STAR Series
I
I
ASSESSMENT REPORT
ON MANGANESE
Environmental Protection Agency
il'ice of Research and Development
Washington, D.C. 20460
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EPA-600/6-74-002
April 1975
SCIENTIFIC AND TECHNICAL
ASSESSMENT REPORT
ON
MANGANESE
Program Element No. 1AA001
ROAP No. 26AAA
Assembled by
National Environmental Research Center
Research Triangle Park, North Carolina
for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Office of Program Integration
Washington, D.C. 20460
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental Protection Agency, have
been grouped into series. These broad categories were established to facilitate further development and
application of environmental technology. Elimination of traditional grouping was consciously planned to
foster technology transfer and a maximum interface in related fields. These series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
9. Miscellaneous Reports
This report has been assigned to the SCIENTIFIC AND TECHNICAL ASSESSMENT REPORTS (STAR)
series. This series assesses the available scientific and technical knowledge on major pollutants that would be
helpful in possible EPA regulatory decision-making regarding the pollutants or assesses the state of
knowledge of a major area of completed study. The series endeavors to present an objective assessment of
existing knowledge, pointing out the extent to which it is definitive, the validity of the data on which it is
based, and uncertainties and gaps that may exist. Most of the reports will be multi-media in scope, focusing
on a single medium only to the extent warranted by the distribution of environmental insult.
EPA REVIEW NOTICE
This report has been reviewed by the Office of Research and Development, EPA, and approved for
publication. Mention of trade names or commercial products does not constitute endorsement or
recommendation for use.
DISTRIBUTION STATEMENT
This report is available to the public from Superintendent of Documents, U.S. Government Printing Office,
Washington, D.C. 20402.
11
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PREFACE
Although this report is issued in the Scientific and Technical Assessment Report Series, it differs in several
respects from the comprehensive multi-media format that the Series will usually have because it was nearly
completed prior to the creation of the STAR series in August 1974.
This document was prepared by a task force convened at the direction of Dr. John F. Finklea, Director,
U.S. Environmental Protection Agency, National Environmental Research Center (NERC), Research
Triangle Park (RTF), N.C. Assembly, integration, and production of the report were directed by the Special
Studies Staff, NERC-RTP. The objective of the task force was to review and evaluate the current knowledge
of manganese in the environment as related to possible deleterious effects upon human health and welfare.
Information from the literature and other sources has been considered generally through May 1973.
A report prepared for the U.S. Environmental Protection Agency (EPA) by a National Academy of
Sciences' Panel on Manganese of the Committee on Medical and Biological Effects of Environmental
Pollutants served as a primary reference for this report.
The following persons served on the task force:
From NERC-RTP:
James 0. Baugh
Thomas G. Dzubay
J.H.B. Garner
Douglas I. Hammer
Kenneth J. Krost
John Laskey
James R. Smith, Chairman
Joseph A. McSorley
John Moran
Ronald K. Patterson
Elbert C. Tabor
Darryl J. von Lehmden
Anthony Zavadil
From NERC-Cincinnati:
J. Adams
W.C. Crocker
L.Hall
M.E. Harf
D.K. Hysell
C. Kimmel
J. Lewkowski
R. Miller
W. Moore
J.F. Stara
From EPA's Office of Air Quality Planning and Standards:
Robert D. Coleman
iii
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The substance of this document was reviewed by the National Air Quality Criteria Advisory Committee
(NAQCAC) in public session on November 16,1973. Members of the NAQCAC were:
Arie J. Haagen-Smit, Chairman James McCarroll
Mary 0. Amdur Eugene P. Odum
David M. Anderson Elmer Robinson
Anna M. Baetjer Morton Sterling
Thomas D. Crocker Arthur C. Stern
Samuel S. Epstein Elmer P. Wheeler
C. C. Li John T. Wilson, Jr.
Ernst Linde, Executive Secretary
The report was reviewed by a task force convened under the direction of Dr. J. Wesley Clayton, Jr., of
EPA's Office of Research and Development. Members of this task force were:
Thomas O. Bath Harry Landon
Kenneth Cantor Robert E. McGaughey
A. F. Forziati Robert B. Medz
Thomas L. Gleason Jeannie L. Parrish
Hend Gorchev Lawrence A. Plumlee
Marty Kanarek Jean Pulliam
Irene Kiefer James Shackelford
Thomas Kopp Jay Sinnett
Review copies of this document also have been provided to other governmental agencies and to industrial
and public interest groups.
All comments and criticisms have been reviewed and incorporated in the document where deemed
appropriate.
IV
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TABLE OF CONTENTS
Page
LIST OF FIGURES vi
LIST OF TABLES vi
LIST OF ABBREVIATIONS AND SYMBOLS vii
1. INTRODUCTION 1-1
2. 'SUMMARY AND CONCLUSIONS 2-1
2.1 SUMMARY 2-1
2.2 CONCLUSIONS 2-2
3. CHEMICAL AND PHYSICAL PROPERTIES 3-1
3.1 REFERENCES FOR SECTION 3 3-2
4. MEASUREMENT TECHNIQUES 4-1
4.1 SAMPLING 4-1
4.1.1 Ambient Air 4-1
4.1.2 Water 4-1
4.1.3 Food 4-1
4.1.4 Soil 4-1
4.1.5 Biological Tissues 4-2
4.1.6 Stationary Source Emissions 4-2
4.1.7 Mobile Source Emissions 4-3
4.2 ANALYTICAL TECHNIQUES 4-3
4.2.1 Inorganic Manganese Compounds In Air 4-3
4.2.2 Organic Manganese Compounds In Air 4-6
4.3 REFERENCES FOR SECTION 4 4-6
5. ENVIRONMENTAL APPRAISAL 5-1
5.1 ORIGIN AND ABUNDANCE 5-1
5.1.1 Natural Sources 5-1
5.1.2 Man-Made Sources 5-1
5.2 CONCENTRATIONS 5-9
5.2.1 Air 5-9
5.2.2 Water 5-23
5.2.3 Food 5-24
5.2.4 Soil 5-24
5.2.5 Biological Tissues 5-26
5.2.6 Estimate of Daily Human Exposure 5-26
5.3 TRANSPORT AND MODELING 5-27
5.3.1 Dissolution in Fresh Water and Sea Water 5-27
5.3.2 Rainout and Washout 5-27
5.3.3 Microbiological Utilization at Earth's Surface 5-28
5.3.4 Uptake by Soil and Plants 5-28
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5.3.5 Photochemical and/or Thermal Reactions in Lower Atmosphere 5-28
5.4 REFERENCES FOR SECTION 5 5-28
6. BIOLOGICAL EFFECTS 6-1
6.1 EFFECTS ON MAN AND LABORATORY ANIMALS 6-1
6.1.1 Introduction 6-1
6.1.2 Metabolism 6-1
6.1.3 Toxicological Effects 6-2
6.1.4 Mechanisms of Manganese Poisoning 6-3
6.1.5 Community and Occupational Exposure . . . ., 6-4
6.1.6 Maximum Permissible Levels of Manganese and Prevention
of Chronic Manganese Poisoning < > 6-7
6.2 EFFECTS ON PLANTS 6-7
6.3 REFERENCES FOR SECTION 6 6-3
7. CONTROL TECHNOLOGY 7-1
7.1 INTRODUCTION 7-1
7.2 CONTROL DEVICES 7-1
7.3 MANGANESE FUEL ADDITIVES 7-1
Bibliographic Data Sheet 8-1
LIST OF FIGURES
Figure Page
4.1 Particulate sampling train used for collecting manganese 4-2
5.1 Location of fixed sampling stations in Kanawha River Valley. Average manganese
concentrations (/;g/m3) for the study period (1964-65) are indicated for selected
sites 5-12
5.2 Manganese in precipitation (g/ha-mo), September 1966-January 1967 5-17
LIST OF TABLES
Table
3.1 Properties of Manganese and Some of Its Compounds 3-1
4.1 Accuracy of Methods for Analysis of Manganese in Coal and Fly Ash 4-4
4.2 Sensitivity of Analytical Methods for Manganese 4-4
5.1 Consumption of Manganese Ore in the United States, 1970 5-1
5.2 Consumption of Manganese Alloys and Metal in the United States, 1970, by End Use .... 5-2
5.3 Estimated Manganese Emissions by Source, 1968 5-3
5.4 Range of Manganese Concentrations in Source Emission Particulates 5-3
5.5 Material Balance for Manganese at a Coal-Fired Steam Power Plant 5-4
5.6 Manganese Concentration in Coal Fly Ash, by Particle Size 5-4
5.7 Manganese Emissions From Air Pollution Sources in the Chicago, Milwaukee, and Northwest
Indiana Area 5-5
5.8 Manganese Concentrations of Coal, Fuel Oil, Crude Oil, Gasoline, Fuel Additives, and Motor
Oil 5-6
5.9 Effect of Manganese Fuel Additive on Exhaust Particulate 5-8
vi
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Table
Page
5.10 Effect of Manganese Fuel Additive on Percent Carbon In Exhaust Participate 5-8
5.11 Number of NASN Stations Within Selected Annual Average Manganese Concentration
Intervals, 1957-69 5-10
5.12 NASN Stations With Annual Average Manganese Concentrations Greater Than 0.5 Mg/m3 • 5-11
5.13 Manganese Concentrations, Kanawha Valley Area, 1964-65 5-13
5.14 Manganese Concentrations, Birmingham Area, 1964-65 5-14
5.15 Quarterly and Annual Size Distributions for Suspended Particles Containing Manganese,
1970 5-16
5.16 Estimated Hourly Manganese Concentrations, EPA Model 5-18
5.17 Estimated 24-Hour Manganese Concentrations, EPA Model 5-19
5.18 Traffic Volumesrand Meteorological Conditions For 24 Hours, EPA Model 5-20
5.19 Estimated Hourly Manganese Concentrations, Ethyl Model 5-21
5.20 Estimated 24-Hour Manganese Concentrations, Ethyl Model 5-21
5.21 Estimated Maximum Manganese Concentrations, Ethyl Model 5-22
5.22 Estimated Street Canyon Manganese Concentrations, Ethyl Model 5-22
5.23 Manganese Concentrations in U.S. Water Systems 5-24
5.24 Manganese Concentrations in Groups of Principal Foodstuffs 5-24
5.25 Micronutrient Concentrations in Soils and Rocks 5-25
5.26 Estimated Daily Background Dose Of Manganese 5-26
6.1 Effects of Acute Excess of Manganese Injected Subcutaneously in Rats 6-2
LIST OF ABBREVIATIONS AND SYMBOLS
AMP
BaP
°C
CO
EDTA
EPA
g/gal
g/ha-mo
HC
HC1
HN03
H20
H2S04
kg/km2-mo
LDso
m/sec
m3/day
mg
mg/kg
mg/liter
mg/m2 -mo
mg/m3
MMT
Adenosine monophosphate
Benzo[a] pyrene
Degrees Celsius
Carbon monoxide
Ethylenediaminetetraacetic acid
U. S. Environmental Protection
Agency
Grams per gallon
Grams per hectare per month
Hydrocarbon
Hydrochloric acid
Nitric acid
Water
Sulfuric acid
Kilograms per square kilome-
ter per month
Lethal dose to 50 percent of
subjects
Meters per second
Cubic meters per day
Milligrams
Milligrams per kilogram
Milligrams per liter
Milligrams per square meter
per month
Milligrams per cubic meter
Methylcyclopentadienyl man-
ganese tricarbonyl
Mn
Mn2+,Mn3+,etc.
MnCl2
MnO2
Mn032-,Mn042-,etc,
Mn3O4
MT
Mg/g
Mg/liter
Mg/ml
Mg/m3
Hm
NAQCAC
NASN
NERC
ng ,
ng/cm
ng/m3
NH3
NOX
PHS
ppb
ppm
RTP
TEL
Manganese
Manganese cations
Manganese chloride
Manganese dioxide
Manganese anions
Manganese oxide
Metric tons
Micrograms per gram
Micrograms per liter
Micrograms per milliliter
Micrograms per cubic meter
Micrometers (10"6 meters)
National Air Quality Criteria
Advisory Committee
National Air Surveillance Net-
works, EPA
National Environmental Re-
search Center
Nanograms
Nanograms per square
centimeter
Nanograms per cubic meter
Ammonia
Oxides of nitrogen
Public Health Service
Parts per billion
Parts per million
Research Triangle Park, N. C.
Tetraethyl lead
vu
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ABSTRACT
This report is a review and evaluation of the current knowledge of manganese in the environment as related
to possible deleterious effects on human health and welfare. Sources, distribution, measurement, and
control technology are also considered. Manganese is associated with small particles in the air.
Concentrations measured in ambient air averaged 0.1 jug/m3 (annual)' with, a maximum of 8.3 jug/m3
(annual) near a large source. ' *' *- '
In Norway, a form of pneumonia was attributed to airborne manganese in a community where
concentrations were measured at 46 Mg/m3. Manganese poisoning characterized by progressive central
nervous system deterioration has occurred under occupational exposure but apparently not from
atmospheric exposure. Control of fine particulate emissions should reduce manganese emissions
considerably.
Vffl
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SCIENTIFIC AND TECHNICAL ASSESSMENT
REPORT ON MANGANESE
1. INTRODUCTION
The purpose of this document is to summarize the current knowledge of manganese in relation to its effects
upon human health and welfare and the environment; and to evaluate this knowledge base with a view
toward the need to control the release of manganese into the environment from anthropogenic (man-made)
sources.
The U. S. Environmental Protection Agency (EPA) is required by the Clean Air Act as amended to
promulgate standards and regulations for the control of air pollutants that are deleterious to human health
and welfare. Human illness has been associated with excessive exposure to manganese. Decisions relating to
the control of manganese as an air pollutant must be based not only upon knowledge regarding effects, but
also on sources and subsequent ambient concentrations, transport and behavior in the environment, and
available control technology. These aspects of the problem are reviewed to the extent deemed appropriate
for decision-making processes. Sampling and analytical techniques are examined in order that the validity of
available data may be evaluated.
It is generally accepted that manganese is an essential trace element for all living organisms; however,
deleterious effects may result from excessive exposure. In this report, appraisals of effects are presented,
and estimates of exposure-response relationships are noted when justified by available data. Manganese
enters the human body principally via food, water, and air. The relative importance of each of these intake
routes is examined. In addition, the principal anthropogenic sources of manganese are identified, and
applicable control technology is assessed.
1-1
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2. SUMMARY AND CONCLUSIONS
2.1 SUMMARY
Manganese (Mn) is among the trace elements least toxic to mammals; however, exposure to abnormally high
concentrations resulting from anthropogenic sources has resulted in adverse human health effects.
Manganese poisoning is characterized by progressive deterioration of the central nervous system, sometimes
accompanied by unrelated pneumonitis.
The majority of cases have been associated with the breathing of manganese dust or fumes from mining or
metallurgical operations. An outbreak of a form of pneumonia in inhabitants of Sauda, Norway, was
attributed to manganese emissions from a ferromanganese plant. Absorption via the gastrointestinal tract
and through the skin has also been reported. An outbreak of manganese poisoning in Japan was attributed
to ingestion of manganese-contaminated well water. In the early stages of poisoning, removal of the victim
from the polluted environment usually clears up manganism; however, in chronic cases, the effects on the
central nervous system are not completely reversible.
Manganese has been classified as an essential trace element for both plants and animals, including man.
Generally, organs and tissues do not accumulate large concentrations of manganese. Excretion normally
occurs via the biliary route in the feces.
Plant species differ widely in manganese requirements and tolerances. The availability of manganese to
plants is dependent upon the oxidation state of the manganese in soil. Excessive amounts of divalent
manganese can be toxic to plants. Microbial action appears to play an important part in making manganese
available to plants.
Manganese is one of the more abundant elements in the earth's crust. It is widely distributed in soils,
sediments, rocks, and water; it is thought to be present in all organisms. At least JJDQ. minerals contain
manganese; however, it does not occur naturally as a metal. The concentration of manganese in soil ranges
from near zero to 7,000 micrograms per gram (jug/g) with a rough average of about 850 Mg/g- The
concentration of dissolved manganese in sea water varies between 0.4 and 10 micrograms per liter (jug/liter)
and in fresh water the concentration ranges from less than 1 to over 100 jug/liter. Manganese appears to
be omnipresent in foodstuffs, with concentrations ranging from a trace to 275 /jg/g. The maximum
concentrations of manganese in foodstuffs are found in nuts, tea, and spices.
The 1970 total consumption of manganese in the United States was over a million metric tons. Most of the
concentrate is used in the production of ferromanganese. Approximately 90 percent of the manganese
consumed in the United States goes into production of iron and steel where it nullifies the effects of sulfur;
no substitute material has been found for this purpose. Manganese is also used as an alloying agent for steel,
aluminum, and copper. Other uses include the manufacture of dry cell batteries, welding rod coatings and
fluxes, dyes, paints, varnish dryers, fungicides, and Pharmaceuticals. Manganese compounds are added to
boiler and turbine fuels to improve combustion and suppress smoke and are used as antiknock agents in
gasoline.
The principal sources of ambient environmental pollution by manganese are emissions from metallurgical
processing plants and reprocessing waste materials. Emissions to the atmosphere from industrial plants and
processes will vary considerably, depending upon the process involved and the degree of control exercised.
2-1
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Particle emissions from a ferromanganese blast furnace are generally in two size ranges; dust particles >20
micrometers O^im), and fume with particle sizes ranging from 0.1 to 1.0 /urn. It has been reported that the
dust particles comprise approximately 20 percent of the total particulate emissions, and fumes
approximately 80 percent.
The reported mass median diameter of suspended particles containing manganese in the ambient air is
approximately 2.
With the use of available control technology, the unit contribution to the ambient atmospheric
concentration of manganese should be relatively small from iron and steel. It has been estimated that over
80 percent of the total national manganese emissions in 1968 was from iron, steel, and ferroalloy
production. Dust from the handling of raw materials in metallurgical processing, and other production
activities such as the manufacture of chemicals, fertilizers, fungicides, and dry cell batteries, may result in
local manganese pollution problems.
Disposal of waste products may contribute to the manganese contamination of local water sources. Few
cases of manganese contamination of soil have been reported. Such contamination would come primarily
from fertilizers, fly ash, and mine effluents.
Manganese has been found in measurable amounts in practically all samples of suspended particulate matter
collected by the National Air Surveillance Networks (NASN) from the air of some 300 urban areas. The
highest concentrations, as expected, are found in the vicinity of ferromanganese alloy plants or related '
activities. The NASN urban average manganese concentration is less than 0.2 micrograrh per cubic meter
(jug/m3), but several cities have annual averages in the 0.5 to 3.3/ig/m3 range. Occasional 24-hour
concentrations as high as 14.0jig/m3 have been measured. Annual averages as high as 8.3 jUg/m3 havev
occurred in small communities located near a large point source in the highly industrialized Kanawha River
Valley of West Virginia. In Norway, concentrations of over 4j6 yg/m3 have been reported in the vicinity
of a ferromanganese furnace. Approximately 80 percent of manganese in the suspended particulate matter
from six large cities in the United States was associated with particles in the respirable size range— that is, 5 (
jum or less in diameter. The existence of manganese in the smaller particles favors a widespread distribution
of this pollutant. Such distribution has been confirmed by the analysis of precipitation samples collected at
many remote locations in the United States.
Manganese in the atmosphere is associated primarily with particulate matter. Thus, the principal
mechanisms for manganese removal from the air are precipitation, gravitational settling, and absorption at
the earth's surface. Manganese may be involved in the atmospheric conversion of sulfur dioxide to sulfuric
acid, although in the presence of ammonia, the manganese concentrations in the ambient air may not be
high enough to affect that conversion. The reaction, however, of manganese dioxide with nitrogen dioxide
to form manganese nitrate may occur in the atmosphere.
The use of presently available control technology for stationary sources would reduce manganese emissions
to the atmosphere. Availability of control technology for fine particulates would further reduce emissions
to the atmosphere.
2.2 CONCLUSIONS
The natural abundance of manganese, and its dynamic behavior in the environment- which involves
physical, chemical, and biological activity-make it difficult to assess the contribution and effects of
man-made sources. Much of our knowledge concerning the toxicity of manganese is based upon clinical
studies of individuals with manganese poisoning resulting from exposure to high concentrations. Much
remains unknown about the biochemical and toxicological effects of manganese. No cases of manganese
poisoning have been reported from exposure to concentrations less than the recommended occupational
threshold limit of 5 mg/m3 (8 hours per day, 40 hours per week), although some argue that the safety
2-2 MANGANESE
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margin is low for susceptible persons. Based upon the present state of knowledge and available data, the
following conclusions can be drawn:
• Manganese is an essential element for all living things. ""
• Adverse health effects may occur from exposure to high concentrations of manganese, particularly
in the form of dust and fumes. ^
• There is currently no evidence that human exposure to manganese at the levels commonly
observed in the ambient atmosphere results in adverse health effects. The only human health
effects attributable to manganese in ambient air were found in persons living in the immediate
vicinity of two major point sources in Norway and Italy. Manganese pollution is presently a local
problem, but the widespread use of manganese fuel additives would make man-made emissions
more ubiquitous. There is no evidence that predicted manganese concentrations resulting from the
use of methylcyclopentadienyl manganese tricarbonyl would result in adverse health effects;
however, icspiratory irritant effects from long-term or frequent exposure to low concentrations
have not been thoroughly investigated.
• Most effects from manganese in humans appear to result from prolonged inhalation. ""
• Manganese pollution of water does not appear to be a problem except possibly in isolated cases of
waste disposal. s/
• Atmospheric concentrations of manganese observed in urban areas can be attributed primarily to
man-made sources. The principal source of atmospheric emissions is metallurgical processing. "-
• Particulate control technology available and/or under development should be adequate to maintain
the atmospheric concentration of manganese at an acceptable level; however, control of fine
particulate matter that contains manganese remains to be evaluated as this technology is applied.
Summary and Conclusions 2-3
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3. CHEMICAL AND PHYSICAL PROPERTIES
Manganese (Mn) does not occur naturally as a metal; however, over 100 minerals contain manganese as a
natural constituent. Among manganese-containing minerals are sulfides, anhydrous and hydrous oxides,
carbonates, anhydrous and hydrous silicates, anhydrous and hydrous phosphates, arsenates, tungstates,
and borates. Oxides, carbonates, and silicates are the most important. Like iron, manganese occurs in the
divalent and trivalent forms. The chlorides, nitrates, and sulfates of manganese are highly soluble in water,
but the oxides, carbonates, and hydroxides are only sparingly soluble. Two reviews provided the following
information.1'2
Manganese is a gray-white metal resembling iron, but it is harder and more brittle. It is especially noted for
imparting hardness to metal alloys. The physical and chemical properties of manganese and some of its
compounds are listed in Table 3.1.
Table 3.1. PROPERTIES OF MANGANESE AND SOME OF ITS COMPOUNDS1'2
Name
Manganese
Manganese
dioxide
Manganous
carbonate
Manganous
chloride
Manganous
acetate
Potassium
perman-
ganate
Chemical
symbol
or
formula
Mn
Mn02
MnC03
MnCI2
Mn(C2H302)2
•4H2O
KMn04
Atomic
or
molec-
ular
weight
54.94
86.94
114.94
125.84
245.08
158.04
Specific
gravity
7.2
5.026
3.125
2.997
(25°)
1.589
2.703
Melting
point,
°C
1 244±3
(-0)535
Decom-
poses
650
Decom-
poses
Boiling
point,
°C
1962
1190
<240
Solubility
Reacts in hot or cold H2O.
Soluble in dilute acid.
Insoluble in hot or cold
H2O, HNO3, or acetone.
Soluble in HCI.
65 mg/liter (25° C)
Soluble in dilute acid.
Insoluble in NH3 and
alcohol.
622g/liter (10°C)
1238g/liter (100°C)
Soluble in alcohol.
Insoluble in ether and NH3.
Soluble in cold H20 and
alcohol.
28.3g/liter(0°C)
250g/liter (65°C)
Decomposes in alcohol.
Soluble in H2S04.
Very soluble in methyl
alcohol and acetone.
3-1
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Manganese can exist in eight different oxidation states (0, 1+, 2+, 3+, 4+, 5+, 6+, 7+), of which the bivalent
form (Mn2+) is the most stable. Elemental manganese is a highly reactive metal. The lower oxidation states
are usually in the form of cations (e.g., Mn2+, Mn3+, Mn4+), while the higher oxidation states form anions
(e.g., Mn032-,Mn041-).
The toxicity of manganese compounds appears to depend upon the type of manganese ion present and the
oxidation state of manganese. It has been suggested that manganese cations are more toxic than the anion
forms. The permanganate anions, although 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 more toxic than the
trivalent cation. While manganese oxides such as MnO, Mn304, Mn203, and MnO2 are toxic to rats, the
higher oxides appear to be the most toxic. The associated anion is reported to affect the toxicity of
manganese; for example, manganese citrate is more lethal than manganese chloride.
Mn has three principal uses: In steelmaking as a reagent to reduce oxygen and sulfur and as an ingredient in
special alloy steels; in the manufacture of dry-cell batteries for depolarization; as MnOj, and in the
chemical industry, as an oxidizing agent, for the production of potassium permanganate and other
manganese chemicals. Manganin, an alloy containing manganese, copper, and nickel, is used in electric
resistance coils. Manganese also is one of the components of manganese-bronze and certain alloys with
desirable magnetic properties. Several salts are used as driers for linseed oil. The manganates and
permanganates are oxidizing agents used for disinfection, bleaching, and as laboratory reagents. Manganous
acetate is used in dyeing, tanning of leather, in fertilizers, and as a chemical catalyst. Manganese sulfate is
used as a trace element in poultry and animal feeds. Organic manganese compounds are added to vehicular
and stationary source fuels as smoke inhibitors and to vehicular fuels as antiknock agents.
Manganese and its compounds are active chemicals which either react with materials or catalyze other
reactions. Their effect on catalytic oxidation appears to be of prime importance in relation to air pollution.
Sulfur dioxide and nitrogen dioxide react readily with manganese dioxide to produce soluble sulfates,
dithionates, and nitrates. These reactions have been utilized to remove sulfur dioxide from flue gases; more
important is the fact that small amounts of manganese, usually as manganese sulfate formed in the reaction
of manganese dioxide with sulfur dioxide, will catalyze the oxidation of sulfur dioxide to sulfur trioxide.
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.
3.1 REFERENCES FOR SECTION 3
1. Stokinger, H. E. Manganese. In: Industrial Hygiene and Toxicology, 2nd rev. ed. Volume II. Fassett, D.
W., and D. D. Irish (ed.). New York, Interscience Publishers, 1962. p. 1079-1082.
2. Sullivan, R. J. Preliminary Air Pollution Survey of Manganese and Its Compounds. National Air
Pollution Control Administration, Raleigh, N.C. Publication No. APTD 69-39. October 1969. 54 p.
3-2 MANGANESE
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MEASUREMENT TECHNIQUES
4.1 SAMPLING
4.1.1 Ambient Air
Analytical procedures presently available require collection on filters of the particulate matter containing
manganese. The filter material must be chosen with great care so that trace amounts of manganese in the
filter do not distort the results. A typical glass-fiber filter contains about 400 nanograms per square
centimeter (ng/cm2) of manganese,1 which would correspond to a concentration of 70 nanograms per
cubic meter (ng/m3 ) if the filters were used in a high volume sampler operating for 24 hours at a flow rate
of 1.5 cubic meters per minute. Specially selected flash-fired glass-fiber filters with only 20 ng/cm2 of
manganese were found acceptable for use by the National Air Surveillance Networks (NASN).3 Organic
membrane filters contain 10 ng/cm2 of manganese.3 In view of the measured size distributions for particles
in ambient air,4 the filtration efficiency for 0.3 micrometer (jum) particles should be at least 99 percent.
The efficiencies of various filter media have been studied by Lockhart et al.s
4.1.2 Water
The following considerations are important in sampling water for manganese: selection of sampling sites,
frequency of sampling, sampling equipment, and sample preparation. Brown et al.6 provide more specific
information.
Particulate matter may be filtered from water by use of membranes or other suitable filtration material.
Once the particulates are collected on a filter, the analytical problems are almost identical to those
described for analysis of air. The methods of optical spectroscopy, neutron activation, and X-ray
fluorescence are all useful and have some of the same advantages and limitations that they have for the
analysis of particulates in air. Atomic absorption is the standard EPA method for determining manganese in
water.7
4.1.3 Food
There are no particular difficulties in obtaining food samples. After collection of the samples, handling
depends on the methods of analysis. Except for analysis by neutron activation, the samples are ashed by
wet or dry methods, and the manganese is acid-extracted. For instrumental neutron activation analysis, the
sample is analyzed without prior preparation.
4.1.4 Soil
The aim of soil sampling is to obtain a sample representative of a particular area. Problems arise in areas
having soils of variable composition where large sampling errors can occur. The sampling error can be
estimated by obtaining duplicate samples from random sites within a sample area. A given sample can be
analyzed twice to determine the precision of the laboratory method.8
4-1
-------
4.1.5 Biological Tissues
The manganese content of body fluids or tissues is not a reliable index of exposure to manganese. Blood or
urine from persons with signs or symptoms of manganese poisoning have not shown high levels of
manganese. There is, however, a rough correlation between urine levels and average air concentrations.9 The
average concentration of manganese is 1 to 8 micrograms per liter (jug/liter) for urine and 2 to 10
micrograms per 100 grams for blood.9
Some evidence indicates that manganese concentrates in hair after exposure to increased concentrations.
The use of hair as an indicator of exposure is complicated by the fact that manganese in hair is associated
with the structures which confer hair color. Very low concentrations are associated with white hair and
other unpigmented structures.
4.1.6 Stationary Source Emissions
Two factors are essential to obtaining reliable emission data—a sampling procedure that provides
representative samples and an analytical method that has the required sensitivity, selectivity, and accuracy.
Sampling of stationary .air pollution sources for manganese must be done isokinetically by means of a
sampling train with substantial efficiency for removing manganese. The source sampling train,10 EPA
Method 5, is shown in Figure 4.1. Particulates collected in the probe, on the filter, and in the water-filled
impingers are analyzed for manganese.
PROBE
HEATED AREA FILTER HOLDER THERMOMETER CHECK
\/ / VALVE
_---/
REVERSE-TYPE
PITOTTUBE
PITOT MANOMETER
ORIFICE
VACUUM
LINE
THERMOMETERS
MAIN VALVE
y
4-2
DRY TEST METER AIR-TIGHT
PUMP
Figure 4.1. Particulate sampling train used for collecting manganese.10
MANGANESE
-------
4.1.7 Mobile Source Emissions
Manganese is emitted from mobile sources as a component of participate matter. Concentrations in
emissions from these sources vary, depending upon the trace manganese levels in the fuel or fuel additives,
if any. Mobile source particulates may be collected by total or proportional sampling of the hot exhaust or
by proportional sampling of the exhaust mixed with dilution air; the latter allows cooling and condensation
of the higher-molecular- weight organics associated with short-time ambient exhaust particulates. The latter
method also provides a more realistic assessment of the mass and composition of the primary mobile-source
particulate. Collection with this technique can be by means of a single filter, multiple filter, beta gauge, or
particle size fractionating device. The particulate can then be analyzed directly or after dissolution in an
appropriate solvent. Gaseous samples may be collected by the cold trap technique or on a chromatographic
column.
4.2 ANALYTICAL TECHNIQUES
4.2.1 Inorganic Manganese Compounds In Air
4.2.1.1 Optical Spectroscopy—Spectrographic methods have been used extensively to detect and quantify
manganese and other trace metals in air samples and other materials. With suitable variations in sample
preparation, available standard methods can be used equally well for air or for biological samples having
manganese concentrations in the microgram range. Cholak and Hubbard11 describe a spectrochemical
method in which the manganese is isolated from interferences and concentrated in a small volume by
complexing with sodium diethyl-dithiocarbamate and extracting with chloroform before analyzing with the
spectrograph. Tabor and Warren12 briefly discuss a semiquantitative method suitable for estimation of
trace metals, including manganese, in samples collected on glass-fiber filters such as those commonly used in
sampling community air. Spectroscopy has several advantages: it can be made specific, or nearly so, for
almost any element; it has adequate sensitivity for most types of air samples; and it can be used to
determine a number of elements in the sample concurrently. A disadvantage is that a substantial investment
in space and money is necessary. Also, a high degree of skill is needed in this rather specialized field of
analysis.
In the field procedure used by the NASN, atmospheric particulate matter is collected on a glass-fiber filter
that is returned to the laboratory.3 A portion of the filter is ashed in a 1-Torr oxygen atmosphere for 1
hour at 150°C. The trace elements are extracted by refluxing for 3 hours with an acid mixture.13
Presumably this extraction procedure removes trace elements from the particulate with a much higher
efficiency than it does the elements in the filter blank. The recovery of particulate manganese by this
procedure has been determined to be quite good. By means of a high resolution grating emission
spectrometer, NASN personnel routinely analyze for manganese as well as for 15 other elements. The
sensitivity for manganese is 10 ng/m3, assuming a 2200-cubic meter (m3) air sample.3
4.2.1.2 Atomic Absorption—The use of atomic absorption analysis for trace metals, including manganese,
in the atmosphere was described recently.1-13 This method has advantages over other methods. It is
relatively simple to use and is highly specific for a given element. Its sensitivity is at least as good as, and in
many cases is better than, that of other methods. Using the same extraction procedure as that used for
emission spectroscopic analysis, Thompson et al.13 found a sensitivity of 1 nanogram per cubic meter
(ng/m3), assuming a 2000-m3 air sample. The method is fairly free of interferences, except for possible
matrix effects, which can generally be avoided by diluting the sample solution so that the content of
dissolved solids is less than 0.5 percent. When glass-fiber filters are used, silica extracted from the fibers can
interfere with the determination of manganese, zinc, iron, and possibly other elements, unless they are
removed by the presence or addition of calcium to the solution14 before the sample is subjected to atomic
absorption analysis. This method has also been used to determine manganese in water and in other
materials. The sensitivity varies from 1 to 5 jug/liter depending on the material being analyzed.13 Flameless
atomic absorption Spectroscopy, a modification of the basic technique, is sensitive to 0.02 jug/liter of
Measurement Techniques 4.3
-------
manganese in solution.2 In view of these concentrations and the fact that little or no sample preparation is
required, atomic absorption spectroscopy is well suited to the analysis of manganese in solution.
4.2.1.3 Neutron Activation-Neutron activation analysis has been found most suitable for the determina-
tion of very low concentrations (nanogram range) of manganese, as well as up to 32 other elements. With
this method, it is essential that the particulate matter be collected on filters that are very low in trace
elements. Certain membrane and ashless paper filters have been found to be quite satisfactory. With the use
of a polystyrene filter, a sensitivity of 0.6 ng/m3 has been reported by Dalton et al.1 s An advantage of the
neutron activation method is that it is nondestructive. The manganese reaction product has a relatively
short half-life (2.58 hours), but one that is long enough so that the manganese content can be determined
after a brief cooling period following exposure to the neutron flux.
Manganese was one of 15 chemical elements analyzed in an interlaboratory study. Compared with the
certified concentration value determined by the National Bureau of Standards, participating laboratories
achieved substantial accuracy with instrumental neutron activation analysis of coal and fly ash. Table 4.1
summarizes the accuracy of various analytical methods used in this study.16 Neutron-activation analysis is
generally more sensitive than other analytical methods. By way of comparison, the sensitivity for
manganese by several analytical methods is shown in Table 4.2.*s
Table 4.1. ACCURACY OF METHODS
FOR ANALYSIS OF MANGANESE IN COAL AND FLY ASH16
Analytical method
Instrumental neutron
activation analysis
Atomic absorption
spectrophotometry
Optical emission
spectroscopy
No. labs compared
Coal
7
14
3
Fly ash
8
14
3
Accuracy, %a
Coal
5.3
14.8
12.6
Fly ash
5.5
13.6
4.6
aThe signed difference between the mean value of measured analysis and the
accepted true value expressed as a percent of the accepted true value:
accuracy, % =-
xTrue~x
xTrue
•x 100
4-4
Table 4.2. SENSITIVITY OF ANALYTICAL
METHODS FOR MANGANESE
Analytical method
Neutron activation analysis
Optical emission spectroscopy (DC arc)
Atomic absorption spectrophotometry
Spark source mass spectrometry
Detection limit, nanograms
0.005
10.
0.5
0.05
MANGANESE
-------
4.2.1.4 Spark Source Mass Spec/rowerry-Manganese in gasoline can be analyzed satisfactorily by the use
of spark source mass spectrometry. The preparation procedure involves an oxidation step with bromine
after the addition of an erbium spike. This is followed by freeze-drying to remove the liquid and a final
drying at 17°C to remove the odors of gasoline. The residue remaining is mixed with graphite until
homogenous, and an electrode is pressed for analysis; the spark source mass spectrometer is equipped with
photographic plate output.17
4.2.1.5 X-ray Fluorescence-Whsis speed and the cost of analysis are not of major concern, the methods
discussed above are more than adequate. The use of an X-ray fluorescence spectrometer, however, offers
the opportunity for a low-cost nondestructive elemental analysis in less than 10 minutes. Birks et al.18
analyzed a number of particulate samples from stationary sources, using a conventional crystal diffraction
spectrometer. With an analysis time of 100 seconds per element, they reported the concentration of 12
elements. The sensitivity for manganese on a Whatman 41 filter is estimated to be 30 ng/cm2. For a
24-hour sampling period, at a flow rate of 7 liters per minute per square centimeter this corresponds to a
sensitivity of 3 ng/m3. Birks18 made a complete elemental analysis with much greater sensitivity in 100
seconds, using multichannel analyzers with 14 to 24 crystals.
Advances in electronics and in solid state detectors for X-rays by Gouldinget al.19'21 created widespread
interest in energy dispersive X-ray fluorescence spectroscopy. Using this technique, Giaque et al.22
analyzed a number of types of specimens including air filters for at least 12 elements, and Rhodes et al.23
conducted an extensive elemental analysis-for up to 15 elements — of the suspended particulate matter
collected at 38 stations in Texas. Various methods of excitation of samples for X-ray analysis were studied
by Cooper.24 His study indicates that use of either X-ray tubes or radioactive sources is the most efficient
and cost-effective for routine analysis.
Goulding25 developed a prototype automated sampling station and X-ray analysis system. The analytical
system uses an X-ray tube with three separate secondary fluorescers. A detection limit of 5 ng/m3 for
manganese is obtained for a 300-second analysis by the use of a copper fluorescer, along with a 0.8-/am
pore-size millipore filter that has been sampling air for 2 hours. In the presence of excessively high
concentrations of iron in the atmosphere, the method will be less sensitive for manganese. X-ray
fluorescence may be used to analyze manganese in solutions if the sample is prepared by freeze drying.
4.2.1.6 Wet Chemical Methods9—The periodate method is the classic wet chemical method of analyzing air
samples for manganese. It can be used in almost any chemical laboratory with relatively simple equipment.
The final colorimetric estimation of permanganate formed by oxidation of manganese can be made
satisfactorily with Nessler tubes, if necessary. The sensitivity is rather poor, however, in comparison with
that of other methods.
The technique has also been widely used for determining total manganese in the soil, for which it is rapid
and reliable. The intensity of the permanganate color is stable and reproducible if no reducing agents are
present. This method is considered to give a poor estimate of manganese available to plants. The
colorimetric method26 has been widely used, however, for analysis of soils.
Because manganese may exist in water-soluble form, as exchangeable Mn2+, as organically bound
manganese, and as various oxides of manganese, analytical techniques have been developed to determine the
amounts of manganese present in each of these forms. Because of the importance of manganese in plant
nutrition, emphasis has been placed on developing methods to determine its availability to plants.
The availability of manganese to plants has usually been measured as divalent manganese in soil solution
and as exchangeable manganese. The former is extracted with water, and the latter is measured by
extracting soil with a strong salt solution: a 1 molar solution of calcium or magnesium nitrate is widely
used.
Measurement Techniques 4.5
-------
Insoluble oxides of divalent and tetravalent manganese are reduced to the soluble divalent form.
Measurements of the amounts of trivalent and tetravalent forms give an indication of the relative research
power of the soil for producing soluble manganese.
4.2.2 Organic Manganese Compounds in Air
Although it is unlikely that manganese would be present in organic form in the ambient air, it is desirable to
develop a method for sampling and analyzing air for these compounds to confirm their presence or absence.
No such method appears at hand in the scientific literature. It seems logical that some of the procedures
presently being used for the determination of methylcyclopentadienyl manganese carbonyl in gasoline or
other liquid fuels might be modified to determine these compounds in the atmosphere. A number of
methods developed for other metal carbonyls could be modified to determine manganese carbonyls. A
recent Russian publication cited in the National Academy of Sciences report9 mentions a method for
determining cyclopentadienyl manganese tricarbonyl vapor in air, developed by M. S. Bykhovskays, but
gives no reference to pertinent literature or to procedural details.
4.3 REFERENCES FOR SECTION 4
1. Hwang, J. Y. Trace Metals in Atmospheric Particulate and Atomic Absorption Spectroscopy. Anal.
Chem. 44:20A-27A, 1972.
2. Reference Method for the Determination of Suspended Particulates in the Atmosphere. Federal
Register. 36 (84): Part II, 8191-8194, April 1971.
3. Air Quality Data for 1968. U. S. Environmental Protection Agency. Research Triangle Park, N. C.
Publication No. APTD-0978. August 1972.
4. Whitby, K. T., R. B. Husar, and B. Y. H. Liu. The Aerosol Size Distribution of Los Angeles Smog. J.
Colloid Interface Sci. 39: 177-204,1972.
5. Lockhart, L. B., Jr., R. L. Patterson, Jr., and W. L. Anderson. Characteristics of Air Filter Media Used
for Monitoring Airborne Radioactivity. Naval Research Laboratory, Washington, D. C. Report No.
6054. December 1963.
6. Brown, E., M. W. Skougstad, and M. J. Fishman. Techniques in Water Resources Investigations, Book
5. U. S. Geological Survey, Washington, D. C. 1970. Chapter Al.
7. Methods for Chemical Analysis of Water Waste. U. S. Environmental Protection Agency, Analytical
Quality Control Laboratory, Cincinnati, Ohio. 1971.
8. Helena Valley, Montana, Area Environmental Pollution Study. U. S. Environmental Protection Agency,
Research Triangle Park, N. C. Publication No. AP-91. January 1972. p. 65-66.
9. Manganese. National Academy of Sciences. Washington, D. C., 1973. 191 p.
10. Standards of Performance for New Stationary Sources. Federal Register. J<5(247):24888-24890
December 23,1971.
11. Cholak, J., and D. M. Hubbard. Determination in Air and Biological Material. Amer. Ind. Hyg. Ass. J.
27:356-360,1960.
12. Tabor, E. C., and W. V. Warren. Distribution of Certain Metals in the Atmosphere of Some American
Cities. A.M.A. Arch. Ind. Health 77:145-151, 1958.
4-6 MANGANESE
-------
13. Thompson, J. J., G. B. Morgan, and L. J. Purdue. Analysis of Selected Elements in Atmospheric
Particulate Matter by Atomic Absorption. Atomic Absorption Newsletter. 9:53-57, 1970.
14. Salvin, W. Atomic Absorption Spectroscopy. New York, Interscience Publishers, 1968.
15. Dalton, M. Trace Physical Methods. New York, Interscience Publishers, 1965.
16. Von Lehmden, D. J. Symposium on Trace Element Analysis of Coal, Fly Ash, Fuel Oil, and Gasoline.
U. S. Environmental Protection Agency, Research Triangle Park, N. C. May 16-17, 1973.
17. Jungers, R. C. U. S. Environmental Protection Agency, Research Triangle Park, N. C. Unpublished
data.
18. Birks, L. S., J. V. Gilfrich, and P. G. Burkhalter. Development of X-Ray Fluorescence Spectroscopy for
Elemental Analysis of Particulate Matter in the Atmosphere and in Source Emissions. Work carried out
for the U. S. Environmental Protection Agency by the Naval Research Laboratory, Washington, D.C.,
under Interagency Agreement No. 690114. 1972. 42 p.
19. Goulding, F.S., J. Walton, and D.F. Malone. Nucl. Instrum. Methods. 71:273, 1969.
20. Goulding, F.S., J.T. Walton, and R.H. Pehl. IEEE Trans. Nucl. Sci. NS-17 (1):218, 1970.
21. Landis, D.A., F.S. Goulding, R.H. Pehl, and J.T. Walton. IEEE Trans. Nucl. Sci.NS-18(l):l\5, 1971.
22. Giauque, R.D., F.S. Goulding, J.M. Jaklevic, and R.H. Pehl. Trace Elemental Determination with
Semiconductor Detector X-Ray Spectrometers. Anal. Chem. 45:671-681, 1973.
23. Rhodes, J.R., A.H. Pradzynski, and C.B. Hunter. Energy Dispersive X-Ray Fluorescence Analysis of Air
Particulates in Texas. Environ. Sci. Technol. 6:922, 1972.
24. Cooper, J. Comparison of Particle and Photon Excited X-Ray Fluorescence Applied to Trace Element
Measurements of Environmental Samples. Nucl. Instrum. Methods. 706:525-538, 1973.
25. Goulding, F.S. and J.M. Jaklevic. X-Ray Fluorescence Spectrometer for Airborne Particulate
Monitoring. Prepared under Interagency Agreement No. EPA-IAG-0089 (D)/A by Lawrence Berkeley
Laboratory, Berkeley, Calif. U.S. Environmental Protection Agency, Research Triangle Park, N. C.
Report No. EPA-R2-73-182. April 1973.
26. Dobritskaya, Y.I. In: Agrochemical Methods in Study of Soils. Acad. of Sciences, U.S.S.R. Translation
by U. S. Department of Agriculture, Washington, D. C. 1965.
Measurement Techniques 4-7
-------
5. ENVIRONMENTAL APPRAISAL
5.1 ORIGIN AND ABUNDANCE
5.1.1 Natural Sources
Manganese ore deposits are widespread throughout the tropical and warmer temperature zones of the earth.
The largest deposits are in the Caucasus and the Dnieper Basin of Russia and in Mainland China. In the
United States, lower grade ores are found in the Appalachian and Piedmont regions, in Arkansas, and in the
western states. Surrounding areas can be assumed to have an abnormally high concentration of manganese
in soil and water.
Manganese is considered to be the 12th most abundant element in the earth's crust. It is exceeded in
abundance, for example, by aluminum, iron, magnesium, and titanium, but is more abundant than nickel,
copper, uranium, zinc, lead, and vanadium. The concentration of manganese in the earth's crust ranges from
near zero to 7,000 jug/g. The highest concentrations are found in clay and deep-sea sediment. Pyrolusite, a
mineral form of jnanganese_dioxide, is one of the more common manganese oxide minerals. An abundance
of manganese nodules has been found on the deep ocean floor. Insofar as is known, all plants and animals
contain manganese.
5.1.2 Man-Made Sources
5.1,2.1 Stationary Sources— Approximately 90 percent of the manganese produced is used in metallurgical
processes, primarily in the form of ferromanganese. Either synthetic or natural dioxide is used in the
mattuikctu,re^)f_batteries, and a variety of manganese or manganese-containing ores are used in the chemical
industry. The primary uses of manganese are summarized in Tables 5.1 and 5.2.l
Table 5.1. CONSUMPTION OF MANGANESE ORE IN THE
UNITED STATES, 19701
Use
Manganese alloys and metal
Pig iron and steel
Dry cells, chemicals, and miscellaneous
Total
Gross weight of ore, a
metric tons
1,889,483
96,960
141,100
2,127,543
aBy definition, manganese ore contains at least 35 percent manganese (natural).
5-1
-------
Table 5.2. CONSUMPTION OF MANGANESE ALLOYS AND METAL
IN THE UNITED STATES, 1970, BY END USE1
Use
Steels:
Carbon
Stainless and heat-
resisting
Alloy (excluding stainless
and tool)
Tool
Cast irons
Superalloys
Alloys (excluding alloy steels
and superalloys)
Miscellaneous and unspecified
Totals
Gross weight, metric tons
Ferromanganese
High-
carbon
642,313
1,647
97,239
755
7,624
393
4,848
29,181
784,000
Medium- and
low-carbon
82,395
4,438
24,785
110
2,109
40
1,055
1,619
116,551
Silico-
manganese
79,061
7,534
24,167
..b
6,439
1,654
5,796
124,651
Spiegeleisen
10,052
..b
1,511
6,578
100
18,241
Manganese
metal8
4,353
6,020
1,764
. .b
10
327
8,469
1,091
22,034
aNearly all electrolytic.
Withheld to avoid disclosing individual company confidential data, but included in "Miscellaneous and unspecified."
Manganese is emitted from various sources primarily as manganese oxides. Because of its many valence
states, however, manganese may interact with other substances to form many compounds.2 Physical forms
emitted are particulate in nature, and more than 50 percent of these particulates are in the submicron
particle size range.2
In 1968 about 17,000 metric tons (MT) of manganese were emitted into the atmosphere over the United
States (Table 5.3). About 47 percent resulted from production of ferroalloys and about 37 percent from
the production of iron and steel.3 Coal was also a significant source of manganese emissions.
Manganese concentrations in emissions depend on several factors, including manganese content of raw
material and/or fuel, process type, method of operation, and the efficiency of the particulate control
system. Therefore, a source emission concentration range rather than a specific emission factor is reported
for selected stationary sources. Table 5.4 summarizes the manganese concentration range in particulate
emissions collected isokinetically downstream from control systems for several source categories.4'5
5-2 MANGANESE
-------
Table 5.3. ESTIMATED MANGANESE EMISSIONS BY SOURCE, 19682
Source category
and group
Mining
Processing
Manganese metal
Manganese alloys
Total
Reprocessing
Carbon steel
Cast iron
Welding rods
Nonferrous alloy
Batteries
Chemicals
Total
Consumptive uses
Coal
Oil
Total
Incineration and other disposal
Sewage and sludge
All sources
Emissions,
metric tons
5
290
8,050
8,340
3,910
2,490
20
50
80
270
6,820
1,760
6
1,766
160
17,091
Table 5.4. RANGE OF MANGANESE CONCENTRATIONS IN SOURCE
EMISSION PARTICULATES4
Source
Coal-fired power plants
Lead smelters
Cement plants
Iron and steel foundries
Municipal incinerators
Concentration, M9/9a
1 to 1,000
0.01 to 1
100 to 1,000
10 to 1,000
100 to 1,000
aSamples collected with EPA Method 5 sampling train5 and analyzed by optical emission
spectroscopy.
Environmental Appraisal
5-3
-------
Recently, coal-fired power plants have been the subject of several material balance studies for trace metals.
An in-depth study was done on the Allen Steam Plant at Memphis, Tennessee (Table 5.5). This power plant
is a 240-megawatt unit operated at 80 percent of full load. Based on the results from the electrostatic
precipitator inlet and outlet, the efficiency for manganese removal is higher than 90 percent.6
Considerable research is under way to determine trace element concentration by particle size. A study of
sized fly ash from three coal-fired power plants found the manganese concentration evenly distributed by
particle size (Table 5.6).7
Table 5.5. MATERIAL BALANCE FOR MANGANESE AT A COAL-FIRED
STEAM POWER PLANT6
Run
No.
5
7
9
Mass flow, g/mina
Coal
66
64
67
Slag
tank
solids
41
39
46
Fly ash
Precipitator
inlet
22
21
16
Precipitator
outlet
0.62
1.1
Precipitator
efficiency, %
...
97
93
aSamples collected isokinetically using an alundum filter followed by a millipore filter and analyzed by instrumental neutron
activation.
Table 5.6. MANGANESE CONCENTRATION IN COAL FLY ASH,
BY PARTICLE SIZE7'3
Particle size, ^m
1.3
2.0
4.6
8.5
13.0
22.0
33.0
>33.0
Source A
270
189
157
122
156
148
156
158
Concentration, /ig/g
Source B
328
334
339
344
344
363
370
301
Source C
256
235
317
255
208
221
219
246
aFly ash sized using a Bahco classifier and analyzed by instrumental neutron activation.
5-4 MANGANESE
-------
Roughly 90 percent or more of the manganese consumed in the United States is used in the production of
iron and steel.8 A source emission inventory in a highly industrial area with uncontrolled iron and steel
manufacturing should reflect the high emissions from this source. Calculated emissions for the large
industrial area of Chicago, Milwaukee, and Northwest Indiana, where iron and steel manufacturing is the
predominant source of manganese emissions, do indeed reflect high emissions (Table 5.7).9
Table 5.7. MANGANESE EMISSIONS FROM AIR POLLUTION
SOURCES IN THE CHICAGO, MILWAUKEE,
AND NORTHWEST INDIANA AREA9
Source
Coal burning
Coke burning
Fuel oil burning
Iron and steel manufacturing
Emissions,
metric tons/year
60
5
5
4,500
5.1.2.2 Fuels—Manganese concentrations for coals mined in various areas of the United States are
summarized in Table 5.8.10'11 Table 5.8 also summarizes the manganese contents of selected residual fuel
oils and crude oils.12 One type of fuel oil, residual fuel oil No. 6, is commonly used in electric power plants
and large industrial boilers. Crude oil is of concern because several power plants have shifted from burning
residual fuel oil to burning crude oil directly due to the increasing cost of low-sulfur residual fuel oil.13 As
of February 1972, three East Coast utilities were burning a total of 5,400 m3/day of crude oil, an amount
which has greatly increased in the last few years.
As part of EPA's Nationwide Fuel Surveillance Network, gasoline is collected by the 10 EPA Regions for
extensive analysis. Samples are analyzed for approximately 25 elements, including manganese. Table 5.8
includes a summary of manganese concentrations in gasolines collected in the spring of 1972. The gasolines
collected were from retail service station pumps and represent fuels used in motor vehicles at the time and
in the area of collection.14
5.1.2.3 Consumer-Purchased Fuel Additives and Motor Oil—In anticipation of regulations on the
registration of fuels and fuel additives, pursuant to Section 211 of the 1970 Clean Air Act, EPA has started
to analyze consumer-purchased fuel additives for trace elements. As the first step of this surveillance effort,
fuel additives were purchased from retail stores in the Research Triangle Park area and analyzed for trace
elements. The manganese content of these off-the-shelf additives are shown in Table 5.8.ls
As part of the EPA's Nationwide Fuel Surveillance Network, crankcase lubricating oils are being collected
for trace element analysis. Table 5.8 shows the manganese content of several grades of one brand of motor
Environmental Appraisal 5-5
-------
Table 5.8. MANGANESE CONCENTRATIONS OF COAL, FUEL OIL, CRUDE OIL,
GASOLINE, FUEL ADDITIVES, AND MOTOR OIL10 16
Sample
Coal
Residual fuel oil
Crude oil
Regular gasoline
Brand A
Brand B
Premium gasoline
Brand A
Brand B
Fuel additives
Gas treatment
Fuel-mix tune up
Engine tune up
Gas power booster
Gas treatment
Gasoline antifreeze
Gas booster
Carburetor tune up
Motor oil
Number
of samples
76
20
20
10
9
10
8
3
3
3
3
3
3
6
3
4
Average
concentration
37 ^tg/g
0.136 //g/g
0.031 iiQ/9
<0.005 /.ig/ml
<0.0066/zg/ml
0.0144 ;ug/ml
0.0052 Aig/ml
0.038 j^g/ml
<0.5 pg/ml
< 0.003 ;ug/ml
0.009 jug/ml
0.012 jug/™'
0.007 ng/m\
0.051 (ig/m\
0.023 jitg/ml
Range
5 to 80 jug/g
0.01 2 to 0.27 jug/g
< 0.001 to 0.1 5 jug/g
<0.001 to 0.01 jug/ml
<0.001 to 0.01 /ig/ml
0.002 to 0.03 ng/m[
0.002 to 0.02 Mg/ml
0.019 to 0.042 jug/ml
<0.5 /zg/ml
<0.003 jug/™'
0.008 to 0.010 /xg/ml
0.01 6 to 0.019Mg/ml
0.006 to 0.009 /jg/ml
0.008 to 0.096 /xg/ml
0.272 to 2.71 /ug/ml
<0.004 to 0.08 jug/ml
5.1.2.4 Manganese as a Substitute for Lead in Fuels—The use of manganese compounds in fuels, principally
as a smoke inhibitor, has been increasing. Currently around 450,000 kilograms of such additives are used
per year, principally as smoke suppressants in residual-oil-fired stationary power plants, stationary gas
turbines, and aircraft turbine overhaul facilities. One such compound, methylcyclopentadienyl manganese
tricarbonyl (MMT), was introduced in 1958 as a supplemental antiknock material for use with tetraethyl
lead (TEL). At the present time, MMT is receiving attention as a TEL substitute for use in the
limited-lead/phosphorus , fuels EPA. regulations required by July 1, 1974.17 Current use in gasoline,
however, is very limited.
The following is a brief summary of information provided by the Ethyl Corporation, the developer of MMT
as an additive for unleaded gasoline.18
Use of MMT at the recommended maximum concentrations in gasoline (0.033 g/liter or 0.125 g/gal)
provides, on the average, 2.2 road octane numbers which could represent a saving in crude oil of
about 1 percent. The upper limit of MMT concentration is governed by engine durability problems at
higher concentrations. Manganese in MMT is converted to Mn3 O4 in the exhaust. Typically about 0.1
percent of the MMT is emitted from the tailpipe unburned. This rapidly decomposes in sunlight (in
less than 2 minutes) with indications that the manganese is converted to a mixture of manganese
oxide and carbonates. There is no evidence of the formation or presence of any manganese carbonyl
compound. The organic portion of the solids appears to be a mixture of oxides, esters, and polymers.
5-6
MANGANESE
-------
In tests conducted by Ethyl Corporation, benzofa] pyrene (BaP) was reduced in exhausts when MMT
was added. The use of MMT in test vehicles resulted in no significant differences in exhaust
particulate concentrations. It is estimated that the size range of airborne manganese particles in the
ambient atmosphere resulting from the use of MMT in gasoline would be the same as that of lead
particles, i.e., 0.2 to 0.4 micron (mass median equivalent diameter). Using lead as a model, the use of
MMT in gasoline would result in an increase of manganese concentration in urban atmospheres of
0.25 jig/m3 or less. The use of MMT compared with clear gasoline in test vehicles did not adversely
affect either regulated (HC, CO, and NOX) or unregulated emissions. Tests conducted using exhaust
from a car operating on fuel containing 0.125 g Mn/gal had no significant effect on the rate of
oxidation of S02 in ambient air. In test car operations, MMT, compared to clean fuel, did not lessen
the effectiveness of exhaust catalysts in oxidizing unburned hydrocarbon and carbon monoxide.
Under extreme operating conditions some plugging of monolithic exhaust catalyst has occurrred;
however, rapid catalyst deterioration has been observed under similar operating conditions without
the use of manganese additive.
The possibility of savings of 1 percent in crude oil by the use of MMT is very attractive. It raises the very
fundamental question, however, of whether manganese is preferable to lead. A number of related questions
must be answered before a definitive answer to the basic question is available. Estimates of manganese
concentrations resulting from the use of MMT in gasoline must be confirmed, as must the estimated effects
of MMT on other exhaust emissions. Further work also needs to be done on the effect of MMT on catalyst
and vehicle operation. The manganese concentrations that would result from the use of MMT are estimated
later with other concentration data in Section 5.2.1.4.
The Ethyl Corporation summary indicates there would be no significant difference between particulate
emissions from clear fuels and fuels containing manganese. Tests sponsored by EPA, however, indicate that
particulate emissions increase up to 100 percent when MMT is added to the fuel. Neither of the studies
accurately characterizes the particulate matter physically and chemically. Size versus mass distributions
were obtained in both studies, but size versus number distributions were obtained in neither. Since the
manganese particulates tend to be confined to the submicron range, the number of particles emitted may be
equally as important as the mass.
Present studies suggest that manganese exhaust particulate is very similar to lead exhaust particulate in size
distribution and in percent emitted relative to that burned in the fuel. The mass median equivalent diameter
is 0.1 to 1 jum, depending on mileage, driving cycle, etc. Unlike TEL, however, MMT does not require a
scavenger (ethylene dichloride and ethylene dibromide for TEL) to remove its combustion products from
the engine combustion chamber and exhaust manifold. Exhaust manganese particulate is principally Mn304
with traces of Mn203. Current data suggest that none of the parent manganese compound is exhausted.
Typical exhaust particulate data for fuels with and without additives are shown in Tables 5.9 and 5.10.
Studies conducted by the Ethyl Corporation on the conversion of sulfur dioxide to sulfur trioxide suggest
that manganese would have relatively little effect on the presence of sulfates. The importance of the sulfate
and sulfuric acid problem, however, requires full evaluation of this aspect. The Ethyl Corporation tests were
conducted in a 100-m3 black polyethylene bag and the mixture was not irradiated.
The effect of manganese fuel additives upon nonregulated emissions from mobile sources (for example,
polynuclear aromatic hydrocarbons, phenols, aldehydes, and oxygenates) is not known. Limited data
suggest that manganese results in a reduction in the percentage of carbon in exhaust particulate (Table
5.10). Further work is also needed to ascertain the effect of manganese gasoline additives on regulated
emissions (carbon monoxide, hydrocarbons, and nitrogen oxides).
The EPA fuel regulations requiring that a fuel of limited lead and phosphorous be available by July 197417
were based upon the fact that lead and phosphorus adversely affect the performance of exhaust catalytic
control devices. Such devices will be used by most, if not all, of the domestic automobile manufacturers in
model year 1975 and thereafter. The suggested use of manganese compounds as substitute antiknocks for
Environmental Appraisal 5-7
-------
Table 5.9. EFFECT OF MANGANESE FUEL ADDITIVE
ON EXHAUST PARTICULATE15.8
Fuel
91 octane
clear
91 octane
plus 0.25
g Mn/gald
Commercial
leaded
regular
Vehicle
number
10
12
15
16
Vehicle
miles'1
2,900
4,250
6,500
8,600
11,000
13,000
15,000
2,000
4,000
6,000
8,400
10,000
10,000
10,360
7,900
8,260
Exhaust
particulate,
g/mic
0.005
0.004
0.007
0.007
0.006
0.008
0.009
0.02
0.02
0.027
0.022
0.04
0.116
0.094
0.09
0.11
a1972 Chevrolet 350 CID, 60 mi/hr cruise condition, air-diluted particulate collected on
142-mm glass fiber filter, 1-ft'/min isokinetic-proportional sample. (1972 Chevrolet
5.7-liter displacement, 96 km/hr cruise condition, air-diluted particulate collected on
142-mm glass fiber filter, 28.3 liter/min isokinetic-proportional sample).
bMultiply by 1.6 to get kilometers.
cMultiply by 0.62 to get grams/kilometer.
dMultiply by 0.26 to get grams/liter.
Table 5.10. EFFECT OF MANGANESE FUEL ADDITIVE
ON PERCENT CARBON IN EXHAUST PARTICULATE19.3
Fuel
91 octane
clear
91 octane plus
0.25 g
Mn/gald
Vehicle
number
D-2547
D-2549
Vehicle
miles0
6,917
8,592
10,739
3,964
5,975
8,361
Carbon in
exhaust
particulate, %
43 to 48
28
72
47
18
24 to 29
Exhaust
particulate.
g/mic
0.04
0.05 to 0.07
0.04 to 0.06
0.08
0.09 to 0.16
0.09 to 0.15
a1972 Federal Test Procedure,20 1972 Chevrolet 350 CID (5.7 liter displacement), cold start condition, air-diluted
particulate collected on glass fiber filter.
"Multiply by 1.6 to get kilometers.
cMultiply by 0.62 to get grams/kilometer.
dMultiply by 0.26 to get grams/liter.
5-8
MANGANESE
-------
this fuel raises questions as to the effect of manganese on these devices. Limited studies indicate that
manganese may be detrimental to the performance of certain such devices under specific operating
conditions. More research on this problem is required.
5.2 CONCENTRATIONS
5.2.1 Air21'22
Few attempts have been*made to evaluate the impact of major manganese sources on the ambient air in the
immediate vicinity of these sources. Practically all data relating to the extent of manganese pollution have
been acquired from studies aimed at the general definition of the nature and extent of air pollution on a
national or, in a few instances, on a local scale. The number of major sources is relatively small, thus
restricting somewhat the areas expected to have high levels of manganese in the air. Smaller sources are
widespread; consequently, manganese would be expected to be present as a common pollutant in most
atmospheres. The major portion of manganese emitted is in the form of smaller particles favoring wide
distribution over considerable distances.
5.2.1.1 Manganese in Suspended Paniculate Matter
5.2.1.1.1 NASN studies—Beginning in 1957, samples of suspended particulate matter collected at
approximately 300 urban and 30 nonurban National Air Surveillance Network (NASN) sites have been
analyzed for trace metals including manganese.23'24 The spectrographic method employed in the analysis
has sufficient sensitivity to detect manganese in practically all urban and in many nonurban samples, thus
providing a broad data base.
The 1,000 station-years of data for urban and nonurban NASN sites for 1957-69 are summarized in Table
5.11 and the sites categorized into four different concentration ranges. All nonurban and a majority of
urban sites fall into the lowest concentration interval. Except for the earliest period (1957-1963), there is a
remarkable consistency in the distribution among the four concentration intervals. The deviation is
understandable, since the 128 station-years of data obtained during the first 7-year period are from a
relatively small number of sites and are not as representative as the data for subsequent years. The national
annual average urban concentration is well below 0.20 Mg/m3.
NASN sites for which average concentrations have been 0.5 /ug/m3 or greater are listed in Table 5.12.
Higher concentrations for shorter average times (quarterly and 24-hour) have been included to show
maximum exposures, which may be of considerable significance in the evaluation of the potential biological
effects of airborne manganese. The presence on this list of Johnstown, Charleston, and Niagara Falls is to be
expected, as all are known to have ferromanganese or silico-manganese industries in the immediate areas.
Both annual and maximum 24-hour averages for Johnstown were consistently high, apparently because
source strength, location, topography, and meteorological conditions favor retention of pollutants in the air
over the area. The high levels in Canton and Gary are no doubt related to the use of manganese products in
the local steel industries. Sources of the high levels found in Philadelphia, Lynchburg, and Knoxville have
not been discovered. Occasional elevated 24-hour values have been reported for other cities with annual
average concentrations well below 0.5 Mg/m3: Cleveland, Ohio, 260; Cincinnati, Ohio, 2.80; Youngstown,
Ohio, 2.10; Hammond, Indiana, 1.80; and East Chicago, Illinois, 1.70. Available data do not provide an
adequate base for drawing valid conclusions with respect to long-term trends in ambient manganese
concentrations.
Environmental Appraisal 5.9
-------
Table 5.11. NUMBER OF NASN STATIONS WITHIN SELECTED ANNUAL AVERAGE
MANGANESE CONCENTRATION INTERVALS, 1957-19G923
Year
1957-
1963
1964
1965
1966
1967
1968
1969
1957-
1969
No. stations
Percent
No. stations
Percent
No. stations
Percent
No. stations
Percent
No. stations
Percent
No. stations
Percent
No. stations
Percent
No. stations
Percent
< 0.099
76
59.4
68
73.1
132
84.1
113
88.3
121
85.2
126
86.9
169
80.9
805
80.4
Concentration interval, jug/m3
0.100-0.199
29
22.7
12
12.9
14
8.9
8
6.3
13
9.2
11
7.6
23
11.0
110
11.0
0.200-0.299
10
7.8
6
6.5
5
3.2
4
3.1
4
2.8
2
1.4
9
4.3
40
4.0
> 0.300
13
10.2
7
7.5
6
3.8
3
2.3
4
2.8
6
4.1
8
3.8
47
4.7
Total
128
100
93
100
157
100
128
100
142
100
145
100
209
100
1002
100
5-10
MANGANESE
-------
Table 5.12. NASN STATIONS WITH ANNUAL AVERAGE MANGANESE
CONCENTRATIONS GREATER THAN 0.5 /ug/m3 23-24
Year
1958
1959
1960
1961
1963
1964
1965
1966
1967
1968
1969
Station
Charleston, W.Va.
Johnstown, Pa.
Canton, Ohio
Gary, Ind.
Canton, Ohio
Philadelphia, Pa.
Johnstown, Pa.
Philadelphia, Pa.
Charleston, W.Va.
Johnstown, Pa.
Philadelphia, Pa.
Lynchburg, Va.
Charleston, W.Va.
Niagara Falls, N.Y.
Knoxville, Tenn.
Johnstown, Pa.
Niagara Falls, N.Y.
Johnstown, Pa.
Philadelphia, Pa.
Manganese concentration, jug/m3
Average
0.61
2.50
0.72
0.97
0.57
0.70
1.44
0.62
1.33
2.45
0.72
1.71
0.60
0.66
0.81
3.27
0.66
1.77
0.50
Max. quarterly
1.10
5.40
1.10
3.90
1.70
2.50
1.70
1.30
1.50
1.30
2.10
1.30
Max. 24-hr
7.10
7.80
2.20
3.10
2.90
> 10.00
6.90
3.70
> 10.00
14.00
Environmental Appraisal
5-11
-------
5.2.1.1.2 Kanawha Valley study25-As part of a comprehensive air pollution study of the Kanawha River
Valley in the vicinity of Charleston, West Virginia, conducted during 1964-65, 24-hour samples of
suspended particulate matter were collected at 14 strategically located sites of a 27-station network (Figure
5.1). Sampling sites were placed from Falls View to Nitro, a distance of about 80 km (50 mi). Samples from
selected sites were composited on a seasonal basis (fall 1964, winter 1964-65, spring 1965, summer 1965)
and the composites analyzed for trace metal content by the NASN emission spectrographic procedure. The
high concentrations of suspended manganese found at the Smithers and Cedar Grove sites are noteworthy
(Table 5.13), as is the excessively high winter concentration at the Montgomery site; concentrations found
at these sites far exceed those occurring at other NASN stations. The study report offers no clear
explanation of the elevated manganese levels found, but it is quite obvious that the major source was the
ferromanganese plant in the nearby Alloy area (Figure 5.1), with additional contributions from a large
coal-burning industrial steam-generation plant in the same general area.
These Kanawha Valley data represent the only documented single-source study done in the United States.
The impact of this source on the surrounding area is clearly shown by both the ambient air and settled
manganese data (Figure 5.1 and Table 5.13). The fall and winter ambient air data dramatically demonstrate
that, with favorable topography and meteorologic conditions, one strong source can exert an influence over
a considerable distance. The Smithers and Montgomery communities have the highest seasonal manganese
concentrations documented to date — 11 and 13 Mg/m3, respectively.
NORTH CHARLESTON, WEST
OUNBAR
WEST OF NITRO
27
WEST OF
ST. ALBANS
26
NORTH CHARLESTON, EAST
CREDE
•V
WEST CHARLESTON
SOUTH CHARLESTON, WEST
SOUTH CHARLESTON, EAST
S CHARLESTON
_ xx
KANAWHA_CITY
13v *14 EAST CHARLESTON
1
12 SOUTH MALDEN
2.5
BELLE (CEDAR GROVE
80
.0
MARMET11
CHESAPEAKE
CHELYAN 8
SMITHERS
/
4 BOOMER
ALLOY
MONTGOMERY
HEIGHTS
1 FALLS VIEW
Figure 5.1. Location of fixed sampling stations in Kanawha River Valley. Aver&ge manganese
concentrations (^g/mS) for the study period (1964-1965) are indicated for selected sites.25
5-12
MANGANESE
-------
Table 5.13. MANGANESE CONCENTRATIONS, KANAWHA VALLEY AREA, 1964-1965
25
Sampling site and number
Falls View (1)
Smithers (5)
Montgomery (6)
Cedar Grove (7)
Marmet (11)
KanawhaCity (13)
Charleston (15)
West Charleston (17)
North Charleston, West (19)
South Charleston, East (20)
Dunbar (22)
St. Albans (24)
Nitro (25)
Nitro-West (27)
Suspended participates, ^g Mn/m3
Seasonal averages
Fall
1964
11.00
4.20
3.30
2.00
0.43
0.59
Winter
1964-65
3.40
6.50
13.00
3.50
3.60
1.10
0.91
0.96
0.52
0.26
0.24
0.44
0.28
0.08
Spring
1965
4.50
1.80
0.53
0.23
0.06
0.10
Summer
1965
3.00
0.32
0.27
0.17
0.06
0.09
Study period
average
8.30
2.45
1.30
0.67
0.25
0.27
Settled participates,
mg Mn/m2 -mo
(study period
average)
193
27
1.3
1.1
0.8
2.4
3.2
0.8
0.9
Environmental Appraisal
5-13
-------
5.2.1.1.3 Birmingham study16 -Seasonal levels of trace metals were determined on suspended particulate
matter samples collected at 10 Birmingham, Alabama, area sampling sites during 1964-65. No exceptionally
high concentrations were discovered at any sampling site (Table 5.14); however, seven of the 10 sites would
fall into the two highest concentration intervals of Table 5.11. Although a large steel plant was operating in
the area during this study period, there is no evidence that any ferromanganese alloy was being produced
concurrent with the sampling. In contrast to the Kanawha Valley situation, while the annual average levels
for the truly urban sites ranked in the highest interval, no "hot spots" were uncovered during this study.
Table 5.14. MANGANESE CONCENTRATIONS, BIRMINGHAM AREA, 1964-196526
(/ug Mn/m3)
Place
Bessemer
Birmingham
Birmingham
Birmingham
Birmingham
Fairfield
Irondale
Mt. Brook
Tarrant
Vesta via
Average
Site
1
3
4
5
7
1
1
1
1
1
Seasonal averages
Spring
0.21
0.33
0.82
0.45
0.69
0.36
0.30
0.21
0.39
0.27
0.40
Summer
0.18
0.35
0.50
0.72
0.35
0.21
0.33
0.25
0.44
0.14
0.35
Fall
0.15
0.35
0.58
0.45
0.12
0.15
0.12
0.19
0.29
0.09
0.25
Winter
0.11
0.18
0.95
0.20
0.45
0.10
0.21
0.12
0.46
0.07
0.29
Study period average
0.16
0.30
0.71
0.46
0.40
0.20
0.24
0.19
0.40
0.14
0.32
5.2.1.1.4 Other stages-Rhodes et al.27 employed the energy dispersive X-ray fluorescence technique to
determine the trace metals in suspended particulate samples collected at 12 of the 38 Texas Air Quality
Network Stations on the same day in June 1971. Concentrations were below the minimum detectable limit
(0.023Mg/m3) at four of the 12 stations. At the other eight sites, concentrations ranged from 0.01 to 0.11
Mg/m . In July 1971, similar samples were taken on 3 days at 17 stations in Corpus Christi. Most samples
were below the minimum detectable level; the highest level found was only 0.08 Mg/m3. The objective of
this study was to investigate an analytical technique rather than to delineate the extent of trace metal air
pollution in Texas; consequently, the data must be considered inadequate in terms of defining air quality.
Brar et al.28 employed neutron activation analysis to determine the trace metal content of samples of
particulate matter collected April 4,1968, at 20 sampling stations in Chicago and two in the suburban area.
Concentrations of manganese on this particular day ranged from O.l'O to 0.90 Mg/m3 in the city, with an
overall average of 0.45 Mg/m3. The highest concentrations were in the Loop and the industrialized
southeastern areas. The results of this single day's sampling indicate that Chicago's average manganese
pollution ranks in the upper 5 percent of the nation's urban areas.
5-14
MANGANESE
-------
A study was conducted some 40 years ago in the immediate vicinity of a manganese alloy plant located in
Sauda, Norway.8 Although the analytical method employed underestimated the manganese levels, the
results show that ambient air concentrations in the area reached at least 65 Mg/m3 of manganese oxide or
46 jug/m3 of manganese.
5.2.1.1.5 Size distribution of paniculate manganese in the ambient air—Lee et al.29 have determined the
concentration of trace metals in quarterly composites of the different particle size range samples collected
by means of cascade impactors operated at each of the six Continuous Air Monitoring Stations operated in
conjunction with NASN. The particle size distribution data for manganese (Table 5.15) demonstrate quite
clearly that at least 50 percent of the mass of suspended manganese is associated with particles having a
Stokes equivalent diameter of 2 /urn or less and that approximately 80 percent of the manganese is found in
the respirable (< 5 jum) particle size range. These findings agree with reports indicating that much of the
manganese emitted into the atmosphere is associated with particles in the 0.1- to 5-jum range.
5.2.1.2 Manganese in Settled Particulates—Very little information is available relative to the deposition on
land and water of manganese from major sources. The Kanawha Valley Study data (Table 5.13) provide
some indication of the amount of manganese deposited in the vicinity of a source of unknown magnitude
(Smithers, Montgomery); in addition the data show that appreciable amounts may be deposited in
industrial areas somewhat remote from known sources (North Charleston, South Charleston) with a high
particulate deposition (dustfall) rate.
5.2.1.3 Manganese in Precipitation—Washout of manganese has been reported from the atmosphere at
stations distributed throughout the United States.40 Monthly composite samples of precipitation collected
at each station during the period September 1966 to January 1967 were analyzed for manganese by atomic
absorption spectrophotometry. The average manganese washout (Figure 5.2) ranged from below detectable
at Mauna Loa, Hawaii; Amarillo, Texas; and the Tampa, Florida, airport to a maximum of 54 grams per
hectare per month (g/ha-mo) at Caribou, Maine; with intermediate depositions of 31 and 26 at Midway and
O'Hare airports (Chicago), respectively, and 23 at Sault St. Marie, Michigan. The high value for Caribou
appears to be an anomaly, but it may result from the industrial megalopolis that is spread out in the upwind
direction. The Albany, New York, data however, showing an average of 5 g/ha-mo, do not support this
explanation. The Chicago airport data no doubt reflect industrial contributions, while the Sault St. Marie
value is probably attributable to the ore handling and industrial activities in that area. The overall data
indicate the widespread prevalence of manganese in the air over the whole of the United States. Because the
majority of the stations were at relatively isolated sites with respect to major industrial areas, the data do
not show the immediate influence of major sources.
5.2.1.4 Manganese from Mobile Sources—Section 5.1.2.4 indicated the use of manganese compounds in
fuels is not very widespread at the present time, but may become more significant with the possible
substitution of compounds such as MMT (methylcyclopentadienyl manganese tricarbonyl) for TEL
(tetraethyl lead) as a primary fuel additive. The Ethyl Corporation18 estimates that if these manganese
compounds are used as a supplement in 50 percent of the gasoline used in the United States, the most that
would be added to urban 24-hour air concentrations would be 0.05 to 0.2 fig Mn/m3 This estimate assumed
that the manganese emissions would be proportionate to the known lead emissions and distributions.
Manganese concentrations resulting from the use of MMT in gasoline were estimated independently by EPA
and the Ethyl Corporation (Tables 5.16 to 5.22). Estimates were made for various distances from the edge
of a 2-kilometer segment of a six-lane highway. Receptors were assumed perpendicular to the highway.
Maximum hourly vehicle flow was assumed to be 12,000, and total 24-hour flow was 216,000.
Environmental Appraisal 5-15
-------
Table 5.15. QUARTERLY AND ANNUAL SIZE DISTRIBUTIONS FOR
SUSPENDED PARTICLES CONTAINING MANGANESE, 197029
City
Chicago, III.
No. of samples
Avg. concentration, jug Mn/m3
Avg. mass median diameter, ^m
Percent <2jum
Percent <5 jum
Cincinnati, Ohio
No. of samples
Avg. concentration, jug Mn/m3
Avg. mass median diameter, p.m
Percent <2 /urn
Percent < jum
Denver, Colo.
No. of samples
Avg. concentration,^ Mn/m3
Avg. mass median diameter, urn
Percent <2 /urn
Percent < ^m
Philadelphia, Pa.
No. of samples
Avg. concentration, ng Mn/m3
Avg. mass median diameter, jum
Percent < 2 ^m
Percent -< 5 jum
St. Louis, Mo.
No. of samples
Avg. concentration, jug Mn/m3
Avg. mass median diameter, um
Percent <2^tm
Percent <5 um
Washington, D.C.
No. of samples
Avg. concentration, jug Mn/m3
Avg. mass median diameter, /urn
Percent <2 /zm
Percent <5 um
Quarter
1
4
0.03
2.02
50
1
0.01
1.42
63
4
0.01
1.37
64
2
0.05
1.40
66
5
0.04
2.01
50
5
0.03
1.61
61
2
6
0.04
1.86
53
6
0.31
2.16
46
5
0.02
1.34
64
6
0.02
1.66
58
5
0.03
2.23
46
6
0.01
1.43
63
3
7
0.04
2.03
50
7
0.30
2.24
44
7
0.02
1.90
52
7
0.04
2.43
43
9
0.04
2.36
43
6
0.02
1.49
62
4
4
0.03
1.75
55
4
0.19
2.16
46
5
0.03
2.25
45
5
0.10
3.04
33
3
0.02
2.20
47
6
0.02
1.52
64
Annual
21
0.03
1.91
52
80
18
0.17
2.14
47
90
21
0.02
1.75
55
82
20
0.05
2.27
45
80
22
0.03
2.20
47
78
23
0.02
1.54
62
90
5-16
MANGANESE
-------
• 3
NUMERALS INDICATE ACTUAL
MEASURED CONCENTRATIONS
T BELOW MINIMUM DETECTABLE
• 0 TO 9 g/ha-mo
0 10 TO 19 g/ha-mo
0 > 20 g/ha-mo
Figure 5.2. Manganese in precipitation (g/ha-mo), September 1966-January 1967.40
Environmental Appraisal
5-17
-------
oo
Table 5.16. ESTIMATED HOURLY MANGANESE CONCENTRATIONS, EPA MODEL
Vehicles
using MMT,
%
100
50
25
Distance
from highway,
meters
1
10
50
100
500
1
10
50
100
500
1
10
50
100
500
Max.
cone.,
A/g/m3
18
11
4.6
2.8
0.73
9.2
5.5
2.3
1.4
0.36
4.6
2.7
1.1
0.69
0.18
MMT = 0.125 g/gal
Wind
angle,
degrees
2
4
7
11
32
2
4
7
11
32
2
4
7
11
32
Cone, with wind
perpendicular,
Atg/m3
3.1
2.8
2.0
1.5
0.59
1.5
1.4
1.0
0.76
0.30
0.77
0.70
0.51
0.38
0.15
Max.
cone.,
M9/m3
8.4
5.0
2.1
1.3
0.33
4.2
2.5
1.0
0.63
0.17
2.1
1.2
0.52
0.31
0.083
MMT = 0.057 g/gal
Wind
angle,
degrees
2
4
7
11
32
2
4
7
11
32
2
4
7
11
32
Cone, with wind
perpendicular,
ng/m3
1.4
1.3
0.92
0.69
0.27
0.70
0.64
0.46
0.35
0.13
0.35
0.32
0.23
0.17
0.067
-------
Table 5.17. ESTIMATED 24-hour MANGANESE CONCENTRATIONS. EPA MODEL
Vehicles
using MMT,
%
100
50
25
Distance
from highway.
meters
1
10
50
100
500
1
10
50
100
500
1
10
50
100
500
0
Concentration, pg Mn/m
MMT = 0.125g/gal
With
highway
81°-261°
3.4
1.2
0.26
0.088
0.021
1.7
0.62
0.13
0.044
0.011
0.85
0.31
0.065
0.022
0.0054
With
highway
111°-291°
1.7
0.92
0.53
0.37
0.10
0.87
0.46
0.27
0.18
0.05
0.43
0.23
0.13
0.092
0.026
MMT = 0.057 g/gal
With
highway
81°-261°
1.5
0.57
0.12
0.040
0.0098
0.77
0.28
0.060
0.020
0.0049
0.39
0.14
0.030
0.010
0.0024
With
highway
111°-291°
0.79
0.42
0.24
0.17
0.047
0.39
0.21
0.12
0.084
0.023
0.20
0.11
0.061
0.042
0.012
Environmental Appraisal
5-19
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Table 5.18. TRAFFIC VOLUMES AND METEOROLOGICAL CONDITIONS FOR 24 HOURS,
EPA MODEL
Hour
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
Total
No.
vehicles,
103/hr
3.5
2
1.5
1.5
3
7
12
12
12
10.5
10.5
11
11
11
12
12
12
12
12
11.5
11
9
8.5
7.5
216
Wind
directions,
degrees
224
264
258
261
259
261
263
259
257
264
260
258
259
259
171
176
191
194
186
223
229
269
298
300
Wind
speed,
m/sec
3.1
1.5
1.
1.
1.
1.
0.7
0.5
0.7
1.
1.
1.5
1.
1.
2.6
2.
2.6
2.6
2.6
2.6
2.6
1.5
1.5
1.
Stability
class
6
6
6
6
6
6
6
6
5
4
3
2
1
1
2
3
3
4
5
6
6
6
6
6
Mixing
height
—
—
--
~
—
~
—
~
~
745
988
1231
1474
1717
1717
1717
1717
1719
—
—
—
—
—
—
5-20
MANGANESE
-------
Table 5.19. ESTIMATED HOURLY MANGANESE CONCENTRATIONS,
ETHYL MODEL
Vehicles
using MMT,
%
100
50
25
MMT = 0.1 25 g/gal
Distance
from
highway.
meters
1
10
50
100
500
1
10
50
100
500
1
10
50
100
500
Max.
cone..
jug/m3
2.42 to 3.63
1.43 to 2. 13
0.67 to 1 .00
0.43 to 0.64
0.12 to 0.17
1.21 to 1.83
0.72 to 1.07
0.33 to 0.51
0.21 to 0.32
0.07 to 0.09
0.61 to 0.91
0.36 to 0.53
0.17 to 0.25
0.11 to 0.16
0.03 to 0.04
Wind
angle.
degrees
3
5
9
12
34
3
5
9
12
34
3
5
9
12
34
Cone, with
wind per-
pendicular.
M9/m3
0.64 to 0.99
0.48 to 0.72
0.20 to 0.31
0.1 3 to 0.20
0.09 to 0.1 5
0.32 to 0.48
0.24 to 0.36
0.11 to 0.16
0.07 to 0.11
0.05 to 0.08
0.1 6 to 0.24
0.12to0.19
0.05 to 0.08
0.04 to 0.05
0.03 to 0.04
MMT = 0.057 g/gal
Max.
cone..
WI/m3
1.10 to 1.65
0.65 to 0.97
0.31 to 0.45
0.20 to 0.29
0.05 to 0.08
0.56 to 0.83
0.33 to 0.49
0.1 6 to 0.23
0.11 to 0.15
0.03 to 0.04
0.28 to 0.41
0.1 6 to 0.24
0.08 to 0.1 2
0.05 to 0.08
0.01 to 0.03
Wind
angle.
degrees
3
5
9
12
34
3
5
9
12
34
3
5
9
12
34
Cone, with
wind per-
pendicular.
pg/m3
0.29 to 0.44
0.22 to 0.33
0.09 to 0.1 3
0.07 to 0.09
0.04 to 0.07
0.1 5 to 0.23
0.12to0.17
0.05 to 0.07
0.04 to 0.05
0.03 to 0.04
0.07 to 0.11
0.05 to 0.09
0.02 to 0.04
0.02
0.01 to 0.02
Table 5.20. ESTIMATED 24-hour MANGANESE CONCENTRATIONS, ETHYL MODEL3
Vehicles
using MMT,
%
100
50
25
Distance from highway,
meters
1
10
100
200
500
1
10
100
200
500
1
10
100
200
500
Concentration, (igMn/m^
MMT = 0.1 25 g/gal
0.48 to 0.72
0.36 to 0.54
0.1 5 to 0.23
0.10 to 0.15
0.07 to 0.11
0.24 to 0.36
0.1 8 to 0.27
0.08 to 0.1 2
0.05 to 0.08
0.04 to 0.06
0.12 to 0.18
0.09 to 0.1 4
0.04 to 0.06
0.03 to 0.04
0.02 to 0.03
MMT = 0.057 g/gal
0.22 to 0.33
0.17 to 0.25
0.07 to 0.10
0.05 to 0.07
0.03 to 0.05
0.11 to 0.17
0.09 to 0.1 3
0.04 to 0.05
0.03 to 0.04
0.02 to 0.03
0.06 to 0.08
0.04 to 0.06
0.02 to 0.03
0.01 to 0.02
< 0.01 to 0.01
meteorological case, wind perpendicular to road.
Environmental Appraisal
5-21
-------
Table 5.21. ESTIMATED MAXIMUM MANGANESE CONCENTRATIONS,
ETHYL MODEL3
Vehicles
asing MMT,
100
50
25
Distance from highway,
meters
1
10
50
100
500
1
10
50
100
500
1
10
50
100
500
Wind angle,
degrees
3
5
9
12
34
3
5
g
12
34
3
5
g
12
34
Concentration, jug Mn/m3
MMT = 0.125 g/gal
1.82 to 2.73
1.07 to 1.60
0.50 to 0.75
0.32 to 0.48
0.09 to 0.1 3
0.91 to 1 .37
0.54 to 0.80
0.25 to 0.38
0.1 6 to 0.24
0.05 to 0.07
0.46 to 0.68
0.27 to 0.40
0.13 to 0.19
0.08 to 0.1 2
0.02 to 0.03
MMT = 0.057 g/gal
0.83 to 1.24
0.49 to 0.73
0.23 to 0.34
0.1 5 to 0.22
0.04 to 0.06
0.42 to 0.62
0.25 to 0.37
0.12 to 0.17
0.08 to 0.11
0.02 to 0.03
0.21 to 0.31
0.1 2 to 0.1 8
0.06 to 0.09
0.04 to 0.06
0.01 to 0.02
Worst meteorological case, maximum concentrations for least favorable wind angle.
Table 5.22. ESTIMATED STREET CANYON MANGANESE CONCENTRATIONS,
ETHYL MODEL3
Vehicles
using MMT,
%
100
50
25
Distance from highway.
meters
1
10
1
10
1
10
Concentration, jug Mn/m^
MMT = 0.1 25 g/gal
0.84 to 1.26
0.43 to 0.65
0.42 to 0.63
0.22 to 0.33
0.21 to 0.32
0.10 to 0.16
MMT = 0.057 g/gal
0.38 to 0.57
0.19 to 0.29
0.1 9 to 0.29
0.10 to 0.15
0.10 to 0.14
0.05 to 0.07
Worst meteorological case, 1.5-meter elevation.
5-22
MANGANESE
-------
The mathematical models used to develop these estimates were based upon available roadside measurements
for lead and carbon dioxide; a proportionality factor was used for computing manganese concentrations. It
was assumed that 20 percent of the manganese in the gasoline would be emitted from the exhaust. Neither
of the models has been validated. EPA is currently measuring carbon monoxide and sulfate concentrations
in the vicinity of major freeways in California, and these data will provide a basis for validating the EPA
model. Since current use of MMT is limited, however, the models cannot now be validated for manganese
concentrations.
Since neither of the models has been validated, the estimates obtained cannot be considered significantly
different. The EPA model, however, does predict maximum concentrations four to five times higher than
the Ethyl model. The two models have not been analyzed in detail to determine the reasons for the
difference. Some of this difference can be attributed to the fact that more stable meteorological conditions
were assumed for the EPA model — conditions that would not be expected to occur more than once per
year. Further, the EPA model does not consider the thermal effects due to the heat generated from the fuel
burned. It is generally agreed that this factor would be significant in cases of slow-moving or stalled traffic,
but there is a question concerning the relative importance of the thermal effects as compared with the
turbulent wake effect when traffic is moving at reasonable speeds.
Based on the model estimates, the expected manganese concentration under worst conditions would be less
than 5 jug/m3 for a 24-hour averaging time. For comparison, the maximum average 24-hour manganese
concentrations in 1968 in three large cities were: Washington, 0.09 Aig/m3; Los Angeles, 0.07; and Chicago,
0.26. Cities with major manganese emitting industries close by have significantly higher levels: Pittsburgh,
1.10 Mg/m3; Johnstown, 14.00; and East Chicago, 0.67.24
5.2.2 Water
The manganese in fresh water consists of dissolved and suspended salts. In the United States, most studies
of the manganese in fresh water have determined the total amount of manganese in the sample, not
individual compounds. In 1938, the surface waters of eight Wisconsin lakes were found to contain between
3 and 23 jug/liter. A more recent study of surface waters from lakes in Maine revealed concentrations
varying from 0.02 to 87.5 ng/liter and a mean concentration of 3.8 /ug/liter. Analysis of Mississippi River
water at Fairport, Iowa, showed 80 to 120 Mg/liter of manganese. The median manganese concentration of
52 samples from 15 large U.S. rivers was 20 jug/liter. Various investigators have found the concentration of
manganese dissolved in sea water to vary between 0.4 and 10 /L(g/liter.
Manganese in the public water supplies of the hundred largest cities ranges from 0 to 2.5 milligrams per liter
(mg/liter) for treated water. A U.S. Public Health Service (PHS) study of 969 community water supplies
found a maximum concentration of 1.32 mg/liter of manganese at the consumer's tap; also, 211 of 2,595
samples exceeded the PHS Drinking Water Standard of 0.05 mg/liter.30 The PHS Drinking Water Standard
was established on the basis of aesthetic and economic considerations rather than physiological hazards.31
The manganese concentrations in a number of U.S. water systems are summarized in Table 5.23.32 Based
upon these values and assuming a daily water consumption of 2 liters, the daily ingested dose of manganese
from drinking water would range from 6 to 100 /^g/day.
Environmental Appraisal 5-23
-------
Table 5.23. MANGANESE CONCENTRATIONS IN U.S. WATER SYSTEMS32
System
Ohio River
Mississippi River
Columbia River
Great Lakes
Concentration
range,
yug/liter
6 to 30
9 to 50
3 to 5
5 to 5
Detection,
% of samples
17
11
13
4
5.2.3 Food
The manganese contents of foods are shown in Table 5.24.33 In a more detailed listing,8 nuts, tea, and
spices contain the highest concentrations-35, 276, and 263 jug/g wet weight, respectively.
Table 5.24. MANGANESE CONCENTRATIONS IN GROUPS OF PRINCIPAL FOODSTUFFS33
Class of food
Grains and cereals
Dairy products
Meat and poultry
Fish and seafood
Fruit
Nuts (edible part only)
Vegetables
Condiments and beverages
Fats and oils
Manganese concentration,
Mg/g (wet weight)
1.17 to 30.76
0.00 to 1.88
0.00 to 0.75
0.00 to 0.12
0.20 to 4.68
0.38 to 35.09
0.24 to 12.74
0.00 to 275.58
0.00 to 4.95
5.2.4 Soil
Manganese is considered to be the 12th most abundant element in the earth's crust. It is found in igneous,
sedimentary, and metamorphic rocks. Igneous rocks have been reported to contain 950 Mg/g, shales 850
Mg/g, sandstones 50 jzg/g, and limestones 1100 /Jg/g. Most important from an environmental point of view is
the distribution of manganese in the soil. The concentration depends on the parent rocks from which the
soil was formed and the amount of manganese they contained (Table 5.2S).34
5-24
MANGANESE
-------
Table 5.25. MICRONUTRIENT CONCENTRATIONS IN SOILS AND ROCKS34
Element
Boron
Manganese
Iron
Cobalt
Copper
Zinc
Molybdenum
Earth's
crust
10
1,000
50,000
40
70
80
2.3
Basic
rocks
10
2,000
86,000
45
140
130
1.4
Acid
rocks
15
600
27,000
5
30
60
1.9
Sedi-
mentary
rocks
12
670
33,000
23
57
80
2
Soils
10
850
38,000
8
20
58
2
Soils have an average manganese content of 800 to 850 Mg/g-8 Manganese in the soil is found in a
water-soluble form in the soil solution, in the exchangeable Mn2 + as organically bound manganese, and as
various manganese oxides. The amount of manganese in solution, as well as on the exchange complex, is
very low in alkaline soil. A dynamic equilibrium is thought to exist between the manganese in soil solution,
adsorbed on the exchange complex, and the precipitates of higher oxides or hydroxides.35
Manganese cycles in the soil have been postulated. In these cycles, divalent manganese (Mn2+) is
transformed through biological oxidation to the less-available trivalent form (Mn ); later through
dismutation, the Mn3 + is reduced biologically to Mn2+. A dynamic equilibrium exists between all forms.36
The oxidizing power of higher oxides increases with acidity; therefore, reduction by organic matter is more
likely at low pH values. If the oxygen tension is low, biological reduction can take place at any pH value.
Bacterial oxidation is very slow or absent in very acid soils, and Mn2+ predominates since organic matter
can reduce the higher oxides. In alkaline soils, the Mn2+ nearly disappears; bacterial oxidation is rapid and
reduction by organic matter is slow. In well-aerated soils above a pH of 5.5, soil microorganisms can oxidize
the Mn2+ rapidly.3 7 The rate of exchange between the various forms is not known at the present time.
The solubility of manganese is markedly affected by microbial process. Microorganisms are active in
catalyzing both the oxidations and the reductions in which manganese is precipitated or solubilized. These
microorganisms are spread universally throughout the biosphere and are probably important in precipitating
the manganese found in sediments. Under anaerobic and reducing conditions, sulfate-reducing bacteria
precipitate manganese. The availability of manganese in the soil may be affected by microorganisms in the
following ways:
• Release of inorganic ions during decomposition of organic material.
• Immobilization of ions by incorporation into microbial tissue.
• Oxidation of manganese, generally to a less available form.
• Reduction of an oxidized form of manganese under conditions of limited oxygen tension.
• Indirect transformation through changes in pH or oxidation potential.38
Environmental Appraisal 5-25
-------
Manganese in soil exhibits a very pronounced seasonal variation. This is probably due to oxidation and
reduction induced by microbial action.34 Summer seems to favor the manganous (Mn2+) form and winter
the manganic (Mn3+) form, though the opposite is said to be true in alkaline soils. Tisdale and
Bertramson39 have indicated that a relationship between elemental sulfur and manganese exists and
influences the availability of manganese.
5.2.5 Biological Tissues
Under average environmental concentrations of manganese, terrestrial mammals concentrate available
manganese up to a factor of 10, whereas marine plants and fish concentrate it by factors of 100,000 and
100 respectively. The average manganese concentration for terrestrial mammals may be as high as 1.0 ^g/g
wet'tissue.8 Tissue concentrations of manganese range from 0.2 jug/g in muscle to 3.3 Mg/g in bone, with an
average of from 0.2 to 0.3 Mg/g wet tissue.8 In addition to bone, tissues showing high levels of manganese
are liver (2.5 jug/g), pituitary (2.5 jug/g), pancreas (1.9 jug/g)> and kidney (1.2 Mg/g)-8
In humans, approximately 10 percent of the average daily dietary intake of manganese is absorbed through
the gastrointestinal tract. Manganese absorption through the gastrointestinal tract is correlated with the
available iron and the iron balance in the body. When an adequate amount of iron is available, manganese
uptake is minimal, but when the iron supply is insufficient, manganese uptake is increased. This may be of
concern to pregnant women and to undernourished groups because the resulting physiological anemia
would promote gastrointestinal manganese uptake.
Manganese uptake in the lung is more efficient than that through the gastrointestinal tract by a factor of 3.
An average size man (70 kg) inhaling an atmosphere that contained 5 mg/m3 would absorb approximately
0.5 mg/g wet tissue per day.
5.2.6 Estimate of Daily Human Exposure
Only small segments of the population are exposed to manganese levels in excess of the current Threshold
Limit Value for industrial exposure (5 mg/m3 for 8 hours) for air or in excess of the PHS Drinking Water
Standard (0.05 mg/liter). Those directly involved in manganese mining and refining operations or living near
production facilities for ferromanganese, steel, aluminum, copper, alloys, and voltaic cells may be exposed
to higher levels.
The daily intake for nonoccupationally exposed individuals will vary widely, depending primarily upon the
diet. Intake from food is much greater than that from inhalation or the ingestion of water. Schroeder et
al.33 estimate the daily background dose of manganese to be about 3000 Mg/day (Table 5.26). Although
the average intake of manganese from inhalation is small in comparison with that from food, in the cases of
occupational exposure, it appears to be the major route of absorption.
Table 5.26. ESTIMATED DAILY BACKGROUND DOSE OF MANGANESE33
Exposure
Inhalation
Ingestion
Food
Water
Dose, jug/day
3,000
5
5-26 MANGANESE
-------
5.3 TRANSPORT AND MODELING
No transport model exists to describe the global distribution of manganese. Such a model is required to
determine a mass balance for manganese in order that emissions into the environment can be related to the
various transformations in the total manganese cycle. The model should be able to account for the present
levels of manganese, and must be able to predict the impact, including long-term effects on the
environment, that may be caused by a change in input.
A necessary input into the model will be the rates of emission of manganese compounds into the
environment. While the major paths by which manganese enters the environment are known, the total loss
of manganese by the various escape routes is unknown. Accurate and up-to-date measurements on particle
size, the rate of loss of these substances into the environment, and the distribution of emissions within the
environment are needed before manganese compounds can be modeled.
The major sources of manganese in the atmosphere are manganese alloy, steel, and iron production. Minor
sources are wind-blown soil, auto exhaust, mining operations, dry-cell battery production, fertilizers,
fungicides, and synthetic manganese oxide production. The manganese compounds emitted from these
sources can be classified as either fume or dust.
In manganese alloy production, 20 percent of the particles emitted have diameters greater than 20 /urn, and
80 percent of the solids present in the gas as it leaves the furnaces is a typical fume, with particle sizes
ranging between 0.10 and 1.0 jLtm. Similar size particles are produced in the iron and steel industries. Fly
ash particles from oil-burning boilers range from less than 0.01 to 20 jum, depending on the degree of
atomization of the oil, mixing efficiency, flame temperature, firebox design, flue gas path through the
boiler to the stack, and number of collisions between fly ash particles. Manganese particles emitted by the
combustion of manganese fuel additives will be in a size range less than 0.1 /urn.
Considering the sources and size distribution of manganese, prevailing winds will be the main transport
mechanism. Therefore, manganese particles will be deposited on land or water by gravitational settling and
diffusion, washout, or rainout. If these removal mechanisms are dominant, the atmospheric residence time
of manganese-containing particles will depend greatly on size and the amount of atmospheric precipitation.
The large particles will be deposited near the source, and only the fine particles will be transported to
remote areas.
Possible sources of soil contamination include aerosols, pesticides, limestone and phosphate fertilizers,
manures, sewage sludge, and mine waste—all of which can add to the manganese burden of fresh water and
sea water. Reentrainment of dust and soil containing manganese has not yet been studied.
Once transport mechanisms have been developed for manganese, it will be necessary to determine the
ultimate fate of the degradation products in order to model this pollutant. The following six transformation
and removal processes should be considered for manganese.
5.3.1 Dissolution in Fresh Water and Sea Water
All waters contain manganese derived from soil and rocks. Seawater manganese is found mostly as MnO2,
some of which can be explained by earlier observations that several genera of bacteria common to soils and
ocean muds precipitate manganese oxides from manganese salts.
5.3.2 Rainout and Washout
Sampling for six metals at 32 stations in the United States indicates that manganese in atmospheric
precipitation is derived primarily from human activity.40
Environmental Appraisal 5-27
-------
5.3.3 Microbiological Utilization at Earth's Surface
In addition to the soil and ocean mud bacteria mentioned above, bacteria have been considered to be an
agent in the formation of bog manganese ores. Recent research has demonstrated that manganese can be
separated from refractory manganiferous materials by the action of by-products formed as a result of
microbial metabolism,
5.3.4 Uptake by Soil and Plants
Plants apparently absorb manganese primarily in the divalent (Mn2+) state.8 Lowering the soil pH or
reducing soil aeration by flooding or compaction favors the reduction of manganese to the Mn2+ state and
thereby increases its solubility and availability to plants. Heavy fertilization of acid soils without
liming-particularly with materials containing chlorides, nitrates, or sulfates-may also increase manganese
solubility and availability. The availability of soil manganese is closely related to the activities of
microorganisms that alter pH and oxidation-reduction potentials. Under some conditions of pH and
aeration, the addition of organic compounds to soil can increase the chemical reduction of manganese and
its uptake by plants. Although manganese and iron metabolism appear closely related in plants, the two
elements behave differently—iron binds largely to citrate and moves as an anion, but manganese acts as a
cation and does not bind with citrate.
5.3.5 Photochemical and/or Thermal Reactions in Lower Atmosphere
Sulfur dioxide, emitted into the atmosphere in the presence of sunlight and water vapor, is converted to
sulfur trioxide and then to sulfuric acid. Ammonia or some metal compounds, including those of
manganese, can promote this reaction. At the manganese concentrations normally present in the ambient
atmosphere, the oxidation of sulfur dioxide resulting from the presence of manganese is not expected to be
significant. Ammonia in the air is probably the rate-controlling factor in atmospheric sulfur dioxide
oxidation.
Manganese dioxide reacts with nitrogen dioxide in the laboratory to form manganous nitrate, which is
toxic. There is the possibility of such a reaction occurring in the atmosphere; however, it has not been
observed.
5.4 REFERENCES FOR SECTION 5
1. DeHuff, G. L. Manganese. In: Minerals Yearbook 1970, Volume I. Bureau of Mines, U. S. Department
of Interior. Washington, D. C. 1972. p. 691-703.
2. Sullivan, R. J. Preliminary Air Pollution Survey of Manganese and Its Compounds. National Air
Pollution Control Administration. Raleigh, N.C. Publication No. APTD 69-39. October 1969. 54 p.
3. National Inventory of Sources and Emissions: Manganese. Prepared under Contract No. CPA 70-128 by
W. E. Davis and Associates, Leawood, Kansas. U. S. Environmental Protection Agency. Research
Triangle Park, N. C. August 1971. 37 p.
4. tee, R. E., and D. J. von Lehmden. Trace Metal Pollution in the Environment. J. Air Pollut. Contr
Ass. 2J(10):853-857,1973.
5. Standards of Performance for New Stationary Sources. Federal Register. J6:(247):24876-24895,
December 23, 1971.
5-28 MANGANESE
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6. Bolton, N. E., W. S. Lyon, R. I. van Hook, A. W. Andren, W. Fulkerson, J. A. Carter, and J. F. Emery.
Trace Element Measurements at the Coal-Fired Allen Steam Plant, Progress Report June 1971-January
1973. Oak Ridge National Laboratory, Oak Ridge, Tennessee. Report No. ORNL-NSF-EP-43. March
1973.83 p.
7. Von Lehmden, D. J. Manganese in Fly Ash. U. S. Environmental Protection Agency, National
Environmental Research Center, Research Triangle Park, N. C. May 1973. Unpublished data.
8. Manganese. Washington, D.C., National Academy of Sciences. 1973. 191 p.
9. Winchester, J. W., and G. D. Nifong. Water Pollution in Lake Michigan by Trace Elements from
Pollution Aerosol Fallout. Contribution No. 161, Department of Meteorology and Oceanography, and
No. 110, Great Lakes Research Division, University of Michigan, Ann Arbor, May 1970.
10. Ruch, R. R., H. J. Gluskoter, and N. F. Shimp. Occurrence and Distribution of Potentially Volatile
Trace Elements in Coal; Interim Report, Jan.-Dec. 1972. Work done under EPA Contract 68-02-0246
by Illinois State Geological Survey. Environmental Geology Notes 61. 1973. 43 p.
11. Swanson, V. E. Composition and Trace-element Content of Coal and Power Plant Ash. In: Southwest
Energy Study, Part II. U.S. Geological Survey. Denver, Colo. January 1972. 65 p.
12. Bryan, D. E. Development of Nuclear Analytical Techniques for Oil Slick Identification (Phase 1).
Work done under AEC Contract No. AT(904-3)-167 by Gulf General Atomic. Report No. 9889.1970.
13. Van Dyke, L. F. U. S. Power Firms Begin Burning Crude. Oil Gas J. 70(6):28-30, February 7, 1972.
14. Jungers, R. J. Manganese in Gasoline. U. S. Environmental Protection Agency, National Environ-
mental Research Center, Research Triangle Park, N. C. May 1973. Unpublished data.
15. Von Lehmden, D. J. Manganese in Fuel Additives. U. S. Environmental Protection Agency, National
Environmental Research Center, Research Triangle Park, N. C. May 1973. Unpublished data.
16. Jungers, R. J. Manganese in Motor Oil. U. S. Environmental Protection Agency, National Environ-
mental Research Center, Research Triangle Park, N. C. May 1973. Unpublished data.
17. Regulation of Fuels and Fuel Additives. Federal Register. 40 CFR Part 80. Vol. 38, No. 6. p.
1258-1261. January 10,1973.
18. Personal Communication with J. F. Faggan. Ethyl Corporation. Ferndale, Mich. January 1974.
19. A Study of Measurement Methods and Instruments for the Determination of the Effects of Particulate
Exhaust Emissions of Additives and Impurities in Gasoline. Work done under EPA Contract
68-02-0332 by Dow Chemical Company, Midland, Michigan. Report in preparation.
20. Test Procedures for Vehicle Exhaust and Fuel Evaporative Emissions. Federal Register
35(219): 17294-17303 .November 10, 1970.
21. Sullivan, R. J. Preliminary Air Pollution Survey of Manganese and Its Compounds. National Air
Pollution Control Administration. Raleigh, N. C. Publication No. APTD 69-39. October 1969. 54 p.
22. Von Lehmden, D. J., R. H. Jungers, and R. E. Lee. The Determination of Trace Elements in Coal, Fly
Ash, Fuel Oil and Gasoline; Part 1 - A Preliminary Comparison of Selected Analytical Techniques. U. S.
Environmental Protection Agency, Research Triangle Park, N. C. (Presented at American Chemical
Society Meeting. Dallas. April 1973.)
Environmental Appraisal 5-29
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23. National Air Surveillance Network, Manganese Data, National Aerometric Data Bank. U. S.
Environmental Protection Agency, Office of Air Quality Planning and Standards, Research Triangle
Park, N. C. 1957-1969. Unpublished data.
24. Air Pollution Measurements of the National Air Sampling Networks: Analyses of Suspended
Particulates 1957-1961, Public Health Service Publication No. 978, Cincinnati, Ohio, 1962. Air Quality
Data 1962, Public Health Service, Cincinnati, Ohio, 1963. Air Quality Data 1963, Public Health
Service, Cincinnati, Ohio, 1965. Air Quality Data 1964-1965, Public Health Service, Cincinnati, Ohio,
1966. Air Quality Data 1966 Edition, Public Health Service, Durham, N. C. National Air Pollution
Control Administration Publication No. APTD 68-9, 1968. Air Quality Data for 1967, U.S.
Environmental Protection Agency, Research Triangle Park, N. C., Publication No. APTD-0741., 1971.
Air Quality Data for 1968, U. S. Environmental Protection Agency, Research Triangle Park, N. C.,
Publication No. APTD-0978, 1972.
25. Kanawha Valley Air Pollution Study. National Air Pollution Control Administration. Research Triangle
Park, N. C. Publication No. APTD 70-1. March 1970. 367 p.
26. Hauser, T. R., J. J. Henderson, and F. B. Benson. The Polynuclear Hydrocarbon and Metal
Concentration of the Air Over the Greater Birmingham Area. U. S. Environmental Protection Agency,
National Environmental Research Center, Research Triangle Park, N. C. April 1971. Unpublished
report.
27. Rhodes, J. R., A. H. Pradzynski, C. B. Hunter, J. S. Payne, and H. L. Lindgren. Energy Dispersive
X-Ray Fluorescence Analysis of Air Particulates in Texas. Environ. Sci. Technol. 6:922-927,1972.
28. Brar, S. S., D. M. Nelson, E. L. Kanabrocki, C. E. Moore, C. D. Burnham, and D. M. Halton. Thermal
Neutron Activation Analysis of Particulate Matter in Surface Air of the Chicago Metropolitan Area.
Environ. Sci. Technol. 4:50-54, 1970.
29. Lee, R. E., S. S. Goranson, R. E. Enrione, and G. B. Morgan. The NASN Cascade Impactor Network;
Part II, Size Distribution of Trace-metal Components. Environ. Sci. Technol. 6:1025-1030, 1972.
30. Community Water Supply Study; Analysis of National Survey Findings. U. S. Department of Health,
Education, and Welfare, Public Health Service, Environmental Health Service, Bureau of Water
Hygiene. Washington, D. C. 1970. 123 p.
31. McKee, J. E., and H. W. Wolf. Water Quality Criteria. State Water Quality Board, Sacramento, Calif.
Publication No. 3-A. 1963. 548 p.
32. Kroner, R. C., and J. F. Kopp. Trace Elements in Six Water Systems of the United States. Amer. Water
Works Ass. 1.57(2)150-156, 1965.
33. Schroeder, H. A., D. D. Balassa, and I. H. Tipton. Essential Trace Elements in Man; Manganese, A
Study in Homeostasis. J. Chronic Dis. /P:545-571,1966.
34. Hodgson, J. F. Chemistry of the Micronutrient Elements. Advan. Agron. 15:119-159, 1963.
35. Wier, D. C., and H. M. Miller, The Manganese Cycle in Soil; I-Isotopic-Exchange Reactions of Mn-54 in
Alkaline Soil. Can. J. Soil Sci. 42:105-114, 1962.
36. Zajic, J. E. Microbial Biogeochemistry. New York, Academic Press, 1969. p. 157-167.
37. Leeper, G. W. The Forms and Reactions of Manganese in the Soil. Soil Sci. 6J:79-94, 1947.
5-30 MANGANESE
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38. Alexander, M. Introduction to Soil Microbiology. New York, John Wiley and Sons, 1967. 472 p.
39. Tisdale, S. L., and B. R. Bertramson. Elemental Sulfur and Its Relationship to Manganese Availability.
Soil Sci. Soc. Amer. Proc. 74:131-137, 1950.
40. Lazrus, A. L., E. Lorange, and J. P. Lodge, Jr. Lead and Other Metal Ions in United States
Precipitation. Environ. Sci. Technol. 4(l):55-58, 1970.
Environmental Appraisal 5-31
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6. BIOLOGICAL EFFECTS
6.1 EFFECTS ON MAN AND LABORATORY ANIMALS
6.1.1 Introduction
Manganese is an essential trace element in all living things and is ubiquitously distributed in nature.1 ~2 One
of its major functions appears to be as a coenzyme in various metabolic processes, localized mainly in the
mitochondria. While in trace amounts manganese is beneficial, industrial exposure of man to various
manganese compounds has been associated with two different clinical pictures: chronic manganese
poisoning affecting the central nervous system and a manganic pneumonia.
Manganese poisoning is a hazard in the mining and processing of manganese ores and in the use of
manganese alloys in the steel industry, and in chemical industries. In manganese mining, dry high-speed
drilling produces dust containing a large percentage of manganese dioxide; this, coupled with poor
ventilation, provides the setting for most of the cases of chronic manganese poisoning reported in the
literature, although other sources are known.3
Chronic manganese poisoning can result from exposure to high concentrations of manganese dust after only
a few months, although it usually results from exposures of two to three years. Manganese may be absorbed
by inhalation, ingestion, or through the skin. Most effects appear to result from prolonged inhalation,
although some studies have shown that a greater amount of the metal enters the body by means of the
intestinal absorption route. The damage produced is reversible if the patient is removed from exposure, but
a sensitivity can evidently develop since persons who have recovered seem to be prone to contracting the
illness again.
Acute manganese poisoning is extremely rare. Chronic exposure is seldom fatal but may result in permanent
crippling. Diagnosis is difficult unless a history of exposure for at least three months is present. The
symptoms are sleepiness, muscular twitchings, cramps in the legs, increased tendon reflexes, a peculiar
characteristic spastic gait, emotional disturbances, and a fixed mask-like expression. Exposure to manganese
dust has produced croupous pneumonia which frequently affects only one lobe of the lung. There is a high
mortality rate from the pneumonia.4
6.1.2 Metabolism
Extensive reviews by Cotzias and coworkers1'5 provide much of the understanding of manganese
metabolism including absorption, excretion, turnover rates, and tissue profiles. Manganese metabolism is
regulated by the adrenal glands. Ingested manganese is absorbed through the intestine and is concentrated
in the Liver. Manganese accumulates in organs rich in mitochondria and is selectively concentrated within
mitochondria.6 Although some may be distributed to the tissues, most of the excess metal is discharged via
the bile or by other gastrointestinal routes, thereby keeping the manganese profile among various tissues
relatively stable. A small percentage of the manganese excreted to the intestine is reabsorbed and is
transported in the plasma in its trivalent form. Mahoney and Small7 identified fast and slow components of
the manganese disappearance curves that had respective half-times of 4 days and 39 days in humans. They
found the biological half-time to be influenced by intake of manganese, amount of iron in storage, and
hemoglobin concentration in the blood. They reported a half-time of 10 to 15 days in rats; this is supported
by the work of Moore et al.8, who found that the retention times of MMn were similar when the source
6-1
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was either MnCl2 or MMT (methylcyclopentadienyl manganese tricarbonyl). The inorganic form, however,
was excreted almost exclusively in the feces, while the organic form was excreted both in feces and in urine.
Skeletal structures, hair, liver, pancreas, and kidney contain concentrations of manganese that are
characteristic of those tissues but that vary little among species. Generally, organs and tissues do not
accumulate large concentrations of manganese.
Alstatt et al.9 have shown that manganese and iron metabolism are closely related. The high degree of
individual susceptibility of miners to chronic manganese poisoning has resulted in attempts by several
investigators to relate it to nutritional deficiencies, specifically iron-deficiency anemia. Mena et al.10 state
that there is a proportionality between the intestinal absorption of iron and manganese in man and animals.
Furthermore, it has been shown that anemia leads to an increased absorption of both iron and manganese.
Chronic exposures to high levels of manganese increase hemoglobin values and erythrocyte counts, which
indicates that manganese stimulates production of erythrocytes, as does iron-deficiency anemia. Recovery
from anemia caused by improper nutrition is much prompter following the administration of ferrous sulfate
and manganese chloride than of ferrous sulfate alone, which demonstrates the relationship between the
effect of manganese on erythrocyte production and the intestinal absorption of manganese in anemic
individuals.
6.1.3 lexicological Effects
The toxicity of specific manganese compounds appears to depend upon the type of manganese ion present
and the oxidation state of the manganese; the divalent manganese cation is reported to be two and one-half
to three times more toxic than the trivalent cation. While most oxides are toxic to rats, the higher valence
oxides are more toxic than the lower ones.
Table 6.1 summarizes the results of several studies of the effects of acute manganese excess in rats.
Table 6.1. EFFECTS OF ACUTE EXCESS OF MANGANESE INJECTED
SUBCUTANEOUSLYIN RATS
Dose of
manganese,
mg/kg body wt
50
53 to 60
53 to 60
150
300
170 or more
300
Time elapsed
when effect
noted, hr
10
4
24
20
12to 18
18
48
Effect
Increase in hemoglobin and
hematocrit.
Reduced bile flow rate, changes in
liver ultrastructure characteristic
of reduced bile flow.
Bile flow higher than controls.
Ultrastructural changes not as
severe as at 4 hours.
Increase in hemoglobin, hematocrit.
mean corpuscular volume, serum
chloride, phosphorus, and
magnesium. Decrease in serum
calcium and iron.
Maximum increase in hemoglobin
and hematocrit.
Necrotic changes in hepatic tissues.
Apparent increase in iron content
of spleen and liver.
Reference
11
12
12
11
11
11
11
6-2
MANGANESE
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Male rabbits intravenously injected with 1.1 to 1.5 mg MnCl2/kg body weight for up to 32 days showed
hyperactivity after the first week but later became hypoactive.13 There were tremors of the head and legs
at the end of the exposure period. Pathomorphologic changes were greatest in the liver and least in the
kidneys and intestine. The liver was necrotic and inflamed and had an appearance similar to that found in
acute cirrhosis.
Hysell et al.14 conducted studies with rats to determine the morphologic changes and tissue
concentrations of manganese that occurred following oral intubation (stomach tube) of the fuel additive,
MMT. Dosages varied from 15 to 150 mg/kg body weight. Deaths that occurred took place within 6 days
after exposure; survivors appeared normal at 14 days. The LD50 after 14 days was 58 mg MMT/kg body
weight. The manganese concentrations in tissues from animals dying after exposure depended on the dose
and were rather high. At 14 days after ingestion, the manganese concentrations in survivors had decreased
to approximately the normal range. There was no way to determine whether the observed toxicity was
related to the intact MMT molecule or to some metabolite of the compound. It is apparent, however, that
the toxic effects observed were not the result of acute manganese toxicity since acute toxicity occurs at
much higher dosage levels than those used and since the pattern of hepatic lesions observed in these animals
was markedly different from that seen in acute toxicity. The presence of high levels of manganese in the
tissues, along with histopathological changes, suggests that the manganese was transported there as a
metabolic product of the MMT. In addition, the occurrence of high levels of manganese in organs that
normally have a low manganese content supports this hypothesis.
Moore et al.15'16 exposed golden hamsters and albino rats for 8 hours per day for 56 days to automotive
engine exhaust that contained about 0.12 to 0.13 mgMn/m3 (the manganese resulted from the addition of
MMT to the gasoline). No gross changes in general conditions or appearance were observed in any of the
animals. No gross abnormalities were noted in any of the hamsters or rats except for the usual chronic
respiratory disease lesions in the rats. Microscopic examination of the tissues from the hamsters showed
minimal changes related to exposure to exhaust emissions but no changes that could be related specifically
to the presence of MMT.
A study in which cerebral tissues were examined by Jonderko and Szczurek17 led to the conclusion that
manganese poisoning directly affects functional parts of the brain; however, local circulatory disturbances
also may produce changes in the central nervous system. Chandra and Srivastava18 gave rats 8 mg MnCl2/kg
intraperitoneally for 180 days and found that the occurrence of degenerated neurons was maximal when
the manganese concentration in brain was at a maximum; thus, the extent of damage to brain cells appears
to be directly related to the amount of manganese in the brain..
Borisenkova19 compared the effects from inhalation of dusts containing ferromanganese, silicomanganese,
manganese dioxide, or iron oxide in rats exposed to 70 to 150 mg/m3 for 4 months. The motor reflex, as
indicated by the response of hind limb muscles, was affected between 7 and 12 weeks after the beginning of
exposure to ferromanganese, after 12 to 15 weeks exposure to manganese dioxide, and after 15 to 16 weeks
exposure to silicomanganese. Iron oxide produced no changes compared to controls. Changes in
morphology of the brain were consistent with changes seen in the motor reflex, so that the primary effect
appeared to be exerted on the central nervous system. After 4 months of inhalation, rats contracted
interstitial chronic pneumonia from exposure to any of the compounds, including iron oxide.
6.1.4 Mechanisms of Manganese Poisoning
Brain function is dependent upon the transmission of nerve impulses between nerves to affect a certain
end-organ response such as muscle contraction. Four chemicals function in the transmission of nervous
impulses (dopamine, norepinephrine, serotonin, and acetylcholine). Furthermore, there is variable
distribution of these neurotransmitters in specific structures of the brain. The regional localization of these
neurotransmitters is significant because the normal functioning of the brain is controlled by excitatory
(norepinephrine and dopamine) and inhibitory (serotonin) neurons and because regions high in various
concentrations may be classified as inhibitory or excitatory.
Biological Effects 6-3
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Many of the symptoms of chronic manganese poisoning are similar to Parkinson's disease and both have as
\ the basis of their symptomatology the abnormal function of the extrapyramidal system of the brain.4 This
' system is associated with gross, coordinated movements of large parts of the body involving control of
simultaneous contraction and relaxation of many different muscles. Normal functioning of this motor
system depends upon a balance of two "antagonistic" groups of neurotransmitters.
Manganese can affect oxidative enzyme systems whose integrity is needed to continue to supply the energy
required for the degradation and synthesis of the various chemical compounds that function in nerve
transmissions.20 Mandell and Spooner21 have shown that alteration of these compounds may influence
behavior, which is noteworthy in view of the behavioral symptoms of the intermediate phase of chronic
manganese poisoning. Klawans22 states that both Parkinson's disease and chronic manganese poisoning
have as their basis unantagonized excitation of certain nerve centers because dopamine production is
reduced as the result of a nerve tract lesion.
In a study of mutagenesis, Buttin and Komberg23 mentioned that processes such as genetic recombination
might be affected by manganese via its influence on enzymes that control the structure and metabolism of
the genetic material, deoxyribonucleic acid (DNA). The subcellular structure of ribosomes is dependent
upon divalent cations, usually magnesium; but manganese can be substituted for magnesium in both the
binding together of the two ribosomal subunits and the binding of messenger ribonucleic acid (RNA) to the
whole ribosome.
6.1.5 Community and Occupational Exposure
Numerous instances of manganese intoxication have been reported since the disease was first recognized in
1837 by Couper. Initially, the disease was recognized in individuals working in manganese ore mills, battery
factories, and the iron and steel industry, but most of the more recent cases of manganism have involved
manganese miners. The disease is characterized by psychomotor disturbances, emotional instability,
restlessness or apathy, hallucinations, flight of ideas, compulsory acts, and verbosity. Neurological
symptoms such as weakness, excess salivation, and headaches are consistent features of the illness as well.
Neurological signs of the disease include muscular tension, mask-like expression, gait disturbances,
monotonous speech, tremor, and various sensory changes.
Airborne manganese-containing dust is implicated as the cause of manganese intoxication "by the
observations that the time of onset of manganism is inversely related to the concentration in the air of the
agent, and that, in rough terms, the severity of the disease is apt to be directly related to this
concentration."24 However, neither the particle-size distribution of the manganese dust nor the dose of
manganese dust that can cause manganism is known.
6.1.5.1 Community Exposure—One epidemic of manganese intoxication in Japan was caused by well-water
contaminated by manganese and zinc leached from discarded batteries. Observed symptoms included loss
of appetite, constipation, mask-like expression, excess salivation, painful leg joints, tremor, transient double
vision, memory loss, and melancholia. One patient died, and large quantities of manganese and zinc were
found in the organs examined at autopsy. Although the total doses of manganese consumed by the
intoxicated individuals were not known, analysis of the well-water revealed 14 mg of manganese tetroxide
per liter. | L| j,v.~ / J_, f>L/
Managanese has been implicated in the pathogenesis of lobar pneumonia. Following the opening of a
ferromanganese smelting plant in Sauda, Norway, in 1923, an increased incidence of lobar pneumonia was
noted in workers in the plant and in the townspeople.26 At first it was thought that this community was
experiencing an epidemic of unusually virulent pneumonia, but the situation remained unchanged for many
years without subsiding. Subsequent investigations27"29 showed that:
6-4 MANGANESE
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• Mortality from pneumonia in Sauda was eight times that of the rest of Norway.
• The number of cases of pneumonia and deaths from pneumonia varied with the amount of manganese
alloy produced at the plant.
• Infection rates and types of pneumococci were normal in all parts of the community-only the
pneumonia morbidity and mortality rates were high.
• Smoke near the plant contained 54 percent silica and 2.56 percent manganese oxide.
Concentration of manganese in the atmosphere of Sauda reached a maximum of 64 ;ugMn304/m3, which
corresponds to 46 ng Mn/m3, at a point 3 kilometers from the plant. However, the method used to analyze
for manganese was later found to give low results. The dose of inhaled manganese was not known.
A similar community situation in the vicinity of another ferromanganese plant in Aosta, Italy, was reported
by Povoleri,30 but was not subjected to as detailed study. Both the Norwegian and Italian communities
were situated in deep, narrow valleys, which suffered from severe air stagnation and pollution, particularly
in winter.
In addition to the above, excess illness and death from pneumonia frequently has been reported in other
manganese industries in Europe. Of particular interest are the reports of Davies,31'32 who made
observations in England in a factory producing permanganates under very unfavorable wartime working
conditions. The particle size of the dust was very small, which favored pulmonary deposition. In addition to
noting an excess of pneumonia, Davies observed that other less serious respiratory illnesses-for example,
bronchitis and pharyngitis—were above expected frequency. He reached the conclusion that manganese, at
least in very fine particles, could both enhance the severity of infection and produce chemical pneumonitis,
bronchitis, and pharyngitis.
Two recent Japanese reports33'34 describe careful studies conducted by Kanazawa University medical
faculty on school children located at different distances from a ferromanganese plant. Manganese dustfall
measured monthly for 3 years averaged about 200 kilograms per square kilometer per month
(kg/km2-month) in the vicinity of the plant, compared with 8 kg elsewhere in Kanazawa. Total dustfall and
sulfation rates were similar for all parts of the city. Some 24-hour suspended particulate measurements
made in the plant neighborhood out to 300 meters showed levels from 4 to 260 jug Mn/m3. These results
are too meager to judge critical exposure level. Students in the junior high school 100 meters from the plant
had higher prevalence of nose and throat symptoms, higher history of pneumonia, and lower pulmonary
function than did students in a similar school in another part of the city remote from the manganese plant.
In the students of the exposed school, pulmonary function was lowest in those with longer residence in the
area and in those who lived closer to the factory. Following this study, controls were installed in the
ferromanganese plant over a period of several months. These measures reduced the manganese dustfall from
200 to 20 kg/km2-month. A resurvey of the two schools showed no change in the control school.
Prevalence of nose and throat symptoms in the polluted school decreased to a level comparable to that of
the control school. Lung function of children in the polluted school was also improved and similar to that
in the control school, except in the oldest group of boys who still showed some deficit. These two studies
have apparently bracketed a level of environmental manganese at which health effects begin to appear. The
effects identified are apparently mainly reversible. The critical level is, however, not well identified in a
quantitative sense.
Suzuki35 made observations on pneumonia morbidity in another part of Japan. He found higher history of
pneumonia rates in school children and their families near a ferromanganese plant than in a control group
not so exposed. Primary schools were used, and the data were not separated by age groups. Similar
differences in pneumonia history were found in groups of workers employed in the polluting factory or
residents living nearby, as compared to suitable control groups. A study now underway in Yugoslavia36 has
also noted higher pneumonia morbidity in workers employed in a ferromanganese plant and in an adjacent
Biological Effects 6-5
-------
electrode plant when compared with a remote aluminum fabricating plant with very low manganese
exposure.
6.1.5.2 Occupational Exposure to Manganese—Manganese poisoning, as discussed earlier in this chapter, is a
hazard in mining and processing manganese ores, and in use of manganese alloys in the steel industry and
manganese compounds in chemical industries. It is attributable primarily to exposure to dusts containing
manganese dioxide. Over 400 cases of chronic manganese poisoning have been described, and the clinical
symptomatology has been the subject of several reviews and numerous case reports.37'38 Chronic
manganese poisoning can be caused by exposure to high concentrations of manganese dust for only a few
months, although onset of symptoms usually occurs after 2 to 3 years of continuous exposure. Poisoning
follows a slow progressive course. Cotzias5 has described three phases of chronic manganism: the prodromal
period, the intermediate or psychiatric phase, and the period of severe neurological disorders. A significant
aspect of chronic manganese poisoning is marked individual susceptibility to the disease, since many miners
are exposed to manganese dusts but only a small percentage develop symptoms. Individual susceptibility
may be related to individual variations in the excretory capacity of the liver and kidney which may lead to
accumulation of toxic levels of manganese.4 Liver lesions and a decreased bile flow rate as results of
manganism have been reported by Witzleben.12
6.1.5.3 Clinical Diagnosis—There is no specific diagnostic test for chronic manganese poisoning, although
measurement of urinary manganese concentrations has some value. The normal urinary concentration is 8
to 10 /ug/liter and reflects the general level of exposure to manganese. Urinary concentrations, however, do
not correlate well with the clinical severity of the symptomatology associated with manganism. Blood levels
of manganese provide little clinical information, and blood urea nitrogen, fasting blood sugar, enzymes, and
electrolytes are usually normal. Rodier4 mentions diminished excretion of 17-ketosteroids in 81 percent of
his patients, and changes in the relative concentrations of white blood cells in 52 percent. Furthermore, he
reports an increased basal metabolic rate in 57 percent. Manganese content in hair was decreased by about
70 percent in his patients with chronic manganese poisoning. Kesic and Hausler39 found increased
hemoglobin values and erythrocyte counts and decreased monocyte counts. Cotzias5 reported that
cerebrospinal fluid tends to show a slight increase in cellular and protein content with manganese poisoning.
6.1.5.4 Pathology—There have been only four documented reports40"43 of pathological changes in man
from manganese exposure. One case involved advanced cirrhosis of the liver. All four cases involved
degeneration of nervous tissue in the brain.
Pentschew states that the neuropathological findings in monkeys and cats showed such striking similarities
with those in human cases of manganese encephalopathy that they could be said to be identical.44
6.1.5.5 Treatment of Chronic Manganese Poisoning—Treatment of chronic manganese poisoning has
recently undergone a basic change that reflects a better understanding of the pathophysiology of the
condition. Early attempts using various chelating agents; primarily ethylenediamine-tetraacetic acid
(EDTA), were contradictory but did seem to produce some improvement in the condition if used in the
early phase of poisoning when, presumably, neurons had not yet been destroyed. After structural
neurological injury, no improvement could be expected. The results of Penalver45 and Tepper46 confirmed
this and regarded treatment with chelaters as ineffective. Whitlock et al.47 reported that treatment with
intravenous calcium-EDTA mobilized body deposits of manganese, as evidenced by increased urinary
manganese levels, and led to improvement in muscle strength and coordination within two to three months
after treatment. Wynter48 had poor results with EDTA in seven cases of advanced manganese poisoning but
encouraging results in one patient with symptoms of the early stages. The essentially negative results should
be expected, inasmuch as crippled ex-miners no longer exposed to manganese dust apparently clear the
manganese overload that produced their neurological damage and its symptoms, even though the damage
itself is not reversible.49 Consequently, in the absence of appreciable manganese pools, chelating agents
could not be expected to have any effect. Only in healthy miners still exposed to manganese should tissue
manganese levels be sufficiently high to be amenable to chelating agents.
6-6 MANGANESE
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Recognizing that a similar biochemical defect was present in Parkinson's disease, Mena et al.50 administered
large amounts of L-dopa to six patients. Five showed reduction in or disappearance of muscle rigidity, got
around better, and regained the sense of balance. The sixth patient showed adverse effects upon L-dopa
administration- but did respond favorably to 5-hydroxytryptophane, a precursor of serotonin. This
favorable result was attributed to the fact that decreased muscle tone, which is sometimes present in
chronic manganese poisoning but is hardly ever found in Parkinsonism, is the product of a low serotonin
level in the striatum of the brain stem. Evidence that further implicates serotonin in the condition was
demonstrated by Goldstein et al.51 and Poirier et al.52 They found that dopamine exerts its tremor
producing effect by competing with serotonin for the same receptors.
6.1.6 Maximum Permissible Levels of Manganese and Prevention of Chronic Manganese
Poisoning
6.1.6.1 Maximum Levels-It is generally accepted that the Threshold Limit Value of 5 mg/m3 (8 hours per
day, 40 hours per week) carries a low margin of safety for those occupationally exposed to manganese. The
lowest average concentration at which a case of chronic manganese poisoning has been found is 30 mg/m3.
This occurred in a manganese mill in which the worker was exposed to manganese dioxide dust. In several
steel plants in which workers were exposed to manganese fumes, even lower exposures produced chronic
poisoning.47'53
The present Public Health Service drinking water standard for manganese is 0.05 mg/liter. Presently, there
are no ambient air quality or stationary or mobile source emission standards specifically for manganese.
6.1.6.2 Elimination of Occupational Exposure—Occupational chronic manganese poisoning can be
controlled if certain preventive measures are taken. These include frequent periodic examinations of all
individuals who are exposed to maganese in their work. Individuals applying for work in a mine should be
screened for the presence of conditions that might predispose them to manganese toxicity, such as hepatic
and renal disease, blood abnormalities, organic lesions of the central nervous system, or progressive
pulmonary disease. Individual proven protection measures include initial and periodic medical examina-
tions, transfer of individuals who have liver or lung disease to areas of less exposure, and the use of hygienic
measures including changing clothes after each shift to ensure cleanliness among workers.4 8
Technical measures should be directed mainly toward controlling emissions from the drilling and crushing
of ores. Dry drilling of blast holes and blasting itself cause dust clouds that remain suspended in the air for
long periods of time. Thus, it would be advantageous to blast at the end of the shift so that the men would
be out of the mine when the manganese concentration is most intense. Ventilation should be used to
remove the dust, and water spraying should be available to keep the dust down.
6.2 EFFECTS ON PLANTS
Manganese is an essential micronutrient for plants, which assimilate the element in the divalent form from
the soil. Therefore, the availability of manganese to plants depends on whether it is present in soil in the
divalent, tetravalent, or some other oxidation state. The form present in the soil is dependent upon the
acidity of the soil, the microbial population, the presence of oxygen, and the availability and abundance of
organic matter. Deficiency of manganese can often be a significant factor in reducing crop yields.
Manganese deficiency commonly occurs in soils that are rich in organic matter and have pH values above
6.5. It has been shown that the capacity of plants for absorbing manganese varies according to species.24
In a study of 20 different species of flowering plants, some had a capacity for absorbing manganese that
was 20 to 60 times greater than those with the lowest capacity for absorbing the element. A review by
Sparr5 s indicates the fertilization requirements for different crops and soil regions in the United States.
Biological Effects 6-7
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The Mn2+ form of manganese, in excessive amounts, can result in manganese toxicity. Manganese toxicity
usually occurs under conditions of reduced oxygen tension such as occur when soils are flooded and when
the pH is on the acid side.
In one study of plant damage, celery plants in a crop grown on reclaimed deep acid peat soil developed
necrotic lesions on leaflets and the petiole. Concentrations of manganese in the affected parts ranged from
10 to 270 ppm, depending on the extent to which the parts were affected.56 In nutrient culture
experiments, toxic effects developed when manganese concentrations in the tissues of tobacco reached
3,000 ppm24 and, in mango, 800 ppm.5 7 Bean (Phaseolus vulgaris) is particularly susceptible to manganese
toxicity and has been suggested as a test organism for the study of manganese toxicity. Healthy leaves were
found to contain 40 to 90 ppm of manganese and affected leaves 1,104 to 4,261 ppm.24 Manganese tends
to accumulate in the leaves of plants, thus plant tops are good indicators of the manganese concentrations
in plants and in the soil.
Microbial interactions with manganese have already been discussed in the section dealing with manganese in
the soil. Microbial action is extremely important in chemical transformations of manganese in the soil.
The effects of high concentrations of manganese in the soil upon plants and the microbiota have received a
great deal of attention; however, the effects of high concentrations of manganese on wildlife have received
little study, primarily because of lack of information.
6.3 REFERENCES FOR SECTION 6
1. Cotzias, G. C. Manganese. In: Mineral Metabolism: An Advanced Treatise. Vol. 2B. Comar, C. L., and
F. Bonner (eds.), New York, Academic Press, 1962. p. 403442.
2. Schroeder, H. A., J. J. Balassa, and I. H. Tipton. Essential Trace Elements in Man: Manganese, A Study
in Homeostasis. J. Chronic Dis. 79:545-571, 1966.
3. Rodier, J. Manganese Poisoning in Moroccan Miners. Brit. J. Ind. Med. 72:21-35, 1955.
4. DuBois, K. P. and E. M. K. Ceiling. Textbook of Toxicology. New York, Oxford Univ. Press, 1959. p.
146.
5. Cotzias, G. C. Manganese in Health and Disease. Physiol. Rev. 55:503-532,1958.
6. Maynard, L., and G. C. Cotzias. The Partition of Manganese Among Organs and Intracellular Organelles
of the Rat. J. Biol. Chem. 274:489-495, 1955.
7. Mahoney, J. P., and W. J. Small. The Biological Half-Life of Radio-manganese in Man and Factors
which Affect this Half-Life. J. Clin. Invest. 47:643-653, 1968.
8. Moore, W., W. Crocker, L. Hall, D. Adams, and J. F. Stara. Metabolic Aspects of Methylcyclopenta-
dienyl Manganese Tricarbonyl (MMT) in Rats. U. S. Environmental Protection Agency, Environmental
Toxicology Laboratory, Cincinnati, Ohio. 1973.
9. Alstatt, L. B., S. Pollack, M. H. Feldman, R. C. Reba, and W. H. Crosby. Liver Manganese in
Hemochromatosis. Proc. Soc. Exp. Biol. Med. 724:353-355,1967.
10. Mena, I., K. Horiuchi, K. K. Burke, and G. C. Cotzias. Chronic Manganese Poisoning. Individual
Susceptibility and Absorption of Iron. Neurology. 79:1000-1006, 1969.
6-8 MANGANESE
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11. Baxter, D. J., W. O. Smith, and G. C. Klein. Some Effects of Acute Manganese Excess in Rats. Proc.
Soc. Exp. Biol. Med. 779:966-970, 1967.
12. Witzleben, C. L. Manganese Induced Cholestasis: Concurrent Observations on Bile Flow Rate and
Hepatic infrastructure. Amer. J.Pathol. 57:617-625, 1969.
13. Jonderko, G., and Z. Szczurek. Pathomorphological Studies of Inner Organs in Experimentally Induced
Manganese Poisoning. Int. Arch. Gewerbepathol. Gewerbehyg. 23(2): 106-116, 1967.
14. Hysell, D. K., W. Moore, J. F. Stara, and R. Miller. Oral Toxicity of 2-Methycyclopentadienyl
Manganese Tricarbonyl (MMT) in Rats. U. S. Environmental Protection Agency, Environmental
Toxicology Laboratory', Cincinnati, Ohio. Paper in Process. 1974.
15. Moore, W., D. K. Hysell, R. Miller, R. Hinners, and M. Malanchuk. Exposure of Laboratory Animals t6
Atmospheric Manganese from Automotive Emissions. U. S. Environmental Protection Agency,
Environmental Toxicology Laboratory, Cincinnati, Ohio. Paper in Process. 1974.
16. Stara, J., W. Moore, D. Hysell, S. Lee, J. Lewkowsky, L. Hall, K. Campbell, and M. Wiester. Toxicology
of Methylcyclopentadienyl Manganese Tricarbonyl (MMT) and Related Manganese Compounds
Emitted from Mobile and Stationary Sources. In: Proceedings of the Fourth Annual Conference on
Environmental Toxicology. Air Force Medical Research Laboratory, Wright-Patterson Air Force Base,
Ohio. December 1973. p. 251-270.
17. Jonderko, G. and Z. Szczurek. Pathomorphological Changes in the Liver During Experimental Chronic
Manganese Poisoning. Int. Arch. Gewerbepathol. Gewerbehyg. 25:165-180, 1969.
18. Chandra, S. V., and S. P. Srivastava. Experimental Production of Early Brain Lesions in Rats by
Parenteral Administration of Manganese Chlorides. Acta Pharmocol. Toxicol. 25:177-183, 1970.
19. Borisenkova, R. V. Industrial Dust of Some Manganese-Containing Metal Alloys. In: Toxicology of
Rare Metals. IzraePson, Z. I. (ed.). Translated for the U. S. Atomic Energy Commission and the
National Science Foundation by the Israel Program for Scientific Translations. 1967. p. 200-210.
20. Shimizu, M., and N. Morikawa. Histochemical Studies of Succinic Dehydrogenese of Brain in Mice,
Rats, Guinea Pigs, and Rabbits. J. Histochem. Cytochem. 5:334-345, 1957.
21. Mandell, A. J., and C. E. Spooner. Psychochemical Research Studies in Men. Science. 762:1442-1453,
1968.
22. Klawans, H., Jr., M. M. Ilahi, and D. Shenker. Theoretical Implications of the Use of L-Dopa in
Parkinsonism. Acta. Neurol. Scand. 46:409-411, 1970.
23. Buttin, G., and A. Kornberg. Enzymatic Synthesis of DNA: Utilization of Deoxyribonucleoside
Triphosphates by E. coli Cells. J. Biol. Chem. 247(22):5419-5427, 1966.
. Manganese. Washington, D. C., National Academy of Sciences. 1973. 191 p.
25. Kawamura, R., H. Ikuta, S. Fukuzumi, R. Yamada, S. Tsubaki, T. Kodama, and S. Kurata. Intoxication
by Manganese in Well Water. Kitasaho Arch. Exp. Med. 18:145-169, 1941.
26. Wefring, K. Pneumonia in the Area of the Sauda Factories in Ryfytke (in Norwegian). Tids. Norsk.
Laeg. 49:553-568 and 602-612, 1929.
Biological Effects 6-9
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27. Elstad, D. Observations on Manganese Pneumonia (in German). In: Proceedings of VIII International
Congress on Industrial Medicine. Leipzig, Thieme. 1939. Volume 2, p. 1014-1022.
28. Elstad, D. Factory Smoke Containing Manganese as Contributing Cause in Pneumonia Epidemics in an
Industrial District (in Norwegian). Nord. Med. 3:2527-2533 and 2544-2552, 1939.
29. Riddersvold, J., and K. Halvorsen. Bacteriological Investigations on Pneumonia and Pneumococcus
Carriers in Sauda, an Isolated Industrial Community in Norway. Acta. Pathol. Microbiol. Scand.
20:272-298,1943.
30. Povoleri, F. Bronchopneumonia and the Production of Ferromanganese (in Italian). Med. Lav.
J
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43. Stadler, H. Histopathology of the Brain Resulting from Manganese Poisoning (Zur Histopathology des
Gehirns be: Manganvergiftung). Z. Ges. Neurol. Psychiat. 154:62-76, 1936.
44. Pentschew, A., F. F. Ebner, and R. M. Kovatch. Experimental Manganese Encephalopathy in Monkeys.
J. Neuropathol. Exp. Neurol. 22:488-499,1963.
45. Penalver, R. Manganese Poisoning. Ind. Med. Surg. 24:1-7, 1955.
46. Tepper, L. B. Hazards to Health. Manganese. New Eng. J. Med. 264:347-348,1961.
47. Whitlock, C. M., S. J. Amuso, and J. B. Bittenbender. Chronic Neurological Disease in Two Manganese
Steel Workers. Amer. Ind. Hyg. Ass. J. 27:454-459,1966.
48. Wynter, J. E. The Prevention of Manganese Poisoning. Ind. Med. Surg. 37:308-310,1962.
49. Cotzias, G. C., K. Horiuchi, S. Fuenzalido, and I. Mena. Chronic Manganese Poisoning. Clearance of
Tissue Manganese Concentrations with Persistence of the Neurological Picture. Neurology. 18:376-382,
1968.
50. Mena, I., J. Court, S. Fuenzalida, P. S. Papavasiliou, and G. C. Cotzias. Modification of Chronic
Manganese Poisoning: Treatment with L-Dopa and 5-Hydroxytryptophane. New Eng. J. Med.
252:5-10,1970.
51. Goldstein, M., B. Anagnoste, A. F. Battista, W. S. Owen, and S. Nakatani. Studies of the Amines in the
Striatum in Monkeys with Nigral Lesions. The Disposition, Biosynthesis and Metabolites of (H3)
Dopamine and (C14) Serotonin in the Striatum. J. Neurochem. 76:645-653,1969.
52. Poirer, L. J., T. L. Sourkes, G. Vovier, R. Boucher, and S. Carabin. Striatal Amines, Experimental
Tremor and the Effect of Harmaline in the Monkey. Brain. 59:37-55,1966.
53. Tanaka, S., and J. Lieben. Manganese Poisoning and Exposure in Pennsylvania. Arch. Environ. Health.
79:674-684,1969.
54. Alexander, M. Introduction to Soil Microbiology. New York, John Wiley and Sons. 1967.
55. Sparr, M. C. Micronutrient Needs - Which, Where, on What - In the United States. Soil Sci. Plant
Anal. 7:241-262,1970.
56. Gallagher, P. A. Manganese Toxicity in Celery. Nature. 276:391-392,1967.
57. Sahaya, R. K., and D. L. Singh. Effect of Excess Manganese on Mango Plants. Proc. Bihar Acad. Agric.
Sci. 5:121-124,1962.
Biological Effects 6-11
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7. CONTROL TECHNOLOGY
7.1 INTRODUCTION
The emission of manganese particulates probably will be controlled simultaneously with paniculate
emissions from steel furnaces and by the same particulate control equipment. There is no assurance,
however, that manganese emissions will be reduced proportionately with other particulate emissions
because a high percentage of manganese emissions are fine particles less than 1 nm in diameter.
The primary deficiencies in the control of trace metals result from a lack of basic information. Before a
meaningful program can be formulated and executed, key questions must be answered:
• Which of these metals are environmentally harmful?
• Where and to what extent are the harmful ones being released to the environment, and in what
physical/chemical form?
• What are the best ways to control release of harmful trace metals?
All three questions are being studied by groups within EPA; the last two are being considered in various
particulate emissions testing programs, in programs to develop control systems for combustion or
metallurgical processes, and in clean fuels programs.
Two basic approaches are involved in EPA work currently under way on emission control technology
applicable to trace metals: research and development for evaluation of existing devices for fine-particulate
control and demonstration of improved particulate control systems for specific major problem industries
(for example, electric utility and iron and steel). Pilot equipment for controlling sulfur oxides or
particulates is also being tested to determine its capability for removing other pollutants, including trace
metals such as manganese, chromium, vanadium, and nickel.
7.2 CONTROL DEVICES
Manganese from steel furnaces is controlled by various types of collectors, including electrostatic
precipitators, high-efficiency wet scrubbers, and fabric filters. Four physical factors make dust collection
economically difficult: the small particle size (as low as 0.01 Mm), the large volume of gas, the high gas
temperature, and the low economic value of the recovered material. Recent data indicate that electrostatic
precipitators may bejespecially effective for removing fine particulates.
7.3 MANGANESE FUEL ADDITIVES
Manganese fuel additives may cause problems associated with stationary as well as mobile sources. Control
of emissions from burning fuels containing antiknock and smoke-inhibiting additives may require special
systems. The hazards of these organic manganese additives will be identified in EPA's fuel additive research
and development program.
7-1
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA 600/6-75-002
4. 1
I I Lt AND SUBTITLE
Scientific and Technical
on Manganese
2.
Assessment Repor
/.AUIHOH(a)
9. P
12.
15
16
17.
a.
tKI-URMING ORGANIZATION NAME AND ADDRESS
National Environmental Research Center
Office of Research and Development
Environmental Protection Agency
Research Triangle Park, N. C.
SPONSORING AGENCY NAME AND ADDRESS
SUPPLEMENTARY NOTES
3. RECIPIENT'S ACCESSIOI*NO.
5. REPORT DATE
•t April 1975
6. PERFORMING ORGANIZATION CODE
8. PERFORMING ORGANIZATION REPORT NO'.
10. PROGRAM ELEMENT NO. 1AA001
ROAP No. 26AAA
11. CONTRACT/GRANT NO.
13. TYPE OF REPORT AND PERIOD COVERED
Final Report
14. SPONSORING AGENCY CODE
ABSTRACT
This report is a review and evaluation of the current knowledge of
manganese in the environment as related to possible deleterious effects
on human health and welfare. Sources, distribution, measurement, and
control technology are also considered. Manganese is associated with
small particles in the air. Concentrations measured in ambient air
averaged 0.1 yg/m3 (annual) with a maximum of 8.3 yg/m3 (annual) near a
large source.
In Norway, a form of pneumonia was attributed to airborne manganese
in a community where concentrations were measured at 46 yg/m3- Manganese
poisoning characterized by progressive central nervous system deterioration
has occurred under occupational exposure but apparently not from atmospheric
exposure. Control of fine particulate emissions should reduce manganese
emission considerably.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
Manganese Measurement
Transport Control
Pneumonia
CNS
Ecology
Toxicology
18.
DISTRIBUTION STATEMENT
Release unlimited
b.lDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Group
Manganese 07B 07B
Manganism 04A 13B
Environment 06E
06E.06J
06F
06T
19. SECURITY CLASS (This Report/ 21. NO. OF PAGES
Unclassified 71
20. SECURITY CLASS (This page) 22. PRICE
Unclassified
EPA Form 2220-1 (9-73) g_-|
U.S. GOVERNMENT PRICING OFFICE: 1975 - 640-883/670 - Region 4
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