining
8, 400 MT of organochlorine wastes, under the conditions imposed
by EPA in the two research permits, was an environmentally com-
patible means of disposing of the wastes. (7,8)
On December 12, EPA issued an interim permit to Shell for
incineration of the remaining wastes. The special conditions for
disposal activities were the same as in the second research permit.
The remaining wastes were incinerated in two loads, on December
19-26 and December 31, 1974-January 7, 1975.
7. Biglane, Kenneth E. Staff Report Regarding Application of Shell
Chemical Company and Ocean Combustion Services, B. V., For
Permit No. 730D008C Pursuant to the Marine Protection,
Research, and Sanctuaries Act of 1972. U. S. Environmental
Protection Agency, Oil and Special Materials Control Division,
Washington, D.C., Dec. 12, 1974.
8. Preliminary Report, Marine Environmental Monitoring of Vulcanus
Research Burn II, December 2, 1974. U.S. Environmental Pro-
tection Agency, Oil and Special Materials Control Division,
Washington, D. C., Dec. 10, 1974.
16
-------
HI. DESCRIPTION OF VULCANUS
The M/T Vulcanus is a double-hull, double-bottom vessel
that meets all applicable requirements of the Intergovernmental
Maritime Consultative Organization (IMCO) concerning transport
of dangerous cargo by tanker. (See Figure III-l for photograph of
Vulcanus and Table in-1 for specifications.) Before being permitted
to operate in U.S. waters, she was modified to meet requirements
of the U. S. Coast Guard. Originally a cargo ship, she was
converted to her present use in 1972. Her size—an overall length
of 102 meters, a beam of 14.4 meters, and a maximum draft of
7.4 meters--enables her to operate worldwide. She is also able
to operate in rough weather. Her crew numbers 16--10 to operate
the vessel and six solely to operate the incinerators. Two diesel
engines drive the single propeller to give cruising speeds of 10
to 13 knots.
TANKS AND PUMPS
The vessel's cargo tank capacity of 3, 503 cubic meters (cbm)
is divided into 15 cargo tanks ranging in size from 115 to 574 cbm.
The engine room is separated from the cargo tanks by double bulk-
heads; the pump room and generator are situated in between. Tanks
are filled from above through a manifold on deck with the usual
tank tops. The vessel is not fitted with a loading pump, although
a portable pump can be brought on board. She requires 2 days
17
-------
Figure III - 1
M/T "Vulcanus" incinerating organochloride wastes of the Shell Chemical Company in the Gulf of Mexico.
Source: U.S. Environmental Protection Agency, Region VI Laboratory, Houston, Texas
-------
TABLE III-l
SPECIFICATIONS OF M/T VULCANUS INCINERATION VESSEL
Length overall
Breadth
Draft, maximum
Deadweight
Speed
Tank capacity
Number of tanks
Tank coating
Loading equipment
Hose connections
Safety equipment
Waste to be processed
Incinerators
Outside diameter
Inside diameters
Height
Dwell time
Air supply
Burners
Incinerator capacity
101. 95 meters
14. 40 meters
7.40 meters
4, 768 metric tons
10-13 knots
3, 503 cubic meters (cbm)
15, ranging in size from
115 cbm to 574 cbm
No coating in tanks, pipes, pumps, etc.
All equipment consists of low carbon steel
Not available, but can be placed on
board, if required
10.2, 15.2, and 20. 3 centimeters
(4, 6, 8 inches) in diameter
Specially designed for this task and in
accordance with latest regulations of
IMCO, Scheepvaart-Inspectie (The Hague),
and the U. S. Coast Guard
Must be liquid and pumpable. May contain
solid substances in pieces up to 5 centi-
meters in size. Must not attack mild steel
2
5. 50 meters
4. 80 meters
10. 45 meters
0.5-1.5 seconds
180,000 cubic meters/hour
3/incinerator (Saacke type)
20-25 tons/hour
Source: Ocean Combustion Services
-------
to load all tanks. Pipes leading from the tanks into the incin-
erators run through an elaborate manifold in the pump room,
where another pipe system leads to the incinerators. The pumps
can reduce lumps of soft materials as large as 5 centimeters
to 0. 2 centimeter. Generally, any tank can be connected to any
incinerator. Safety mechanisms guard against spillage from tanks
during loading. Tanks are not washed between loads, and the
vessel is designed so that the tanks cannot discharge directly to
the ocean except in emergency conditions.
INCINERATORS
Two combustion chambers lined with silica firebrick are
located at the stern of the Vulcanus. Their maximum outer dia-
meter is 5. 5 meters, and the inside diameter is 4. 8 meters.
The total height, including the stack, is 10.45 meters. The volume
of each combustion chamber is calculated to be 88 cbm, and the
dwell time is 0. 5-1. 5 seconds. Each chamber has three burners
with rotating cup fuel injection systems that provide vortex
turbulence and distribution of feed throughout the entire chamber.
It is theoretically possible to simultaneously burn six different
wastes with different flashpoints. Total waste throughput is 20
to 25 MT per hour. About 9 days are required to burn a shipload
of wastes.
In operation, the furnace is preheated with fuel oil to a mini-
mum of 1, 200° C. The wastes are fed to the incinerators using
the injection pumps connected to one or more tanks. The feed rate
20
-------
is regulated to maintain the desired temperature by manually
adjusting the valves to the pumps. Fuel oil must be continuously
injected for wastes having a heating value below 3, 000 kilo-
calories per hour. If the temperature in the incinerators drops
below the required temperature, the waste supply shuts off. If
the flame in the burner goes out for any reason, an alarm sounds
and a light goes on automatically.
During normal operation, each burner requires cleaning once
during a 9-day burn; burners are usually cleaned sequentially
to maintain high combustion temperatures. The waste tanks are
gauged and logged manually by the operator. The total air feed
capacity is 180, 000 cbm per hour. An alarm light goes on if
the air flow is insufficient, but there is no equipment for moni-
toring excess air flow to the incinerator. Two diesel generators
with a total capacity of 750 kilowatts supply power for the two
incinerator systems.
RECORDING AND CONTROL EQUIPMENT
A control panel on the Vulcanus contains meters recording
temperatures inside the incinerators at two points, a time clock
with date, control lamps showing when burners and pumps are
switched on, and a Decca-Navigator MK21 for positioning.
However, the Decca Navigator system is not compatible with the
U. S. navigation system, so another means of navigation is
required--LORAN equipment, for example. There is no equipment
21
-------
to measure wind speed. The control panel is photographed by
an automatic camera every 15 minutes. At the start of the voyage,
government officials can seal the "black box" on the bridge which
contains this gear, then inspect it at the end.
22
-------
IV. PERMIT REQUIREMENTS DURING VULCANUS MISSIONS
The permits granted by EPA for incineration of the Shell wastes
imposed special conditions. (9-11) In route to the prescribed site
(Figure IV-1) the Vulcanus had to navigate around four reefs.
During incineration, the Vulcanus had to:
+ Be within a prescribed site, which is from 26° 20 minutes
minutes to 27° 00 minutes north latitude, and from 93°
20minutes to 94 degrees 00 minutes west longitude. The
4,770 square kilometer site, designated by EPA and
accepted by the U.S. Coast Guard and Army Corps of
Engineers, is outside any existing dump site. (12)
+ Maintain a position downwind from any vessel other than
those engaged in environmental monitoring.
+ Maintain an effective wind velocity over the incinerator
stacks of 10 knots (to be comprised of wind or vessel
speed or both).
9. U. S. Environmental Protection Agency Research Permit No.
730D008C. Issued under Marine Protection, Research, and
Sanctuaries Act (Ocean Dumping), Washington, D. C., Oct. 10,
1974.
10. U.S. Environmental Protection Agency Research Permit No.
730D008C(2). Issued under Marine Protection, Research, and
Sanctuaries Act (Ocean Dumping), Washington, D. C.,
Nov. 27, 1974.
11. U.S. Environmental Protection Agency Interim Permit No.
730D008C(3). Issued under Marine Protection, Research, and
Sanctuaries Act (Ocean Dumping), Washington, D. C.,
Dec. 12, 1974.
12. Federal Register, Vol. 39, No. 202, p 37057-8, Oct. 17, 1974.
23
-------
Figure IV-1 Incineration site for Vulcanus missions.
24
-------
The incineration process itself had to meet certain require-
ments. Total feed rate of wastes was not to exceed 25 MT per
hour. (The first research permit specified 20 MT, but con-
ditions were revised during incineration to 25 MT to prevent
operational problems.) No incineration was to occur below
1,200° C, except that during Research Burn I, eight 4-hour burns
could be made to determine combustion efficiencies at different
temperatures. The permits required that temperature be measured
at two points within each incinerator. On Research Burn I, the
minimum average combustion temperature had to be maintained at
1,400° C (a running 4-hour average). On subsequent burns the
average temperature was dropped to 1, 350° C.
On Research Burn I, combustion efficiency had to be maintained
at no less than 99. 9 percent. After reviewing the analyses of stack
emissions from the first burn, and in response to comments from
representatives of the Gulf States, EPA required several modi-
fications in monitoring of stack emissions to better determine the
combustion efficiencies. Oxygen and carbon monoxide were to be
monitored continuously and the results recorded on strip charts.
Oxygen levels in the stack gas were to be no lower than 3 percent
to ensure complete combustion and no higher than 10 percent to
minimize formation of chlorine gas. Another modification required
by EPA was that emissions of unburned organochlorine compounds
were not to exceed 10 ppm, and the sampling system was required
-------
to demonstrate that it was trapping at least 50 percent of the
organochlorine emissions. These emissions, along with chlorine
levels were to be determined at least twice during each 24-hour
incineration period. In addition, the sampling line was to be
heated to eliminate condensation of stack gases.
A time clock with control lamps was required to show when
the incinerators were operating The automatic camera was to
photograph the control panel every 15 minutes, and the box on the
bridge was to be sealed. In addition, the interim permit called
for the Vulcanus to keep a separate log book and surrender it to
EPA or the Coast Guard at the conclusion of each voyage or upon
command. The Vulcanus Master was to enter the following infor-
mation each watch:
+ Time and data.
+ Black box temperature readings in combustion room.
+ Controller temperature reading.
+ Waste feed rates.
+ Switching of waste tanks.
+ Wind speed and direction.
+ Location.
Monitoring the ambient air and the marine environment, an
important part of the two research burns, was substantially reduced
in the interim burns. To make the plume visible to monitoring
26
-------
vessels and aircraft, the second research permit and the interim
permit required the Vulcanus to carry a device for adding ammonia
to incinerator emissions. The interim permit called for unan-
nounced flights to be made over the vessel while it was incinerating.
27
-------
V. RESULTS OF RESEARCH PERMIT BURNS
Shell Chemical, its contractor, and EPA, with the support of
state and other Federal agencies, monitored the two research permit
burns. (For a chronology of events in the two research burns, see
Table V-l.) A two-man Shell research team on board the Vulcanus
monitored incinerator conditions (feed rates and combustion temp-
eratures) and combustion efficiencies, as well as meteorological
conditions. An EPA observer was also on board. (A technical report
on Shell's monitoring activities is attached as Appendix A.) Effects
on the marine environment were monitored principally by scientists
aboard the R/V Oregon II and the M/V Orca. During the second
research burn, an aircraft from EPA's National Environmental
Research Center (NERC) in Las Vegas, Nev. , monitored the plume
to detect its size, shape, and HC1 concentration.
Many of the monitoring systems used were research prototypes
designed especially to obtain data on this unique method of incineration.
Numerous problems were encountered; nevertheless, enough infor-
mation was collected to meet EPA's monitoring objectives.
FEED RATES AND COMBUSTION TEMPERATURES (13)
During Research Burn I, the waste feed rates averaged 21.2 MT
per hour over the 8-day incineration. On Research Burn II, the rates
averaged 24. 5 MT per hour. Feed rates were measured by the time
required to empty the tanks of a known volume.
13. Badley, J. H., A. Telfer, E. M. Fredericks. At-Sea Incineration
of Shell Chemical Organic Chloride Waste, Stack Monitoring Aboard
the M/T "Vulcanus". Technical Progress Report BRC-CORP 13-
75-F. Shell Development Co., Bellaire Research Center, Houston,
Tex., 1975.
29
-------
TABLE V-l
CHRONOLOGY OF RESEARCH PERMIT BURNS,
OCTOBER 14, 1974 - DECEMBER 12, 1974
Event
Time Date (1974)
RESEARCH BURN I
M/T Vulcanus departs Deer Park, Tex.
Incinerators start to heat
M/V Orca arrives burn site
M/T Vulcanus arrives burn site
U. S. Coast Guard conducts aerial monitoring
Incineration starts
Incineration stops temporarily
M/V Orca departs burn site
R/V Oregon II arrives burn site
Incinerators start to heat
Incineration restarts
R/V Oregon II conducts monitoring
R/V Oregon II departs burn site
M/V Orca arrives burn site
M/V Orca conducts monitoring
Meeting on monitoring, New Orleans, La.
M/V Orca conducts monitoring
M/V Orca departs burn site
U. S. Coast Guard conducts aerial monitoring
R/V Oregon II arrives burn site
R/V Oregon II conducts monitoring
R/V Oregon II conducts monitoring
Incineration ends
M/T Vulcanus departs burn site
R/V Oregon II conducts monitoring
R/V Oregon II departs burn site
M/T Vulcanus arrives Port of Houston, Tex.
Technical meeting to evaluate data,
Washington, D. C.
Technical conference to evaluate Research
Burn I, Houston, Tex.
EPA grants second research permit,
effective Nov. 28-Dec. 16, 1974
1100
2100
1000
1100
(PM)
0430
0630
0038
2300
2000
0730
-
1930
0500
-
1300
-
1730
1000
1900
-
-
0400
0900
-
2200
0900
1000
1000
Oct. 14
Oct. 14
Oct. 15
Oct. 15
Oct. 15
Oct. 16
Oct. 16
Oct. 17
Oct. 17
Oct. 19
Oct. 20
Oct. 20
Oct. 20
Oct. 21
Oct. 21
Oct. 22
Oct. 22
Oct. 22
Oct. 24
Oct. 27
Oct. 27
Oct. 28
Oct. 28
Oct. 28
Oct. 28
Oct. 28
Oct. 29
Nov. 7
Nov. 14
Nov. 27
30
-------
TABLE V-l (CONT. )
Event Time Date (1974)
RESEARCH BURN II
Meeting to develop monitoring program,
Deer Park, Tex. 0800 Nov. 30
M/T Vulcanus departs Port of Houston, Tex. 1750 Nov. 30
Incinerators start to heat 1200 Dec. 1
Incineration starts 0710 Dec. 2
EPA aircraft departs on first mission 1140 Dec. 2
EPA aircraft departs on second mission 0930 Dec. 3
M/V Orca Arrives burn site 1130 Dec. 3
M/V Orca conducts monitoring - Dec. 3
EPA aircraft departs on third mission 0910 Dec. 4
M/V Orca conducts monitoring - Dec. 4
M/V Orca conducts monitoring - Dec. 5
M/V Orca departs burn site 1250 Dec. 5
Laboratory analyses start 1400 Dec. 6
Incineration ends 0945 Dec. 9
M/T Vulcanus arrives Port of Houston, Tex. 1040 Dec. 10
Briefing to EPA, Region VI, Dallas, Tex. 1000 Dec. 10
Technical meeting on monitoring requirements
for interim permit, Houston, Tex. 0800 Dec. 11
EPA grants interim permit, effective
Dec. 12, 1974-Jan. 20, 1975 - Dec. 12
Source: Records in EPA Headquarters, Oil and Special
Materials Control Division, Washington, D.C.
The compositions of the waste feeds were similar during the two
burns; both contained 63 percent chlorine, 29 percent carbon,
4 percent hydrogen, 4 percent oxygen, and traces of heavy metals
(Table V-2). Chlorine and oxygen were determined by neutron
activation, carbon and hydrogen by conventional combustion techniques,
and trace metals--except arsenic--by atomic adsorption. Arsenic
was converted to arsine and determined colorimetrically with silver
diethyldithiocarbonate. The major components of the waste feeds
31
-------
TABLE V-2
ELEMENTAL ANALYSIS OF WASTE FEEDS
IN RESEARCH BURNS
Research Burn I
Research Burn II
(% by weight)
29 29. 3, 29. 3
4 4.1, 4.1
4 3.7
63 63.5
(parts per million)
Carbon
Hydrogen
Oxygen
Chlorine
Copper
Chromium
Nickel
Zinc
Lead
Cadmium
Arsenic
Mercury
0.51
0.33
0.25
0.14
0.05
0.0014
<0. 01
<0.001
1.1
0. 1
0. 3
0. 3
0.06
0. 001
<0. 01
<0.002
Source: Badley, J. H., A. Telfer, E.M. Fredericks. At-Sea In-
cineration of Shell Chemical Organic Chloride Waste,
Stack Monitoring Aboard the M/T "Vulcanus. " Technical
Progress Report BRC-CORP 13-75-F. Shell Development
Co., Bellaire Research Center, Houston, Tex. 1975.
-------
were determined by gas chromatography. 1, 2, 3-Trichloropropane
was the largest single component (Table V-3).
Except for brief periods, flame temperatures, as measured with
an optical pyrometer, met permit conditions (Table V-4). Low temp-
eratures occurred in Research Burn I when feed rates were reduced
to conduct experimental burns called for in the permit and whenever
the burners were cleaned. At lower temperatures, carbon accum-
ulated, necessitating more frequent cleaning.
Two platinum -platinum /10 percent rhodium thermocouples were
mounted in each incinerator. One, located about 5 centimeters
from the inner surface of the firebrick, measures temperatures 200°
to 350° C lower than flame temperatures; they were referred to as
"indicator" temperatures since they were indicated on the panel of
the combustion room and in the sealed box. The second thermo-
couple, located 1. 3 centimeters from the surface, closed the feed
shutoff valve when its temperature dropped below 800° C. It could
also be used as a thermometer at higher temperatures by manually
searching for the temperature setting at which the feed valve relay
clicked. The temperatures thus measured—the "controller" temp-
eratures--were 100° to 250° C lower than flame temperatures.
In addition, Shell mounted another thermocouple on the probe
used to sample stack gases in each incinerator. However, the hot,
acid conditions in the stacks were extremely destructive to these
thermocouples, so they provided no useable data during the two
research burns.
33
-------
TABLE V-3
MAJOR COMPONENTS OF WASTE FEEDS
IN RESEARCH BURNS, PERCENT BY WEIGHT
Research Research
Burn I Burn II
1, 2, 3 Trichloropropane 27 28
Tetrachloropropyl ether 6 6
1,2-Dichloroethane 11 10
1,1,2 -Trichloroethane 13 13
Dichlorobutanes and heavier 11 10
Dichloropropenes and lighter 20 22
Allyl chloride 3 3
Dichlorohydrins 9 8
Specific gravity (25° F) 1.30 1.29
Source: Badley, J. H., A. Telfer, E. M. Fredericks. At-Sea
Incineration of Shell Chemical Organic Chloride Waste,
Stack Monitoring Aboard the M/T "Vulcanus. " Technical
Progress Report BRC-CORP 13-75-F. Shell Development
Co., Bellaire Research Center, Houston, Tex. 1975.
34
-------
TABLE V-4
INCINERATOR TEMPERATURES DURING RESEARCH BURNS, °C
(JO
\J\
Starboard Oven, °C
Date
Research
Burn I
Oct. 22
Oct. 24
Oct. 25
Oct. 26
Oct. 27
Research
Burn E
Dec. 2
Hour
5:00 p.m.
4:30 p.m.
10:10 a.m.
2:00 p.m.
6:35 p. m.
10:35 a.m.
6:00 p.m.
4:30 p.m.
8:30 p.m.
6:50 a.m.
7:15 a.m.
9:45 a. m.
10:10 a.m.
11:25 a.m.
1:10 p.m.
1:25 p.m.
4:00 p.m.
6:30 p.m.
10:00 p.m.
Indicator
1150
1150
1150
1150
1160
1130
1100
1130
1170
850
900
1030
1060
1090
1130
1150
1160
1180
1200
Controller
1220
1240
1230
1240
1250
1110
990
1310
1190
_
-
-
-
-
-
-
-
-
-
Pyrometer
1500
-
1450
1420
1450
1370
-
1450
1440
_
-
-
1500
-
-
1550
-
-
-
Port Oven, °C
Indicator
1150
1150
1165
1165
1170
1110
1130
1150
1170
900
940
1060
1080
1110
1140
1160
1160
1180
1200
Controller
1260
1270
1220
1220
1290
1090
1200
1330
1300
_
-
-
-
-
-
-
-
-
-
Pyrometer
1500 .
1450
1450
1450
1440
1340
1450
1450
1500
_
-
-
1570
-
-
1590
-
-
-
-------
TABLE V-4 (CONT'D)
INCINERATOR TEMPERATURES DURING RESEARCH BURNS, °C
tx)
Starboard Oven,
Date
Hour
Indicator
Controller
°C
Pyrometer
Port Oven, °C
Indicator Controller
Pyrometer
Research
Burn E
Dec. 3
Dec. 4
Dec. 5
(cont. )
7:20 a.m.
10:10 a.m.
12:25 p.m.
1:00 p.m.
2:35 p.m.
4:00 p.m.
5:15 p. m.
6:45 p. m.
7:30 p.m.
8:45 p. m.
10:25 p.m.
6:40 a.m.
9:00 a.m.
12:00 a.m.
1:30 p.m.
3:00 p.m.
5:00 p. m.
9:00 p.m.
3:00 a.m.
8:30 a.m.
10:30 a.m.
11:00 a.m.
2:00 p.m.
3:00 p.m.
3:40 p.m.
6:15 p. m.
10:00 p.m.
1220
1220
1200
1200
1190
1190
1130
1200
1200
1200
1200
1240
1220
1190
1180
-
-
1200
1190
1160
1180
1180
1180
1180
1180
1190
1200
_
-
-
-
-
-
-
-
1270
-
-
1340
-
-
1260
1180
1180
1300
_
1180
-
-
-
-
1260
-
1270
1600
-
-
1520
-
-
-
-
1560
-
-
1580
-
-
1550
-
-
1610
_
1550
-
-
-
-
1520
-
1570
1190
1200
-
-
-
-
-
-
1270
-
— —
1360
-
-
1180 1300
-
-
1220
_ _
1220
-
-
-
-
1320
-
1240
1590
-
-
1480
-
-
-
-
1510
-
—
1590
-
-
1580
-
-
1510
_
1500
-
-
-
-
1570
-
1560
-------
TABLE V-4 (CONT'D)
INCINERATOR TEMPERATURES DURING RESEARCH BURNS, °C
Starboard Oven, °C
Port Oven, °C
Date
Hour
Indicate"?Controller Pyrometer Indicator ControUer Pyrometer
u>
Research -
Burn n (cont. )
Dec. 6 7:30 a.m.
8:00 a.m.
10:00 a.m.
11:15 a.m.
12:00 a.m.
4:00 p.m.
7:30 p.m.
Dec. 7
Dec. 8
Dec. 9
11:30 p.m.
8:15 a.m.
11:15 a.m.
12:30 p.m.
4:00 p.m.
7:00 p.m.
11:00 p.m.
8:30 a.m.
10:15 a.m.
12:15 p.m.
2:50 p.m.
4:30 p.m.
8:00 p.m.
12:00 p.m.
6:30 a.m.
1100
1160 1220
1140
1140
1150
1150
1170
1180
1210 1180
1160
1160 1250
1160
1180
1200
1210
1190
1180
1160
1180
1180
1160
1160
1500
1550
• _
1500
-
1540
1570
1590
—
1570
-
1590
-
1610
1580
~
1570
1180
~ ~
1320
-
1240
-
1310 1340
1200
1210
1200
1200
1160
1180
-
"• ~
-
1500
1520
~
1570
-
1580
1510
1570
—
1530
-
1550
-
1530
1520
—
1480
Source: Badley, J. H., A. Telfer, E.M. Fredericks. At-Sea Incineration
of Shell Chemical Organic Chloride Waste, Stack Monitoring Aboard
the M/T "Vulcanus. 'r Technical Progress Report BRC-CORP 13-75-F.
Shell Development Co., Bellaire Research Center, Houston, Tex. 1975.
-------
The optical pyrometer gave the most reliable temperature
data. Because the controller and indicator thermocouples were
•insulated with firebrick and hence shielded from the acid, they were
more dependable than the Shell thermocouples. One indicator therm-
ocouple failed in the second burn, but enough data had been gathered
to establish a correlation between pyrometer and controller readings.
On the interim permit burn, EPA required that a log be kept of
both controller and indicator temperatures to provide backup data.
EFFICIENCY OF INCINERATION
In Research Burn I, the efficiency of the incineration
process was calculated in two ways--as the over-all efficiency of
combustion and as the degree of oxidation of organochlorides. (13)
The figures were calculated on the basis of carbon material balance
and organochlorine material balance. (For details on the method
of calculation, see Appendix A.) The unburned carbon atoms in
the stack gas were assumed to be proportional to the number of
carbon atoms in the waste itself. The amount of hydrochloric acid
collected by a specially designed water scrubber was a measure
of the amount of waste burned. Thus, the calculated efficiencies
depend principally on the analysis of organic material in the feed,
the analysis of hydrochloric acid collected, and the ratio of carbon
atoms to chlorine atoms in the waste. The results do not depend
on, or are insensitive to, the waste flow rate, the combustion
air rate, the size of the stack gas sample, and analysis of carbon
-------
dioxide or oxygen in the stack gas. They also do not depend on any
assumed molecular weight or specific composition of the chemical
compounds sampled.
In Research Burn II, combustion was considered complete
if stack emissions contained less than 1, 000 ppm of carbon monoxide,
3 to 10 percent oxygen, and less than 10 ppm of organochlorine
compounds. (14)
Stack Sampling Problems
The experimental problems involved in sampling and analyzing the
stack gases were formidable. (13) The exit gases were hot--in the
range of 1,100° to 1, 200° C--and corrosive, since they contained
5 to 6 percent hydrogen chloride (HC1). They were damaging to probes
inserted into the stack, as well as to analytical equipment. The
sample ports in the stacks were not suitable for conventional traversing
of the stack diameter. They were inclined 20° from the horizontal
and quite near the top of the stack. A probe inserted more than
halfway emerged above the top rim. Furthermore, access to the
stack during burning was limited because the exterior at the top was
hot and exposed to high concentrations of HC1 during wind gusts.
IT. FrTck, G. William. Report of the Presiding Officer. Technical
meeting held Nov. 14, 1974, in Houston, Tex., regarding appli-
cation of Shell Chemical Company for Permit No. 730D008C
pursuant to the Marine Protection, Research, and Sanctuaries
Act of 1972, Appendix A., U. S. Environmental Protection Agency,
Oil and Special Materials Control Division, Washington, D. C.
Nov. 27, 1974.
39
-------
Shell used a water-cooled Vycor glass probe for sampling the gases.
It was inserted into the port and rigged so it could traverse, by
manipulations from the deck level, across part of the stack.
Another constraint was a crowded ship with no space provided for
monitoring equipment to analyze the incinerator emissions. The only
space available for the analytical equipment required a sample line
of about 20 meters from the probe. The line--of 0. 63centimeter
(1/4-inch), thin-walled Teflon tubing--carried the combustion
products to the sample train for analysis.
The sample train for monitoring combustion efficiency in
Research Burn I contained two water scrubbers for absorbing HC1,
water-soluble unburned carbon compounds (most likely partially
burned hydrocarbons or hydrocarbon fragments), and water-soluble
organochlorides (Figure V-l). HC1 was measured by titration with
caustic. About 90 percent of the unburned carbon compounds were
in the water scrubbers. The remaining 10 percent (most likely meth-
ane or methane-like fragments) were measured in a Beckman 109A
flame ionization detector. The fractional combustion efficiency based
on unburned hydrocarbons is one minus the sum of the ratios of soluble
and insoluble hydrocarbons to carbon dioxide concentration.
Organochlorides were isolated from the water scrubber solution and
concentrated over macroreticular resins, removed with methknol, and
determined by combustion-microcoulometry.
Chlorine and water-insoluble organochlorides were determined in
a separate section of the sampling train. Chlorine gas was absorbed
140
-------
PROBE
GLASS
WOOL
G»S
IMPINGERS
HELICES
WATER IN ALL THREE
VENT
Figure V-l.
Sampling Train for Stack Gas Analysis,
Research Burn I
Source: Badley, J. H., A. Telfer, E. M. Fredericks. At-Sea
Incineration of Shell Chemical Organic Chloride Waste,
Stack Monitoring Aboard the M/T ' Vulcanus. " Technical
Progress Report BRC-CORP 13-75-F. Shell Development
Co., Bellaire Research Center, Houston, Tex. 1975.
1*1
-------
in a sodium arsenite scrubber and excess arsenite determined iodomet-
rically. The water-insoluble organochlorides were absorbed in an
isopropyl alcohol scrubber and determined directly by combustion-
microcoulometry. The fractional combustion efficiency based on un-
burned organochlorine compounds is one minus the ratio of unburned
organochlorine in stack gas (as chloride) to the total chloride in stack
gas.
Results From Burn I
Seven samples were taken during Research Burn I; in all cases, the
probe was inserted 28 centimeters into the stack gas stream, and the
combustion products were carried to the sampler train through 21.3
meters of Teflon tubing. Analysis indicated that the efficiency of com-
bustion of hydrocarbons was in excess of 99. 9 percent (Table V-5).
(13) Analysis of the water and isopropyl alcohol scrubber solutions
showed that, for the most part, the unburned materials were not
organochlorides--destruction of organochlorides was also in excess of
99.9 percent. The burn was continuously monitored for 119 hours of
the total of 190. 5 hours required to incinerate the wastes. During 77
hours of monitoring, no organochlorides were detected. For the re-
maining 42 hours, 2 parts per million (ppm) were found in the water
scrubber solution. No insoluble organochlorides were detected. Spot
checks made for chlorine detected 60 to 140 ppm.
Spot checks of carbon dioxide and oxygen were made (using a Burrell
Model B Industro Gas Analyzer) to determine the amount of excess
air in the incinerator and to calculate the combustion efficiencies. Ex-
cess air valves of about 100 percent were calculated.
-------
TABLE V-5
OVERALL EFFICIENCY OF COMBUSTION
OF HYDROCARBONS,RESEARCH BURN I
Sample
source
Water
scrubber
Flame
ionization
detector
Analysis
Total
organic
carbon
Hydro -
carbons
Fraction Combustion efficiency, %
uncombusted
Range Average Range
0.00013-
0.00065 0.00034 99.92-
99.98
0.00007-
0.00028 0.00014
s
Average
99.95
Source: Badley, J. H., A. Telfer, E. M. Fredericks. At-Sea Incin-
eration of Shell Chemical Organic Chloride Waste, Stack
Monitoring Aboard the M/T Vulcanus. " Technical Progress
Report BRC-CORP 13-75-F. Shell Development Co., Bellaire
Research Center, Houston, Tex. 1975.
Results From Burn II
Shell data on Research Burn II (Table V-6) show oxygen concen-
trations in the 9.0 to 12.5 percent range, which corresponds to 90 to
160 percent excess air. Measurements of oxygen and carbon monoxide
were made with a Beckman Model 715 analyzer and a Beckman Model
864 analyzer, respectively (Figure V-2). These levels did not generally
lead to higher chlorine concentrations. Except for single readings of
360 and 350 ppm, chlorine concentrations were below 200. The con-
centrations of carbon monoxide varied between 25 and 75 ppm, as
measured by the Beckman analyzer 864, which uses a nondispersive
infrared detector. The two Beckman instruments were interfaced with
the sampling system to permit in-line dynamic calibration.
-------
TABLE V-6
ANALYSIS OF STACK GAS EMISSIONS, RESEARCH BURN II
Probe location
Series
number
1
1
1-2
3-5
6
7-8
9-10
1-12
3-16
21-22
Oven
Stb'd
Port
Port
Stb'd
Stb'd
Stb'd
Port
Port
Depth,
cm
22
134
134
117
117
25
134
134
i
CO, 02, HC1, C12,
ppm % % ppm
75 11.3 5.
6.
6.
25 9.8 5.
35 10.0 5.
40 9.0 6.
35 10.6 5.
50 12.5 4.
3 50
1 350
2 <10
2 70
7 180
0 40
3 360
0 50
Unburned
organochlo rides,
of feed
<0.
<0.
<0.
0.
0.
0.
<0.
<0.
002
002
002
013
008
007
004
005
1. Organochlorides as Cl.
Source: Badley, J. H., A. Telfer, E. M. Fredericks. At-Sea
Incineration of Shell Chemical Organic Chloride Waste,
Stack Monitoring Aboard the M/T "Vulcanus. " Technical
Progress Report BRC-CORP 13-75-F. Shell Development
Co., Bellaire Research Center, Houston, Tex., 1975.
-------
.WATER
COOLED
PROBE
— INJECTION POINT FOR DICHIOROETHANE
IN INTEGRITY TEST
HEATED LINE, 40FT.
li
.7(0.8
/min
FILTER
GBS
IMPINGERS
WATER
MIDGIT
IMPINGERS
i' '
Oj
ANALYZER
BECKMAN
715
CO
ANALYZER
BECKMAN
864
_I PUMP
IRON EMPTY
HELICES
AND
WATER
SNNoOH
.IN NoA,O2
IPA
FILTER
AND
CRITICAL
ORFICE
.2.1/min
PUMP
Figure V-2. Sampling Train for Stack Gas Analysis,
Research Burn U
Source: Badley, J. H., A. Telfer, E.M. Fredericks. At-Sea
Incineration of Shell Chemical Organic Chloride Waste,
Stack Monitoring Aboard the M/T Vulcanus. " Technical
Progress Report BRC-CORP 13-75-F. Shell Development
Co., Bellaire Research Center, Houston, Tex. 1975.
-------
Organochlorides in the stack gases were below the detection
limit of 1 to 3 ppm, except for two excursions to 7 and 8 ppm. In
the worst case, the ratio of organochloride atoms in the stack gas
to those in the feed was 0.00015, which can be taken~to indicate
greater than 99. 9 percent of the organochlorides were destroyed.
The samples in Research Burn II were transferred from the
probe (inserted at distances ranging from 22 to 134 centimeters)
to the scrubbers through 18.3 meters of Teflon tubing, all but the
first and last 3 meters heated to 150° C. Crude traverse experi-
ments suggest that the location of the probe did not significantly
affect the results.
Two tests were run to measure the recoveries of organochlor-
ides. In a field test, a concentrated vapor solution of 1,2-dichlor-
oethane was injected into the sample line at the probe end; 72 percent
was recovered in the scrubbers. In a second test, an experimental
set-up was designed and assembled to test the absorption of known
amounts of 1, 2-dichloroethane in water and isopropyl alcohol under
conditions simulating stack sampling aboard the Vulcanus. In this
laboratory test, 90 percent of the chemical was recovered.
Following Research Burn I, Shell collected data for the loss of
organochlorides stored in Teflon bags as a basis for estimating
the loss of similar compounds during sampling of air through 21.4
meters of Teflon tubing. Assuming that the tubing and bag materials
have similar absorption and permeation characteristics for organo-
-------
chlorides, loss of these compounds in the sampling tube would be
insignificant, according to the Shell data. (For details on per-
formance tests on the sampling train and the bag loss tests, see
Appendices A and B.)
PLUME CHARACTERISTICS
The stack gases were invisible, posing problems in tracking
movement of the plume of pollutants downwind of the Vulcanus.
Plans called for aerial monitoring during both burns, but equip -
malfunctions prevented flights in the first burn. Consequently, data
on the first burn were gathered at sea level by the R/V Oregon n.
On the second burn, data were gathered by an EPA aircraft from
NERC-Las Vegas.
Oregon n Cruises—Burn 1(15)
During Research Burn I, a scientific party of 13, largely from
EPA, was aboard the Oregon n, a fisheries research vessel owned
and operated by the National Oceanic and Atmospheric Administration.
She is 52 meters long, carries a crew of 18, and is equipped with
the winches and cables needed for oceanographic work. The vessel
carries LORAN for navigation and two radar sets. There are both
wet and dry laboratories, as well as an aquarium room.
The Oregon n made two cruises--one at the beginning and one
at the end of the first research burn. The first, October 17 to 20,
emphasized identifying the plume and sampling to determine the
immediate impact in the area directly affected. The second
llviPreliminary Technical Report on Incineration of Organochlorine
Wastes in the Gulf of Mexico. U. S. Environmental Protection
Agency, Oil and Special Materials Control Division, Washington,
D. C. Nov. 13, 1974.
47
-------
cruise, October 27 and 28, made similar measurements, but its
primary mission was to systematically sample a large area to
detect any long-range impacts.
The primary instrument used in the Oregon's plume studies
was a Geomet hydrogen chloride monitor, which was provided and
operated by the National Aeronautics and Space Administration's
Langley Research Center in Hampton, Va. With the HC1 monitor,
the Oregon could run a search pattern around the Vulcanus axid, to
some extent, map the plume of stack emissions at sea level by
direct measurement, rather than by inference from other factors.
The plume could not be mapped completely, because with only one
instrument, simultaneous measurements could not be made at several
altitudes of the plume.
The Geomet monitor was located on the Oregon's foredeck 6
meters above the surface of the sea. This location protected it from
any Oregon operating stack emissions and also permitted quick verbal
transmittal of monitoring results to the ship's bridge. The sampling
strategy was to approach the Vulcanus on its leeward side using a
predetermined sampling pattern and to rely on the monitor to indicate
when the plume was contacted. The data were then used to design the
next sampling pass. Sampling was confined mainly to a 90 degree arc
downwind of the Vulcanus beginning a few hundred meters behind the
ship and extending to about 5. 5 kilometers or 3 nautical miles (n.mi.).
-------
The Geomet instrument uses a chemiluminescent reaction to
monitor HC1 in ambient air in concentrations ranging from below
50 parts per billion (ppb) to 100 ppm. Below 50 ppb, the instru-
ment's accuracy is + 10 percent; above 50 ppb, it is + 5 percent.
Repeatability of measurements is + 2 percent. Minimum detection
limit is 10 ppb. The instrument recorded continuously on a strip
chart, and the chart was marked at 5-minute intervals simultaneously
with navigational readings on the bridge. The raw data were used in
the running plot, but the strip charts were analyzed later to elimin-
ate any possible anomalies due to hysteresis of the instrument
or to sunlight or salt spray.
The two cruises occurred under different sets of ambient
conditions. During the first cruise, winds were from the East
generally at speed of 8 to 10 knots, while during the second cruise
they were from the East Southeast at speeds of 17 to 21 knots. In
each case, the plume was found and transects run at several dis-
tances from the Vulcanus. During the first cruise, the plume was
tracked both while the Vulcanus was drifting and while it was
underway. Data from the second cruise were taken only while the
Vulcanus was drifting.
The results from the two cruises were consistent. With the
Vulcanus drifting, the plume was found directly downwind at distances
apparently directly related to wind speed. With Vulcanus underway,
the plume was found downwind at the resultant of the vectors of wind
-------
speed and vessel movement. The plume appeared only as an inter-
mittent faint yellow smudge; it moved downwind from the Vulcanus
in a generally horizontal direction to a distance of about 360 meters
(0. 2 n. mi. ), at a wind velocity of 10 knots, before it reached the
surface of the ocean. During the second cruise, only the flames
could be seen. At no time did the plume give any indication of
moving straight up into the sky.
For the first cruise, with windspeeds generally 8 to 10 knots,
the closest observations to Vulcanus were at about 460 meters
(0.25 n. mi.). A comprehensive search pattern was run from
4, 630 to 460 meters, (2. 5 to 0. 25 n.mi.) where HC1 was detected.
Concentrations measured were in the low ppb range. Later in the
first cruise, a few
scattered instantaneous readings as high as 450 ppb were found at
2, 780 meters (1. 5 n.mi.) from the Vulcanus, but no plume pattern
could be established. At the time, winds were gusting as high as
20 knots and beginning to shift direction.
On the second cruise, with reasonably steady winds, values higher
than 3 ppm HC1 were observed at a distance of 926 meters (0. 5 n.mi.)
from the Vulcanus; at 740 meters (0.4 n.mi.), values were as high as
7 ppm HC1. Similar values at 926 meters were found on two successive
passes.
In all, the plume was contacted 17 separate times (Table V-7).
Each contact ranged from 2 to 10 minutes. The maximum concen-
trations observed ranged from 0. 01 to 7 ppm. Normal HC1 back-
50
-------
TABLE V-7
MONITORING OF VULCANUS PLUME RESEARCH BURN 1(1)
Date Rise from Return to Maximum
baseline baseline concentration
(local time) (local time) (ppm)
October 20 0811:452
(first cruise) 1151
1348
1429
1454
1557:30
1759:15
1804:30
1817:15
October 27 2223
(second cruise) 2256:15
2323:45
2337:15
2347:15
2354:10
October 28 0022:45
9939:20
0813:45
1153:15
1358
1434
1500
1604
1803
1811
1820
2233
2300
2325:45
2342:30
2351:20
2358
0027
0034
1. Data corrected for hysteresis.
2. 0811:45 = 0811 hours and 45 seconds
3. Minimum detection limit.
4. Maximum concentration between 0. 1 and 0. 2
0. 0103
0.010
0.077
0.026
0.300
1.35
0.435
0.310
0.040
2.9
0. 1004
1.8
3.15
3.9
7.25
0.680
0.390
ppm
Title of
maximum
(local time)
0812:15
1152
1352:15
1431:30
1454:45
1600
1801
1850
1817:45
2225:20
2256:45
2324:25
2341:25
2349:25
2354:50
0023:15
0030:40
Source: National Aeronautics and Space Administration, Langley
Research Center, Hampton, Va.
51
-------
ground in the Gulf of Mexico was below the monitor's detection limit
of 10 ppb. There was no instrument response in the visible Vulcanus
plume during stack warm-up and before any wastes were incinerated.
Aerial Monitor ing--Burn 11(16)
On Research Burn n, a twin Turbo-Beech aircraft from NERC-
Las Vegas made cross wind and axial passes through the plume on
December 2, 3, and 4, the first three days of incineration. Because
of its previous experience in monitoring HC1 in solid fuel rocket
motor exhaust, the Air Force School of Aerospace Medicine at Brooks
Air Force Base in Texas was asked to assist EPA in the monitoring.
The Air Force provided a coulometer and a chemiluminescent analyzer
for use on board the aircraft and provided technical assistance.
Additional details on equipment and procedures are given in
Appendix C.
Equipment
The aircraft is equipped with two 4-centimeter (inside diameter)
sampling probes extending about 2 meters beyond the nose. (Figure V-3)
The probes duct air to the various sampling and monitoring instruments
in the cabin. On the Vulcanus mission, three monitoring instruments
and a "grab" sampler were carried.
16. Aerial Monitoring of the Plume Generated by at-Sea Incineration
of Organochlorine Wastes. U. S. Environmental Protection Agency,
National Environmental Research Center, Las Vegas, Nev. Feb. 5,
1975.
-------
-
Figure V-3 Environmental Protection Agency NERC — Las Vegas aircraft with sampling probes and monitoring instruments.
Source: U.S. Environmental Protection Agency, National Environmental Research Center, Las Vegas, Nevada.
-------
An Environment One Corporation condensation nuclei monitor
k
(CNM) wa's used to track the plume. It is capable of detecting as
low as a few hundred condensation nuclei per cubic centimeter
(cm3) and up to 10 million on the highest range. The most suitable
"O
range during this project was 100, 000/cnrfull scale, where typical
o
centerline concentrations were from 30, 000 to 80, 000/cm . The
CNM was read out on a strip-chart recorder in front of the co-pilot's
seat, from where the crew chief directed the sampling mission. The
flight record, including altitude, positon, time, and other pertinent
information, was kept on this chart.
The HC1 concentration was monitored with a Geomet Model 401
chemiluminescent analyzer. Sample air was brought to the analyzer
through a 0. 5-centimeter (inside diameter) polypropylene tube. In
order not to expose the sample air to metal, the tubing was placed
inside one of the two aircraft sampling probes and secured at the
inlet with a perforated stopper. HC1 data were recorded on a strip
chart and later compared to the CNM strip chart. The limit of
detection is about 0. 01 ppm.
A Dohrmann Model C-200-B coulometer, in a modified package
for field use, was carried as a backup to the chemiluminescent
instrument, and, more importantly, a's the primary standard for
calibration of the HC1 monitoring system.
Grab bag air samples were collected in Tedlar bags with
capacities of 0.1 cubic meters at about the same relative location
-------
in the plume each day, 400 meters downwind at 210 to 240 meters
mean sea level (MSL). The samples were taken from the same
sampling probe as was used to monitor the condensation nuclei
during maximum CNM deflection.
Axial passes were made to determine how far downwind the
instruments could detect the plume and how steeply the plume
rose. As the aircraft traversed the length of the plume, the
looping of the plume showed up as a series of concentration maxima
and minima on the CNM chart.
Distances were calculated by multiplying the time in the cloud
(as shown by recorded CNM data) by the aircraft ground speed.
Altitudes were taken directly from the aircraft pressure altimeter,
which was set each day just before starting a mission.
Results
The data collected on concentrations of HC1 and condensation
nuclei showed that the top of the airborne plume trailed back from
the Vulcanus stack at an angle of about 20 degrees from the horizontal,
reached a maximum altitude of 850 meters MSL, and fanned out
horizontally to a width of about 1, 200 meters at a distance of 2, 400
meters downwind from the stack.
Aerial photographs of the plume made visible when the Vulcanus
injected ammonia showed that the plume was "looping, " indicating
an unstable temperature structure at the lower elevations (Figure V-4.)
Axial passes through the length of the plume at 830 and 850 meters
55
-------
CT-
Figure V-4 Plume of ammonium chloride from M/T "Vulcanus" induced by addition of ammonia
to the stack emissions.
Source: U.S. Coast Guard, Corpus Christ!, Texas
-------
MSL, near the maximum altitude of the plume, confirmed the
looping phenomenon, and the monitoring instruments indicated that
the distance between tops of successive loops averaged 1,400 meters.
(These data are represented in Figure V-5.)
Where the plume began to level off at 850 meters, a small
white cloud (also observed aboard the Vulcanus) formed. Several
of these clouds followed the ship, all at about the same altitude.
Two were measured, and the average dimensions were 860 meters
wide and 60 meters thick. After the Vulcanus released ammonia,
the clouds appeared to be at the tops of the loops in the plume
and were probably condensed water vapor from the combustion
process. Condensation nuclei were detected both in and out of
these white clouds, as well as at altitudes greater than that of
the clouds.
The maximum HC1 concentration in the Vulcanus plume,
measured on the first and third days of monitoring, was 3 ppm.
The maximum on the second day was 1. 8 ppm. All three maxima
were encountered in about the same relative position each day--
100 to 240 meters in altitude, and between zero and 400 meters
downwind.
In areas of low HC1 concentrations, the correlation between
CNM and HC1 concentrations was not good, probably because the
HC1 analyzer was operating at its limit of detection. However,
in concentrations greater than 0.1 ppm, both instruments ro-
57
-------
VULCAN US PLUME ELEVATION
DECEMBER 4,1974
(Plotted numbers are condensation nuclei maxima in 103/cc.)
900
800
a: 700
LLJ
UJ600-
£ LU500'
Q
— ^ /i nn -
i ^UU
•
3300~
^**»
200-
100-
^J
SHIP
All RKfi W^»_ AYIAI PA^SFS
_ *. » • * R K P j~ ^^ £
rnn N / a \ DS\U ^ s \ / 1 •
pi/p J2rf~v>. f * \ / . f/**~^\ /^r%r^\~" " 66 * ' ^ /I
~"BI\lj if* t ^ . * ' JlT ' 3\ «. f\^^^ v / \tf
TOP EDGE /"\ .' V\ ^' \ /' ^ \ /^ N\^x ^--'
OF PLUME/ - CONDENSATION ^~'
V WHITE CLOUD
X/SPSRAL N
c/j DESCENT^!
LU ^^^ _^^
C/5
CO
f< i
a
,!g.
/ 00
/ s
/ ZZ
OC'
.u-
/ ••
'BKG
•32 i
3 BAGS
^ • "^Jt
75
51 *-
BKG
-BKG
• .1 . 77
X
V
N
1
10
•35
19 4. 22
24 -^
, \ / N '
74 ' \ / x /
•1 /
• ' y/
UT ' 1 1 1 1— ! 1 1 1 1 1 — // —
1 2 3 4 5 6 7 8 9 10 11
13
DISTANCE DOWNWIND, KILOMETERS
NOTE:
FIGURE V-5
To portray all data on one sheet, abscissa has been reduced by a factor of five compared to the ordinate.
Dotted lines represent extremities of plume based on axial pass data and visual observations.
Source: U.S. Environmental Protection Agency National Environmental Research Center, Las Vegas, Nevada.
-------
sponded simultaneously to the plume.
The grab bag air samples were analyzed at the National
Environmental Research Center in Research Triangle Park, N. C. „
by Fourier Transform Infrared Spectrometry. The results in-
dicated that the samples were low in pollutants.
CHEMICAL AND BIOLOGICAL IMPACT ON THE MARINE ENVIRONMENT
The constituents of the Vulcanus plume that might damage the
marine environment were:
+ HC1, exhausted from the stacks in large quantities.
+ Any organochlorides not destroyed during incineration.
+ Trace toxic metals in the waste.
All three constituents will be dissolved in the water where the
stack emissions reach the ocean surface. Organochlorides and
trace toxic metals may enter the food chain and be bioaccumulated, with
potentially adverse effects on the marine ecosystem. All three
constitutents can have immediate impacts in the area directly affected
by the plume, but they may also have long-range impacts in the
general area.
Determination of pH, chlorinity, organochlorides, and trace
metals was used to detect both short-term and long-term effects; in
addition, phytoplankton counts, zooplankton counts, and determination
of chlorophyll-a and adenosine triphosphate (ATP) concentrations were
used to assess long-term effects.
59
-------
Additional details on equipment and procedures used are given in
Appendix D. Additional data are given in Appendix E.
Short-Term Effects
pH and Chlorinity
The major component of stack emissions that would have an
immediate impact on the ocean is HC1. As an acid, it might depress
the pH slightly, despite the very strong buffering capacity of sea
water. Should the pH change, it would be of slight duration. The
addition of the chloride ion from HC1 would be a permanent change
in sea water. However, chloride ion is present in sea water at con-
centrations of about 20, 000 ppm, so that any such changes would be
hard to detect, particularly in view of the very rapid dilution
occurring immediately after the HC1 dissolves.
Oregon n cruises. On Research Burn I, the Oregon took four water
samples at locations under high concentrations of HC1 in the plume--
one sample during the first cruise was taken at a location with a
plume concentration of 450 ppb. (13) However, the plume was not
positively identified on the run, so there may be some doubt as to
whether the sample was actually taken in the plume. The pH and
chloride data for the station were the same as for the two control
stations for this cruise (Table V-8).
On the second cruise of the Oregon, three samples were taken in
t
the plume at or near locations indicated by analysis of the plume data
60
-------
TABLE V-8
SHORT-TERM EFFECTS FROM INCINERATION,
FIRST CRUISE OF OREGON DURING ~
RESEARCH BURN I
Parameter
Plume station
1-3
Control stations
TTT
1-2
Distance from
Vulcanus- nautical
miles (meters)
1.5 (2,780)
west
1 (1,850) 1 (1,850)
astern ahead
pH (standard units)
Chlorinity (parts
per thousand)
Organochlorides
(ppb)
HC1 in plume (ppb)
8.35
20.09
<0. 5
450
8.3 8.38
20.09 20.09
<0.5 <0. 5
Source: Preliminary Technical Report on Incineration of Organo-
chlorine Wastes in the Gulf of Mexico. U. S. Environmental
Protection Agency, Oil and Special Materials Control Divis-
ion, Washington, D. C. Nov. 13, 1974.
61
-------
to be the point where the plume initially touched down. Analysis of
these three samples, as well as of samples from two control stations
taken upwind from the Vulcanus immediately after the plume stations
were taken, showed no significant differences (Table V-9). The
depression of the pH by 0.15 unit and the increase of chlorinity by
about 0. 5 parts per thousand at one station over the controls are
values well within the limits of detection of the methods. Even if
the changes represented actual impact on the ocean, the impact
was so slight as to be barely measurable and would pose no threat
to the marine environment.
The grid of 16 stations designed primarily to examine long-term
effects showed nothing other than random sampling and analytical
variation in pH and chlorinity, as well as in organochlorides and
trace toxic metals.
Orca cruises. The Orca, a 30-meter long oceanographic research
vessel, had been operated for many years by the Scripps Institution
of Oceanography and later by Texas A&M University. She is equipped
with both LORAN and radar. Under contract to Shell, TerEco Corp.,
of College Station, Tex., leased the Orca for sea-level monitoring
on Research Burn I. On Research Burn n, EPA contracted with
TerEco for the services of the Orca.
On the first research burn, the Orca ran three types of sampling
patterns--Transect, Axial, and Axial Control (Figures V-6 and V-?).(l7)
IT. A Field Monitoring Study of the Effects of Organic Chloride Waste
Incineration on the Marine Environment in the Northern Gulf of
Mexico, Prepared by TerEco Corp., ^College Station, Tex., under
contract to Shell Chemical Co., Houston, Tex., Oct. 30, 1974.
62
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TABLE V-9
SHORT-TERM EFFECTS FROM INCINERATION,
SECOND CRUISE OF OREGON DURING
RESEARCH BURN I
Parameter Plume stations Control stations
"IPS D73IF4~ II-5 II-6
Distance from 0.75 0.5 0.25 5.5 7.5
Vulcanus-nautical (l, 390) (926) (463) (10,186) (13,900}
miles (meters) downwind upwind
pH (standard 8.05 8.2 8.2 8.2 8.2
units)
Chlorinity (parts 20.48 20.26 20.09 19.98 19.87
per thousand)
Organochlorides <0.5 <0.5 <0.5 <0.5 <0.5
(ppb)
HC1 in plume 2.5 7 4.5
(ppb)
Source: Preliminary Technical Report on Incineration of Organo-
chlorine Wastes in the Gulf of Mexico. U. S. Environmental
Protection Agency, Oil and Special Materials Control
Division, Washington, D. C. Nov. 13, 1974.
63
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°f
93°43
°'
93°42
'
93040'
«
93°39'
26
X PH
0 R-C1
r 26°32'
- 26°31'
u 26
26°29'
Figure V 6 Illustration of Transect sampling pattern run by the ORCA, Research Burn I
Source: A Field Monitoring Study of the Effects of Organic Chloride Waste Incineration on the Marine Environment
on the Northern Gulf of Mexico. Prepared by TerEco Corporation, College Station, Texas, under contrast
to Shell Chemical Company, Houston, Texas. October 30, 1974
64
-------
93°45\
93*44'
i
93°43'
i
93°42'
i
93°41'
i
93°40'
Axial control sampling
(Direction, East to West)
-0-
• 26*28'
Axial sampling
(Direction. West to East)
B 8 X X X X X X B 0 B [Xl XX X 0 8 B
VULCANUS
• 26°27'
.Wind
•090"
X
0
pH
R-C1
Neuston
Phytoplankton-Cell Counts
- 26°2&'
26°25'
Figure V-7 Illustration of Axial and Axial Control sampling.
Patterns Run by the ORCA, Research Burn I
Source: A Field Monitoring Study of the Effects of Organic Chloride Waste Incineration on the Marine Environment
in the Northern Gulf of Mexico. Prepared by TerEco Corporation, College Station, Texas., under contract
to Shell Cheminal Company, Houston, Texas. October 30, 1974.
65
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Analysis of about 100 sea water samples showed no differences be-
tween the fallout and control areas (Table V-10). In the fallout
areas, pH ranged between 8. 30 and 8.40; in control areas, the range
was 8.32 to 8.37.
On the second research burn, the Orca made four test runs
downwind of the Vulcanus and three control runs upwind to determine
the immediate effects of incineration. Following a prescribed pattern
(Figure V-8), the Orca took samples throughout a 24-hour period.
No significant differences were detected between pH and chlorinity
values of the test and associated control runs, even though the tests
were able to delineate differences in sampling techniques (selective
vs. random sampling) and to detect differences in day and night carbon
dioxide content of the waters. (18)
Organochlorides
Samples collected by the Oregon on Research Burn I were analyzed
for Organochlorides using gas chromatographic-mass spectrographic
techniques. Results were below the 0. 5 ppb limit of detection. (15)
The organochloride content of the water samples gathered by
the Orca was determined at the Shell Development's Bellaire Research
Center. (17,18) The method involved concentration and separation from
inorganic chlorides on macroreticular resins, elution with methanol,
TIL Sea-Level Monitoring of the Incineration of Organic Chloride Waste
by M/T Vulcanus in the Northern Gulf of Mexico, Shell Waste Burn
No. 2 Prepared by TerEco Corp., College Station, Tex., under
Contract No. 68-01-2829 with U. S. Environmental Protection
Agency, Washington, D. C. Jan. 10, 1975.
66
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TABLE V - 10
SHORT-TERM EFFECTS FROM INCINERATION,
ORCA CRUISE DURING RESEARCH BURN I
Location
Transect 1
Transect 2
Transect 3
Axial Run 1
Axial Control 1
Axial Run 2
Axial Control 2
Axial Run 3
Axial Control 3
Axial Run 4
pH Range
8.30-8.31
8.30-8.31
8.30-8.31
8.35-8.40
8.32-8.33
8.32-8.33
8.35-8.36
8.35-8.37
8.36-8.37
8.37-8.40
R-C1
25 ppb
25 ppb
25 ppb
25 ppb
25 ppb
25 ppb
25 ppb
25 ppb
25 ppb
25 ppb
Cu
6.7
6.7
5.0
6.7
6.7
4.6
2.2
[ Sampling Pairs
Source: A Field Monitoring Study of the Effects of Organic Chloride
Waste Incineration on the Marine Environment in the Northern
Gulf of Mexico. Prepared by TerEco Corp., College Station,
Tex., under contract to Shell Chemical Co., Houston, Tex.
Oct. 30, 1974.
67
-------
FIGURE V-8
SAMPLING PATTERN RUN BY THE ORCA
TO DETERMINE IMMEDIATE EFFECTS
WIND DIRECTION
VULCANUS™
//ii\
P=DISTANCE FROM
VULCANUS AT
HIGHEST
OBSERVED PLUME
CONCENTRATION
A DISTANCE OVER WHICH READINGS WERE FOUND
e SWEEP ANGLE
O SAMPLING STATIONS FOR pH AND CHLORINITY
m PLANKTON TOW
DAY PHYTOPLANKTON
NIGHT ZOOPLANKTON
x SAMPLING STATIONS FOR TRACE METALS AND
ORGANOHALOGENS
Source:
Sea-Level Monitoring of the Incineration of Organic Chloride Waste by M/T "Vulcanus" in the Northern
Gulf of Mexico, Shell Waste Burn No. 2 Prepared by TerEco Corporation, College Station, Texas, under
Contract No. 68-01-2829 with U. S. Environmental Protection Agency, Washington, D. C.
January 10, 1974.
68
-------
and specific detection of organochlorides using microcoulometry;
the limit of detection was 25 ppb of chloride. Results in 57 samples
on Research Burn I and 12 in Research Burn II were below the
detectable limit; samples were from both fallout and control areas.
Trace Metals
Samples gathered by the Oregon during Research Burn I were
analyzed for eight trace toxic metals (arsenic, cadmium, chromium,
copper, lead, mercury, nickel, and zinc) by atomic absorption
techniques after extraction with methyl isobutyl ketone. No systematic
changes were detected, although there were some apparently random
variations. (15)
Copper at 510 ppb was the metal present at the highest concen-
tration in the wastes incinerated in the first research burn. Shell
used it as a tracer on samples collected by the Orca to establish
concentrations of all the heavy metals in the ocean. Copper in sea
water samples collected from the location of maximum fallout
(1. 8 to 2.2 nautical miles, or 3, 340 to 4, 080 meters from the
Vulcanus) ranged from 2. 2 to 6. 7 ppb (Table V-10); the range in
the control area was 4. 6 to 6. 7 ppb. (17) A total of 21 samples was
analyzed by atomic absorption.
On Research Burn n, the Orca gathered 12 samples for analysis
of copper and zinc by atomic absorption. Shell laboratories found
no significant differences between the test and control samples (Table
69
-------
TABLE V-ll
ANALYSIS OF TRACE METALS IN SEA WATER,
ORCA CRUISE DURING RESEARCH BURN H
Sample
1
2
3
10
11
12
4
5
6
7
8
9
Identification
Test 1
Test 1
Test 1
Test 3
Test 3
Test 3
Control 1
Control 1
Control 1
Control 2
Control 2
Control 2
Copper,
pg/ml
0.006
0.005
0.005
0.006
0.005
0.006
0.005
0.005
0.005
0.004
0.003
0.004
Zinc,
jig /ml
0.007
0.008
0.004
0.005
0.007
0.005
0.005
0.006
0.004
0.004
0.004
0.004
Source: Sea-Level Monitoring of the Incineration of Organic
Chloride Waste by M/T Vulcanus in the Northeran Gulf
of Mexico, Shell Waste Burn No. 2. Prepared by TerEco
Corp., College Station, Tex., under Contract No.
68-01-2829 with U. S. Environmental Protection Agency,
Washington, D. C., Jan. 10, 1975.
70
-------
Long-Term Effects
Even if no effects can be detected immediately in the ocean
there may still be long-term adverse effects from incineration.
To identify any such effects, a sampling grid of 16 stations was
laid out to include the area which the plume specifically covered
during the last 24 hours of the first research burn. This area
was also downwind and downcurrent of the dump site and there-
fore offered the greatest potential for picking up any cumulative
effects. Points selected were 11,100 meters (6 n.mi.) apart in
the area selected from drift estimates and other movements of the
Vulcanus during the last 24 hours; the grid size was selected to
assure that any impacts during this period would be found at
stations within the grid. These stations, and six other stations,
were sampled during the Oregon's second cruise. There were
no significant changes in pH, chlorinity, organochlorides, and
trace metals. Four phytoplankton samples were collected; no
differences were detected between control and plume samples. (15)
In an effort to use some of the more subtle indicators of bio-
logical activity as possible guides to any impacts on the dump site,
chlorophyll-a and ATP were included in the sampling program.
Chlorophyll-a is recognized as an indicator for phytoplankton activity.
While it is persistent even after cells have died, any suppression
of chlorophyll-a in an impacted area would be a strong indicator of
adverse impact. ATP is essential to life processes. Its use to
71
-------
indicate effects of pollution, while still in the research stage,
shows promise of being a sensitive and reliable indicator of subtle
damage. Analysis of 20 samples for chlorophyll-a and 21 for ATP
gave no evidence of any long-range impact from the incineration
of organochlorine wastes. (15) However, there was very little life
in the dump site. The chlorophyll-a and ATP levels were both
generally low, and the phytoplankton counts were extremely
low--500 to 1,140 organisms per liter. Thus, it is possible that
effects could be observed in more abundantly populated areas.
Furthermore, the dump site has drift currents, and it is likely
that no single parcel of water ever had anything but momentary
contact with the stack emissions. In an area of little or no net
water movement, the results might be different.
Six phytoplankton and six zooplankton samples collected by
the Orca during Research Burn I were also analyzed; again, no
deleterious effects were observed. (17)
During the initial period of combustion on the second research
burn (December 3 to 5), the Orca made tows in the test and control
zones for phytoplankton and zooplankton. (18) On the phytoplankton
samples, less than 3 ppm of organochlorides were detected, which
is the limit of detection in the sample sizes provided for analysis
(Table V-12). Analysis for copper and zinc revealed nothing to
indicate with certainty that the plume fallout had caused any
appreciable increases.
72
-------
TABLE V-12
ANALYSIS OF TRACE METALS AND ORGANO-
CHLORIDES IN PLANKTON, ORCA CRUISE
DURING RESEARCH BURN II
Zooplankton
Tow 1
Test 1
Tow 2
Control 1
Tow 3
Test 4 2,
Tow 4
Control 3
Whole Liquid Solid
sample, % %
grams
454 90 10
716 74 26
162 71 29
904 71 29
Liquid Solid
Copper, Zinc, Organo- Copper, Zinc Organo-
mg/1 mg/1 chlorides ppm ppm chlorides
ppm ppm
0.15 0.
0.15 0.
•
0.67 0.
0:93 0.
16 1.4 85 19
05 0.4 16 18
20 0.2 6 13
04 2.0 11 28
3
3
3
3
Phytoplankton
Test 3
Control 2
Whole
sample,
grams
276
281
Whole sample
Copper,
mg/1
0.036
0.030
Zinc, Organo-
mg/1 chlorides, ppm
0.09 3
0.08 3
Source: Personal communication. W. R. Harp, Jr., to B.N. Bastian, Shell Chemical Co.,
Houston, Tex., Dec. 19, 1974.
-------
The zooplankton samples were separated into liquid and solid
phases in a scheme devised by the Shell laboratories. No dif-
ferences between test and control organisms were detected in the
concentration of organochlorides in the solid phase. The con-
centrations in the liquid phases, however, varied from 0. 2 to 2. 0
ppm. This was probably not due to plume fallout because the level
in one of the test samples was lower than its control. Also, the
samples contained varying amounts of tar balls, despite attempts
to avoid them in sampling. The tar materials were high in
organochlorides, although for the most part they were of higher
molecular weight than those in the Shell wastes.
Effects on Birds
Possible effects of the Vulcanus project on birds were consid-
ered. Of special concern were migrating birds--blue-winged teal
and certain song birds, for example - -that could traverse the site
during their fall and spring migrations. According to a Shell wildlife
specialist, the birds would generally migrate at 1, 000 to 5, 000 feet,
where HC1 concentrations would be very low. (19) Furthermore, the
birds would probably be warned off areas of high concentrations when
they encountered lower concentrations that are irritating but not
toxic. With strong physiological drives to complete their migration,
the birds would probably not linger in the incineration site.
19. Gusey, W. F. Potential Effects of at Sea Incineration of Organic
Chloride Wastes on Migrating Birds, Shell Chemical Co., Houston,
Tex., Nov. 1, 1974.
-------
VI. RESULTS OF INTERIM PERMIT BURNS
FEED RATES AND COMBUSTION TEMPERATURES
The major reporting requirement of the interim permit was
that the Master of the Vulcanus maintain log sheets on operating
conditions, which were identical to those of the second research
permit. These log sheets were transmitted to the EPA Regional
Office in Dallas, Tex., at the end of the incineration. (For a
chronology of events under the interim permit, see Table VI-I.)
The waste feed rate log for the first load indicates that the
discharge rate varied from 23. 2 to 25. 0 MT/hour, with consec-
utive discharge from the tanks. On the second load, discharge
to the incinerators again was from one tank after another, but
various tanks had to be mixed in order to maintain temperature
because the wastes contained a large amount of slop water. The
entire second load of 4,103 MT was discharged over a period
of 167 hours, for an average rate of 24. 5 MT/hour.
Once during each watch, entries were made on the operational
log to indicate combustion temperatures, wind speed, direction,
and position. (Copies of log sheets are shown in Appendix F.)
The controller temperature never dropped below 1,230°C for
either incinerator; the maximum temperature was 1,360°C. The
wind speed was between 20 to 40 knots, with the exception of
January 5 and 6, when the wind speed was 10 to 13 knots. For
the first incineration period, the winds blew mostly from the
75
-------
southeastern quadrant, and duringthe second period from both
the northeastern and southeastern quadrants, with some apparent
exceptions in each case.
TABLE VI-1
CHRONOLOGY OF INTERIM PERMIT BURNS,
DECEMBER 18, 1974 - JANUARY 9, 1975
Event
Time
Date (1974-75)
M/T Vulcanus departs
Port of Houston, Tex. 0705 Dec. 18
Incineration starts 0330 Dec. 19
U. S. Coast Guard conducts
aerial monitoring 1804 Dec. 20
U. S. Coast Guard conducts
aerial monitoring 1445 Dec. 23
U. S. Coast Guard conducts
aerial monitoring 1451 Dec. 24
Incineration ends 0330 Dec. 26
M/T Vulcanus arrives
Deer Park, Tex. 0300 Dec. 27
M/T Vulcanus departs Port
of Houston, Tex. 1525 Dec. 30
Incineration starts 0900 Dec. 31
U.S. Coast Guard conducts
aerial monitoring 1410 Jan. 3
U.S. Coast Guard conducts
aerial monitoring 1044 Jan. 4
U. S. Coast Guard conducts
aerial monitoring 1025 Jan. 6
Incineration ends 0800 Jan. 7
M/T Vulcanus arrives Port
of Houston, Tex. 1405 Jan. 8
M/T Vulcanus departs Port
of Houston, Tex., for Europe 0400 Jan. 9
Source: Records in EPA Headquarters, Oil and Special
Materials Control Division, Washington, D. C.
76
-------
MONITORING ACTIVITIES
As recommended by EPA after the research burns, the U. S.
Coast Guard conducted unannounced aerial surveillance of the
disposal site during incineration. Overflights occurred on
December 20, 23, and 24 for the first load and on January 3,
4, and 6 for the second load. In each case, photographs and a
sea state report were provided to EPA.
The report for the January 3 overflight by the U.S. Coast
Guard Air Station at Corpus Christi, Tex., provided the first.
documented record that a visible plume was produced upon
incineration. Theoretical models had predicted that under specific
meteorological conditions, including high relative humidity, HC1
gas would condense in water droplets to form a white cloud of
HC1. Reports and photographs indicate a white plume had resulted
from incineration of organochlorine wastes in Europe. However,
incineration of the Shell wastes in the Gulf of Mexico under
research permits, with both vessel and aircraft surveillance,
had produced no natural plume during the monitoring and data
gathering surveys. A notation on the photograph report forwarding
the exposed film from January 3 stated that a plume was visible
when the aircraft arrived on scene, the skies were overcast,
with visibility of 1/2 mile (800 meters) in the rain, 3-foot
(1 meter) seas, and a 15-knot wind. The photographs from that
overflight show a dense white plume (Figure VI-1).
77
-------
00
Figure VI-1 Natural plume of stack emissions due to meteorological conditions.
Source: U.S. Coast Guard, Corpus Christi, Texas.
-------
The report from the flyover on the next day, January 4,
indicates that, with a scattered cloud cover, no plume was visible.
Ammonia was added for tracking the plume. Photographs show no
plume upon arrival, but an induced plume of ammonium chloride
after addition of ammonia. This cloud is thin and wispy, especially
in comparison with the plume from the previous day. Again, on
January 6 no plume was visible, and one was induced with ammonia.
Although notations were not made on the reports of the overflights
on December 20, 23, and 24, a comparison of the photographs
from these flyovers to the January ones strongly suggests there
was a visible plume on two of those days, which corresponds to
the informal verbal reports.
79
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APPENDIX
A. AT SEA INCINERATION OF SHELL CHEMICAL
ORGANIC CHLORIDE WASTE
Stack Monitoring Aboard the M/T "Vulcanus"
BY
J.H. Badley, A. Telfer, E. M. Fredericks
TECHNICAL PROGRESS REPORT BRC-CORP 13-75-F
Project No. 83347
Dispersion Measurements (Ocean Disposal)
Reviewed by: M. A. Muhs
Participants: P. Glickstein, P. H. Hughes. J. D. Jobe, H. Joki,
C. R. McGowin, J. C. Raia, W. T. Shebs
Released by: M. A. Muhs
Reference: Based on work through March 1975
RELR 1105, pp. 30-113
81
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BRC-CORP 13-75-F
TABLE OF CONTENTS
Abstract Hi
Introduction 1
Summary and Conclusions 1
The M/T "Vulcanus" 2
Description 2
Operation 3
The Stack Sampling Problem 5
Calculation of Stack Gas Composition 6
Stoichiometry 6
Effect of Excess Air on Stack Gas Composition 6
First Voyage: Sampling Apparatus and Procedure 7
Sample Ports 7
Probe 7
Sample Line 10
Scrubber Train 10
Instruments 14
Procedure 14
Optical Pyrometer 15
i
First Voyage: Results 15
Sampling Targets 15
Data Summary Log 15
Feed Rates 15
Oven Temperatures 15
Experimental Difficulties 17
Treatment of Data 17
Combustion Efficiency 18
83
-------
BRC-CORP 13-75-F
Second Voyage: Sampling Apparatus and Procedure 20
Sample Ports 20
Probe and Support Assemblies 20
Sample Line 20
Scrubber Train 20
Instruments 26
Procedure 27
Optical Pyrometer 27
Second Voyage: Results 27
Sampling Targets ... 27
Data Summary Log 27
Experimental Difficulties 27
Feed Rates 28
Oven Temperatures 29
Treatment of Data 29
Organic Chloride Destruction Efficiency 31
Sample Collecting System Integrity Tests 32
Field Test 32
Laboratory Test 33
Probe Failure Causes 35
First Voyage -. 35
Second Voyage 35
Comments 35
Appendix A_1
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BRC-CORP 13-75-F
ABSTRACT
To aid in securing a permit for ocean burning of Shell Chemical's organic chloride waste,
two stack sampling campaigns were conducted aboard the incinerator ship M/T "Vulcanus," The goal
was to measure the extent of the destruction of the waste in the ship's incinerators.
Sampling conditions were severe as the stack gas was very hot and corrosive. Water cooled,
glass lined probes were designed and used for satisfactorily extracting samples. On the first voyage organic
compounds in the stack gas were found to be less than 6.1% of the feed, in accord with the requirements
specified by the Environmental Protection Agency. On the second voyage, in addition to demonstrating
compliance with the limit of 0.1% of feed in the stack gas, it was shown that gas taken from either
of the two incinerators on the ship or from locations near the wall or center of the incinerators had
essentially the same composition. Shipboard and laboratory tests of the integrity of the sampling system
indicated that losses were not significant and within the limits allowed.
KEY WORDS: Stack gas monitoring, organic chlorides, waste material, ship, M/T Vulcanus,
incineration, waste disposal, sampling, Environmental Protection Agency, effluent,
marine environment.
-------
BRC-CORP 13-75-F 1
TECHNICAL PROGRESS REPORT BRC-CORP 13-76-F
AT-SEA INCINERATION OF SHELL CHEMICAL ORGANIC CHLORIDE WASTE
BY
J. H. BADLEY, A. TELFER, AND E. M. FREDERICKS
INTRODUCTION
This report describes the stack gas sampling done on two voyages of the M/T "Vulcanus."
The aim of this work was to measure the destruction of organic chloride wastes from the Shell Deer
Park Manufacturing Complex during ocean combustion. This monitoring was a portion of a general
study of the effect of the combustion products from the Vulcanus on the environment in the vicinity
of the burn site. This study was done in accord with requirements of permits 730D008C and
730D008C (2) issued by the United States. Environmental Protection Agency, under the authority of
the Marine Protection, Research and Sanctuaries (Ocean Dumping) Act. Copies of the permits are given
in the Appendix. The location of the permit burn site was the rectangle between 26°20' to 27° north
latitude and 93°20' to 94° west longitude. This is about 165 miles southeast of Galveston, Texas.
With regard to this monitoring program, the basic requirement of both permits was that
at least 99.9% of the waste be destroyed in the incineration. To test conformance with this requirement
required monitoring of the effluent stack gas for uncombusted feed during operation of the incinerators.
While general emission monitoring techniques have been described for power plant stacks, municipal
incinerators and many other kinds of combustion equipment, the unusually high temperatures and the
corrosive gases involved made stack gas sampling much more difficult in this project. This required
the design and use of special equipment and procedures which are described in this report.
SUMMARY AND CONCLUSIONS
Through the use of specially designed water cooled probes, the incinerator effluents were
collected in impingers and analyzed chemically. Some constituents were also determined directly by
instruments. Components monitored were unburned hydrocarbons and organic chlorides, hydrogen
chloride, chlorine, oxygen and carbon monoxide. In addition, combustion temperatures and feed rates
were observed. Experimental difficulties during the first of two monitoring missions prevented monitoring
for periods of times deemed optimumal. However, because improved apparatus was used, monitoring
was more complete during the second mission.
The following observations were made as a result of our monitoring program:
1) Feed rates and incinerator temperatures were within the ranges specified by the permits.
2) Oxygen concentrations in the effluent gases indicated about 100% excess air was used during
combustion. This is in the range allowed by the permits and which permitted high combustion efficiencies.
3) From the measurement of organic carbon in the scrubbers and from measurements with
a total hydrocarbon analyzer, the combustion efficiency of the organic carbon in the feed was found
to be 99.92-99.98% safely more than the 99.9% required.
4) Generally, trace organic chlorides were not observed. Based on the limit of detection of
the analytical procedure, destruction of organic chloride was 99.984-99.998% complete. This was greatly
in excess of the 99.9% required by the permit.
87
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BRC-CORP 13-75-F
5) Low concentrations of carbon monoxide (25-210 ppm) observed in the effluent gas were
consistent with a highly efficient combustion process. The permit allowed concentrations up to
1000 ppm.
6) Chlorine concentrations ranged upwards to 890 ppm. These were in the range expected
from combustion temperatures and did not present any hazard.
7) Emissions from both incinerators on the "Vulcanus" were similar and judging from the results
of crude traverse experiments, the location of the probe did not have a significant effect on the values
measured.
8) The recovery efficiency of the sampling system for a typical organic chloride in the waste
(1,2-dichloroethane) in the low ppm range was 72% in a shipboard test and 90% in a laboratory test.
This indicated no significant sampling line losses and both values were greater than 50% required by
the permit.
In conclusion, we have devised a scheme for testing high temperature incinerator stack gases.
From the results observed, it is apparent that the incinerators on the "Vulcanus" are highly efficient
(> 99.9%) in the combustion of our organic chloride wastes. This is in agreement with earlier European
studies where high combustion efficiencies were also observed.
THE M/T "VULCANUS"
Description
The Motor Tank "Vulcanus" is a chemical tanker fitted with two large incinerators aft of
the bridge. Figure 1 is a picture of the vessel. Some of the ship's specifications are given in the table
below.
Length overall 101.95 meters (334'6")
Breadth 14.40 meters (45'11")
Draft - max. 7.40 meters (24'5")
Deadweight 4,768 metric tons
Tank capacity 3,503 cubic meters
Figure 1. The M/T "Vulcanus"
The ship is managed by Ocean Combustion Services, B.V., P. 0. Box 608, Rotterdam, The Netherlands.
-------
BRC-CORP 13-75 F
The vessel is of double bottom construction with a clearance between tanks and hull of
1.1 meters. The engine room and cargo tanks are separated by rooms for the waste feed pumps and
for the auxiliary generator which powers the incinerator system.
The cargo is carried in 15 tanks of size ranging from 574 down to 115 m^. The tanks
are filled from above through, a manifold on the deck. Discharge lines from the tanks run through
an elaborate manifold in the pump room. Generally, any tank can be connected to any of six burners
in the incinerators. The only way the cargo tanks can~be emptied is through the incinerators. This
construction feature was required for operation out of Dutch ports. The pumps can reduce lumps of
soft materials as large as 5 cm to 0.2 cm size.
Each incinerator has an outer diameter of 5.50 m (18.0 ft). The brick lining is 0.35 m
thick, so the inside diameter is 4.8 m (15.7 ft). The ovens are 10.45 m (34.3 ft.) high and can be
lifted out for repairs. Each incinerator is equipped with three burners located roughly symetrically abound
the bottom of the ovens. These are directed toward the axis of the oven at a slight angle from the
corresponding diameter of the oven. Small lumps in the feed from the pump room do not interfere
with the burner performance.
Air for the combustion is supplied by large blowers of 90,000 m^/hr capacity for each
incinerator. Power for these blowers and other parts of the incinerator system is supplied by a separate
auxiliary generator of 750 kw rating at 440v and 60 Hertz. (The main ship power system is 250v,
50 Hertz).
Temperatures during operation of the incinerators are measured by two platinum
platinum/10% rhodium thermocouples in each oven. Each pair is located in a well opposite one of
the burners. One of the thermocouples is about 1/2-inch from the inside surface of the fire brick.
It is connected to a control system which will shut down the feed to the incinerator if the temperature
falls below 800°C. This is a safety feature. However, above 800°C, the control unit can be used as
a thermometer by moving the set point up to the existing temperature. Because this system responds
comparatively rapidly to changes in temperature, it is used to determine temperatures at which waste
feed is started and for other operational controls. These temperatures are referred to in the text as
"controller temperatures."
Behind the control thermocouple in the same well, at a depth of about 2 inches below
the inside surface of the fire brick, is a second, separate thermocouple. This is connected to two indicating
meters, one in the incinerator control room and the second in a console on the ship's bridge. Because
of its greater distance from the inner surface, this thermocouple registers lower temperatures and responds
more slowly than the controller thermocouple. Temperatures from it are referred to in the text as
"indicator temperatures."
On the bridge is a panel in an enclosure referred to as the "black box" which displays
the necessary information to assure interested parties that wastes are being burned at proper temperatures,
and, in Europe where the DECCA Navigator can receive suitable land based signals, at the proper location.
A picture of the panel is shown in Figure 2. An 8 mm movie camera photographs this console each
15 minutes. The camera, or indeed access to the whole black box, can be sealed by government
authorities. Notice that the panel shows merely where pumps to the six burners are on or off; no
provision is made for measuring feed flow rates because meters would introduce potential for leaks and
plugging. In practice, average feed rates are obtained by timing the emptying of each of the feed tanks.
Operation
The ship's tanks are normally loaded using the customer's onshore pumps, as the ship is
not equipped with loading gear. This can be provided, however, in special cases of need. Loading
time for each of the two voyages described here was about 48 hours. After traveling to the designated
burn site at 11 knots, the ship warms up the incinerators while burning gas oil or other non-hazardous
fuel. Warm-up time depends on the length of time between operations and how wet the brick lining
is.
89
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BRC-CORP 13-75-F
M/T "VULCANUS" - RECORDING EQUIPMENT
This panel is enclosed in a "black box", which can be
sealed by the respective authorities.
Data recorded
by automatic camera:
Temperatures inside incinerators
Temperatures at outlet of incinerators
Day/Month/Time
Waste injection pumps on/off
Vessel's position (Decca Navigator Mk 21)
Camera takes photo automatically every 15 minutes.
All equipment is fed by vessel's own generators, but switches
to built-in batteries automatically in case of black-out
Figure 2. "Black Box" Panel
-------
BRC-CORP 13-75-F
The longest time required is about 24 hours. When the oven temperature reaches 1100
to 1200C as shown by the controller, the burners are switched to waste feed one at a time. Feed
rates are adjusted to achieve a controller temperature in excess of 1300°C.
The burners contain moving parts which become coated with coked feed and require periodic
•cleaning. Under normal operation this is required once a day. The burners are taken out of service
one at a time for this operation. Usually the operation is a short one and the oven temperature does
not fall far below 1300°C.
The feed rates expressed in weight units, depend on the-specific gravity of the feed, and
also on its heat of combustion. Shell Chemical organic chloride wastes has a specific gravity of 1.3
and heat of combustion of about 3300 cal/g(6000 Btu/lb). The corresponding feed rates were in the
range 20 to 25 metric tons/hr (1000 kg/hr) for the total feed rate.
Normally the excess air rate is not measured. The air for the combustion is also used to
cool the burners and their driving motors so operation at the maximum possible air rate is beneficial
in this respect. The available 180,000 m3/hr corresponds to 110 to 170% excess air for the Shell
Chemical feed composition.
When operating in Europe, a DECCA-Navigator MK21 is used to locate the ship in a
designated area for waste burning. As the shore based signals needed for use of this system are not
available on the Gulf Coast, the ship's personnel used celestial navigation, and when necessary, dead
reckoning to position the ship during the first voyage. A LORAN Navigation unit was installed and
used during the second voyage.
THE STACK SAMPLING PROBLEM
The permits required that the organic chloride waste be burned under conditions ensuring
99.9% combustion efficiency. It is clearly not possible to measure this efficiency directly by accounting
for the amount of feed into the oven and the amount of HCI and CC>2 out because none of the variables
involved can be measured with the requisite 0.1% or better accuracy. For example, feed rates cannot
be measured in real time at all and the volumes pumped from the tanks are not known to the required
accuracy. Measurement of the mass of combustion products requires estimation of stack gas
concentrations, velocity and the diameter of the stack. Not even the diameter can be measured to
0.1% because the surface roughness of the fire bricks is greater than the 5 mm or so corresponding
to the limit. Gas velocity measurements under much less difficult conditions are seldom better than
5% in accuracy, and stack gas compositions data reliable to 0.1% are very difficult to obtain.
The situation led to a different approach based solely on the analysis of the feed and the
stack gas streams. The feed analysis permits the calculation of the number of moles of stoichiometric
products, that is, moles of stack gas formed by combustion with exactly enough air to react with a
mole of carbon in the feed and its associated hydrogen. Then an analysis of the stack gas for oxygen
permits the calculation of the amount of excess air. The sum of the stoichiometric products and excess
air is the total number of moles of stack gas formed per mole of carbon in the feed. In these tests
it was of the order of 13 to 15 moles/mole. Then analysis of the stack gas for minor components
in mole fraction of stack gas can be converted to mole fraction of the carbon by multiplying by the
total moles of stack gas per mole of carbon in the feed.
The experimental problems involved in sampling and analyzing the stack gas are formidable.
The stack gases are hot, i.e., in the range of 1100 to 1200°C, and corrosive as they contain 5-6% hydrogen
chloride. Not only are the conditions within the stack inimical to probes inserted in the stack, but
the corrosive gases are potentially damaging to analytical equipment such as the flame ionization detector
for hydrocarbons. Another constraint on sampling the Vulcanus' incinerator stack gases is the lack of
space aboard the ship. The only available room for the analytical equipment requires a sample line
about 60 feet long. Finally, the sample ports are not suitable for conventional traversing of the stack
91
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BRC-CORP 13-75-F
diameter. They are inclined about 20° from the horizontal and quite near the top of the stack. A
probe inserted more than halfway into the stack emerges above the top rim. Furthermore, normal access
to the stack during burning is not possible because the exterior at the top is hot and exposed to high
concentrations of hydrogen chloride during wind gusts. These considerations led to the design of a
water cooled probe and a system for moving the probe in and out of the stack which permits the
operator tp stand some distance away. As details of ths design differ somewhat for probes used on
the two voyages, the two probes are discussed separately in later sections.
CALCULATION OF STACK GAS COMPOSITION
Stoichiometry
The concentrations of the major components in the stack gas can be calculated from the
feed composition by means of the equation:
CHmClr
= CO2 + nHCI +
m- n
H2O + 3.76
m- n
2
(1)
This is based on the reasonable assumption that all, or at least the major part of the chlorine goes
to HCI, the carbon goes to C02 and the hydrogen is divided between H20 and HCI. The actual chemical
reactions involved are more complex. However, thermodynamic equilibrium calculations indicate that,
at the high stack temperatures found here, HCI is indeed the major chlorine containing product and
.that the chlorine content should be low.
From Equation (1) it is seen that in the absence of excess air, the concentrations of the
major components of the stack gas are:
where
CO2 = 100/S
HCI = 100n/S
H2O = 100(m n)/2S
N2 = 3.76 [1 + (m n)/4 P/2J/S
percent
percent
percent
percent
S 1 + n + (m - n)/2 + 3.76 [1 + (m - n)/4 - p/2]
S = 4.76 + 1.44m - 0.44n - 1.88p
Suppose now there is a small fraction of the feed, say 0.001, which does not burn. Its
concentrations in the stack gas in the absence of excess air will be 0.001/S' where S' = 0.999S + 0.001.
Since S is of the order of 6.6, one can say S = S* and that the concentration of the unburned material
is 0.001/S without any significant error.
Effect of Excess Air on Stack Gas Composition
When excess air is present, the stack gas contains oxygen in the concentration:
100(moles 02)
%O2 =
4.76(moles 02) + S
92
(2)
-------
BRC-CORP 13-75-F
and solving for the moles of 02:
moles
/ %02 \
\21 - %09 /
4.76 \21 - %02
Based on the observed %02 the following concentrations can be calculated:
100
(3)
%C02
4.76 (moles 02> + S
1
100
S
1 +
(
%02
(4)
21 - %02
100
S
(5)
%HCI
100n
(6)
Table 1 displays the compositions of the organic chlorides burned on the two voyages.
Summarized below are numerical values for moles of stack gas per mole of carbon in the feed, and
the concentrations of- CC>2 and HCI, basis no excess air.
Moles stack gas/mole carbon in feed
CO2, %
HCI, %
Voyage
First
6.63
15.1
11.0
Second
6.68
15.0
10.9
FIRST VOYAGE: SAMPLING APPARATUS AND PROCEDURE
Sample Ports
The location of the sample ports and their dimensions are shown in Figure 3. Only the
starboard oven was sampled.
Probe
The high temperature of the stack gas, 1100 to 1200°C, makes the use of a water cooled
probe imperative. The corrosive nature of the stack gas requires the use of a glass liner. The probes
used on the first voyage conformed to the general dimensions shown in Figure 4. The inner liner of
the probe is Vycor glass, the water cooled parts type 316 stainless steel. Probe Number 1, shown in
Figure 4, was equipped with a platinum, platinum 10% rhodium thermocouple. Unfortunately, this
probe was damaged during the initial oven warm-up and probe Number 2 was needed for all of the
actual sampling work. This probe was not equipped with a built-in thermocouple, but an 8 ga.
chromel-alumel thermocouple was used instead.
93
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BRC-CORP 13-75-F
Table 1. Waste Feed Properties
ELEMENTAL ANALYSIS
c
H
0
Cl
Cu
Cr
Ni
Zn
Pb
Cd
As
Hg
Voyage 1
Voyage 2
Percent
29
4
4
63
29.3, 29.3
4.1, 4.1
3.7
63.5
ppm
0.51
0.33
0.25
0.14
0.05
0.0014
< 0.01
< 0.001
1.1
0.1
0.3
0.3
0.06
0.001
< 0.01
< 0.002
COMPONENT ANALYSIS
1,2,3 Trichloropropane
Tetrachloropropyl Ether
1 ,2-Dlchloroethane
1 , 1 ,2-Trichloroethane
Dichlorobutanes & Heavier
Dichloropropenes & Lighter
Allyl Chloride
Dichlorohydrins
Percent
27
6
11
13
11
20
3
9
28
6
10
13
10
22
3
8
Empirical Formula CHi . es Clo.73Cb. Io CHi . 68Clo. 73Oo. O94
Specific Gravity, ||| 1.30 1.29
Heat of Combustion
cal/g 3300
BTU/lb 6000
-------
BRC-CORP 13-75-F
SHIP KEEL
RIM
77.
•«—6"
73/0 J»/J
24"
2" ID
|
.70" DIAMETER HOLES
ON 4.33" RADIUS
Figure 3. Port Locations and Dimensions
95
-------
10
BRC-CORP 13-75-F
SEAL
NUT
V DIAMETER
STAINLESS STEEL TUBE
I" DIAMETER STAINLESS STEEL
\\\\\\\\\\\\\\\\\\\\\\\\\\\
\\\\\\\\\\\\\\\\\\\\\\\\\
\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\i
N\\\\\\\\\\\\\V
\\\\\\\\\\\\\\\\\\\\\VK
\\\\\\\\VJ K\\\\\
s/t DIAMETER
STAINLESS STEEL TUBE
Figure 4. Probe Dimensions, First Voyage
The probe was rigged for partial traversing of the stack by manipulations from the deck
level. Two cables permitted, respectively, pulling the probe further into the stack and withdrawing it.
This arrangement is shown in Figure 5. Figures 6 and 7 are photographs of the probe in place in
the starboard stack before the oven was heated up. After the initial probe failure demonstrated vividly
the harsh conditions in and near the stack, plans to move the probe in and out of the stack during
testing were canceled. Particularly, it was feared that the high temperatures near the stack wall would
destroy the vinyl plastic water hose. All samples were taken with the probe inserted 11 inches into
the stack gas stream as shown in Figure 7.
The 8 ga. chromel-alumel thermocouple failed after about 18 hours of waste burning.
Sample Line
Sample gas from the probe was withdrawn through a quarter inch, thin-walled Teflon line.
This was supported by a 1-inch manilla rope rigged between the oven catwalk railing and a railing near
a porthole in Room 9 of the ship. The length of the Teflon line required was about 70 feet.
Scrubber Train
The gas from the probe was passed through a scrubber train and then analyzed for gaseous
hydrocarbons, chlorine and organic chlorides. Scrubber trains used in the first part of the test were
not efficient in removing hydrochloric acid from the gas stream because fog, generated when the sample
entered the water trap, was not removed by the filters then employed. The final train developed in
this work is shown in Figure 8. The water scrubbers were Greenberg-Smith impingers (500 ml capacity)
used in a somewhat novel way. The caps of the first two were firmly packed with glass wool to provide
effective filters for the HCI fog. In the third "impinger", the impinger impactor plate was removed.
About 150 cc of iron wire helices were added to improve the vapor liquid contact and to provide a
reducing agent for the chlorine remaining in the gas. The helices were 1 to 3 turns, 1/4-inch diameter
of Number 14 soft iron wire. Two hundred to 250 cc of deionized water were added to each
Greenberg-Smith impinger before each experiment. The midget impingers were of 25 ml capacity and
equipped with ball joint connectors.'
96
-------
3D
O
Tl
Figure 5. Probe Support System - First Voyage
-------
OJ
ID
o
n
o
3>
-o
Figure 6. Hose and Sample Line Connections
-------
00
30
a
6
o
33
-o
CO
•vl
(71
Figure 7. Location of Probe in Stack — First Voyage
-------
14
BRC-CORM3-75-F
PROM
[V
GLASS
WOOL Y£
GiS
IMPINGERS
HELICES
WATER IN ALL THREE
1
VENT VENT
Figure 8. Scrubber Train - First Voyage
Instruments
Total hydrocarbons were measured in a side stream withdrawn through a Beckman 109A
hydrocarbon analyzer.3' Span gas (7.3 ppm methane) and ultrazero air were provided for standardization.
The instrument was equipped with capillaries for use with 40% hydrogen, 60% nitrogen fuel. The output
of the instrument was fed to one channel of a two channel Hewlett Packard Model 7128A recorder."'
A nominal 10 mv recorder range was used, together with a 15-inch per hour chart speed.
The gas analyzer used for CC>2 and C>2 was a Burred Model B Industro Gas Analyzer.0'
Fresh solutions were introduced into the apparatus before use.
Procedure
Gas was pulled continuously through the probe, sample line, water scrubbers and Beckman
instrument at a rate of 1/2 to 1 liter/min. by a vacuum pump. From time to time, the scrubber water
was changed and the "fat" solution reserved for analysis at the Bellaire Research Center. There it was
analyzed for hydrochloric acid, total organic carbon and organic chloride contents. Methods for the
last two determination are given in the Appendix.
a) Beckman Instruments Corp., 2500 Harbor Blvd., Fullerton, CA 92634.
b>Hewlett-Packard 195 Page Mill Road, Palo Alto, CA 94306.
c'Burrell Corporation, 2223 Fifth Ave., Pittsburgh, PA 15219.
100
-------
BRC-CORP 13-75-F 15
At intervals, a portion of the gas which passed through the water scrubber was withdrawn
through the midget impinger train for 15 minutes at about 1 liter/min. The first impinger contents,
containing an initially known amount of alkaline sodium arsenite, were back titrated in the standard
manner at Bellaire Research Center to determine oxidants, reported as chlorine. The next two impingers,
containing isopropyl alcohol, were analyzed for organic chloride.
Optical Pyrometer
An optical pyrometer (Pyro Optical Pyrometer, Model 85d') was used to measure the flame
or firebrick surface temperature in the combustion zone. This model pyrometer is designed to measure
temperatures up to 2500°F (1382°C). Almost all the actual firebox temperatures observed were off
scale on the high side. An estimated value was recorded as the raw datum. These readings were corrected
for losses in energy reaching the pyrometer by absorption of the furnace sight glass window and for
the emissivity of the firebrick. Fifty °C was added to the raw data to make this correction. Optical
transmission tests in the laboratory after the first voyage validated the use of the value for this correction.
FIRST VOYAGE: RESULTS
Sampling Targets
The specific targets of the sampling program for the first voyage were:
1) continuous monitoring of gaseous water insoluble hydrocarbons,
2) continuous monitoring of top of the stack temperature,
3) integrated total organic carbon analyses of stack gas, and
4) spot analyses of stack gas for organic chlorides, 02, C02 and C^.
In addition to this information from Shell personnel efforts, data obtained by the ship's
crew were acquired. These included indicator and controller temperatures and estimates of average feed
rates from the times required to empty various tanks.
Data Summary Log
A Summary Log of the data acquired by Shell personnel on the first voyage is given in
the Appendix. This shows the chronological relationships among the observed values of total
hydrocarbons, oven temperatures and the times the various scrubber samples were taken.
Feed Rates
The average waste feed rates are shown in Table 2. These are below the maximum value
specified in the permit and its supplement.
Oven Temperatures
Representative indicator and controller temperatures and all the optical pyrometer
temperatures are given in Table 3. All of the optical pyrometer values are 1370°C or higher. The
occasional low controller values were said by the ship's engineers to be due to water in the feed or
to taking a burner out of service for cleaning.
Pyrometer Instrument Co., Inc., Northvale NJ 07647.
101
-------
16
BRC-CORP 13-75-F
Table 2. Waste Feed Rates - First Voyage
Tank
Number
2C
1C
4C
5C
3C
2S
3S + 4S
5S
Volume
tf
550
436
420
Start
Day
Oct. 20
21
22
425 ! 23
408
244
510
24
25
26
i
226
27
Hr
0730
1200
1430
1630
1800
1700
0600b
1400
End
Day
Oct. 21
22
23
24
25
26
27
28
Hr
1200
1430
1630
1800
1700
0600
1000 c
0400
Time
Hrs
28.5
26.5
26.0
25.5
23.0
13.0
27.0
14.0
Volume
Burned
H*
520
420
395
400
388
230
480
210
Feed
Rate
t/hra
23.7
20.6
19.8
20.4
21.9
23.0
23.1
19.5
a) t = metric tons (1000 kg)
b) Central Daylight Time
c) Central Standard Time
Table 3. Oven Temperatures — First Voyage
Date
Oct. 22
Oct. 24
Oct. 25
Oct. 26
Oct. 27
Hour
5:00 p.m.
4:30 p.m.
10:10 a.m.
2:00 p.m.
6:35 p.m.
10:35 a.m.
6:00 p.m.
4:30 p.m.
8:30 p.m.
Starboard Oven, °C
Indicator
1150
1150
1150
1150
1160
1130
1100
1130
1170
Controller
1220
1240
1230
1240
1250
1110
990
1310
1190
Pyrometer
1500
-
1450
1420
1450
1370
-
1450
1440
Port Oven, °C
Indicator
1150
1150
1165
1165
1170
1110
1130
1150
1170
Controller
1260
1270
1220
1220
1290
1090
1200
1330
1300
Pyrometer
1500
1450
1450
1450
1440
1340
1450
1450
1500
102
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BRC-CORP 13-75 F 17
Experimental Difficulties
Many experimental difficulties were encountered. The first probe installed burned up in
the gas oil warm-up on October 16 because the water cooling failed. This destroyed the Pt/Pt Rh
thermocouple. The chromel-alumel thermocouple lasted about 18 hours.
Problems were encountered in cleaning up the stack gas for presentation to the
Beckman 109A Hydrocarbon Analyzer. Intensive effort was required to keep the 109A running, The
final gas scrubbing train devised seemed adequate, however, as there was no smell to the gas coming
through it. The iron helices appear to be quite effective in removing chlorine and the two water and
filter scrubbers appear to remove the HCI completely while passing the harmless carbon dioxide.
The second probe failed after 5 days of use for reasons that are- poorly understood and
are discussed briefly in a later section of this report.
The oxygen and carbon dioxide values were erratic. This may have been caused by leaks
in the connection to the gas analyzer. For this reason, the measured oxygen and carbon dioxide values
were not used in the calculations. Instead, estimated values were used, based on data obtained on the
second voyage.
Treatment of Data
The following quantities were measured or tested for the contents of the water scrubbers:
hydrochloric acid (HCI) equivalents/liter, total organic carbon (TOCm) mg/liter, and organic chlorides
(RCImw) mg/liter as chlorine. On the midget impinger contents the following quantities were determined:
remaining reducing power of sodium arsenite solution (RP) equivalents/liter and organic chloride content
of the isopropyl alcohol (RCImj) mg/liter as chlorine. Also measured were the average total hydrocarbon
concentration of the scrubbed gas over the period during which the water scrubbers collected HCI, (THCm)
ppm. The volumes, (Vm) liters, of gas passed through the midget impingers were estimated from rates
measured by a calibrated rotameter and the corresponding time.
The unburned carbon in the stack gas was measured in two parts: (1) water soluble carbon
in the water scrubbers and (2) gaseous water insoluble carbon as determined by the total hydrocarbon
instrument.
The ratios of the amounts of these materials to the CO2 serve as the basis for the calculation
of the ratio of unburned carbon to carbon in the feed.
For the first part, the ratio TOC/HCI was calculated by the relation:
(TOCm) X 10-3
TOC/HCI = <7)
12(HCIm)
As there are 0.73 moles of Cl per mole of carbon in the feed,
TOC/C02 = 0.73 TOC/HCI (8>
or
™o/™ (0.73)(TOCm) X 10-3
TOC/C02 = (9)
12(HCIm)
In the second step, the ratio THC/C02 was calculated from (THCm) and the stoichiometric
concentration of CO2- Two corrections were required in calculating this ratio. The first arose from
the diminished response of the flame ionization detector to chlorine containing compounds.
103
-------
18 BRC-CORP 13-75-F
O. L. Hollis and W. V. Hoyes6' measured the response factors for a number of halogenated
compounds relative to 2-methylpentane on a weight basis. Values ranged from 0.08 to 0.41. However,
in this work, the flame ionization detector response was calibrated in terms of parts per million carbon
(methane), whereas in Hollis and Hayes paper the response was measured relative to a given weight
of sample. To convert their response factors to a ppm carbon basis, one multiplies them by the ratio
83.7/%C, where %C is the percent carbon in the compound. When this is done, it is found that the
least responsive compound in their table (CH2CI2) still gives a response of 0.6 of that of methane.
Surprisingly, CCI4 with a sample weight response factor of 0.08 has a carbon response factor of 0.86.
Thus dividing the observed (THCm) by 0.5 is a conservative correction for calculating a maximum THC
concentration.
The (THCm) values are concentrations of total hydrocarbons in stack gas that has been
diluted by excess air. Accurate values of oxygen content of the stack gas were not obtained on the
first voyage. In view of later work on the second voyage, a reasonable value for this parameter is
10%.
In accord with equation (5) developed in an earlier section, the stoichiometrically calculated
concentration of CC>2 (151000 ppm) is divided by 2.
Introducing the above correction leads to:
(THCm)/0.5 4(THC)m
THC/C02 = = — (10)
(151000)72 151000
The percent unburned waste was calculated as 100[TOC/CC>2 + THC/CC>2] percent or
unburned carbon per 100 mole carbon in the waste feed. The combustion efficiency was calculated
as 100 minus the percent unburned waste.
The oxidation of arsenite was taken as due only to absorbed chlorine gas. From the
equivalents of arsenite oxidized, the moles of chlorine were calculated and then divided by the moles
of gas sampled (Vm/24.5) to determine concentration of Cl2 in the stack gas.
Generally, no organic chlorides were detected by the methods specific for them. In two
tests where they were detected, (water scrubbers in tests 7 and 8), the amounts were smaller by an
order of magnitude than those found by the total organic carbon which also detected chlorine-free carbon
compounds.
Combustion Efficiency
The results of the determination of combustion efficiency are shown in Table 4. It is seen
that the efficiencies range from 99.92 to 99.98% based on the carbon analyses, and all are well over
the 99.9% required by the permit.
No organic chlorides were found in the midget impinger contents during any of the tests.
The limit of detection was 1 ppm of organic chloride in the gas. The water scrubbers for tests 7 and
8 were found to contain about 0.056 meq/liter chloride as organic chloride. The atomic ratio of CI/C
in the trapped organic compounds was about 0.02 while that of the feed was 0.73, indicating that
destruction of the chlorine moiety is more complete than that of the carbon portion of the molecules.
The ratio of uncombusted chlorine to HCI is 16 X 10'6 and 50 X 10"6 for tests 7 and
8 respectively. If all of the water unsoluble carbon compounds are considered to be organic compounds
with the minimum response factor of 0.6, one can calculate a measure of completeness of combustion
based solely on organic chlorides detected. This is, for the worst case, 100[1 THC/CC>2 " 3!>
or 99.97 or 99.98% which is, of course, much larger than the 99.9% specified in the permit.
e>Anal. Chem. 34, 1223-1226 (1962).
101+
-------
Table 4. Stack Gas Composition — First Voyage
CD
3D
3D
•o
co
•ij
01
o
VJ1
Sample Mo.
2
3
4
5
6
7
8
Time
Start
20/0900
20/1100
20/1900
21/1100
21/1800
23/1400
24/0900
End
20/1100
20/1900
21/1100
21/1800
23/1400
24/0900
25/0800
Concentrations in
Stack Gas
THC
ppm
25
10
10
10
-
10
15
Clfl
ppm
-
60
-
140
-
-
130
Impinger Catch
TOC
eq/1
0.0005
0.0009
0.0028
0.0008
0.0014
0.0013
0.0010
HC1
eq/1
0.711
2.43
7.83
4.61
3.23
3.43
1.12
Ratios
TOC/COa
0.00051
0.00027
0.00026
0.00013
0.00032
0.00028
0.00065
THC/COa
0.00017
0.00007
~0. 00007
0.00007
-
0.00007
0.00012
Unburned
Waste
%
0.07
0.03
0.03
0.02
-
0.04
0.08
Combustion
Efficiency
%
99.93
99.97
99.97
99.98
-
99.96
99.92
-------
20
BRC-CORP 13-75-F
Table 4 also shows that the chlorine contents of the stack gas are low (60-140 ppm) as
expected from the high combustion temperature and thermodynamic calculations.
SECOND VOYAGE: SAMPLING APPARATUS AND PROCEDURE
Sample Ports
Provisions were made to sample the stack gas from both ovens during the second voyage.
These consisted of the installation of duplicate probe assemblies in ports in both ovens. These were
located symetrically about the axis of the ship and in a position that allowed a single sample line to
serve alternately each probe. Details of the ports are shown in Figure 3.
Probe and Support Assemblies
The second voyage probes were changed somewhat in design in an effort to avoid some of
the problems encountered on the first trip. The probe design is shown in Figure 9. The probe is longer
by two feet so that it will reach nearly the center of the stack, its outer wall is made of pipe instead of
tubing for added strength and the glass liner protrudes slightly beyond the end of the jacket. The liner
is mainly VYCOR glass tubing with a short length of vitreous silica tubing fused to the outer end.
The additional weight and length of the probe made a support system necessary. This is
shown in Figures 10 and 11. One end of the support is bolted to the port flange, the outboard end
is braced with cables to the catwalk.
The location of the tip of the probe in the stack is shown in Figure 12.
Sample Line
The outer ends of the probe assemblies were quite close together as is shown in Figure 13.
A single heated line was connected alternately to one or the other. The connection was through about
10 feet of 1/4-inch then wall Teflon tubing. The heated line was electrically traced and thermally insulated
1/4-inch Teflon tubing.f> The heated section was 40 feet long and equipped with an iron constanton
thermocouple. A variable transformer was used to control the voltage supply to provide a temperature
of over 80°C. The connecting ends of the tubing were stainless steel and corroded some during the
test. The heated section was connected to the scrubber train by approximately 10 feet of bare 1/4-inch
Teflon tubing. While the air temperature at the probe end of the line was high enough to prevent
condensation there, there was some condensation in the line before the first trap. This probably came
from the scrubber train end of the line. The line was always well drained into the first water scrubber.
Scrubber Train
The scrubber train used on the second voyage is shown in Figure 14. It was essentially
the same as that used during the latter part of the first voyage with the addition of an empty large
impinger at the end of the train. This was intended to prevent water from reaching the instruments
if the impingers were accidentally hooked up backward.
Five N NaOH instead of 1N NaOH was used in the first midget impinger to assure
an excess during the longer sampling periods used during the second voyage. The midget impingers
were cooled in ice water.
f' Dekoron 2150 Electrically Traced Bundle System, Samuel Moore and Co., Mantua, Ohio 44255.
106
-------
7'
SLIT END
FOR GUIDE
1" STAINLESS STEEL PIPE
K\\\\\^\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\V
TUBING TO FIT OVER
7mm GLASS ROD
\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\vo
'/«" NPT
00
I
75/036/5
\Qv_
HOLE
BORE THRU
FOR 7mm TUBING
PROVIDE FITTING
FOR 7mm _
TO '/4M TUBING
STAINLESS STEEL "T" BRACE
Figure 9. Probe Dimensions — Second Voyage
BORE THRU FOR
1/4* TUBING
•VWIDE
-------
CD
ZD
o
6
O
33
u
•ij
01
Figure 10. Probe Support Assembly — Oven End
-------
00
3J
O
6
o
30
•o
u
•vl
(JI
Figure 11. Probe Support Assembly - Outer End
-------
,
03
1X3
O
6
o
33
CO
•ij
01
Figure 12. Location of Probe in Stack - Second Voyage
-------
CD
3D
3
Tl
NJ
cn
Figure 13. Sample Line Hookup
-------
26
BRC-CORP 13-75-F
GBS
IMPINGERS
MIDGIT
IMPINGERS
SN No OH
.IN NoAiO2
IPA
ir—fl-0!
ri-l FILTER
AND
U CRITICAL ,
ORFICE
PUMP
Figure 14. Scrubber Train, Second Voyage
At the higher concentrations and low temperatures used here, sodium carbonate crystallized
out during the tests. No harm was done however, because the impinger jet did not plug.
Instruments
Carbon monoxide was measured with the aid of one of two nondispersive infrared
instruments: a Mine Safety Appliances Corporation LIRA 3038' instrument 0-1000 ppm or a Beckman
Model 864") carbon monoxide analyzer. The latter instrument, although intended fpr use in the 0-5%
range, was adjusted to have a 0-1000 range in these tests. This led to a relatively noisy signal output
but by estimating median values over several minutes or so values estimated to be within 10 ppm of
the correct result were obtained. Oxygen content was measured with the aid of a Beckman Model 715
Process Oxygen Analyzer.") Electrical outputs from these instruments were directed to a Westronics
Model MIIE') 24 point recorder through a custom made signal conditioning interface. Also displayed
on this recorder were wind speed and direction data from a Meteorology Research Incorporated
Model 1074'^ Weather Sensor mounted on a mast aft of the bridge. The wind data were used in plume
location studies but are not discussed in this report. The output from the iron constanton thermocouple
embedded in the cover of the heated sample line was also displayed in the recorder output.
9) Mine Safety Appliances Co., 400 Penn Center Blvd., Pittsburgh, PA 15235.
") Beckman Instruments, Inc., 2500 Harbor Blvd., Fullerton, CA 92634.
')Westronics, Inc., P. O. Box 11250, Fort Worth, TX 76110.
i) Meteorology Research, Inc., Box 637, Altadena, CA 91001.
112
-------
BRC-CORP 13-75-F 27
Procedure
As on the first voyage, gas was pulled continuously through the probe, sample line, water
scrubbers and instruments at a rate of about 1 liter/min. The side stream through the midget impingers
flowed at a rate of about 230 cc/min. Except for unavoidable interruptions, for changing solutions,
the midget impinger train sampling was continuous when the instruments were working. Usually several
sets of midget impinger samples were taken between changes of scrubber water.
The water, arsenite and isopropyl alcohol solutions were analyzed at the Bellaire Research
Center for, respectively strong acidity as HCI, aresenite consumed as chlorine and organic chlorides in
both arsenite and isopropyl alcohol solutions. Standard analytical techniques were used for the first
two determinations; organic chlorides were determined by the method given in the Appendix.
Optical Pyrometer
During the second voyage, the fire box temperatures were measured with the aid of a Leeds
and Northrup Model 8621^ optical pyrometer. The reported values have been corrected by adding
50°C to the raw data as discussed in an earlier section for the first voyage. Although special thermocouples
were installed in the fire box and stack of both ovens, none of them gave reliable readings and no
data from them are reported.
SECOND VOYAGE: RESULTS
Sampling Targets
The specific targets of the sampling program for the second voyage were:
1) continuous monitoring of carbon monoxide and oxygen,
2) integrated organic chloride and chlorine contents of the stack gas,
3) gas samples from both ovens,
4) at least partial traversing of a stack radius to test for concentration gradients within the
stack, and
5) demonstration of the integrity of sample recovery system.
As on the first voyage, the information obtained by Shell personnel was supplemented by
data acquired by the ship's crew. These included indicator and controller temperatures and estimates
of average feed rates from the times necessary to empty various tanks.
Data Summary Log
A Summary Log of the data obtained by Shell personnel on the second voyage is given
in the Appendix. This shows the chronological relationships between observed values of carbon monoxide,
oxygen, oven temperatures and the times various scrubber samples were taken.
Experimental Difficulties
Fewer problems were encountered on the second voyage than on the first. However, not
everything went smoothly. When the first probe was inserted completely into the starboard stack, the
sample line and first water scrubber filled up with probe cooling water. As discussed in more detail
k> Leeds and Northrup, Sunnytown Pike, North Wales, PA 19454.
113
-------
28
BRC-CORP 13-75-F
in a later section this was probably caused by a weld failure in the probe. The probe was replaced
by the back-up spare. The initial plan was to use the LIRA Model 303 carbon monoxide analyzer
but an error in connecting up the scrubber train flooded the instrument with water. Even after clean
up the instrument was not drift free. Later examination showed that the cell thermostat was not working.
The Beckman instrument was used instead for the latter part of the work. At 2 points electrical noise
problems developed which were traced to the custom recorder interface and fixed. These difficulties,
while annoying, did not seriously impede the main effort to obtain data.
The probe in the port oven failed a few hours before the end of the burn because the
water hose was damaged by the high temperature near the stack. Probes in both ovens distorted when
inserted all the way. This problem is discussed in more detail in a later section. Even though the
glass liner was broken, the seal of the glass tube at the outboard end ensured the withdrawal of undiluted
stack gas.
Feed Rates
The waste feed rates observed during the second voyage are shown in Table 5. Within the
limits of accuracy imposed by the errors in estimating the amount of waste left in a tank when the
incinerator feed was switched to another, the feed rates are in compliance with the permit. The time
of tank switching may have been in error for tank 3S. because one rate is high and the other low
but the average is about the same as the other rates.
Table 5. Waste Feed Rates — Second Voyage
Tank
Number
2C
4C
1C
5C
3C
2S
5S
3S
4S
Volume
M3
550
420
436
425
408
244
226
290
220
Start
Day
Dec. 2
3
4
5
6
7
7
8
8
Hr.
0755
1225
0940
0820
0645
0400
1730
0600
1900
End
Day
Dec. 3
4
5
6
7
7
8
8
9
Hr.
1225
0940
0820
0645
0400
1730
0600
1900
0930
Time,
Hrs.
28.5
21.3
21.7
22.4
21.3
13.5
12.5
13.0
14.5
Volume
Burned
M3
520
395
420
400
388
230
210
275
205
Feed
Rate .
t/hra>
23.7
24.1
25.2
23.2
23.7
22.1
21.8
27.5
18.4
a) t = metric tons (1000 kg)
-------
BRC-CORP 13-75-F 29
Oven Temperatures
The oven temperatures shown in Table 6 followed the pattern established during the first
voyage. Values of the pyrometer temperatures below 1400°C generally were associated with an
interruption of feed to one or more burners. By inspection of the table it is seen that the controller
temperatures were about 180°C higher than the indicator values. In a similar way the pyrometer
temperatures were about 350°C higher than the indicator values. The initial indicator value of 850°C
is more than 350 C below the flame temperature because the steady-state temperature had not been
reached at the indicator sensor's location 2 inches in from the surface of the firebrick.
Treatment of Data
The following quantities were measured on the scrubber water corresponding to one or more
midget impinger train samples: total organic chloride (RCIW), microequivalents as chlorine, and total
hydrochloric acid (HCIW), equivalents. On the contents of the midget impinger train were measured:
total reducing power of the remaining sodium arsenite solution (RP), microequivalents, and total organic
chlorides, (RCIj), microequivalents as chlorine.
The volumes (Vj), liters, of gas drawn through the midget impinger train was determined
from flow rate observations and the corresponding times. Carbon monoxide (CO), ppm and oxygen
(%02> %v were measured continuously with the instruments listed earlier and the data over the indicated
time periods averaged graphically on the recorder strip charts.
The concentration of organic chlorides in the stack gas was calculated from the sum of
the contributions from the water scrubber contents and those from the midget impinger train using
the following equations:
%02 \
—I X
21 /
(RCiw) . _.. ,
RCIs1 = — (1 —} X 0.109, ppm
(HCIW)
where
0.109 is the stoichiometnc fraction of HCI in the stack gas, and
RCIs1 = contribution from the water scrubber,
24 5
RCIs2 = RCIj —— , ppm
^i
where
24.5 = the ideal gas volume (liters/mole) at 26°C, a value reasonably close to room temperature,
RCIS2 = contribution from the midget impinger train.
RCIS = (Rs1 + Rs2), ppm
The concentration of all molecules containing chlorine atoms (assuming one Cl/molecule as
' in HCI) in the stack gas can be calculated from stoichiometry and the dilution due to excess air (% 02)
according to equation (6) derived on page 7 by making appropriate substitutions and changing the
multiplier from 100 to 106 to yield parts per million instead of percent:
/ (%02)\ ft
0.73 ( 1 — I X 106
V 21 /
Concentration of Cl containing molecules or HCI = ppm
6.68
115
-------
30
BRC-CORP 13-75-F
Table 6. Oven Temperatures — Second Voyage
Date
Dec. 2
Dec. 3
Dec. 4
Dec. 5
Dec. 6
Dec. 7
Dec. 8
Dec. 9
Hour
6:50 a.m.
7:15 a.m.
9:45 a.m.
10:10 a.m.
11:25 «.».
1:10 p.m.
1:25 p.m.
4:00 p.m.
6:30 p.m.
10:00 p.m.
7:20 a.m.
10:10 a.m.
12:25 p.m.
1:00 p.m.
2:35 p.m.
4:00 p.m.
5:15 p.m.
6:45 p.m.
7:30 p.m.
8:45 p.m.
10:25 p.m.
6:40 a.m.
9:00 a.m.
12:00 a.m.
1:30 p.m.
3:00 p.m.
5:00 p.m.
9:00 p.m.
3:00 a.m.
8:30 a.m.
10:30 >.m.
11:00 ,.iu.
2:00 p.m.
3:00 p.m.
3:40 p.m.
6:15 p.m.
10:00 p.m.
7:30 a.m.
8:00 a.m.
10:00 ».m.
11:15 a.m.
12:00 a.m.
4:00 p.m.
7:30 p.m.
11:30 p.m.
8:15 a.m.
11:15 a.m.
12:30 p.m.
4:00 p.m.
7:00 p.m.
11:00 p.m.
8:30 a.m.
10:15 a.m.
12:15 p.m.
2:50 p.m.
4:30 p.m.
6:00 p.m.
12:00 p.m.
6:30 «.».
Starboard Oven, °C
Indicator
830
900
1030
1060
1090
1130
1150
1160
1180
1200
1220
1220
1200
1200
1190
1190
1190
1200
1200
1200
1200
1240
1220
1190
1180
1200
1190
1160
1180
1180
1180
1180
1180
1190
1200
1100
1160
1140
1140
1150
1150
1170
1180
1210
1160
1160
1160
1180
1200
1210
1190
1180
1160
1180
1180 '
1160
1160
Controller
1270
1340
1260
1180
1180
1300
1180
1260
1270
1220
1180
1250
Pyrometer
1500
1590
1600
1520
1560
1580
1550
1610
1530
1520
1570
1500
1550
1500
1540
1570
1590
1570
1590
1610
1580
1570
Port Oven, *C
Indicator
900
940
1060
1080
1110
1140
1160
1160
1180
1200
1190
1200
-
-
-
-
-
1180
1310
1200
1210
1200
1200
1160
1180
Controller
1270
1360
1300
1220
1220
1330
1240
1180
1320
1240
1340
Pyrometer
1570
1590
1590
1480
1510
1590
1580
1510
1500
1570
1560
1500
1520
1570
1580
1510
1570
1530
1550
1530
1520
1480
116
-------
BRC-CORP 13-75 F
31
Dividing the observed concentration (RCIs, ppm) of organic chlorides in the stack gas by the concentration
of Cl-containing molecules gives the fraction of unburned organic chloride. With unburned organic chloride
expressed as a percentage (%RCIUD) the relation is:
(%RCIUB) = '
(RCIS)(6.68)
(0.73)
X 10'4
/
Destruction efficiencies are equal to 100 - %RCIUD.
Concentrations of Q% and CO were observed directly and the concentration of C>2 was
calculated in the same manner as in the first mission.
Organic Chloride Destruction Efficiency
Table 7 is a summary of the stack gas analyses and the values for organic chloride destruction
efficiencies calculated from them. The destruction efficiencies are all much higher than the 99.9% specified
in the permit. Furthermore, it is evident that the two ovens are equivalent and that moving the probe
toward the center or toward the wall of the stack has no systematic effect on the levels of any of
the gases tested. The values found for chlorine are quite erratic but at no time were they unexpectedly
high. The oxygen levels correspond to 90 to 160% excess air. The levels of CO concentration are
quite low and indicate again that the combustion efficiency is very high.
Table 7. Gas Analysis and Organic Chloride Destruction Efficiency
RC1 Series
Number
1-2
3-5
6
7-8
9-10
11-12
13-16
21-22
Probe Location
Oven
Stb'd
Port
Port
Stb'd
Stb'd
Stb'd
Port
Port
Depth,
in
9
55
55
48
48
10
55
55
CO
ppm
75
-
-
25
35
40
35
50
Oa
%
11.3
-
-
9.8
10.0
9.0
10.6
12.5
HCl
%
5.3
6.1
6.2
5.2
5.7
6.0
5.3
4.0
cia
ppm
50
350
<10
70
180
40
360
50
RCluB
%
of feed
< 0.002
< 0.002
< 0.002
0.013
0.008
0.007
< 0.004
< 0.005
Destruction
%
>99.998
>99.998
>99.998
99.987
99.992
99.993
>99.996
>99.995
a) Organic chlorides as Cl.
117
-------
32
BRC-CORP 13-75-F
SAMPLE COLLECTING SYSTEM INTEGRITY TESTS
An important condition of the second permit is the requirement that the sample collecting
system recover at least 50% of an organic chloride "spike" introduced into the stack end of the sample
line.
Two such integrity tests were made, one in the field and one in the laboratory.
Field Test
During the collection of three sets of midget impinger samples and the associated scrubber
water, a concentrated vapor solution of 1,2-dichloroethane (DCE) was injected into the sample line through
a Tee at the probe end of the heated line. The vapor solution was generated by shaking liquid DCE
in a 50 ml syringe. The syringe was then mounted on a motor drive and the plunger advanced at
a rate corresponding to 0.109 cc vapor/min. The average temperature at the syringe during the tests
was 26°C at which temperature the vapor pressure of DCE is 0.118 atm. The measured flow rate through
the sampling system was 960 cc/min. Thus 0.109 cc/min of gas with a partial pressure of 0.118 atm
injected into the sample stream gave a composition of (106) (0.109) (0.118)/960 = 13.3 ppm for the
spiked gas.
During the total sample collection period, the gas flow as measured from the amount of
HCI in the GBS impingers was 12.6 moles. The corresponding amount of the spike is
12.6 X 13.3 M moles DCE or 12.6 X 26.6 ju eq CI" = 335 ju eq.
Although the DCE was fed into the line continuously over the 280 min of sampling time,
the recovered material was found only in the last set of midget impingers. The nature of the delay
is not understood, but as can be seen from the following calculations, 72% of the total amount of
DCE introduced was recovered in the last set. This delay did not persist into later experiments as
is indicated by the normal low levels of organic chloride found in later tests.
The flow rate through the midget impinger (Ml) train was 200 ml/min, thus the total RCI
in the gas stream was 42.2 X 960/200 or 203 ju/eq. The total recovery is shown in the following
table.
Recovery System
GBS Impingers
MI Impingers
Subtotal
Total
NaOH
I PA -A
IPA-B
RCl, M- ecl
Basis Side
Stream
2.0
37.8
2.4
42.2
-
RCl, M, eq
Basis Total
Gas Stream
34.5
203
237.5
Fraction Recovered (237.5/335) .72
118
-------
BRC-CORP 13-75-F 33
Laboratory Test
An experimental set-up was designed and assembled to test the absorption of known amounts
of 1,2-dichoroethane (DCE) in water and isopropyl alcohol (IPA) under conditions which simulate stack
sampling aboard the ship.
The experimental set-up is shown in Figure 15. "Zero Air" and hydrogen chloride gas were
metered into a manifold from high pressure cylinders. The zero gas flow was set at 2 liters/min and
the hydrogen chloride at 50 ml/min, giving a concentration of HCI in air of 2.5%. It was difficult
to measure the flow of the acid gas because of its corrosivity, so the regulated flow of HCI was absorbed
in water and weighed until the proper flow had been obtained. DCE was placed in a 100 ml syringe,
the syringe pumped back and forth several times until most of the liquid had been expelled but some
droplets remained. The organic chloride vapor was sampled and analyzed by the
combustion-microcoulometric technique described in the Appendix and found to contain 5.1% by volume
of DCE. The syringe drive was set at 0.066 ml/min for the air-DCE mixture thus delivering 0.0033 ml/min
of DCE into the 2 liter/min gas flow. This concentration of DCE in the acid stack gas, 1.6 ppm,
approximates shipboard conditions.
Most of the synthetic gas was vented, but 220 ml/min was drawn through 40 ft of the
sample line used on the first voyage. The gases were next drawn through two Greenburg-Smith impingers
containing 250 ml of water. The impingers were immersed in an ice bath. The gases were next drawn
through 24 ml of caustic sodium arsenite in a midget impinger in ice and then through two midget
impingers in ice containing 24 ml each of nonograde isopropyl alcohol. Finally the gaseous mixture
was drawn through a filter and a critical orifice which set the flow at 220 ml/min. All tubing was
Teflon; all joints were either Teflon, glass, or polyproylene. No heating was employed and ambient
temperature in the fume hood was 22°C.
The gases were turned on, flow rates checked, and allowed to flow to vent for 1 hour.
At this time, the vacuum pump was turned on and the absorbers connected and the flow drawn through
the absorption train. The experiment was continued for 10 hours. At the end of each hour, the first
IPA scrubber was disconnected momentarily and 25 ;u1 taken for analysis for organic chlorides by the
combustion-coulometric method. The water absorbers were not disturbed. At the end of the experiment,
both the water absorbers and the two IPA solutions were analyzed for organic chloride.
The amount of organic chloride added to the absorption train was calculated from the
concentration of organic chloride in the syringe, the syringe flow rate, the total time, and the flow
ratios of vent to absorption train. The value was found to be 0.222 ml or 9.2 ^g moles. The entire
250 ml of each water absorber was passed through XAD-4 resin, the organic chlorides desorbed from
the resin with methanol and the methanol analyzed for organic chloride by the
combustion-microcoulometric technique. Each absorber was found to contain 1.7 M9 moles. The IPA
absorber, which was analyzed every hour, contained nothing for the first 5 hours then the concentration
slowly increased until it reached 4.52 jug moles. The second IPA absorber, which was only analyzed
at the tenth hour, contained 0.36 jug moles. The four values of recovered organic chlorides total
8.28 jug moles. Dividing this value by the amount added yields 90% recovery of the dichloroethane.
119
-------
VENT
ZERO AIR
HCI (GAS)
75/01* /*
DCE VAPOR
100ml SYRINGE
SYRINGE
DRIVE
PUMP
24ml 24ml 24ml
NoA»Oj I PA I PA
A - MILLIPORE FILTER
B = CRITICAL ORIFACE
Figure 15. Laboratory Apparatus for Sample Recovery - Integrity Test
CD
3D
a
•D
•j
(J1
-------
BRC-CORP 13-75-F 35
PROBE FAILURE CAUSES
Out of a total five sampling probes tried, only one lasted for the duration of the burn.
The reasons for this are several and different for the two kinds of probes.
First Voyage
The first probe installed was damaged by overheating when the cooling water was accidentally
turned off. The damage caused was severe warping of the probe and the separation of the thermocouple
sheath formerly tack welded to the outside of the probe.
The second probe failed for more obscure reasons. About six days into the burn, water
was observed coming from the port into which the probe was inserted. The flow increased to a point
which necessitated sacrificing the probe. It seems unlikely that liquid condensate corroded the outside
of the probe as suspected at the time. The cause of this failure is unknown at this time. The corrosive
power of the hot gases is graphically shown in Figure 16. This is the remains of the probe in the
stack after three days without cooling.
Second Voyage
The first probe inserted into the starboard oven probably failed because differential expansion
of the outer and inner tubes broke the weld at the cold end. This caused the parts to separate, break
the glass tubing and admit water to the sample line. This theory is supported by the fact that the
flow of water into the sample line diminished when the probe was withdrawn.
Differential expansion probably caused the severe warping of the other probes used on the
second voyage. The extent of the warping is shown in Figure 17. It appears possible that the outside
of the probe extended in length sufficiently to stress the metal beyond its yield point and caused the
observed bend.
The severity of the probe environment is again illustrated by the corrosion of the probe
tip shown in Figure 18.
Comments
It is our belief that we have demonstrated (see Table 7} that the two ovens are equivalent
and that it is unnecessary to traverse the diameter of the stack to secure reliable stack gas samples.
If this is true, then probe construction for future tests can be greatly simplified. The probe can be
shorter, and provisions need not be made for moving it in and out. Furthermore, the outside of the
probe can be provided with a ceramic jacket to deflect the hot gases and a packing gland can be used
to seal the inner tube to the outer one so that the tubes may move longitudinally relative to one another.
These modifications seem likely to improve the chances of a new, water jacketed glass lined probe lasting
through a sampling campaign. Care must be taken, however, to use heat resistant hose for the water
lines near the oven as temperatures there will destroy ordinary vinyl tubing.
121
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C3C
X
O
o
O
n
-o
oo
Figure 16. Probe in Stack After First Voyage
-------
BRC-CORP 13-75-F
37
Figure 17. Bend in Probe After Second Voyage
-------
38
BRC-CORP 13-75-F
Figure 18. Probe Nozzle After Second Voyage
-------
BRC-CORP 13-75-F
APPENDIX
-------
BRC-CORP 13-75-F
APPENDIX
Page
EPA Permit 730D008C A-1
EPA Permit 730D008C (2) A-15
Determination of Trace Organic Chlorides in Sea Water and Waste Water - Combustion-Coulometric
Method A-21
Determination of Total Organic Carbon in Natural Waters Including Brines - Wet Oxidation Infrared
Method A-27
Summary Log - First Voyage A-31
Summary Log - Second Voyage A-37
Stack Gas Analytical Results - Second Voyage A-45
126
-------
BRC-CORP 13-75-F A-1
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
Washington, D. C. 20460
Permit No. 730D008C
Name of Permittees Shell Chemical Company, Inc., and
Ocean Combustion Services, B.V.
Effective Date October 10, 1974
Expiration Date October 26, 1974
MARINE PROTECTION, RESEARCH, AND
SANCTUARIES ACT (OCEAN DUMPING) RESEARCH PERMIT
In reference to the following application:
Application Number: 730D008C
for a permit authorizing the transportation for incineration in com-
pliance with the provisions of the Marine Protection, Research, and
Sanctuaries Act of 1972, as amended (hereinafter referred to as the
Act),
Shell Chemical Company ("Shell"), and
Ocean Combustion Services, B.V. ("OCS")
hereinafter called Permittees, are authorized to transport material for
Incineration from the Shell facility at P. 0. Box 2633, Deer Park,
Texas, all in accordance with the following general and special con-
ditions :
General Conditions
1. All transportation and incineration authorized herein shall
be consistent with the terms and conditions of this permit.
2. a. Transportation to, and incineration at any location other
than that authorized by this permit shall constitute a violation of the
terms and conditions of this permit.
b. Transportation and incineration of any material more fre-
quently than, or in excess of, that identified and authorized by this per-
mit, or incineration of material not authorized by this permit, shall
constitute a violation of the terms and conditions of this permit.
127
-------
A.2 BRC-CORP 13-75-F
3. The Permittees shall allow an authorized EPA representative
and the U. S. Coast Guard representative:
a. To enter the Permittees' premises or vessels in which
material to be discharged is located;
b. To have access to and copy any records required to be
kept under the terms and conditions of this permit or the Act;
c. To inspect any monitoring equipment or monitoring method
required in this permit;
d. To sample any materials discharged or to be discharged; or
e. To take such other action as is necessary or appropriate
to determine whether the terms and conditions of this permit have been
fulfilled.
A. The Issuance of this permit does not convey any property rights
in either real or personal property, or any exclusive privileges, nor
does it authorize any injury to private or public property or any inva-
sion of personal rights, nor any infringement of Federal, State or*local
laws or regulations.
5. If the dumping of material which is regulated by this permit
is dumped due to emergency to safeguard life at sea in locations or In
a manner not in accordance with the terms of this permit, the Permittees
shall, In accordance with 40 C.F.R. Section 224.2(c), notify by radio,
telephone or telegraph the Administrator and the appropriate U.S. Coast
Guard district of the incident as soon as possible and make a full
written report to the Administrator and the Coast Guard within 10 days.
6. Unless the context otherwise requires, terms used in this permit
which are defined in Section 3 of the Act shall have the same meaning
herein,
Special Conditions
1. Description of Material
a. The waste to be shipped for incineration is a mixture of
organic chlorides from five process waste streams. The constituents of
each waste stream are described in Appendix A and in the Analysis and
Characterization of Five Organic Waste Streams Proposed for Deep-Sea
Disposal submitted by the Permittees. The levels in the wastes to be
incinerated shall not be in excess of the concentrations or amounts set
forth in Appendix A.
128
-------
BRC-CORP 13-75-F A-3
b. The character of the material being discharged shall not
be altered in its content from the amounts listed in Appendix A by the
addition of wastewater from sources other than those identified above.
2. Amount of Material
a. The Permittees are authorized to transport and inciner-
ate material described in Paragraph 1 in an amount not in excess of
A,200 metric tons.
3. Transportation and Barging Activities
a. The port of departure for the dumping of the material
described herein is Houston, Texas. The Permittees are authorized to
transport the material described herein from the Shell facility to
such port of departure to ocean waters.
b. During loading operations, there shall be no loss of
material to any waterway.
c. The Permittees are authorized to incinerate the described
wastes in a site which is defined in longitude and latitude as follows:
From 26 degrees 20 minutes to 27 degrees 00 minutes
north latitude
From 93 degrees 20 minutes to 94 degrees 00 minutes
west longitude
d. Permittees shall navigate around, by a radius of 15 nau-
tical miles, the reefs found at the following coordinates:
West Flower Gardens:
27 degrees 53 minutes north latitude
93 degrees 48 minutes west longitude
East Flower Gardens:
27 degrees 55 minutes north latitude
93 degrees 36 minutes west longitude
e. Permittees shall also navigate around by a radius of 5
nautical miles the reefs found at the following coordinates:
129
-------
A-4 BRC-CORP 13-75-F
Stetson Bank:
28 degrees 10 minutes north latitude
94 degrees 18 minutes west longitude
Claypile Bank:
28 degrees 20 minutes north latitude
94 degrees 09 minutes west longitude
4. Means of Transportation
a. The means of transportation shall be the following named
vessel:
Company Ship Capacity
Hansa Lines Vulcanus 4,200 metric tons
b. The Permittees shall place this permit or a copy of this
permit In a conspicuous place In the vessel which will be used for the
transportation and incineration herein authorized.
5. Special Conditions
a. Permittees shall begin the incineration of the wastes only
after the combustion chamber reaches a temperature of 1200 degrees C.
There shall be no incineration at less than 1200 degrees C. The Permittees
shall be required to maintain a minimum average combuslon temperature of
1400°C (a running four-hour average), except that Permittees shall be
allowed to determine the combuslon efficiency as a function of average
combustion temperatures of 1100°C, 1200°C, 1300°C, and 1500°C, during
two four-hour burns at each such average combustion temperature.
b. Permittees shall maintain no less than a 99.9 percent
combustion efficiency at any time except during evaluations of com-
bustion efficiency pursuant to subparagraph a.
130
-------
BRC-CORP13-75-F A-5
c. The toal feed rate of waste into the incinerators shall be
no greater than 20 metric tons/hr.
d. Permittees shall so position and navigate the ship during
incineration as to maintain a position downwind from any vessel other
than those engaged in environmental monitoring. There shall be no less
than an effective wind velocity of 10 knots to be passing the incin-
erator stacks (to be comprised of wind or vessel speed or both.)
e. Permittees shall insure their position within the discharge
site at all times by on-board navigational aids, and shall maintain
documentation of position at all times.
6. Monitoring Requirements
a. The Vulcanua shall have equipment installed and In; use which
shall constantly measure the temperature at two points Inside each Incin-
erator. The Vulcanus at two points shall have In operation a time clock
with control lamps showing when the incinerators are in operation. There
shall be an automatic camera which will photograph the control panel
every 15 minutes. The monitoring equipment noted in this paragraph shall
be sealed by the proper governmental authorities at the initiation of the
voyage, and available for inspection at the conclusion of the voyage.
b. There shall be installed and in operation a Beckman 109A
flame ionizatlon detector device, calibrated on shore against standard
mixtures of methane in air, which device shall make regular stack tests
for emissions of total hydrocarbons.
c. The Permittees shall regularly monitor the combustion
efficiency of the Vulcanus.
d. Permittees shall monitor the fallout of hydrogen chloride
and other chemicals from the incineration by use of the oceanographlc
ship Miss Freeport. which shall be equipped with devices to measure pH
levels, to make phytoplankton counts, and to take neuston net tows.
Periodic measurements shall be made of pH, phytoplankton and zooplankton
in the vicinity of the area in which there is fallout, and In areas
outside the fallout zone within the dumping area consistent with the
recommendations of the Presiding Officer dated October 9, 1974.
e. All data collected by or on behalf of Permittees and
calculations by Permittees based thereon shall be retained and supplied
to EPA and made available for public Inspection as soon as possible.
131
-------
A'6 BRC-CORP13-75-F
f. In addition to the specific monitoring requirements set
forth above, Permittees shall, after consultation with EPA, conduct
such other monitoring or other studies as may be necessary or appropriate
to carry out the recommendations set forth in the Report of the
Presiding Officer dated October 10, 1974.
g. It is contemplated that extensive monitoring will be
carried out by EPA and other federal agencies. The Permittees shall
cooperate with all such monitoring personnel. This cooperation shall
Include communication of geographical position, assistance in navi-
gation, and the making available of accomodations for one observer on
board the Vulcanus during the period of the research permit, if so
requested by EPA.
October 10, 1974
dministrator
132
-------
BRC-CORP 13-75-F A-7
APPENDIX A
ANALYSIS OF C LIGHT ENDS
(Approximately 15% of Total Waste)
COMPONENT Xw
2-Chloropropane )
)
Ethyl Chloride ) 17
)
2-Chloropropene )
1-Chloropropane 22
3-Chlorc-l-propene 18
Acrolein 5
1,1-Dichloroethane 4
Isopropyl Alcohol + Dichloronethane 0.7
Benzene 0.7
1,1-Dichloropropane 1
3,3-Dichloropropene + Acetonitrile + Chloroform 4
1,2-Dichloropropane 11
1,2-Dichloroethane 0.2
2,3-Dlchloropropene 14
cis 1,3-Dichloropropene 0.4
Epichlorohydrin 0.4
2,3-Dichloro-l-propanol 0.2
l-Chloro-2,3-dihydroxy Propane 0.2
Watei 0.6
Unidentified 0«6
100
133
-------
A.g BRC-CORP 13-75-F
ANALYSIS OF C HEAVY ENDS
(Approximately 25% of Total Waste)
COMPONENT %w
1,2-Dichloropropene 0.1
Epichlorohydrin 2
2-Chloroallyl Alcohol 0.5
1.2.3-Trichloropropane 70
1,3-Dichloro-2-propanol 0.7
l,2-Dichloro-3-propanol 10
l-Chloro-2,3-Dlhydroxypropane 0.2
Tetrachloropropyl Ethers 14
Unidentified 2
Water 0.5
100
-------
BRC-CORP13-75-F A-9
ANALYSIS OF VCM HEAVY ENDS
(Approximately 25Z of Total Waste)
COMPONENT %w
1-Chlorobutane 0.3
Tetrachloroethylene 0.9
1,1,1-Trichloroethane 0.8
1,2-Dichloroethane 15
1,2-Dichlorobutane 0.7
Dichlorobutenes 5
Chlorobenzene 2
1,1,2-Trichloroethane + 1,1,1,2-Tetrachloroethane 58
1,2-Dichlorohexane 1
2-Chloroethanol + 1,4-Dichlorobutane 0.6
Pentachloroethane 0.5
Hexachloroethane 0•4
1,2,3-Trichlorobutane 0.9
1,2,3-Trlchloropropene 0.8
1,1,2,2-Trichloroethane 5
bis(2-Chloroethyl)ether 1
1,2,4-Trichlorobutane 1
Water 0-
Unknowns —L.
100
135
-------
A-10 BRC-CORP13-75-F
ANALYSIS OF VCM TARS
(Approximately 25% of Total Waste)
COMPONENTS
Trichloroethylene 0-2
Tetrachloroethylene 0-2
1,1,1-Trichloroethane 0.4
1,2-Dichloroethane 36
1,2-Dichlorobutane + Unknown Butadiene 0.3
Dichlorob utenes 1 . 8
Chlorobenzene 0.7
1,1,2-Trichloroethane + 1,1,1,2-Tetrachloroethane 15
1,2-Dichlorohexane 0.6
2-Chloroethanol + 1 , 4-rDichlorobutane 0.7
Pentachloroe thane 0.6
Hexachloroe thane 0.6
1,2,3-Trichlorobutane 1
1,2,3-Trichloropropane 0.8
1,1,2,2-Tetrachloroethane 5
bis (2-Chloroethyl) ether 3
1,2,4-Trichlorobutane 5
c3-c6cix 14
Unspecified Aroma tics 2
Unknowns 2
Freon-Soluble Material 4
Freon-Insoluble Material 6
Water _ 0.1
100
136
-------
BRC-CORP 13-75-F A'11
ANALYSIS OF "D-D" FLASHER BOTTOMS
(Approximately 10% of Total Waste)
COMPONENT %w
3-Chloro-l-propene 0.3
Benzene 0.2
313-Dichloro-l-propene 1.5
1,2-Dichloropropane 17
2,3-Dichloro-l-propene 2
cis-l,3-Dichloropropene 13
trans-l,3-Dichloropropene 15
Trichloropropenes 4
1,2,3-Trichloropropane 4
Unknowns 7
Preon-Soluble Material 24
Freon-Insoluble Material 12
100
137
-------
A-12
BRC-CORP 13-75-F
Metals
Chromium
Lead
Nickel
Mercury
Cadmium
Zinc
Copper
Arsenic
Physical Chemical Properties
Specific Gravity
Average % by wt.
0.15 ppm
2.0 ppm
0.67ppm
0.OlOppm
0.002ppm
0.28 ppm
1.2 ppm
0.03 ppm
1.10-1.35
138
-------
BRC-CORP13-75-F
A-13
TEUGRAPHIC MESSAOE
EKVL80KXEXTAJ, PROTECTION ACEKCT
6950106 5J.2722E990 "
!>«U *•*"«»
10/25/74
H*CXMA7)ON CAU
A. Rogera
755-0753
DHCLAJ
D
D
D
TO
;TO:
KX. NOMSAN D. RADFORD. JR.. ESQUTBE
VISSON, ELELSS, EZAELS, COKKALLT & SMITH
PI£5I Cm NAIIOX^L EAKK
HOUSTON. TEXAS 77092
THE
urrrEES noaa ETA OCEAN DISCHARGE FEKHIT so. 73OXXWC.
TO THE JSCJSOATias OF Sgni CHEH1CAL ttKPAKY OBGANOCHLORIMB
[HASTES BY THE OCEAN QCIXERATIOS SHIP yuLCAtgjs. HAVE KEQDESTID
BIFICA77ONS OF TEE FEEMT TO ALLOW A MAYTMIBI KASTE FEED BATE OF
OS METRIC TORS FEE tidCtt AKD AN £XI^SlO« UP iHt EFFECTIVE PATE OT THE
JFEDHT. TOE FEEMTT EXFIKES ON OCTOBtR 26. 1974. VT CCtMWICATTOH 07
"DCTOSER 24, i»74. FKOM KR. R. E. VAN XKCEN OF SHELL cnoaui
•EPA HAS BEEH INFOEMED T3AI SHELL NO LOOTER REQUESTS A MODIFICATION IN
182 PERXir'C RCQ01&ED QPEKATDiG TEHTEEATDHZS.
THE PURPOSE OF THE. FEDOT WAS TO ALLOW SHELL AMD OCS TO INCINERATE
4200 METRIC TONS OP SHELL'S WASTES OH AN EXFERTKEKIAL BASIS. 8ECAUM
JMB VPLCAKUS EXPCTJiiMCEP TECHNICAL DIFFICUITUS ASD KAS CSABLE TO
CCMffiMCE T1IE TK^TMiTBATTflM OK THE DAT CONT£21PLATED VBSS TBS PERMIT HAS
ISSUED, THE FEBKZTTZE5 VOL BE IK VIOLATION UHUSS AH ERZKSiaR IS
Tm> ACTUAL HIOCK& OF DATS OK HHICfl IKCDCESAIICK -WELL BE
CAUIED OUT IS MOT CHANCED.
' •«>
i«
!! 7B'-JS K«
139
-------
A-14
BRC-CORP 13-75-F
TBLEGRAFHJC WE5SAG*
nt or MOSMit
MUt C*4 i>f t'J.lM'. >/Cl7rt» I >/T
TO
TO:
THE REQUTRtKKKT OF A 2O MSTB1C Tt35iS FER HOCK FEED BATE. COtflAIKED
IS THE EKISTJCiG FE2MTT, WAS 2ASED UPOS THE TESTWWT BT SHEli AT THE
PCBL1C U£ARIKG TO 1H£ EmCT THAT THIS TEROCGHFirr KATE VOCID ALLC7W
ACB1EVEHEKT OF TliE DESIKLD CCKECSTICB; TEMTEEATTEZS. TOD HAVE STATTD
TO EPA THAT RJLESS THE HOT EATE IS ALLOWED TO FLCCTUAT! TO 25 METRIC
TONS PER BODE THE CCKEC5T10S TEMPERATURES KA10UTED 3T
•nrr nx. PCTTVTT w»v ^JTT TC ATTAJVTO.
THE SEELL 8EQDEST K« MODIFICATIONS VTli HOT AFFECT TIIE
TOTAL SCRNTJSG TTKE CaVTDiPLATED BT THE OXIGISAL PtKHIT AND WI14, HOT
LESSEN THE EPA 1EKPESATUEZ ASH COMBUSTION EFFICII3CY K£QC1K£KEXTS,
PERMIT KO. 730DOOSC TS EESE5T AKEHDED TO FEOVIBE THAT fflt E&PLKATION
DATE IS 11:59 P.K., OCTOBER 30, 1974, AHD THE MAXIMUM WASTK THROWCaPtTT
RATE SHALL BE 25 METPac TCSS PER BOtK. ALL OTHES CONDIHOUS AND
BEQU1RZKESTS Of THE PtWflT ISSUED ON OCTOBER 10, 1974. KEKAIH 1M KFFECT.
(OCTOBER 25, 197*
(JOES R. QDARLES
DEFUTT AJMTRISTIATOR
CXCLAS
: <«l 101 H KB
1)40
-------
BRC-CORP13-75-F A-15
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
Washington. D. C. 20460
Permit No. 730D008C (2)
Name of Permittees Shell Chemical Company, Inc., and
Ocean Combustion Services, 13. Y.
Effective Date November 28, 1974
Expiration Date December 16, 1974
MARINE PROTECTION. RESEARCH, AND
SANCTUARIES ACT (OCEAN DUMPING) RESEARCH PERMIT
In reference to the following application:
Application Number: 730D008C
for a permit authorizing the transportation £o~c incineration in com-
pliance with the provisions of the Marine Protection, Research,
and Sanctuaries Act of 1972, as amended (hereinafter referred to
as the Act).
Shell Chemical Company r:She!l':). and
Ocean Combustion Services, B. V. ("OCS")
hereinafter called Permittees, are authorized to transport material
for incineration from the Shell facility at P. O. Box 2633, Deer Park,
Texas, all in accordance with the following general and special
conditions:
General Conditions
1. All transportation and incineration authorized herein shall be
consistent with the terms and conditions of this'permit.
2. a. Transportation to, and incineration at any location other
than that auhtorized by this permit shall constitute a violation of the
terms and conditions of this permit.
b. Transportation and incineration of any material more fre-
quently than, or in excess of, that identified and authorized by this
permit, or incineration of material not authorized by this permit,
shall constitute a violation of the terms and conditions of this permit.
-------
A-16 BRC-CORP13-75-F
3. The Permittees shall allow an authorized EPA representative
and the U.S. Coast Guard representative:
a. To enter the Permittees' premises or vessel in which
material to be discharged is located;
b. To have access to and copy any records required to be kept
under the terms and conditions of this permit or the Act;
c. To inspect any monitoring equipment or monitoring method
required in this permit;
d. To sample any materials discharged or to be discharged; or
e. To take such other action as is necessary or appropriate to
determine whether the terms and conditions of this permit have been
fulfilled.
4. The issuance of this permit does not convey any property rights
in either real or personal property, or any exclusive privileges, nor
does it authorize any injury to private or public property or any inva-
sion of personal rights, nor any infringement of Federal, State or local
laws or regulations.
5. If the dumping of material which is regulated by this permit
is dumped due to emergency to safeguard life at sea in locations or i*i
a manner not in accordance with the terms of this permit, thp T^pr-mUf^
shall, in accordance with 40 C. F. R. Section 224. 2(c), notify by radio,
telephone or telegraph the Administrator and the appropriate U.S. Coast
Guard district of the incident as soon as possible and make a full
written report to the Administrator and the Coast Guard within 10 days.
6. Unless the context otherwise requires, terms used in this permit
which are defined in Section 3 of the Act shall have the same meaning
herein.
Special Conditions
1. Description of Material
a. The waste to be shipped for incineration is a mixture of
organic chlorides from five process waste streams. The constituents of
each waste stream are described in Appendix A to the; first research
permit issued under application number 730D008C (effective October 10,
1974 to October 26, 1974) and in the Analysis and Characterization of
Five Organic Waste Streams Proposed for Deep-Sea Disposal submitted
-------
BRC-CORP13-75-F A-17
by the Permittees. The levels in the wastes to be incinerated shall
not be in excess of the concentrations or amounts set forth in Appendix A.
b. The character of the material being discharged shall not
be altered in its content from the amounts listed in Apendix A to permit
no. 730D008C by the addition of wastewatcr from sources other than those
identified above.
2. Amount of Material
a. The Permittees are authorized to transport and inciner-
ate material described in Paragraph 1 in an amount not in excess of
4, 200 metric tons.
3. Transportation and Barging Activities
a. The port of departure for the dumping of the material
described herein is Houston, Texas. The Permittees are authorized to
transport the material described herein from the Shell facility to
such port of departure to ocean waters.
b. During loading operations, there shall be no loss of material
to any waterway.
c. The Permittees are authorized to incinerate the described
wastes in a site which is defined in longitude and latitude as follows:
From 26 degrees 20 minutes to 27 degrees 00 minutes
llOrth lai.ii.Utle
From 93 degrees 20 minutes to 94 degrees 00 minutes
west longitude
d. Permittees shall navigate around, by a radius of 15 nau-
tical miles, the reefs found at the following coordinates:
West Flower Gardens:
27 degrees 53 minutes north latitude
93 degrees 48 minutes west longitude
East Flower Gardens:
27 degrees 55 minutes north latitude
93 degrees 36 minutes west longitude
-------
BRC-CORP 13-75-F
e. Permittees shall also navigate around by a radius of 5
nautical miles the reefs found at the following coordinates:
Stetson Bank:
28 degrees 10 minutes north latitude
94 degrees 18 minutes west longitude
Claypile Bank:
28 degrees 20 minutes north latitude
94 degrees 09 minutes west longitude
4. Means of Transportation
a. The means of transportation shall be the following named
vessel:
Company Ship Capacity
Hansa Lines Vulcanus 4, 200 metric tons
b. The Permittees shall place this permit or a copy of this
permit in a conspicuous place in the vessel which will be used for
the transportation and incienration herein authorized.
5. Special Conditions
a. Permittees shall begin the incineration of the wastes only
after the combustion chamber reaches a temperature of 1200 degrees C
measured as a flame temperature, and there shall be no incineration
at less than this temperature. The Permittees shall maintain at least
an average flame temperature of 1350 C. while incinerating the wastes.
b. Permittees shall so Operate the incinerators that there is
no less than a 99. 9 percent destruction of the wastes.
c. The total feed rate of waste into the incinerators shall be
no greater than 25 metric tons/hr.
d. Permittees shall so position and navigate the ship during
incineration as to maintain a position downwind from any vessel other
than those engaged in environmental monitoring. There shall be no less
than an effective wind velocity of 10 knotts to be passing the incinerator
stacks (to be comprised of wind or vessel speed or both. )
-------
BRC-CORP13-75-F A-19
e. Permittees shall insure their position within the discharge
site at all times by on-board navigational aids, and shall maintain
documentation of position at all times.
f. Permittees shall have installed and in operating condition a
radio or other communications device which is capable of voice
transmission to the mainland from the Vulcanus when in the discharge
zone.
6. Monitoring Requirements
a. The Vulcanus shall have equipment installed and in use which
shall constantly measure the temperature at two points inside each incin-
erator. The Vulcanus shall have in operation a time clock with control
lamps showing when the incinerators are in operation. There
shall be an automatic camera which will photograph the control panel
every 15 minutes. The monitoring equipment noted in this paragraph
shall be sealed by the proper governmental authorities at the initiation
of the voyage, and available for inspection at the conclusion of the
voyage.
b. The Permittees shall regularly monitor the organochlorine,
carbon monoxide and oxygen emissions from the Vulcanus.
c. Permittees shall monitor the fallout of hydrogen chloride
and other chemicals from the incineration by use of a monitoring
ship, which shall be equipped with devices to measure pH
levels and obtain samples to determine rhlorinity. Periodic measure-
ments shall be made of pH and chlorinity in the vicinity of the area
in which there is fallout, and in areas outside the fallout zone.
d. All data collected by or on behalf of Permittees and
calculations by Permittees based thereon shall be retained and supplied
to EPA and made available for public inspection as soon as possible.
e. In addition to the specific monitoring requirements set
forth above, Permittees shall, after consultation with EPA, conduct
such other monitoring or other studies as may be necessary or
appropriate to carry out the recommendations set forth in Appendix I
to the Staff Report attached to the Supplementary Decision of the
Administrator, both dated November 27, 1974.
-------
A-20 BRC-CORP 13-75-F
f. It is contemplated that monitoring may be carried out by KPA
and other federal agencies. The Permittees shall cooperate with all
such monitoring personnel. This cooperation shall include
communication of geographical position, assistance in navigation, and the
making available of accomodations for two observers on board the
Vulcanus during the period of this research permit, if so requested by
EPA.
•
November 27, 1974 Administrator
-------
BRC-CORP 13-75-F A.21
Shell Research Complex Method Series SRC 4X 12/75
SHELL DEVELOPMENT COMPANY
ANALYTICAL DEPARTMENT
DETERMINATION OF
TRACE ORGANIC CHLORIDES IN SEA WATER AND WASTE WATER
COMBUSTION • COULOMETRIC METHOD
Scope
1) The method is applicable to the determination of organic chlorides in sea water and waste
water in the range of 0.05-10 ppm. Inorganic halides do not interfere. Organic bromides, if present,
will interfere.
Method Summary
2) The sea or waste water sample is passed through a small bed of macroreticular resin which
passes the inorganic salts and retains the organic material. The bed is washed free of residual salts
with de-ionized water and the organic material eluted with a small amount of methanol. A portion
of the methanol solution is burned in a hot quartz tube with oxygen and the resulting hydrogen chloride
titrated automatically with coulometrically generated silver ion.
Apparatus
3) a) Quartz combustion tube. The quartz combustion tube is made from General Electric
type 204 clear fused quartz. The details of its construction are shown in Figure 1. Other types of
quartz may require more frequent replacement, due to a higher rate of devitrification, but are otherwise
suitable. The tube is heated to 950°C with a furnace 42 cm long and 2 cm ID. The furnace contains
50 feet of 16 ga Kanthal "A" wire and is operated, through a variable autotransformer, at 115 V ac.
Any furnace of similar design is suitable.
b) Sample vaporization heater. The sample vaporization section of the combustion tube
is heated to 225°C with a Briskeat High Temperature heating tape insulated with "Samox" fiber,
1/2 inch X 2 feet long. It is operated at 115 V ac and controlled with a variable autotransformer.
c) Detector. An automatic microcoulometer capable of generating silver ions with a
suitable pair of indicating electrodes. (Dohrmann Microcoulometer, Model C-200B, with a T-300 titration
cell, Dohrmann Instruments, 1062 Linda Vista, Mountain View, California.)
d) Oxygen humidifier. The oxygen is humidified by passage through a 500 ml gas washing
bottle containing 200 ml of de-ionized water. Catalog No. K-65800, Kontes Glass Company, Vineland,
New Jersey, or similar.
e) Integrator. An optical planimeter or disc integrator is required for measurement of
peak areas.
f) Recorder. A 0-1 mv strip chart recording potentiometer, Hewlett Packard Model 1728
or similar.
g) Sample injector. Hamilton Microsyringe, 0-25 jul, Model 702N.
h) Serum cap. Size "A", 6 mm plug OD X 8 mm plug length X 10 mm top OD. Aloe
Scientific Company Catalog Number 72400. Frequent replacement of the serum cap will be required.
i) Resin column. The chromatographic column used to carry out the salt separation
is shown in Figure 2. Any similar column with the same diameter to length ratio will be suitable.
-------
C/l
33
O
10
to
-J
Ul
-455-
oo
1
1
1
1
* I
J~ ^ ^ 1
rt > <
r~ \ s < i *
\12/5 16 OD \
DIMENSIONS IN mm
b> 900 *r
DRAW DOWN
1 TO 1 ID \
"X \
^
*s 4
7 OD « 2 ID 10 OD'
VYCOR VYCOf
6 OD
_ (TO FIT 1/4".
SWAGELOCK)
-M« 225 "C
w— ^u-»n
~^5^
/
* 4 ID
t BULB
If
M
GRIND FLAT
AND
FIRE POLISH
FOR
^SERUM CAP
JD
(D
Figure 1. Quartz Tube for the Vaporization and Combustion of Trace Amounts of Organic Chlorides
_
OJ
X
8.
CD
3)
O
6
o
3)
TJ
U
•ij
01
-------
BRC-CORP 13-75-F
A-23
Shell Research Complex Method Series
SRC4X 12/75
-40-
9« 7
XAD-4 RESIN
PYREX WOOL PLUG-
DRAW TIP DOWN,
TO 1.5 mm
100
300
100
ALL DIMENSIONS IN mm
MATERIAL: PYREX
Figure 2. Resin Column
-------
A-24
BRC-CORP 13-75-F
SRC4X 12/75
Shell Research Complex Method Series
Reagents
4) a) Amberlite XAD-4. Nonionic Polymeric Adsorbent, Mallinckrodt No. 3412.
b) Methanol. Pesticide Quality. Matheson Coleman Bell No. 484.
c) Helium. Pure grade, pressure regulated.
d) Oxygen. Pure grade, pressure regulated.
Note 1. Oxygen lines are normally degreased with a chlorinated solvent. It is essential
that all traces of this solvent be removed before application of this method.
e) Titration solvent. Seventy percent Reagent Grade acetic acid, 30 percent de-ionized
water. It is better to make up small amounts (500 ml) of this reagent as required rather than to make
a large amount which could become contaminated in storage.
f) Standards. Alkyl chlorides of the type that might be encountered in the waste water
or sea water. A wide variety of these compounds is available from Eastman Kodak Company, Rochester,
New York. Use highest purity available.
g) Silver nitrate. Ten percent solution of Reagent Grade crystals in de-ionized water.
Procedure
5) a) Assemble the apparatus as shown in Figure 3. Adjust the helium pressure and control
valve so that 60 ml/min flows through the combustion tube and titration cell. Allow the combustion
furnace to reach 950°C and the sample vaporization heater to reach 225°C.
SAMPLE VAPORIZATION
HEATER TAPE
SAMPLE INJECTION
SERUM
HELIUM
MICROCOULOMETRIC
TITRATOR
TITRATION CELL
POTENTIOMETRIC
RECORDER
Figure 3. Combustion - Coulometric Apparatus for the Determination of Organic Chlorides
Note 2. Do not allow the sample vaporization zone to exceed 225°C because of the probable
thermal dehydrochlorination of some of the more sensitive alkyl chlorides.
Adjust the oxygen flow to 400 ml/min. Clean the titration cell, fill the cell with fresh
titration solvent, set the bias control at 235 mv, and allow the cell to come to a null balance.
Note 3. The operator should become completely familiar with the Dohrmann
microcoulometer and the titration cell by a thorough study of the literature supplied with the instrument.
b) Set up a suitable number of resin columns. As the salt removal step requires
approximately 2 hours and the combustion-titration step requires only a few minutes, it has been found
convenient to have half as many columns as there are samples to be analyzed in a day. Plug the
-------
BRC-CORP 13-75-F A-25
Shell Research Complex Method Series SRC 4X 12/75
end of each column with a small piece of glass wool, add 4 ml of Amberlite XAD-4 resin and tap
the column lightly to settle the packing. Wash each column with three successive 50 ml portions of
pesticide grade methanol. Save the last 10 ml from the last wash for a blank determination. Wash
each column with three successive 50 ml portions of de-ionized water. The columns are now ready
for use and should be lightly capped to prevent contamination.
Note 4. A strong amine odor will be present during the initial methanol washings and
this operation should be done in a hood or well ventilated area if the odor is objectional to laboratory
personnel.
c) Prepare a known concentration of a typical organic chloride in sea water or water
of the same salt content as the waste water. The concentration should be approximately the same
as that expected in the sample water (1-5 ppm). Prepare a mixture of the same organic chloride in
pesticide grade methanol in a concentration that is 50. times higher than the standard prepared in water.
Weigh 500 g of the water mixture in a suitable container and pass it through the resin bed. It is
convenient to add 75-100 ml at a time to the reservoir on the top of the column. Do not allow the
bed to go dry during this operation. It may be necessary to pump the entrapped air from the resin
bed with a small rubber bulb to achieve free flow from the column. Wash the column with 50 ml
of de-ionized water and test the latter portion of the effluent with 10 percent silver nitrate solution
to ensure that no residual salt remains in the column. If the silver nitrate test is positive, continue
washing until the test is negative. Allow the column to drain dry, place a 10 ml volumetric flask under
the tip of the column, add 10 ml of pesticide grade methanol to the top of the column, and collect
the effluent. It may be necessary to add a small additional portion of methanol to the top of the
column to fill the volumetric flask to the mark.
d) Slowly inject (2-5 /Jl/sec) 25 //I of the methanol solutions retained from the final
washing of the resin into the quartz tube with a Hamilton microsyringe. Adjust the sensitivity of the
coulometer and recorder so that a small (5-10 percent of full scale) peak is recorded with a steady
baseline. Calculate the apparent chloride content of the methanol as per section 6. It should be no
greater than 0.1 ppm and be reproducible to ±3 percent. If the blank is appreciably higher, additional
washing of the columns or an alternate source of methanol will be required. Slowly inject 25 /il portions
of the methanol concentrate of the water standard and the methanol standard. Calculate the chloride
content using the blank value determined above. Results should agree to within ±3 percent of the
known values. Weigh 500 g of the sea water or waste water sample and analyze it in the same manner
as has been descirbed for the standard samples. If the waste water samples contain a large amount
of sediment, filter the sample before weighing through Whatman No. 1 paper. Wash the filter paper
with a small portion of de-ionized water.
Calculation
6) a) Determine the area of the chloride peak in cm^ with a planimeter or disc integrator.
b) Calculate the microequivalents of chloride in the sample in the following manner:
(V)(S)(A) x 10*
H eq of Cl =
(R) x 96, 500
where V = recorder sensitivity, volts/cm
A = peak area, cm*
S = reciprocal of recorder chart speed, sec/cm
R = ohms, coulometer output, and
96,500 = Faraday's constant
151
-------
A-26 BRC-CORP 13-75-F
SRC 4X 12/75 Shell Research Complex Method Series
c) Calculate the chloride content, ppm by weight, as follows:
( microequivalents of CI)(35.5) x 103 grams of methanol
Cl, ppm = — x
(micro! iters of sample)(sample density ) grams of water
d) To calculate +he results in terms of the individual organic chloride, substitute the
appropriate molecular or equivalent weight for the value of 35.5, in the above equations.
e) In applying the method in a routine fashion, all values in the above equations will
remain constant except the area of the chloride peak. It is convenient to derive a factor relating area
in integrator counts or planimeter readings to ppm. Once the area factor has been found for several
known mixtures, the chloride content of unknown samples may be quickly calculated.
152
-------
BRG-CORP 13-75-F A 27
DETERMINATION OF
TOTAL ORGANIC CARBON IN NATURAL WATERS
INCLUDING BRINES - WET OXIDATION INFRARED METHOD
Method
The method consists of oxidizing a standard volume of acidified sample with potassium
persulfate («2S2Og) in a sealed glass ampule. Oxidation is conducted in an autoclave at 175°C for
16 hours. The generated carbon dioxide is swept out of the ampule with nitrogen, passed through
a washing and drying train, and subsequently into a nondispersive infrared analyzer where it is measured
with a digital integrator. Standard solutions are used to establish a calibration curve which relates the
response of the analyzer to organic carbon. About thirty samples can be run in a working day.
Apparatus
Illustrations of the ampule rack, and pressure vessel are given in Figure 1.a' The pressure
vessel serves to provide an external water vapor pressure that is of the same order of magnitude as
the internal pressure within the glass ampule as the sample is oxidized by potassium persulfate.
A schematic diagram of the apparatus for determining the carbon dioxide generated by the
wet oxidation procedure is shown in Figure 2. Compressed nitrogen is used to sweep the carbon dioxide
through the system. A flow controller (Millaflow upstream controller) is used to adjust and maintain
the gas flow at 250 cc/min; a constant flow through the infrared analyzer is essential for reproducible
operation of the infrared analyzer and digitizer. The nitrogen is scrubbed with ascarite to remove any
trace contamination of carbon dioxide. The T-assembly is used to open the ampule and permit quantitative
removal of the carbon dioxide. The T is constructed of stainless steel and accommodates a 1/8-inch
OD steel tube which can slide vertically through it; leakage around the tube is prevented by means
of an "0" ring seal. The neck of the ampule containing the sample is inserted into a short section
of tygon tubing (3/8-inch OO) attached to the bottom of the T-assembly. The gas washing bottle is
filled with glass beads which serve to minimize dead volume in the system; it contains 25 ml of acidified
potassium iodide solution (10 g Kl in 25 ml-10% h^SO^. The potassium iodide solution removes any
free chlorine from the generated gas and should be renewed frequently. Finally, the washed gas is
dried by passing over magnesium perchlorate before it enters a Beckman Model 215A infrared analyzer
which has been sensitized for the detection of carbon dioxide. The analyzer signal is measured by
an Infotronics Model CRS-208 digital integrator and recorded on a 10-mv recorder. An injection port
is included in the system to allow for the introduction of pure carbon dioxide to check instrument
conditions.
Procedure
1) The glass ampules are cleaned batch-wise by heating in a muffle furnace at 625°C for 1/2 hour.
2) A volume of potassium persulfate equivalent to 600 mg of the reagent is added to a cleaned
ampule by means of a glass scoop; 0.5 ml of 6 percent phosphoric acid is added followed by 2 ml
of sample. The sample volume can be measured with sufficient accuracy with a 2 ml hypodermic syringe.
The sample mixture is then purged with nitrogen for 3 min to remove inorganic carbon as carbon dioxide.
The nitrogen is passed through a tube of silica gel immersed in liquid nitrogen to remove interfering
impurities.
a' This equipment can be purchased from Oceanography International, 512 West Loop, College
Station, Texas 77840.
153
-------
A-28
BRC-CORP 13-75-F
3) The ampule is stoppered with a septum pierced by a No. 22 gauge hypoderm.c needle. It
is then sealed in a gas-oxygen flame. The septum protects the sample from combustion products of
the flame, and the needle allows the gas in the stoppered ampule to expand sufficiently to prevent
blowout of the glass wall during the operation. In this way the ampule is sealed without contamination
of the sample from the flame.
4) When a sufficient number of ampules have been prepared they are placed in the rack and
autoclaved in the pressure vessel for 16 hours at 175°C in an appropriate oven. About 1500 ml of
water are added to the pressure vessel before the ampules are inserted.
5) The pressure vessel is allowed to cool to room temperature before being opened. The neck
of a sealed ampule is then inserted into the typon tubing of the T-assembly shown in Figure 2, and
the train purged with nitrogen until the analyzer indicates the absence of atmospheric carbon dioxide.
With the sweep gas flowing, pressure is exerted at the neck of the ampule to break it open, and the
steel tube is inserted into the sample mixture. The released carbon dioxide is swept out in the nitrogen
gas stream and is detected by the analyzer. The output is integrated and digitized electronically.
6) A series of standards consisting of aqueous dextrose solutions and blanks are treated in the
same manner as the samples. (Standards and blanks were prepared with water which had been freed
of organic carbon by redistilling tap distilled water containing 1 ml of phosphoric acid and 10 g of
potassium persulfate per liter; Silver Seal distilled water purchased from Houston Distilled Water Company
was also found satisfactory.)
7) The organic carbon content in the sample is determined from the amount of carbon dioxide
measured by means of a calibration curve established with the standard dextrose solutions. Variations
in the sensitivity of the infrared analyzer require that the calibration curve be checked daily.
10 ml. GLASS AMPULE
AMPULE RACK FOR PRESSURE VESSEL PRESSURE VESSEL FOR USE IN
(43 AMPULE CAPAC.TY) GRAV1TY CONVECTION OVEN.
T1.m., (ACCOMODATES TWO AMPULE RACKS)
Figure 1. Illustrations of the Apparatus Used for the Wet Oxidation at 175°C
of the Organic Matter in Water Samples
-------
BRC-CORP 13-75 F
A-29
GAS HOW I250ce/min) \
TOGGLE CAPm.RYr
VALVE.->APIilARV
?
N, GAS o 1 H
SUPPLY FLOWT
CONTROLLER IJJ/
ASCARITE
TUBE ' — L5
Fl(
ME
•
7I-J»».J
Figure 2. Flow Diagram of th
j INJECTION
-, PORT
r
^j
>W
FER
e Equipmei
/TEFLON TUBING
VO.D. /^\
SSTUBE 1 \
. T-ASSEMBLV
TYGON
TUBING
AMPULE
GAS W
(KI
it Used for Determi
ft /
Rj / »VENT
•••» i i
(oo< / 1
?••£: J /
&"* v^x / ;
;sg M9|C104 2 / /
r.J« DRYING TUBE/ ^
||; GLASS I /
t 3^ BEADS I / iNfdARED
n V CO, ANALYZER
ASHING BOTTLE
-Afl-HjSCU TQ
INTEGRATOR
&
RECORDER
ning the Carbon Dioxide Generated by
the Wet Oxidation of Organic Matter in Water
155
-------
Summary Log - Firit Voyage
CD
3D
O
6
o
a
•o
w
•Nj
„
Oci 14
Oct. 15
Oct. 16
Oci. 17
Oct. 18
Oci 19
Oci 20
Hour
2:00 PM
5:00 AM
10.00 PM
7:00 AM
8:00 AM
9:00 AM
10:00 AM
11:00 AM
12:00 AM
1:00 PM
2:00 PM
3:00 PM
4:00 PM
5:00 PM
6:OOPM
7:00 PM
8:00 PM
9:00 PM
10.00 PM
11:00 PM
12:00 PM
Temperature, %
Stack
1220
1220
1250
1220
1220
1230
1230
1220
1170
1220
1170
1120
1120
1120
1120
Failed
Starboard Oven
Ind.
950
1000
1060
1100
1180
Contr.
1120
1320
1340
1370
1360
1300
1250
Pyrom.
Port Oven
Ind.
910
950
1010
1050
1180
Contr.
1150
1320
1340
1370
1360
1330
1250
Pyrom.
Analysis
THC.
ppm
8
6
6
5
2
2
-
1
2
3
3
2
2
4
4
4
4
Time to
Stand 'n
hr
_
-0.5
-IS
-2.5
-36
-0.3
-OS
+0.6
-0.5
-1.5 '
-0.3
-1.3
-2.3
-3.3
-4.3
Water Sample
Start
2
3
4
End
2
3
RCI
Sample
1. 2
3
CO,,
%v
42
0,,
%v
16.3
Feed
Rate,
t/hr
22
24
Remarks
Ship left Shell dock.
Attempted to burn waste.
Failed due to plugged feed lines.
Ship's engineers clearing feed lines
and pumps.
Start oven heat up.
Start burning wane at request of
EPA monitoring personnel.
Average THC - 6 ppm. Water 2 period.
Replaced plugged capillary on 109 A.
Feed rate from gaging tank.
Feed rate from gaging tank.
Average THC * 2 ppm. Water 3 period.
-------
Summary Log - First Voyage (Cont'd 1)
u
NJ
OO
D.ly
Hour
Oci 21 1.00 AM
2 00 AM
3.00 AM
4-00 AM
Temperature, °C
Slack
5.00 AM
6.00 AM
7.00 AM
8.0O AM
9.00 AM
10 00 AM |
11 00 AM
12 00 AM
Ocl 21 1:00 PM
2 00 PM
3 oo PM ;
4 00 PM
5:00 PM
6:00 PM
7:OO PM
8:00 PM
9 00 PM
10:00 PM
11:00 PM
12:00 PM
Starboard Oven
Ind.
1230
1130
1210
1230
1240
Contr.
Pvrom.
Port Oven
Ind.
1230
1130
1210
1230
1240
Contr.
Pvrom.
Analysis
THC.
ppm
4
3
3
3
2
1
1
2
2
-
0
1
1
1
1
1
1
-
2
-
-
-
1
1
Time to
Stand'n
hr
-5.3
-6.3
-7.0
-8.0
-9.0
-10
-O.5
-1.5
+0.5
-0.5
-1.5
-0.3
-1.3
-2.3
-0.5
-1.5
-3.5
-0.5
-1.5
Water Sample
Start
5
6
End
4
5
RCI
Sample
C02.
%v
3.7
5.4
6.9
02.
%v
14.2
11.9
9.7
Feed
Rate,
t/hr
23.7
19.5
Remarks
No adjustment in span needed.
Feed rate reduced.
Tank 1C Empty.
Span gas through traps.
Average THC = 1 ppm. Water S period.
Rearranging sample train.
Feed rate by gaging.
/
Adjust of Span not reliable.
CO
3
r>
6
o
33
CO
^J
-------
Summary Log - Firtt Voyag* (Cont'd 2)
CO
30
O
§
30
•o
s
Day
Oct. 22
Oct. 22
Hour
1:00 AM
2:00 AM
3:00 AM
4:00 AM
5:00 AM
6:00 AM
7:00 AM
8:00 AM
9:00 AM
10:00 AM
11:00 AM
12:00 AM
1:00 PM
2:00 PM
3:00 PM
4:00 PM
5:00 PM
6:00 PM
7:00 PM
8:00 PM
9:00 PM
10:00 PM
11:00 PM
12:00 PM
Temperature, t
Stack
Starboard Own
Ind.
Contr.
Pyrom.
1500
Port Oven
Ind.
Contr.
Pyrom.
1500
Analyiii
THC,
ppm
0
0
0
0
0
0
-
—
-
-
_
1
10
10
9
14
-
-
-
1
-
-
-
Time to
Stand'n
hr
-2.5
+0.3
-0.7
-1.7
-2.7
-3.7
-0.3
-1.3
-2.3
-3.3
-4J
-0.3
Water Sample
Start
End
RCI
Sample
434
C02.
%v
0,.
%v
Feed
Rate,
t/hr
19.9
Sample capillary plugged1 in 109.
Replaced it by e needle valve.
Tank 1C empty.
10-minute spike over 1O ppm THC
S-fliinute spike over 10 ppm THC
Cleaning e burner in oven.
Adjuring 109A span.
Recorder pen dry.
Adjustment of span not reliable.
\J»
VO
CO
CO
-------
Summary Log • Pint Voyage (Cont'd 3)
Dav
Oct. 23
Oct. 23
Hour
1:00 AM
2:00 AM
3:00 AM
4:OO AM
5:00 AM
6:00 AM
7:00 AM
8 OO AM
9:OO AM
10:00 AM
11 OO AM
12:00 AM
1:OO PM
2:OO PM
3:00 PM
4:OO PM
5:00 PM
6:OO PM
7:00 PM
8:OO PM
9:00 PM
10:00 PM
11:00 PM
12:00 PM
Temperature, °C
Stack
Starboard Oven
Ind.
1140
Contr.
1220
Pyrom.
-
Port Oven
Ind.
1150
Contr.
1260
Pyrom.
1420
Analysis
THC,
ppm
_
-
-
-
-
:
-
~
-
-
-
-
-
-
-
-
3
5
2
1
Time to
Stand'n
hr
-0.3
-1.3
-2.3
-3.3
Water Sample
Start
7
End
6
RCI
Sample
COj,
%v
02.
%v
Feed
Rate,
t/hr
19.1
Sample pressure regulator on 109A
plugged. Shut 109A down.
Cleaned up and overhauled 109 A sample
inlet system. It was very dirty.
Installed improved traps.
Average THC not available for water period 6.
Tank 4C empty.
,
00
31
O
U
•vl
01
-------
CD
3D
O
Summary Log - Flrit Voyage (Cont'd 4)
3D
•o
i
Day
Oct. 24
Hour
1:00 AM
2:00 AM
3:00 AM
4:00 AM
5:00 AM
6:00 AM
7:00 AM
8:00 AM
9:00 AM
10:00 AM
Oct. 24
11:00 AM
12:00 AM
1:00 PM
2:00 PM
3:00 PM
4:00 PM
5:00 PM
6:00 PM
7:00 PM
8:00 PM
9:00 PM
10:00 PM
11:00 PM
12:00 PM
Temperature. 1C
Stack
Starboard Oven
Ind.
1150
Conn.
1240
Pyrom.
-
Port Oven
Ind.
1170
Contr.
1270
Pyrom.
1450
Analyiii
THC.
porn
0
0
3
6
4
3
3
3
3'
-
0
1
4
3
1
0
1
90
7
15
4
3
5
3
Tim* to
hr
-5.3
-O.3
-1.3
-2.3
-3.3
-4.3
-5.3
-4T3
-1.3
-OJ
-1.3
-2.3
-3J
-4.3
-0.3
-14
-23
-3.3
-4.3
-6.3
-6.3
-7.3
-8.3
Water. Simple
Sun
8
End
7
RCI
Sample
9
CO,,
%v
3.7
Oj.
%v
6.0
Feed
Rate.
t/hr.
Remark!
2-minju ipike in THC over 10 pom.
20-minute epik* in THC over 10 ppm.
10 ppm taken for average.
Average THC - 3 ppm. Water Period 7.
Adjusting apen of 1O9A.
Zero gat give* HIGHER THC then teat temple.
THC - 10 ppm taken for average.
Burner failure and deenout, 24 min. THC > 10 ppm
4-minute spike > 10 ppm.
Burning gas oil hare. THC value not in average.
Burning wane.
u
Ol
-------
Summary Log — First Voyage (Cont'd 5)
Day
Oct. 25
Oct. 25
Oct. 26 """
Hour
1:00 AM
2:00 AM
3:00 AM
4:00 AM
5:00 AM
6:00 AM
7:00 AM
8:00 AM
9:00 AM
10:00 AM
11:00 AM
12:00 AM
1:00 PM
2:00 PM
3:00 PM
4:00 PM
5:00 PM
6:00 PM
10:00 AM
; 2:00 PM
Oct .27 ! 4:00 PM
8:00 PM
Temperature, °C
Stack
Starboard Oven
Ind.
1150
1150
1160
1130
1150
1170
Contr.
1230
1240
1250
1110
1230
1190
Pyrom.
1450
1420 ••
1450
1370
1330
1450
Port Oven
Ind.
1165
1170
1170
1110
1150
1170
Contr.
1220
1220
1290
1090
1230
1300
Pyrom.
1450
1450
1440
1340
-
1450
Analysis
THC,
ppm
5
4
3
3
2
2
2
2
12
0
0
0
Time to
Stand'n
hr
+7.5
+6.5
+5.5
+4.5
+3.5
+2.5
+1.5
+0.5
-0.5
+3.0
+2.0
+1.0
Water Sample
Start
9
End
8
RCI
Sample
C02,
%v
1.0
02.
%v
19.4
Feed
Rate,
t/nr
Remarks
Average THC = 4, for Water Period 8.
3-minute spike over 10 ppm
Span found to be 16 ppm before adj.
Adjusting span.
Cleaning burner, 12 ppm is amax.
Oj content indicates probe is not
extracting stack gas.
Water in feed.
Cleaning a burner in port oven.
00
3J
o
6
o
-------
CO
00
9
Summary Log - Second Voyage
U)
Day
Dec. 2 AM
Dec. 2 PM
Hour
1:00
2:00
3:00
4:00
5:00
6:00
7:00
8:00
9:00
10:00
11:00
12:00
1:00
2:00
3:00
4:00
5:00
6:00
7:00
8:00
9:00
10:00
11:00
12:00
Temperature, °C
Starboard Oven
Indicator
850
1060
1090
1130
1160
1180
1200
Controller
Pyrometer
1500
1590
Port Oven
Indicator
900
1080
1110
1140
1160
1180
1200
Controller
Pyrometer
1570
1590
Analysis
Water
Start
End
RCI
Start
End
CO,
ppm
02.
Remarks
Start Waste Feed
•
3D
•o
^
w
•ij
en
-------
Summary Log - Second Voyage (Cont'd 1)
CO
oo
Day
Dec. 3 AM
Dec. 3 PM
Hour
1:00
2:00
3:00
4:00
5:00
6:00
7:00
8:00
9:00
10:00
11:00
12:00
1:00
2.00
3:00
4:00
5:00
6:00
7:00
8:00
9:00
10:00
11:00
12:00
Temperature, °C
Starboard Oven
Indicator
1220
1220
1200
1200
1190
1190
1190
1200
1200
1200
Controller
1270
Pyrometer
1600
1520
1560
Port Oven
Indicator
1180
1200
Controller
1270
Pyrometer
1590
1480
1510
Analysis
Water
Start
1
End
1
RCI
Start
1
2
End
1
2
pn
IAJ,
ppm
10
25
25
25
25
30
25
20
20
-
70
15
55
45
50
75
75
65
-
-
25
35
30
25
°%
9.9
9.8
10.1
10.4
9.6
9.9
10.2
9.2
9.8
-
12.0
12.5
11.0
11.0
11.0
11.3
10.0
10.0
-
-
10.5
11.3
11.3
11.1
Remarks
Starboard Probe, 9" Insertion
00
3)
o
8
3)
u
•vl
01
-------
00
3D
Summary Log - Second Voyage (Cont'd 2)
Day
Dec. 4 AM
Dec. 4 PM
Hour
1:00
2:00
3:00
4:00
5:00
6:00
7:00
8:00
9:00
10:00
11:00
12:00
1:00
2:00
3:00
4:00
5:00
6:00
7:00
8:00
9:00
10:00
11:00
12:00
Temperature. °C
Starboard Oven
Indicator
1240
1220
1190
1180
1180
1180
1200
Controller
1340
1260
1300
Pyrometer
1580
1550
1610
Port Oven
Indicator
1180
Controller
1360
1300
1220
Pyrometer
1590
1580
1510
Analysis
Water
Start
2
3
End
2
3
RCI
Start
3
4
5
6
End
3
4
5
6
CO,
ppm
25
30
35
40"
30
35
35
_
-
-
-
-
-
_
-
-
-
-
-
-
-
170
170
180
02,
%
10.1
10.2
9.5
9.4
10.0
9.5
10.2
—
-
-
-
-
-
_
-
-
-
-
-
-
-
10.5
10.0
9.5
Remarks
Starboard Probe, 9" Insertion
Port Probe. 55" Insertion
/
•o
w
«J
01
(O
-------
Summary Log — Second Voyage (Cont'd 3)
ON
Day
Dec. 5 AM
Dec. 5 PM
Hour
1:00
2:00
3:00
4:00
5:00
6:00
7:00
8:00
9:00
10:00
11:00
12:00
1:00
2:00
3:00
4:00
5:00
6:00
7:00
8:00
9:00
10:00
11:00
12:00
Temperature, C
Starboard Oven
Indicator
1190
1160
1180
1180
1180
1180
1190
1200
Controller
1180
1260
1270
Pyrometer
1530
1520
1570
Port Oven
Indicator
Controller
1220
1330
1240
Pyrometer
1500
1570
1560
Analysis
Water
Start
4
End
RCI
Start
i
4
End
7
8
-
7
8
CO.
ppm
190
200
200
200
200
210
180
220
-
-
-
-
-
35
50
30
25
0
0
—
-
-
90
90
02.
%
9.5
9.5
9.5
9.2
9.2
9.5
10.0
9.2
-
Remarks
Port Probe, 55" Insertion
-
-
-
10.5
10.5
10.1
9.8
10.8
10.0
-
-
-
10.0
10.0
CD
JO
o
6
, o
33
-o
-------
00
Summary Log - Second Voyage (Cont'd 4)
Day
Dec. 6 AM
Dec. 6 PM
Hour
1:00
2:00
3:00
4:00
5.00
6:00
7:00
8:00
9:00
10:00
11:00
12:00
1:00
2:00
3:00
4:00
5:00
6:00
7:00
8:00
9:00
10:00
11:00
12:00
Temperature, C
Starboard Oven Port Oven
Indicator
1110
1160
1140
1140
1150
1150
1120
Controller
1220
Pyrometer
1500
Indicator
1180
1550
Controller
Pyrometer
1500
1520
Analysis
Water
Start
5
End
5
RCI
Start
9
10
11
12
End
9
10
11
12
f*n
uu,
nnm
MM"1
70
75
40
30
20
20
170
25
-
-
30
35
40
25
-
40
40
30
35
35
-
-
-
25
%
9.6
9.8
10.5
10.0
9.8
9.5
13.0
8.8
-
-
10.6
10.0
10.8
10.0
-
9.2
9.0
10.2
8.8
10.5
-
-
-
9.2
Remarks
Starboard Probe, 48" Insertion
Starboard Probe. 10" Insertion
O
3
TJ
W
•ij
cn
-------
Summary Log — Second Voyage (Cont'd 5)
Day
Dec. 7 AM
Hour
1:00
2:00
3:00
4:00
5:00
6:00
7:00
8:00
9:00
i 10:00
Temperature, °C
Starboard Oven
Indicator
1210
Controller
1180
j
i
Dec. 7 PM
11:00
12:00
1:00
2:00
3:00
4:00
5:00
i 6:00
7:00
8:00
9:00
10:00
11:00
12:00
1160
1160
1250
1160 i
1
1180
1200
1310
1
Pyrometer
1500
1540
1570
1590
Port Oven
Indicator
Controller
1320
1200
1240
1340
Pyrometer
1570
1580
1510
1570
Analysis
Water
Start
6
End
6
RCI
Start
13
14
15
16
End
13
14
15
16
CO,
ppm
35
30
30
35
30
35
55
-
-
_
-
-
-
-
-
35
50
15
25
35
40
25
40
35
02,
%
9.0
9.6
11.0
11.0
9.5
9.5
8.6
-
-
_
-
-
-
-
-
12.0
11.0
10.S
12.0
10.6
11.0
12.2
10.2
10.6
Remarks
Port Probe, 55" Insertion
00
3)
O
6
o
3)
-o
VI
-------
Summary Log - Sacond Voyage (Confd 6>
CD
3D
§
2)
•o
to
•SI
or
Day
Dec. 8 AM
Dec. 8 PM
Dec. 9 AM
Hour
1:00
2:00
3:00
4:00
5:00
6:00
7:00
8:00
9:00
10:00
11:00
12:00
1:00
2:00
3:00
4:00
5:00
6:00
7:00
8:00
9:00
10:00
11:00
12:00
1:00
2:00
3:00
4:00
5:00
6:00
Temperature, °C
Starboard Oven
Indicator
•
1200
1190
1180
1160
1180
1180
1160
1160
Controller
Pyrometer
1570
1590
1610
1580
1570
Port Oven
Indicator
1210
1200
1200
1160
1180
Controller
Pyrometer
1530
1550
1530
1520
1480
Analysis
Water
Start
7
8
End
7
8
RCI
Start
17
18
19
20
21
22
End
17
18
19
20
21
22
CO,
nnm
ppm
30
25
15
25
35
40
25
35
30
40
—
25
35
70
30
25
50
30
50
35
-
45
50
50
40
30
40
02.
%
10.5
10.2
10.2
10.5
11.0
9.0
10.0
10.0
11.5
11.8
-
12.0
11.2
12.2
11.8
12.2
12.2
12.2
12.5
12.5
-
12.5
12.7
12.8
12.8
12.3
12.5
Remarks
Port Probe, 55" Insertion
',
Probe Failed at About 4:00 AM
Burn Completed at 7:00 AM
CO
-------
Stack Gas Analytical Remlti - Second Voyage
RC1
Series
Number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
Concentration In Stack Gas
CO
ppm
70
75
-
-
-
-
35
25
-
35
-
40
-
50
25
35
30
40
35
30
50
50
Q>
X
12.0
11.3
-
-
9.3
9.0
10.5
9.8
10.0
10.0
10.0
9.0
11.5
10.5
12.0
10.6
11.5
11.8
11.2
11.8
12.2
12.5
HC1
%
4.7
5.0
-
-
6.1
6.2
5.6
5.8
5.7
5.7
5.7
6.2
4.9
5.6
4.7
5.6
4.9
4.8
5.1
4.8
4.6
4.4
"a
ppm
100
30
890
600
330
C 10
50
70
60
170
60
40
650
380
380
340
90
80
30
14
20
40
GBS Implngers
HC1, eq
A
0.275
0.73
0.132
0.821
0.644
0.674
0.554
0.606
B
0.01
0.002
-
0.019
0.001
0.01
-
RC1, n eq
A
0.62
1.35
0.31
2.9
24.3
2.6
20.7
23.1
B
0.77
0.62
-
-
5.0
2.2
13.8
0.7
RCl in
Gas
ppm
0.26
0.17
0.13
0.21
2.8
0.40
3.2
1.7
Midget Impinged
RCl, n eq
SNNaOH
-
-
-
-
-
.
10.0*)
-
4.0")
2.5
2.3
-
-
-
-
-
2.0
IPA-A
< 1.1
< 1.1
< 1.1
< 1.1
< 1.1
< 1.1
1.4
-
0.8
-
2.0
1.6
-
-
-
-
-
-
37.8
1.3
-
-
IPA-B
.
-
-
-
-
-
-
-
•
-
-
2.4
-
-
-
Gas
Volume,
liters
26
24
18
18
20
20
30
31
20
19
25
20
20
12
12
12
18
20
18
18
19
18
RCl in
Cas
ppm
< 1.0
< 1.0
< 1.3
< 1.3
< l.l
< 1.1
1.0
7.5
0.9
4.7
4.0
1.8
2.2
< 2.0
< 2.0
< 2.0
< 1.3
< 1.1
52.5
1.6
< 1.2
< 1.3
Total
RCL in
Cas
ppm
< 1.3
< 1.3
< 1.5
< 1.5
< 1.3
< 1.2
1.2
7.7
3.6
7.4
6.7
4.6
2.6
< 2.4
< 2.4
< 2.4
< 4.0
< 3.8
55.7")
2.3
< 2.9
< 3.0
Fraction
Feed
RCL in
Stack
Gas
< 0.00003
< 0.00002
< 0.00003
< 0.00003
< 0.00002
< 0.00002
0.00002
0.00013
-
0.00008
0.00007
0.00007
0.00005
< 0.00004
< 0.00004
< 0.00004
< 0.00006
< 0.00006
0.00109
0.00005
< 0.00005
< 0.00005
a) Probably due to contamination because the IPA solutions show no RCl.
b) Spiked sample.
CD
30
O
§
JO
•o
w
•Ij
01
>
-------
APPENDIX B. LOSS OF ORGANOCHLORIDES
IN TEFLON BAGS (1)
1. Personal communication. W. M. Anderson to technical superin-
tendent. Deer Park manufacturing complex. Shell Chemical Co.,
Deer Park, Tex., Nov. 19, 1974.
173
-------
Following Research Burn I, Shell collected data for the loss
of organochlorides stored in Teflon bags as a basis for estimating
the loss of similar compounds during sampling of air through 21. 4
meters of Teflon tubing.
Loss of organochlorides was determined during storage in
Teflon, FEP Type A, 0.13-millimeter thickness bags, 15. 2 x 30. 5
centimeters (928 square centimeters of surface area). A 1,000-cc
mixture of all of the components to be tested was prepared in the
\
Teflon bag and the bag contents were analyzed by gas chromato-
graphy using a 3 meter x 0. 32 centimeter column packed with
Durapak Carbowax 400/Porosil C, 100 to 120 mesh. The carrier
gas flow rate was 30 cc/minute and the column temperature was
programmed from 70° to 170°C at 4° C/minute.
A flame ionization detector was used. The bag contents were
analyzed immediately after make-up and after storage for 8-and
24-hour periods. The decrease in area of the chromatographic
peaks corresponding to the various components was calculated as
percent bag loss. Bag loss data were obtained for mixtures
containing the various organochloride components at concentration
levels of 5 and 30 to 50 ppm(v). The bag losses (Table B-l) for
most of the components tested at the 5 ppm(v) level were less than
10 percent. The loss of organochlorides was not instantaneous
as would be the case for adsorption, but was time dependent,
as would be expected for absorption or diffusion.
175
-------
TABLE B-l
TEFLON BAG LOSS DATA FOR ORGANIC CHLORIDES (1)
Component
Vinyl chloride
Ethyl chloride
Isopropyl chloride
Allyl chloride
Ethylene dichloride
1 , 2 - Di chlo r op ropane
cis 1, 3 -Dichloropropene
Epichlorohydrin
trans 1, 3 -Dichloropropene
1, 2, 3 -Trichloropropane
Initial
ppm(v)
5
43
5
46
6
49
8
54
4
41
5
33
35
5
27
5
33
2
11
Storage
8 -Hour,
% loss
1
2
0
4
0
2
2
4
8
7
4
7
12
0
2
18
11
13
22
time
24 -Hour,
% loss
6
7
5
7
4
5
9
9
19
19
15
17
29
26
28
42
35
45
47
1. FEP Type A Teflon, 0.13-millimeter thick; bag measured 15.2 x
30. 5 centimeters; sample volume, 1, 000 ml.
Source: Personal communication. W.M. Anderson to technical
superintendent, Deer Park manufacturing complex, Shell
Chemical Co., Deer Park, Tex., Nov. 19, 1974.
176
-------
The Teflon tubing used for collecting air samples during incin-
eration at sea with the Vulcanus was 21. 4 meters x 0. 64 centimeters
outside diameter (0.48 centimeters inside diameter). The inside
surface area of the tubing was therefore 3,225 square centimeters,
or about 3.5 times the surface of the Teflon bags used in the Shell
experiments. With a sampling rate of 5 liters/ minute, the residence
time was calculated to be 4. 7 seconds.
Assuming that the tubing and bag materials have similar absorp-
tion and permeation characteristics for organic chlorides, loss of
these compounds in the 21.4-meter Teflon sampling tube would be
insignificant considering the residence time of 4. 7 seconds compared
to the 8-hour storage time in Teflon bags.
177
-------
APPENDIX C. EQUIPMENT, CALIBRATION PROCEDURES,
AND AIRCRAFT DATA FROM AERIAL ~
MONITORING OF RESEARCH BURN II (1)
1. Aerial Monitoring of the Plume Generated by at-Sea Incineration
of Organochloride Wastes. U. S. Environmental Protection Agency,
National Environmental Research Center, Las Vegas, Nev.
Feb. 5, 1975
179
-------
DESCRIPTION OF EQUIPMENT
Condensation Nuclei Monitor
The Environment One Corporation condensation nuclei monitor
(CNM) operates on the same principle as a cloud chamber. Sample
air is drawn into a humidifying chamber where it is saturated with
water vapor. The moist air is then pulled into the detection chamber
where it is expanded adiabatically to about 300 percent super-
saturation. Any condensation nuclei in the sample air serve as
embryos on which water droplets form. The number of particles
per volume is estimated by the light attenuation across the chamber
as detected by a photo cell monitoring a light source. The sample
cycle is repeated once every second.
Chemiluminescent Analyzer
The Geomet Model 401 chemiluminescent analyzer detects HC1
on the basis of the exothermic oxidation, by hypochlorous acid, of
5-amino-2, 3-dihydro-l, 4-phthalazinedione (luminol) in alkaline
solution. The intensity of light generated by this reaction is linearly
proportional to the HC1 concentration in the incoming gas stream.
The intensity is monitored by a photomultiplier detector containing
two reaction cells, one for detection of HC1 and the other for
reference. The hypochlorous acid is formed in the inlet to the
detector cell by reaction of HC1 with a sodium bromate/bromide
coating on an alumina tube (40 cm by 2mm, inside diameter); a
similar, but uncoated, tube is employed in the reference cell to
181
-------
account for any interfering gases; molecular chlorine is the only
known signal contributor. At a nominal sample flow rate of 1, 600
cubic centimeters per minute (cm3/min), the response time of the
chemiluminescent HC1 detector is 1 second to 90 percent of full-
scale deflection with a detection limit for HC1 of about 0. 01 ppm.
However, the instrument may function on one of three operating
ranges to provide nominal HC1 detection capability over concen-
trations of 0 to 0. 5 ppm (IX scale), 0 to 5 ppm (10X scale),
and 0 to 50 ppm (100X scale).
Coulometer
A Dohrmann Environmental Corporation Model C-200-B
coulometer, in a modified package for field use, was carried as
a backup to the chemiluminescent instrument, and more importantly,
as the primary standard for calibration of the HC1 monitoring
system. The microcoulometric detection of HC1 is based on auto-
matic titration of chloride ion as precipitated silver chloride. The
continuous monitoring instrument consists of a microcoulometric
titration cell, electronic control console, integrating recorder, air
pump, and flow meter.
The heart of the system is the titration cell, which contains
acetic acid electrolyte and four electrodes: a sensing pair (silver
vs. silver acetate) and a generating pair (silver vs. platinum). The
concentration of silver ions in the cell is adjusted to 10~7 Molar
by applying a bias potential of 250 millivolts across the sensing
182
-------
electrode pair. Any change in silver concentration (by precip-
itation of silver chloride) is detected by the sensing electrodes as
a potential difference which leads through the coulometer amplifier
to the generation of silver titrant at the generator electrode. The
current required is recorded via a precision series resistance on
a potentiometric recorder. Integration of the area under the peak
of the recorded current yields the quantity of electricity, in
coulombs, required for the reaction. Because Faraday's laws are
obeyed and the reaction is stoichiometric, the microcoulometer
is a primary standard for chloride, and the quantity of chloride in
the sample is calculated from:
w = 35.453 x 106 A =367.4 A (1)
96,501 R R
where w = weight of chloride, nanograms
A = coulogram peak area, millivolt-seconds
R = series resistance, ohms
The detection limit for batch samples injected by syringe is
about 3 nanograms.
In the continuous sampling mode, the response and dynamic
range of the microcoulometer can be varied by adjustment of the
sample flow rate and/or instrument range (series resistance).
Again, since Faraday's laws apply, the steady state concentration
of HC1 is calculated from:
183
-------
Y = 13, 927 E T x 760 (2)
f R" "273 '
where Y = HC1 concentration, ppm
E = steady state response, millivolts
f = sample flow rate, cm^ /min.
R = range, resistance, ohms
T = sample temperature, ° K
P = ambient pressure, mm Hg
The smallest steady state deflection of the voltage recorder
which can be detected accurately in about 0. 03 millivolts. Sub-
stituting this value for E into equation (2), setting R to 50 ohms,
and f to 100 cm3 /min, the steady state detection limit of the
coulometer is found to be about 0T1 ppm HC1. The response time
required for the instrument to indicate 90 percent of a change
in sample concentration is approximately 40 seconds.
CALIBRATION PROCEDURES
The chemiluminescent analyzer and the rnicrocoulometer were
connected to the polypropylene sample line by means of glass tees
and short lengths of polypropylene tubing. This manifold arrange-
ment ensured that the two instruments were sampling from the same
air stream. During calibration, the calibration gas was introduced
through the inlet of the sampling probe at the front of the aircraft
and pumped through with a small diaphragm pump at a rate of 2
liters per minute. During sampling missions, the pump was
removed from the line because the ram air pressure of 10 mm
184
-------
Hg above ambient provided an excess of sample air for both
instruments.
The source of calibration gas was a cylinder containing a
nominal 88 ppm of HC1 in balance nitrogen gas: this was diluted
with ambient air in a glass mixing chamber. Mixing was enhanced
with a magnetic stirrer. A micrometer needle valve controlled the
flow rate from the HC1 cylinder and provided concentrations ranging
from 0.14 to 16 ppm as determined by integrated coulometric data.
The coulometer itself was calibrated by injecting 5 microliters of
a standard aqueous solution of Nad (26 nanograms/ microliter)
prepared in the laboratory at Brooks Air Force Base. The daily
average chloride recovery, utilizing at least three injections per
day, resulted in the values, 99.2+1.1 percent, 97. 4 + 4. 3 percent,
and 102. 7 + 4. 7 percent for the three sampling days.
Calibration gas was introduced into the inlet probe for two
reasons: to provide an in situ calibration and to condition the lines
with HC1 in order to minimize subsequent sample losses. The
system was calibrated before and after each flight with the exception
of the preflight calibration on the second day. In general, the HC1
analyzer did not behave well over this time period. The sensitivity
increased from about 0. 02 ppm/volt on the first day to about 0.12
ppm/volt by the end of the third day.
AIRCRAFT DATA
Aircraft data for three missions are presented in Tables
185
-------
C-l through C-6. Data for crosswind passes through the Vulcanus
plume are listed in Tables C-l, -3, and -5, whereas data for
axial passes through the length of the plume are listed in Tables
C-2, -4, and -6. For crosswind passes, each line of data represents
one pass. In Table C-6, more than one line was needed to represent
some of the axial passes. Here, each line represents a maximum
in a succession of maximum and minimum concentrations encoun-
tered by the aircraft. These maxima are evidence of looping, which
was also visible following injection of ammonia at the stack.
In tables of both crosswind and axial data, values listed in the
"Distance" column are distances in meters downwind from the ship
(as estimated by the aircraft pilot) where corresponding maximum
concentrations of condensation nuclei (CN) and HC1 were detected.
The width of the plume was calculated by measuring the time base
of the CNM recorder peaks resulting from crosswind passes and
multiplying by the aircraft ground speed. The "1/2-Width" was
calculated graphically by measuring the width of the same peaks
at 1/2 the maximum peak height in order to provide an indication
of the concentration gradient across the plume.
Using the same graphical methods outlined above, "intercept
lengths" were calculated for axial passes. These values repre-
sent the distance in meters that the aircraft was recording positive
CNM readings at the stated altitude. Passes 3, 4, and 5 of Table
C-6 list three or more intercept lengths for each pass. This can
186
-------
TABLE C-l
AERIAL MONITORING OF RESEARCH BURN II,
CROSSWIND PASSES ON FIRST MISSION (DEC. 2, 1974)
Position
Downwind
distance
Time of from ship, Altitude,
Max.
CN1,
Q O
day meters meters lO^/crri'
1326 400
1327.5 400
1329 400
1309 400
1330.5 400
1332 400
1319 800
1320 800
1318 2,400
1317 2,400
1319.5 2,400
1312 3,200
1314 3,200
1314 3,200
1 . Condensation nuclei.
2. HC1 base line averaged 0
3. Extrapolated to off- scale
240
180
150
150
120
90
200
90
300
240
180
200
120
90
. 1 1 ppm
value.
2
47
36
330
64
6
40
34
25
9
19
3
12
4
during
cone.
HC1,
ppm
BKG2
0.23
0.33
24
23
BKG2
O.I3
0.1
0.07
0.08
O.I3
_5
_5
_5
Plume
Width,
meters
660
1,100
950
1,800
980
950
1,100
1,100
900
900
1,000
1,100
1,100
740
1/2 -Width,
meters
450
500
530
480
580
610
530
610
530
530
610
740
660
500
first mission.
4. Off-scale; no extrapolation attempted.
5. Recorder disconnected.
Source: Aerial Monitoring of the Plume Generated by the at-Sea
Incineration of Organochloride Wastes. U.S. Environmental
Protection Agency, National Environmental Research Center,
Las Vegas, Nev. Feb. 5, 1975
18?
-------
TABLE C-2
AERIAL MONITORING OF RESEARCH BURN II,
AXIAL PASSES ON FIRST MISSION (DEC. 2, 1974)
Position
Time of
day
1352
1350
1348
1346
1344
1342
1340
1335
Location of
max. cone. ,
downwind
distance
from ship,
meters
0-400
0-400
0-400
0-400
0-400
0-400
0-400
0-400
Altitude,
meters
430
370
300
240
180
120
110
120
Max.
CN1,
103/cm3
5
44
70
110
140
58
164
90
cone.
HC1,
ppm
_2
_2
2
2~3
23
0.8
33
23
Plume
intercept length,
meters
1,300
1,100
1,300
1,300
1,800
2,700
6,900
3,400
1. Condensation nuclei.
2. Scale set too high to register.
3. Extrapolated to off-scale value.
Source: Aerial Monitoring of the Plume Generated by the at-Sea
Incineration of Organochloride Wastes. U.S. Environmental
Protection Agency, National Environmental Research Center,
Las Vegas, Nev. Feb. 5, 1975.
188
-------
TABLE C-3
AERIAL MONITORING OF RESEARCH BURN II,
CROSSWIND PASSES ON SECOND MISSION (DEC. 3, 1974)
Position
Time of
day
1148
1149.5
1151
1152.5
1114
1115.5
1117.5
1119
1120.5
1122.5
1124
1125.5
1110
1102. 3
1104
1106
1107
1201
Downwind
distance
from ship,
meters
400
400
400
400
800
800
800
800
800
800
800
800
1,600
1,600
1,600
1,600
'l,600
2,400
Max. cone.
Altitude,
meters
340
300
240
180
t
490
430
370
300
240
180
120
60
300
240
180
120
60
240
CN1,
103/cm3
_3
_3
30
5
BKG6
68
56 0.
31
50 0.
20 0.
40 0.
42
1
36
27
1
2
21
HC12,
ppm
BKG4
BKG4
0.45
0.07
BKG4
0.4
2/0.1
0.3
4/0.1
3/0.1
4/0.1
0.4
BKG4
0.02
BKG4
BKG4
BKG4
BKG4
Plume
Width,
meters
_3
_3
_3
1,400
1,100
1,200
1,600
1,200
900
1,100
_3
1,000
1,100
980
1,200
740
1,400
1/2 -Width, Temp'
meters ° C
_3
_3
530 14
1,000
610 12
660 13
580 13
610 14
610 15
610 15.5
1,100
_ 7
660
500
7
500
740
1. Condensation nuclei.
2. Second value, where given, derived from coulometer data.
3. Monitor noisy; no usable data.
4. HC1 baseline averaged 0.17 ppin during second mission.
5. Extrapolated to off-scale value.
6. Signifies baseline response, less than 10 /cm .
7. Monitor signal too small to estimate width at 1 /2 maximum value.
Source: Aerial Monitoring of the Plume Generated by the at-Sea
Incineration of Organochloride Wastes. U.S. Environmental
Protection Agency, National Environmental Research Center,
Las Vegas, Nev. Feb. 5, 1975
189
-------
TABLE C-4
AERIAL MONITORING OF RESEARCH BURN II,
AXIAL PASSES ON SECOND MISSION (DEC. 3, 1974)
Position
Location of
max. cone.,
downwind
Max. cone.
Time of
day
1143
1156
1159
1203.5
1208
1213
1214
1216
distance
from ship,
meters
0-400
0-400
0-400
0-400
0-400
0-400
0-400
0-400
Altitude,
meters
430
240
240
210
210
210
210
210
rMl rrri 2 Plume
03' ' intercept length,
10 /cm ppm meters
19
45
64
80
77
80
68
80
0.1/0.1
0.43
0.83/1.5
0. 3
1 3/1.6
0.9/1.8
0.8/1.3
0.8/1.2
4,500
2,100
1,800
2, 700
2,100
1,000
1,000
1,500
1. Condensation nuclei.
2. Second value, where given, derived from coulometer data.
3. Extrapolated to off-scale value.
Source: Aerial Monitoring of the Plume Generated by the at-Sea
Incineration of Organochloride Wastes. U.S. Environmental
Protection Agency, National Environmental Research Center,
Las Vegas, Nev. Feb. 5, 1975.
190
-------
TABLE C-5
AERIAL MONITORING OF RESEARCH BURN II,
CROSSWIND PASSES ON THIRD MISSION (DEC. 4, 1974)
Position
Downwind
distance
Time of from ship, Altitude,
day meters meters 1
1100.5 800
1103 800
1158.8 800
1046 800
1048 800
1056.5 800
1049.5 800
1151 800
1053 800
1054 800
1045 1,600
1101.5 2,400
1059.5 2,400
1057.5 2,400
1047 2,400
1048.5 2,400
1050 2,400
1052 2,400
1054 2,400
1. Condensation nuclei.
370
340
340
340
300
300
240
180
120
60
340
370
340
300
300
240
180
120
60
Max.
CN1,
03/cm3
BKG2
BKG2
32
BKG2
3
BKG2
100
75
51
BKG2
BKG2
1
10
22
35
19
24
74
1
2. Signifies baseline response, less than 1
3. HC1 baseline averaged
0.25 ppm
during
cone.
HC1,
ppm
BKG3
BKG3
0.1
BKG3
BKG3
BKG3
0.8/0. 14
0.2
0.2
0.08
BKG3
'BKG3
BKG3
BKG3
BKG3
BKG3
BKG3
BKG3
o.i6
o
,000/crn .
Plume
Width,
meters
270
1,200
1,000
950
_5
950
1,100
1,800
1,100
900
1,100
950
1/2 -Width,
meters
510
470
510
510
_5
510
560
510
560
430
470
_5
Temp,
°C
14
15
15
16
16
14
15
15
15
16
18
third mission.
4. Second value derived from coulometer data.
5. Monitor signal too low
to estimate width of peak.
6. Estimate from microcoulometer
data.
Source: Aerial Monitoring of the Plume Generated by the at-Sea
Incineration of Organochloride Wastes. U.S. Environmental
Protection Agency, National Environmental Research Center,
Las Vegas, Nev. Feb. 5, 1975
191
-------
TABLE C-6
AERIAL MONITORING OF RESEARCH BURN II.
AXIAL PASSES ON THIRD MISSION (DEC. 4. 1974)
Position
Location of
max. cone. ,
Pass
1
2
3
4
5
6
7
Time
of
day
1126.7
1128
1130.5
1130.8
1131
1122.8
1123.2
1123.5
1118
1118.6
1119.4
1120
1120.8
1107
1107.4
1107.7
1105
1109
downwind
distance
from ship.
meters
0
6,100
11,000
9,500
8,400
5,500
3,900
2,600
0
2,700
6,300
9,300
13,000
2,300
3,500
4,300
400
400
Max. cone.
Altitude.
meters
910
910
850
850
850
820
820
820
790
790
790
790
790
240
240
240
240
240
i
fivr
\^i^» .
0 0
lO^/cni
BKG3
BKG3
0
4
BKG3
9
20
8
BKG 3
1
7
66
1
77
45
22
100 .
37
Hfl ^
AlV^J. f
ppm
BKG4
BKG4
BKG4
BKG4
BKG4
BKG
BKG
BKG
BKG4
BKG4
BKG4
BKG4
BKG4
0.5
0.5/0.
0.5
0.3/0.
0.4/0.
Plume
intercept
length,
meters
1,100
1,300
1,000
770
950
1,800
2,200
3.200
8
6
5
Remarks
Above visible plume
End of visible plume
Entered visible NH 4C1
InNH4Cl
Above little white cloud
In NH4C1
InNH4Cl
InNH4 Cl
In little white cloud
In little white cloud
Out of visible plume
Out of visible plume
Bag #1
192
-------
TABLE C-6 (cont.)
Position
Pass
8
9
10
Time
of
day
1136
1138
1141
Location of
max. cone.
distance
from ship,
meters
400
400
400
*
Altitude.
meters
240
240
150
Max. cone. Plume
CN1.
103/cm3
69
100
170
„-,, 2 intercept
HC1 ' length.
ppm meters
0.6
!5/3
!5/3
Remarks
Bag #2
Bag #3
Close-up photograph
1. Condensation nuclei.
2. Second value, where given, derived from couloxneter data.
3. Signifies baseline response, less than 1,000/cm .
4. HC1 baseline averaged 0.25 ppm during third mission
5. Extrapolated to off-scale value. ^
Source: Aerial Monitoring of the Plume Generated by the at-Sea
Incineration of Organochloride Wastes. U.S. Environmental
Protection Agency, National Environmental Research Center,
Las Vegas, Nev. Feb. 5, 1975.
193
-------
be visualized by drawing a level path through the convolutions of
the plume such that the path enters and leaves portions of the
looping plume several times.
Although the data are presented in metric units, altitudes
were measured by the aircraft pressure altimeter in feet, and
distances downwind from the ship were estimated by the pilot in
miles. The aircraft ground speed was calculated from the air
speed indicator readings in knots and adjusted for average wind
speeds, also reported in knots. As a test of the pilot's judgment
for distance, range finder readings were taken at three different
passes claimed by the pilot to be 1 mile from the ship. The range
finder values were 1.10, 1.15, and 1. 05 miles, indicating that
the pilot's estimates were adequate for the purposes of this study.
The results of the Fourier Transform Infrared Spectrometry
analyses are presented in Table C-7. In general, these results
indicate that the air samples were low in pollutant concentration.
In urban morning air, the concentrations of carbon monoxide and
paraffinic hydrocarbons generally run higher than the highest
measured from any of the bags. The only unusual aspect of the
air in any of the bags was the 10 ppm benzene measured in bag
#4 of December 2.
Several other compounds could have been measured, but
were not detected in any of the samples. They are listed here,
with their estimated lower limits of detectable concentrations:
hydrochloric acid, 0. 5 ppm; acetylene, 0. 1 ppm; ethylene, 0. 2 ppm;
carbon tetrachloride, C. 05 ppm; phosgene, 0. 1 ppm.
19k
-------
TABLE C-7
AERIAL MONITORING OF RESEARCH BURN II,
POLLUTANTS IN GRAB BAG SAMPLES
Non-methane
Bag no.
and date
#1. 12/2/74
#2, 12/2/74
#3, 12/2/74
#4. 12/2/74
#1. 12/3/74
#2, 12/3/74
#1, 12/4/74
#2, 12/4/74
#3, 12/4/74
Carbon
dioxide
340 + 10
370 + 20
380+ 20
370 + 20
330 + 10
330+10
370 + 20
330 + 10
Carbon
monoxide
1.9 + 0.3
2.9 + 0.4
3.4+0.4
2.8 + 0.4
0.2+0.2
0.3 + 0.1
2.6 + 0.3
0.3 + 0.1
Methane
1.5 + 0.2
1.5 + 0.2
1.7 + 0.3
1.5 +0.2
1.5+0.2
1.5+0.2
1.5+0.2
1.5 +0.2
paraffin
carbon
atoms
0.5+0.2
1.0 + 0.4
1,0+0.4
1.0+0.4
0.2- + 0.2
0.2 + 0.2
0.4+0.2
0.2 + 0.2
Freon-11
Benzene (CFC1 3>
0.0
0.0
0.0
10.0+2.0
0.0
0.0
0.0
0.0
0.00
0.09
0.12
0.07 •
0.00
0.00
0.00
0.00
Bag deflated during shipment
1. Analysis by Fourier Transform Infrared Spectrometry performed by
U.S. Environmental Protection Agency, National Environmental Research
Center, Research Triangle Park, N.C.
Source: Aerial Monitoring of the Plume Generated by the at-Sea Incineration
of Organochloride Wastes. U.S. Environmental Protection Agency,
National Environmental Research Center, Las Vegas, Nev. Feb. 5, 1975.
195
-------
APPENDIX D. EQUIPMENT AND PROCEDURES FROM
SEA-LEVEL MONITORING OF EFFECTS
ON MARINE ENVIRONMENT
197
-------
The effects of incineration on the marine environment were
monitored during the first research burn by both the R/V Oregon 11(1)
and the M/V Orca(2); on the second research burn, only the Orca
was on the scene. (3)
R/V OREGON II
Ship Movements
On each of the Oregon's two cruises, the initial effort was to
find the piume and to attempt to identify its limits and points of highest
concentrataion. This required a systematic search by Oregon with
very precise navigation at all times during the search pattern. To
meet these requirements, the Oregon ran a search pattern in the
quadrant downwind from the Vulcanus while it was drifting; a running
plot was maintained of the Oregon's position relative to the Vulcanus
and HC1 readings in the air at each position.
Simultaneous readings of HC1 concentration, Oregon's true course
and pit log speed, and the radar range and bearing of the Vulcanus
T~. Preliminary Technical Report on Incineration of Organochlorine
Wastes in the Gulf of Mexico. U.S. Environmental Protection
Agency, Oil and Special Materials Control Division, Washington,
D. C. Nov. 13, 1974.
2. A Field Monitoring Study of the Effects of Organic Chloride Waste
Incineration on the Marine Environment in the Northern Gulf of
Mexico. Prepared by TerEco Corp., College Station, Tex., under
contract to Shell Chemical Co., Houston, Tex. Oct. 30, 1974.
3. Sea-Level Monitoring of the Incineration of Organic Chloride Waste
by M/T Vulcanus in the Northern Gulf of Mexico, Shell Waste Burn
No. 2. Prepared by TerEco Corp., College Station, Tex., unde'r
Contract No. 68-01-2829 with U.S. Environmental Protection
Agency, Washington, D.C. Jan. 10, 1975.
199
-------
from the Oregon were recorded every 5 minutes while the Oregon
was sweeping arcs at a constant distance from Vulcanus. The
Oregon's speed was adjusted so that no more than a 12-degree change
in relative bearing would occur in any 5-minute interval. (This was
to avoid running the plume too rapidly to obtain good data on its
dimensions.) Higher speeds than optimum were maintained on some
arcs in the second cruise, however, because the sea conditions pre-
vailing did not permit lower speeds.
With the Vulcanus underway, the Oregon did not have enough
speed to run such a comprehensive systematic search pattern. The
Oregon therefore paralleled the Vulcanus1 s course at a constant
range, moving forward of the plume and then dropping back to pick
it up again.
Wind speed and direction were obtained on the Oregon with a
hand-held anemometer operated from the flying bridge; the data
were correlated with vessel speed and course at the time of reading,
and the true wind speed and direction calculated from these data at
half-hour intervals during plume runs and at longer intervals during
other operations. Similar observations were reported from Vulcanus
at half-hour intervals.
Relative humidity was obtained by a sling psychrometer.
Water Movement
.Data on water circulation and dispersion consisted of one experiment
using a dye (Rhodamine WT) and the log of the movement of the Vulcanus
200
-------
while drifting. Pilot charts for the area indicated a general southerly
drift of about 0. 5 knots throughout the dump site, but with a westerly
component in the northern part of the site and an easterly component
in the southern part.
The drift of the Vulcanus during the first cruise, when it was in
the northeastern part of the dump site, suggested a strong surface
current (about 2.4 knots) to the East or Southeast. In this part of
the dump site, the surface water temperature decreased sharply
(2° C.). Position data provided by the Vulcanus during this period
suggested a current of this magnitude along the entire eastern side
of the dump site, since dead reckoning positions were in error in the
magnitude and direction attributable to the effects of such a current.
During the second Oregon cruise, the Vulcanus, while drifting,
moved in a westerly direction at rates of 0. 7 and 1. 3 knots in the
last day of the burn. Since the drift was with the wind, which was
about 20 knots, the drift rate of the surface waters could not be
estimated separately from that of the Vulcanus.
The experiment with the dye as a tracer was used to determine
the diffusion processes in the surface layer. The diffusion rate at a
wind speed of 10 knots was calculated to be about 7, 000 times per
hour—that is, any concentration of an inert constituent entering the
ocean from the plume would be reduced by a factor of 7, 000 within an
hour after it entered the ocean. This implied that any direct impacts
on the ocean of minor constituents of the stack emissions would be
undetectable in a very short time.
201
-------
Sampling Procedures
Water samples were taken below the plume itself and in a larger
area exposed to plume constituents. On the first cruise, an area of
probable contact was identified by a dye marker dropped overboard
from the Oregon as it passed through an area of peak concentration.
Samples were then taken in the area identified by the dye, but not
in the dye patch itself. On the second cruise, the plume was much
more stable, and it was possible to hold the Oregon in the plume
during sampling.
To identify any long range impact, a sampling grid of 16 stations
was laid out over the area that the plume specifically covered during
the last 24 hours of the burn. The grid was also downwind and down-
current of the dump site and therefore offered the greatest potential
for picking up cumulative effects. Points selected were 1, 852 meters
(1 n. mi.) apart in the area, chosen on the basis of drift estimates and
other movements of the Vulcanus during the last 24 hours; the grid
size was selected to assure that any impacts during this period would
be found at stations within the grid.
All samples were surface samples taken by a bucket lowered over
the side by a rope. A metal bucket was used for organic chloride
samples, a plastic bucket for all other samples. On the first cruise,
all sampling was from the bow to avoid any possibility of disturbing
the surface prior to sampling; on the second cruise, sampling was
202
-------
from the afterdeck because the state of the sea made sampling from
the bow unsafe.
Analytical Procedures
Samples for pH were run immediately on at least two standard
laboratory instruments --Fisher, Leeds and Northrup, or Beckman.
The meters were standardized with buffers at pH 4. 0, 7. 0, and 10. 0
prior to each use; electrodes were stored in sea water to avoid
electrode shock.
Chlorinity
On the first cruise, chlorides were titrated on board, but the
results proved unsatisfactory. Samples from the second cruise were
stored in dry bottles previously rinsed with distilled water, then
analyzed onshore by the Raytheon Company by the standard Mohr
titration for chloride in sea water. The company uses the method
routinely for primary calibration of its instruments.
Q rganochlorides
Organo chloride samples were stored in acetone-washed bottles
for analysis onshore. Samples of the upper 1 to 10 centimeters of the
surface were preserved with petroleum ether for detection of any
potential impact on the surface microbiological communities. Total
organochlorides were determined in EPA laboratories by gas
chromatographic-mass spectrographic techniques. Sensitivities
for typical compounds are:
203
-------
Vinyl chloride 0. 5 ppb
Methylene chloride 0. 4 ppb
Chloroform 0. 1 ppb
Carbon tetrachloride 0. 3 ppb
1, 1, 2-Trichloroethylene 0. 1 ppb
1,1, 2, 2-Tetrachloroethylene 0. 2 ppb
Trace Metals
Samples for trace metals analysis were stored in dry glass or
plastic containers previously rinsed with distilled water. Samples
were analyzed in EPA laboratories by atomic absorbtion techniques
after extraction with methyl isobutyl ketone.
P hy toplankton
Phytoplankton samples were preserved with formalin or Lugol's
solution, then counted in EPA laboratories by direct microscopic
examination.
Chlorophyll-a
Chlorophyll-a samples were filtered through 0.45-micron
millipore filter and dried for analysis by standard procedures at
American University.
ATP
Levels of adenosine triphosphate (ATP) were determined onboard
immediately by a research technique involving extraction of ATP from
cell material and conversion of the ATP to an optically active compound.
The NASA research team onboard the Oregon had used the technique
previously in studying water pollution.
20k
-------
M/V ORCA
Research Burn 1(2)
In Research Burn I, the Orca used three types of sampling
patterns:
+ Transect--carried out downwind from the Vulcanus,
running transversely across the axis of the atmospheric
plume.
+ Axial--taken along the axis of the atmospheric plume,
beginning 7,400 meters (4 n.mi.) directly downwind
from the Vulcanus and proceeding into the wind, with
the last sample being taken at 740 meters (0. 4 n. mi.)
from the Vulcanus.
+ Axial control--conducted parallel to the axis of the
atmospheric plume and well outside the area affected by
incineration.
Samples for pH, organic chloride, and zooplankton were collected
while the Orca was underway at approximately 5 knots; phytoplankton
samples were collected while the Orca was adrift. All sampling was
while the Vulcanus was incinerating. The axial control runs consisted
of a 1, 850-meter (1-n.mi.) neuston tow, with a phytoplankton sample
taken at the beginning of the tow, and organic chloride and pH samples
at the beginning, middle, and end of the tow.
Samples for pH and organic chloride determinations were collected
from surface waters in a 2-gallon porcelain bucket. For pH analysis.
205
-------
the receiving 8-ounce bottles were thoroughly rinsed and filled to
three-fourths capacity. Samples were analyzed aboard the Orca with
an Orion Research lonalyzer, Model 801/digital pH meter. The
instrument was standardized with two buffers: pH 4. 01 and 9.18.
Samples were analyzed within 2 hours of collection. For organic
chloride analysis, the receiving 32-ounce bottles were thoroughly
rinsed and filled to capacity. The samples were analyzed by Shell
Development's Bellaire Research Center.
Since any deleterious effects of the incineration process on marine
organisms would be greatest in the surface waters, a special collecting
device was used to collect zooplankton. With this sampling device,
the neuston net, only the upper 1 meter of the water column was
sampled. The neuston net consists of a nylon mesh bag attached to
a rectangular aluminum frame. The net has a mouth opening of 1x2
meters, a length of 10 meters, and a mesh aperture of 1 millimeter.
A sampling depth of 0. 5 meters was sought; however, due to con-
sistently high waves, the sampling depth varied from 0 to 1 meters.
In all cases, the net was towed for 1, 850 meters; thus the amount
of surface area sampled was 3, 700 square meters.
The neuston net was used only on Axial and Axial Control runs.
On Axial runs the net was towed from a distance of 4, 810 meters
from the Vulcanus to 2, 960 meters from the Vulcanus. During Axial
Control runs, the net was towed the entire 1, 850-meter distance of
the run.
206
-------
At the end of each tow, the zooplankton sample was placed into
a 1-gallon jar. Within 10 minutes the sample was photographed
with a movie camera. After the photography, the sample was
grossly examined, and the approximate number and variety of living
organisms were recorded. After 2 to 3 hours, the viability of the
organisms was again checked visually. The sample was then
preserved with buffered formaldehyde and returned to TerEco's
land-based laboratory for an enumeration of the organisms.
Phytoplankton samples were collected from a depth of 1 meter
with a Nisken bottle at the end of each Axial neuston tow and at the
beginning of each Axial Control neuston tow.
Research Burn 11(3)
Sampling Procedures
In four test runs in the second research burn, the Orca collected
samples of surface water for determination of pH, chlorinity, alka-
linity, organochlorides, copper, and zinc. The samples were
collected by a 2-gallon polyethylene bucket slung from a nylon rope
while the Orca was underway.
Zooplankton samples were collected with the neuston net weighted
to ride just below the surface in order to avoid collecting large amounts
of tar balls, plastics, and other extraneous materials. The net was
towed at 3 knots. Samples, drained and transferred with some fluid
to a glass jar, were frozen.
Phytoplankton samples were collected with a Hans en type net with
20?
-------
a mouth opening of 20 cm, a length of 1. 5 meters, and a 35-micron
mesh. It was towed just under the surface at 3 knots. Samples were
stored in glass jars and frozen.
Analytical Procedures
The only analysis conducted aboard Orca was pH. Determinations
were generally made within 8 minutes after collection. A Corning
Model 112 digital pH meter standardized at pH 9.180 was utilized.
Sample and buffer temperatures were always within 1° C at 23. 7° +
0. 5° C. During the analyses conducted for Test Run I and Control
Run I, the line voltage variation caused the meter to fluctuate + 0. 01
pH unit. During the remainder of the pH determinations, the instru_
ment was connected to a 12-volt lead-acid battery via a 110-volt
transistorized inverter. Fluctuations of the instrument were.reduced
to a maximum of +_ 0. 003 pH units.
Water samples were placed in thoroughly rinsed 8-ounce bottles,
tightly capped, and returned to the shore laboratory for chlorinity
analysis by the Mohr titration method. Samples were compared with
Copenhagen standard sea water to obtain chlorinity values. A standard
working curve was generated by using dilutions of Copenhagen stand-
ard sea water (19. 3755 parts per thousand Cl). The precision of this
method is + 0. 03 parts per thousand.
Water samples collected on Test Run II and Control Run II were
analyzed for total alkalinity. A potentiometric titration method
using mathematical determination of end points was utilized.
208
-------
Organic chloride samples were placed in acetone-washed quart
glass bottles and sealed with Teflon-lined caps.
Water samples collected for copper and zinc analyses were
placed in quart polyethylene bottles to which 2 ml of redistilled
concentrated nitric acid had been added as a preservative. These
samples were analyzed by atomic absorption in the laboratories of
Shell Development Company.
The frozen zooplankton and phytoplankton samples were also
analyzed for organochlorides and metals by Shell. (4) The zoo-
plankton samples were thawed and separated by decantation and
filtration into solid and liquid phases. The liquid phase was
clarified by ultracentrifugation and analyzed for zinc and copper by
atomic absorption and organochlorides in same manner as sea
water samples. Depending on the amount of liquid available for the
organochloride analysis the limit of detection was 25 to 65 ppb.
Portions of the solid zooplankton samples were solubilized by
oxidative digestion and analyzed by atomic absorption for copper
and zinc. A second portion (50 grams) of the solid was added to
a blender with 200 ml of 90/10 hexane-ethyl ether. The mixture
was vigorously blended for 10 minutes, the solvent decanted and
allowed to settle, and a portion specifically analyzed for organo-
chlorides us.ing the microcoulometric technique. Since there was
C Personal communication. W. R. Harp. Jr., to B. N. Bastian,
Shell Chemical Co., Houston, Tex., Dec. 19, 1974.
209
-------
no concentration of the sample on the resin column with this
technique, the limit of detection was 3 ppm.
In the case of phytoplankton analyses, the paucity of organ-
isms in the sea water (and thus the samples) argued against
separate analyses of water and organisms. The organochloride
detection limit for the whole sample was estimated to be 3 ppm.
210
-------
APPENDIX E.
ADDITIONAL DATA FROM
OREGON II MONITORING OF MARINE
ENVIRONMENT (1)
1. Preliminary Technical Report on Incineration of Organochlorine
Wastes in the Gulf of Mexico. U. S. Environmental Protection
Agency, Oil and Special Materials Control Division, Washington,
D-C., Nov. 13, 1974.
211
-------
TABLE E-l
SAMPLING STATIONS, FIRST CRUISE OF OREGON II
Station No.
Date
Time
Location
Water Depth
Wind Direction
Wind Velocity
Sea State
Precipitation
Slicks
Chlorinity(%J
PH
Organohalogens (ppb)
Metals (ppb) See note
Arsenic
Cadmium
Chromium
Copper
Lead
M ercury
Nickel
Zinc
Hri
Control
Station 1-1
10/18/74
1800
27 01.0'N*
93 43. 5'W *
app. 480 fm
NE
8 kts
light seas
none
none
20.09
8.3
vOHm
< 05
<1
-------
TABLE E-2
SAMPLING STATIONS, SECOND CRUISE OF OREGON II
Station No.
Date
Time
Location
Water Depth
Air Temperature
Wind Direction
Wind Velocity
Relative Humidity
Cloud Cover
Sea State
Precipitation
Slicks
Water Temperature
Chlorinity(%)
pH
oGC Cill
Organohalogens (ppb)
Metals (ppb)- -See note
r\r senic
Cadmium
v^nr om lu m
v^opper
Mercury
INlCKei
Zinc
Chlorophyll a
phytoplankton
ATP bucket sample
(ugATP/1. seawater)
HCI (ppm)
OTT "D/-voi + i -1M llrr.4- \f T T T
ll Position wrt. VU.LJ.
Trawl
Control
Station 1
10/27/74
0925-0955
27° 54.3'N
91C 33.1'W
143 fm
79" F
90° T
13 kts
58%
1/10
1-2 ft. seas
none
none
25. 2 C Bucket
20.37
8.22
-.-5™
540 (cells/1)
""^^
0.014
o
Station 2
10/27/74
2330-2340
26C 38'N
93° 41 'W
0.75mi fr.VUL.
app. 800 fm
78" F
150C T
19 kts
73%
2/10
3-5 ft. seas
none
none
25 C
20.48
8.05
<0.5
<0.02
** n A
V U. Tb
1 * OO
Ofifi
. o o
0.019
£1.00
1 .70
0.42
1140 (cells/1)
0.056
2.5 ppm
Station 3
10/27-10/28/74
2355-0015
26° 38'N
93e 41'W
0.5 mi fr.VUL
.app. 800 fm
77C F
157* T
22 kts.
79%
2/10
4-5 ft. seas
none
none
app. 26 C
20.26
8.2
<0.5
2C
. O
<0. 02
/*(") A
S.U. *±
q c 1
O . D J-
^0 20
0.015
± i O O
3.16
980 (cells/1)
0.046
7 DDKl
1 ^fi-1 Q° T
i oo A y & j.
Station 4
10/28/74
0105-0115
26° 38'N,
93° 41'W
0.2 mi fr. VUL
app. 800 fm
77C F
140° T
20 kts
77%
7/10
4-5 ft. seas
rain shower
none
app. 26 c C
20.09
8.2
<0.5
37
. /
5.33
^U . rt
1Cf\
. bU
2 a K
. bb
0.037
2p o
. oo
5.88
0.08
87 0 f no! ~\ o /"} \
u * w v t- CA -LH/ J. )
0.067
4.5 ppm
1 7c C >T
J- i O X
Station 5
10/28/74
0300
26" 39.5'N
93C 37.5'N
5.5 mi E. fr.VUL
app. 800 fm
77 'F
160' T
18 kts
75%
2/10
5 ft. seas
none
none
app. 26 * C
19.98
8.2
<0. 5
0.36
<,0. 4
3.13
1C n
. 50
0.025
O . O O
6.33
Ono
. uy
0.016
due east
Station 6
10/28/74
0320
26° 40'N
93° 37.5'W
7.5 mi E. fr. VUL
app. 800 fm
77° F
160° T
18 kts
75%
2/10
5 ft. seas
none
none
app. 26° C
19.87
8.2
<0. 5
0. 21
<0. 4
2. 28
1. 00
0.087
2. 00
7.70
0.11
0.032
due east
one jelly fish
Note: Preliminary analytical data not rounded off to significant figures.
-------
TABLE E-2 (CONT'D)
SAMPLING STATIONS. SECOND CRUISE OF OREGON II
Station No.
Station II-7
Station II-8
Station II-9
Station 11-10
Station 11-11
Station 11-12
VI
Date
Time
Location
Water Depth
Air Temperature
Wind Velocity
Precipitation
CM ; „!. e
Water Temperature
Chlorinity(%)
PH
Organohalogens (ppb)
Metals (ppb) see Note
Arsenic
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Zinc
Chlorophyll a
ATP bucket sample
(ugATP/1. sea water)
HC1 (ppm)
10/28/74
0835-0845
26° 38' N
93° 38' W
app. 800 fm
72° F
28 kts
71 M
1 1 10
1 / 1 n
none
app. 26° C
20.09
8.2
<0.5
3.7
0.02
-------
TABLE E-2 (CONT'D)
SAMPLING STATIONS, SECOND CRUISE OF OREGON II
Station No.
Station 11-13
Station 11-14
Station 11-15
Station 11-16
Station 11-17
Station 11-18
ON
Date
Time
Location
Water Depth
Sea State
Slicks
Water Temperature
Chlorinity(%)
PH
Organohalogens (ppb)
Metals (ppb) See note
Arsenic
Cadmium
Chromium
Copper
Lead
Mercury
Nickel '
Zinc
Chlorophyll a
Phytoplankton
ATP bucket sample
(ug ATP /I. seawater)
HfT /nnm)
O II Position wrt VUL
Trawl
10/28/74
1416
26° 44'N
93a 44'N
app. 800 fm
app 83° F
app. 26° C
19.98
8.2
<0. 5
<1
<0. 04
<;0.4
9.45
<0.40
Contaminated
31.66
<0. 05
0.08
0.043
10/28/74
1511
26° 38'N
93° 44'W
app. 800 fm
app 83° F
app. 26° C
20.09
8.2
<0. 5
<1
<0.04
<0.4
4.54
1.25
0.037
2.91
<0. 05
0.04
0.034
10/28/74
1546
26° 28'N
93P 50'W
app. 800 fm
app. 26°' C
19.98
8.2
<0. 5
<1
<0.04
<0.4
3.08
<0.40
<0. 010
3.75
0.75
0.11
0.027
10/28/74
1635
26" 44'N
93° 50'W
app. 800 fm
app. 26° C
19.98
8.2
<0.5
5.5
<0.04
<0.4
2.87
<0. 40
<0.010
2.50
<0. 05
0.00
0.060
10/28/74
1712
26* 50'N
93°50'W
app. 800 fm
app. 26° C
19.98
8.2
<0. 5
<1
0.54
<0.4
3.41
12.00
Contaminated
3.75
31.66
0.04
Lost
10/28/74
1800
26° 56'N
93° 50'W
app. 800 fm
7Q° V
1 A *7 O fT>
OC 1^+r"
O / 1 A
app. 26° C
19.87
8.2
<0.5
8.7
<0. 04
<0.4
0.25
<0.40
<0. 010
2.50
0.15
0.00
0.041
Note: Preliminary analytical data not rounded off to significant figures.
-------
TABLE E-2 (CONT'D)
SAMPLING STATIONS, SECOND CRUISE OF OREGON II
Station No.
Station 11-19
Station 11-20
Station 11-21
Station 11-22
ro
Date
Time
Location
Water Depth
Air Temperature
Wind Direction
Wind Velocity
Relative Humiditty
Cloud Cover
Sea State
Precipitation
Slicks
Water Temperature
Chlorinity(%)
pH
Secchi
Organohalogens (ppb)
Metals
-------
APPENDIX F. LOG SHEETS FROM INTERIM PERMIT BURNS
219
-------
OPERATIONAL LOG
(All Information To Be Recorded At Least Once Each Watch)
Waste Type: Organic Chloride
Waste Origin: Shell Deer Park Mar .'acturing Complex
Deer Park, Texas
Black Box Temp.
as Read in
Date
12/19/74
12/20/74
12/21/74
12/21/74
12/23/74
12/24/74
12/25/74
12/26/74
Combustion Room
Time
0400
0800
1200
1600
2000
0000
6400
0800
1200
1600
2000
0000
0400
0800
1200
1600
2000
0000
0440
0800
1200
1600
2000
0000
0400
0800
1200
1600
2000
0000
0400
0800
1200
1600
2000
0000
0400
0800
1200
1600
2000
0000
Port
.
1030
1090
1150
1170
1180
1200
1200
1200
1180
1195
1190
1200
1210
1200
1205
1220
1210
1215
1200
1200
1200
1200
1200
1170
1200
1190
1190
1200
1175
1190
1190
1200
1180
1185
1190
1190
1195
1190
1200
1200
1200
Stb.
.
1020
1110
1170
1180
1160
1200
1200
1200
1200
1210
1220
1210
1220
1200
1215
1220
1240
1235
1215
1200
1200
1210
1200
1190
1170
1190
1200
1210
1165
1200
1200
1180
1200
1200
1185
1190
1200
1190
1200
1200
1180
Controller
Temp.
Port
_
1300
1270
1300
1310
1320
1330
1320
1330
1300
1300
1310
1330
1330
1330
1320
1330
1310
1330
1310
1300
1310
1300
1300
1290
1350
1290
1290
1340
1230 •
1290
1320
1300
1310
1320
1170
1295
1300
1260
1330
1330
1290
Stb.
-B
1300
1290
1300
1290
1280
1300
1300
1310
1300
1310
1330
1310
1310
1310
1320
1350
1340
1320
1300
1270
1300
1310
1290
1270
1290
1310
1300
1360
1230
1300
1300
1240
1300
1300
1170
1250
1300
1260
1350
1320
1260
Wind
Speed
39
24
17
20
18
21
22
24
19
15
15
21
19
14
16
20
12
19
19
27
27
30
36
19
19
27
37
35
34
36
29
29
34
30
20
14
20
12
15
18
26
27
Wind
Dir.
205
210
175
180
180
180
180
350
360
360
360
040
045
050
035
070
130
140
160
150
150
140
140
140
160
160
180
140
160
180
180
170
180
180
180
195
180
120
140
150
160
190
Location
Lat.
TJ
26 50
26 37
26 35
26 33
26 32
26 31
26 30
26 23
26 38
26 47
26 40
26 33
26 30
26 24
26 42
26 52
26 47
26 42
26 38
26 40
26 38
26 37
26 35
26 42
26 38
26 35
26 36
26 42
26 30
26 37
26 33
26 28
26 25
26 29
26 46
26 41
26 37
26 30
26 23
26 37
26 33
26 32
Long.
W
93 52
93 41
93 39
93 38
93 37
93 37
93 34
93 30
93 36
93 40
93 36
93 31
93 33
93 34
93 42
93 44
93 42
93 41
93 38
93 30
93 26
93 31
93 51
93 41
93 38
93 35
93 33
93 28
93 23
93 41
93 41
93 42
93 44
93 40
93 32
93 32
93 34
93 30
93 31
93 33
93 40
93 41
221
-------
WASTE FEED RATE LOG
Waste Type; Organic Chloride
Waste Origin: Shell Deer Park Manufacturing Complex
Deer Park, Texas
Date
19/12/74
20/12/74
21/12/74
22/12/74
23/12/74
24/12/74
24/12/74
25/12/74
25/12/74
Tank
Designation •
2 C
4 C
1 C
5 C
3 C
2 p + s
3 p + s
4p + s
5 p + s
Time
Start
Discharge
0330
0830
0630
0630
0430
0130
1330
0130
1530
Time
Stop
Discharge
20-12 0830
21-12 0630
22-12 0630
23-12 0430
24-12-0130
24-12 1300
25-12 0130
25-12 1530
26-12 0330
Volume
Discharged
Metric Tons
710
526
556
525
518
301
300
347
300
Discharge
Rate
Metric Tons/Hr.
24.4
23.9
23.2
23.9
24.7
25.0
24.8
24.8
24.8
222
-------
OPERATIONAL LOG
(AU Information To Be Recorded At Least Once Each Year)
Waste Type: Organic Chloride
Waste Origin: Shell Deer Park Manufacturing Complex,
Deer Park, Texas
Black Box Temp.
as Read in
Date
12/31/74
02/01/75
01/02/75
01/03/75
01/04/75
01/05/75
01/06/75
01/07/75
Combustion Room
Time
1200
1600
2000
0000
0400
0800
1200
1600
2000
0000
0400
0800
1200
1600
2000
0000
0400
0800
1200
1600
2000
0000
0400
0800
1200
1600
2000
0000
0400
0800
1200
1600
2000
0000
0400
0800
1200
1600
2000
0000
0400
0800
Port
990
1095
1145
1175
1190
1200
1200
1200
1200
1205
1200
1200
1200
1200
1200
1200
1200
1200
1195
1195
1200
1205
1200
1200
1200
1200
1200
1200
1195
1200
1200
1195
1200
1205
1190
1200
1190
1195
1200
1210
1200
1140
Stb.
995
1110
1160
1185
1200
1205
1200
1200
1205
1200
1210
1195
1200
1200
1200
1190
1200
1200
1200
1200
1200
1210
1195
1200
1200
1200
1200
1200
1195
1200
1200
1200
1190
1200
1200
1205
2300
1195
1205
1200
1210
1130
Controller
Temp.
Port
1280
1300
1300
1310
1310
1310
1300
1290
1300
1305
1290
1290
1300
1290
1300
1310
1300
1310
1300
1290
1320
1310
1300
1310
1300
1290
1280
1290
1200
1290
1290
1280
1290
1310
1300
1300
1280
1290
1300
1310
1300
1250
Stb.
1250
1300
1295
1300
1290
1300
1300
1300
1300
1305
1310
1280
1290
1320
1330
1280
1300
1320
1300
1310
1310
1310
1280
1330
1-320
1310
1290
1290
1290
1290
1300
1320
1290
1300
1290
1300
1290
1290
1310
1300
1310
1240
Wind
Speed
18
18
15
17
15
14
12
30
31
13
24
28
20
20
22
24
15
21
16
31
36
38
30
32
34
24
15
12
13
12
11
10
11
10
11
13
13
11
14
21
20
15
Wind
Dir.
135
150
140
150
140
130
140
070
050
130
160
150
135
135
160
180
160
i80
160
335
025
010
340
350
020
360
030
090
070
160
020
135
140
130
160
110
140
135
140
160
135
130
Location
Lat.
N
26 39
26 38
26 37
26 35
26 31
26 28
26 26
26 36
26 42
26 38
26 37
26 35
26 35
26 35
26 33
26 30
26 43
26 42
26 42
26 38
26 30
26 31
26 43
26 34
26 28
26 33
26 39
26 34
26 29
26 25
26 46
26 44
26 42
26 39
26 38
26 34
26 24
26 31
26 29
26 27
26 27
26 37
Long.
w
93 39
93 37
93 37
93 38
93 38
93 39
93 41
93 40
93 35
93 35
93 36
93 35
93 34
93 30
93 26
93 25
93 40
93 40
93 39
93 38
93 40
93 40
93 40
93 40
93 43
93 41
93 40
93 40
93 39
93 38
93 40
93 37
93 34
93 33
93 29
93 27
93 26
93 25
93 24
93 24
93 23
93 37
223
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WASTE FEED RATE LOG
Waste Type: Organic Chloride
Waste Origin: Shell Deer Park Manufacturing Complex
Deer Park, Texas
Time
Tank Start
Total
Time Volume
Stop Discharged
Date
12/31/74
01/01/75
01/02/75
01/03/75
01/04/75
01/05/75
01/05/75
01/06/75
01/06/75
Designation
2 C
4 C
1 C
5 C
3 C
WT 2 pt + sb
WT 3 pt + sb
WT 4 pt + sb
WT 5 pt + sb
Discharge
0900
1300
1100
1000
0900
0600
1830
0600
2030
Discharge
1/1 1300
1/2 1100
1/3 1000
1/4 0900
1/5 0600
0/5 1850
1/6 0600
1/6 2030
1/7 0800
•Metric Tc
689.6
551.7
567.0
542.2
508.3
311.6
285.3
357.6
289.7
Discharge
Rate
Metric Tons/Hr
4103.0 MT
Total 4103 MT incinerated in 167 hours - 24.5 MT/h. average discharge rate.
No discharge rate per tank can be given, as due to the large amount of slop
water received, various tanks had to be mixed in order to maintain temperature.
A breakdown in the controlcurrent circuit occured in the night of 1/5 to 1/6.
Various indicator lamps did extinguish.
224-
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BIBLIOGRAPHY
Report to congress on Hazardous Waste Disposal. U. S.
Environmental Protection Agency, Office of Solid Waste
Management Programs, Washington, B.C., June 30", 1973.
Miller, Taylor O. Report of the Presiding Officer. Public
Hearing held Oct. 4, 1974, in Houston, Tex., concerning
Shell Chemical Co. application for permit No. 730D008C to
dispose of organochlorine wastes. U. S. Environmental
Protection Agency, Oil and Special Materials Control Division,
Washington, D. C., Oct. 9, 1974.
U. S. Environmental Protection Agency Research Permit No.
730D008C. Issued under Marine Protection, Research, and
Sanctuaries Act (Ocean Dumping), Washington, D. C., Oct. 10,
1974.
Federal Register. Vol. 39, No. 202, p 37057-8, Oct. 17, 1974.
A Field Monitoring Study of the Effects of Organic Chloride Waste
Incineration on the Marine Environment in the Northern Gulf of
Mexico. Prepared by TerEco Corp., College Station, Tex., under
contract to Shell Chemical Co., Houston, Tex., Oct. 30, 1974.
Gusey, W. F. Potential Effects of at Sea Incineration of Organic
Chloride Wastes on Migrating Birds, Shell Chemical Co.,
Houston, Tex., Nov. 1, 1974.
Preliminary Technical Report on Incineration of Organochlorine
Wastes in the Gulf of Mexico. U. S. Environmental Protection
Agency, Oil and Special Materials Control Division, Washington,
D.C., Nov. 13, 1874.
Frick, G. William. Report of the Presiding Officer Technical
meeting held Nov. 14, 1974, in Houston, Tex., regarding
application of Shell Chemical Company Permit No. 730D008C
pursuant to the Marine Protection, Research, and Sanctuaries
Act of 1972. U. S. Environmental Protection Agency, Oil and
Special Materials Control Division, Washington, D.C., Nov.
27, 1974.
Train, Russell E. Supplementary decision of the Administrator
regarding application of Shell Chemical Company for Marine
Protection, Research, and Sanctuaries Act Permit No. 730D008C.
U. S. Environmental Protection Agency, Oil and Special Materials
Control Division, Washington, D. C., Nov. 27, 1974.
225
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U. S. Environmental Protection Agency Research Permit No.
730D008C(2). Issued under Marine Protection, Research, and
Sanctuaries Act (Ocean Dumping), Washington, D. C., Nov. 27>
1974.
Preliminary Report, Marine Environmental Monitoring of
Vulcanus Research Burn II, December 2, 1974. U.S.
Environmental Protection Agency, Oil and Special Materials
Control Division, Washington, D.C., Dec. 10, 1974.
Biglane, Kenneth E. Staff Report Regarding Application of
Shell Chemical Company and Ocean Combustion Services,
B. V. , For Permit No. 730D008C Pursuant to the Marine
Protection, Research, and Sanctuaries Act of 1972. U.S.
Environmental Protection Agency, Oil and Special Materials
Control Division, Washington, D.C., Dec. 12, 1974.
U. S. Environmental Protection Agency Interim Permit No.
730D008C(3). Issued under Marine Protection, Research, and
Sanctuaries Act (Ocean Dumping), Washington, D. C., Dec. 12,
1974.
Sea-Level Monitoring of the Incineration of Organic Chloride
Waste by M/T Vulcanus in the Northern Gulf of Mexico, Shell
Waste Burn No. 2. Prepared by TerEco Corp., College
Station, Tex., under Contract No. 68-01-2829 with U.S.
Environmental Protection Agency, Washington, D. C., Jan. 10,
1975.
Aerial Monitoring of the Plume Generated by at-Sea Incineration
of Organochloride Wastes U. S. Environmental Protection Agency,
National Environmental Research Center, Las Vegas, Nev. ,
Feb. 5, 1975.
Badley, J. H., A. Telfer, E.M. Fredericks. At-Sea Incineration
of Shell Chemical Organic Chloride Waste, Stack Monitoring
Aboard the M/T "Vulcanus". Technical Progress Report BRC-
CORP 13-75-F. Shell Development Co., Bellaire Research
Center, Houston, Tex., 1975.
226
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing}
1. REPORT
2.
3. RECIPIENT'S ACCESSION- NO.
4. TITLE AND SUBTITLE
Disposal of Organochlorine
Wastes by Incineration At Sea
5. REPORT DATE
July 1975
Date of Preparation
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
T.A. Wastler, Carolyn K. Offutt, Charles K.
Fitzsimmons, Paul Des Rosiers
8. PERFORMING ORGANIZATION REPORT NO,
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Oil & Special Materials Control Division (WH-UU8)
Office of Water and Hazardous Materials
U.S. Environmental Protection Agency
Washington, D.C. 20h6>0
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
12. SPONSORING AGENCY NAME AND ADDRESS
Oil & Special Materials Control Division
Office of Water and Hazardous Materials
U.S. Environmental Protection Agency
Washington, D.C. 20U60
13. TYPE OF REPORT AND PERIOD COVERED
Final-Oct. 197^-Jan. 1973
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
IB.ABSTRACT : The lirst oliicially sanctioned incident ol ocean incineration in
United States occurred aboard the M/T Vulcanus in the Gulf of Mexico from October
197^ through January 1975 under an ocean dumping permit issued by the U.S.
Environmental Protection Agency under the authority of the Marine Protection,
Research, and Sanctuaries Act of 1972, as amended, to the Shell Chemical Company
in Deer Park, Texas, for ocean incineration of Organochlorine wastes.
The report describes the monitoring activities undertaken to evaluate ocean
incineration as a disposal method. A total of 16,800 metric tons of waste were
incinerated at a maximum rate of 2.5 metric tons per hour with a 1200°C' minimum and
a 1350°C average flame temperature. Stack gas emissions were mentioned for plume
dispersion characteristics and to determine combustion efficiency. The findings
indicate that more than 99-9 percent of the wastes were oxidized. Marine monitoring
surveys indicate that there were no measurable increases in concentrations of trace
metals and organochlorides in the water and marine life.
Results of the project indicate that ocean incineration could be a viable
alternative of waste disposal which should be considered along with other disposal
methods including direct ocean disposal, land disposal, and land incineration.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS C. COS AT I Field/Group
Ocean Waste Disposal
Scean Dumping .
cean Incineration
Incineration
Waste Disposal (Industrial)
Gulf of Mexico
vulcanus
Shell Chemical Company
8. DISTRIBUTION STATEMENT
Releasable to public
19. SECURITY CLASS (ThisReport/
unclassified
21. NO. OF PAGES
238
20. SECURITY CLASS (Thispage)
unclassified
22. PRICE
EPA Form 2220-1 (9-73)
227
U.S. GOVERNMENT PRINTING OFFICE: 1975- 210-810/10
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