EPA-600/2-78-087
April 1978
ENVIRONMENTAL ASSESSMENT:
AT-SEA AND LAND-BASED INCINERATION
OF ORGANOCHLORINE WASTES
by
S.F. Paige, L.B. Baboolal, H.J. Fisher,
K.H. Scheyer, A.M. Shaug, R.L Tan, and C.F. Thorne
TRW, Inc.
One Space Park
Redondo Beach, California 90278
Contract No. 68-02-2660
Program Element No. 1AB606
EPA Project Officer: Ronald A. Venezia
Industrial Environmental Research Laboratory
Office of Energy, Minerals, and Industry
Research Triangle Park, NC 27711
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, DC 20460
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PREFACE
The United States Environmental Protection Agency (EPA) is currently pre-
paring an environmental impact statement (EIS) on the proposed use of an area
in the North Atlantic as a "burn zone" for shipboard incineration activities.
This report is being submitted to EPA as a support document to assist in the
preparation of their EIS.
ii
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CONTENTS
Preface ii
Figures vi
Tables vii
Abbreviations and Symbols ix
1. Background and Summary 1
Background 1
Summary 5
2. Organochlorine Wastes, Emissions and Transport Paths ... 7
General Description of Organochlorine
Wastes and Emissions 7
Projected Transport Paths of Emission
Constituents 9
Land-Based Incineration
At-Sea Incineration
3. Land-Based Alternative 18
General Description 18
Incineration Process
Operation Parameters for Incinerators
General Description of Emissions
Monitoring Equipment
Method of Storage and Transportation
Simulation of Air Quality Changes: Land-Based
Incineration 24
Scrubber Wastewater Characterization 28
Characteristics of Slowdown from
Recirculating Scrubbers
Characteristics of Single Pass Scrubber Effluent
Handling of Scrubber Wastewater
iii
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CONTENTS (continued)
Potential for Malfunction and Accidents:
Land-Based Incineration 36
Categories of Failure Modes - General
Incineration Facility Configuration
Failure Mode Analysis
Counter-measures and Contingency Planning
Discussion of Environmental Impacts for
Land-Based Incineration 41
4. The At-Sea Alternative 45
General Description 45
Description of the M/T Vulcanus System
Simulation of Air Quality Changes for
At-Sea Incineration
Water Quality Changes Associated
With At-Sea Incineration 54
Potential for Malfunctions and Accidents: At-Sea
Incineration 60
Categories of Failure Modes - General
Incineration Vessel Configuration
Failure Mode Analysis
Countermeasures and Contingency Planning
Discussion of Environmental Impacts for
At-Sea Incineration 64
IV
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CONTENTS (continued)
Appendices
A - Derivation of the Production Rate for Organochlorine
Chemicals, and Corresponding Generation of Wastes A-l
B - Air Quality Simulation B-l
C - Calculations for Characterization of Single
Pass Scrubber Wastewater C-l
D - Development of Model to Determine Effects of
At-Sea Incineration on Ocean Water Quality D-l
E - Determination of Effective Stack Heights E-l
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FIGURES
Number Page
1 Location of proposed burn zone 4
2 Land-based incineration process 20
3 Vortex liquid waste incinerators 21
4 Flow sheet of scrubber water at a land-based incinerator .... 23
5 Liquid waste incinerator schematic 37
6 Ship headings relative to wind directions which avoided
plume impact on ship 59
7 Locations of functional processes of the M/T Vulcanus 61
APPENDICES
FIGURES
B-l. Ground level concentration as a function of downwind distance
at three effective stack heights, h. Emission rate is
6.05 kg/hr B-15
B-2. Ground level concentration as a function of downwind distance
at three wind speeds, u. Emission rate is 6.05 kg/hr B-16
0-1 Plot of HC1 as a function of x and y D-4
D-2 Isopleths for HC1 concentration (scale-linear) D-5
VI
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TABLES
Number Page
1. Estimates of National of Organic Chemical Production
and Corresponding Wastes 1
2. Definition of Destruction Efficiency Terms 11
3. Summary Analytical Data of Organochlorine Wastes
Burned at Selected Land-Based Facilities 13
4. Trace Metal Concentration in Scrubbing Solution from
a Land-Based Incineration Facility 15
5. Elemental Analysis of Organochloride Wastes (Shell
Waste) Burned At-Sea During U.S. EPA Monitored Tests 17-
6. Stack Emissions Used for Land-Based Air Quality Simulation 30
7. Results of Air Quality Simulation for Land-Based Incineration:
HC1, Trace Metals, Unburned Wastes and Particulates 31
8. Parameters Related to Scrubber Water and Waste Handled
by Two Land-Based Liquid Injection-Incinerators 33
9. Results of Scrubber Water Quality Calculations 33
10. Incineration Process Failure Mode Analysis:
Land-Based Facility 38
11. Summary of Air and Water Quality Effects Associated
with Land-Based Incineration 42
12. Analysis of Organochlorine Waste Burned At-Sea
(Shell Waste) 48
13. Elemental Analysis of Shell Waste 49
14. Emission Rates Used for At-Sea Air Quality Simulations:
HC1 and Unburned Wastes 49
15. Emissions Rates Used for At-Sea Quality Simulation:
Inorganics 50
vii
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TABLES
(continued)
16. Results of Air Quality Simulation for At-Sea
Incineration: HC1, (Jnburned Wastes, and Inorganics 51
17. Results of Air Quality Simulation for At-Sea
Incineration: Selected Trace Elements 52
18. Hydrogen Chloride (HC1) Concentrations Measured in Air
on Board the M/T Vulcanus 58
19. Incineration Process Failure Mode Analysis:
At-Sea Facilities 63
20. Summary of Major Air and Water Quality Effects
Associated with At-Sea Incineration 64
APPENDICES
TABLES
A-l. Estimates of National Organic Chemical
Production and Corresponding Wastes A-l
B-l. Emission Rates Used for Air Quality Simulation B-6
B-2. Average Wind Speeds (Meters/Second) and
Prevailing Wind Direction for Three Coastal Areas B_8
B-3. Annual Percent Frequency of Pasquill Stability
Categories for all Wind Directions and Speeds g_g
B-4. Results of Air Quality Simulation for Land-Based
Incineration: HC1, Trace Metals, Unburned Waste
and Particulates3 B-10
B-5. Results of Air Quality Simulation for At-Sea
Incineration: HC1, Unburned Wastes and Inorganics3 B_1:l
B-6. Results of Air Quality Simulation for At-Sea
Incineration: Selected Trace Elements9 B_12
D-l. The Factor (x,y) for a Range of Values of
x and y (x,y in Meters) D-3
E-l. Input Data Used in Plume Rise Calculations E-2
viii
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LIST OF ABBREVIATIONS AND SYMBOLS
x -- Ambient Concentration in Grams/Cubic Meters
C-5,6 -- Hexachlorocyclopentadiene
gm or g -- Grams
h -- Effective Stack Height
kcal -- Kilocalorie
kg -- Kilogram
km -- Kilometer
kt -- Knots
m -- Meter
o c
/ig/m Microgram/Cubic Meter (10~ grams/cubic meter)
/Jim -- Micrometer (micron, 10~ meters)
_3
mg -- Milligram (10 grams)
3
mg/m -- Milligram/Cub
m/s -- Meters/Second
_Q
ng -- Nanograms (10 grams)
n
nm Nanometers (10~ meters)
ppb -- Parts Per Billion
ppm -- Parts Per Million
Q -- Pollutant Release, Emission or Discharge Rate
a -- Standard Deviation in Plume Width in Horizontal
y Direction
a -- Standard Deviation in Plume Width in Vertical
Direction
tonnes -- Metric Tonnes = 1000 kilograms
3 -3
mg/m -- Milligram/Cubic Meter (10 grams/cubic meter)
IX
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SECTION 1
BACKGROUND AND SUMMARY
BACKGROUND
Modern technological society produces large quantities of industrial
waste. These wastes are comprised primarily of materials generated during
manufacturing processes. According to a 1973 estimate, approximately nine
million tonnes of toxic waste are produced every year within the United
States [1]. More recent estimates have ranged from 30 to 40 million tonnes
per year [2,3,4]. A sizable portion of the nation's toxic wastes are
materials produced by the organic chemical manufacturing industry [3].
Table 1 presents preliminary estimates of the production of organic chem-
icals (as defined by Standard Industrial Classification (SIC) Codes 2861,
2865 and 2869), and corresponding wastes. Values are given for the years
1977, 1983 and 1989, with breakdowns for organochlorine production and
resulting wastes. The derivation of these values is discussed in
Appendix A.
TABLE 1. ESTIMATES OF NATIONAL ORGANIC CHEMICAL PRODUCTION
AND CORRESPONDING WASTES
Total Production (in thousand tonnes)
Organic Chemicals
Organic Wastes
Organochlorines
Organochlorine Wastes
1977
93,435
2,302
13,340
440
1983
143,578
4,249
20,500
606
1989
201,254
6,354
28,730
907
Source: See Appendix A
Prior to passage of the Marine Protection, Research, and Sanctuaries Act
(MPRSA) of 1972'(Public Law 92-532), as amended (Public Law 93-254), some
of the organochlorine wastes generated in the United States were dumped
at designated ocean dumping sites under the auspices of the U.S. Army Corps
of Engineers and the U.S. Coast Guard. MPRSA required that ocean dumping be
1
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regulated under permit by the U.S. Environmental Protection Agency (EPA).
Regulations promulgated as a result of MPRSA prohibited the direct dumping
of several hazardous wastes including organochlorine wastes.
Other organochlorine waste disposal methods which have been used in
the U.S. include recycling, chemical destruction, drum burial, pumping
into sealed sites within geological formations, and land-based incinera-
tion [5,6]. U.S. chemical companies which needed to dispose of sizeable
quantities of organochlorine wastes began investigation of another disposal
alternative: at-sea incineration. This disposal method had been used
extensively for European wastes and it attracted the attention of various
U.S. companies with waste disposal problems. One claim was that at-sea
incineration was environmentally acceptable for the disposal of organo-
chlorine wastes. This claim was based on the following facts: 1) at-sea
incineration activities take place 30 to 200 miles from shore (depending
on regulations); 2) due to its high chloride concentration, seawater
offers an attractive sink for inorganic chlorides in the combustion products;
and 3) because seawater is highly buffered, it is capable of neutralizing
HC1 (one of the combustion products of organochlorine incineration) without
undergoing any change in pH.
This report considers two alternative disposal procedures which can
be effectively used for organochlorine wastes. The procedures are 1) land-
based incineration, and 2) at-sea incineration utilizing shipboard incin-
erators. The primary purpose of this report is to provide a generalized
description of the environmental impact associated with each system.
The data base for this analysis is comprised of field test results,
personal contacts with manufacturers and operators of incinerator facil-
ities, modeling and simulation, and information from selected resources
in the literature. The overall approach consisted of the following ele-
ments: 1) identification of combustion products generated by organochlorine
incineration at land-based and at-sea facilities, 2) general characteriza-
tion of the transport and fate of these materials within air, water and
land environments; and 3) identification and prediction of general envir-
onmental impacts that may result from the effects of these combustion
products.
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EPA has proposed the designation of an area in the North Alantic to
be used for at-sea incineration activities. The coordinates of the pro-
posed burn zone are given below:
Latitude Longitude
39° 40'N 72* O'W
39° O'N 72° 30'W
This locates the burn area approximately 145 km east of Capy May, New
Jersey. Figure 1 shows the position of the proposed burn zone in relation
to the northeastern coast of the United States. At-sea incineration anal-
yses in this report will be focused on this location.
Discussions concerning land-based incineration will be based primarily
on data obtained during incinerator test burns at a facility considered to
be representative of the commercial waste disposal industry.
Some limitations apply to the analysis. First, the emphasis of the
report will be liquid injection incinerators. However, the analysis
presented in this report is based primarily on environmental effects of
combustion products. Organochlorine materials having identical elemental
compositions and undergoing similar destruction efficiencies will yield
similar combustion products regardless of 1) physical state (i.e. liquid
or solid) of the initial material or 2) type of incinerator used. One
would not expect combustion production products to be exactly the same,
notable differences being these listed below:
Burning of solids may leave an ash residue and the resulting
combustion gases may have a higher particulate loading.
Atomization of liquid wastes during injection into the incin-
erator produces droplets which are likely to be much smaller
than the parcels which undergo combustion during the inciner-
ation of solid wastes. Because larger particles take longer
to burn, solid wastes may require longer retention times to
achieve the same destruction efficiency.
Secondly, the discussion of environmental impacts will not deal with
the problems encountered during the transportation of waste from the waste
generator to the disposal facility.
Time limitations have prevented a comprehensive literature survey.
In many cases, the incinerator operators contacted were reluctant to
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SCALE IN MILES
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Richmond
Fioure 1. Location of Proposed Burn Zone (Shaded Area).
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provide detailed information describing their process operation. Therefore,
there will be topics not covered, and the description of the land-based
facility will rely to some extent on field tests performed previously,
personal experience and engineering judgment.
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SUMMARY
This report provides a description of at-sea and land-based incinera-
tion systems and an assessment of corresponding environmental impacts.
Major finding of the analysis are summarized below. Statements listed
are generalizations that apply to the generic categories of land-based
and at-sea incinerator systems.
A major difference between at-sea and land-based incineration
is the pathway by which combustion products exit the facility.
For land-based facilities, the combustion products are trans-
ferred primarily to the scrubber water and this represents a
major impact route. With at-sea systems, combustion products
go directly to the atmosphere, from which they are partitioned
between air and water environments.
Major uncertainties and data gaps for the at-sea incineration
system relate to the:
- Size distribution and compostion of particulates produced.
- Need for data to better describe the ultimate fate of plume
and plume constituents during the typical "coning aloft"
pattern of plume behavior (i.e., where the plume does not
seem to touch the down).
- Extent to which HC1 in plume could add to acid rain problems.
Major uncertainties and data gaps for the land-based incineration
system relate to the extent to which:
- Solids removed from the incinerator or entrained in scrubber
water contain heavy metals and unburned wastes.
- Heavy metals and unburned wastes are dissolved in scrubber
water.
- Effects on land and groundwater quality (via leachate from
landfills) are site specific and depend on the soil charac-
teristics.
- Details on plant operations are available.
f Incineration is attractive because available technology can
attain greater than 99.9% destruction efficiency.
t The compostion of wastes being destroyed in the incinerator
must be determined. Waste compostion determines the nature
of the emissions and the resulting environmental impact.
More fail-safe and contingency plans in case of malfunction
upset, or accident have been developed for at-sea incineration
than for its land-based counterpart.
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0 In case of catastrophic or periodic malfunction accidents at
either facility, the potential for acute adverse effects on the
environment is greater at the land-based facility due to its
close proximity to population centers, and areas of environmen-
tal concern.
0 Land-based facilities utilizing alkaline scrubber water may con-
tribute additional total dissolved solids (IDS) to water resources.
Depending on the organochlorine waste incinerated, the scrubber
wastewater could have IDS values higher than seawater. For
inland areas, discharge of wastewater with IDS values approaching
or higher than seawater will have a more significant impact
because there is not an ocean nearby to serve as an appropri-
ate sink.
0 Land-based facTr'ties with HC1 recovery scrubbers may provide an
opportunity for resource recovery, depending on the purity of
HC1 produced and market demand.
0 At-sea systems can effectively dispose of organochlorine wastes
at a much faster rate than land-based facilities. If land-based
facilities utilized scrubber water in proportion to that which
would be needed if they had comparable feed rates, the scrubber
wastewater problems would increase significantly.
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SECTION 2
ORGANOCHLORINE WASTES, EMISSIONS AND TRANSPORT PATHS
GENERAL DESCRIPTION OF ORGANOCHLORINE WASTES AND EMISSIONS
Organochlorines can be generally defined as that family of synthetic
organic compounds which contain chlorine, carbon, and hydrogen. For the
purposes of this report, oxygen could also be a constituent of an organo-
chlorine, because the presence of this element would have no effect on the
nature of the combustion products produced during incineration. On the
other hand, the presence of nitrogen, sulfur, or phosphorus in combination
with the above elements would generate different types of emissions (proba-
bly N02, S0o» and PoOc, depending on combustion conditions). Therefore,
organic compounds containing nitrogen, sulfur and phosphorus will not be
considered in great detail, and only brief mention will be made of impacts
associated with the incineration of these compounds.
In addition to the major elemental constituents of organochlorine
wastes (i.e., Cl, C, H and possibly 0) other elements are expected to be
present in trace quantities. These may include metals (such as cadmium,
lead, mercury, and chromium) and various organic contaminants. However,
there are stringent controls for both at-sea and land-based incineration
of organochlorine wastes containing metals. The Intergovernmental Mari-
time Consultative Organization (IMCO) has guidelines for at-sea incinera-
tion, and the U.S. Government has regulations and permit requirements
which also apply to this type of activity [7,8]. For land-based facil-
ities, regulations promulgated as a part of the Resource Conservation
and Recovery Act (RCRA) will establish: (1) limits on the kinds of mater-
ials amenable to land-based incineration, and (2) performance standards
describing appropriate disposal procedures. Controls for both at-sea and
land-based incineration activities will have the ultimate effect of
imposing limits on the kinds and quantities of trace constituents con-
tained in organochlorine wastes to be incinerated.
Organochlorine wastes are generally produced during chemical manu-
facturing and other industrial processes. Specific categories of com-
pounds include a large number of pecticides (e.g., DDT, 2,4,5-T, aldrin,
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dieldrin, kepone, etc.) which may have been off-specification or in surplus
and a series of low molecular weight chlorinated aliphatic hydrocarbons
produced as non-salable wastes during organic synthesis reactions (e.g.,. vinyl
chloride monomer wastes). The percent chlorine content of organochlorines
is variable. Some wastes can contain as little as 10% or less chlorine,
while hexachlorocyclopentadiene (C-5,6) production wastes may contain as
much as 77% chlorine [9]. The average chlorine content of the organo-
chlorine wastes generated in 1975 was 60.6% [6].
Throughout this report, emphasis will be placed on an organochlorine
waste material generated during the production of vinyl chloride monomer
and other chemicals at Shell Oil Company's Deer Park, Texas plant. This
waste will often be referred to as "Shell waste." Emissions data are
available for at-sea incineration activities involving Shell wastes.
However, no emissions data are available for the incineration of this
waste at land-based facilities. Therefore, the analysis concerning land-
based incineration will be based on data obtained during the incineration
of other liquid organochlorine wastes at these facilities. Emissions data
were selected to be representative of the emissions expected to be pro-
duced during the incineration of Shell wastes.
Combustion of a simple organochlorine is described by:
CHC1CC12 + 202 -2 C02 + HC1 + C12
Water is also a combustion product. The above is a theoretical chemical re-
action. In practice, controlling temperature and other combustion parameters
results in limiting chlorine production to negligible amounts.
Thus, under optimal combustion conditions, the major products result-
ing from organochlorine combustion are COo, HC1 and HUO. Trace inorganics
present in the initial wastes will also be found in the combustion products.
The amount of CO and unburned waste will depend on the completeness of
combustion.
Combustion efficiency (CE) and destruction efficiency (DE) are two
parameters often used to describe an incinerator's effectiveness in dis-
oosing of organic wastes. The CE value for a certain burn is based on
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measurements of CO and CC^ concentrations of the hot gases leaving
the combustion chamber. The expression which is usually used to make this
determination is
CC09 " CCO
CE (%) = - £ - x 100
where
C = measured concentration of carbon dioxide
CpQ = measured concentration of carbon monoxide
Carbon monoxide and carbon dioxide concentrations must be expressed in
the same units.
Destruction efficiency is basically a measure of the difference
between the amount of wastes being fed to the incinerator and the amount
of waste contained in the exiting gas stream. A variety of sampling,
analysis, and calculation procedures can be used to determine the destruc-
tion efficiency of a particular burn. Table 2 lists four alternative
methods of determining destruction efficiency. These methods are among
those used for recent at-sea incineration tests [10]. If combustion is
very complete, waste material will often be undetectable within final stack
emissions. In such a situation, the detection limit of the analysis tech-
nique can be used to provide an upper bound on the amount of material which
could be in the gas stream.
PROJECTED PATHS OF EMISSION CONSTITUENT TRANSPORT
In general, the efficient combustion of organochlorine generates the
following categories of combustion products:
Hydrogen chloride (proportional to chlorine in waste).
t Unburned waste components in trace amounts.
Particulates which could contain salts of trace metals, and/or
adsorbed unburned wastes.
t Small amounts of clinker or ash-like materials which do not leave
with the stack gases, but form as deposits on the incinerator
burner or interior walls.
10
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Other innocuous gases (Ct^ and HUO).
§ Carbon monoxide.
The pathway taken by a constituent as it exits the incinerator varies with
the type of incinerator, nature of the constituent, and operating
practices.
Land-Based Incineration
For the most part, the analysis presented in this section (and gen-
erally throughout the report) will be based primarily on information
obtained during monitored incineration runs at a land-based facility
deemed to be representative of modern commercial disposal operations [11].
Emissions data are not available for the incineration of Shell wastes at
this facility. However, selected data obtained during the incineration
of other materials at this facility, and other materials at other facil-
ities were used to provide an indication of the behavior of emission
constituents.
Contaminants will be transported from the land-based incineration
system as constituents of the flue gas, the scrubber water effluent, and
solid residue.
Table 3 gives the composition of organochlorine wastes as reported
in various studies of land-based incineration facilities. It can be
expected that prior to entry into the scrubbing system over 99.9% of the
chlorine in the organochlorine waste will be converted to hydrogen
chloride. Depending on the destruction efficiency of the incinerator,
not more than 0.05% of the original mass of chlorine will be present in
the form of unburned organochlorine wastes, and as reported (no C12 de-
tected, 0.33 ppm detection limit [9]) it is expected that negligible
amounts of the original mass of chlorine will appear as C1? in stack
gases.
Even though the destruction efficiency of the incinerator is not 100%,
test results from several land-based systems indicated that no organic
wastes were found in the scrubbing water, and none was detected in the
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TABLE 3. SUMMARY ANALYTICAL DATA FOR ORGANOCHLORINE
WASTES BURNED AT SELECTED LAND-BASED FACILITIES
Elemental Analysis
Element
Trace Elements
Element
Chromi urn
Copper
Manganese
Lead
Arsenic
Mercury
Barium
Cobalt
Selenium
Vanadium
Aluminum
Zinc
Fluorine
Iron
Silicon
Calcium
Sodium
Composition, %
Carbon
Hydrogen
Nitrogen
Sulfur
Chlorine
20.76
0.67
0.008
0.019
23.28
- 54.80
- 2.80
- 8.92a
- 0.22
- 76.47
Concentration, ppm
12 - 25
1.9 - 13
0.33 - 28
7 - 800 (ppb)
1 - 600 (ppb)
10 (ppb)
36 - 5000 (ppb)
42 (ppb)
3 - 600 (ppb)
4 - 600 (ppb)
10
16
800 (ppb)
28
28
28
28
Source: This table is a summary of data presented in References 9, 10,
11, 12 & 13.
This relatively high nitrogen composition reflects inclusion of nitro-
chlorobenzene wastes burned at the facility considered to be representa-
tive of commercial incineration. If this compound were not included in
the table, nitrogen levels would range up to a maximum of 0.37%.
13
-------
stack gases. This indicates that the overall destruction efficiency of
the system is better than 99.999% (via calculations based on detection
limits of analysis method).
Various trace metals in the organochlorine wastes will be transported
from the system in all of the previously mentioned modes. The greatest
concentration of these contaminants will appear in the solids that result
from combustion. Generally, solid residues produced during incineration
of materials such as the Shell wastes will leave the incinerator as parti-
culates in hot combustion gases. Most of these particulates will be
removed during the scrubbing process and become either suspended or dis-
solved solids within the scrubber wastewater. Suspended solids contained
in scrubber wastewater will end up as a sludge which will accumulate in
holding tanks or other types of impoundments such as settling or evapora-
tion ponds. Other precipitates may be formed within scrubber wastewater
due to intentional or unintentional pH changes and other chemical reactions.
Particulate material which dissolves in the scrubber water will contri-
bute to the total dissolved solids (TDS) content of this wastewater stream.
Additional TDS contributions are due to 1) absorption of HC1, 2) use of
alkaline materials in scrubber water to facilitate HC1 removal via acid-
base neutralization reactions, and 3) salts which result from these
reactions.
In some cases, a solid residue will form on tips of the burners or
walls of the incinerator. These materials (called clinkers) are not gen-
erally produced in large amounts, but analyses obtained at one land-based
installation show that they contain trace metals and high percentages of
carbon (88-99%) [9].
Some of the trace metals may be emitted from the stack either as con-
stituents of particulate emissions or in some other form. These results
show trace metals such as lead to be present in stack gases in concen-
trations of 3 to 5 pg/m3 [12].
The overall quality of the scrubber water can range from 1800 to
50,000 mg/liter of total dissolved solids. Generally speaking, 1300 to
11,000 mg/liter are composed of chlorides. The remainder will be made up
of sodium, various inorganics and trace metals. Tests at one facility
14
-------
indicated that the concentration of heavy metal is less than 10 ppm. This
is the maximum allowable concentration for wastewater entering the sewers
which .serve thjs facility. Table 4 gives the breakdown of trace metals found
in the scrubber wastewater [9].
The hygroscopic contaminants, such as NaCl and any heavy metal salts,
upon release to the atmosphere could act as cloud condensation nuclei and
be washed from the atmosphere by rain or be removed by normal fallout.
The other chlorides present will undergo the types of chemical reaction
previously outlined.
The solid residue, clinker, and residue from scrubbing water settling
tanks or evaporation ponds could contain several potentially hazardous
materials, for example, the concentration of lead can range from 10 to 50mg
per kg of residue. In order to insure the least adverse effects from such
elements, which have an accumulative effect on animal life, they should be
properly disposed of in accordance with federal guidelines mandated by the
Resource Conservation and Recovery Act of 1976 (RCRA).
At-Sea Incineration
The analysis presented here will be based primarily on data obtained
during the March 1977 cruise of the M/T Vulcanus.
TABLE 4. TRACE METAL CONCENTRATIONS IN SCRUBBING SOLUTION
FROM A LAND-BASED INCINERATION FACILITY
Element Concentration, ppm
Copper 0.07 - 0.23
Chromium 0.01 - 0.38
Lead 0.02 - 0.54
Zinc 0.12 - 0.74
Manganese 0.06 - 0.59
Cobalt 0.05 - 0.12
Antimony 0.18 - 0.24
Source: Reference [9].
15
-------
Table 5 gives the elemental composition of organochlorine wastes as
reported in various studies conducted on wastes incinerated at sea.
Because there is no scrubbing system, combustion products will be trans-
ported from the system as constituents of stack gas or of any solid resi-
due formed during combustion. Observers of the at-sea incineration process
have indicated that the small amount of clinker formed is knocked loose
and dropped back into the combustion zone [14]- Therefore, it will be
assumed that 100% of the matter entering the combustion system will exit
via the stack gases and be released to the atmosphere. Stack test results
indicate that less than 0.005% of the organic wastes are present in the
stack gas. Destruction efficiency is, therefore, over 99.995%.
More than 99.9% of the chlorine in the waste will be converted to
hydrogen chloride and emitted to the atmosphere. Although the fate of the
gaseous hydrogen chloride once it exits the stack is not totally under-
stood, the surface of the ocean has a pH of 8.3 and is an excellent sink
for gaseous hydrogen chloride [15].
Unburned organochlorine wastes will be present in stack gas only in
amounts which are well below detection limits. Photochemical reactions
may cause this waste to be broken down into its hydrocarbon constituents
and chlorine in the atmosphere. These hydrocarbons and chlorine will be
removed from the atmosphere by rain and gas-to-liquid interactions (either
physical or chemical) at the ocean's surface, or, if they reach land, they
may be removed by interaction with soil or be taken up by vegetation in
gas exchange [17,18]. However, it should be stressed that at all points
in this process, the hydrocarbons and chlorine from unburned organo-
chlorines will be in concentrations well below detection limits.
During the March 1977 Vulcanus burn of Shell wastes, solid residues
accumulated on burner heads. Frequent routine cleaning of the burners
was necessary to remove these deposits. Samples of the residues were
analyzed, and results showed the presence of all major Shell waste consti-
tuents (many at the 0.1 g/kg level). Other materials were found including
organics (some chlorinated) considered to be polymeric tars [10]. It is
16
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TABLE 5. ELEMENTAL ANALYSIS OF ORGANOCHLORINE WASTES (SHELL WASTE)
BURNED AT SEA DURING U.S. EPA MONITORED TESTS
Elemental Analysis
Element
Carbon
Hydrogen
Nitrogen
Sulfur
Chlorine
Trace Elements
Element
Cu
Cr
Ni
Zn
Pb
Cd
As
Hg
Si
P
T1
Ca
Br
Composition Range, %
29.0 - 30.01
4.0 - 4.17
0 - 0.012
0 - 0.009
62.6 - 63.5
Concentration, ppm
0.51 - 1.1
0.1 - 0.33
0.25 - 0.30
0.14 - 0.30
0.05 - 0.06
0.001 - 0.0014
<0.01
0.001 - 0.002
<500
50 - 500
50 - 500
<25
Trace
Source: This table is a summary of data presented in References 10, 16
and 17.
17
-------
not known exactly how the total mass of the burner head residues compares
with the mass of wastes burned, but it is probable that burner residues
represent a small percentage.
Trace metals present in the organochlorine wastes will be released
into the atmosphere in quantities equal to the amount present in the waste
feed stock. As mentioned in a previous section, regulatory controls will
allow at-sea incineration of only those wastes with acceptable trace
metal levels. Various trace elements, particularly heavy metals found in
the organochlorine waste, will most likely exit the stack in the form of
salts as part of the particulate loading. It has been reported that only
random traces of these elements were found in samples taken of ocean water,
and only random slight increases in the concentration of metals such as
copper were noted [17]. Therefore, it can be assumed that trace metals
will be well dispersed throughout the plume and will be removed from the
atmosphere by washing (e.g., by rain) or by fallout.
18
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SECTION 3
LAND-BASED ALTERNATIVE
GENERAL DESCRIPTION
This section describes the land-based incineration industry. The
description is based on data obtained from incinerator manufacturers [19],
companies which incinerate various wastes [20,21,22,23,24], and the results
of field testing performed by TRW as a part of their program "Destroying
Chemical Wastes in Commercial Scale Incinerators," EPA Contract Number 68-
01-2966 [9,11,12,13]. Some of the information that will be presented does
not apply specifically to the incineration of organochlorine wastes, but
this information does provide a representative picture of the general state
of the art.
Incineration Process
Land-based incineration of heavily chlorinated materials requires two
basic components, the combustion chamber and the scrubber. Figure 2 shows
these two components in relation to other supporting elements of land-based
incineration facilities. There are many variations of the process in current
use. If the heating value of the organochlorine waste is below 3000 kcal/kg,
it is mixed with auxiliary fuel either prior to or during injection with com-
bustion air through a burner into the combustion chamber. At this point the
mixture is ignited and the organic content of the waste is destroyed. Typically,
liquid incinerators use throat mixing burners where the liquid waste is atomized
to increase the surface area available for thermal destruction. One example
of a throat mixing burner is the vortex type burner shown in Figure 3. The
vortex burner operates by feeding combustion air into the chamber tangentially
to the flow, thus producing a vortex. This process tends to increase turbulence
and prolongs residence times, thereby improving completeness of combustion.
Combustion products of heavily chlorinated organochlorine wastes are
usually passed through a scrubber after leaving the combustion chamber.
Such scrubbers are designed to remove primarily particulates and HC1, but
other combustion products may also be abstracted (e.q., NO , C19, soluble
f\ L.
organics, etc). The most common type of scrubber system consists of a
venturi scrubber followed by a packed tower or a separator tank with a
19
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PRESSURE FOR TYERES
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AIR TUYERES,
TUYERE AIR SHELL
AND PLENUM
EFFLUENT TO SCRUBBERS
AND STACK
REFRACTORY WALL
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RING
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(FORCED DRAFT)
TUYERE AIR SHELL
BAFFLE SHELL
Figure 3. Vortex liquid waste incinerators,
Source: Reference [35].
21
-------
demister. Figure 4 shows the system at one disposal facility [9]. In the
venturi scrubber, the combustion gases are passed through a venturi tube
which constricts the flow, and thereby causes high gas velocities. At the
point of constriction, low pressure water and in some cases caustic are
added to enhance removal of the HC1 formed during combustion. There is
very short contact time in the throat of the venturi. However, the
extreme turbulence in the venturi promotes intimate contact, predominantly
by impaction.
The venturi scrubbing process involves either a single pass of the
scrubbing fluid or recirculation of the scrubbing fluid. If recirculation
is used, scrubber fluid is recirculated through the venturi scrubber until
the total dissolved solids (TDS) content reaches approximately 3% [22].
When this occurs, a portion of the scrubbing fluid is removed (blowdown)
and new scrubbing fluid is added to make up for the fluid lost as blowdown.
The blowdown from the single pass or recirculation scrubbing systems is
neutralized (as needed) before delivery to on-site wastewater treatment
processes, on-site storage facilities (e.g., evaporation ponds), or dis-
pensing to the municipal sewer or a receiving water body.
Alternative types of scrubber systems have been designed to recover
HC1 produced during organochlorine incineration. Such systems can produce
commercial grade hydrochloric acid streams with concentrations ranging
between 20% and 60% HC1 [22]. These systems utilize aqueous solutions to
absorb HC1 from the combustion chamber effluent gas stream, and the result-
ing solution is concentrated via water extraction procedures. Residual
HC1 that may be left in the remaining combustion gas stream can be removed
by passing this stream through an alkaline neutralization tower, or by
using conventional gas scrubbing procedures.
With regards to scrubber systems, the emphasis of this report will be
directed towards scrubbers which remove HC1 primarily by neutralization
reactions. HC1 recovery systems were mentioned to highlight the fact that
they represent a viable alternative to conventional scrubbing techniques.
Such systems may assume greater importance and use in response to the
implementation of RCRA.
22
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23
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Operation Parameters for Incinerators
As a result of a review of available literature, contact with incinera-
tor manufacturers, and field sampling experience, a variety of parameters
have been identified which are often used in describing incinerators and
their operation. These parameters include the incinerator's waste feed
rate, design heat release rate, residence time of materials in the combus-
tion zone, temperatures achieved, destruction and/or combustion efficiency
achieved, and frequency of incinerator use. It is reasonable to expect
that the values of these parameters wil.l vary with different incinerators
located at different disposal facilities. Therefore, the information pre-
sented below regarding these parameters represents ranges of values which
may be observed at various industrial installations and commercial disposal
facilities.
An incinerator's capacity for disposing of wastes is generally
described in terms of its waste feed rate and design heat release rate.
Units for expressing waste feed rate depend on the type of waste being
incinerated. For incinerators which accept solid wastes, feed rates are
listed in terms of pounds per hour or kilograms per hour. If the wastes
are in liquid form, units of gallons per hour or liters per hour are used.
Volumetric rates can be converted to mass feed rates if the density of
the waste is know. For wastes with high heat contents, the waste feed
rate may also be limited by the design heat release rate.
Because the emphasis of this report is directed at incinerators
capable of burning liquid organochlorine waste, this was the main type of
incinerator considered in our survey. Feed rates for incinerators in the
facilities surveyed ranged from 80 liters per hour (20 gallons per hour)
to 2840 liters per hour (750 gallons per hour). The incinerators involved
in a recent TRW Program ("Destroying Chemical Wastes in Commercial Scale
Incinerators11) had heat release capabilities which ranged from 15 million
kcal/hour (59 million Btu/hour) to 28 million kcal/hour (110 million Btu/
hour).
For the incinerators surveyed, residence times varied from 0.111 to
12 seconds [12] and temperatures achieved ranged from 870°C to 1378°C
(1500°F to 2500°F).
24
-------
Frequency of incinerator use depends on the amount of wastes available
for incineration, the rate at which the waste is incinerated, and periodic
shutdown of the plant as required by normal maintenance. Some commercial
waste disposal facilities receive enough waste to keep their incinerators
operating 24 hours per day, 7 days per week [11]. At other facilities,
incinerators may be operated only as long as there is waste available
to burn.
Some wastes have heat contents which are too low to support combustion
at temperatures required for adequate destruction. In these situations,
such wastes are blended with other wastes with higher heat contents, or
supplemented with fuel oil. These procedures are performed prior to injec-
tion or concurrent to the feeding of the waste into the incinerator.
General Description of Emissions
Available data were used to develop a general description of the
nature and quantities of emissions that have been measured at facilities
incinerating organochlorine wastes. Three types of emissions considered
are stack gases, scrubber wastewater and solid residues.
Stack Gases
Reports studied [9, 11, 12, 13] show that the waste destruction effi-
ciencies reached in liquid incineration processes are better than 99.99%.
In only one case was the demonstration efficiency less than 99.999%.
Waste constituents were not detected in combustion zone gases or in stack
gases being vented to the atmosphere. The particulates found in the stack
gases were in concentrations generally less than 100 milligrams per cubic
meter (mg/m ) [12]. At a facility considered to be typical of those
capable of accepting organochlorine wastes, the measured particulate load-
o
ing varied between 14 and 16 mg/m [11].
Scrubber Wastewater
As mentioned previously, scrubbing processes for organochlorine incin-
eration systems are designed to remove combustion products which may have
adverse impacts if emitted directly to the atmosphere. Constituents in
this category are HC1, particulates, and any trace amounts of unburned
waste that may be present.
25
-------
If water is the scrubbing fluid, the wastewater effluent will contain
suspended particulates, dissolved HC1 (i.e., hydrochloric acid), and other
soluble constituents which may be present (e.g., trace quantities of
organics and waste constituents that may be soluble). If alkaline scrub-
bing solutions are used, the HC1 will undergo neutralization reactions to
produce additional water and salts (either NaCl or CaC^ depending on
whether NaOH or Ca(OH)p was used in the scrubbing solution). Because
alkaline materials are often used in excess, residual amounts of these
substances will be present. The wastewater will also contain suspended
particulates and any soluble combustion products. Available analysis data
of scrubber wastewater from incinerators burning organochlorine wastes
showed no measurable amount of these wastes [9,11]. Furthermore, the con-
centration of trace metals was in the ppm range prior to on-site treatment.
In general, total dissolved solids (IDS) concentrations usually ranged
from 500 to 50,000 mg/liter.
Solid Residues of Combustion
The generation of solid residues from the burning of Shell wastes is
not expected to be a significant problem. Observations made during at-sea
incineration of Shell wastes indicate solid deposits were formed on the
tips of the burners and sides of incinerator walls [14]. However, it was
estimated that the amounts of solid residues formed were small in relation
to the total mass of combustion products [14]. Furthermore, data obtained
during the land-based incineration of nitrochlorobenzene (a liquid waste)
indicate no ash formation, and apparently any solids produced leave the in
incinerator as particulates entrained in the gas stream or as suspended
solids in scrubber wastewater. Data are not available concerning gas stream
participate loading or suspended solids in scrubber water resulting from the
burning of Shell wastes. Analysis of solid residues from the incineration
of hexachlorocyclopentadiene (C-5,6) wastes showed mostly carbon (89-98%)
and no measureable quantities of the waste [9].
Monitoring Equipment
Instrumentation capability of most incineration companies studied
show measurements are made for all process parameters, including tempera-
tures, pressures end flow rates. However, regulations currently in effect
for facilities burning a specific organochlorine material (polychlorinated
26
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biphenyls, PCBs, 40 CFR part 761) and regulations soon to be established as a
part of RCRA include stipulations which will require additional continual and
intermittent monitoring equipment [26,27]. PCB regulations were promulgated
as a result of the Federal Toxic Substances Control Act (Public Law 94-469).
These regulations stipulate that during initial use of an incinerator, and
after any modification, the following constituents have to be monitored: 02,
CO, C09, NO , HC1, organic chlorides, PCB chemical substances and total parti-
£- /\
culates [26]. Continuous monitoring is required of 02, CO and C02- Other
performance standards are stipulated regarding temperature, residence time,
combustion efficiency, maximum allowable stack emission (when incinerating non-
liquid PCB wastes), and automatic cutoff systems for below optimal operation
conditions [26].
RCRA was enacted to control the manner in which hazardous waste dis-
posal facilities are operated, thus the incineration of organochlorine
wastes will be subject to RCRA's regulations. The preliminary draft of
RCRA regulations requires not only monitoring of various incinerator
parameters (e.g., temperature, concentrations of 02, COo and 0, etc.),
but there are also requirements for the monitoring of ambient air (at the
facility's perimeter), and scrubber water [27].
Methods of Storage and Transportation of Wastes and Residues
The manner in which a waste is handled on-site is dependent on plant
design, plant storage facilities, and heat content of the fuel. Wastes
received for incineration at a disposal facility are either incinerated
directly (in some cases via pumping directly from the tank truck), or
stored until they can be handled more conveniently. A plant operator may
want to store some of the incoming wastes with higher heating values to
possibly blend with other wastes which have heating values too low to
support combustion alone.
Development of acceptable procedures for both storing and handling hazard-
ous wastes has been mandated by RCRA and therefore, these processes will be re-
gulated. The preliminary draft of RCRA regulations requires that wastes be
stored in a manner which precludes discharge. There are also requirements for
spill prevention and diking of storage areas in order to mitigate the effects
of spills which may occur.
27
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SIMULATION OF AIR QUALITY CHANGES: LAND-BASED INCINERATION
Gaussian diffusion and transport models were used to simulate the air
quality changes expected as a result of land-based incineration activities.
A detailed description of the simulation analysis is presented in Appendix B.
Air quality simulations were based on emissions and other data obtained
at an incineration facility considered to be representative of a modern U.S.
commercial disposal facility capable of accepting organochlorine wastes. The
incineration system at this facility consists of a liquid injection burner
and a rotary kiln both of which feed a common afterburner [11], While the
first of these burners is for liquids only, the rotary kiln is capable of
burning liquids, sludges, and solids fed as fiber packs. The unit operates
24 hours per day, seven days per week, and it can achieve temperatures in
excess of 1090°C (2000°F) and residence times between 2 and 3 seconds [11].
Combustion gases pass through the afterburner, a venturi scrubber system, and
finally out a 30 meter (98 foot) stack to the atmosphere. The scrubber fluid
is a 32% Ca(OH)2 solution.
Under absolute optimal conditions, the feed rate to the two burners in
the incinerator can reach 2840 liters per hour (750 gallons per hour). How-
ever, the typical average feed rate (which also takes into account normal
maintenance downtime) is estimated to be about 2270 liters per hour (600
gallons per hour).
Data concerning the plant's operation and physical dimensions were used
to derive effective stack height, an important input to air quality simula-
tion models. These parameters included physical stack height (30 meters),
stack diameter (2 meters), and operation data obtained during the incineration
of nitrochlorobenzene wastes (an average stack velocity of 8.7 meters/sec, and
temperature of exiting stack gases during waste incineration of 60°C). The
derived effective stack height was 96.5 meters. The details of this calcula-
tion are presented in Appendix E.
The meterological inputs which were used in the air quality simulations
were also considered to be representative of conditions at the hypothetical
New Jersey site. Specific parameters used were a wind speed of 4.0 meters/
second and a D Stability Category. As is common in air quality modeling, it
28
-------
was assumed that pollutants remain airborne with no identifiable sinks at
the ground level.
Air quality simulations were performed for four parameters: HC1, parti-
culates, trace metals (Ti, Ni, and Cr) and unburned wastes. The emission
estimates for the first three of these were obtained during the incineration
of nitrochlorobenzene (NCB) wastes at the selected representative facility.
The elemental composition of this compound is listed below:
Weight Percent
Carbon 46.14
Hydrogen 2.80
Nitrogen 8.92
Chlorine 23.28
Sulfur 0.02
Due to the presence of significant quantities of nitrogen, NCB would not quali-
fy as an organochlorine according to the definition previously given to this
term. However, the NCB burn was the only source of available data that was
potentially applicable to this analysis. It was also felt that the levels of
selected emission constituents, (excluding those due to the nitrogen content),
would generally be representative of organochlorine wastes at a modern disposal
facility. For example, the HC1 removal achieved by the scrubber at this facil-
ity (99.5% to 99.8%) is about the same as that required in draft RCRA regula-
tions (>99%) [11,27]. Furthermore, tests at another facility indicate that
even better removal efficiencies are obtainable [9]. These tests showed that
HC1 was undetectable in stack gases produced during the incineration of an
organochlorine waste with a 62% chlorine content [9].
The emission rates for the unburned waste were determined artifically
and based on the destruction efficiency achieved during the NCB burn. NCB
o
constituents were not detected in the exiting combustion gas (0.05 mg/m was
the detection level); therefore, the calculated destruction efficiency is
>99.999%. For the air simulation analysis, it was assumed that 0.01% of the
waste feed was emitted as unburned wastes. The feed rate would be approxi-
mately 3 tonnes/hour, assuming that waste alone was being fed.
29
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The emissions used in the air quality simulation are listed in Table 6.
The results of the simulation are presented in Table 7. These results re-
present ground level concentrations expected to occur along the plume center-
line. The data show that maximum concentrations are generally reached 3000
meters downwind of the source. The relatively high effective stack height
generally precludes ground level effects from the plume within the first 300
to 400 meters from the source. In general, all of the simulated concentra-
o
tions are low (none reach the vg/m level) and would not be detectable by
common analytical techniques. The maximum HC1 concentration listed is equi-
valent to a value of 0.0004 ppm.
TABLE 6. STACK EMISSIONS USED FOR LAND-BASED AIR QUALITY SIMULATION
(All rates in kg/hr)
HC1
0.895
Parti culates
1.03
Trace Metals, Each
0.00069
Unburned Wastes
0.3
Notes: 1. Emission rates for HC1 , particulates, trace metals, and unburned
wastes are all based on a dry volumetric flow rate of 68877 m3/hr.
Concentrations of HC1, particulate and trace metals in the stack
gases are 13 mg/m3, 15 mg/m3 and 0.01 mg/m^, respectively.
2. Trace metals include Ti, Ni and Cr, each at the listed concentra-
tion level. These concentrations are based on analysis of the
waste and not on stack gas measurements.
3. Emission estimates for unburned wastes were based on a 99.99%
destruction efficiency and a hypothetical waste feed rate of 3
tonnes/hr considered to be the average feed rate for Shell waste
at one of the largest U.S. incinerators.
30
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TABLE 7. RESULTS OF AIR QUALITY SIMULATION FOR LAND-BASED INCINERATION
HC1, TRACE METALS, UNBURNED WASTE AND PARTICULATES3
Distance Downwind
GROUND LEVEL CONCENTRATION
>m Facility
Meters)
100
200
300
400
500
600
700
800
900
1000
2000
3000
4000
5000
6000
7000
8000
9000
10000
20000
30000
HC1
(ng/m3)
.00
.00
.00
.00
.07
2.88
9.20
31.03
57.47
148.08
477.06
536.61
489.52
425.73
367.13
317.79
277.36
244.06
216.52
90.42
51.90
Trace Metals
(Ti.NI &Cr,ea)
(ng/m3)
.00
.00
.00
.00
.00
.00
.01
.02
.04
.11
.37
.41
.38
.33
.28
.25
.21
.19
.17
.07
.04
Unburned
Waste
(ng/m3)
.00
.00
.00
.00
.02
.96
3.09
10.40
19.26
49.63
159.91
179.87
164.09
142.70
123.06
106.52
92.97
81.81
72.58
30.31
17.40
Participates
(ng/m3)
.00
.00
.00
.00
.08
3.31
10.59
35.71
66.14
170.41
549.02
617.55
563.36
489.95
422.51
365.72
319.19
280.87
249.18
104.05
59.73
Simulation parameters were: effective stack height = 96.5 meters, and
wind speed = 4.0 meters/second.
31
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SCRUBBER WATER CHARACTERIZATION
In this portion of the report, two different waste streams will be
characterized. The streams are 1) the effluent resulting from single pass
scrubbing; and 2) blowdown from recirculating scrubbers. No data were
available to evaluate the composition of the wastewater effluence from HC1
recovery processes discussed previously. However, it can be expected that
the HC1 recovery processes will have much lower TDS concentrations than
systems which do not recovery HC1 because a large proportion of the dis-
solved ions would be removed during recovery of the acid.
Analysis of the scrubber wastewater for undestroyed waste (organic
content) showed no organic constituents present above detection levels
which ranged from 0.1 to 0.5 ppm [11]. Detection levels range due to
various types of organic analyses performed (i.e., gas chromatography,
infrared spectrophotometry and low resolution mass spectrometry), inter-
fering species in effluent analyzed and the organic component of the sample
being detected. Analysis data that applied specifically to suspended
solids in the scrubber water were not available.
Characteristics of Blowdown from Recirculating Scrubbers
Blowdown from recirculation systems occurs when the salinity reaches
approximately 3 percent. This relates to a TDS value of 30,000 milligrams
per liter [22]. The blowdown rate is variable, depending on the amount of
chlorine in the liquid incinerated and on the liquid feed rate.
Characteristics of Single-Pass Scrubber Effluent
The characteristics of single-pass scrubber effluents are highly
variable, depending on the chlorine content of the liquid incinerated, the
liquid feed rates, the scrubber solution feed rates and the efficiency of
the scrubber. Because single-pass systems have so many variables, it is
not possible to obtain a normal or average TDS concentration. However, it
is possible to estimate the magnitude of TDS concentration. This has been
done by using two sets of data shown in Tables 8 and 9. The data were
picked because their operating parameters produced two extremes in scrubber
water quality, as shown in Table 9. Generally, scrubber wastewaters will
contain TDS concentrations less than 40,000 milligrams per liter.
32
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TABLE 8. SCRUBBER WATER AND WASTE PARAMETERS FOR TWO LAND-BASED LIQUID
INJECTION INCINERATORS
Waste Incinerated
Hexachlorocyclo-
pentadiene3
Nitrochloro-
benzeneb
Fresh Scrubber Water Feed
Rate (liters/min)
Caustic Solution Feed Rate
(liters/min)
Type of Solution Used
Liquid Waste Feed Rate
(kilograms/hr)
Elemental Chlorine Content
of the Waste
60
23.8
12% NaOH
52.8
77%
3200
8.5
32% Ca(OH)2
1893
10%
?Source: Reference 9
Source: Reference 11
TABLE 9. RESULTS OF SCRUBBER WATER QUALITY CALCULATIONS
Waste Incinerated
Hexachlorocyclo-
pentadiene
Nitrochloro-
benzene
Chlorides (milligrams/liter)
Calcium (milligrams/liter)
Sodium (milligrams/liter)
Total Dissolved Solids
(milligrams/liter)
11,000
25,670
36,670
1,300
530
1,830
Calculations are presented in Appendix C.
33
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Handling of Scrubber Wastewater
Scrubbers used at facilities which incinerate organochlorine materials
are designed to remove HC1 and particulates that may be generated as combus-
tion products. Therefore, treatment normally includes clarification (to re-
move particulates), neutralization (to take care of any residual acid or base
that may still be present), and dilution (to help control IDS levels). Parti-
culates which are insoluble in the scrubber fluid become suspended solids in
the scrubber wastewater. If the particulates dissolve in the scrubber fluid,
they contribute to the wastewater's IDS level. Suspended solids in scrubber
wastewater generally present little, if any, problems because their concen-
trations are usually less than 5 mg/liter. Suspended solids are usually re-
moved by on-site settling ponds.
Wastewater with either high or low pH levels must be neutralized prior
to final discharge (to a municipal sewer, or receiving stream). This is
usually accomplished by adding either acid or base.
The high concentration of total dissolved solids (due to NaCl, CaCl2
and in some cases the excess NaOH not used to neutralize HC1) must be reduced.
This is usually accomplished by piping scrubber effluents to in-plant treat-
ment systems or by diluting with other plant process streams and storing in a
holding pond or lagoon.
In geographical locations with high evapotranspiration rates, solar
evaporation could be used as a method for disposing of scrubber wastewater.
For such a method to be considered environmentally acceptable, the scrubber
wastewater would have to be devoid of potentially volatile materials which are
hazardous. The ponds used for evaporation would have to be periodically
drained, and the accumulated sludge removed.
Information contained in a draft position paper concerning RCRA indicates
that EPA regulatory officials may consider residue resulting from the incinera-
tion of hazardous wastes as also being hazardous [28]. Moreover, preliminary
drafts of RCRA's regulations state that one of the general guidelines of RCRA
is that waste disposal activities should be performed in a manner which pre-
cludes discharges to the environment [27]. If these concepts and rules are
implemented within the regulatory controls required by RCRA, significant
34
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restrictions will be imposed on the manner in which scrubber wastewater is
handled. Three stipulations from the draft RCRA regulations indicate that
such restrictions may indeed be imposed. These stipulations are (1) scrubber
wastewater must be impounded prior to discharge or disposal, (2) releases
must occur through a point source, and (3) discharge is to take place in a
manner which allows for composite sampling for compliance testing. Thus,
scrubber wastewater discharged to municipal sewers may be routinely sampled to
insure that it doesn't contain unacceptable levels of unburned organochlorine
wastes or toxic elements. Similarly, the sludges, or other sediments collect-
ed from settling ponds, evaporation ponds, or other types of lagoons may also
contain unburned wastes or toxic trace elements (abstracted from the combus-
tion gases as particulates, or formed as precipitates following chemical
reactions occurring in the pond). These sludges will have to be disposed of
in a manner consistent with the objectives of RCRA.
35
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POTENTIAL FOR MALFUNCTION AND ACCIDENTS: LAND-BASED INCINERATORS
Categories of Failure Modes - General
Incineration process failure events, for the purpose of environmental
consideration, are critial when degraded performance or accidental release
of hazardous materials occur. An accidental shutdown, without any polluting
consequence, is a failure event that results only in an increased cost of
operation.
It is well known that industrial equipment malfunctions are only
partially caused by mechanical or material failures. The other chief con-
tributor to faulty operations comes from people problems, either through
operator errors and negligence, vandalism, or deliberate violation of
operating policies and legal constraints. The possibility of any of
these malfunction causes occuring has been included in the subsequent
analyses.
Incineration Facility Configuration
The functional diagram of an incineration faciltiy, shown in Figure 5
for a land-based operation, indicates that most components of the system
are in a "series" configuration; each series component must be adequately
functioning to avoid degraded performance. A few process components may
be in a "parallel" configuration allowing a switchover to another component
when problems are detected with the on-stream component. Waste feed line
filters will usually have two or more units in parallel, and even feed
pumps may be "spared" (duplicated) if plant processing rates are determined
to be especially critical. Multiple burners in an incinerator are not
considered to be redundant components because the loss of any burner will
result in degraded performance.
Failure Mode Analysis
A detailed breakdown of potential malfunctions and accidents at each
process element is shown in Table 10. The likelihood of any of these
malfunctions occuring is very difficult to estimate in most cases, except
for some estimates of industrial equipment on-stream time that have been
developed from substantial statistical reports [29, 30, 31]. The likelihood
36
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I
o
S-
o
p
to
S_
-------
TABLE 10. INCINERATION PROCESS FAILURE MODE ANALYSIS: LAND-BASED FACILITY
PROCESS
ELEMENT FAILURE CAUSES
- Overfill on level
interlock failure
- Leakage due to pump
CONSEQUENCE
Waste spill
Small waste spill
seal, valve packing
material corrosion,
etc.
Inclusion of unauthor-
ized waste by subversion
of quality control procedures
Leakage due to pump seal,
material corrosion, etc.
- Filter plugging
Nozzle plugging (low
flow detection)
Atomization air loss on
air blower failure
Burner flame loss (flameout)
due to loss of fuel pressure,
loss of primary combustion
air, coking, or water slug
in feed
- Improper fuel rate
- Improper air/fuel ratio
- Injection into a cool com-
bustion zone on startup
- Scrubbing solution circulat-
ing pump fails
- Weak scrubbing solution
- Pump, valve, or tank leaks
- Chemical addition pump fails
- Pump, valve, or tank leaks
Possible incineration
difficulties
Small waste spill
None if filters switched
on high pump discharge
pressure measurement
Temporary shutdown
Failure to combust, toxic
vapor discharge, liquid
accumulation
Transient toxic vapor dis-
charge prior to automatic
shutdown (due to flame
loss detection or low
combustion temperature).
(A water layer in the tank
can be isolated by conduc-
tivity measurement and
interlocked with the waste
feed pump.)
Excess waste product in dis-
charae.
Inefficient combustion
Inefficient combustion .
High HC1 concentration in
stack gases
Not much change; even water
scrubbing is very effective
for HC1 removal
Scrubbing solution spill (no
consequence if water is used
for scrubbing)
Low pH discharge
Small wastewater spill
38
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of vandalism, in particular, is difficult to estimate because vandalism
at industrial facilities is very infrequent when normal security pre-
cautions are taken. When security is lax, however, the results of
vandalism can be very serious. A recent example of this is the van-
dalism of waste storage tanks at a North Carolina facility, in which the
contents of the tanks were drained into the city water supply. Furthermore,
unattended equipment in the field may be subject to theft, rifle shootings,
and other damage possibilities.
In addition to potential problems listed in Table 10, there are a
variety of operation practices which may also result in adverse environ-
mental impacts, or damage incidents. An example would include the
use of unlined ponds as a storage facility for wastewater streams which
could contain constituents of the waste. Soluble constituents may be
from solids in the wastewater and find their way to groundwater.
Pond overflow could occur during heavy rainstorms and result fn the
introduction of waste constituents into the surface water streams,
Countermeasures and Contigency Planning
The largest hazardous spill possibility at a land-based facility
exists in the storage tank and transfer area. This entire area should be
paved, diked, and drained to a catch basin with pumped return to the
storage tanks. Absorbent material should be ready to use for cleanup
in the event of a leak or failure in other parts of the system. Each
facility must be well-regulated and have contingency plans specifying
requirements and fail safe devices to minimize the effects of a failure.
The extent,to which any of the potential problems identified in prior
discussions become real world problems.will be significantly influenced
by regulations expected to be established as a result of RCRA. The
legislation and its regulations were initiated partly in response to
problems and damage incidents resulting from accidents and improper
disposal practices. Thus, it is reasonable to expect regulations
ultimately promulgated pursuant to RCRA will be directed at preventing
situations which caused problems in the past. Draft regulations which
respond to RCRA's Section 3004 ("Standards Applicable to Owners and Opera-
tors of Hazardous Waste Treatment, Storage and Disposal Facilities" provide
39
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specific mandatory provisions and procedural guidelines for the manner
in which hazardous waste incinerators, and other types of disposal facilities
should be operated. The aim of these provisions and guidelines is to
preclude the kinds of incidents which could lead to adverse effects on
public health and/or the environment. In addition, the draft regulations
contain sections which cover "Emergency Procedures and Contigency Plans"
and "Security". The requirements within these sections deal specifically
with potential problem areas discussed previously. If new problem areas
arise which are not covered by promulgated RCRA regulations, provisions
within RCRA and its regulations allow for the establishment of new
regulations and/or permit requirements.
40
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DISCUSSION OF ENVIRONMENTAL IMPACTS FOR LAND-BASED INCINERATION
Table 11 summarizes the major air and water impacts that may result
from land-based incineration. Generally, all concentrations appear to be
low with respect to those necessary to cause immediate adverse impacts.
The maximum HC1 concentration is 536.6 nanograms/cubic meter or 0.0004 ppm.
This is approximately four orders of magnitude less than the TLV of 5 ppm.
This concentration is also lower than the sensory threshold levels reported
in the literature, and also below any known effect level [32]. The most
stringent of the National Ambient Air Quality Standards (NAAQS) for parti-
culates (60 fig/m - annual geometric mean) is an order of magnitude larger
than the maximum predicted particulate concentration. It should also be
stressed that tests showed no emission of unburned wastes from the stack,
and the emissions rate used in the model was based on a 99.99% DE, while
the calculated DE was 99.999%. Therefore, the predicted concentrations of
unburned wastes are conservative.
Water quality impacts will be reflected in the need for additional
downstream treatment and in possible adverse effects of heavy metals and
high TDS. These adverse effects include direct impacts on treatment plant
processes (e.g., process upsets and/or receiving water bodies if these
materials were not removed by the treatment process) and indirect effects
of any trace metals or unburned waste that might be associated with the
sludges resulting from treatment.
All effluent streams (stack gas, spent scrubbing solution, sludge,
clinker, bottom ash, and treated scrubbing solution) have the potential of
adversely affecting the soil. Impacts on the soil can be manifested in
several ways, ranging from no adverse effects to contamination of the soil,
vegetation, and groundwater.
The combustion products which are entrained in the stack will even-
tually he removed from the atmosphere, as previously discussed, and will
come irit.o contact with the soil or surface water. The effects and inter-
actions of these contaminants with surface water have been previously
discussal, and their interaction with the soil will be addressed in the
discussion of residue handling.
41
-------
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Clinker and any bottom ash formed will contain primarily inorganic and
carbonaceous compounds. Less than 3% of the total weight of carbonaceous
compounds will be trace compounds, including heavy metals. Because of the
presence of these heavy metals, these solids should be disposed of in
landfills approved for hazardous wastes.
The spent scrubbing solution, if sent to an on-site settling tank or
pond, will generate two streams. One stream will be the clear liquid
effluent which may be suitable for sending to municipal treatment facil-
ities. The other stream will be sludge or solid residue from the settling
process, which, because it will contain heavy metals and perhaps some
organics, should be disposed of in an approved landfill.
The spent scrubber solution may not be treated on-site, but rather
disposed of directly into the municipal sewage system. The results of this
will be that the sludges generated by the municipal treatment process will
contain heavy metal contaminants which will be landfilled and, depending
on the destruction efficiency of the incinerator, the liquid effluents
could potentially contain small amounts of organochlorine wastes. However,
if DEs are kept at the levels achieved on test burns, (it is expected that
regulatory controls will insure that is the case), no unburned wastes will
be expected in the scrubber wastewater.
The effects of the contaminants once deposited onto or into the soil
vary as a function of the type and porosity of the soil, the weather condi-
tions and the mobility of the individual contaminants [33]. For example,
cyanide (CN~) and selenium (HSeO^" and Se03=) are relatively mobile
in the soil, while metal cations, such as iron (Fe++), zinc (Zn++), lead
(Pb ), copper (Cu ) and beryllium (Be++) are less mobile in the soil [33].
The effects of the hydrocarbon-associated sediment are a function of
the depth of the sedimentation layers. Hydrocarbons in surface sediments
near outfalls will closely resemble the original suspended solids. Once
incorporated into the sediment, microbial decay will occur, leaving cyclo-
paraffin-. and other aromatics to predominate at depths close to 50 centi-
meters | !4],
43
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The magnitude of any of these effects cannot be determined accurately
using available data. If the concentration of heavy metals and unburned
wastes in waste scrubber water is found to be too high, then additional
treatment may be required. If these high concentrations are found in
wastewater treatment sludges, then the chosen disposal method for the
solids will have to insure that air and water resources are not
contaminated.
RCRA required that the Administrator of the Environmental Protection
Agency promulgate standards applicable to hazardous treament, storage,
and disposal facilities. These standards include requirements for operating
methods, and practices, location and design of facilities, and contingency
plans for minimizing unanticipated damage from treatment, storage, or
disposal of hazardous waste. These regulations, along with the existing
PCB regulations, will have a major effect on insuring that the incineration
of organochlorine wastes at land-based facilities will proceed in an
environmentally acceptable manner.
44
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SECTION 4
AT-SEA ALTERNATIVE
GENERAL DESCRIPTION
Recently, at-sea incineration has been carried out in three ships, the
Matthias II, the Matthias III and the M/T Vulcanus. Matthias II is a
vessel of 1000 deadweight tons and operated primarily in Europe.
Matthias III is a modified tanker of 19,300 dead weight tons and was built
to burn both liquids and solids. However, it was only used for a short time
and is currently out of service because it did not perform satisfactorily.
The M/T Vulcanus burns only liquid wastes and is a double-hull,
double-bottom vessel that meets all applicable requirements of the Inter-
governmental Maritime Consultative Organization (IMCO) concerning transport
of dangerous cargo by tanker. Before being permitted to operate in
U.S. waters, it was modified to meet requirements of the U.S. Coast Guard.
Originally a cargo ship, it was converted to its present use in 1972.
Its size--an overall length of 102 meters, a beam of 14.4 meters, and a
maximum draft of 7.4 metersenables it to operate worldwide. It is
also able to operate in rough weather. The crew numbers 18, 12 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. The
waste is carried in 15 tanks, the walls and bottoms of which form the
inner hull and bottom. The space between the two hulls is used for ballast.
Ballast tanks may be filled with seawater and emptied independently as
required to trim and balance the ship. The tanks range in size from
115 to 574 cubic meters, with an overall waste capacity of 3503 cubic
meters. Tanks are filled through a manifold on deck using a dockside
loading pump. During normal operation, the waste tanks can be discharged
only through the incinerator feed system. There is, however, provision for
discharging the cargo into the ocean if an appropriate emergency arises.
45
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Waste is burned on the M/T Vulcanus in two identical refractory lined
furnaces located at the stern of the ship. Each incinerator consists of
two main sections, a combustion chamber and a stack, through which the
combustion gases pass sequentially. Air for the combustion is supplied
by large fixed speed blowers rated at 90,000 cubic meters/hour capacity
for each incinerator. Liquid wastes are fed to the incinerator by means
of electrically driven pumps. There are no air pollution control devices
on the incinerators, but there is an emergency automatic waste shutoff
system which prohibits the flow of waste to the burners if the furnace
temperature drops below a preselected level.
SIMULATION OF AIR QUALITY CHANGES FOR AT-SEA INCINERATION
Gaussian diffusion and transport models were used to simulate the air
quality changes expected as a result of at-sea incineration activities. A
detailed description of the simulation analysis is presented in Appendix B.
As explained in Appendix B, simulations were based on a set of meteoro-
logical and other conditions considered to be generally representative of
those likely to occur under real world circumstances. The calculation of
effective stack height (an important input parameter for diffusion models)
was based on data obtained on the M/T Vulcanus during the March 1977 burn.
The wind speed and atmospheric stability category used were selected after
review of measured and statistical data for shore locations in the general
vicinity of the proposed North Atlantic burn zone. (Measured wind speed data
are not available for the proposed off-shore site, therefore, data from the
nearest shore-based meteorological stations were used instead.)
Wind speed (i.e., speed of the diffusing layer) is an input parameter
which significantly influences predicted downwind pollutant concentrations.
(Generally, increasing wing speed decreased downwind concentration.) When
an incinerator ship is moving, the relative wind speed, as measured at the
stack, may be greater than the speed of the diffusing layer. However, rela-
tive wind speed was not used as an input to the diffusion modeling performed
here. This is because the materials emitted from the stack will assume the
average speed of the diffusing layer shortly after they are discharged to the
atmosphere. One result of this is that downwind concentrations near the
source may be lower (due to the additional mechanical turbulence from the
46
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ship's velocity) than estimated in this study. Downwind concentrations
will also tend to be decreased by the fact that a moving source distributes
its emissions into a larger volume of air per unit time (i.e., if the
relative wind speed is greater than that of the diffusing layer).
The diffusion model employed in the air quality simulation assumed
perfect reflectivity and conservation of pollutants in the diffusing layer.
That is, it is assumed that the chemical species emitted remain airborne
and are not abstracted from the atmosphere by either chemical or physical
processes. There are a variety of technical arguments against this
assumption. However, there is no technique available which takes
pollutant-marine boundry layer interactions into account for the type
of air quality simulation being performed here.
The emissions rate used for the air quality simulation is based
on test data from the March 1977 Gulf of Mexico cruise of the M/T
Vulcanus. The wastes burned were produced during the manufacture of
ally! chloride, epichlorohydrin, dichloroethane, and vinyl chloride by
the Shell Chemical Company. They were stored at the Shell Company's
Deer Park, Texas plant, near Houston. Composition of the waste is
given in Table 12. Elemental analysis of a typical organochlorine
waste is shown in Table 13. This waste shown was incinerated in the
Gulf of Mexico during two burns in 1974, and is similar in composition
to the waste incinerated during the March 1977 burn.
Emission rates used for the at-sea incineration are shown in
Tables 14 and 15. These estimates were made assuming feed rates and
emissions characteristics of the M/T Vulcanus furnaces. Emissions
data for particulates were not obtained during the March 1977 burn.
However, data were available describing waste compostion and emissions
of various inorganic constituents of the waste. These data were con-
verted to mass emission rates and summed in order to derive an estimate
of exported particulate emission.
47
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TABLE 12. ANALYSIS OF ORGANOCHLORINE WASTE BURNED AT-SEA ("SHELL WASTE")
Physical Characteristics:
Loss on ignition
Gross Thermal Content
Specific Gravity
99.8%
6,950 Btu/lb
1.28
Elemental Analysis:
Element
Carbon
Hydrogen
Nitrogen
Sulfur
Halogens as chlorine
Composition,
30.01
4.17
0.012
0.009
62.60
Other Minor
Constituents
Element
Si
P
T1
Ca
Br
Organic Composition:
Concentration, ppm
>500
50 - 500
50 - 500
<25
Trace
Compound
1,2,3-Trichloropropane
Dichloropropenes (3)
Dichloropropane
Trichloroethane
1,2-Dichloroethane
1,1-Dichloroethane
Dichloropropanol
Chloropropene (Allyl Chloride)
Chloropropanes (2)
Chloroethane
Trichloromethane (Chloroform)
Tetrachlorobutenes (2)
Acrolein (Propenal)
Chlorobenzene
Bis(2-Chloroethylether)
Unidentified Chloro-and
Oxychloro-Compounds
Water
Est. Cone.
(% w/w)
18
11
18
12
10
0.9
6.2
5.7
5.8
0.6
0.5
2.4
0.2
3.3
1.9
3
0.5
Source: Reference [10]
48
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TABLE 13. ELEMENTAL ANALYSIS OF SHELL WASTE
Carbon
Hydrogen
Oxygen
Chlorine
Copper
Chromium
Nickel
Zinc
Lead
Cadmium
Arsenic
Mercury
BURN I
% by weight
29
4
4
63
(parts per million)
0.51
0.33
0.25
0.14
0.05
0.0014
<0.01
<0.001
BURN II
29.3
4.1
3.7
63.5
1.1
0.1
0.3
0.3
0.06
0.001
<0.01
<0.002
Source: Reference 17
TABLE 14. EMISSION RATES USED FOR AT-SEA AIR QUALITY SIMULATION : HC1
AND UNBURNED WASTES
Emissions Rate
Average Waste Feed Rate cS"truct!on
3 Efficiencies
HC1 Unburned Wastes
22 tonnes/hr (22X106gm/hr) 99.99% (max 14.16X106gm/hr 2.2X103gm/hr
observed)
99.96% (min 14.16X106gm/hr 8.8X103gm/hr
observed)
Notes: 1) Data are for both furnaces of the M/T Vulcanus.
2) HC1 emission rate assumes a 62.6% chlorine content in the
waste, and a volumetric flow rate of 8700 Nm3/hr of HC1 is dis-
charged from both stacks.
49
-------
The "summed inorganics" column of Table 15 presents the results of
this derivation. It should be noted that these results compare favorable
with laboratory analysis data indicated 0.2% of a Shell waste sample
remained as residue following ignition and combustion.
Air quality simulation results for at-sea incineration activities are
presented in Tables 16 and 17. The listed concentrations correspond to
the following set of conditions: an effective stack height of 125.5 meters,
a wind speed of 4.0 meters/second, and a D (neutral) stability category.
Under these conditions, maximum ground-level concentrations for plume
constituents are predicted to occur 4000 meters downwind from the source.
The predicted concentration for HC1 never reach the threshold limit
value (TLV) of 5 mg/m considered to be safe for 8-hour occupational
exposure. Maximum expected concentration for HC1 is 4.4 mg/m . Maximum
concentrations predicted for all other constituents vary from a high
2
of 2.4 ng/m (for unburned wastes, assuming the minimum measured DE) to
a low of 31 nanograms/m (for arsenic and cobalt, each).
TABLE 15. EMISSION RATES USED FOR AT-SEA AIR QUALITY SIMULATION:
INORGANICS
(All units in kg/hr)
Summed
Low
53
Inorganics
High
72
Specific Elemental Constituents
Cu/Zn
0.7
As/Co
0.1
Pb/Ti
0.4
Ni
2
Cr
4
F
1
Notes: 1) Data are for both furnaces of the M/T Vulcanus
2) Data on the concentration ranges of inorganics in the wastes
and in stack emissions were collected and converted to mass
emission rates. These rates were summed for all inorganics,
and are considered to represent estimates of expected parti-
culate emissions for the at-sea incineration of Shell wastes.
i) When two elements are listed, the noted emission rates are for
each constituent.
50
-------
TABLE 16. RESULTS OF AIR QUALITY SIMULATION FOR AT-SEA INCINERATION:
HC1, UNBURNED WASTES AND INORGANICS.a /
Distance Down-
wind From Ship
(Meters)
100
200
300
400
500
600
700
800
900
1000
2000
3000
4000
5000
6000
7000
8000
9000
10000
20000
30000
GROUND LEVEL CONCENTRATION
HC1
(yg/m3)
.00
.00
.00
.00
.00
.10
.84
8.09
25.43
144.67
2082.66
2849.86
4422.80
4389.32
4116.79
3777.38
3438.65
3124.50
2843.01
1318.93
781.14
Unburned Wastes
(ug/m3)
99.96% DEb
.00
.00
.00
.00
.00
.06
0.00
0.01
0.02
0.09
1.29
2.39
2.75
2.73
2.56
2.35
2.14
1.94
1.77
0.82
0.49
99.99% DE&
.00
.00
.00
.00
.00
.00
.00
.00
.00
.02
.32
.60
.69
.68
.64
.59
.53
.49
.44
.20
.12
Inorganics
(ug/m3)
High
.00
.00
.00
.00
.00
.00
.00
.04
.13
.74
10.59
19.58
22.49
22.32
20.93
19.21
17.48
15.89
14.46
6.71
3.97
Low
.00
.00
.00
.00
.00
.00
.00
.03
.10
.54
7.80
14.41
16.55
16.43
15.41
14.14
12.87
11.69
10.64
4.94
2.92
Simulation parameters were: effective stack height = 125.5 meters, wind
speed = 4.0 meters/seconds, and stability
category = D (neutral).
5DE= Den ruction efficiency.
51
-------
TABLE 17. RESULTS OF AIR QUALITY SIMULATION FOR AT-SEA INCINERATION-
SELECTED TRACE ELEMENTSa
Ground Level Concentration
Downwind Distance
From Ship (Meters) p
(ng/m3) (ng/m3) (ng/m3)
100 .00 .00 .00
200 .00 .00 .00
300 .00 .00 .00
400 .00 .00 .00
500 .00 .00 .00
600 .01 .01 .00
700 .06 .04 .02
800 .57 .40 .23
900 1.80 1.26 .72
1000 10.22 7.15 4.09
2000 147.08 102.96 58.83
3000 271.08 190.32 108.75
4000 312.34 218.64 124.94
5000 309.98 216.99 123.99
6900 290.73 203.51 116.29
7000 266.76 186.73 106.71
8000 242.84 169.99 97.14
9000 220.66 154.46 88.26
10000 200.78 140.54 80.31
20000 93.14 65.20 37.26
30000 55.17 38.62 22.07
Simulation parameters were: effective stack height = 125.5 meters,
wind sp
-------
TABLE 17. RESULTS OF AIR QUALITY SIMULATION FOR AT-SEA INCINERATION
(continued) SELECTED TRACE ELEMENTS3
Downwind Distance
From Ship (Meters)
100
200
300
400
500
600
700
800
900
1000
2000
3000
4000
5000
6000
7000
8000
9000
10000
20000
30000
Simulation parameters were: effective stack height - 125.5 meters
wind speed = 4.0 metprs/second, and stability category = D (neutral).
As/Co
(ng/m3)
0.00
0.00
0.00
0.00
0.00
0.00
0.00
.06
.18
1.02
14.71
27.19
31.24
31.00
29.07
26.68
24.28
22.06
20.08
9.32
5.52
Ground Level Concentration
Cr
(ng/m3)
0.00
0.00
0.00
0.00
0.00
.03
.24
2.28
7.18
40.87
588.32
1087,53
1249.38
1239.92
1162.93
1067.06
971.37
882.63
803.11
372.58
220.66
Ni
(ng/m3)
0.00
0.00
0.00
0.00
0.00
.01
.12
1.14
3.59
20.43
294.16
543.77
624.69
619.96
581.47
533.53
485.68
441.31
401.56
186.29
110.33
53
-------
WATER QUALITY CHANGES ASSOCIATED WITH AT-SEA INCINERATION
Parameters affecting the impact of at-sea incineration of organo-
chlorine wastes on the ocean environment are listed below:
Completeness of combustion and destruction
Feed rate of organochlorine wastes
Waste composition
Plume behavior
Products of combustion (i.e., HC1 and small amounts of unburned waste
and inorganics that may be present) can reach the ocean only via the plume.
The plume model which has been developed describes the behavior of a typi-
cal plume from a source such as the M/T Vulcanus.
The composition of the emissions which form the plume reflect the
composition of the waste. The concentration of materials in the plume is
dependent on the waste feed rate, the amount of air available to the com-
bustion process, overall destruction efficiency, and the atmospheric condi-
tions which are found over the burn area.
Atmospheric conditions over the ocean are generally stable so that the
plume behavior is often consistent and can be reasonably predicted by a
model. It is generally agreed that under stable conditions the plume tends
to expand regularly and remain above the surface of the ocean for up to
60 km from the source. Such a situation is designated "coning aloft."
However, as a result of direct observations during at-sea incinera-
tions in the North Sea, the Gulf of Mexico, and the South Pacific, addi-
tional parameters have been found to be important in plume behavior. These
include the wind speed (relative to the speed of the ship) and the attitude
of the ship with respect to the wind direction. These parameters exert
effects on the plume which appear to be due to the turbulence or aero-
dynamic downwash produced by the superstructure of the ship. The result
is impingement by the plume on the ship or on the ocean near the ship.
54
-------
In the plume behavior model used in this discussion, HC1 produced
during the combustion of the organochlorine waste is used as a "tracer" for
the plume. It should be understood that the plume contains other gases,
principally hUO and COo, with minor amounts of NO , CO, unburned waste,
and salts of trace metallic constituents present in the waste.
Under the conditions of at-sea incineration used in this discussion,
the weight ratio of HC1 to unburned waste varies from 1200:1 (DE = 99.96%)
to 6400:1 (DE = 99.99%). Whatever unburned waste enters the ocean from
the plume, therefore, can be estimated from the HC1 content of the plume.
On the other hand, the concentration of inorganic material in the plume is
directly proportional to the amount in the original waste, and is not
affected by destruction efficiency. It is, however, affected by the
amount of combustion air and, of course, by the behavior of the plume
itself.
The model used to estimate expected seawater concentrations of plume
constituents released during at-sea incineration is presented in Appen-
dix D. Illustrative examples using the model are also presented in
Appendix D. It should be noted that the model is conservative in that it
assumes that 100% of the emitted plume constituents dissolve in a specified
body of ocean water. Under real-world conditions, the "coning aloft" mode
of plume behavior is more typical. Therefore, a sizable portion of the
plume constituents will remain airborne for significant distances downwind.
These constituents would not interact with the ocean water in the near
vicinity to the source, and if interaction does take place downwind,
the concentration of the constituent would be at much decreased levels.
The illustrative examples presented in Appendix D show that, assuming a
mixing depth of 20 meters (in accordance with the initial mixing criteria
for ocean dumping regulations [7] ), the seawater concentration for unburned
waste is expected to be 92 X 10 ppb. The corresponding concentration for
HC1 would be 0.197 ppm. This calculated concentration neglects the fact
that ocean water is a highly buffered, slightly alkaline fluid, and there-
fore, would rapidly neutralize HC1 contributed by the plume. Consequently,
an overall HC1 concentration increase of 0.2 ppm would not be detected,
via a pH change in seawater, and an 0.2 ppm increase in chlorine ion would be
negligible compared with the 19,000 ppm chloride background of the ocean.
55
-------
Furthermore, for a constituent that was in the waste at a concentration
of 1000 ppm (0.1%), the resulting seawater concentration would be 0.39 ppb.
(Analysis of waste similar to that incinerated during the March burn shows
that copper was the most abundant trace metal, and the highest concentration
measured in the waste was 1.1 ppm, three orders of magnitude smaller
than the 1000 ppm used in the above calculation.) Thus, based on the model
and the general composition of the wastes burned in the Gulf of Mexico, the
seawater quality changes that can be attributed to at-sea incineration
activities are on the order of fractions of ppb.
The intensity of the effect that at-sea incineration would have on
ocean water quality is significantly influenced by plume behavior. From
plume dynamics, one can draw conclusions about plume behavior at various
ship attitudes. In the burn zone, it is often necessary for the ship
to maneuver so as to remain within the prescribed boundaries, or to drive
in a given direction with respect to the wind in order to avoid plume
impingement on the decks. Furthermore, drifitng broadside to the wind is
sometimes desirable when the weather is appropriate, because it saves
fuel and conserves the ship's position within the burn zone.
Three basic attitudes of the ship have been considered. These are:
1) Ship driving directly into the wind
wind
T
i
2) Ship drifting broadside to the wind
4wind
3) Ship driving at right angles to the wind
« wind
56
-------
Experience has shown that these three sets of conditions can affect
the concentrations in the plume, and may even force the plume down onto
the ocean or onto the ship.
The three basic attitudes of the ship are arranged below in order of
decreasing severity of impact on the water quality. The effects differ
slightly depending on whether plume touchdown occurs close to or far from
the ship. For plume touchdowns close to the ship, water quality impact
severity is in the following decreasing order:
Drifting broadside
Driving directly into wind
Moving at 90° to wind
For plume touchdown far from the ship, water quality impact severity assumes
the following decreasing order:
Driving directly into wind or drifting broadside (equal severity)
t Moving at 90° to wind
Although the best defined conditions are those of heading directly into the
wind, there is enough evidence to validate the above generalizaitons.
During the at-sea incineration of organochlorine wastes by the M/T
Vulcanus in the Gulf of Mexico [10], and more recently, in the Pacific [35]
some experiments in plume control were undertaken. It was found that a
ship's attitude closer than 50° to the wind resulted in the plume impinge-
ment, while taking the wind more directly toward the port or starboard
beam moved the plume off the ship and onto the ocean.
Results are summarized in Table 18. Data were taken with a Drager
apparatus, using a standard HC1 measurement tube. From the table, a plot
was made (Figure 6) which was used successfully by the personnel of the
M/T Vulcanus to alter the ship's speed and direction so as to avoid plume.
impingement on the deck.
57
-------
TABLE 18. HYDROGEN CHLORIDE (HC1) IN AIR ON BOARD M/T VULCANUS
DATE
7-14-77
7-15-77
7-16-77
7-17-77
7-18-77
.
7-19-77
7-20-77
220
7-21-77
7-22-77
1800
7-23-77
TIME
1600
2000
0800
1000
0800
1600
0940
1600
1020
1020
2030
2040
2400
1000
1010
1400
1410
0800
2200
0800
2000
0800
1800
0800
1800
1810
1820
1830
1840
1850
1900
RELATIVE
LOCATION HUMIDITY
%
Port, Comb Deck
Port, Main Deck
Port, Comb. Deck
Port, Comb Deck
Port, Comb Deck
Comb. Rm Foward
Comb. Rm Rear
Port, Main Deck
Port, Comb Deck
Port. Main Deck
Comb. Room
Fan tall
Fantall
Fan tall
Fantall
Fantall
Fantall
Fantall
Port, Main Deck
Port, Main Deck
Port, Comb Deck
Port, Comb Deck
Port, Boat Deck
Port, Boat Deck
Port, Comb Deck
Starboard,
Comb Deck
Starboard,
Comb Deck
Fantall
Starboard,
Comb Deck
Starboard.
Comb Deck
Starboard,
Comb Deck
Starboard,
Comb Deck
84
80
88
84
88
84
84
88
80
82
82
84
84
84
82
82
78
78
86
88
86
82
84
84
84
84
84
84
84
84
84
84
SHIP
HEADING
340°
340°
360°
005°
348°
350°
350°
360°
360°
360°
360°
150°
160°
160°
045°
035°
040°
030°
350°
360°
350°
345°
330°
350°
005°
140°
150°
150°
155°
150°
150°
150°
WIND DIR.
AND FORCE
000°-8 m/s
060°-10 m/s
100°-12 m/s
100° -10 m/s
075° -8 m/s
060° -3 m/s
060° -8 m/s
065°-10 m/s
070° -9 m/s
090°-11 to
20 m/s
090°-11 to
20 m/s
105°-12 m/s
106°- 12 m/s
100°- 12 m/s
090°-16 m/s
090°-16 m/s
080°-12 m/s
080°-12 m/s
080°-9 m/s
085° -9 m/s
075° -8 m/s
055°-9 m/s
050°-7 m/s
060°-8 m/s
095° -8 m/s
080° -6 m/s
080° -6 m/s
080° -6 m/s
080° -6 m/s
080° -6 m/s
080°-6/m/s
080° -6 m/s
TEMP
°C/°F
27.2/81
26.7/80
26.7/80
26.7/80
26.1/79
26.7/80
26.7/80
26.7/80
27.2/81
28.3/63
28.3/83
26.7/80
26.7/80
26.1/79
27.2/81
27.2/81
27.5/81.5
27.5/81.5
26.7/80
26.7/80
26.7/80
26.9/80.5
26.7/80
26.7/80
26.7/80
26.7/80
26.7/80
26.7/80
26.7/80
26.7/80
26.7/80
26.7/80
BARO-
METER
(mb)
1012.2
1012.2
1012.5
1012.5
1014.5
1013.8
1013.8
1014.8
1013.0
1014.0
1014.0
1014.5
1014.5
1014.5
1014.0
1014.0
1014.0
1014.0
1015.3
1014.9
1015.0
1013.9
1014.5
1013.0
1014.3
1012.4
1012.4
1012.4
1012.4
1012.4
1012.4
1012.4
CONC.
HC1
(ppm)
0
0
2.0
0
0
0
0
0
0
0.5
0.5-
1.0
2.0
0
0
3.0
0
2.0
0
0
0
0
0
0
0
0
10.0
2.0
0
4.0
0
0
0
NOTES
Drifting
Drifting
Drifting
Drifting
Drifting
Drifting
Drifting
Drifting
Drifting
Drifting
Drifting
40 RPM
40 RPM
40 RPM
40 RPM
40 RPM
40 RPM
40 RPM
Drifting
Drifting
Drifting
Drifting
Drifting.,
Drifting
Drifting
103 RPM
103 RPM
103 RPM
103 RPH
75 RPH
75 RPM
75 RPM
58
-------
X
JS
co
Q
W
W
CO
2
o
M
H
M
Q
Z
O
CJ
O
CM
Q
W
CO
Q P^
a o
M Pi
Es a.
4J
O
O)
r-
-o
TJ
t- Q.
CD O
i- 4->
4-> O
(O A3
r- Q.
to CU
CDE
C 3
-5 "o.
10
O) T3
^: cu
-o
O-'r-
r- O
^ >
CO
-------
POTENTIAL FOR MALFUNCTIONS AND ACCIDENTS: AT-SEA INCINERATION
Categories of Failure Modes - General
From an environmental viewpoint, incineration equipment failure
events are critical when degraded performance or accidental release
of hazardous materials occur. An accidental shutdown, without any pollut-
ing consequence, is a failure event that only results in an increased cost
of operation.
It is well-known that industrial equipment malfunctions are only
partially caused by mechanical or material failures. The other chief con-
tributor to faulty operations comes from people problems, either through
operator errors and negligence, vandalism, or deliberate violation or
operating policies and legal constraints. The possibility of any of these
malfunction causes occurring has been included in the subsequent analyses.
Incineration Vessel Configuration
A functional schematic of the M/T Vulcanus at-sea incineration vessel
is shown in Figure 7. Essentially, an incineration ship is a double-hulled
vessel with under deck tankage forward for waste cargo; living, eating,
sleeping, communications and ship navigation areas amidships; and a
combustion area with associated controls and components (waste homogenizers,
burners, automatic waste shutoff) at the stern. The pumps for the waste
are located amidships below decks and beneath the living quarters; and the
engine room is usually aft of the pump room and below decks. On upper
deck space, above the living quarters and between the bridge and the
incinerators are the blowers which supply the combustion air to the
burners.
The waste handling and combustion operations are thus in-line func-
tional processes, and, with the combustion air blower system, form the
three principal unit operations of the at-sea incineration system.
60
-------
o
V.
ct
o
o
s:
=>
CO
O
OJ
0)
-------
Failure Mode Analysis
Potential malfunctions and accidents are listed in Table 19. Estimates
of the probability of these malfunctions occurring are subjective, except in
the cases where statistical records of industrial equipment downtimes or
fail rates are available [29,30,31].
Vandalism on an incineration ship is considered unlikely because the well-
being of the crew is so closely tied to performance and safety. Moreover, op-
portunities and access to the operating equipment are not possible because of
the confined nature of an incineration vessel.
Countermeasures and Contingency Planning
The greatest possibility of spills during an at-sea incineration opera-
tion is during loading. Hatches are open, samples are being taken, and
exposed flex lines are under pressure. An additional source of contamination
is the bilgewater associated with the room containing the pumps used for mov-
ing the organochlorine waste to the incinerator and between storage tanks.
There are typically occasional leaks from these pump seals. Small,
but detectable -amounts of the cargo wastes eventually find their way to bilge.
Bilges should not be pumped into channels, at dock side or at sea. This
would be a procedural violation. Provision must be made to dispose of the
bilge, possibly through the incinerator, where it can be burned with fuel.
'\
i
If flameout occurs as the result of a slug of noncombustible material
(e.g., water) entering the waste feed lines and passing through one or more
burners, subsequent incoming waste will be vaporized. Vaporization will
occur due to the latent heat in the Incinerator. This vapor will be emitted
directly to the atmosphere. To prevent this failure mode, a positive and
rapid waste feed shutoff system must be available. Such a system or device
should rely on direct sensing of the burner flames (ultraviolet or infrared
detectors) rather than secondary measurements which may have an inherent lag
before response to a flameout.
62
-------
TABLE 19 . INCINERATION PROCESS FAILURE MODE ANALYSIS
PROCESS
ELEMENT
FAILURE CAUSES
CONSEQUENCE
Tank
Filling
Waste Transfer
thru Pump &
Filter
Waste Injection
to Incinerator
Combustion
Atmosphere
- Overfill on level
interlock failure
- Leakage due to pump
seal, valve packing
material corrosion,
etc.
- Inclusion of unauthor-
ized waste by subversion
of quality control procedures
- Leakage due to pump seal,
material corrosion, etc.
- Deliberate bypassing of
incinerator (ocean
operations).
- Filter plugging
Nozzle plugging (low
flow detection)
Atomization air loss on
air blower failure
Burner flame loss (flameout)
due to fuel loss of pressure,
loss of primary combustion,
air, coking, or water slug
iii feeU
Improper fuel rate
Improper air/fuel ratio
Injection into a cool com-
bustion zone on start-up
Waste spill
Small waste spill
Possible incineration
difficulties
Small waste spill
Waste spill
None if filters switched
on high pump discharge
pressure measurement
Temporary shut-down
Failure to combust, toxic
vapor discharge, liquid
accumulation
Transient toxic vapor dis-
charge prior to automatic
shutdown on flame loss
detection (or lower combus-
tion temperature). (A water
layer in the tank can be
isolated by conductivity
measurements and interlocked
with the waste feed pump)
Excess waste product in dis-
charge
Inefficient combustion
Inefficient combustion
63
-------
DISCUSSION OF ENVIRONMENTAL IMPACTS: AT-SEA INCINERATION
Table 20 summarizes the major air and water quality effects that
can be expected to result from at-sea incineration.
TABLE 20. SUMMARY OF MAJOR AIR AND WATER QUALITY EFFECTS
ASSOCIATED WITH AT-SEA INCINERATION
HC1
4422
Air Quality9
(pg/m3)
Inorganics Unburnedc Copper
Wastes
22.49 2.75 0.22
Water Quali
(ppb)
HC1 Unburned
Wastes
197 0.09
ity
Copper
.04
Maxima for stipulated meterological conditions: effective stack height =
125.5 meters, wind speed =4.0 meters/second, and stability category = D.
Based on summation of inorganic constituents in wastes; provides an
estimate of particulate concentrations.
°Based on lowest average of observed destruction efficiencies (99.96%),
as determined by different analysis methods.
°Copper and zinc are the metallic waste constituents with the highest
emission rates.
The HC1 concentrations are expected to be high because there is no
scrubbing of the combustion gases. Due to its buffering capacity, one
cubic meter of ocean water is capable of neutralizing 80 gm of HC1
(80,000 ppb) [36]. Thus, a 197 ppb contribution of HC1 from plume
touchdown would never be detected by a pH change.
A Threshold Limit Value of 5 ppm has been established for HC1. This
level represents the maximum allowable HC1 concentration for humans in
the work area. Excursions beyond this level for periods greater than 15
minute-, result in either intolerable irritation, or chronic or irreversible
tissue .lamage [37]. Maximum levels predicted as a result of at-sea incin-
eration are below this TLV.
64
-------
The predicted maximum ambient unburned waste concentration is close
to four times larger than corresponding parameters predicted for the land-
based facility. The difference is caused by differences in the emission
rates and effective stack heights used for the two sets of simulations.
The effects of these two differences are counteractive. As shown in
Appendix B, predicted downwind concentrations are dependent on the magni-
tude of mass emission rates. The unburned waste emission rate for at-sea
incineration is 7.3 times than that for the land-based facility. Thus,
based on this fact alone, one would expect ambient concentrations predicted
for at-sea incineration to also be 7.3 times larger. However, the higher
effective stack height used for the simulations of at-sea incineration has
the counteractive effect of reducing the magnitude of predicted ground-
level downwind concentrations. For the simulations presented here, the
overall effect of these reductions was to generate predicted unburned waste
concentrations which were 38 times (as opposed to the 7.3 factor expected)
larger than those for the land-based facility.
However, even through the concentrations within the plume from at-sea
incineration are larger than those predicted for land-based facilities,
these are nevertheless quite small. The maximum predicted level of 2.5
corresponds to a concentration of 0.6 ppb if one assumes that the
major waste constituent (dichloropropane) comprises all of the unburned
waste. This maximum concentration is predicted to occur 4000 meters down-
wind from the ship. It is expected that diffusion processes will effective-
ly decrease these concentrations at locations further downwind;if any
remnants of the plume reach land (145 km away from the proposed North Atlantic
burn zone) concentrations would be even lower.
The site and nature of environmental impacts associated with plume con-
stituents will depend on plume behavior and the various physical properties
of constituents within the plume. If conditions during the burn cause the
plume to behave in a coning aloft mode, then gaseous plume constituents,
(and particulates that are small enough to behave like gases), will be trans-
ported to points at varying distances downwind. During downwind travel,
plume constituents will undergo continual dilution by diffusion type processes.
If pi unit- touchdown occurs at locations close to the ship, then the
65
-------
corresponding air and water environments will be most affected by constituents
which may be in the plume. More information on the size distribution of
particulate matter will be required to determine whether particulates will
be removed directly by gravity, or whether it will remain suspended and
possibly serve as condensation nuclei.
During a 1974 burn of Shell waste aboard the M/T Vulcanus, water samples
were obtained in the vicinity of plume touchdown [16]. Analyses of these
samples showed no significant difference in pH and copper (the most abundant
heavy metal constituent of the waste) as compared with samples from control
areas. Organochlorine wastes were undetected at, in the water the 0.5 ppb
level.
During this same burn, ambient air quality measurements were made by
both ships and airplanes downwind from the M/T Vulcanus. HC1, the most
abundant plume constituent, was measured and used as an indicator of plume
location. Ground level concentrations of HC1 ranged from 0.01 to 7 pom,
the maximum occuring of 926 meters downwind from the M/T Vulcanus. Aerial
measurements indicate the plume reached a maximum attitude of 850 meters,
and extended downwind to a distance of 2,400 meters at which point HC1 con-
centrations were below the detection limit of 0.01 ppm. The highest concen-
tration noted during aerial monitoring was 3 ppm.
Marine Biological Effects
Biological specimens (phytoplankton and zooplankton) were also taken
during the 1974 burn [16]. Examination of chlorophyll-a (an indicator of
phytoplankton activity) levels, and adenosine triphosphate (ATP) levels
in the specimen showed no deleterious or subtle adverse impacts [16].
A series of biological tests were also associated with the March 1977
burn. Laboratory experiments with various concentrations of Shell waste
culminated with the following results [38]:
Seven of 14 fish (Fundulus Grand is.) exposed to 74 ppm of Shell
waste died within 41 hours. Death was apparently due to respira-
tory complications.
0 At a concentration of 7.4 ppm, no effect on fish mortality was
noted.
66
-------
o Enzyme systems (catalase and P-450) of fish exposed to 1.0 ppm
showed a marked response.
The P-450 enzymes are located in the liver and are required for the
metabolism of foreign chemicals introduced into an organism. The response
noted (an increase in the P-450 activity) reflects the presence of an
foreign material that has to be metabolically altered prior to excretion.
This effect is seen as an indication of a potential problem.
In addition to the laboratory tests, the same fish species was exposed
to the plume of the M/T Vulcanus during incineration. Exposure was accom-
plished by using a device called a Biotal Ocean Monitor (BOM), which allows
specific organisms to be exposed under field conditions and then retrieved.
The BOM tests showed an elevation in the activity of P-450 enzymes. However,
when exposed fish were returned to the laboratory and left in clean water
for a few days, the enzyme activity returned to the level found in control
organisms.
The experimenters concluded that the overall effects are localized and
temporary [38], and do not represent drawbacks to the use of at-sea incinera-
tion for organochlorine waste disposal.
Organic Materials Found During Combustion
Analysis of the feedstock for at-sea incineration is usually used to
indicate the kinds of materials which would be delivered to the air and
water environment. Recently, analyses of stack gases have indicated the
presence of organic compounds which were not present in the original
waste. Samples drawn from the stack of the M/T Vulcanus during the at-sea
incineration of Herbicide Orange contained a variety of aromatic compounds
which were not found in the original feedstock. Possible sources of these
materials are synthesis in the flame or partial decomposition of waste feed.
Conditions in the incinerator during Herbicide Orange combustion were:
flame temperature average of 1500°C with a range of 1375°C (low) to
1610°C (high); dwell time or 1.09 sec (average) with a range of 0.91 to
1.31 se< ; a waste feed rate of 14 - 15 tonnes/hour; and a waste destruction
eff icier,. y of 99.999% [35].
67
-------
The presence of metals in liquid organochlorine wastes has been
demonstrated. The metal content will appear in the stack gases (and thus
the plume) as particulate matter. The quantity of metal salts or metal
oxides in the plume is independent of combustion efficiency and is directly
proportional to the metal content of the waste itself. Control of the
metal content of waste which is accepted for at-sea incineration, becomes
the responsibility of regulatory agencies to ensure that wastes with
unacceptably high metal content are not approved for burning at sea. The
control must be implemented, however, by restrictions based on air and
water quality requirements. The metal content permitted in waste thus
becomes a function of the plume model and of the at-sea incineration
process, (e.g., dilution in the plume, feed rate of waste, total combustion
air and speed of the incineration ship).
Currently there is no ship capable of burning solids in an acceptable
manner. During past burns on the Matthias, entire drums of wastes were fed
into the incinerator; there were indications of high particulate emissions.
These emissions were due to the quantities and nature of inorganic consti-
tuents contained in the wastes and/or to the drum itself.
68
-------
REFERENCES
1. U.S. Environmental Protection Agency, Office of Solid Waste Management.
Report to Congress on Hazardous Waste Disposal. June 30, 1978.
2. Kaufman, H. B., United States Environmental Protection Agency's Industry
Studies on Hazardous Waste Management. U. S. Environmental Protection
Agencv, Hazardous Waste Management Division, February 1, 1977.
y
3. Berkowitz, J. B., Hazardous Waste Management-Adding Land-Based Disposal
to Federal Regulations of Pollutant Discharge, August 12, 1977.
4. Luziir, E.C., R. Testani, and A. B. Giles. The Potential for National
Health and Environmental Damages from Industrial Residue Disposal.
September 15, 1976.
5. Fisher, H. J., and R. A. Venezia. Ocean Incineration of Organochloride
Wastes, 1977. Paper presented at annual meeting of the Air Pollution
Control Association, Toronto, Canada, June 20-24, 1977.
6. Russel, R. R., and J. A. Mraz, Hydrochloric Acid Recovery from Chlorinated
Organic Waste, Carbon Products Division, Union Carbide Corporation, Cleve-
land, Ohio, in Industrial Process Design for Pollution Control Volume 5,
Proceeding for an AICHE Workshop, Midland, Michigan, November 1972.
7. Federal Register 41, No. 125, June 28, 1976, p. 26644.
8. Intergovernmental Maritime Consultative Organization, Technical Guidelines
on the Control of Incineration of Wastes at Sea, included in Annex II,
decided upon at the second consultative meeting, post March 1977.
9. TRW. Destroying Chemical Wastes in Commercial Scale Incinerators,
Facility Report No. 1, the Marquardt Company. U.S. Environmental Pro-
tection Agency, Office of Solid Waste Management Programs, October 1976.
10. U. S. Environmental Protection Agency. At-Sea Incineration of Organo-
chlorine Wastes On-Board the M/T Vulcanus. EPA-600/2-77-196,
September 1977.
11. TRW. Destroying Chemical Wastes in Commercial Scale Incinerators;
Facility Report No. 6. Prepared for the U. S. Environmental Protection
Agency, June 1977.
12. TRW Destroying Chemical Wastes in Commercial Scale Incinerators;
Fin.il Report Phase II. Prepared for the U. S. Environmental Protection
Agt-my, November 1977.
69
-------
REFERENCES
(continued)
13. Arthur D. Little, Inc. Destroying Chemical Wastes in Commercial Scale
Incinerators, 3 M Company Chemolite System. Prepared for the U. S.
Environmental Protection Agency, July 1977.
14. Personal communication, Dr. H. J. Fisher, TRW Environmental Engineering
Division, Redondo Beach, California, February 23, 1978.
15. Committee on Medical and Biologic Effects of Environmental Pollutants.
Chlorine and Hydrogen Chloride. National Academy of Sciences, 1976.
16. Wastler, T.A., C. K. Offutt, C. K. Fitzsimmons, and P. E. Des Rosiers.
Disposal of Organochlorine Wastes by Incineration at Sea. U. S.
Enviornmental Protection Agency, Office of Water and Hazardous
Material, July 1975.
17. U. S. Environmental Protection Agency. Final Environmental Impact
Statement; Designation of a Site in the Gulf of Mexico for Incineration
of Chemical Wastes. EPA-EIS-WA 76X-054, July 8, 1976.
18. Hesketh, H. E., Understanding and Controlling Air Pollution, Ann Arbor
Science Publishers, Inc. 1973.
19. Personal communication. Mr. Walt Erbe, The Trane Thermal Company.,
Conshohocken, Pa., November 3, 1977.
20. Personal communication. Mr. Brinkman, Liquid Disposal Co., Utica,
Michigan, February 14, 1978.
21. Personal communication. Mr. R. S. Tiews, E. I. DuPont de Nemours & Co.
Wilmington, Delaware, February 15, 1978.
22. Personal communication. Mr. Bruns, Hyon Waste Management Co., Chicago
Illinois, February 13, 1978 and November 15, 1977.
23. Personal communication. Shell Chemical Plant and Refinery Employee,
May 19, 1978.
24. Personal communication. Rollins Environmental Services Employee,
April 18, 1978.
25. Ottinger, R. S., J. L. Blumenthal, D. F. Dal Porto, G. I. Gruber, M. J.
Santy, and C. C. Shih. Recommended Methods of Reduction Neutralization,
Recovery of Disposal of Hazardous Wastes, Vol. Ill, Disposal Process
Description - Ultimate Disposal, Incineration, and Pyrolysis Process.
70
-------
REFERENCES
(continued)
Report prepared by TRW for the U. S. Environmental Protection Agency,
February 1973.
26. Polychlorinated Biphenyl regulations, (40 CFR Part 761), Federal
Register, 42_, No. 100, May 24, 1977, p. 26564.
27. Draft regulations Subpart D, EPA (40 CRF Part 250) in response to RCRA.
28. EPA, Internal document, Draft Position Paper on Incineration Regulations
in Response to RCRA, November 29, 1977.
29. Mclntire, J. R., Measure Refinery Reliability, Hydrocarbon Processing,
May 1977.
30. Finley, H. F., Maintenance Management for Today's High Technology Plants.
Hydrocarbon Processing, January 1978.
31. Lancaster, J. F., What Causes Equipment to Fail. Hydrocarbon Processing,
January 1975.
32. Stahl, D. R., Air Pollution Aspects of Hydrochloric Acid. September 1969
Report prepared by Litton Systems Inc., for the National Air Pollution
Control Administration.
33. Fuller, W. H., Movement of Selected Metals, Asbestos, and Cyanide in
Soil: Application to Waste Disposal Problems. EPA-600/2-77-020 U. S.
Environmental Protection Agency, Cincinnati, Ohio. April 1977.
34. Van Vleet, E. S., J. G. Quinn. Input and Fate of Petroleum Hydrocarbons
Entering the Providence River and Upper Narrangansett Bay from Wastewater
Effluents. Environmental Science and Technology, Vol. 11, No. 12,
November 1977.
35. U. S. Environmental Protection Agency. At-Sea Incineration of Herbicide
Orange On-Board the M/T Vulcanus. Contract No. 68-01-2966, February 1978.
36. Grasshoff, K., Kiel University, Extract from his report on: "Possible
Effects of Burning Chlorinated Hydrocarbons At-Sea" as included in
Appendix N of Final Environmental Statement: Disposition of Orange
Herbicide by Incineration, Department of the Air Force, November 1974.
37. American Conference of Governmental Industrial Hygienists, TLV - Threshold
Limit Value For Chemical Substances and Physical Agents in the Workroom
Environment with Intended Changes for 1973.
38. TerEco Corporation, A Report on the Philadelphia Dumpsite and Shell
Incineration Monitoring, Box 2848, College Station, Texas, undated.
71
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APPENDIX A
DERIVATION OF PRODUCTION RATE FOR
ORGANOCHLORIME CHEMICALS, AND CORRESPONDING UASTES
Table 1 from the text is repeated below for the purpose of describing the
derivation.
Table A-l. ESTIMATES OF NATIONAL ORGANIC CHEMICAL
PRODUCTION AND CORRESPONDING HASTES.
Organic Chemicals
Organic Wastes
Organochlorines
Organochlorine Wastes
TOTAL
1977
93,435
2,302
13,340
440
PRODUCTION (in
1983
143,578
4,249
20,500
606
thousand tonnes)
1989
201,254
6,354
28,730
907
The values for organic chemical production and organic wastes (the first
and second rows in Table A-l) were obtained from a current investigation spon-
sored by the U.S. Maritime Administration [A-l]. Estimates for 1983 and 1989
are based on chemical growth rate and the expected impact of federal air,
water and solid waste regulations on industrial waste generation. Air and
water regulations will tend to increase the amount of residuals resulting
from pollution control processes, while the regulatory requirements generated
by the Resource Conservation and Recovery Act (RCRA) will tend to encourage
recycling and recovery, thereby decreasing the quality of waste materials
requiring disposal [A-l].
A-l
-------
Total organochlorine production (third row) for the years noted was ex-
trapolated from data generated by an organic chemical manufacturer [A-2] . In
deriving the listed estimates, it was assumed that the production of organo-
chlorine materials represented the same proportion of total organic chemicals
in 1983 and 1989 as it did in 1977.
Except for 1977, estimates of organochlorine wastes (the fourth row) were
obtained via the use of a factor which indicates the amount of wastes which are
generated during the manufacture of organic chemicals. The factors used were
determined empirically from the data in the first and second rows of Table A-l,
and varied from 2.96% (for 1983) to 3.16% (for 1989). The organochlorine waste
factor of 3.30% for 1977 was obtained from Reference [A-2].
REFERENCES
A-l Personal communication, M. Holepsky, Global Marine, Newport Beach,
California (under contract to the United States Maritime Administration),
March 1978.
A-2 Russell, R. R. and J. A. Mraz, Hydrochloric Acid Recovery from
Chlorinated Organic Waste, Union Carbide Corp, Cleveland, Ohio. In
dustrial Process Design for Pollution Control, Vol. 5, proceedings of
an AIChE workshop; Midland, Michigan, November 1-3, 1972, Page 38.
A-2
-------
APPENDIX B
AIR QUALITY SIMULATION METHODOLOGY
A computer simulation of air quality impacts that would result from
at-sea and land-based incineration was performed using the most representa-
tive set of physical parameters and meteorological conditions that could be
determined from the available data. In this appendix the formulation of the
model is presented and the inherent limitations of the analysis are discussed.
The values of the input data are given and the results of a sensitivity
analysis performed for two parameters are shown. The results of the air
quality simulation are presented and the air impacts associated with at-sea
and land-based incineration are briefly discussed.
TECHNICAL APPROACH
Downwind concentrations of gaseous pollutants can be simulated with a
conventional Gaussian diffusion plume model which assumes a continuous point
source of strength Q. The basic equation used in the calculation is
X(x'y'z) = 2 TT uQcr a exp [~ y' ?'/2 °y2 H exp [ - (z-h)2/2 a/]
+ exp [- (z+h)2/2 a/]} (B-l)
where x(x,y,z) is the concentration downwind from the source at x,y,z; Q is
the continuous point source strength (i.e., emission rate); h is the effective
stack height; u is the mean wind speed; and a and a are the horizontal and
vertical standard deviations of the plume. In the above formulation the
x-axis is aligned with the mean wind speed, the y-axis is in the crosswind
direction, and the z-axis is in the vertical.
To obtain the downwind concentration at ground level, equation (B-l)
simplifies to
a
y z
B-l
-------
When gases and particulates are released from a point source they are
carried downwind and are dispersed by atmospheric turbulence. Particulates
will have an additional downward component of velocity at their terminal
velocity, vg. As the gases or particulates approach the ground, a fraction
will be deposited on the surface or on vegetation by direct sedimentation,
inertial impaction, adsorption, chemical reaction and other mechanisms. This
removal causes the downwind flux of airborne gases or particulates to decrease.
In the conventional Gaussian plume model described in Equation (B-l), no
account is made for gravitational settling of particulates or for deposition
mechanisms.
Overcamp [B-l] has proposed a modification of the Gaussian plume model for
the deposition of fine and heavy particulates and gases. It combines a down-
ward-sloping plume to account for settling and the assumption of a constant
deposition velocity. The general equation for the concentration
v y
*(x'y'z) = 2*u?a exp £ * y2/2ay2]
-------
The air quality simulation results presented in this report were not able
to incorporate particulate settling or deposition mechanisms due to the
unavailability of specific data. Particle size and the characteristics of the
surface, among other parameters, would need to be known before settling and
deposition could be included in the analysis. Therefore, ground-level
downwind concentrations were calculated from Equation (B-2) using the most
representative set of physical parameters and meteorological conditions that
could be determined from the available data.
A word needs to be said about the diffusion and transport of pollutants
over large bodies of water. It has been long known that the turbulence spec-
trum (and hence the diffusion) over water is different from that over land
[B-2.B-3] at comparable stabilities. Raynor et al. [B-4] reported diffu-
sion observations at sea which showed little spreading and marked departure
from the standard Pasquill-Gifford curves. This apparently occurs for two
reasons. First, the ocean surface is a dynamic one in contrast to the static
land surface. Therefore, the roughness height, z , which among other para-
meters determines the turbulence intensity, becomes a function of the stage of
wave development. Kitaigorodskii [B-5] derived expressions from determining
an "equivalent sand roughness" element, z , of the sea surface. This value
was found to be dependent on the Reynold's number at the surface. Second,
density stratification over water is controlled not only by heat flux but also
by water vapor flux because of the intense evaporation which takes place at
the water surface. Monin [B-6] has taken this into account by redefining the
stability parameter, L, in terms of the latent heat of vaporization, the Bowen
ratio and the L which would occur over land.
Gifford [B-7] suggested in principle a method for obtaining the
equivalent Pasquill-Gifford stability over water. He suggested that the z$
and L over water be first found, then the equivalent Pasqui11-Gifford turbu-
lence level be found from either Golder's [B-8] or Smith's [B-9] nomograms.
Using values characteristic of the ocean, it was found that L could range any-
where between 20-40% of its "equivalent over-land" value, confirming the
greater stability of the air mass over the ocean.
Portrlli [B-10] recently reviewed the subject of diffusion over water.
The turbulence intensity of the atmosphere over the ocean was found to depend
B-3
-------
on (1) the temperature difference between the air and the ocean surface, and
(2) the roughness of the ocean surface. It was difficult, however, to obtain
quantifiable results (in particular for a and a- ) over the ocean which
could be compared with the equivalent land values. Therefore, in this report,
the at-sea values for these diffusion parameters were assumed to be the same
as the corresponding land values.
LIMITATIONS OF THE ANALYSIS
There are a series of inherent problems and other factors which could
have significant effects on the nature and applicability of results from this
type of simulation analysis. In this section these problems and factors will
be identified and measures taken (if any) to mitigate their effects will be
be described.
The first problem involves inter-facility variations of those factors
that affect effective stack height. Factors of importance include the
following:
(1) The physical height of the stack's terminus above ground level (or
sea level for ships)
(2) The ambient temperature lapse rate, effluent velocity, temperature
of the effluent, and stack radius.
Numerical studies (e.g., see the sensitivity analysis performed in a
later section of this appendix) have shown that ground level concentrations
are strongly dependent on effective stack height. There is no simple way of
designing this analysis to reflect these individual differences; therefore,
the results in this report should be viewed as approximate concentrations
expected to occur under the conditions imposed by a set of specified input
parameters.
A second problem relates to differences in the meteorological conditions
that may exist at individual facilities. Predicted ambient concentrations are
strongly dependent on the selected meteorology. Atmospheric mixing over the
ocean is generally conceded to be less than that over land, but the exact
quantities are not yet known. As with the previous problem, there is no way
of determining meteorological conditions that would be universally representa-
tive of at-sea and land-based conditions. However, information is presented
B-4
-------
in the model input sections of this appendix which shows that the selection of
meteorological parameters is validated to some extent by available data. The
simulation was performed under a set of conditions which were considered to be
the most representative of the land-based and at-sea facilities. It was
assumed that these conditions would persist over long averaging times (on the
order of 24 hours), even though such a persistence is highly unlikely. In
addition, other special meteorological circumstances (fumigation, looping and
trapping) may also be conducive to high pollution build-ups expecially around
the land-based site.
Another level of difficulty stems from a void in our knowledge of aerosol
scavenging and chemical reaction of pollutants in the atmosphere. Hydrogen
chloride by virtue of its deliquescent nature, can be expected to be absorbed
by moisture typically present in marine environments. HC1 may also combine
with other salt complexes and condensation nuclei present over the ocean.
Similarly, unburned wastes and total organics may themselves enter into chem-
ical reactions with marine aerosols or, at the very least, provide nucleation
centers (condensation nuclei } for droplet formation. A determination of the
consequences of the types of chemical reactions and the resulting scavenging
of combustion products is beyond the scope of this study. However, in this
analysis it is assumed that no scavenging takes place.
MODEL INPUT
The inputs to the diffusion model used for the air quality simulation in
this report were the following: emission or discharge rate; effective stack
height; wind speed; and atmospheric stability category.
The emission rates used as inputs to the model are shown in Table B-l.
These emission rates were obtained from actual test data measured during the
operation of at-sea and land-based incinerators [B-12, B-13, B-14, B-15].
Sections 3 and 4 of this report provide details on how emission rates were
determined.
The physical stack height of the land-based incineration facility is 30
meters. The approximate distance of the top of the stack above the water!ine
for the at-sea facility is 15 meters. Effective stack height values were
calculated to be 96.5 meters for the land-based facility and 125.5 meters for
B-5
-------
TABLE B-l. EMISSION RATES USED FOR AIR QUALITY SIMULATION0
Constituent
Emission Rate (kg/hr)
At-Sea Incineration
Land-Based Incineration
HC1
Unburned Wastesb
Inorganics
14.16 X 10°
8.8 (99.96% DEC)
2.2 (99.99% DEC)
72.0
53.0
0.895
0.3
Parti culates
F
Cr
Ni
Ti
Pb/Ti
Cu/Zn
As/Co
1.0
4.0
2.0
0.4
0.7
0.1
1.03
6.9 X 10"4
6.9 X 10"4
6.9 X 10"4
aEmission rates are based on sampling and analysis data obtained at two
operating facilities [B-12, B-13, B-14, B-15]. See Sections 3 and 4 of
this report for a detailed description of now emissions were determined.
^The magnitude of this emission is determined by the use of destruction
efficiency for the at-sea facility and detection limits for the land-
based facility. See Sections 2 and 3 of this report.
CDE = Destruction Efficiency.
B-6
-------
the at-sea facility. See Appendix E for the methodology that was used to
determine these value.
A mean wind speed of 4.0 meters per second was used in all simulations.
Table B-2 summarizes average wind speeds and directions for three on-shore
sites closest to the North Atlantic area under consideration as a site for
at-sea incineration. Averages at these three sites were 4.0 meters per
second at Trenton, 4.6 meters per second at Newark and 4.8 meters per second
at Atlantic City. The value of 4.0 meters per second was selected because
the use of this value would result in higher ground level concentrations.
Table B-3 shows the annual percent frequency of Pasquill categories
for all wind directions and speeds at seven cities across the United States.
The D stability (neutral) is the most commonly occuring, while the A category
(highly unstable) is the least. All simulations were performed for neutral
(Class D) atmospheric stabilities.
SIMULATION RESULTS
Simulation of ambient air quality effects associated with at-sea and
land-based incineration operations was performed using the model and inputs
described in the previous section and the results are shown in Tables B-4 thru
B-6.
B-7
-------
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Land-Based Incineration
The highest ground-level concentration for land-based incineration
can be expected from participates. A maximum of 0.62 jig/m3 occurs at
3 km downwind from the source. (See Table B-4).
TABLE B-3. ANNUAL PERCENT FREQUENCY OF PASQUILL STABILITY
CATEGORIES FOR ALL WIND DIRECTIONS AND SPEEDS
Birmingham, Alabama
Tucson, Arizona
Los Angeles, Calif.
Miami, Florida
Chicago, Illinois
New York, New York
Philadelphia, Pa.
A
1
2
0
0
1
0
0
B
7
10
4
5
5
3
5
Pasquill Stabil
C
12
14
15
14
11
10
11
ity Category
D E
44 36*
33 41*
48 13
42 39*
55 12
67 13
51 14
F
19
17
6
18
*Indicates E and F categories combined. (After Reference B-ll).
Unburned waste concentrations from land-based incineration activities
appear small. At 3 km downwind from the source concentration is O.lS/ig/m3.
At-Sea Incineration
As shown in Tables B-5 and B-6 the highest predicted concentrations
are due to HC1 emissions. A ground level maximum of 4.42^g/m occurs at
4 km downwind from the ship.
The ambient levels for unburned wastes from at-sea incineration are
much lower than for HC1. This is due to a lower emission rate for unburned
waste as compared to that for HC1. In turn, the differences in emission
rates are related to 1) the relatively high combustion efficiency of the
incinerator, and 2) the fact that scrubbers are not used for at-sea inciner-
ation. Therefore, all HC1 produced is emitted while unburned waste emissions
are assumed to be, and in fact are, combustion efficiency limited. The
maximum unburned waste concentration is calculated to be 2.75 jzg/m at a
location 4 km downwind from the ship.
B-9
-------
TABLE B-4. RESULTS OF AIR QUALITY SIMULATION FOR LAND-BASED INCINERATION:
HC1, TRACc METALS, UNBURNED WASTE AND PARTICULATESa
GROUND LEVEL CONCENTRATION
Distance Downwind
From Facility
(Meters)
100
200
300
400
500
600
700
800
900
1000
2000
3000
4000
5000
6000
7000
8000
9000
10000
20000
30000
HC1
(ng/m3)
.00
.00
.00
.00
.07
2.88
9.20
31.03
57.47
148.08
477.06
536.61
489.52
425.73
367.13
317.79
277.36
244.06
216.52
90.42
51.90
Trace Metals
(Ti,Ni & Cr,ea)
(ng/m3)
.00
.00
.00
.00
.00
.00
.01
.02
.04
.11
.37
.41
.38
.33
.28
.25
.21
.19
.17
.07
.04
Unhurried
Waste
(ng/m3)
.00
.00
.00
.00
.02
.96
3.09
10.40
19.26
49.63
159.91
179.87
164.09
142.70
123.06
106.52
92.97
81.81
72.58
30.31
17.40
Particulates
(ng/m3)
.00
.00
.00
.00
.08
3.31
10.59
35.71
66.14
170.41
549.02
617.55
563.36
489.95
422.51
365.72
319.19
280.87
249.18
104.05
59.73
Simulation parameters were: effective stack height = 96.5 meters, and
wind speed =4.0 meters/second.
B-10
-------
TABLE B-5. RESULTS OF AIR QUALITY SIMULATION FOR AT-SEA INCINERATION:
HC1, UNBURNED WASTES AND INORGANICS.3
GROUND LEVEL CONCENTRATION
Distance Down-
wind From Ship
(Meters)
100
200
300
400
500
600
700
800
900
1000
2000
3000
5000
6000
7000
8000
9000
10000
20000
30000
HCL
.00
.00
.00
.00
.00
.10
.84
8.09
25.43
144.67
2082.66
2849.86
4389.32
4116.79
3777.38
3438.65
3124.50
2843.01
1318.93
781.14
Unburned Wastes
99.96% DEt
.00
.00
.00
.00
.00
.06
0.00
0.01
0.02
0.09
1.29
2.39
2.73
2.56
2.35
2.14
1.94
1.77
0.82
0.49
' 99.99% DEb
.00
.00
.00
.00
.00
.00
.00
.00
.00
.02
.32
.60
.68
.64
.59
.53
.49
.44
.20
.12
Inorganics
(/ig/rn3)
High
.00
.00
.00
.00
.00
.00
.00
.04
.13
.74
10.59
19.58
22.32
20.93
19.21
17.48
15.89
14.46
6.71
3.97
Low
.00
.00
.00
.00
.00
.00
.00
.03
.10
.54
7.80
14.41
16.43
15.41
14.14
12.87
11.69
10.64
4.94
2.92
aSimulation parameters were: effective stack height - 125.5 meters,
wind speed - 4.0 meters/second.
DE - Destruction efficiency.
B-ll
-------
TABLE B-6. RESULTS OF AIR QUALITY SIMULATION FOR AT-SEA INCINERATION:
SELECTED TRACE ELEMENTS3
Downwind Distance
Ground Level Concentration
Cu/Zn
Pb/TI
II Oil 1 \J
=ters)
TOO
200
300
400
500
600
700
800
900
1000
2000
3000
4000
5000
6000
7000
8000
9000
10000
20000
30000
(ng/m3)
.00
.00
.00
.00
.00
.01
.06
.57
1.80
10.22
147.08
271.08
312.34
309.98
290.73
266.76
242.84
220.66
200.78
93.14
55.17
(ng/m3)
.00
.00
.00
.00
.00
.01
.04
.40
.26
7.15
102.96
190.32
218.64
216.99
203.51
186.73
169.99
154.47
140.54
65.20
38.62
(ng/m3)
.00
.00
.00
.00
' .00
.00
.02
.23
.72
4.09
58.83
108.75
124.94
123.99
116.29
106.71
97.14
88.26
80.31
37.26
22.07
B-12
-------
TABLE B-6. RESULTS OF AIR QUALITY SIMULATION FOR AT-SEA INCINERATION:
(continued) SELECTED TRACE ELEMENTS
Downwind Distance
As/Co
Ground Level Concentration
Cr
Ni
1 UUI -Ml 1 p
Meters)
TOO
200
300
400
500
600
700
800
900
1000
2000
3000
4000
5000
6000
7000
8000
9000
10000
20000
30000
(ng/m3)
0.00
0.00
0.00
0.00
0.00
0.00
0.00
.06
.18
1.02
14.71
27.19
31.24
31.00
29.07
26.68
24.28
22.06
20.08
9. -32
5.52
(ng/m3)
0.00
0.00
0.00
0.00
0.00
.03
.24
2.28
7.18
40.87
588.32
1087.53
1249.38
1239.92
1162.93
1067.06
971.37
882.63
803.11
372.58
200.66
(ng/m3)
0.00
0.00
0.00
0.00
0.00
.01
.12
1.14
3.59
20.43
294.16
543.77
624.69
619.96
581.47
533.53
485.68
441.31
401.56
186.29
110.33
B-13
-------
SENSITIVITY ANALYSIS
The purpose of this sensitivity analysis is to describe the manner in
which predicted ground level concentrations vary in response to changes in
key input parameters. For the purpose of this analysis an emission rate of
6050 grams/hour was used.
Ground level concentration as a function of three effective stack
heights is shown in Figure B-l. At an effective stack height, h, of 10.0
meters and a wind speed, u, of 0.5 meters/second, a peak concentration of
3
3040 yg/m occurs at 0.5 km downwind. As h is doubled to 20 m, concentra-
tion is reduced to 810 yg/m but now occurs further downwind at 0.9 km.
Increasing the effective stack height to 30.0 m further reduces the ground
level maximum concentration to 267 yg/m which now occurs even further
downwind at 2.0 km. An increase in the effective stack height by a factor
of two causes approximately a four-fold decrease in ground level concentra-
tion and increasing the effective stack height by a factor of three causes
approximately a 12-fold decrease in ground level concentration. This
demonstrates the strong influence of effective stack height on ground level
concentration.
The dependence of concentration on wind speed is shown in Figure B-2.
Increasing wind speed by a factor of 2 reduces ground level concentration
by exactly one-half. This may be inferred directly from Equation (B-l) in
which concentration is inversely proportional to wind speed.
B-14
-------
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B-16
-------
REFERENCES
B-l Overcamp, T. J. A General Gaussian Diffusion - Deposition Model for
Elevated Point Sources. J. Appl. Meteor., ]£, 1976, pp.1167-1171.
B-2 Slade, D. H. Atmospheric Diffusion Over Cheseapeake Bay. Monthly
Weather Rev., 90, 1962, pp.217-224.
B-3 Van Der Hoven, I. Atmospheric Transport and Diffusion at Coastal
Sites. Nuclear Safety, IB, 1967, pp.490-499.
B-4 Raynor, G. S., P. Michael, R. M. Brown, and S. Seth-Raman. A Research
Program on Atmospheric Diffusion from an Oceanic Site. American Meteor.
Society Symposium on Atmospheric Diffusion and Air Pollution, Santa
Barbara, California, Sept. 9-13, 1974, pp. 289-295.
B-5 Kitaigorodskii, S. A. The Physics of Air-Sea Interaction, 1970. Trans.
from Russian and publ. by Israel Program for Scientific Translastions,
1172-50062, Jerusalem, 1973, v and 237 pp.
B-6 Monin, A. S. The Atmospheric Boundary Layer. Annual Review of Fluid
Mechanics, 2_, 1970, pp 225-250.
B-7 Gifford, F.A. Turbulent Diffusion-Typing Schemes. A Review, Nuclear
Safety, Vol. 17, No. 1, 1970, pp. 25-43.
B-8 Colder, D. Relations Among Stability Parameters in the Surface
Boundary Layer. Meteor. 3^ 1972, pp. 47-58.
B-9 Smith, F. B. A Scheme for Estimating the Vertical Dispersion of a
Plume from a Source Near Ground Level. Proc. of the Third Meeting of
the Expert Panel on Air Pollution Modeling, NATO-CCHS Report No. 14,
Brussels, 1972.
B-10 Portelli, R. V. A Brief Summary of Scientific Literature Dealing with
Diffusion Over Water. Presented at the Meeting on Incineration at Sea,
London, England, March 21-25, 1977.
B-ll Holzworth, G.C. Climatological Aspects of the Compostion and
Pollution of the Atmosphere. World Meterol. Organization Tech.
Note No. 139, 1974.
B-l 7
-------
REFERENCES (Continued)
B-12 "At-Sea Incineration of Organochlorine Wastes Onboard the M/T Vulcanus,"
Environmental Protection Technology Series EPA-600/2-77-196.
B-13 "Destroying Chemical Wastes in Commercial Scale Incinerators," Contract
No. 68-01-2966, Facility Report No. 1: The Marquardt Company,
October 1976, prepared for EPA.
B-14 "Destroying Chemical Wastes in Commercial Scale Incinerators," Final
Report Phase II, Contract No. 68-01-2966, June 1977, prepared for EPA.
B-15 "Destroying Chemical Wastes in Commercial Scale Incinerators," Facility
Report No. 6. Prepared for the U.S. Environmental Protection Agency,
June 1977.
B-18
-------
APPENDIX C
CALCULATIONS FOR CHARACTERIZATION OF
SINGLE PASS SCRUBBER WASTEWATER
Assumptions used for this analysis are:
1) All of the HC1 formed during combustion is transferred into the
scrubber wastewater. The maximum amount is assumed because this
will be the worst case.
2) Seventy-five percent of the water feed to the scrubber is lost due
to entrainment by the gas stream [C-l].
Analysis of scrubber wastewater quality at the Marquardt Company. Data
obtained from reference [C-2].
Data:
Waste Incinerated - Hexachlorocyclopentadiene
Chlorine in Waste - 76.5%
Caustic Feed Rate - 23.8 liters/min
- type of caustic - 12% NaOH - specific Gravity =0.95
Water Feed Rate - 60 liters/min
Waste Feed Rate - 52.8 Kg/hr
Calculation of chloride content of scrubber wastewater:
(% Cl in waste) (waste feed rate) . Chlor1de concen.
equation i. (?5%) (scrubber solution feed rate) tration in
wastewater
(.765) (52.8 kg/hr) (j^-j^) (1.0 x 106mg.) = 11,000
_ kg mg/l
(.75) (73.8 1/min)
C-l
-------
Calculation of calcium or sodium ion concentrations in wastewater
- Calculation of mass flow rate of solution
23.8 liters/min x .95 kg/liter = 22.61 kg/min
- Calculation of NaOH flow rate at 12% of solution
.12 x 22.61 kg/min = 2.71 kg/min NaOH
- Calculation of percent Na ions at 57.5% of NaOH
.575 x 2.71 kg/min = 1.56 kg/min
- Calculation of Na ion concentration in wastewater
(1.56 kg/min) (1.0 x IP6 mg/kg) = K^QQ
(.75) (73.8 liters/min)
Cl" ions - 11,000 nig/liter
Na* ions - 25.700 mg/liter
IDS 36,700 mg/liter
Analysis of scrubber wastewater quality at Rollins Environmental Services,
Data obtained from reference [C-3].
Data:
Waste Incinerated - Nitrochlorobenzene
Chlorine in Waste - 10.0%
Caustic Feed Rate - 8.5 liters/min
- type of solution - 32% Ca(OH)£ specific gravity 0.87
Water Feed Rate - 3200 liters/min
Waste Feed Rate - 1893 kg/hr
Calculation of chloride content in wastewater using equation 1.
(.10) (1893 kg/hr) ({jfr m1n) (1.0 x IP6 mg/kg) = Ij314mg/1
(.75) 3200 liters/min
Calculation of calcium concentration in wastewater
- mass flow rate of solution
8.5 1/min x .87 kg/liter = 7.4 kg/min
C-2
-------
- mass flow rate of Ca(OH)2 at 32% of solution
7.4 kg/min x .32 = 2.37 kg/min Ca(OH)2
- mass flow rate of calcium ion at 54% of Ca(OH)?
.54 x 2.37 kg/min = 1.28 kg/min
- calculation of calcium concentration
1.28 kg/min xl.Ox IP6 mg/kg = 533mg/liter
(.75) 3200 liter/mln
Chloride ions
Calcium ions
1,300 mg/liter
530 mg/liter
IDS
1830 mg/liter
C-3
-------
REFERENCES
C-l Final Environmental Statement; Disposition of Orange Herbicide by
Incineration, Department of the Air Force, November 1974.
C-2 TRW Systems for U.S. Environmental Protection Agency, Office of Solid
Wastes Management Programs, Facility 1 Report, Marquardt Company
Destroying Chemical Wastes in Commercial Scale Incinerators,
October 1976.
C-3 Arthur D. Little, Inc. Destroying Chemical Wastes in Commercial Scale
Incinerators, 3M Company Chemolite System. Prepared for the U.S.
Environmental Protection Agency, July 1977.
C-4
-------
APPENDIX D
DEVELOPMENT OF MODEL TO DETERMINE THE EFFECTS OF
AT-SEA INCINERATION ON OCEAN WATER QUALITY
Derivation of the model assumes stable conditions over the ocean and
selects an arbitrary set of conditions of ship and speed. The model covers
only those conditions under which the ship drives directly into the wind.
In this discussion a generalized representation is derived for the "foot-
print" of contours (in 2 dimensions) of isopleths of contaminants as a func-
tion of distance aft of the centerline of the incinerator on a vessel. The
distance aft is designated x^; the lateral dimension, y_, is measured from a
line (perpendicularly) represented by the ship's velocity (resultant of ship's
speed and wind velocity) which is designated u^. Distance above the ocean's
surface is z.
A general expression is given by:
x = Q n
-------
n = nondimensional parameter associated with atmospheric stability
h = effective stack height (i.e., where the plume bends over) above
the ocean surface,meters.
z = distance above surface of ocean in meters.
Because the ambient air over the surface of the ocean is slightly stable most
of the time (approximately 90%), the value for n is taken as 0.25. The cor-
2 ~~
responding value for c = 0.014 for an effective stack height of h = 24 meters.
As a representative example, u_ equals 10 meters/second. In the example,
the total efflux from the stack of all constituents is Q = 4469 gm/moles/second
with 7.06% being HC1, Q(HC1) = 315.5 gm/moles/second. For any other values of
Q the results can be ratioed since X varies directly as Q. Thus at the ocean
surface (z = 0).
X HC1 (ppmv) =
3.214
10'
.1.75
exp
exp
- 71.43 y'
.1.75
41,143
.1.75
x
This is for the case of QHC1 = 315.5 gm-moles/sec and u = 10 meters/sec. The
factor
F (x,y) = exp
- 71.43
.1.75
defines reductions in concentrations off-axis. Table D-l provides the multi-
plication factor for off-axis concentrations. Figure D-l is a plot showing var-
iations of off-axis concentrations of up to 120 meters.^ From the figure, one
can make x-y plots of contours of equal concentration levels by replotting
from the graph values for x and y, assuming a given value of concentration.
For example, if one takes 10 ppmv and moves horizontally, one comes to values
for y, beginning with y = 0, 10, 20, . . . . , etc., which correspond to val-
ues of x in meters (distance aft of the stack). In the case of y, which is
the distance from the centerline defined by the ship's motion, one would plot
points on both sides of 'the centerline.
The linear plot shows a true picture of the "footprint" of the plume
(Figure D-2).
D-2
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1000
CL
Q.
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10,000
Figure D-l. Plot of HC1 as a function of x and y.
D-4
-------
5000
4500.
4000
3500
o
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c
3000
2500,
45 2000
1000
500
,x = 10 ppnv
x = 17 ppmv
x = 30 ppmv
Direction of Ship Motion
200 200
Distance (M) frorr Center!ine of Plume
(At Ocean Level)
Figure D-2. Isopleths for HC1 concentration (scale-linear)
D-5
-------
If in the plume formula, u = 10 meters/sec (19.4 knots), assume the
ship's speed to be 9.7 knots (5 m/sec) with an equivalent headwind of 9.7
knots (5 m/sec). With an effluent gas content of 7.06% HC1, the plume model
described gives HC1 isopleths as shown in Figures C-l and C-2. It will
be noted from Figure C-2 that the isopleth of 10 ppmv of HC1 encompasses ap-
proximately an elliptical ocean surface pattern almost 5000 meters in length
and at its widest point 270 meters wide.
From the available data, one may calculate:
1) An area of plume contact with the ocean surface (the footprint bound-
ed by a 10 ppmv isopleth) is 1,060,288 meters2. (Assume an ellipse,
major and minor axes 5,000 and 270 meters.)
2) The plume is laid down across the ocean at 5 meters/second.
9.7 kt x 6088 ft/hr \ =5 meters/second
3600 sec/hr x 3.28 ft/meter /
3) At 5 meters/second, one plume footprint (5000 meters x 270 meters) is
laid down in 1000 seconds.
/ 5000 meters \
y 5 meters/second )
n area of ocean e<
plume in one hour.
fi 2
4) An area of ocean equal to 3.6 x 10 meters is thus covered by the
/3600 second \ 1,060,288 meters2
\ 1000 second /
5) The volume available for dilution is 7.2 x 10^ meters , assuming the
mixing zone to be 20 meters thick.
(3.6 x 106 meters2 x 20 meters)
6) A total of 8 .8 kg/hr of unburned material is delivered to the ocean
via the plume, assuming a waste feed rate of 22 tonnes/hr and a mini-
mum destruction efficiency of 99.96%. The unburned material is
assumed to be 100% organochlorine materials.
D-6
-------
7) The concentration of material in the mixing zone is calculated as
follows:
(Assume 8.8 kg of waste to be dissolved in 7.2 X 107 m ). The diluted
waste concentration is: - -
fi 8.8 kg X KT X 10
a) 1.22 X 10"b mg/mer
b) 1.22 X 10"3 ppb (ppm X 103 = ppb)
The quantity of minor constituents in the waste, for example, copper
(Cu), which would appear in the mixing zone can be estimated in a similar way.
If a waste were to contain Cu at a 1.0 ppm level, the concentration in the
-4
mixing zone would be 3 X 10 ppb.
The emission rate of HC1 has been calculated to be 14.16 X 10 gm/hour.
Assuming that the total amount is dissolved in the ocean via the plume, the
7 3
volume of water affected per hour is 7.2 X 10 m .
The concentration of HC1 resulting from the above conditions is as
f ol 1 ows :
14.16 X 106 X 103 mg HCl/hr
concentration HC1 =
7.2 X 107 X 103liter/hr of ocean covered
concentration HC1 = 0.197 ppm
D-7
-------
APPENDIX E
DETERMINATION OF EFFECTIVE STACK HEIGHT
The effective stack height used in the air quality simulations is
given by
h = h + Ah
where h is the physical height of the stack and Ah is the plume rise
above the stack exit.
There are over 30 plume-rise formulas in the literature. All require
empirical determination of one or more constants and some formulas are
totally empirical. For the purpose of this analysis the Briggs plume-rise
formula was chosen to calculate final rise in stable conditions with wind.
This formula gave the minimum rise for the meteorological conditions
chosen and it is valid for rise into stable air in which the stability
parameter, s, is constant (E-l and E-2). The equation is
J
/ c \
Ah = 2.6
where v, is the wind speed, s is a stability parameter and F is a quantity
that is proportional to the rate of buoyancy emission from the stack. The
stability parameter, s, is defined as
where g is gravitational acceleration, T is the absolute temperature of
the ambient air, and -^ = (^-1 +9.8°C/km, the potential temperature
gradient. A value of -1.5°C per 100 m was used for ^. The buoyance flux,
F, can (>( expressed as
E-l
1
-------
F _ . o
" Ts gw/
where AT is the stack effluent temperature minus the ambient air tempera-
ture, T is the absolute temperature of the stack air, w is the stack-gas
effluent velocity, and r is the inside radius of the stack.
Table E-l lists the input data used in the plume rise calculations.
Using this data, effective stack heights of 96.5 m and 125.5 m were found
for land-based and at-sea incineration, respectively.
TABLE E-l. INPUT DATA USED IN PLUME RISE CALCULATIONS*
Temperature of stack air ( C)
Temperature of ambient air ( C)
Stack radius (m)
Stack-gas effluent velocity (m/sec)
Stack height (m)
Wind speed (m/sec)
Land-Based
Incineration
60
20
1.0
8.7
30
4.0
At -Sea
Incineration
1200
20
1.7
2.3
15
4.0
*Based on information contained in References E-3 and E-4.
E-2
-------
REFERENCES
E-l. Briggs, Gary A, et al., Meteorology and Atomic Energy, David H. Slade,
ed., U. S. Atomic Energy Commission, TID-24190, July 1968
E-2. Briggs, Gary A., Plume Rise, U. S. Atomic Energy Commission,
TID-25075, Nov. 1969.
E-3. TRW. Destroying Chemical Wastes in Commercial Scale Incinerators;
Facility Report No. 6. Prepared for the U. S. Environmental Protec-
tion Agency, June 1977.
E-4. U. S. Environmental Protection Agency. At Sea Incineration of
Organochlorine Wastes On-Board the M/T Vulcanus. EPA-600/2-77-196,
Sept. 1977.
E-3
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TECHNICAL REPORT DATA
/Please read Instructions on tlie reverse before < ompletirlf/
1 R£DORT NO
EPA-600/2-78-087
T,TLE ANDSUBT.TLE Environmental Assessment: At-Sea and
Land-Based Incineration of Organochlorine Wastes
3 RECIPIENT'S ACCESSION NO.
5 REPORT DATE
April 1978
6. PERFORMING ORGANIZATION CODE
7 AUTHOR,3>g p Paige, L. B.Baboblal, H.J. Fisher, K.H.
Scheyer, A.M.Shaug, R.L.Tan, and C.F.Thorne
8. PERFORMING ORGANIZATION REPORT NO.
9 PERFORMING ORGANIZATION NAME AND ADDRESS
TRW, Inc.
One Space Park
Redondo Beach, California 90278
10. PRC-3RAM ELEMENT NO.
1AB606
11 CONTRACT/GRANT NO
68-02-2660
= C'\SO3ING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REROFtT AND PERIOD COVERED
Final; 1-3/78
14. SPONSORING AGENCY CODE
EPA/600/13
is. SUPPLEMENTARY NOTES
919/541-2547.
project officer is Ronald A. Venezia, Mail Drop 62,
16 ABSTRACT
The report provides a generalized description of at-sea and land-based
incineration of organochlorine wastes and an assessment of their corresponding
impacts. The data base for at-sea incineration was obtained during a series of
burns, between April 1974 and March 1977. Data describing land-based inciner-
ation were obtained from a review of the literature, and a brief survey of companies
involved in commercial use and manufacture of incinerators. The report includes:
(1) typical organochlorine waste compositions, (2) descriptions of emissions pro-
duced during at-sea and land-based incineration, (3) a simulation of corresponding
air quality changes, (4) a description of predicted paths of transport of emission
constituents, (5) estimates of water quality changes associated with both types of
incineration, (6) an assessment of the potential for malfunction which could pro-
duce adverse environmental effects, (7) a general discussion of the kinds of envi-
ronmental impacts associated with the incineration processes, and (8) identification
of areas where there are needs for upgrading existing systems and data gaps which "
limit the comprehensiveness of the analysis.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b IDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Pollution
Incinerators
Ships
Sea Water
Chlorine Organic
Compounds
Waste Disposal
Organic Wastes
Chlorine
Industrial
Processes
Pollution Control
Environmental Assess-
ment
At-Sea Incineration
Land-Based Incineration
Organochlorine
13B
13J
08J
07C
07B
13H
13 - ST^iBUTiONi STATEMENT
Unlimited
19 SECURITY CLASS fThis Report,
Unclassified
21 NO OF PAGES
115
20 SECURITY CLASS (This page)
Unclassified
22 PRICE
EPA Form 2220-1 19-73)
E-4
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