APTD-1140
NATIONAL INVENTORY
or soi-i{<:i<;s
AND EMISSIONS:
BARIUM - 1969
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Air and Water Programs
Office of Air Quality Planning and Standards
Research Triangle Park, North Carolina 27711
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APTB-1140
NATIONAL INVENTORY
OF
SOURCES AND EMISSIONS;
by
W. E. Davis § Associates
9726 Sagamore Road
Leawood, Kansas
Contract No. 68-02-0100
EPA Project Officer: C. V. Spangler
Prepared for
ENVIRONMENTAL PROTECTION AGENCY
Office of Air and Water Programs
Office of Air Quality Planning and Standards
Research Triangle Park, N.C. 27711
May 1972
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The APTD' (Air Pollution Technical Data) series of reports is issued by
the Office of Air Quality Planning and Standards, Office of Air and
Water Programs, Environmental Protection Agency, to report technical
data of interest to a limited number of readers. Copies of APTD reports
are available free of charge to Federal employees, current contractors
and grantees, and non-profit organizations - as supplies permit - from
the Air Pollution Technical Information Center, Environmental Protection
Agency, Research Triangle Park, North Carolina 27711 or may be obtained,
for a nominal cost, from the National Technical Information Service,
5285 Port Royal Road, Springfield, Virginia 22151.
This report was furnished to the Environmental Protection Agency
in fulfillment of Contract No. 68-02-0100. The contents of this report
are reproduced herein as received from the contractor. The opinions,
findings, and conclusions expressed are those of the author and not
necessarily those of the Environmental Protection Agency. The report
contains some information such as estimates of emission factors and
emission inventories which by no means are representative of a high
degree of accuracy. References to this report should acknowledge the
fact that these values are estimates only.
Publication No. APTD-1140
11
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PREFACE
This report was prepared by W. 2. Davis & Associates
pursuant to Contract No. 68-02-0100 with the Environmental
Protection Agency, Office of Air Programs.
The inventory of atmospheric emissions has been prepared
to provide reliable information regarding the nature, mag-
nitude, and extent of the emissions of barium in the United
States for the year 1969.
Background information concerning the basic characteristics
of the barium (barite) industry has been assembled and in-
cluded. Process descriptions are given, but they are brief,
and are limited to the areas that are closely related to exist-
ing or potential atmospheric losses of the pollutant.
Due to the limitation of time and funds allotted for the study,
the plan was to personally contact all of the mining and pro-
ducing companies and about twenty percent of those in each
major emission source group to obtain the required informa-
tion. It was known that published data concerning the atmos-
pheric emissions of barium were virtually nonexistent, and
contacts with industry ascertained that atmospheric emissions
were not a matter of record. The barium emissions and
iii
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emission factors that are presented are based on the summa-
tion of data obtained from production and reprocessing com-
panies. Additional information was acquired during field
trips to inspect the air pollution control equipment and ob-
serve processing operations.
IV
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ACKNOWLEDGEMENTS
This was an industry oriented study and the authors express
their appreciation to the many companies and individuals in
the barium (barite) industry for their contributions.
We wish to express our gratitude for the assistance of the
various societies and associations, and to the many branches
of the Federal and State Governments.
Our express thanks to Mr. C. V. Spangler, Project Officer,
EPA, Office of Air Programs, Research Triangle Park,
N. C. , for his helpful guidance.
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CONTENTS
SUMMARY 1
Emissions by Source 2
Emissions by Regions 3
Emission Factors 4
MINERAL SOURCES OF BARIUM 6
MATERIAL FLOW THROUGH THE ECONOMY . . 8
Chart 9
USES AND EMISSIONS OF BARIUM
Mining 10
Processing 12
Production of Metallic Barium 17
Production of Barium Chemicals 18
End Product Uses of Barium 28
Oil and Gas Well Drilling Mud ...... 28
Glass 29
Paint 33
Rubber 34
Miscellaneous 37
SOURCES OF INADVERTENT BARIUM EMISSIONS
Coal 40
Oil 44
Iron and Steel 45
UPDATING OF EMISSION ESTIMATES 47
VI
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TABLES
Table I Emissions by Source 2
Table II Emissions by Regions 3
Table III Emission Factors 5
Table IV Average Barium Content in Ash
of Coal 43
FIGURES
Figure I Material Flow Through the Economy . . 9
Figure II Barium Compounds Produced from
Barite 13
Figure III Barium Sulfide Produced from Barite. . 19
Figure IV Barium Carbonate Produced from
Barium Sulfide 21
Figure V Barium Hydroxide Produced from
Barium Carbonate 23
Figure VI Barium Stearate Produced from
Barium Hydroxide 25
VI1
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SUMMARY
The flow of barium in the United States has been traced and
charted for the year 1969 (Figure I). The consumption was
934, 000 tons, while domestic production totaled 603, 000
tons. Imports and exports were 344,000 and 10,000 tons,
respectively.
Emissions to the atmosphere during the year were 15,420
tons (Table I). Nearly 18 percent of the emissions resulted
from the processing of barite, more than 28 percent from
the production of chemicals, 23 percent from the manufacture
of various end products, and about 26 percent from the com-
bustion of coal. The wear of rubber tires was a relatively
minor emission source.
Emission estimates for processing, chemical production,
and the manufacture of end use products are based on un-
published data obtained from industrial sources.
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TABLE I
Source Category
M ining
Processing
Chemical Production
End Product Uses
Other Emission Sources
EMISSIONS BY SOURCE
1969
Source Group
Emissions - Tons
Emissions
Well Drilling Mud
Glass
Paint
Rubber
Miscellaneous
Coal
Cast Iron
30
2,700
4,400
4,240
70
40
30
600
3, 500
4, 050
4, 000
50
--
17. 5
I
28. 5
27. 5
26. 5
TOTAL,
15,420
100. 0
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TABLE II
EMISSIONS BY REGIONS
Region No. 1
Region No. 2
Region No. 3
Region No. 4
TOTAL
Tons
5, 170
5,260
3,870
1, 120
15,420
Region No. 1
Arizona
California
Colorado
Idaho
Montana
Nevada
New Mexico
Oregon
Utah
Washington
Wyoming
Illinois
Indiana
Iowa
Kansas
Alabama
Arkansas
Delaware
Florida
Georgia
Kentucky
Connecticut
Maine
Massachusetts
Region No. 2
Michigan
Minnesota
Missouri
Nebraska
Region No. 3
Louisiana
Maryland
Mississippi
North Carolina
Oklahoma
South Carolina
Region No. 4
New Hampshire
New Jersey
New York
North Dakota
Ohio
South Dakota
Wisconsin
Tennessee
Texas
Virginia
West Virginia
District of
Columbia
Pennsylvania
Rhode Island
Vermont
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EMISSION FACTORS
The emission factors presented herein are the best cur-
rently available. They were determined through a combi-
nation of methods consisting of: (1) direct observation of
emission data and other related plant processing and engi-
neering data; (2) estimates based on information obtained
from literature, plant operators, and others knowledgeable
in the field; (3) calculations based on experience and per-
sonal knowledge of metallurgical processing operations; and
(4) specific analytical results where available.
The basic data used to calculate the emission factors are
contained in the files of the Contractor.
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TABLE III
EMISSION FACTORS
Mining
Processing
Barium Chemicals
100 lb/1, 000 tons barite mined
5 Ib/ton barite processed
50 Ib/ton barite processed
End Product Uses of Barium
Oil and Gas Well Drilling 110 lb/1, 000 tons barite used
Glass Manufacture 2 Ib/ton barium processed
Paint Manufacture 2 Ib/ton barium processed
Rubber Tire Wear 0. 3 Ib/million miles
Other Emission Sources
Coal
Cast Iron
15 lb/1,000 tons of coal burned
5 lb/1,000 tons of process
weight
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MINERAL SOURCES OF BARIUM
Barium (Ba) is a relatively soft, silver white metal that
occurs in nature only in combination with other elements.
It is found in small quantities in most igneous rocks; how-
ever, the only minerals that are commercially important
are barite (BaSO^) and witherite (BaGG^). These minerals
are mined almost entirely for the production of barium
compounds.
Barite is widely distributed. It occurs in large deposits in
many parts of the world, including several areas in the United
States. The most important barite-producing countries are
the United States, West Germany, U. S. S. R. , Mexico, Italy,
Greece, Iceland, Canada, and China. In the United States
the leading producer during 1969 was Nevada, supplying 30
percent of the total. Missouri produced 28 percent; Ark-
ansas, 20 percent; Georgia, 12 percent; and Alaska, Cali-
fornia, North Carolina, and Tennessee accounted for the re-
maining 10 percent.
The world reserves of the mineral witherite are limited. It
is found only in small quantities in the United States and is
not mined commercially in this country. The only commercial
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production in the world comes from a mine in Northumber-
land, England.
Domestic sources of barium, other than barite, have been
investigated and reported by the Bureau of Mines, the U. S.
Geological Survey.,, and others. These reports indicate some
barium is found in coal, feldspar, and mica.
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MATERIAL FLOW THROUGH THE ECONOMY
The sources and uses of barium in the United States during
1969 are shown in Figure I. The domestic production total-
ing 603, 000 tons was about 64 percent of the quantity con-
sumed and the remainder that was needed was imported prin-
cipally from Mexico, Ireland, Canada, Peru, Italy, Greece,
and Morocco.
The most important application of barium during 1969 was
in oil and gas well drilling muds. About 74 percent was used
for this purpose as a weighting agent, barite being suitable
because of its chemical inertness, high density, and low cost.
A significant amount of barium (14 percent) was used for mis-
cellaneous purposes in the electronic, ceramic, and plastic
industries; also in ink fillers, green fire, oils and greases,
beet sugar refining, and water treatment. Other categories
employing barium were glass (4 percent), paint (3 percent),
and rubber (one percent).
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BARIUM
MATERIAL FLOW THROUGH THE ECONOMY - 1969
(Thousand Tons)
SOURCES USES
603
DOMESTIC PRODUCTION*"
344
IMPORTS
10
EXPORTS
INDUSTRY STOCKS
934
692
DRILLING MUD
41
GLASS
29
PAINT
RUBBER
129
MISCELLANEOUS
35
PROCESSING LOSSES)
Data source - U. S. Bureau of Mines.
CONSUMER
Figure I
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USES AND EMISSIONS OF BARIUM
MINING
During 1969 about 89 percent of the barite was produced in
the states of Nevada, Missouri, Arkansas, and Georgia.
It was mined both by open-pit and underground methods, and
the operations performed at the different mine sites varied
somewhat principally because of the type of ore mined.
In Nevada the ore is high-grade and processing is relatively
simple in order to prepare it for use as oil well drilling
mud. Typically, it is mined, crushed, and screened at the
mine site. The fines that are discarded contain 70 to 75 per-
cent barium sulfate, while the ore shipped to the mill con-
tains about 92 percent. On the other hand, the barite ore
currently mined in Arkansas is approximately 50 percent
barium sulfate and processing operations at or near the mines
are more complex.
In Missouri the situation is entirely different. The barite
is mined or removed from residual deposits which are about
90 percent clay. Operations at the mines include removal
of the clay from the barite using log washers with the fine
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barite in the overflow recovered by tabling and froth flota-
tion. Residual deposits also occur in Georgia, Tennessee,
and several eastern states.
From the sta.ndpoint of emissions to the atmosphere, the
principal losses that occur at barite mine sites are those
that are due to blasting, ore handling, crushing, loading,
and hauling. At one mining location which is typical of many
others, the ore loosened by blasting is loaded on trucks for
transport to the crusher. The road used is graveled with
discarded barite ore and considerable dust is created by
movement of the trucks.
During this study 6 barite mines were visited in Arkansas
and Nevada, but records concerning emissions were not
available. Based on site inspections, the Contractor :s esti-
mate of barium emissions to the atmosphere from sources
of mining is 100 pounds per thousand tons of barite ore
mined. Barium emissions to the atmosphere during 1969
totaled approximately 30 tons.
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PROCESSING
Barite, sometimes referred to as barytes, heavy spar, or
tiff, is processed in several different ways depending upon
the purity of the ore mined and the use intended for the end
product. Currently the ore produced in Nevada is relatively
pure (about 80 to 85 percent BaSO.) and it may be processed
in a dry condition, whereas the ore now mined in Arkansas
contains considerably less barium sulfate and must be up-
graded by flotation. In Missouri and Georgia the clay must
be washed away from the barite, which is otherwise rela-
tively pure.
Commercially 4 classifications of barite are commonly used.
Crude barite is the raw material for producing barium sul-
fide (BaS), commonly called black ash, which is a compound
from which many other useful chemicals are produced as
shown in Figure II. Coarsely ground barite (20 mesh) is a
form preferred by the glass industry. It is added to the mix
to lower the melting point of the glass melt. Finely ground
(minus 325 mesh) is the product for which there is the great-
est demand. It is used as a weighting agent in oil and gas
well drilling mud. Finely ground (bleached and treated) is
a. refined product suitable as a. filler for paints.
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BARIUM COMPOUNDS PRODUCED FROM BARITE
BaSO
Barite
BaSO
'4
Heated with Coal
Black Ash
BaS
Na2SO4
1
Blanc
ZnSO4
, '
fixe Lithe
i
pone
co2
or
Na2CO3
i
Ba
:o3
HC1
1
Ba<
^2
Heat + C
I
BaO
HNO,
\
Ba(NO3)2
H2O
T
Ba(OH2)'8 H2O
Kirk, R. E. and Othmer, D. F. ; Encyclopedia of Chemical
Technology - Vol. 3; 2nd rev. ed. : John Wiley & Sons, Inc.;
New York, N. Y. ; 1968; p. 82.
Figure II
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In Nevada the ore is usually crushed and screened at the
mine, then hauled to the mill where it is crushed again prior
to pulverizing in a ball or Raymond mill. Most of the prod-
uct is for use in oil well drilling muds and is shipped in bags
or in bulk by railroad or truck. At one of the 4 locations in-
spected in Nevada during this study, large quantities of dust
were observed as the ore was dumped from trucks at the mill.
The open conveyor system from the stockpile to the process-
ing plant was also a source of barium sulfate emissions. One
cyclone collector was the only air pollution control equipment
in service and it was obviously not an effective installation.
At another plant the ore was only crushed and screened prior
to shipment to another processing location. There was no
air pollution control equipment.
At one of the 3 milling operations inspected in Arkansas3
the ore received by trucks from the mine wa.s dumped into
a crusher bin before entering the crusher where it was mixed
with water. The next operations consisting of wet grinding
and flotation were followed by drying prior to preparation of
the product for shipment. There were some emissions to
ihe a.rmosphere as the ore was dumped from the trucks and
during drying. Even though a water spray was used in the
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exhaust stack of the dryer, the emissions were quite notice-
able. At this plant about. 80 percent of the product is bulk
loaded and shipped in closed hopper cars. The remaining
20 percent is bagged in the shipping department where bag
filters are employed to control the emissions. Inspections
at the other 2 plants revealed that dust collection systems
are used that include both cyclones and bag filters. Gener-
ally, the inspections indicated that the degree of emission
control was about the same at all 3 mills in Arka.n.sas.
Processing operations in Missouri and Georgia are simila.r,
consisting of washing followed by drying, milling, and ship-
ping. The principal sources of emissions to the a.tmosphere
are drying, milling, and materials handling. Air pollution
control equipment installed includes cyclone collectors and
bag filters. Drying temperature is cont:.roiled to protect the
filter bags and this effectively prevents chemica.l conversion.
of the barite. Particulate emissions are reported to be
BaSO^ minus 325 mesh, probably averaging less than 4
microns.
While this study was in progress 13 companies were contacted
regarding the production of crude and ground barite. The
emission data furnished by one company was essentially
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complete, and that from 4 others contained some informa-
tion concerning various parts of the processing plants. The
data obtained from industry indicate that barium emissions
to the atmosphere due to the milling of barite ore range from
2 to 8 pounds per ton of barite produced. The emissions are
principally in the form of barium sulfate dust, with the par-
ticle size in the range of one to 10 microns V.
Based on 1,077,000 tons of barite production during 1969 _/
and average emissions of 5 pounds of barium per ton of barite
produced, the barium emissions in the United Stated totaled
nearly 2,700 tons.
1- Private communication.
2- Minerals Yearbook; Bureau of Mines; 1969.
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PRODUCTION OF METALLIC BARIUM
Metallic barium may be produced either by carbon reduction
or by electrolysis; however, direct reduction methods have
almost entirely supplanted fused-salt electrolysis. The most
effective process is one which reduces barium oxide with a
suitable nonreactive, nonvolatile element such as silicon
or aluminum.
One method of conducting the basic reaction is as follows.
Barium oxide and aluminum powder are briquetted and placed
in a horizontal metal retort, which is heated to 2, 000 or
2, 200 F for about 8 hours at a pressure of about 0. 1 milli-
meters of mercury. A water-cooled condenser fixed at one
end of the retort is used to condense the barium vapor.
At present only a small amount of metal is produced for use
in alloys and as a "getter" to remove the final traces of gas
from electron tubes during their manufacture. Nevertheless,
there is a large potential market provided the cost of the
metal could be reduced substantially. Due to limited metal
production during 1969, barium emissions were negligible.
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PRODUCTION OF BARIUM CHEMICALS
In the United States all major barium chemicals are pro-
duced using barite as the raw material for the manufacture
of barium sulfide, BaS, also known as black ash. Subse-
quently, the black ash is the raw material for producing
barium carbonate, BaCO,; barium chloride, Bad?; blanc
fixe, BaSO^; and other barium compounds. In turn barium
carbonate may be used to make barium oxide, BaO;- barium
hydroxide, Ba(OH)2; and barium nitrate, BafNCs)^.
To make black ash. the barite is ground to about 20 mesh
f
and mixed with coal of 1/2 inch size, approximately 5 parts
barite to one part coal, then reduced at high temperature to
barium sulfide (Figure III). There are 2 major types of re-
ducing furnaces, the batch rotary and the continuous process.
Batch rotary furnaces are brick lined, fired with gas, oil,
or coal, and normally charged through a side door. In about
3 hours after the fire is started, as the temperature ap-
proaches 2, 100 to 2. 200 F, the charge becomes slightly
sticky. At this point reduction is practically complete, the
fire is turned off. and the charge is dumped. In the contin-
uous process, the feed is at the rear of the furnace with
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BARIUM SULFIDE PRODUCED FROM BARITE
Barite
Coal
<
MILLING
(dry)
i
MIX
i
r
ER
i
REDUCING
FURNACE
t
Gas
1
*DUST COLLECTOR
1
Barium Sulfide
Dust.
Return
to
Process
Figure IIJ
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heat applied countercurrent to the flow of coal (or coke).
Barite and black ash are discharged at the front of the long
kiln.
If the black ash is used in the same plant to produce barium
carbonate, it is conveyed to a grinding and dissolving plant
where it is ground in a wet ba.ll mill or a hammer mill be-
fore it is separated from the insoluble gangue by hot water
leaching.
There are 2 basic methods for producing barium carbonate.
One method is to react black ash with sodium carbonate fol-
lowed by precipitation, washing, dewatering, drying, and
grinding (Figure IV). The other method is a straight gas-
sing process using carbon dioxide to react with the black ash.
Barium chloride is another chemica] produced from black
ash. A barium sulfide solution is treated with hydrochloric
acid in a rubber-lined agitated reaction vessel that is equip-
ped with a gas outlet pipe to carry away the hydrogen sulfide
generated during processing. The resulting barium chloride
Jiquor is concentrated by evaporation and crystallization,
and the hydrogen sulfide is normally burned to sulfur dioxide
in a flare stack.
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BARIUM CARBONATE PRODUCED FROM BARIUM SULFIDE
Ba.rium Sulfide
MILLING
(wet)
Water
LEACH TANK
Sodium Carbonate
REACTION
TANK
Precipitated
Barium Carbonate
Barium Carbonate
Figure IV
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B]anc fixe, used principally a.s a pigment extender, is a pure
form of barium sulfate. Its preparation is quite similar to
that of barium carbonate, except that sodium sulfate is used
instead of sodium carbonate.
The steps in the manufacture of barium oxide and barium
hydroxide are shown in Figure V. Using barium carbonate
as the raw material, the oxide may be prepared by dissociat-
ing the carbonate at high temperatures after mixing with car-
bon in some form such as coke or carbon black. The hydrox-
ide is produced by dissolving the oxide in hot water, filtering
the insoluble material, and separating the hydrated crystal
in a crystallizer. Dewatering, drying, and packaging are the
final processing steps. An alternate method for making rthe
hydroxide is to start with black ash as the raw material and
use a catalyst to produce the hydroxide directly.
Lithopone is used extensively in rubber, paint, and numer-
ous other products. It. is manufactured by adding a solution
of zinc sulfate to barium sulfide leach liquor. The resulting
mixture is then filtered, washed, dried, calcined under con-
trolled conditions, milled, and packaged for shipment.
Many other barium chemicals produced in smaller quantities
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BARIUM HYDROXIDE PRODUCED FROM BARIUM CARBONATE
Carbon black,
coke, or tar
Barium Carbonate
Barium Oxide
i
f
Gas
FURNACE
DUST
COLLECTOR
Dust
I
Return
to
Process
Barium Hydroxide
Figure V
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include barium ferrite used in magnets for electrical de-
vices; barium silicate and barium stearate which are in-
gredients in stabilizers for polyvinyl chloride; barium ti-
tanate and barium zi.rconat.e that are employed in the man--
ufactv>^ of various electronic articles. These compounds
have gained oopula.rity during recent years and their import-
ance rriay increase in the future. Figure VI is a. flow dia-
gram showing the principal steps in preparing barium stearate.
The procedures are somewhat the same for barium silicate,
except the raw material is barium chloride and it is reacted
with sodium silicate gel.
The manufacture of barium titanate and barium zirconate
are also similar. Barium ca.rbonate is dry mixed with titan-
ium dioxide or zirconium oxide after which the mix. is ca.1-
clined, milled, dewatered, dried, and pulverized.
From the standpoint of emissions to the atmosphere;, the
production of black ash is the most important bc.rium chem-
ical. The emissions that occur during unloading, stockpiling,
materials handling, grinding, mixing, and reducing are re-
ported to be barite and barium sulfide with the size of most
particles less than 5 microns. In genera.] the ai.r pollution
control equipment consists of settling chambers and cyclone
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BARIUM STEARATE PRODUCED FROM BARIUM HYDROXIDE
Water
Stearic Acid
Barium Hydroxide
REACTION TANK
Steam Heat
(Indirect)
Gas
DUST COLLECTOR
Barium Stearate
Dust
Return
to
Process
Figure VI
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collectors; however, at one plant that was inspected part
of the flue gas from the reducing furnace was cleaned in
wa.ter scrubbers so that it: could be used a.s the carbon di-
oxide source for the ba.rium ca,:rbonate unit.
Other barium chemical processes that ha.ve been described
are also troubled with emissions to the atmosphere, but to
a somewhat lesser extent. Materials handling, grinding,
mixing, calcining, and drying are the operations that account
for most of the particulate discharge. In many instances
materials handling, mixing, and grinding emissions are un-
controlled.
Estimates of emissions were obtained from 4 major producers
of barium compounds; however, it was evident that: most of
the da.ta was for certain production units and did not include
plant emissions from all sources. Generally, the only emis-
sion, estimates were those concerning controlled sources.
i
Based on the estimates from .industry and the information ob-
tained during plant inspections, barium emissions to the at-
mosphere from sources of chemical production are estimated
by the Contractor at 50 pounds per ton of ba rite processed.
The ground and crushed ba.rite used for chemicals during
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1969 ha.s been reported by the Bureau of Mines as 177, 570
tons *J; therefore, the barium emissions to the atmosphere
during the year tota.led 4,400 tons.
.1.- Minerals Yearbook; Bureau, of Mines; 1969.
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END PRODUCT USES OF BARIUM
Manufacturers in all industries were contacted during this
study concerning materials handling, manufacturing oper-
ations, pollution control equipment, and emissions to the
atmosphere as related to the production and use of barium
and barium compounds. The information obtained indicates
that barium emissions are negligible except in those manu-
facturing operations and end product uses that are describted
herein.
Oil and Gas Well Drilling Mud
The major use for barium is as a weighting agent in oil and
gas well drilling muds. For this purpose it is used in the
form of barite containing about 92 percent or more barium
sulfate. The principal requirements are chemical inertness,
high density, fineness, and low cost. Some iron oxide and
other impurities are not objectionable as long as the barite
meets these requirements and has a specific gravity of at
least 4. 2.
Drilling muds serve several purposes. They help lubricate
and cool the drilling bit, plaster the walls of the drill hole
to prevent caving, carry the cuttings up to the ground surfa.ce,
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and restrain high pressure thus preventing blowouts. In
rotary drilling the bit is rotated by means of a hollow shaft
and the mud is pumped downward inside the shaft removing
cuttings as they are formed and carrying them upward in the
annular space between the shaft and the wall of the drill hole.
The barite prepared for use in drilling mud is ground to 95
percent minus 325 mesh at the mill and shipped in bags or
in bulk. Atmospheric emissions at the well drilling sites
are those associated with unloading and handling the mater-
ial. There were no atmospheric emission records available
from those contacted about the use of barite in drilling mud;
therefore, the Contractor's estimate of 110 pounds of barium
emissions per thousand tons of barite is based on observa-
tions of material handling emission problems at shipping
points.
During 1969 about 1. 240, 000 tons of barite (692, 000 tons
barium content) were used in well drilling muds; therefore,
barium emissions to the atmosphere totaled about 70 tons.
Glass
The second most important use of barium is in the manu-
facture of glass. It is used for several specific purposes
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in the form of barite, barium carbonate, barium nitrate,
barium hydroxide, and barium oxide. It fluxes the heat in-
sulating froth that forms on the melt surface, thereby effect-
ing a saving in fuel. It acts as an oxidizer and decolorizer.
It also makes the glass easier to work and increases its
brilliance.
Glass manufacturers usually prefer barite with a maximum
of 1. 5 percent silicon dioxide, 0. 15 percent aluminum oxide,
and 0. 15 percent iron oxide, as well as a minimum of 98 per-
cent barium sulfate. The preferred particle size ranges
from 30 to 140 mesh.
Raw materials for glass manufacture are shipped in packages
or in bulk. Unloading may be accomplished by manual labor,
vibrator-gravity, drag shovels, or vacuum systems. Meth-
ods of material storage vary widely, but in a large installa-
tion the raw materials for the glass mix are often stored in
gravity feed storage hoppers and are fed directly to the weigh-
ing and mixing room. Minor ingredients are usually stored
in their original containers. Gullet (waste glass or rejected
ware to be remelted) must be transported to an area where
the glass is segregated by type.
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Glass batch mixitng systems range from full automation to
hand operations. Most mixers are of the rotating-barrel
type which tumble the batch upon itself in a revolving drum.
During a batch mixing process the materials are dry or near-
ly dry, which causes a loss by dusting. The glass furnace
charging may be done manually or automatically, and con-
tinuously or intermittently.
Basically, the manufacture of glass is a high-temperature
conversion of raw materials into a homogeneous melt for
fabrication into useful articles.
There are 3 types of melting units used in the glass industry.
Clay "pots" which may be open or covered are used where
quantities or special compositions do not justify the use of a
tank. This process involves a relatively high proportion of
manual handling. The day tank melts batches up to several
tons. Finally, most glass is melted in large, direct-fired,
regenerative-type furna.ces.
Following melting there are several ways to accomplish the
forming of glass. The container industry generally is based
on modifications of the blowing technique. Glass also may
be pressed, cast, rolled, or drawn. Glass fibers can be
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made continuously by mechanical drawing, and a glass to be
pulverized is dribbled or ladled into water to produce ''dry
gage" glass.
Final glass operations include finishing and secondary form-
ing operations. Finishing operations may include any one
or combinations of the following: flame cut-off, sawing,
score and break, score-thermal crack off, thermal crack
off, drilling, grinding, polishing, engraving, acid etching,
glazing, and sealing. Secondary forming operations may
then be used to produce difficult shapes. Before the glass
becomes a finished product, a final treatment of tempering
or staining may be required.
Although not all glass manufacturers use barium, the infor-
mation obtained from 8 companies using about 44 percent of
the barium indicates the particle size of emissions is less
than one micron and the magnitude of emissions is about 2
pounds per ton of barium processed. During 1969 the glass
industry used 41, 000 tons of barium; therefore, emissions
in the United States due to the production of glass totaled
about 40 tons during the year.
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Paint
Various barium compounds, including barium sulfate, bar-
ium carbonate, and lithopone, are used in the manufacture
of paint. They are chemically inert and their most import-
ant pigment properties are high specific gravity, relatively
low oil absorption, easy wettability by oils and vehicles, and
easy grinding. They are useful where highly acidic or alka-
line conditions are encountered because of their stability
toward acids and bases.
Barium sulfate is used to produce several pigments. The
lithopone-type cadmium yellow contains from 63 to 66 per-
cent barium sulfate. A medium red shade contains only 59
percent. Lithopone used in the manufacture of white pigment
is composed of 70 percent ba.rium sulfate and 30 percent zinc
sulfide. Another white pigment is 75 percent barium sulfate
and 25 percent anata.se titanium dioxide.
Most operations during the manufacture of paints are carried
out in closed equipment. Dry pigments, however, are usually
received at the plant in bags and there are emissions to the
atmosphere that occur: (1) when the bags are unloaded and
emptied into storage bins; and, (2) when the pigments are
added to the mixers.
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Although several paint manufacturers contacted during this
study indicated they no longer use barium, information was
obtained concerning Implants that still use it in paint manu-
facture. Cyclone-type dust collectors are used at 5 plants,
bag collectors at 5 others, and there is no emission control
equipment at 8 plants. Based on an industry estimate for 8
plants, the barium emissions average 2 pounds per ton of
barium processed. During 1969 about 29, 000 tons of barium
were consumed in paint manufacture and emissions to the at-
mosphere totaled about 30 tons.
Rubber
Barium sulfate is used as a filler in rubber to improve pro-
cessing properties and lower the cost of the finished prod-
uct. It is used along with the raw rubber, accelerators,
plasticizers, reinforcing pigments, antioxidants, retarders,
and vulcanizing agents. The crude rubber is broken down
in the masticating and mixing mill5 which consists of two
rolls revolving at different speeds with heating and cooling
as desired. During the milling operation, carbon black,
zinc oxide, sulfur, and other ingredients are added. After
milling, the rubber is run through calenders where it is
forced into thin sheets and fabric is introduced. Next, the
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carcass is formed and the assembled tire is vulcanized at a
temperature of 260 to 340 F.
The principal emissions to the atmosphere occur when the
finely divided dusts are introduced into the batch at the rub-
ber mills and mixers. Generally, this equipment is provided
with hoods to carry away heat generated by the process, as
well as particulate and fumes from the rolls.
Information obtained from 3 major producers of vehicle
tires and other rubber products shows that cyclone and bag
type dust collectors are commonly used for controlling emis-
sions to the atmosphere. Such equipment is not specifically
to control barium emissions, but it is located at positions
where it is also effective for that purpose. The industry rep-
resentatives were not able to supply records regarding the
ma.gnitude of barium emissions but they provided estimates
indicating that the emissions resulting from rubber manufac-
turing are negligible.
The only significant emissions of barium that occur during
the production and use of rubber products appear to be those
due to the wear of vehicle tires. Although barium is not used
in all tires, the average dosage is in the range of 4 to 5 pounds
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per ton of rubber and the average quantity per vehicle tire
is about 0. 03 pound. During 1969 motor travel in the United
States was about 1. 05 x 10^ miles including passenger cars,
motorcycles, busses, and trucks. The life of a tire aver-
ages 20, 000 miles and when replaced, 20 percent of the rub-
ber is worn away _/. Calculated on the basis of 4 tires per
vehicle, the barium emissions resulting from the wear of
tires during 1969 totaled about 600 tons.
] - Private communication.
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Miscellaneous
In the United States during 1969 about 12.9,000 tons (nearly
14 percent) of the barium was used in the form of barite
and barium chemicals in processing or as an ingredient, in
various products including cosmetics, cloth, leather, lino-
leum, oilcloth, plastics, Pharmaceuticals, printers' ink,
photographic paper, rat poison, depilitories, pyrotechnics,
lubricating oil detergents, water softeners, sugar, and die-
sel fue] additives.
The information obtained from industry about the use of bar-
ium in these end products was valuable in connection with
establishing the type of processing operations, the quantity
of barium consumed, and the kind of air pollution controls
employed; however, only 2 companies provided emission
estimates. In genera], most processing emission sources
with little or no control, are those related to materials
handling.
One relatively new source of barium emissions to the atmos-
phere is the rapidly expanding plastics industry. Vinyl stab-
ilizers are used to prevent discoloration during processing
and also serve to maintain certain desirable properties during
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the useful life of the product. In recent years the number
of stabilizers available has increased considerably and
those based on combinations of barium, cadmium, and phos-
phite have become very popular. Although emissions due to
the manufacture of barium stabilizers were probably low in
1969, they may become significant in the future.
Numerous compounds that contain heavy metals are market-
ed as additives for various kinds of oils, including those used
for fuel and lubrication. Some for diesel, distillate, and re-
sidual oils are used as dispersants, stabilizers, and inhibi-
tors, while others are intended to improve combustion.
Those compounds for lubricating oils are principally used as
detergents. Additives containing barium also are ingredients
in fluids for hydraulic equipment and automatic transmissions.
During this study more than 200 additives were examined and
26 were found that contained barium /; however, reliable
information was not available concerning the actual amount
of barium used in additives.
1- "Effects of Fuel Additives on Air Pollutant Emissions
from Distillate-Oil-Fired Furnaces"; Environmental
Protection Agency; Office of Air Programs Publication
No. AP-87; June, 1971.
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As stated above, about 129, 000 tons of barium were used in
the manufacture of various products. Emission data avail-
able from industry were limited. Based on the type of pro-
cessing operations and air pollution controls employed, the
Contractor's estimate of barium emissions for the year 1969
is 3, 500 tons. It is likely this estimate is low; it is reason-
ably certain that it is not high by more than 30 percent.
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SOURCES OF INADVERTENT BARIUM EMISSIONS
COAL
A search has been conducted and information has been found
regarding the barium content of coal, ash of coa], and fly
a.sh emissions from coal fired power plants.
With respect to fly ash, there is a study of emissions from
coal fired power plants that has been made which shows the
analysis of several fly ash samples. Six power boilers were
tested, each a different type, and each value reported was
the average of at least 2 tests. Two of the boilers were fired
with Illinois coal: 2 burned Pennsylvania coal; one used
some coal from Ohio and some from West Virginia; one
burned part Kentucky and part West Virginia coal. The coal
burned during the tests represented only a small portion of
the coa.l mined in the various regions of the United States.
Ba.rium concentrations in the fly ash samples taken before
fly ash collection ranged from 3. 65 to 27. 2 x 10 grains
per scf /. The average was 14. 5 x 10 grains per scf.
1- Cuffe, Stanley T. and Gerstle, Richard W. ; "Emissions
from Coa] Fired Power Plants"; Public Health. Service
Publication No. 999-AP-35; 1967.
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Ca.lculations have been made based on:
(a) 516, 084, 000 tons of bituminous and anthracite coal
consumed in the United States during 1969 /;
(b) 160 scf of flue gas per pound of coal;
(c) 14. 5 x 10 grains per scf barium concentration;
(d) 85 percent efficiency of control; and
(e) 90 percent application of control.
The barium emissions calculated in this manner totaled
4,.000 tons. .
During the combustion of coal, barium is discharged with the
ash; part with the bottom ash and part with the fly ash. The
fly ash averages about 65 percent of the total ash.
Many samples of coal have been analyzed and the barium con-
tent reported as shown in Table IV. Calculations have been
made based on:
(a) 516, 084, 000 tons of bituminous and anthracite coal
consumed in the United States during 1969 /;
1- Minerals Yea.rbook; Bureau of Mines; 1969.
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(b) 89 pprn average barium concentration in coal;
(c) fly ash 65 percent of total ash;
(d) 85 percent efficiency of control; and
(e) 90 percent application of control.
The barium emissions calculated in this manner totaled
7, 000 tons.
516, 084, 000 x 89 x 10'6 x 0. 65 Pi - (0. 85 x 0. 90)1 - 7,
000
In this report the figure of 4, 000 tons is used as the barium
emissions to the atmosphere during 1969 due to the combus-
tion of coal.
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TABLE IV
AVERAGE BARIUM CONTENT IN ASH OF COAL,
Frequency of Ba Content
Reglon Detection - % of Ash - %
Eastern Province 100 0. 0876
Interior Province 100 0. 0399
Western States 100 0. 1467
Average Barium Content of Coal
Ash Content Ba Content
of Coal - % of Coal - %
9.3 0.0081
10.5 0.0042
9.8 0.0143
0. 0089
OJ
I
NOTE - The above table based on "Spectrochemical Analyses of Coal Ash for Trace
Elements"; Bureau of Mines RI 7281; Table 1; July, 1969.
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-44-
OIL
In order to estimate barium emissions to the atmosphere
due to the combustion of fuel oil, it is necessary to deter-
mine the barium content and the quantity of oil received
from numerous foreign and domestic sources. Information
was located showing the analyses of more than 100 samples
of domestic crude; however, the situation was different with
respect to residual oils and foreign crude. The only reliable
information available on residual oil was that regarding
nickel and vanadium.
Due to the lack of reliable data, there is no estimate of emis-
sions set forth in this report other than a suggested range of
values. Based on the Contractor's studies of other metal
emissions due to the burning of fuel oil, barium emissions
should range between 100 and 1,000 tons for the year 1969.
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IRON AND STEEL
During this study spectrographic analyses of dust samples
from 3 iron foundries have been examined and they show
barium is present in all samples, the content ranging from
0. 01 to 0. 07 percent l_l.
The cupola is the most popular method for producing cast
iron and the rate of particulate emissions from gray iron
cupolas has been reported as 4 to 26 pounds per ton of pro-
cess weight not including emissions from materials handling,
charging, or other non-melting operations.
Based on information obtained from industry the particulate
emission factor is estimated at 22 pounds per ton of process
weight, including melting and non-melting operations. The
degree of emission control is approximately 25 percent.
Calculations show that with 0.03 percent barium in the par-
ticulate, the emission factor is 0. 005 pound of barium per
ton of process weight.
During 1969 the pig iron, and scrap used by iron foundries
1- Private communication.
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-46-
totaled 18,594,000 tons /; therefore, barium emissions
to the atmosphere due to the production of cast iron were
50 tons.
There wa.s some information located during research that
indicated barium as a trace element in the discharge from
an open-hearth furnace / but no data was obtained regard-
ing blast, electric, or basic oxygen furnaces. The emis-
sions of barium to the atmosphere during stee] production
are estimated to be less than 200 tons for 1969.
.1- Minerals Yearbook; Bureau of Mines; 1969.
2- "Air Pollution Engineering Manual"; Public Health Serv-
ice Publication. No. 999-AP-40; p. 243: 1967.
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UPDATING OF EMISSION ESTIMATES
The emissions and emission factors presented in this report
are the result of calculations based principally on informa-
tion obtained from industrial sources. They are specifically
for the year 19&9, but ma.y be updated at any time when addi-
tional information is available. Either of the 2 methods de-
scribed herein may be used for updating; however, the longer
procedurej referred to as Method A, will yield results that
are much more reliable.
The procedures to be followed with Method A are essentially
the same as those used during the original study, which are
described briefly as follows. More than 150 inquiries were
sent to processing and reprocessing companies by mail or
delivered during personal visits to plant sites. There was
no reply from 56 companies. Another 59 companies answered
but did not provide data. There were 37 companies that furn-
ished all or part of the data requested and that information
was the basis for emission factors and emission estimates
set forth in this report.
All of the companies that produce barite were requested to
provide the essential data required for the study. Information
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-48-
was obtained concerning 10 of the 19 mining operations in
Arkansas, Georgia, Missouri, and Nevada. The chemical
producing companies and manufacturers of end products
that provided information represented about 40 percent of
the industry capacity.
Regardless of the method selected, the first, step to be taken
when updating the emission estimates is to obtain the latest
issue of the Bureau of Mines Minerals Yearbook, Volume I-II,
which is normally available within 16 to 18 months after the
end of the calendar year (preprints of individual sections are
usually available sooner). This publication shows the quan-
tity of barite sold or used by producers, as well as the quan-
tity imported. It also shows the amount of barite sold by
producers for use in well drilling, barium chemicals, glass,
paint, and other uses. .In this one publication most of the in-
formation is available that is required to update the material
flow cha.rt. for barium. Additional information may be ob-
tained from the commodities specialists at the U. S. Bureau
of Mines.
When using Method A, the emission factors must be revised
by contacting industry to determine the improvements in air
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-49-
pollution collection equipment efficiency and other process-
ing changes affecting barium emissions. The revised emis-
sion factors may then be used with the production quantities
obtained from the Minerals Yearbook or other referenced
sources.
Method B is considerably shorter than Method A and less re-
liable. The only requirement is to revise the material, flow
chart according to the most recent published data and apply
the emission factors shown, in. this report. In reality this
method is only a partial updating. There is no determina-
tion regarding improvements in air pollution control, a shift
in production to more efficient plants, or any other consid-
erations affecting emission factors. The advantage is that
the report can be updated within a few days, rather than
several months.
To update barium emissions from processing, chemical
production, beet sugar refining, plastics, and petroleum
additives, it is preferable to use Method A. The remain-
ing emissions shown in this report may be updated by Method
B without introducing an appreciable error into the results.
-------
BIBLIOGRAPHIC DATA
SHEET
1. Report No.
APTD-1140
3. Recipient's Accession No.
4. Title and Subtitle
National Inventory of Sources and Emissions: Barium - 1969
5- Report Date
May 1972
6.
7. Author(s)
W. E. Davis
Performing Organization Rept.
No.
9. Performing Organization Name and Address
W. E. Davis & Associates
9726 Sagamore Road
Leawood, Kansas
10. Project/Task/Work Unit No.
11. Contract/Grant No.
68-02-0100
12. Sponsoring Organization Name and Address
ENVIRONMENTAL PROTECTION AGENCY
Office of Air and Water Programs
Office of Air Quality Planning and Standards
Research Triangle Park. North Carolina 27711
13. Type of Report It Period
Covered
14.
15. Supplementary Notes
16. Abstracts
Information is provided regarding the nature, magnitude, and extent of the emissions
of barium in the United States for the year 1969. Background information concerning
the basic characteristics of the barium (barite) industry has been assembled and in-
cluded. Brief process descriptions are given; they are limited to the areas that are
closely related to existing or potential atmospheric losses of the pollutant. The
barium emissions and emission factors are based on data obtained from production and
reprocessing companies. Additional information was acquired during field trips to in
spect the air pollution control equipment and observe processing operations. Emis-
sions to the atmosphere during the year were 15,420 tons. Nearly 18 percent of the
emissions resulted from the processing of barite, more than 28 percent from the pro-
duction of chemicals, 23 percent from the manufacture of various end products, and
about 26 percent from the combustion of coal. The wear of rubber tires was a rela-
tivelv minor emission source.
17. Key Words and Document Analysis. 17o. Descriptors
Air pollution
Barium inorganic compounds
Inventories
Exhaust emissions
Industrial wastes
Minerals
Chemical industry
Coal
Combustion products
Tires
17b. Identifiers/Open-Ended Terms
Me. COSATI Field/Group
13B
18. Availability Statement
Unlimited
19. Security Class (This
Report)
UNCL
20. Security Class (Thi;
Page
XINCLASSIF1ED
21. olo. of Pages
56
22. Price
FORM NTIS-SO (REV. 3-721
USCOMM-DC I4863-P7S
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INSTRUCTIONS FOR COMPLETING FORM NTIS-35 (10-70) (Bibliographic Data Sheet based on COSATI
Guidelines to Format Standards for Scientific and Technical Reports Prepared by or for the Federal Government,
PB-180 600).
1. Report Number. Each individually bound report shall carry a unique alphanumeric designation selected by the performing
organization or provided by the sponsoring organization. Use uppercase letters and Arabic numerals only. Examples
FASEB-NS-67 and FAA-RD-68-09.
2. Leave blank.
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4. Title and Subtitle. Title should indicate clearly and briefly the subject coverage of the report, and be displayed promi-
nently. Set subtitle, if used, in smaller type or otherwise subordinate it to main title. When a report is prepared in more
than one volume, repeat the primary title, add volume number and include subtitle for the specific volume.
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from the performing organization.
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9. Performing Organization Name and Address. Give name, street, city, state, and zip code. List no more than two levels of
an organizational hierarchy. Display the name of the organization exactly as it should appear in Government indexes such
as USGRDR-I.
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11. Controct/Grant Number. Insert contract or grant number under which report was prepared.
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Translation of ... Presented at conference of ... To be published in ... Supersedes . . . Supplements
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If the report contains a significant bibliography or literature survey, mention it here.
17. Key Words and Document Analysis, (a). Descriptors. Select from the Thesaurus of Engineering and Scientific Terms the
proper authorized terms that identify the major concept of the research and are sufficiently specific and precise to be used
as index entries for cataloging.
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open-ended terms written in descriptor form for those subjects for which no descriptor exists.
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FORM NTIS-35 (REV. 3-72) OSCOMM-OC I4002-P72
fcU.S. G.P.O.: 1973—746-770/4176, Region No. 4
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