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AIR POLLUTION ASPECTS
OF
BARIUM AND ITS COMPOUNDS
Prepared for the
National Air Pollution Control Administration
Consumer Protection & Environmental Health Service
Department of Health, Education, and Welfare
(Contract No. PH-22-68-25)
Compiled by Sydney Miner
Litton Systems, Inc.
Environmental Systems Division
7300 Pearl Street
Bethesda, Maryland 20014
September 1969
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FOREWORD
As the concern for air quality grows, so does the con-
cern over the less ubiquitous but potentially harmful contami-
nants that are in our atmosphere. Thirty such pollutants have
been identified, and available information has been summarized
in a series of reports describing their sources, distribution,
effects, and control technology for their abatement.
A total of 27 reports have been prepared covering the
30 pollutants. These reports were developed under contract
for the National Air Pollution Control Administration (NAPCA) by
Litton Systems, Inc. The complete listing is as follows:
Aeroallergens (pollens) Ethylene
Aldehydes (includes acrolein Hydrochloric Acid
and formaldehyde) Hydrogen Sulfide
Ammonia Iron and Its Compounds
Arsenic and Its Compounds Manganese and Its Compounds
Asbestos Mercury and Its Compounds
Barium and. Its Compounds Nickel and Its Compounds
Beryllium and Its Compounds Odorous Compounds
Biological Aerosols Organic Carcinogens
(microorganisms) Pesticides
Boron and Its Compounds Phosphorus and Its Compounds
Cadmium and Its Compounds Radioactive Substances
Chlorine Gas Selenium and Its Compounds
Chromium and Its Compounds Vanadium and Its Compounds
(includes chromic acid) Zinc and Its Compounds
These reports represent current state-of-the-art
literature reviews supplemented by discussions with selected
knowledgeable individuals both within and outside the Federal
Government. They do not however presume to be a synthesis of
available information but rather a summary without an attempt
to interpret or reconcile conflicting data. The reports are
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necessarily limited in their discussion of health effects for
some pollutants to descriptions of occupational health expo-
sures and animal laboratory studies since only a few epidemic-
logic studies were available.
Initially these reports were generally intended as
internal documents within NAPCA to provide a basis for sound
decision-making on program guidance for future research
activities and to allow ranking of future activities relating
to the development of criteria and control technology docu-
ments. However, it is apparent that these reports may also
be of significant value to many others in air pollution control
such as State or local air pollution control officials, as a
library of information on which to base informed decisions on
pollutants to be controlled in their geographic areas. Addi-
tionally, these reports may stimulate scientific investigators
to pursue research in needed areas. They also provide for the
interested citizen readily available information about a given
pollutant. Therefore, they are being given wide distribution
with the assumption that they will be used with full knowledge
of their value and limitations.
This series of reports was compiled and prepared by the
Litton personnel listed below:
Ralph J. Sullivan
Quade R. Stahl, Ph.D.
Norman L. Durocher
Yanis C. Athanassiadis
Sydney Miner
Harold Finkelstein, Ph.D.
Douglas A. Olsen, Ph0D.
James L. Haynes
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The NAPCA project officer for the contract was Ronald C.
Campbell, assisted by Dr. Emanuel Landau and Gerald Chapman.
Appreciation is expressed to the many individuals both
outside and within NAPCA who provided information and reviewed
draft copies of these reports. Appreciation is also expressed
to the NAPCA Office of Technical Information and Publications
for their support in providing a significant portion of the
technical literature.
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ABSTRACT
Soluble barium compounds are highly toxic when ingested,
while insoluble compounds, such as the most common barium com-
pound, barium sulfate, are generally nontoxic. Inhaled barium
compounds cause a benign pneumoconiosis, called baritosis.
Ingestion of soluble barium compounds results in strong stimu-
lation of the muscles, including the heart; irritation of the
intestinal tract; and irritation of the central nervous system.
The major sources of barium compounds emitted into the
atmosphere are the • industrial processes involved in the mining,
refining, and production of barium and barium-base chemicals,
and the use of barium compounds as a fuel additive for the
reduction of smoke emissions from diesel engines. Data have
not been found on the quantity of emissions from industrial
processes. Some limited data on barium emissions from diesel
engine exhaust were estimated to be a maximum of 48,000 |jg/m3
(25 percent soluble barium) at full load. No information is
currently available on the concentration of barium or its
compounds in ambient air.
No information has been found on the abatement of
barium air pollution, or on the costs of its abatement or of
damages resulting from barium air pollution. Methods are
available for the determination of barium concentrations in
the atmosphere.
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CONTENTS
FOREWORD
ABSTRACT
1. INTRODUCTION 1
2 . EFFECTS . 2
2.1 Effects on Humans 2
2.2 Effects on Animals 4
2.2.1 Commercial and Domestic Animals 4
2.2.2 Experimental Animals 4
2.3 Effects on Plants 6
2.4 Effects on Materials 6
2.5 Environmental Air Standards 6
3. SOURCES 7
3.1 Natural Occurrence 7
3.2 Production Sources 8
3.2.1 Mining and Milling of Barite 8
3.2.2 Barium Metal 9
3.3 Product Sources 10
3.3.1 Ground Barite 10
3.3.2 Principal Barium Compounds 11
3.3.3 Diesel Fuel Additives 14
3.4 Environmental Air Concentrations 21
4. ABATEMENT 23
5. ECONOMICS 24
6. METHODS OF ANALYSIS 25
6.1 Sampling Methods 25
6.2 Quantitative Methods 25
7. SUMMARY AND CONCLUSIONS 27
REFERENCES 30
APPENDIX 36
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LIST OF FIGURES
1. Barium Compounds Produced from Barite 12
2. Effect of Smoke-Suppressant Additive on Diesel
Exhaust Emissions (1.4-liter engine) 16
3. Effect of Smoke-Suppressant Additive on Diesel
Exhaust Emissions (Direct-injection engine) 17
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LIST OF TABLES
1. Barium Content in Coal Ash 8
2. Properties, Toxicity, and Uses of Barium and Some
Barium Compounds 37
3. Toxicity to Animals of Selected Barium Compounds ... 50
4. Domestic Production of Barite, United States 53
5. Domestic Consumption of Barite 54
6. Ground and Crushed Barite Sold by Producers to
Consuming Industries 55
7. Effect of Additive on Emissions of Polynuclear
Aromatic Hydrocarbons—Mean Total Contents 56
8. Analysis of Solids Emitted from 1.5-Liter
Automotive Diesel Engine 57
9. Analysis of Solids Emitted from 5.8-Liter, Truck-
Type Diesel Engine 58
10. Analysis of Solids Emitted from Two-Stroke
Automotive Diesel Engine 59
11. Analysis of Solids Emitted from Diesel Vehicles . . . 60
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1. INTRODUCTION
Very little information is available on the air pollu-
tion aspects of barium and its compounds; however, the intro-
duction of barium compounds into diesel fuels as a means of
reducing black smoke emissions has focused interest on the
effects of barium in the environmental air. While it is gen-
erally accepted that the insoluble compounds, such as barium
sulfate, are nontoxic, the soluble compounds are known to be
highly toxic when ingested, and inhalation of barium compounds
can produce a benign pneumoconiosis, known as baritosis. How-
ever, the effects of barium air pollution cannot be stated with
certainty because of insufficient knowledge of the effects of
atmospheric concentrations of barium compounds, particularly
in the micron-particle size emitted from exhausts of diesel
engines fueled with smoke-suppressant additives. A summary
of some of the properties, toxicity, and uses of selected
barium compounds are listed in Table 2 in the Appendix.
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2. EFFECTS
2.1 Effects on Humans
The soluble salts of barium are highly toxic when
ingested; barium chloride and barium carbonate, two of the
soluble compounds, have been reported^' -^ to cause toxic symp-
toms of a severe but usually nonfatal degree. One case is
reported-* in which 7 grams of barium chloride taken orally
produced severe abdominal pain and near-collapse, but not
death. However, Patty indicates 0.8 to 0.9 grams to be a
lethal dose. Few cases of industrial poisoning from soluble
barium salts have been reported; most of these have been cases
of accidental ingestion.
Ingested soluble barium compounds produce a strong stimu-
lating effect on all muscles of the body. The effect on the
heart muscle is manifested by irregular contractions followed
by arrest of systolic action. Effects on the gastrointestinal
tract cause vomiting and diarrhea, and on the central nervous
system, violent tonic and clonic spasms followed in some cases
by paralysis.$'19
The symptoms of barium poisoning are excessive saliva-
tion, vomiting, colic, diarrhea, convulsive tremors, slow hard
pulse, and increased blood pressure. The stomach, intestines,
and kidney may hemorrhage, and muscular paralyses may follow.
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Depending on the dose and solubility of the barium compound,
death may occur in a few hours or a few days.19 A death attri-
buted to barium oxide poisoning was reported;^1 however, the
usual effect of exposure to dusts and fumes of barium sulfide,
barium oxide, and barium carbonate is irritation of eyes, nose
91
and throat, and the skin. x
The insoluble barium compounds are generally nontoxic
when ingested. For example, barium sulfate, the most common
of the insoluble barium compounds, is widely used as an opaque
liquid, administered orally, in X-ray examination of the gas-
trointestinal tract. 1
Inhalation of barium compounds is known to cause a
benign respiratory affliction (pneumoconiosis) called barito-
sis,21 which has been reported in workers exposed to finely
divided barium sulfate in Italy, and in barite miners in the
United States, Germany, and Czechoslovakia. 1 It has also
been reported in workers producing lithopone, 0»21 an(g among
workers exposed to barium oxide.19 Generally, baritosis pro-
duces no symptoms of emphysema or bronchitis, and lung function
tests show no respiratory incapacity, although some afflicted
workers complain of dyspnea upon exertion.19 The radiological
appearances are very fine nodules on a reticulated background
evenly distributed through the lung fields.5/19 In the
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majority of cases nodulation disappears if exposure to the
19
barium compound is stopped.
Soluble barium is retained by muscle tissue for about
30 hours, and then the amount of retained barium decreases
slowly. Small amounts of barium become irreversibly deposited
in the skeleton. However, the acceptance level must be limited
as quantitative analysis of human bone reveal no accumulation
above 7 ppm (ashed tissue) throughout a lifetime. Very little
barium is retained by the liver, kidneys, or spleen, and prac-
tically none by the brain, heart, or hair.
Information on the properties, toxicity, and uses of
barium and selected barium compounds is presented in Table 2
in the Appendix.
2.2 Effects on Animals
2.2.1 Commercial and Domestic Animals
No information was found on the effects of barium or
barium compounds on commercial or domestic animals.
2.2.2 Experimental Animals
Miller-'--' reported on the toxicity of exhaust solids
emitted from a laboratory diesel engine which was using fuel
with a barium-base smoke-suppressant additive. The solids
contained carbon, barium sulfate, and smaller amounts of
barium carbonate. The LD50 for these solids was reported in
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excess of 10 grams per kilogram of body weight. The type and
number of animals used in this experiment were not reported.
In a companion experiment, Miller exposed white rats (number
not reported) to 10 times the concentration of airborne exhaust
solids that would be emitted from a bus burning fuel with a
barium-base smoke-suppressant additive. After a series of 10
exposures and fresh-air cycles, the animals were examined for
lung damage. No unusual conditions were found.
Guinea pigs were used to test the effects of inhalation
of barite dust. Nodular granulation of the lungs characteristic
of baritosis was reported.-* Subcutaneous injection of 5,000
|ag/m3 of barium chloride caused acute toxicity and death in
rabbits after 2 to 2^ hours. Chronic poisoning resulted from
repeated injection of 10,000; 5,000; and 2,000 |ag/kg.19
Bronchogenic carcinoma developed in rats injected with
radioactive barium sulfate.19 Study of metabolism in rats
showed 24-hour urinary and fecal excretions to be 7 and 20 per-
cent respectively. Trace amounts of barium were irreversibly
deposited in the skeleton.19 Nadell° injected 0.2 ml/kg of a
30 percent suspension into the hearts of cats and subsequently
found increased pulmonary resistance, decreased pulmonary com-
pliance and functional residual capacity, increased end-expira-
tory transpulmonary pressure, and increased anatomic dead space.
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Examination of the lungs showed that the barium sulfate caused
constriction of the peripheral airways, principally in the
alveolar ducts.
Information on the toxicity of selected barium compounds
74-
to certain experimental animals, as presented by Spector, ^ is
contained in Table 3 in the Appendix.
2.3 Effects on Plants
No data have been found on the effect of environmental
concentrations of barium on plants. Browning-' indicated that
barium is toxic to plant life but gave no information on the
chemical form or concentration, or the type of plant life
involved.
2.4 Effects on Materials
No information has been found on the effect of environ-
mental concentrations of barium on materials .
2.5 Environmental Air Standards
The American Conference of Governmental Industrial
Hygienists at their 29th annual meeting in 1967 recommended an
8-hour threshold limit of 500 |-ig/m3 for occupational exposure
to the soluble compounds of barium in air. No ambient air
quality standards for barium and its compounds are known to
exist for either the United States or any other country.
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3. SOURCES
3.1 Natural Occurrence
Barium is a soft, silvery metallic element found in
nature only in combination with other elements. It frequently
appears as gangue in lead and zinc ore deposits, although it
also occurs in veins. The two main minerals are barite (barium
sulfate, BaSO4) and witherite (barium carbonate, BaCO3).
Barite is by far the most important commercial barium ore.
It occurs in beds or masses in limestone, dolomite, shales,
and other sedimentary formations; as residual nodules resulting
from weathering of barite-bearing dolomite or limestone; and as
gangue in veins or beds together with fluorspar, metallic sul-
fides, and other minerals. The chief barite-producing areas
in the United States are located in Missouri, Arkansas, Georgia,
and Nevada.19 The deposits of impure barite ores found in Ken-
tucky and Tennessee are not worked extensively-
Witherite, which consists of 77.7 percent barium oxide
and 22.3 percent carbon dioxide, is usually found associated
with galena in veins.2/13 The mineral witherite is less com-
mon than barite and is found only in small quantities in the
United States. The largest deposit in this country is in El
Portal, Calif. This ore is not mined commercially in the
United States and very little is imported.
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8
Small quantities of barium are found in most igneous
rocks, and it is a minor constituent of feldspar and mica.^
Trace quantities of barium are also found in coal. The per-
centage of barium found in coal ash from various coal sources
is shown in Table 1.
TABLE 1
BARIUM CONTENT IN COAL ASH1
Percentage of Barium
Source of Coal in Ash
West Virginia 0.05 to 0.44
North Dakota 0.15
Alaska (Nenana field) 0.4 to 0.8
England 0.0 to 4.3
Nova Scotia 0.0018 to 0.22
Germany (Newrode) 0.22
Germany, brown coal 0.0001
Germany <0.1
Portugal, anthracite 0.01 to 0.1
Norway (Spitsbergen) 0.1 to 0.2
3.2 Production Sources
3.2.1 Mining and Milling of Barite
The methods used in mining barite ore vary widely with
the type and size of the deposit and the desired end-product.
Ladoo and Meyers1 list the following mining methods employed
in the United States:
(1) Hydraulic mining of residual barite in clay or use
of power shovels in open pits.
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(2) Blasting barite-bearing shale from open pits.
(3) Underground mining of barite veins or beds.
(4) Blasting of massive barite from open quarries.
Domestic production of barite, by State, is shown in
Table 4 in the Appendix.
The methods for milling of barite depend upon the nature
of the ore and the desired end-product. Approximately 90 per-
cent of the barite being produced is ground and crushed for use
in oil-^well drilling; the remainder is used principally for the
production of barium chemicals and lithopone. For use as a
well-drilling mud—for which the only requirements are fine-
grind, nonreactivity, and high specific gravity-^—the barite
is only ground and bagged. For chemical industrial use, it is
ground, then washed to remove impurities; in some cases it is
passed through a magnetic separator to remove iron impurities.
Barite is marketed in the following grades: crude, hand-
select lump, jig and table concentrates, granular, fine-ground,
fine-ground bleached, and fine-ground off-color.
No information has been found on emission of barium from
mining or milling facilities.
3.2.2 Barium Metal
Barium metal is produced by the reduction of barium oxide
with aluminum, in retorts. The barium oxide and aluminum powder
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10
are heated in the retort to 1,100 to 1,200°C, at low pressures
(0.1 mm of mercury); the metallic barium distills as a vapor
and is condensed and collected.
Barium metal is difficult and expensive to produce. It
is highly reactive in normal atmospheres and combines rapidly,
forming a barium salt. The major uses for metallic barium are
as a getter (to remove residual gases) in radio tubes and as
an alloying agent in the production of barium-nickel alloys
and frarry metal, which is a bearing alloy of lead, barium,
and calcium.2'-^
No data have been found on atmospheric emissions of
barium during the production or use of this metal.
3.3 Product Sources
Barium is used in mineral form (barite) in the oil-
drilling industry and in the manufacture of certain chemicals,
including the white paint pigment lithopone. Barium is also
used as an additive to diesel fuels to suppress black smoke
emissions. The domestic consumption of crude barite in the
manufacture of barium products is indicated in Table 5 in the
Append ix.
3.3.1 Ground Barite
The largest use for ground barite is for oil-drilling
mud. Approximately 5 tons of barite are used for the drilling
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11
of each 1,000 feet of high-pressure well. ^ Other uses are as
a filler in paper, rubber, cloth, linoleum, oilcloth, etc.^-3
Bleached barite, prime white, is used as a pigment and extender
in white paint.
Granular barite is used in the manufacture of glass and
in ceramic glazes and enamels.2'1-^ The amount of ground and
crushed barite sold to the consuming industries is shown in
Table 6 in the Appendix.
No information has been found on the emissions of barite
to the atmosphere from the barite-using plants.
3.3.2 Principal Barium Compounds
Barium chemicals are normally produced from ground or
crushed barite, which is mixed with pulverized coal and roasted
in a kiln, reducing the barite (barium sulfate) to barium sul-
fide (or black ash). The barium sulfide is then converted into
commercial chemicals as shown in Figure 1.
The major barium compounds and their primary uses are as
follows :
(1) Lithopone is a white powder consisting of approxi-
mately 70 percent barium sulfate and 30 percent zinc sulfide.
It is widely used in the manufacture of white pigment and is
also mixed with other pigments as a substitute for white lead.
It is nonpoisonous, and is not blackened by exposure to hydrogen
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Barite
BaSO,
Heated with coal
Na2SO4
1
4
Blanc fixe
(BaS04
Black ash
BaS
rn2
ZnSO4 or
iNa2CU3
V
Lithopone BaC03
1 1
Heat + C HN03
HCI
1
1
BaCI2
1
NaN03
T
Bad
Ba(NO
32
H2O
I
Ba(OH)2 °8H20 Ba02
FIGURE 1
Barium Compounds Produced from Barite'
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sulfide gases. Lithopone is also used in the manufacture of
automobile tires, rubber matting, rubber tubing, and other
high-grade rubber products; as a filler in oilcloth, linoleum,
and window-shade cloth; and in production of printer's ink and
cosmetics.
(2) Barium sulfate, or blanc fixe (BaSO4), is a white,
insoluble, amorphous powder chemically precipitated from bar-
ium sulfate. It is used in the manufacture of coloring com-
pounds and high-grade paint pigments. It also serves as a
filler for rubber goods, linoleum, oilcloth, and glaze powders,
and as a base for lithographic inks. Blanc fixe is also uti-
lized in the manufacture of photographic paper, leather, and
cloth.
An important medical use of barium sulfate, which is
insoluble and nontoxic, is 'as a contrast emulsion in X-ray
examination of the gastrointestinal tract. Because of its
high X-ray absorption capacity, it clearly delineates the
intestinal passages. It is also used medically as an anti-
diarrheal powder.2'3,13
(3) Barium carbonate (BaCO3) serves as a raw material
from which other barium compounds are produced. It is also
used in the ceramic industry to prevent efflorescence, in clay-
wares such as brick and tile, as an ingredient in optical glasses
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14
and fine glassware, in case-hardening of steel, in the manu-
facture of photographic paper, and as a rat poison.2'3
(4) Barium chloride (BaCls) is used as a raw material
in producing blanc fixe, in manufacturing barium colors, as a
sodium hydroxide, and as a water softener. It also serves as
an ingredient in case-hardened steels, and in medicinal prepa-
rations ,2'3'13
(5) Barium nitrate (Ba(N03)2) is used primarily in
green signal flares in pyrotechnics, and to a lesser extent in
medicinal preparations.
(6) Barium oxide (BaO) is used as a raw material in
the preparation of barium peroxide, barium hydroxide, and
barium methoxide. It is also utilized in the manufacture of
o
lubricating oil detergent, as an industrial drying agent,
o
and in case-hardening of steels.
(7) Miscellaneous barium chemicals include barium
hydroxide (Ba(OH)3), barium chromate (BaCrO4), barium chlorate
(Ba(CLO3)3), and barium cyanide (Ba(CN)3). The uses of these,
and other barium compounds, are listed in Table 2 in the Appen-
dix.
3.3.3 Diesel Fuel Additives
Barium-base organometallic compounds have been found
11
effective in reducing black smoke emissions from diesel engines. x'
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15
There are a number of such barium-base additives, the exact
chemical compositions of which are considered proprietary infor-
mation by the companies producing them. Concentrations of 0.075
to 0.200 percent by weight of additive in fuel have been found
effective, with the lower figure of 0.075 percent weight gen-
erally used.
Miller-*-^ reported that the smoke-suppressing effect of
the barium-base additive has been evaluated in diesel engines
manufactured by 21 European and 5 American companies. Smoke
was substantially reduced in all cases. The additive decreases
the amount of the black smoke by reducing the carbon concentra-
tion in diesel exhaust. The mechanism of carbon reduction is
postulated to be inhibition of dehydrogenation of the hydro-
carbon fuel. In addition to its smoke-suppressant function,
the additive is claimed to reduce carbon deposits and provide
wear-protection for injectors and piston rings, while producing
no apparent effect on fuel consumption. ' -^ The effect of a
barium-base additive in reducing smoke emission from a single-
cylinder, direct-injection, 1.4-liter diesel engine operated
at a high load of 100 psi brake mean effective pressure (bmep)
and a moderately high load of 85 psi bmep is shown in Figure 2.
The effect of fuel additive on full-load exhaust smoke from a
4%-inch bore x 6-inch stroke direct-injection engine is shown
in Figure 3. According to Miller, ^ analysis of exhaust gases
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16
ULJ
&
Q
01
oc
60 -
50 -
40 -
z £ 30 -
Ol
i= 20 H
o
Q §,
O
2
10 -
0
100-
80-
60-
40-
20-
0
100 psi bmepb
85 psi bmepb
i^ I I I I I I i I
0.02 0.04 0.06 0.08 0.10 0.12 0.14 0.16 0.18 0.20
CONCENTRATION OF BARIUM IN DIESEL FUEL, % wt
"Hartridge units: units of measurement based on the light-extinction principle,
comparing exhaust gases with clean air.
bpsi bmep: pounds per square inch brake mean effective pressure.
FIGURE 2
Effect of Smoke-Suppressant Additive
on Diesel Exhaust Emissions
(1.4-liter engine)11'12
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17
X
o—-
A
D D Diesel Fuel + 0.3% Additive
_X Diesel Fuel
-O Diesel Fuel + 0.1% Additive
_A Diesel Fuel + 0.2% Additive
50 -
55-2 40 ~
a £ 30 H
§| 20 H
CO
10 -
A.— —
D
1100 1300 1500
Engine Speed, rpm
1700
FIGURE 3
Effect of Smoke-Suppressant Additive
on Diesel Exhaust Emissions
(Direct-injection engine)1?
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18
from a commercial 2-cycle engine and a 4-cycle engine (both
operated at idle and at rated power and speed), using treated
fuel in one case and untreated fuel in the other case, revealed
no significant differences in the percentage of oxygen, carbon
dioxide, or carbon monoxide. However, in two instances a reduc-
tion of 30 percent in unburned hydrocarbons was noted. The
exhaust solids from the tests were also collected and analyzed.
Although little change was noted in the average size of the
particles, the total number of particles was reduced. The
size of particles ranged from 1.5 microns to 74 microns in
diameter with the average size being 16.6 microns. The results
of the chemical analysis varied with type of engine, mode of
operation, and chemical content of the fuel. Solids scraped
from the vehicle muffler after the engine operated at high
speed showed the presence of carbon and barium sulfate.
Golothan reported similar results on tests run on a
5.8-liter, direct-injection engine. The additive had no sig-
nificant effect on carbon monoxide or nitrogen oxide emissions.
Golothan-'--'- also ran tests on the effect of the additive on the
emissions of polynuclear aromatic hydrocarbons. Tests were
run using diesel fuel both with and without the smoke-
suppressant additives in a single-cylinder direct-injection
engine, a multicylinder direct-injection engine, and a
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19
multicylinder precombustion chamber engine. The results are
shown in Table 7 in the Appendix. The data showed that the
influence of the additive on the amount of polynuclear aro-
matic hydrocarbon (PAH) depended on the engine type—the
decrease in PAH was greater for the multicylinder engines than
for the single-cylinder engine. The multicylinder engines are
representative of the engines in use today, and therefore
Golothan concluded that the use of barium antismoke additives
in diesel fuel for modern engines will not increase the health
hazard due to emission of polynuclear aromatic hydrocarbons.
The U.S. Navy ran smoke-suppressant tests on gas tur-
bine engines using an organometallic material containing barium
and found the material effective in reducing smoke. However,
during the tests intolerable amounts of barium carbonate deposit
adhered to the turbine and other flow passages. /22
Golothan-'--'- collected and analyzed the solids emitted
from a number of test diesel engines and some operating diesel
vehicles. The results from various test engines running on test
beds are shown in Tables 8, 9, and 10 in the Appendix. The
results from various vehicles running on road tests or a chassis
dynamometer are shown in Table 11 in the Appendix. Golothan11
summarized the results of his solid emission testing as follows:
(1) Up to about 25 percent of the barium compounds
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20
consisted of soluble barium at a sampling point 10 feet from
the engine, and upstream from the muffler. In certain engines,
however, there was substantial conversion of the insoluble barium
to barium sulfate within the exhaust system itself. In the 1.5-
liter engine operated on the bench with fuel A, for example,
the soluble barium at the end of the pipe was only 0.5 percent
of the total barium, whereas before passing through the muffler,
it was 11.5 percent under the same operating conditions. This
conversion did not appear to occur in all engines, as indicated
by the soluble barium content of 10 percent at the end of the
exhaust pipe of the minibus engine operated on the motorway.
(2) Under certain conditions, especially with fuel con-
taining 0.3 percent by weight of sulfur, the proportion of solu-
ble barium in the exhaust was very small, even when samples were
taken upstream from the muffler.
(3) In most of the engines examined, engine operating
conditions within the range examined had only a minor effect on
the ratio of soluble to insoluble barium.
(4) The ratio of fuel sulfur to barium, even at ratios
much above stoichiometric, has a pronounced effect on the solu-
ble/insoluble barium ratio, with fuel containing 0.3 percent
sulfur, and 0.075 percent by weight of barium antismoke additive.
Doubling the amount of additive not only doubled the total barium,
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21
but also increased the soluble/insoluble barium ratio. Simi-
larly, reduction of the fuel sulfur content from 0.3 to 0.15
percent increased this ratio markedly.
From the data, Golothan11 estimated that the maximum
amount of soluble barium in exhaust gases that would be emitted
at full load would be 12,000 fj.g/m3 . This was based on having
an additive concentration in the diesel fuel of 0.075 percent
by weight of barium and on 25 percent of the total barium in
the exhaust solids being soluble.
The references quoted above gave only a limited amount
of information on the composition of the exhaust gases and solids
from diesel engines using barium-base additives. No information
has been found which provides a complete analysis of the chemi-
cal or physical nature of automobile exhausts, or on the physio-
logical effects of exhaust gases containing compounds of fuel
additives.
3.4 Environmental Air Concentrations
No quantitative data have been found on the concentra-
tions of barium or its compounds in the atmosphere. However,
the National Air Sampling Network is currently collecting air
i -i
samples for barium analysis.
Samples of the environmental air were taken from moving
vehicles in downtown New York, Cincinnati, Washington, Chicago,
-------
22
and Los Angeles in 1967 and 1968, under the auspices of the
Division of Air Quality and Emissions Data, National Air Pol-
lution Control Administration.17 On the basis of these samples,
the presence of barium in the air was established; however,
according to Morgan,17 the present techniques for sampling
from moving vehicles are inadequate for quantitative analysis.
-------
23
4. ABATEMENT
No information has been found on the abatement of barium
or its compounds in the environmental atmosphere. Since most
of the barium processed by industry is in solid form, the con-
ventional methods for removal of solids, such as bag filters,
electrostatic precipitators, and wet scrubbers, should prove
effective in preventing their escape to the atmosphere. No
information has been found on the control of emission of barium-
containing exhaust solids from diesel engines operating with
fuel containing barium-base smoke-suppressant additives.
-------
24
5. ECONOMICS
No information has been found on the economic costs of
barium air pollution or on the costs of its abatement.
Data on the production and consumption of barium and
its compounds are presented in Section 3.
-------
25
6. METHODS OF ANALYSIS
6.1 Sampling Methods
Dusts and fumes of barium compounds may be collected by
any of the usual methods for collection of particulate matter.
For concentrations of barium encountered in ambient air, sam-
pling has to be done with membrane filters.17 Barium solids
from diesel engine exhaust samples have been collected on ana-
lytical-grade filter paper. 1
6.2 Quantitative Method s
Any barium sample soluble in hydrochloric acid can be
analyzed by spectrographic methods.1 Low concentrations of
barium can be quantitatively determined by emission spectro-
graphy or atomic absorption.17 Thompson .et al_.27 reported
that when barium is analyzed by atomic absorption, the mini-
mum
detectable limit is 0.02 |ag/m3 based on an air sample of
2,000 m3.
To convert all the barium collected on a filter to a
soluble form for spectrographic analysis, the filter is ashed
and the ash is dissolved in a hydrochloric acid and nitric acid
mixture.17 Golothan11 separated the soluble and insoluble
barium compounds by digesting the solids on the filter paper
with hydrochloric acid. This acid solution was analyzed
directly for the soluble barium compounds. The solid residue
-------
26
(remaining after the acid treatment) was ashed and treated with
acid and subsequently analyzed to determine the amount of insolu-
ble barium compounds in the original sample.
Industrially, barium is usually determined by precipi-
tating it as insoluble barium sulfate, separating the precipi-
o q
tate, and weighing it. '° When barium is associated with other
alkaline earths such as calcium and strontium, the calcium is
separated as calcium nitrate by dissolving it in a mixture of
alcohol and absolute ether. The barium is then precipitated
as barium chromate from the slightly acidified (acetic acid)
mixture.^
-------
27
7. SUMMARY AND CONCLUSIONS
Metallic barium is highly reactive, and if released to
the atmosphere, quickly becomes converted to a barium salt.
Soluble barium salts are very toxic, and if ingested, have a
strong stimulating effect on all muscles, including the heart.
Symptoms of barium poisoning are excessive salivation; vomiting;
colic; diarrhea; convulsive tremors; slow, hard pulse; and
increased blood pressure. There have been very few reported
deaths due to barium poisoning. Insoluble barium compounds,
such as common barium sulfate, are generally nontoxic. Inhaled
barium compounds are known to cause a benign pneumoconiosis
called baritosis, which does not cause symptoms of emphysema,
bronchitis, or reduced respiratory capacity.
Tests on animals with exhaust solids from a diesel engine
using fuels with barium-base smoke-suppressant additives indi-
cated that the LD50 of these exhaust solids was in excess of 10
grams per kilogram of body weight. Very limited animal studies
with these exhaust solids do not appear to have demonstrated
any acute health effects from the concentrations used; no infor-
mation is available on chronic effects. No information was
found on the effect of barium and its compounds on plants or
materials.
Barium occurs naturally mainly as barite (barium sulfate)
-------
28
and witherite (barium carbonate). Approximately 90 percent
of the barite produced is used as well-drilling mud. Litho-
pone and other barium compounds are produced with the remain-
der. No environmental emission data were found for the mines
or refineries producing barite, lithopone, or any of the other
barium compounds.
A number of proprietary barium-base organometallic com-
pounds used as additives in diesel fuel have been found to be
very effective in reducing smoke emissions from diesel engines.
Tests with diesel engines with and without the smoke-suppressant
additives showed very little change in gaseous emissions.
Analysis of solids emitted from these engines revealed the pre-
sence of barium sulfate and barium carbonate. The soluble
barium carbonate content varied from under 1 percent to about
25 percent of the total barium content of the exhaust solids.
Based on the 25 percent soluble salt content, it was estimated
that the maximum emission of barium from a diesel engine would
be on the order of 48,000 |ag/m3 of exhaust. Sufficient data
are not available to give detailed physical and chemical proper-
ties of these barium-containing diesel engine exhaust solids.
Although no quantitative measurements have been made of
the environmental air concentrations of barium, qualitative
measurements in some major U.S. cities have shown the presence
-------
29
of barium. Samples for quantitative measurements are being
collected at the present time.
No information has been found on techniques for control
of emissions of barium and its compounds. However, for indus-
trial processes, control equipment such as filters, electro-
static precipitators, and wet scrubbers could be used.
No information has been found on the economic costs of
barium air pollution or on the costs of its abatement.
The barium concentration in the atmosphere can be mea-
sured by collecting atmospheric samples on a filter, dissolving
the barium compound, an3 analyzing the solution by spectro-
graphic method s.
Based on the material presented in this report, further
studies are suggested in the following areas:
(1) Expansion of research on characterization and
analysis of exhausts from motor vehicles. Special emphasis
should be given to the various fuel additives, including barium
and its compounds.
(2) Additional research on acute and chronic health
effects related to atmospheric barium and its compounds.
(3) Measurement of ambient air concentrations of barium,
especially in urban areas.
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30
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3. "Barium" and "Barium Compounds," in Kirk-Othmer Encyclo-
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4. Brandt, A. D., Industrial Health Engineering (New York:
Wiley, 1947).
5. Browning, E., Toxicity of Industrial Metals (London:
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6. DeCorso, S. M., _et_ aJ... , Smokeless Combustion in Oil Burning
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7. Deeter, W. F., California's Program to Reduce Diesel Smoke
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8. Elkins, H. B., The Chemistry of Industrial Toxicology
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9. Fiorello, S. C., The Navy's Smoke Abatement Program, Society
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10. Glover, I., The Fuel Additive Approach Towards the Allevia-
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11. Golothan, D. W., Diesel Engine Exhaust Smoke. The Influ-
ence of Fuel Properties and the Effects of Using Barium-
Containing Fuel Additive, Society of Automotive Engineers,
S.A.E.-670092 (1967).
12. Influence of Fuel Properties and Effect of Anti-Smoke
Additives on Diesel Exhaust Smoke, S.A.E. Journal 76(3):
36 (1968).
13. Ladoo, R. B., and W. M. Meyers, Non-Metallic Minerals
(New York: McGraw-Hill, 1951).
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15. Miller, C. O., Diesel Smoke Suppression by Fuel Additive
Treatment, Society of Automotive Engineers, S.A.E.-670093
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16. Minerals Yearbook. Bureau of Mines, U.S. Govt. Printing
Office, Washington, B.C. (1966).
17. Morgan, G., Director, Division of Air Quality and Emissions
Data, National Air Pollution Control Administration, per-
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18. Nadel, J. A., "Alveolar Duct Constriction After Barium Sul-
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19. Patty, F. A., Industrial Hygiene and Toxicology, vol. II
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20. Report of the Medical Lectures and Discussion at the 5th
International Silicosis Convention—Munster Westphalia,
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21. Sax, I. N., Dangerous Properties of Industrial Materials
(New York: Reinhold Book Corp., 1968).
22. Shayeson, M. W., Reduction of Jet Engine Exhaust Smoke with
Fuel Additives, Society of Automotive Engineers, S.A.E.-
670866 (1967).
23. Slade, D. H., Meteorology and Atomic Energy, U.S. Atomic
Energy Commission, Division of Technical Information
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24. Spector, W. S., Handbook of Toxicology, vol. 1 (Washington,
D.C.: Division of Biology and Medicine, National Academy
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25. Stern, A. C., Air Pollution, vol. Ill (New York: Academic
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26. Thomas, C. W., and N. A. Wayman, Atmospheric Behavior of
Airborne Radio Nuclides, Pacific Northwest Lab Annual
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32
27. Thompson, R. J., G. B. Morgan, and L. J. Purdue, Analyses
of Selected Elements in Atmospheric Particulate Matter by
Atomic Absorption, Preprint, presented at the Instrument
Society of America Symposium, New Orleans, La. (May 5-7,
1969).
28. Threshold Limit Values for 1967—Recommended and Intended
Values, 29th Annual Meeting of the American Conference of
Governmental Industrial Hygienists, Chicago (May 1967).
-------
33
OTHER REFERENCES
Ayre, J. E., Human Cell-Dysplasia Following Barium, Ind. Med.
Sura. .35_:393 (1966).
Barium Carbonate Poisoning, J. Am. Med. Assoc. 174:197 (1960).
Barium and Its Inorganic Compounds, Hygienic Guide Series, Am.
Ind. Hyg. Assoc. J. (Nov.-Dec. 1962).
Bauer, G. C. H., et. al.. , A Comparative Study of the Metabolism
of 140Ba and 45Ca in Rats, Biochem. J. .6_3:535 (1956).
Bligh, P. H., and D. M. Taylor, Comparative Studies of the
Metabolism of Strontium and Barium in the Rat, Biochem. J.
£7:612 (1963).
Boekelman, W. A., Barium in Human and Animal Tissues, Ned.
Tiidischr. Geneesk 105:2145 (1961); Chem. Abstr. 56;6519c
(1962).
Boender, C. A., et_ ai_., Iron Absorption and Retention in Man,
Nature 213:1236 (1967).
Boyd, E. M. , and M. Abel, Acute Toxicity of Barium Sulfate
Administered Intragastrically, Can. Med. Assoc. J. 94;849
(1966); Abstr. J. Am. Med. Assoc. 196(6):243 (1966).
Cember, H., et. al.. , Pulmonary Penetration of Particles
Administered by Intratracheal Insufflation, A.M.A. Arch. Ind.
Hyq. Occup. Med. .10:124 (1954).
Cember, H., .et. aJ^-, Pulmonary Effects from Radioactive Barium
Sulfate Dust, A.M.A. Arch. Ind. Health 12:628 (1955).
Cember, H. , et. al.. , The Elimination of Radioactive Barium
Sulfate Particles from the Lung, A.M.A. Arch. Ind. Health
13:170 (1956).
Cember, H. , .et. al_. , The Influence of Radioactivity and Lung
Burden on the Pulmonary Clearance Rate of Barium Sulfate,
Am. Ind. Hvcr. Assoc. J. 22_:21 (1961).
Christensen, H. E. , _et_ aJ__. , Experimental Barium Poisoning,
Paper, 10th Annual Meeting, American Industrial Hygienists'
Association, Detroit, Mich. (Apr. 7, 1949).
-------
34
Diengott, D., _et_ aJ^. , Hypokalaemia in Barium Poisoning, Lancet
2_:343 (1964).
DiPalna, J. R. (Ed.), Drill's Pharmacology in Medicine, 3rd ed
(New York: McGraw-Hill, pp. 709,987,1429-1430, 1965).
DuBois, K. P., and E. M. K. Ceiling, Textbook of Toxicology
(New York: Oxford Univ. Press, p. 139, 1959).
Fairhall, L. T., Industrial Toxicology. 2nd ed. (Baltimore:
Williams & Wilkins, pp. 21-23, 1957).
Fleming, A. J., and C. A. D'Alonzo (Eds.), Modern Occupational
Medicine (Philadelphia: Lea & Febiger, pp. 81-82,386, 1954).
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cal Toxicology of Commercial Products, 2nd ed. (Baltimore:
Williams & Wilkins, Section III, p. 31, 1963).
Goodman, L. S., and A. Gilman (Eds.), The Pharmacological
Basis of Therapeutics, 3rd ed. (New York: Macmillan, pp.
804-805, 1965).
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in Rats, Arch. Pathol. 5_4_:430 (1952).
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Proc. Soc. Exptl. Biol. Med. 104:436 (1960).
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Sulfide Deposits Resulting from Golfball Injury to the Con-
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Industrial Medicine (Philadelphia: Saunders, pp. 221,235,268,
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35
Oettingen, W.F. von, "Poisoning," in A Guide to Clinical
Diagnosis and Treatment. 2nd ed. (Philadelphia: Saunders,
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(Philadelphia: Lea & Febiger, pp. 167-169, 1964).
Truhaut, R., and F. Berrod, Toxicology of Barium. II.
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APPENDIX
-------
APPENDIX
TABLE 2
PROPERTIES, TOXICITY, AND USES OF BARIUM AND SOME BARIUM COMPOUNDS2'3'13'14'25
Compound
Properties
Toxicity
Uses
Barium
Ba
Yellowish-
white,
slightly lus-
trous lumps
mp 850°C
bp 1,140°C
The symptoms of barium poi-
soning are excessive saliva-
tion, vomiting, colic,
violent diarrhea, convulsive
tremors, increased blood
pressure, hemorrhages in
gastrointestinal tract and
kidneys, muscular paralysis
Used as a getter in elec-
tronic tubes and as al-
loying agent with nickel
for spark plug elements.
Emissions from barium-133
and barium-137 are used
as standards in spectrom-
etrv
Barium acetate
Ba(C3H3Os)3-
White crys-
tals. Loses
its H3O of
hydration at
110°C
Poisonous
As mordant for printing
fabrics; in lubricating
oil and grease; as cata-
lyst for organic reactions
Barium benzene
sulfonate
Ba(CsH5S03)s-
White, nacre-
ous leaflets,
fully soluble
in water
Poisonous
In lubricating oil addi
tives
Barium
binoxalate
Ba(HCa04 )„•
2H30
Dihydrate,
very slightly
soluble in
water
Poisonous
(continued )
-------
APPENDIX
TABLE 2 (Continued)
PROPERTIES, TOXICITY, AND USES OF BARIUM AND SOME BARIUM COMPOUNDS
Compound
Properties
Toxicity
Uses
Barium bromate
Ba(Br03)3'H3O
White crystals
or crystalline
powder. De-
composes at
260°C
Poisonous
In preparation of rare
earth bromates; as cor-
rosion inhibitor for low-
C steel
Barium bromide
BaBr,,
mp 847°C
Very soluble
in water.
Colorless
crystals
Poisonous
In the manufacture of
other bromides; in the
preparation of phosphors
Barium
carbonate
BaCO3
White, heavy
powder. Al-
most insolu-
ble in water.
Decomposes at
~1,300°C into
BaO and CO2 .
Soluble in HC1
Poisonous
As rat poison; in ceramics,
enamels; in manufacture of
paper, barium salts, opti-
cal glasses; in case-
hardening steels
(continued)
CO
oo
-------
APPENDIX
TABLE 2 (Continued)
PROPERTIES, TOXICITY, AND USES OF BARIUM AND SOME BARIUM COMPOUNDS
Compound
Properties
Toxicity
Uses
Barium
chlorate
Ba(ClO3)2 *H2O
Hydrate.
Monoclinic
prismatic
crystals.
mp anhydrous
414°C
In pyrotechnics (green
fire); in manufacture of
explosives and matches; as
mordant in dyeing
Barium
chloride
Bad.,
Crystals or
granules or
powder. Very
soluble in
water
Poisonous
In manufacture of blanc
fixe; as mordant for acid
dyes; in weighting and
dyeing textile fabrics; as
boiler compounds for soft-
ening water; as purifying
agent in brines; in manu-
facture of barium colors
and of chlorine and
sodium hydroxide; as flux
for magnesium alloys; in
case-hardened steel
(continued)
-------
APPENDIX
TABLE 2 (Continued)
PROPERTIES, TOXICITY, AND USES OF BARIUM AND SOME BARIUM COMPOUNDS
Compound
Properties
Toxicity
Uses
Barium
chrornate
BaCrO4
Yellow, heavy,
monoclinic
Poisonous
As a pigment almost en-
tirely in anticorrosion
jointing pastes to pre-
vent electrochemical cor-
rosion at junctions of
dissimilar metals; some
use in artists' colors and
in coloring glass, cera-
mics, porcelain. Also
used in metal primers,
pyrotechnic compositions,
safety matches
Barium cyanide
Ba(CN)2
White crys-
talline pow-
der. Slowly
decomposes in
air. Very
soluble in
water
Very poisonous
In electroplating pro-
cesses
Barium
dithionate
BaS2O6-2H2O
Rhombic or
monoclinic,
colorless
crystals
Poisonous
(continued)
-------
APPENDIX
TABLE 2 (Continued)
PROPERTIES, TOXICITY, AND USES OF BARIUM AND SOME BARIUM COMPOUNDS
Compound
Properties
Toxicity
Uses
Barium
ferrocyanide
BaFe(CN)8 '6H2O
Yellow crys-
tals. Decom-
poses at 80°C
Barium
fluoride
BaF0
White powder.
mp 1,353°C
bp 2,260°C
Poisonous
As a flux and opacifier in
vitreous enamels; in the
manufacture of carbon
brushes for motors and
generators; in heat-
treating metals; in em-
balming; in glass manu-
facture
Barium formate
Ba(HCOO)2
Crystals.
Soluble in
water
Poisonous
Barium
hexafluoro-
silicate
BaSiFg
Decomposes at
300°C
Highly toxic, especially when
brought into solution by
alkali
In preparation of silicon
tetrafluoride; as pesti-
cide
(continued)
-------
APPENDIX
TABLE 2 (Continued)
PROPERTIES, TOXICITY, AND USES OF BARIUM AND SOME BARIUM COMPOUNDS
Compound
Properties
Toxicity
Uses
Barium
hydroxide
Ba(OH)3-8H30
White powder.
Slightly solu-
ble in water.
mp 78°C
Dehydrates at
780°C
Poisonous
In manufacture of alkali,
glass; in synthetic rubber
vulcanization; in corro-
sion inhibitors, drilling
fluids, lubricants, pes-
ticides, sugar industry;
as boiler scale remedy/-
in refining animal and
vegetable oils; in soft-
ening water; in fresco
painting
Barium
hypophosphite
Ba(H3P03)S*H30
Monoclinic.
Crystalline
powder
Poisonous
In nickel plating
Barium iodate
Ba(l03)3
White crys-
tals. Be-
comes anhy-
drous at 130°C
Poisonous
Barium iodide
BaI3
Colorless,
odorless crys-
tals
Poisonous
In the manufacture of
other iodides
(continued)
-------
APPENDIX
TABLE 2 (Continued)
PROPERTIES, TOXICITY, AND USES OF BARIUM AND SOME BARIUM COMPOUNDS
Compound
Properties
Toxicity
Uses
Barium
manganate(VI
BaMnO4
Emerald green
powd er.
mp 740°C
Poisonous
As pigment in fresco
painting instead of
Scheele's green because
not so poisonous as latter.
Barium mercu-
ric bromide
BaHgBr4
Very deli-
quescent,
crystalline
mass. Freely
soluble in
water
Poisonous
Barium mercu-
ric iodide
BaHgI4
Yellow or
reddish crys-
tals
Poisonous. See Barium
As an aqueous solution
known as Rohrbach's solu-
tion, for separating
minerals of different den-
sity
Barium nitrate
Ba(N03)2
White crys-
tals or pow-
der.
mp 592°C
Poisonous
In manufacture of BaO2; as
pyrotechnic for green
fire; as green signal
lights; in the vacuum tube
industry
(continued)
-------
APPENDIX
TABLE 2 (Continued)
PROPERTIES, TOXICITY, AND USES OF BARIUM AND SOME BARIUM COMPOUNDS
Compound
Properties
Toxicitv
Uses
Barium nitrite
Ba(NOa)8
White crystals.
Soluble in
water. Decom-
poses at 217°C
Poisonous
In diazotization reactions;
for prevention of corrosion
of steel bars; in explo-
sives
Barium oxalate
BaC2O4
White crystal-
line powder
Poisonous
Barium oxide
BaO
White to yel-
lowish-white
powder or
lumps.
mp 1,923°C
Poisonous
Porous grades are marketed
especially for drying gases
and solvents (particularly
alcohols, aldehydes, and
petroleum solvents).
Swells but does not become
sticky upon absorption of
moisture. Also used for
making barium methoxide,
case-hardening steels, and
lubricating oil detergents
Barium
perchlorate
Ba(ClO4)2'3H20
Colorless
crystals.
Soluble in
water. De-
composes at
400°C
Poisonous
In the determination of
ribonuclease; as absorbent
for water in C and H analy-
sis
(continued)
-------
APPENDIX
TABLE 2 (Continued)
PROPERTIES, TOXICITY, AND USES OF BARIUM AND SOME BARIUM COMPOUNDS
Compound,
Properties
Toxicity
Uses
Barium
permanganat e
Ba(Mn04)3
Brownish-
violet to
black crys-
tals
Poisonous
As dry cell depolarizer
Barium
peroxide
BaO0
White or
grayish-white,
heavy powder.
mp 450°C
Poisonous
In bleaching animal sub-
stances, vegetable fibers,
and straw; as glass de-
colorizer; in manufacture
of H2O2 and oxygen; in
dyeing and printing tex-
tiles; with powdered alu-
minum in welding; in
cathodes; in igniter compo-
sitions. As oxidizing
agent in organic synthesis
Barium phos-
phate dibasic
jBaHPO4
Crystals.
Practically
insoluble in
wat er
Poisonous
In fireproofing composi-
tions; in preparation of
phosphors
Barium
phosphite
BaHPO3
Crystalline
powder
Poisonous
(continued)
Ul
-------
APPENDIX
TABLE 2 (Continued)
PROPERTIES, TOXICITY, AND USES OF BARIUM AND SOME BARIUM COMPOUNDS
Compound
Properties
Toxicitv
Uses
Barium plati-
nous cyanide
BaPt(CN)4
Large dichroic
crystals.
Soluble in
about 35 parts
water
Poisonous
As aqueous solution mixed
with some adhesive and
painted on paper or wood,
exhibits luminescence when
exposed to the invisible
ultraviolet rays of the
spectrum or to roentgen,
radium, or cathode rays;
hence used in radiography
for making X-ray screens
Barium selenate
BaSeO4
Orthorhombic
crystals.
Decomposes by
heat
Poisonous
Barium selenide
BaSe
Cubic micro-
crystalline
powder. De-
composes in
water
In photocells, semicon-
ductors
Barium silicide
BaSi.,
Metal-like,
gray lumps.
Melts at
white heat
For deoxidizing and desul-
furizing steel and for oth-
er metallurgical purposes
(continued)
-------
APPENDIX
TABLE 2 (Continued)
PROPERTIES, TOXICITY, AND USES OF BARIUM AND SOME BARIUM COMPOUNDS
Compound,
Properties
Toxicity
Uses
Barium sulfate
(blanc fixe)
BaSO,
Fine, heavy
odorless pow-
der. Decom-
poses above
1,600°C. Not
soluble in
water or di-
lute acids
Nontoxic. Inhalation pro-
duces a benign pneumoconiosis
called baritosis with no
symptoms of emphysema, bron-
chitis, or reduced respira-
tory capacity
In manufacture of photo-
graphic papers; as filler
for rubber, linoleum, oil-
cloth, storage batteries,
glazed powders, litho-
graphic inks; as a water-
color pigment for colored
paper; as a paper coating.
Med. use: X-ray contrast
medium. Antidiarrheal and
demulcent powder. Vet.
use: X-ray examination of
gastrointestinal tract of
doers and cats
Barium sulfide
BaS
Heavy white
powder.
mp >2,000°C
Poisonous
As depilatory; in luminous
paints; in manufacture of
lithopone; for vulcanizing
rubber, generating H2S.
In commercial depilatory
mixtures for preoperative
preparation
Barium sulfide
(black ash)
BaS
Poisonous
As raw material for other
barium compounds
(continued)
-------
APPENDIX
TABLE 2 (Continued)
PROPERTIES, TOXICITY, AND USES OF BARIUM AND SOME BARIUM COMPOUNDS
Compound
Properties
Toxicity
Uses
Barium sulfite
BaSO3
Odorless white
crystals or
powder
Poisonous
In paper manufacture
Barium
tartrate
White granular
powder
Poisonous
'H3O
Barium
thiocyanate
Ba(SCN)3'H3O
Deliquescent
white crystals.
Very soluble
in water
Poisonous
In dyeing; in photography;
as dispersing agent for
cellulose; in preparation
of thiocyanates of other
metals
B ar i urn
thiosulfate
BaS2O3
Crystalline
powder. De-
composes
Poisonous
In manufacture of explo-
sives, matches; as an
iodometry standard; in
photographic diffusion-
transfer process
(continued)
CD
-------
APPENDIX
TABLE 2 (Continued)
PROPERTIES, TOXICITY, AND USES OF BARIUM AND SOME BARIUM COMPOUNDS
Compound
Properties
Toxicity
Uses
Barium titanate
BaTiO3
Light grey-
buff powder
or crystals.
mp 1,625°C.
Insoluble in
water and
alkalies.
Slightly solu-
ble in dilute
acids
Animal experiments show low
toxicity
In electronic devices, e.g.
as voltage-sensitive dielec-
tric in so-called dielectric
amplifiers, in computer ele-
ments, magnetic amplifiers,
memory devices.
Barium uranium
oxide
BaU3O7
Orange or yel-
low powder
For painting on porcelain
-------
APPENDIX
TABLE 3
TOXICITY TO ANIMALS OF SELECTED BARIUM COMPOUNDS
24
Compound
Barium acetate
Barium carbonate
Barium chloride
Animal
Rabbit
Rabbit
Rabbit
Rabbit
Mouse
Rat
Rat
Rabbit
Pig
Frog
Mouse
Rat
Rat
Rat
Guinea Pig
Rabbit
Rabbit
Rabbit
Rabbit
Rabbit
Rabbit
Routea
or
or
sc
iv
or
or
or
or
7
sc
or
or
sc
iv
sc
or
sc
sc
sc
iv
iv
Dose13
LD
LD
LD
LD
LD
LD50
LD
LD
LD
LD
LD
LD
LD
MLD
LD
LD
LD
LD
LD
LD
LD
Dosage
mg/kg
Value
236
815
96
8-15
200
1,480+340
50-200
170-300
1,000
60
7-14
355-533
45-89
20
50-60
170
40-75
50
113
100-200
4-30
Time
of
Death
24 hr
1% hr
1-8 days
Ul
o
(continued)
-------
APPENDIX
TABLE 3 (Continued)
TOXICITY TO ANIMALS OF SELECTED BARIUM COMPOUNDS
Compound
Barium chloride
(Continued )
Animal
Cat
Cat
Dog
Dog
Dog
Dog
Dog
Pigeon
Pigeon
Chicken
Chicken
Chicken
Sheep
Horse
Horse
Hedgehog
Hedgehog
Routea
sc
iv
or
sc
sc
sc
iv
or
sc
sc
sc
sc
iv
or
iv
or
sc
Dose13
LD
LD
LD
LD
LD
LD
LD
LD
LD
LD
LD
LD
LD
LD
LD
LD
LD
Dosage
mg/kg
Value
18-60
40-60
90
10-20
15-25
1
3002
500
60-80
60-80
50-80
55
5
800-1,200
700
4,800-9,600
50
Time
of
Death
(continued)
-------
APPENDIX
TABLE 3 (Continued)
TOXICITY TO ANIMALS OF SELECTED BARIUM COMPOUNDS
Compound
Barium fluoride
Barium silicof luoride
Animal
Frog
Guinea pig
Guinea pig
Rat
Rabbit
Routea
sc
or
sc
or
or
Dosek
LD
LD
LD
LD50
MLD
Dosage Time
mg/kg of
Value Death
1,375
350
550
175
175
Route: or—oral.
sc—subcutaneous.
iv—intravenous.
3Dose: LD—lethal dose.
LD50—lethal dose which kills 50 percent of the group of test animals
(usually 10 or more).
MLD—minimum lethal dose which kills one of the group of test animals,
Ul
-------
53
APPENDIX
TABLE 4
DOMESTIC PRODUCTION OF BARITE, UNITED STATES16
(Thousand Short Tons)
State
Arkansas
California
Georgia
Kentucky
Missouri
Nevada
New Mexico
South Carolina
Tennessee
All Other
Total
1957-61
(aver )
311
21
*
244
95
*
122
40
833
1962
259
7
109
*
304
138
*
16
27
860
1963
236
5
117
6
287
120
1
*
24
28
824
1964
233
6
109
6
267
149
*
39
21
830
1965 1966
249 233
4 15
* *
329 337
91 139
31 29
148 194
852 947
*withheld to avoid disclosing company confidential data,
included with "All Other."
-------
APPENDIX 54
TABLE 5
DOMESTIC CONSUMPTION OF BARITE16
(Thousand Short Tons)
Year
1957-61 (avg)
1962
1963
1964
1965
1966
In Manufacture of
Ground Barite Barium Chemicals
1,202
1,043
1,048
1,103
1,199
1,215
167
168
182
174
189
202
Total
1,369
1,211
1,230
1,277
1,388
1,417
-------
APPENDIX
TABLE 6
GROUND AND CRUSHED BARITE SOLD BY PRODUCERS TO CONSUMING INDUSTRIES16
Industry
Well drilling
Glass
Paint
Rubber
Und istributed
Total
Well drilling
Glass
Paint
Rubber
Undistributed
Total
1957-61
(avg)
Short
Tons
1,077,006
19,075
16,453
20,213
10,553
1,143,300
Percent
of Total
94
2
1
2
1
100
1964
930,965
56,866
58,396
26,675
3,787
1,076,689
87
5
6
2
100
1962
Short
Tons
934,007
39,017
19,786
26,235
4,045
1,023,000
Percent
of Total
91
4
2
3
100
1965
986,889
70,158
68,827
29,992
12,718
1,168,581
84
6
6
3
1
100
1963
Short
Tons
907,134
56,362
34,611
28,479
3,121
1,029,707
Percent
of Total
89
5
3
3
100
1966
1,022,106
73,660
69,805
38,249
4,605
1,208,515
85
6
6
3
100
Ui
-------
TABLE 7
EFFECT OF ADDITIVE ON EMISSIONS OF POLYNUCLEAR AROMATIC HYDROCARBONS*-
MEAN TOTAL CONTENTS11
(ppm)
Fuel
1.4-Liter, Direct-Injection
Engine, 1 cyl
Load, 100 psi
bmep
Excess Fuel
Condition
5.8-Liter, Direct-
Injection Engine,
6 cyl
1,200 rpm,
Full Load
1.5-Liter, Precom-
bustion Chamber
Engine, 4 cyl
2,000 rpm,
Full Load
Total in Total in Total in Total in Total in Total in Total in Total in
Exhaust Exhaust Exhaust Exhaust Exhaust Exhaust Exhaust Exhaust
Solids Gas Solids Gas Solids Gas Solids Gas
Automotive
gas-oil 823
Automotive plus
.antismoke
additive 1,775
2.08
2.71
727
813
5.69
4.8
440
620
0.43
0.24
605
563
0.72
0.35
*Mainly penanthrene, pyrene, and fluoranthene (proportions not given).
Ul
-------
TABLE 8
ANALYSIS OF SOLIDS EMITTED FROM 1.5-LITER AUTOMOTIVE DIESEL ENGINEa
11
Engine
Speed
(rpm)
1,500
1,500
3,500
1,500
1,500
1,500
3,500
1,500
1,500
Engine
Load (psi,
bmep)
30
90
70
90
30
90
70
90
90
Fuelb
A
A
A
A
B
B
B
C
C
Exhaust Sampling
Position
10 ft from engine
10 ft from engine
10 ft from engine
End of pipe
10 ft from engine
10 ft from engine
10 ft from engine
10 ft from engine
End of pipe
Fuel
Cons umpt ion
(Ib/hr)
3.2
7.2
16.7
7.25
3.2
7.5
16.25
7.3
7.2
Soluble Barium
in Exhaust Solids
(% wt of total Ba_)_
8.5
11.5
10.5
0.5
15.0
25.0
18.0
5.5
0.8
Engine type: 4-cylinder, high-speed, four-stroke-unit prechamber engine, with
Ricardo Mk V combustion chambers.
Fuels: A = automotive gas-oil (0.3% wt sulfur) + antismoke additive to 0.15%
wt barium in fuel.
B = 0.15% wt sulfur fuel + antismoke additive to 0.15% barium in fuel.
C = automotive gas-oil (0.3% wt sulfur) + antismoke additive to
0.075% wt barium in fuel.
-------
TABLE 9
ANALYSIS OF SOLIDS EMITTED FROM 5.8-LITER, TRUCK-TYPE DIESEL ENGINEa
11
Engine
Speed
(rpm)
1
1
2
2
1
1
1
2
2
1
1
,000
,000
,600
,600
,000
,000
,000
,600
,600
,000
,000
Engine
Load (psi,
bmep)
30
100
30
80
100
30
100
30
80
100
100
Fuelb
A
A
A
A
A
B
B
B
B
C
C
Exhaust Sampling
Position
10
10
10
10
20
10
10
10
10
10
20
ft
ft
ft
ft
ft
ft
ft
ft
ft
ft
ft
from
from
from
from
from
from
from
from
from
from
from
engine
engine
engine
engine
engine
engine
engine
engine
engine
engine
engine
Fuel
Consumption
(Ib/hr)
6
19
21
41
6
17
21
42
18
.4
.3
.5
.3
.2
.5
.4
.3
.0
Soluble Barium
in Exhaust Solids
(% wt of total Ba)
1.
13.
8.
9.
13.
17.
24.
23.
23.
7.
8.
9
0
0
5
0
0
0
0
0
5
5
Engine type: 6-cylinder, direct-injection, four-stroke unit.
•"Fuels: A = automotive gas-oil (0.3% wt sulfur) + antismoke additive to 0.15%
wt barium in fuel.
B = 0.15% wt sulfur fuel + antismoke additive to 0.15% wt barium in
fuel.
C = automotive gas-oil (0.3% wt sulfur) + antismoke additive to 0.075%
wt barium in fuel.
00
-------
TABLE 10
ANALYSIS OF SOLIDS EMITTED FROM TWO-STROKE AUTOMOTIVE DIESEL ENGINE3
11
Engine
Speed
(rpm)
1,200
2,000
2,000
Engine
Load . (psi ,
bmep)
93.5
83.0
80.5
Fuelb
A
A
B
Exhaust Sampling
10
10
10
Position
ft from engine
ft from engine
ft from engine
Fuel
Consumption
( Ib/hr )
23.0
36.0
35.4
Soluble Barium
in Exhaust Solids
(% wt of total Ba)
6.5
1.8
25.5
Engine type: 3-cylinder, opposed-piston, automotive two-stroke unit.
DFuels: A = automotive gas-oil (0.3% wt sulfur) + antismoke additive to 0.15%
wt barium in fuel.
B = 0.15% st sulfur fuel + antismoke additive to 0.15% wt barium in
fuel.
-------
TABLE 11
ANALYSIS OF SOLIDS EMITTED FROM DIESEL VEHICLES11
Vehicle
Tanker
7 -ton truck
Minibus
Sedan
Engine
8.4-liter,
direct-
injection
5.4-liter,
direct-
injection
1.6-liter,
prechatnber
1.5-liter,
precharnber
Type of Test
Driving on
test track
Driving on
test track
Driving on
motorway
Chassis
dynamometer
operation
Concentration
of Antismoke
Additive in
Fuel
(% wt Ba)*
0.075
0.15
0.15
0.075
Operating
Condition
Normal
driving for
126 miles
30 mph in
third gear
53 mph in
top gear
60 mph in
top gear
Sample
Collection
Technique
Dismantlable
silencer
Filtration,
end of ex-
haust pipe
Filtration,
end of ex-
haust pipe
Filtration
end of ex-
haust pipe
Soluble Ba
in Exhaust
(% wt of
total Ba)
1.4
5.5
10.0
1.6
*Fuel: automotive gas-oil, containing 0.3% wt sulfur.
------- |