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AIR POLLUTION ASPECTS
OF
MANGANESE 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 Ralph J. Sullivan
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
Inhalation of manganese or its compounds may induce
chronic manganese poisoning (a disease of the central nervous
system) or manganic pneumonia (a croupous pneumonia). Chronic
poisoning is disabling, and manganic pneumonia often results
in death. Two studies, one in Norway and one in Italy, have
demonstrated the health hazards of manganese air pollution.
In addition, manganese compounds are known to act as cata-
lysts in the oxidation of some air pollutants, producing
even more undesirable pollutants. They cause generalized
soiling of materials, but no evidence of damage to plants
is known.
The production of ferromanganese compounds in blast
furnaces provides the most common source of manganese air
pollution. Other sources include the use of organic
manganese fuel additives, welding rods, and incineration of
manganese-containing products. During 1964 the average con-
centration of manganese in the air was 0.10 iag/ma ; the
maximum value recorded was 10 l-ig/m3 . Manganese emissions
are controlled by normal particulate control methods. No
information has been found on the economic costs of manganese
air pollution or on the costs of its abatement. Procedures
exist for the measurement of this material in the atmosphere;
however, discrimination between the various compounds is not
made.
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exist for the measurement of this material in the atmosphere;
however, discrimination between the various compounds is not
made.
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CONTENTS
FOREWORD
ABSTRACT
1. INTRODUCTION 1
2. EFFECTS 2
2.1 Effects on Humans 2
2.1.1 Chronic Manganese Poisoning 3
2.1.2 Manganic Pneumonia 4
2.2 Effects on Animals 10
2.2.1 Commercial and Domestic Animals .... 10
2.2.2 Experimental Animals 10
2.3 Effects on Plants 11
2.4 Effects on Materials 11
2.5 Environmental Air Standards 13
3. SOURCES 14
3.1 Natural Occurrences 14
3.2 Production Sources 15
3.2.1 Iron and Steel Industry 15
3.2.1.1 Ferromanganese Blast Furnaces 16
3.2.1.2 Electric-Arc Furnaces .... 17
3.2.1.3 Other Furnaces 17
3.2.2 Coal 17
3.2.3 Fuel Oil 18
3.3 Product Sources 18
3.3.1 Dry-Cell Batteries « 18
3.3.2 Chemicals 18
3.3.3 Other Sources 19
3.4 Environmental Air Concentrations ....... 20
4. ABATEMENT 21
5. ECONOMICS 22
6. METHODS OF ANALYSIS 23
6.1 Sampling Methods 23
6.2 Quantitative Methods 23
7. SUMMARY AND CONCLUSIONS 25
REFERENCES
APPENDIX
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LIST OF TABLES
1. Properties, Toxicity, and Uses of Some Manganese
Compounds 35
2. Prevalence of Manganism in Miners Working in
Manganese Mines 41
3. Pneumonia Rate on Manganese Workers 44
4. Reported Prevalence of Croupous Pneumonia Among
Manganese Workers 45
5. U.S. Consumption of Manganese Ore and Manganese
Alloys 46
6. Manganese Ore Resources of the U.S 47
7. U.S. Capacity for Steel Production, Jan. 1, 1960 . . 48
8. Producers of Ferroalloys in the U.S. in 1966 .... 49
9. Manganese Emissions from Metallurgical Furnaces ... 50
10. Manganese Emissions from Coal-Fired Power Plants . . 51
11. "Ethyl" Antiknock Compound-Tel Motor 33 Mix 52
12. Concentration of Manganese in the Air 54
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1. INTRODUCTION
Although manganese (Mn) is one of the elements essential
to the human body, a high atmospheric concentration may result
in (1) chronic manganic poisoning, a disease of the central
nervous system, (2) manganic pneumonia, or (3) catalytic
oxidation ' of other air pollutants to more undesirable
compounds.
Air pollution by manganese arises almost entirely from
61
the manganese and steel industries. Fumes from welding rods
and organic manganese compounds may also contribute to air
nn . . 10,11,29.46 __ . , ., . ,
pollution. The organic compounds that have been
tested as additives in gasoline, fuel oil, and diesel oil for
use in both internal combustion engines and turbine engines
may become a source of pollution.
From an air pollution standpoint, the oxides of manganese
61
are the most important of the manganese compounds. Almost
all of the manganese in the atmosphere enters it as manganese
oxides, such as MnO, Mn2C>3, or ^304. However, these oxides
may rapidly react with other pollutants—for example sulfur
dioxide and nitrogen dioxide—to form water soluble manganese
compounds„
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2 . EFFECTS
Manganese can exist in 8 different oxidation states
(0, +1, +2, +3, +4, +5, +6, +7), of which the bivalent form
+2
(Mn ) is the most stable. Elemental manganese is a highly
reactive metal. The lower oxidation states are usually in
+2 +3 +4
the form of cations (e.g., Mn , Mn , Mn ), while the
_2 _o
higher oxidation states form anions (e.g., MnO , MnO ,
Mn04~ ).
The toxicity of manganese compounds appears to depend
upon the type of manganese ion present and the oxidation
state of the manganese. .It has been suggested that
61
manganese cations are more toxic than the anion forms. The
permanganate anions, though strong oxidizing agents which show
some caustic action, are relatively less toxic than the
cations. The bivalent cation is said to be 2.5 to 3 times
38
more toxic than the trivalent cation. Levina and Rabachevsky
reported that while manganese oxides such as MnO, Mn-^O^ Mn O
and MnO were toxic to rats, the higher oxides were the most
toxic .
The associated anion is reported to affect the toxicity
of manganese: manganese citrate is more lethal than manganese
chloride. See Table 1 in the Appendix for the properties,
toxicity, and uses of some manganese compounds.
2 .1 Effects on Humans
Exposure to manganese in the air may result in chronic
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manganese poisoning and/or manganic pneumonia.
2.1.1 Chronic Manganese Poisoning
Chronic manganese poisoning is primarily a disease of
the central nervous system, resulting in total disablement
after exposure to high concentrations of manganese dust
(usually the oxides) for only a few months. The disease is
reversible if it is recognized early and the person is
removed from exposure to the dust. Symptoms include a
peculiar slapping gait, weakness in doing heavy work, cramps
or tremors of the body and extremities, a mask-like expression,
impulsive and uncontrollable laughter, speech difficulty,
hallucinations, insomnia, absentmindedness, and mental
^ . 12,25,27,39,47,66
confusion.
Manganese may be absorbed by inhalation, by ingestion,
or through the skin; most damage results from prolonged
inhalation. High concentrations of manganese are found in the
10,11,29
hair. Radioactive manganese-54 has been used as a
19 42
tracer to study the pathology of manganese poisoning.
35
Manganese is primarily excreted in the feces. Studies
comparing excretion rates in healthy manganese workers and in
persons suffering from chronic manganese poisoning reveal that
healthy workers have a higher-than-normal manganese excretion
rate and persons suffering from manganese poisoning have a
lower-than-normal manganese excretion rate. These results
indicate that the retention of manganese in the body varies
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48,65
with individuals. There is evidence that sensitivity to
manganese poisoning can develop, since persons who have
recovered from the disease appear to be prone to contract it
65
again.
The manganese oxides have been observed to produce
chronic poisoning. No information has been found on the
effects of other compounds of manganese.
65
Wasserman and Mihail have summarized (Table 2, Appendix)
the prevalence of chronic manganese poisoning among manganese
miners. They have also suggested that manganese workers often
suffer from manganoconiosis. Of 820 miners, 209 were suspected
of having manganoconiosis as determined by X-ray.
The average dose of manganese which causes illness has
not been determined. However, miners working with pneumatic
drills in Chilean manganese mines in an atmosphere of
approximately 5,000 particles per cubic meter (less than 10 |a*
diameter) developed manganism in 49 to 480 days, the average
65
time being 178 days.
The disease is controlled mainly by removing the patient
from the dusty environment. In some cases, administration of
calcium disodium ethylenediamine tetracetic acid has increased
61
the excretion rate (primarily in the urine).
2.1.2 Manganic Pneumonia
Manganic pneumonia, often referred to as a croupous
pneumonia, is distinguished by the following symptoms: a sudden
*
l_i: micron ( s).
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onset of pneumonia, intense dyspnea, high temperature,
radiological signs of acute lobar pneumonia, and little
expectoration (often hemorrhagic). Manganic pneumonia does
not respond to antibiotics and is accompanied by a high
mortality rate—four times higher than that for lobar
24
pneumonia.
•28
Elstad reported on conditions which he noted in the
small town of Saude located on the Western shore of Norway.
Until 1932 the town was frequented by tourists. In that year,
a plant built in the town to manufacture manganese alloys
began discharging clouds of dark brown smoke into the
atmosphere. This ended the inflow of tourists into that town,
and gave Saude a reputation as a high morbidity center due
to the frequent occurrence of croupous pneumonia resulting
in a high mortality rate. Data presented by Elstad indicated
that the total mortality in Norway from all causes was the
same as in Saude, amounting correspondingly to 10.7 and 10.1
per 1,000 persons, but mortality due to croupous pneumonia
was 8 times higher in Saude than for Norway in general: 3.27
as compared with 0.4 per thousand persons. In 1924 to 1935
deaths caused by croupous pneumonia accounted for 3.65 percent
of Norway's total mortality, while in Saude it was 32.2
percent or nearly 10 times as high. Postmortem examinations
indicated that the manganese concentration in lung tissues of
persons who died of croupous pneumonia was considerably higher
than normal.
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The high morbidity and mortality caused by croupous
pneumonia in Saude was regarded by Elstad as the result of
systematic manganese discharge into the atmosphere by the
manganese plant. Examination showed that the ventilation
system of the electric smelting furnace was adequate insofar
as the working premises were concerned, but the smoke containing
manganese compounds was discharged into the atmosphere close to
the metallurgical plant. However, at 3 km from the discharge
point manganese concentrations in the air were high, and the
particle diameters were 5(_i or greater. During windy seasons
the smoke was dispersed in a short time, but during periods of
calm or fog, the valley in which the town of Saude was located
was covered with a continuous cloud of smoke. Elstad noted
that the rise in morbidity caused by croupous pneumonia and its
consequent mortality paralleled the increase in the amount of
ferromanganese discharged by the plant. This, according to
Elstad, served as additional evidence of the causal relationship
between the plant's discharges and the local high frequency of
morbidity and mortality caused by croupous pneumonia.
96
Surveys made in the U.S.S.R. of 1,200 residents
indicated that 95.6 percent of the persons interrogated within
a 500-m zone complained of unfavorable effects of the plant
discharges. Residents within the 500-m zone complained of high
dust density. For example, when the wind blew from the plant
toward the residential area, house windows had to be closed;
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clothes could not be hung to dry in the open air; snow became
covered with a layer of black dust; and more frequent
housecleaning became necessary. Morbidity studies established
that among residents of a nearby village, the frequency of
nervous system effects was similar to the frequency of these
effects among the adult population of the industrial town.
No evidence of neurointoxication was found in workers.
Analysis of nasal mucosa smears made of 700 children,
mostly of preschool age, showed the presence of manganese in
62 percent of the cases, frequently amounting to 95 ug. The
water in which the children washed their hands was found to
contain 38,800 |-lg of manganese per square meter of skin area.
These studies also revealed that 34.3 to 48.1 percent of the
children examined suffered from ear, nose, and throat problems.
Neuropathologic studies were made of 204 children; findings,
positive in 16 children only, were represented by light
asthenia, vertigo, neurosis, and vegetative syndrome.
Roentgenological examinations disclosed pulmonary changes in
75 percent of the children, and many of these changes were
tuberculous. Other changes were periobronchitis of differing
degrees, and periovascularitis, thought by the roentgenologist
to be the result of past diseases, especially in repeat cases.
Thus, results obtained in the study of morbidity among children
of the plant village indicated unfavorable shifts in the children's
health. The role played by manganese and in particular by
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8
ferroinanganic dust in the etiology of such tissue diseases as
inflammatory processes of the respiratory passages and sclerotic
lung changes was established with more certainty through animal
experiments. However, such manganese concentrations were tens
and hundreds of times greater than the manganese concentration
allowable in working areas.
51
A similar situation was reported by Pancheri, who
attributed the increased frequency of pneumonia in Aosta, Italy.
to a metallurgical plant emitting manganese dust.
22
Davies observed a high rate (26/1,000 miners) of
pneumonia in manganese workers, and attempted to support the
supposition that manganese produced the pneumonia by means of
experiments on mice. He concluded that mice show "an increased
susceptibility to pneumococci or streptococci" and "in man and
animals, manganese dust in suitable particle size introduced
into the respiratory system will, without the presence of other
23
factors, cause pneumonitis." Dust concentrations of 1,000 to
8,000 particles per cubic meter containing 2,000 to 17,000
3
|jg/m of manganese dioxide were encountered by the workers
studied, yet no cases of chronic poisoning were observed.
63
Van Beukering also reported a higher rate of pneumonia
among manganese miners of South Africa than in a control
group of iron miners. These results are compared with those
of Davies in Table 3 in the Appendix. Again, no cases of
chronic poisoning were observed.
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9
Some of the early studies on manganic pneumonia are
listed in Table 4 in the Appendix. The theory that manganese
causes a disease—manganic pneumonia—rests on statistical
studies which provide evidence of the abnormally high
percentage of pulmonary illnesses in the various sectors of the
manganese industry. However, the thesis that manganese can
33
produce manganic pneumonia is not without opposition. Heine,
unable to produce manganic pneumonia in animal experiments, has
reviewed the literature and proposed that all cases of
pneumonia can be explained by "droughts, long-term unemployment,
undernourishment, weather conditions, etc." Moreover, he
claims that there is no increased susceptibility to infection.
60
In addition, Stocks has attempted to correlate pneumonia with
the presence of trace elements in 23 British cities. His
findings show a correlation between pneumonia and beryllium,
but no correlation of pneumonia with manganese. However, this
lack of correlation may be due to the concentration factor.
The concentrations are quite low, ranging from 0.005 to 0.130
3 3
|jg/m , with most cities having less than 0.050 M-g/m .
All of these findings are based on results of inhalation
of ferromanganese dust or manganese oxides. Some experimental
work with animals shows that similar pulmonary effects occur
with other manganese compounds, such as manganous chloride.
Rats separately injected intratracheally with manganese dioxide
and manganous chloride showed histological changes in the lungs,
discharge of mucus in the epithelial cells of the bronchi,
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10
ragged epithelium, and loosened cells from the basal membrane.
However, the effect of inhaling low concentrations of various
manganese compounds over a long period has not been determined.
2.2 Effects on Animals
2.2.1 Commercial and Domestic Animals
No information has been found in the literature on the
effects of manganese air pollution on wild or domestic animals.
Manganese is often added to the feed of animals, especially
o 7
chickens, to prevent manganese deficiency.
2.2.2 Experimental Animals
Studies with rabbits,22 mice,33 and rats show that these
animals suffer the same types of symptoms as humans.
Joetten36 exposed rabbits to manganese in a ferroman-
ganese metallurgical plant. All of these rabbits later died
of pneumonia either before or after intranasal inoculation
with pneumococci. However, all the control animals inoculated
with pneumococci survived.
Heine33 demonstrated that various forms of manganese proved
toxic to mice: manganese dust (95% Mn), ferromanganese (88-90% Mn),
blast furnace manganese (75% Mn), manganese dioxide (66% Mn),
manganese silicon (60% Mn), manganese ore (50% Mn), vanadium
slag (29.5% Mn as MnO), and Thomas meal (6.7% Mn as MnO). The
degree of toxicity of the various substances was a function of
the manganese content rather than the oxidation state of the
manganese. From a series of experiments on both mice and
guinea pigs he concluded that metallic manganese can be absorbed
through the lungs, skin, and gastrointestinal tract. There was
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11
an increase of manganese in the liver following inhalation
of manganese. In the case of absorption through the skin,
there was an increase of manganese in the liver/ muscles, and
bones. After ingestion, high manganese levels were found
in the brain.
2.3 Effects on Plants
No information has been found on the effects of air
pollution on plants. Manganese is known to be essential to
64
higher plants, and for this reason manganese salts and
58
oxides are used as fertilizers.
2.4 Effects on Materials
Manganese and its compounds are active chemicals which
58
either react with materials or catalyze other reactions.
Their effect on catalytic oxidation appears to be of prime
importance in relation to air pollution. However, soiling
has been a common complaint near ferromanganese plants.
Sulfur dioxide and nitrogen dioxide react readily with
manganese dioxide to produce soluble sulfates, dithionates,
58
and nitrates by the following reactions:
+ SO2 - MnSO4
+ 3S02 - MnS2°6 + MnSO4
Mn02 + 2N02 - Mn(N03)2
These reactions have been utilized to remove sulfur
14,15,53
dioxide from flue gases. But more important is the
fact that small amounts of manganese, usually as manganese
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12
sulfate formed in the reaction of manganese dioxide with
sulfur dioxide, will catalyze the oxidation of sulfur dioxide
20
to sulfur trioxide.
MnSO
Laboratory studies of this reaction showed that the
reaction rate became so rapid when the catalyst concentration
was increased above 15 ppm that it was necessary to design a
16
flow apparatus to measure the rates. Bracewell and Gall
have shown that these reactions will take place in fog.
3
Assuming a water concentration of 200,000 |j.g/m in the air and
a manganese concentration of 0.2 [jg/m in a solution, a sulfur
dioxide concentration of 1,750 [_ig/m would result in a rate of
3
conversion to sulfuric acid of about 25 |jg/ni per hour. The
rate of reaction increases with the increase in the manganese
concentration: the rate is tripled each time the manganese
concentration is doubled. The rate also increases linearly
with the increase in sulfur dioxide concentration. While
other materials such as platinum, graphite, charcoal, vanadium(V)
oxide, chromium(III) oxide, ferric oxide, and nitrogen oxides
will catalyze the oxidation of sulfur dioxide to sulfur tri-
5
oxide, manganese sulfate was found to be the most active.
The manganese concentration in the atmosphere of most cities
is sufficient to catalyze the oxidation. In view of the above
reactions, it may be impossible to find manganese oxides in
the air since they react readily to form sulfates and nitrates.
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13
Catalytic oxidation of hydrocarbons may also take place.
However, very little information was found in the literature on
this subject. Hopcalite, a manganese and copper oxide catalyst,
has been used to catalyze oxidation of hydrocarbons in flue
18,59
gases and automobile exhausts. Normally, these oxidations
take place at high temperatures (100 to 600°C).
Organic catalysts containing methylcyclopentadienyl
manganese tricarbonyl have been marketed by the Ethyl
Corporation. These catalysts burn and form manganese oxides
which promote combustion of organic fuels, including tiny
particles of carbon, and increase the octane rating of the
29,58
fuel.
2.5 Environmental Air Standards
The industrial threshold limit value (8-hour) for
manganese for those occupationally exposed was originally
recommended by the American Conference of Governmental
3
Industrial Hygienists as 6,000 |jg/m . This has since been
62 3
reduced to 5,000 |jg/m . The latter value was also
35
recommended by the American Industrial Hygiene Association.
50,54
The U.S.S.R. has recommended a 24-hour limit of
10 |ag/m for manganese and its compounds. The maximum
allowable one-time concentration is 30
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14
3 . SOURCES
Manganese compounds in the atmosphere are generated
primarily by metallurgical uses in the iron and steel industry .-
organomanganese additives for fuels, and possibly incineration
30,45
of manganese products or manganese-containing products.
These sources all provide oxidizing atmospheres in which
manganese may be oxidized in a variety of ways. When heated
in air the following reactions ' will take place:
307°-600°C
4Mn02 - 2Mn2°3 + °2
800°-1200°C
Heated in Air
4Mn + 30 -> 2Mn2O
Heated in Air
6MnO +0 - 2Mn O
Z, J TT
Thus, most manganese emissions to the atmosphere are in
the form of oxides. However, in the presence of sulfur dioxide
and nitrogen dioxide, these oxides are rapidly converted to
sulfates and nitrates (see Section 2.4).
3 .1 Natural Occurrences
Manganese is widely distributed in the combined state,
ranking 12th in abundance (1,000 ng/g) among the elements in
the earth's crust. It is commonly found associated with iron
ores in concentrations too low in most cases to make its
commercial recovery attractive. The most common manganese
minerals are:
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15
Pyrolusite MnO2 (black) 60-63% Mn
Psilomelane BaMnMn °16(OH) (black) 45-60% Mn
Hausmannite Mn3°4 (brown) 72% Mn
crosite MnCl- (light rose) 47% Mn
Rhodo
Rhodonite MnSiC>3 (reddish brown) 42% Mn
Braunite 3Mn O3 • MnSi03 (black) 63% Mn
Ores containing less than 40 percent of manganese are
usually not suitable for metallurgical purposes.
The manganese mining industry in the United States does
not contribute significantly to air pollution. Only 1 to 2
percent of the total manganese ore processed in this country
14
is domestically mined (see Table 5 in the Appendix). The
States of Montana, New Mexico, and Minnesota have manganese-
44,45,58
producing mines. Table 6 in the Appendix shows the
manganese ore resources in the United States.
3.2 Production Sources
3.2.1 Iron and Steel Industry
Most of the manganese imports are in the form of
manganese ores, over 90 percent of which are used in the iron
45
and steel industry- Therefore, the smelting and refining
of the ore represent the largest potential pollution sources
in the United States. The capacity of steel blast furnaces
and the location of ferromanganese furnaces are given in
Tables 7 and 8 in the Appendix, and emission rates are given
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16
in Table 9 in the Appendix.
3.2.1.1 Ferromanganese Blast Furnaces
Although the number of furnaces producing ferromanganese
is small, the process which they use, if uncontrolled, could
produce more pollution than any of the other metallurgical
55
processes. Uncontrolled emissions in 1951 produced as much
as 8,200,000 to 15,500,000 |j.g/m of exhaust gas, with an
average of 13,700,000 |ag/m . The emissions from two 350-ton
3
f erromanganese furnaces averaged 16,500,000 [ag/m in a gas
3
volume of 3,920 m /min resulting in approximately 142 tons of
dust per day containing 21 to 36 tons of manganese. This
suggests that approximately 0.03 to 0.05 tons of manganese per
ton of ore could be emitted. The ferromanganese blast furnace
45
production was 651,987 tons in the United States in 1966.
This source could contribute from 19,500 to 32,500 tons of
manganese to the atmosphere each year.
The particulates from a ferromanganese furnace are
extremely small, with 80 percent ranging in size from 0.1 to
1 |j. These particulates contain:
15-25% manganese
0.3-0.5% iron
8-15% sodium and potassium oxides
9-19% silica
3-11% alumina
8-15% calcium oxide
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17
4-6% magnesium oxide
5-7% sulfur
1-2% carbon
3.2.1.2 Electric-Arc Furnaces
Dust and fume emissions from an electric-arc furnace
average approximately 10.6 Ib/ton of steel melted, the range
being from 4.5 to 29.4 Ib/ton. These particulates contain
approximately 4 percent of manganous oxide (MnO) with 70 per-
55
cent of the particles less than 5 |j in diameter. Manganese
emissions from electric-arc furnaces producing ferromanganese
may be higher than from those producing steel. Electric-arc
45
furnaces produced 294,223 tons of ferromanganese in 1966.
3.2.1.3 Other Furnaces
Some manganese is found in the particulate material
emitted from basic oxygen and open-hearth furnaces. However,
55
these concentrations are relatively low.
3.2.2 Coal
The concentration of manganese in coal ash varies
between 0.005 and 1.0 percent, depending on the origin of the
1
coal.
Analyses of particulate emissions from six different
31,57
types of coal-fired power plants showed that the concen-
3
tration of manganese emitted ranged between 60 and 400 |_ig/m
as shown in Table 10 in the Appendix.
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18
3.2.3 Fuel Oil.
Dust emissions from burning residual fuel oil average
56
about 55,000 Lig/m3 or approximately 2 g/lb of oil fired.
The concentration of manganese dioxide in the particulate is
approximately 400 l-ig/g. This would result in an emission of
800 |J.g of manganese dioxide per pound of fuel oil burned. A
boiler burning 1,000 pounds of oil per hour would be
discharging 0.8 g of manganese dioxide into the air per hour.
3.3 Product Sources
Approximately 150,000 tons of manganese ore are used by
45
the chemical industry annually and in the production of dry-
cell batteries.
3.3.1 Dry-Cell Batteries
The manufacturing of dry-cell batteries probably does
not constitute an air pollution hazard, although approximately
30,000 tons of high-grade manganese ore are used annually in
45
this industry. However, the disposal of old dry-cell
batteries by incineration could possibly be a source of
manganese air pollution.
3.3.2 Chemicals
Fuel additives represent important manganese chemical
10,11,29,46
products associated with air pollution. These
additives fall into two classes, antiknock compounds and smoke
inhibitors. Both classes of organic manganese compounds have
-------
19
been patented and tested by the Ethyl Corporation. The most
successful antiknock compound is methylcyclopentadienyl
manganese tricarbonyl, which is mixed with tetraethyl lead to
increase the octane rating of gasoline. A typical mixture is
given in Table 11 in the Appendix. More than 2 ml of this
mixture per gallon of gasoline (approximately 36,000 (jg/gal of
manganese) is recommended. The quantity of this mixture
actually used has not been disclosed. However, a large
proportion of the manganese chloride produced in the United
58
States goes into the manufacture of these chemicals.
Chemical fertilizers containing manganese ethylene-bis-
dithidcarbamate (maneb) are another possible source of
manganese air pollution. Approximately 10,000 tons of
58
manganese are used as fertilizers annually.
3.3.3 Other Sources
Numerous studies (see list of other references) concern
the use of manganese for the control of sulfur dioxide,
mercaptans, and sulfides. This use is primarily in wet
scrubbers and probably does not constitute a large source of
pollution.
About 10,000 tons of manganese (20,000 to 25,000 tons
of manganese dioxide) are used annually in welding rods and
58
fluxes for iron and steel. This causes some local
pollution in welding shops, but no information was found
regarding urban air pollution from this source.
-------
20
Permanganates are used in a wide variety of applications,
such as in air pollution control for sulfides and mercaptans,
58
odor control in barnyards, and in water treatment. However,
the largest quantity is used by the chemical industry.
Permanganates also have some applications as bactericides,
fungicides, and astringents in greenhouses, fisheries, etc.
Manganese dioxide is used in safety matches and strikers
58
as well as in fireworks and signal flares.
3.4 Environmental Air Concentrations
Air quality data obtained from the National Air Sampling
2,4,6,7
Network are shown in Table 12 in the Appendix. These
data show that during 1964 the manganese concentration for the
cities studied ranged up to 10 ^ig/m3 , the average being 0.10
p.g/m3 . The highest values, up to 10 |ag/m3, have been recorded
in Charleston, W. Va.
-------
21
4. ABATEMENT
The emission of manganese particulates will be controlled
at the same time as the particulates from the steel furnaces
and incinerators. No special equipment is required to remove
manganese. However, the ferromanganese furnace presents
special problems. '
Control of manganese from steel furnaces is accomplished
by various types of collectors, including electrostatic
precipitators, high-efficiency wet scrubbers, and fabric
13 21
filters. ' Four physical factors make the dust collection
economically difficult: the small particle size (as low as
0.03 M.) , the large volume of gas, the high gas temperature,
and the low value of the recovered material.
Control of emissions from a ferromanganese blast furnace
is more difficult than from other furnaces because the waste
gas temperature is hotter and the dust is finer. Electrostatic
precipitators have been successful in removing approximately
80 to 90 percent of the dust. No economical way of using the
collected dust has been developed.
Control of emissions from burning fuels containing
antiknock and smoke-inhibiting additives may require special
systems. The hazards of these organic manganese additives are
52
to be studied as required by the Clean Air Act.
-------
22
5. ECONOMICS
No information has been found on the economic losses due
to manganese air pollution, or on the costs of its abatement.
Data on the production and consumption of manganese are
presented in Section 3.
-------
23
6. METHODS OF ANALYSIS
6.1 Sampling Methods
Dusts and fumes of manganese compounds may be collected
by any methods suitable for collection of other dusts and fumes;
the impinger, electrostatic precipitator, and filters are
3,27
commonly used.
6.2 Quantitative Methods
Many methods of analysis have been used for the
determination of manganese. In several methods, such as
atomic absorption, emission spectrography, and neutron
activation, the chemical species does not matter. The
essential requirement is a representative sample in the
activation site. With atomic absorption, all of the manganese
32,34,37.40,67
analyzed must be in solution or suspension.
With chemical methods, care must be taken to insure that
the manganese is not only in solution, but also in a single
oxidation state. The most common method of determining manganese
in air samples is a colorimetric method. In this procedure,
the manganese is oxidized to permanganate by periodate ions.
The color of the permanganate ion is very intense and follows
Beer's law over a large range. A 0.5-ft3 sample collected in
a midget impinger is sufficient to determine manganese at a
40
5,000 |-ig/m concentration.
The following sensitivities are listed for the different
analytical methods:
-------
24
Method Sensitivity (iig/g)
Colorimetric permanganate method 0.1
Emission spectrographya' 10-1,000
Neutron activation3' 0.001-1
Atomic absorption3' 0.01-20
Flame photometry ' 0.1-500
The emission spectrographic method is used to analyze
samples collected by the National Air Sampling Network. Working
standards are made by diluting a solution containing 20 p.g/0.05ml
by 1/2, 1/4, 1/8, ... 1/1024. The minimum concentration
detectable by the emission spectrograph is 0.011 for urban air
and 0.0060 for nonurban air. The difference in sensitivity is
due to different extraction methods used in preparing the
sample for emission spectrography.3'8
Sensitivity depends on interfering elements.
•'-'These sensitivities were not determined on air samples.
-------
25
7. SUMMARY AND CONCLUSIONS
Inhalation of manganese oxides may cause chronic manganese
poisoning or manganic pneumonia. Chronic manganese poisoning
is a disease affecting the central nervous system, resulting in
total or partial disability if corrective action is not taken.
Some people are more susceptible to manganese poisoning than
others. Manganic pneumonia is a croupous pneumonia often
resulting in death. The effect of long exposure to low
concentrations of manganese compounds has not been determined.
Manganese compounds are known to catalyze the oxidation
of other pollutants, such as sulfur dioxide, to more undesirable
pollutants—sulfur trioxide, for example. Manganese compounds
may also soil materials.
The most likely sources of manganese air pollution are
the iron and steel industries producing ferromanganese. Two
studies, one in Norway and one in Italy, have shown that the
emissions from ferromanganese plants can significantly affect
the health of the population of a community. Other possible
sources of manganese air pollution are manganese fuel additives,
emissions from welding rods, and incineration of manganese-
containing products, particularly dry-cell batteries.
Manganese may be controlled along with the particulates from
these sources. Air quality data in the United States showed
that the manganese concentration averaged 0.10 l~i.g/m3 and
ranged as high as 10 |-ig/m3 in 1964.
-------
26
No information was found on the economic costs of
manganese air pollution or on the costs of its abatement.
Based on the material presented in this report, further
studies in the following areas are suggested:
(1) The effect of inhalation over varying periods of
time of low concentrations of the manganese compounds found
in the atmosphere.
(2) The chemical composition and particle-size
distribution of the manganese compounds in the atmosphere.
(3) The effect of manganese air pollution on commercial
plants and animals.
(4) Measurement of the concentration of manganese both
near suspected sources and as emitted from suspected sources.
(5) The economic losses due to manganese air pollution.
-------
27
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-------
28
11. Arkhipova, O. G., M. S. Tolgskaya, and T. A. Kochetkova,
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29
22. Davies, T. A. L., Manganese Pneumonitis, Brit. J. Ind. Med.
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28. Elstad, D., Manganholdig Fabrikkrvek som Medvirkende Arsak ved
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NRL Quarterly on Nuclear Science and Technology. Naval Research
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33. Heine, W., Observations and Experimental Investigation of
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-------
30
36. Joetten, K. W., The Use of Animal Experiments for the Detection
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with Intratracheal Injection of Manganese, Gigiena i Sanit.
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39. Mahoney, J. P-, and W. J. Small, Studies on Manganese—III,
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31
49. New York—New Jersey, Air Pollution Abatement Activity,
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32
60. Stocks, P., On the Relationship Between Atmospheric Pollution
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33
OTHER REFERENCES
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APPENDIX
-------
APPENDIX
TABLE 1 PROPERTIES, TOXICITY, AND USES OF SOME MANGANESE COMPOUNDS
43
Compound.
Properties
Toxicity
Uses
Manganese acetate
Mn(C2H302)2-4H20
Pale red,
transparent
crystals.
Decomposes at
1.59°C
As mordant in dyeing, in manu-
facture of bister, as d.rier for
paints and varnishes
Manganese
arsenate
MnHAsQ4
Reddish-white
powder
Poison
Manganese borate
MnB4O7-8H2O
Brownish-white
powder.
Insoluble in
water or
alcohol
In drying varnishes and oils,
as d.rier for linseed oil;
in leather industry
Manganese bromide
-4H2O
Rose-red
mp 64°C
Manganese
carbonate
MnCOo
White powder,
Insoluble in
water or
alcohol
In pigment"manganese white," as
drier for varnishes, in feeds.
Med . use: formerly as hematine
Manganese
chloride
Reddish.
mp 58°C
Occurs by inhalation of
the dust or fumes. Symp-
toms: languor, sleepiness,
weakness, emotional dis-
turbances, spastic gait,
paralysis. Picture resem-
bles Parkinsonism
LD s.c. in mice: 210 mg/kg
In dyeing (manganese bister),
d.isinfecting, purifying natural
gas; as linseed oil drier; in
electric batteries
(continued)
-------
APPENDIX
TABLE 1 PROPERTIES, TOXICITY, AND USES OF SOME MANGANESE COMPOUNDS (Continued)
Compound
Properties
Toxicity
Uses
Manganese
difluoride
MnF;,
Pink quadratic
prisms.
mp 856°C
Manganese dioxid.e
Mn00
Insoluble in
water
See Manganese chlorid.e
LD i.v. in rabbits:
45 mg/kg
This mineral is the source of
manganese and all its com-
pound.s. Largely used, in manu-
facture of manganese steel; as
oxid.izer; in alkaline batteries
(d.ry cells); for making
amethyst glass, decolorizing
glass, painting on porcelain.
The precipitate is used in
electrotechnics, pigments,
browning gun barrels; as d.rier
for paints and. varnishes; in
printing and, dyeing textiles
Manganese
diselenite
Mn(SeO3)2
Orange-yellow
crystalline
powder. De-
composed, by
heat
Manganese
hypo-phosphite
)2-H2O
Pink. When
heated evolves
spontaneously
flammable
phosphine
Med.. use: formerly as hematinic
Manganese iodid.e
MnI2-4H2O
Rose-red crys-
tals. Very
soluble in
water
co
-------
TABLE 1 PROPERTIES, TOXICITY, AND USES OF SOME MANGANESE COMPOUNDS (Continued)
Compound
Properties
Toxicity
Uses
Manganese nitrate
Mn(N03)2-4H20
Pink.
mp 25.8°C
Manganese oleate
Brown. Insoluble
in water
As drier for varnish
Manganese oxalate
MnC0O -2H00
24 2
White crystal-
line powder.
Decomposes at
150°C
Manganese oxide
Mri O.
3 4
Brownish-black
powder. Decom-
poses at 4.7 C
Manganese
phosphate,
diabasic
MnHP04'3H2O
Pink powder
Manganese
pyrophosphate
MnP9O7-3H9O
^ / £*
White powder.
Insoluble in
water
Manganese selenate
MnSeO4«2H2O
Manganese selenide
MnSe
Gray-black
cubic crystals
CO
(continued)
-------
APPENDIX
TABLE 1 PROPERTIES, TOXICITY, AND USES OF SOME MANGANESE COMPOUNDS (Continued)
Compound,
Properties
Toxicity
Uses
Manganese
selenite
MnSeO3'2H2O
Monoclinic crys-
tals. Decomposes
in air
Manganese
sesquioxide
Black fine pow-
d.er. Insoluble
in water
Manganese
silicate
Red crystals or
yellowish-red.
powder. Insolu-
ble in water
As color for special glass; for
producing red glaze on pottery
Manganese
sulfate
MnSO -HO
Pale red. Loses
all water at
400-450°C
In dyeing; for red glaze on
porcelain, boiling oils for
varnishes; in fertilizers for
vines, tobacco; in feeds
Manganese
sulfide
MnS
Pink, green, or
brown powder.
Practically in-
soluble in water
See Manganese
chlorid.e
Manganese
sulfite
MnSO_
Red.d.ish-white
crystalline
powd.er
(continued )
(jO
oo
-------
APPENDIX
TABLE 1 PROPERTIES, TOXICITY, AND USES OF SOME MANGANESE COMPOUNDS (Continued)
Compound.
Properties
Toxicity
Uses
Manganese
trifluoride
Red crystalline
mass. Decomposes
at 3.54°C.
Stable to 600°C
Methyl-
cyclopenta-
dienyl
manganese
Used to reduce smoke in gas
turbine engines, antiknock
add.itive for gasoline
tricarbonyl
CH C H Mn(CO)
354 3
46
Potassium
permanganate
KMnO
Decomposes at
240°C
Dilute solutions are
mildly irritating and.
high concentrations are
caustic
Bleaching resins, waxes, fats,
oils, straw, cotton, silk, and.
other fibers; dyeing wood
brown; printing fabrics;
washing CO in manufacture of
mineral waters; photography;
tanning leathers; reagent in
analytical and organic chem-
istry; purifying water. Med.
use: topical astringent,
antiseptic
LO
-------
APPENDIX
TABLE 1 PROPERTIES, TOXICITY, AND USES OF SOME MANGANESE COMPOUNDS (Continued)
Compound
Properties
Toxicitv
Uses
Manganese
cyclopenta-
dienyl-
tricarbonyl
(MCT)10'4i
CH_Mn(COK
5 b •J
Bright yellow
crystalline pow-
der. Sublimes at
75-77°C
MCT is toxic in low con-
centrations and has marked
cumulative properties. A
concentration of MCT vapor
of the order of hundred
thousands of M.g/m3 of air
is lethal on a one-time
exposure. 10,000 |-ig/m3
caused severe and. lethal
poisoning when adminis-
tered repeatedly. MCT
concentrations of 1,-000
l~ig/m affected the nervous
system and gave rise to
early histological changes
in the respiratory tract.
The new antiknock compound
acts as a mild irritant at
the site of application
but does not penetrate the
skin when in oil and gaso-
line solution. The toxi-
city of MCT is enhanced by
the solvent tetrahydro-
furan used in its manu-
facture. MCT solutions in
this solvent penetrate the
intact skin and give rise
to poisoning
Antiknock compound for in-
ternal combustion engines
-------
APPENDIX
41
TABLE 226
PREVALENCE OF MANGANISM IN MINERS WORKING IN MANGANESE MINES
Location of
Mines
Germany
(Upper
Schleswig)
Spain
Egypt
Morocco
Germany
Chile
U.S.S.R.
Morocco
Rumania
Year of
Survey or
Publication
of Studies
1879
1935
1936
1936
1936
1943
1946
1949
1949-50
No. of
Miners
Examined
65
44
257
576
No. of
Miners
with
Manqanism
40-50
2
26
26
12
64
0
28
10
Per-
icent
3
10.9
Ob ser vat ion s
These mines contain zinc
and manganese deposits.
A diagnosis of manganism
has recently been assigned
to the case which Schlokow
considered to be one of
zinc intoxication
Baader has confirmed the
cases of manganism detected
by the Egyptian authors;
and during the same voyage
in Africa, he has detected
a few cases of manganism in
miners working in the man-
ganese mines of Morocco
The group of subjects ex-
amined consisted of miners
who had worked in the mine
for more than 10 years.
These authors have also
described the presence of
manganoconiosis and man-
ganic pneumonia in the
pathology of miners. This
group also included 11
probable cases
Examination of these miners
was repeated in 1953 and
1956
(continued)
-------
APPENDIX
42
TABLE 2 (Continued)
PREVALENCE OF MANGANISM IN MINERS WORKING IN MANGANESE MINES
location of
Mines
Cuba
U.S.S.R.
Italy
(Tuscany)
Mexico
U.S.S.R.
U.S.S.R.
Chile
Year of
Survey or
Publication
of Studies
1952
1953
1954
1954
1955-56
1956
1957
No. of
Miners
Examined
151
972
170
83
No. of
Miners
with
Manqanism
120
0
0
12
39
39
15
Per-
cent
7.94
4.01
Observations
Examination of these miners
was repeated in 1956
The authors explain the
absence of manganism by
the marked infiltration of
water into the mining
depo sits
Another case was diagnosed
by the same author in a
drill operator who worked
in another mine
75% of the miners examined
have worked in the mine for
more than 10 years. These
39 miners exhibited dis-
orders of the central ner-
vous system which ranged
from the a stheno vegetative
syndrome to the extrapyra-
midal syndrome.
40 other miners displayed
disorders of the peripheral
nervous system. These
authors have also described
the presence of mangano-
coniosis and manganic pneu-
monia in the pathology of
these miners
The groups of subjects ex-
amined consist of miners
who had a high degree of
toxic exposure and of those
who exhibited clinical dis-
orders for which manganism
was suspected
(continued)
-------
43
APPENDIX
TABLE 2 (Continued)
PREVALENCE OF MANGANISM IN MINERS WORKING IN MANGANESE MINES
Location of
Mines
Morocco
Morocco
Ruman ia
Japan
Year of
Survey or
Publication
of Studies
1958
1958
1958
1950-59
No. of
Miners
Examined
223
145
827
237
No. of
Miners
with
Manqanism
9
59
Per-
cent
6.2
7.13
Observations
158 cases of manganism
were found among the drill
operators
These authors have also
described the presence of
mangano con io s i s
30% of the examined miners
suffered from shaking of
the body and of the extrem-
ities, micrography, dis-
orders of walking or of the
coordination of movements,
and especially from sub-
jective disorders. During
the period of examination
(1950-59), the authors
noted the gradual worsen-
ing of the clinical pic-
tures
-------
APPENDIX
44
TABLE 3
PNEUMONIA RATE IN MANGANESE WORKERS
(Rate/1000 Males)
64,30
Year
1938
1939
1940
1941
1942
1943
1944
1945
1946
1947
1948
£L A
1957-5964
196230
Manganese Manganese
Plant Mine
63
50
15
30
24
20
0
26
10
30
26-33
8008
Boots20
Health
Iron Coal Insurance
Mine Mine Society
0.52
0.47
0.91
0.59
0.89
1.2
1.0
0.02
0
0.8-3.6
51
England
and
Wales
1.0
1.2
1.2
1.0
1.2
0.9
0.8
0.9
-------
TABLE 4 . REPORTED PREVALENCE OF CROUPOUS PNEUMONIA AMONG MANGANESE WORKERS
Location of Exposure
Manganite mill
Norwegian town near
f erromanganese plant
Mn mine
Mn mine
Mn ore shippers
Mn mines
Other mines
All industries
Mn mines
Mn mines
Mn mines
Dry-cell factory
Manganite processing plant
Dry-cell factory
Mn mines
Coal mines
Forest
Year of
Study
1913
1923
1923
1930
1931
1932
1932
1932
1932
1935
1936
1937
1939
1957-59
1957-59
1957-59
No. of Percentage of
No. of Workers with Workers with
Workers Croupous Croupous Exposure
Exposed Pneumonia Pneumonia Time
10 5 50 27 mo
32.3
8.2
2
70 37 53 13 yr
442 268 61
11.3
3.8
Most frequent cause of death
64 6 9.4
44 23 52
1
*
5
104 14 (11*) 13.5
2.3-3.3
0.08-0.36
0.78-2.4 £
Workers died of pneumonia.
-------
APPENDIX
TABLE 5
U.S. CONSUMPTION OF MANGANESE ORE AND MANGANESE ALLOYS45
(Short Tons)
Type of
Consumption
1958
1960
1961
1962
1963
1964
1965
1966
MANGANESE OREa
Domestic 45,264 29,080 20,004 24,670 7,135 19,887 24,344 46,159
Foreign 1,452,310 1,917,309 1,697,801 1,840,602 1,834,590 2,221,869 2,848,376 2,323,134
Totalb 1,497,574 1,946,389 1,717,805 1,865,272 1,841,725 2,241,756 2,872,720 2,369,293
For production
of:
Alloys and
metal 1,414,613 1,846,572 1,586,965 1,737,694 1,683,450 2,092,445 2,704,357 2,163,968
Pig iron 5,041 5,805 9,961 14,832 34,830 18,706 27,772 42,941
Chemicals 50,643 65,920 91,470 78,116 94,715 99,670 105,580 128,145
Dry cells 26,604 27,215 28,301 33,625 27,870 30,114 33,865 34,200
FERROMANGANESE
Steel ingots 674,495 755,864 778,003 766,673 852,285 967,550 1,040,502 1,048,429
More than 35% Mn.
Includes more than those listed below.
-------
47
APPENDIX
TABLE 6
MANGANESE ORE RESOURCES OF THE U.S.
Millions of
Location Short Tons
Butte, Mont.
Phillipsburg, Mont.
RESERVES
5.0
.8
Mn, Avq %
14
22.5
POTENTIAL ORE
Aroo stock County, Maine
Cuyuna Range, Minn.
Chamberlain, S. Dak.
Artillery Peak, Ariz.
Leadville, Colo.
Three Kids, Nev.
Pioche, Nev.
313.6
504.0
77.3
174.7
4.0
5.0
4.0
9
5
15.5
4
15
10
10
-------
AJr'i'JKJMlJJ.^X.
TABLE 7
U.S. CAPACITY FOR STEEL PRODUCTION, JAN. 1, I96053
State
Ohio
Pennsylvania
Illinois
Michigan
Texas
Alabama
California
Kentucky
Missouri
Washington
Georgia
New York
Maryland
Oregon
Oklahoma
West Virginia
Indiana
Connecticut
Arizona
Florida
Mississippi
Virginia
Tennessee
New Jersey
Colorado
Minnesota
Massachusetts
Utah
Rhode Island
Delaware
Total
Electric Furnace
No. of
Plants/
Furnaces
8/36
31/105
8/28
4/20
5/12
4/8
3/8
2/5
1/2
3/6
1/2
6/28
2/11
1/3
1/1
1/1
2/7
1/2
1/2
1/1
1/1
2/4
1/2
1/6
91/301
Annual
Capacity
(net tons)
3,078,600
2,888,780
2,400,400
1,178,600
699,080
670,020
628,000
466,190
420,000
401,000
325,000
225,010
180,960
150,000
140,000
117,000
101,500
84,000
60,000
51,000
45,000
40,000
38,000
7,800
14,395,940
Blast Furnace
No. of
Plants/
Furnaces
22/52
23/76
6/22
3/9
2/2
7/22
1/4
1/3
6/17
1/10
2/5
3/23
1/2
2/3
1/4
2/3
1/1
2/5
86/263
Annual
Capacity
(net tons)
18,734,500
26,381,750
7,955,200
5,290,250
925,000
5,817,440
1,997,800
1,058,000
5,947,000
5,480,000
2,646,000
10,324,350
128,000
217,740
922,400
696,000
195,000
1,804,200
96,520,630*
Open-Hearth Furnace
No. of
Plants/
Furnaces
17/169
30/283
6/62
2/27
2/13
3/31
6/30
2/15
1/4
3/47
1/35
1/14
4/120
1/9
1/17
1/9
1/10
1/4
1/7
84/906
Annual
Capacity
(net tons)
22,688,280
34,944,350-
9,842,000
5,420,000
1,825,000
4,786,000
2,727,500
1,363,000
420,000
7,195,000
7,864,000
3,300,000
18,339,000
235,000
1,800,000
973,000
2,300,000
93,000
506,500
126,621,630
Basic Oxygen Steel
Furnace
No. of
Plants/
Furnaces
1/2
1/2
1/5
1/3
4/12
Annual
Capacity
(net tons!
880,000
452,000
1,385,400
1,440,000
4,157,400
*Includes 877,500 tons ferroalloys capacity.
00
-------
49
APPENDIX
TABLE 8
PRODUCERS OF FERROALLOYS IN THE UNITED STATES IN 1966
45
Producer
Plant Location
Product*
Type of
Furnace
The Anaconda Company
Bethlehem Steel Co.
Chromium Mining and
Smelting Corp.
Interlake Steel Corp.
E. J. Lavino & Co.
Manganese Chemicals Corp.
The New Jersey Zinc Co.
Ohio Ferro-Alloys Corp.
Pittsburgh Metallurgical
Company
Tenn-Tex Alloy &
Chemical Corp.
Union Carbide Corp.,
Mining & Metals Div.
United States Steel Corp.
Vanadium Corp. of America
Anaconda, Fla.
John stown, Pa.
Woodstock, Tenn.
Beverly, Ohio
Sheridan, Pa.
Reusens, Va.
Kingwood, W. Va.
Palmerton, Pa.
Philo, Ohio
Niagara Falls/ N. Y,
Houston, Tex.
Alloy, W. Va.
Marietta, Ohio
Ashtabula, Ohio
Sheffield, Ala.
Portland, Oreg.
Rockwood, Tenn.
Birmingham, Ala,
Clairton, Pa.
Duquesne, Pa.
Graham, W. Va»
FeMn
FeMn
FeMn, SiMn
SiMn
FeMn
FeMn
FeMn
Spin
FeMn, S iMn
SiMn
FeMn, SiMn
FeMn, SiMn
FeMn, SiMn
FeMn, SiMn
FeMn
FeMn, SiMn
FeMn, S iMn
FeMn
FeMn
FeMn
FeMn
Electric
Blast
Electric
Electric
Blast
Blast
Electric
Electric
Electric
Electric
Electric
Electric
Electric
Electric
Electric
Electric
Electric
Blast
Blast
Blast
Electric
*FeMn, ferromanganese; Spin, spiegeleisen; SiMn, silicomanganese.
-------
TABLE 9
MANGANESE EMISSIONS FROM METALLURGICAL FURNACES
55
Furnace
Ferromanganese
blast furnace
Open-hearth furnace
Electric-arc
steel furnace*
Basic oxygen furnace
Manganese
in Particulate
I Per cent)
15-25
0.6 (MnO)
4 (MnO)
4.4 (Mn304)
Dust
Emission Rate
pounds dust/ton ore
No Control Control
360
9.3
11
20-40
60
Io7
1.2
0.2-0.4
Manganese
Emission Rate
pounds/ton ore
No Control
54-90
0.056
0.44
0.88-1.76
Control
9-15
0.01
0.044
0.0088-0.0176
*These emissions are based on the production of steel.
ferromanganese, the manganese concentration may be higher.
When electric-arc furnaces produce
U1
o
-------
51
APPENDIX
TABLE 10
MANGANESE EMISSIONS FROM COAL-FIRED POWER PLANTS
Type of Boiler
a
Vertical
c
Corner
Front-wall13
Spreader- stoker0
r_
Cyclone-fired unit0
Horizontally opposed0
UCT,
Before Fly-ash
Collection
1,700
970
3,900
1,400
1,300
2,400
/ma
After Fly-ash
Collection
60
100
370
300
280
170
aFly-ash collector is cyclone-type separator followed by an
electrostatic precipitator.
Fly-ash collector is an electrostatic precipitator.
°Fly-ash collector is a cyclone-type separator.
-------
52
APPENDIX
TABLE 11
"ETHYL" ANTIKNOCK COMPOUND-TEL MOTOR 33 MIX58
Compound Weight %
Tetraethyllead 57.5
Methyl cyclopentadienylmanganese tricarbonyl 7.0
Ethylene dibromide 16.7
Ethylene dichloride 17.6
Other (dye, inerts) 1.2
-------
APPENDIX
53
TABLE 12
CONCENTRATION OF MANGANESE IN THE AIR2'4'6'7
Location
Alabama
Birmingham
Arizona
Phoenix
California
Los Angeles
San Francisco
Colorado
Denver
District of
Columbia
Washington
Georgia
Atlanta
Idaho
Boise
Illinois
Chicago
Cicero
East St. Louis
Indiana
East Chicago
Indianapolis
Iowa
Des Moines
Louisiana
New Orleans
Maryland
Baltimore
— _ —
1954-59
Max
1.86
.03
.20
.16
.30
.60
.20
1.20
.10
,33
Avq
.27
.05
.05
.09
.14
.06
.16
.01
.09
•^-.^^— —
1960
Max
.72
.11
.09
.15
Avg
.26
.05
.03
.07
1961
Max
.11
.32
.35
.52
Avg
.04
.13
.10
.14
1962
Max
.21
.19
.07
.16
.14
.08
.34
.27
.18
.06
.72
Avg
.09
.07
.02
.08
.05
.03
.10
.07
.05
.02
.10
1963
Max
.08
.05
.45
.08
.36
.24
.25
Avg
.03
.01
.08
.03
.08
.08
.09
1964 .
Max
1.60
.25
.09
.06
.05
.17
1.00
.06
.49
Avg!
.3<
.0*
i
.0'
1
.0:
.0:
.0'
.28
-02
.10
(continued )
-------
APPENDIX
54
TABLE 12 (Continued)
CONCENTRATION OF MANGANESE IN THE AIR2'4'6'7
Location
Massachusetts
Boston
Michigan
Detroit
Missouri
St. Louis
Montana
Helena
Nevada
Las Vegas
New Jersey
Newark
New York
Buffalo
New York
North Carolina
Charlotte
Ohio
Cincinnati
Cleveland
Pennsylvania
All en town
Philadelphia
Pittsburgh
Scranton
Tennessee
Chattanooga
Texas
El Paso
1954-59
Max
.03
2.64
.30
.31
9.29
3.86
.70
3.00
Avg
.69
.05
.06
.27
.05
.16
.32
1960
Max
1.80
1.50
Avg
.37
.27
1961
Max
.35
.48
.16
2.40
1.20
9.98
. 36
Avq
.07
.05
.06
.39
.33
.70
.13
.59
1962
Max
.45
.42
.39
.14
.75
.13
2.30
1.70
1.30
1.20
.21
.55
Avq
.10
.10
.07
.05
.17
.05
.43
.31
.25
.26
.10
1963
Max
.42
.13
.12
.12
1.30
.96
3.70
1.40
Avq
.12
-05
.04
.04
.16
.24
.62
.27
1 964
Max
-05
.74
.22
-07
.17
.09
.07
.31
2.00
1.00
1.90
.82
.37
1.10
Avq
.0
.2
.0
.0
.0
.0
.0
.0
.4
.1
.4
.2
.1
.1.
(continued
-------
APPENDIX
55
TABT.S 12 (Continued)
CONCENTRATION OF MANGANESE IN THE AIR 2 ' 4 .. 5 , 7
Location
Washington
Seattle
Tacoma
West Virginia
Charleston
Wisconsin
Milwaukee
Wyoming
Cheyenne
1 9^4-59
Max
.24
1.20
.25
Avq
.07
.32
.05
I960
Max
•
Avg
1961
Max
9.98
Avg
1.85
1962
Max
.29
.12
Avg
.05
.04
1963
Max
.09
Avg
.03
1964
Max
.07
9.98
.47
.02
Avc
.0
1.3.
.1
------- |