1IR POLLUTION ASPECTS
ZINC MD ITS COMPOUNDS
-------
AIR POLLUTION ASPECTS
OF
ZINC AND ITS COMPOUNDS
Prepared for the
National Air Pollution Control Administration
Consumer Protection & Environmental Health Service
Department of Health, Education, and Welfare
(Contract No. PH-22-68-25)
Compiled by Yanis C. Athanassiadis
Litton Systems, Inc.
Environmental Systems Division
7300 Pearl Street
Bethesda, Maryland 20014
September 1969
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FOREWORD
As the concern for air quality grows, so does the con-
cern over the less ubiquitous but potentially harmful contami-
nants that are in our atmosphere. Thirty such pollutants have
been identified, and available information has been summarized
in a series of reports describing their sources, distribution,
effects, and control technology for their abatement.
A total of 27 reports have been prepared covering the
30 pollutants. These reports were developed under contract
for the National Air Pollution Control Administration (NAPCA) by
Litton Systems, Inc. The complete listing is as follows:
Aeroallergens (pollens) Ethylene
Aldehydes (includes acrolein Hydrochloric Acid
and formaldehyde) Hydrogen Sulfide
Ammonia Iron and Its Compounds
Arsenic and Its Compounds Manganese and Its Compounds
Asbestos Mercury and Its Compounds
Barium and Its Compounds Nickel and Its Compounds
Beryllium and Its Compounds Odorous Compounds
Biological Aerosols Organic Carcinogens
(microorganisms) Pesticides
Boron and Its Compounds Phosphorus and Its Compounds
Cadmium and Its Compounds Radioactive Substances
Chlorine Gas Selenium and Its Compounds
Chromium and Its Compounds Vanadium and Its Compounds
(includes chromic acid) Zinc and Its Compounds
These reports represent current state-of-the-art
literature reviews supplemented by discussions with selected
knowledgeable individuals both within and outside the Federal
Government. They do not however presume to be a synthesis of
available information but rather a summary without an attempt
to interpret or reconcile conflicting data. The reports are
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necessarily limited in their discussion of health effects for
some pollutants to descriptions of occupational health expo-
sures and animal laboratory studies since only a few epidemio-
logic studies were available.
Initially these reports were generally intended as
internal documents within NAPCA to provide a basis for sound
decision-making on program guidance for future research
activities and to allow ranking of future activities relating
to the development of criteria and control technology docu-
ments. However, it is apparent that these reports may also
be of significant value to many others in air pollution control,
such as State or local air pollution control officials, as a
library of information on which to base informed decisions on
pollutants to be controlled in their geographic areas. Addi-
tionally, these reports may stimulate scientific investigators
to pursue research in needed areas. They also provide for the
interested citizen readily available information about a given
pollutant. Therefore, they are being given wide distribution
with the assumption that they will be used with full knowledge
of their value and limitations.
This series of reports was compiled and prepared by the
Litton personnel listed below:
Ralph J. Sullivan
Quade R. Stahl, Ph.D.
Norman L. Durocher
Yanis C. Athanassiadis
Sydney Miner
Harold Finkelstein, Ph.D.
Douglas A. Olsen, Ph0D.
James L. Haynes
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The NAPCA project officer for the contract was Ronald C.
Campbell, assisted by Dr. Emanuel Landau and Gerald Chapman.
Appreciation is expressed to the many individuals both
outside and within NAPCA who provided information and reviewed
draft copies of these reports. Appreciation is also expressed
to the NAPCA Office of Technical Information and Publications
for their support in providing a significant portion of the
technical literature.
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ABSTRACT
Zinc and its compounds are generally considered to be
nontoxic; however, high concentrations of certain compounds
can produce harmful effects on humans, animals, and plants.
Zinc is commonly associated with other metals, such as lead,
copper, and cadmium, thus making the effects of zinc air
pollution difficult to distinguish from the effects caused by
its associated metals. Consequently, the specific effects and
the synergistic effects of these metals are not yet fully
understood. The most common effect of zinc air pollution is
the occurrence of "metal-fume fever" which results from the
inhalation of zinc oxide fumes. This nonfatal self-limiting
illness causes fever, nausea, and aching. Deaths have occurred
in humans from accidental exposure to zinc chloride fumes,
while cattle and horses have died from inhaling air contami-
nated with lead and zinc. Laboratory experiments have
confirmed the mildly toxic nature of zinc compounds. Limited
evidence exists concerning plant damage from high concentra-
tions of zinc dust and fumes; no evidence was found of damage
to materials.
Zinc and zinc compounds are emitted into the atmosphere
mainly from the refineries producing primary or secondary zinc
as a principal product or as a by-product, from the refining
of other metals containing zinc as an impurity, in the brass
manufacturing process, or in the application of zinc-galvanizing,
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Large concentrations of zinc emissions are possible from these
sources. Twenty-four-hour-average atmospheric concentrations
of zinc in urban areas of the United States have averaged
0.67 |ag/m3 , with an extreme value of 58.00 (ag/m3 recorded in
1963.
Adequate methods are available for the control of zinc
air pollution from the significant pollution sources. The
extent to which these methods are employed is not known. No
information has been found on the economic costs of zinc air
pollution or on the costs of its abatement. Methods are
available for determining the atmospheric content of zinc
compounds.
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CONTENTS
FOREWORD
ABSTRACT
1. INTRODUCTION 1
2. EFFECTS 2
2.1 Effects on Humans 2
2.1.1 Inhalation 2
2.1.2 Ingestion 6
2.1.3 Skin Contact 9
2.2 Effects on Animals 10
2.2.1 Commercial and Domestic Animals ... 10
2.2.2 Experimental Animals 10
2.2.2.1 Inhalation 10
2.2.2.2 Ingestion 12
2.2.2.3 Injection 14
2.3 Effects on Plants 16
2.4 Effects on Materials 17
2.5 Environmental Air Standards 17
3. SOURCES 19
3.1 Natural Occurrence 19
3.2 Production Sources 20
3.2.1 Mining 20
3.2.2 Smelting and Refining 20
3.2.2.1 Primary Zinc Production . „ . 20
3.2.2.2 Primary Production of Other
Metals 25
3.2.2.3 Secondary Zinc Refining ... 28
3.2.2.4 Secondary Brass and Bronze-
Melting Processes 29
3.3 Product Sources 30
3.3.1 Zinc Galvanizing 30
3.3.2 Brass Production 31
3.3.3 Incineration 32
3.4 Environmental Air Concentrations 33
4. ABATEMENT 34
4.1 Primary Zinc Smelting Operations 34
4.2 Secondary Zinc Melting Operations 36
4.3 Galvanizing Operations 38
4.4 Zinc-Alloy Sweating Operations 38
4.5 Secondary Brass Melting Operations 39
4.6 Open-Hearth and Electric-Arc Furnaces, Steel
Operations 40
4.7 Effectiveness 41
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5. ECONOMICS 42
6. METHODS OF ANALYSIS 43
6.1 Sampling Methods 43
6.2 Quantitative Methods 43
7. SUMMARY AND CONCLUSIONS 45
REFERENCES
APPENDIX
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LIST OF FIGURES
1. Size Ranges of Zinc in the Atmosphere
2. Lung Retention of Inhaled Particles as a Function
of Their Size for the Relevant Region 8
3. Trend Curves for Domestic Primary Zinc Production
and Slab Zinc Consumption 26
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LIST OF TABLES
1. Selected Data on Acute Zinc Toxicity in Experimental
Animals 15
2. Zinc Content in Commercially Important Zinc
Minerals 19
3. Leading Zinc-Producing Mines in the United States in
1967 in Order of Output 21
4. Mine Production of Recoverable Zinc in the U. S., By
States, Listed by Order of Their 1967 Production . . 22
5. Zinc Concentrations at Emission Points of a Zinc
Plant (Donora Area, 1948) 24
6. Estimated Atmospheric Pollution 24
7. Zinc Concentrations During Strike and Post-Strike
Periods in the Steel Industry in Four Communities
(U.S.A., 1956) and Corresponding Probability Levels . 28
8. Dust and Fume Emissions from a Zinc-Sweating Furnace
Controlled by a Baghouse 29
9. Analysis of Fumes from Zinc Galvinizing Kettles ... 31
10. Emissions from Various Types of Brass Furnaces ... 32
11. Smelting Gas Streams and Dust Burden Before Revision
for Filtration of Gases (1951) 36
12. Comparative Data on Hoods Used in Various Types of
Furnaces 37
13. Comparative Data on Air Pollution Control Equipment
Used in Two Secondary-Zinc Melting Operations .... 37
14. Reduction of Emissions from Galvinizing and Brass-
Melting Operations, Los Angeles County, 1950-1960 . . 41
15. Properties, Toxicity, and Uses of Some Zinc Compounds 58
16. Physicochemical Properties of Zinc 70
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LIST OF TABLES (Continued)
17. Primary and Redistilled Secondary Slab Zinc Produced
in the U.S 71
18. Consumption of Zinc in the U.S 72
19. Manufacturers of Zinc Slab in the U.S., 1968 .... 73
20. Primary Slab Zinc Plants by Group Capacity in the U.S.
in 1967 74
21. Secondary Slab Zinc Plants by Group Capacity in the
U.S. in 1967 75
22. Concentration of Zinc in the Air 76
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1. INTRODUCTION
Although zinc is an essential element of the human and
animal body, zinc and its compounds have been found to be toxic
under certain conditions. The most common hazards to health
are the inhalation of zinc oxide fumes (which produces metal-
fume fever) or accidental poisoning resulting from the ingestion
of acidic foods prepared in zinc-galvanized containers. Other
health hazards include corrosive effects on the skin from zinc
salts, irritation and damage to mucous membranes from zinc
chloride fumes, and a possible pneumonitis resulting from
inhaling zinc stearate.
Zinc and its compounds can be found in the atmospheric
environment. The most common sources of zinc emissions are
zinc refineries, the brass industry, and zinc-galvanizing
processes.
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2. EFFECTS
Zinc is generally considered nontoxic to humans,
animals, and plants, and produces no known harmful effects on
materials. However, in certain forms, zinc is toxic to
humans and animals when inhaled or ingested, or when in
contact with the skin. The degree of toxicity varies with
concentrations, type of compound, and mode of application.
2.1 Effects on Humans
Zinc, essential to all living organisms, is a normal
constituent of the human body. It is taken into the body in
the diet or by inhalation, and is eliminated by normal
processes of excretion and perspiration. When normal intake
values are exceeded, zinc poisoning occurs.
The properties, toxicity and uses of zinc compounds
are tabulated in the Appendix (Table 15).
2.1.1 Inhalation
Inhalation intake is normally an unimportant source of
zinc, except where high concentrations cause excessive amounts
of zinc to be added to the body. In this case, normal excre-
tion is not sufficient to discharge the excess, and poisoning
from air pollution occurs. This ailment is common to several
metals, and the most usual one attributable to zinc poisoning.
36
However, Patty notes that effects attributable to exposure
to zinc fumes may in part be caused by cadmium, which occurs
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uniformly as a contaminant in zinc.
Metal-fume fever as a result of zinc oxide inhalation
is a malaria-like illness which lasts approximately 24 hours
12
and is never fatal. The symptoms include fever, malaise and
depression, nausea and sometimes vomiting, dryness of the throat,
and aching of the head and body. After a few hours, the
patient perspires excessively as his temperature and white
blood cell count rise; a chill may occur when the temperature
reaches 103-104 , followed by a drop to normal temperature.
Occasionally, convulsions and mental confusion may occur, as
well as albuminuria and glucose in the urine. Measurable
effects include reduction in the vital capacity of the lung
for as long as 15 hours (in 36 out of 100 cases this condition
33
recurred weekly or even more frequently) and leukocytosis
6 *3 51 *?Q
(12-16 x 10 leukocytes/cm ). Lehmann postulated that
the inhaled zinc fume particles release modified protein into
the body, with the subsequent absorption of the modified
protein resulting in the characteristic response noted with
the injection of a foreign-body. A review of metal-fume
fever from inhalation of zinc oxide is given by Rohrs in the
American Medical Association's Archives of Internal Medicine
39
(1957).
Metal-fume fever is a potential hazard wherever zinc
oxide is an industrial product or by-product: zinc smelting,
manufacture of zinc oxide and zinc powder, the manufacture of
brass, and the welding of galvanized iron. The disease is
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58
self-limiting, and its treatment is symptomatic.
Matsui et al. studied 66 welders who had been exposed
to zinc oxide fumes and dust during electric welding of
galvanized iron pipe in the holds of a ship. Half of the
welders had been employed in welding for less than 5 years and
the remainder for from 5 to 30 years. In 49 of the studied
cases the following symptoms were observed, in order of
frequency:
1. Fever and chills 6. Chest discomfort
2. Arthralgia 7. Vomiting and nausea
3. Myalgia 8. Diarrhea
4. Throat irritation 9. Nasal catarrh
5. Chest irritation 10. Vertigo
Punctiform opacities developed in the lungs of half of
the welders. Measurement of zinc concentrations in the various
holds of the ship during welding showed the following values
(random observations):
Zinc oxide 145,700; 69,700; and 14,600 ug/m3
Zinc dust 245,100 and 81,600 Hg/m3
The degree of zinc concentration in the air appears to
be a factor in determining, the toxicity of zinc oxide. Two
healthy men exposed to 600,000 ^ig/m3 of zinc oxide in the air
developed moderate symptoms of zinc fever. One man, exposed
for 10.5 minutes, inhaled 48,000 fig of zinc and retained
24,000, while the other was exposed for 12 minutes, inhaled
74,000 (J.g of zinc, and retained 37,000. However, Batchelor
Q
et al. studied the case histories of 24 industrial workers
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engaged in zinc production. Although these men had been
exposed during working hours to zinc oxide fumes at concentra-
tions ranging from 3,000 to 15,000 l-ig/m3 for periods ranging
from 2 to 35 years, no acute or chronic effects had developed
and the mean zinc content of the blood was only slightly
above the normal level.
Zinc chloride is usually nontoxic in open atmospheres,
24
but may be toxic when inhaled in confined spaces. Hunter
reports one instance in which 10 deaths and 25 non-fatal
injuries occurred among 70 persons exposed to high concentra-
tions of zinc chloride fumes. The fumes were emitted from a
bank of 79 smoke generators 80 yards from the entrance to a
tunnel in which the men were working. The high concentration
of the fumes in an enclosed space, together with the elevated
heat of the particles, probably produced the highly toxic
effects. Deaths occurred either immediately after the
accident or within a few hours, apparently as the result of
shock together with massive pulmonary edema.
19
According to Gafafer, inhalation of zinc chloride may
produce severe pneumonitis. For instance, when used in smoke-
screening compounds, zinc chloride has been known to produce
insidious chemical pneumonitis among military personnel. It
is also reported to be extremely irritating to eyes, nose,
and throat, possibly producing perforation of the nasal septum,
Exposure to mists or fumes of zinc salts may irritate
the respiratory or gastrointestinal tracts. It has been
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suggested that zinc oxide may block the sebaceous gland ducts
and produce a papulopustular eczema in men packing zinc oxide
56 57
in barrels. Uotila et^ al_. consider zinc stearate to be a
possible causative agent in pneumonoconiosis.
11
In a statistical study, measured concentrations of
trace elements in 28 cities during the period 1957-1961 (with
26 biweekly samples per year) were plotted against the
corresponding rates of mortality from hypertension and arterio-
sclerotic heart disease. Zinc was found to be the only
pollutant, other than cadmium, with a significant coefficient
of association. The value of the correlation coefficient for
zinc was found to be 0.556.
Particle size, an important factor in the retention of
particulate matter by the respiratory system, may be related
to the differing toxic effects of zinc oxide and zinc chloride,
Figure 1 indicates the size (in microns) of zinc particles
found in the atmosphere; Figure 2 presents the retention of
particles by the respiratory system according to the size of
21
the particulate matter.
2.1.2 Ingestion
Normal dietary intake of zinc has been estimated at
10,000 to 15,000 |ag a day. Zinc poisoning may occur on
ingestion of excessive amounts with food and drink, resulting
in an acute transitory illness within minutes. The symptoms
include malaise, dizziness, tightness of throat, vomiting,
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METALLURGICAL DUSTS & FUMES
ZnO FUMES
SMELTER DUST & FUMES
HOT DIP GALVANIZING ZnO & ZnCI2
BRASS SMELTING ZnO
CONDENSED ZINC DUST
SPRAYED ZINC DUST
ELECTRICAL PRECIPITATORS
+4
AIR FILTERS - ATMOSPHERIC DUST
DUST CAUSING LUNG DAMAGE
( microscopic
*
CONVENTIONS
Range of Sizes
Small Range - Average
10
-3
10
-2
10
-1
10'
10
10
Particle Size ( Microns )
FIGURE 1. Size Ranges of Zinc in the Atmosphere
28
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MASS (%)
85
75
65
0>
0.
55
45
35
25
0.1
Total
Respiratory
Tract
Lower Respiratory Tract
0.2 0.3 0.4 0.5
1.0
[ Size In Microns I
3 45
MICRONS
00
FIGURE 2
Lung Retention of Inhaled Particles as a Function of Their
Size for the Relevant Region (Size of Zinc Particles)
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colic, and diarrhea. Treatment is symptomatic. The excess
zinc intake can usually be traced to the preparation of acid
36 37
foods in galvanized containers. '
In a study by Brown of 400 persons exposed to food
contaminated by zinc salts, zinc concentrations of up to 1,200
ppm (dry weight), or 0.12 percent by weight, were found in
some of the 300 or more who developed symptoms of poisoning.
In another case of mass poisoning, 44 out of 51 persons
who drank punch stored in a galvanized container became ill.
Quantitative analysis showed 3,675 ppm of zinc in the punch
(or 3.7 percent) by weight.
46
According to Schroeder e_t_ _al.., acute zinc intoxication
attributed to ingestion of acid foods prepared in galvanized
containers may in fact be caused by the toxic effects of
cadmium as a result of the 1.0 percent or more present in
galvanized materials.
Zinc ion ordinarily is not absorbed in sufficient
36
quantities to cause acute systemic effects.
2.1.3 Skin Contact
Development of dermatitis due to exposure to zinc salts—
such as zinc chromate, zinc cyanide, and zinc sulfate—has
19 18
also been reported. However, according to Freeman , it is rare.
Zinc chloride is caustic and may result in ulceration
of the fingers, hands, or forearms of persons who use it as a
flux in soldering or in other occupations. However, zinc is
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10
not unique in this respect, since this type of effect may be
caused by any strong acid or alkali.
2.2 Effects on Animals
2.2.1 Commercial and Domestic Animals
Stokinger has reported that cattle and horses were
poisoned by inhaling air contaminated by zinc and lead within
5 miles of zinc and lead smelters. The main effects included
emaciation and swelling of limb joints, causing severe
lameness and necessitating slaughter. These effects were
reproduced in animals that were fed samples of dust collected
in the area containing 45 percent lead, 5 percent zinc, and
traces of arsenic and fluoride. The additive effects of zinc
to lead, if any, were not stated.
2.2.2 Experimental Animals
2.2.2.1 Inhalation
Exposure of 132 rats (weighing 250 g each) to zinc
oxide fumes at 400 to 600 (ag/m3 for 10 to 120 minutes
(particle size: 0.7-1.6 M.) resulted in 16 deaths. Other
rats showed a marked fall in body temperature, which was
increased when zinc oxide was irradiated by ultraviolet light
for 50 seconds. In sacrificed animals, 1,100-5,500 u.g of
9
zinc for each gram of lung tissue was found.
Dogs and cats were found to tolerate exposures of
175,000-1,000,000 i-tg/m3 of zinc oxide for periods ranging from
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11
3 to 53 weeks. Nevertheless, glycosuria occurred in the dogs,
while fibrous degeneration of the pancreas was noted in some
of the cats. Exposure to 500-34,400 pg/m3 of zinc oxide for
from one month to one year produced no injury to rats.
Cats exposed to zinc ammonium sulfate (particle size:
<2.5 p) at concentrations ranging from 40,000 to 50,000 pg/m3
for 3 minutes showed increased resistance in total pulmonary
27
air flow, and decreased pulmonary compliance. Guinea pigs
exposed to 1,000 p,g/m3 for 60 minutes (particle size: 0.29-
0.74 p) showed only increased resistance in total pulmonary
flow.5
4
In another study, 42 guinea pigs weighing 200-300 g
were exposed to aqueous 'aerosols of zinc ammonium sulfate at
900 (150-1,800) pg/m3 for one hour (particle size: 0.29 p) .
Another set of 10 guinea pigs of the same weight was exposed
to 1,400 pg/m3 for one hour (particle size: 0.74 p). Still
another group of 21 comparable guinea pigs was exposed to
2,000 (1,500-2,430) pg/m3 for one hour (particle size: 0.5 p) .
Finally, 11 guinea pigs were exposed to 2,400 (1,100-3,600)
pg/m3 for one hour (particle size: 1.4 p). The results of
these tests indicated increased air flow resistance in all
cases except the last (particle size: 1.4 p.) . It was also
found that zinc ammonium sulfate was twice as potent as zinc
sulfate, and approximately three to four times more potent
than ammonium sulfate.
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12
2.2.2.2 Inqestion
40 41 42
Sadasivan ' ' found that rats fed diets containing
0.5 and 1 percent of zinc oxide showed reductions in the
weight and fat content of livers and femurs. As a result,
they developed subnormal calcium-phenyl ratios, increased
excretion of urinary and fecal nitrogen, decreased urinary
excretion of phenyl and sulfur (but increased fecal excretion),
increased urinary uric acid and creatinine, and increased
liver and kidney alkaline phosphatase activities .
22
Heller et al. reported that young rats fed a diet
containing 0.25 percent zinc in the form of zinc dust, zinc
chloride, zinc carbonate, and zinc sulfate showed no reduction
in growth or other apparent effects. Three generations were
maintained and fed the same diet without effects on vigor,
growth, and reproduction or obvious changes of the internal
organs.
62
Waltner et al. reported that feeding zinc carbonate
to rats induced anemia and osteoporosis.
Zinc acetate fed to rats for 4 months at doses of
10,000 to 15,000 |ag per day did not cause intoxication,
44
according to Salant. He also reported that zinc malate fed to
cats for 11 days to 2 months produced no toxic effects.
52
Button et al. found that rats could tolerate concen-
trations of 0.1 percent zinc in the diet, but that more than
0.5 percent reduced their capacity to reproduce, while 1
percent inhibited growth and caused severe anemia and death.
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13
These authors noted that the toxic level for zinc ions—as
measured by adverse effects on growth and hemoglobin levels
and reproduction—ranged between 0.5 percent and 1.0 percent
of the dietary intake for young rats. Diets which incorporated
these levels of zinc in the form of zinc carbonate for 39
weeks produced a drop in hemoglobin levels to 10,200 |jg/100 ml
for the 0.5 percent level and 6,100 iag/100, for the 1.0 percent
52
level, as well as hypochromic or microcytic anemia.
Dietary levels of 500,000 to 700,000 |jg zinc adminis-
tered to rats as zinc carbonate resulted in marked reduction
in liver catalase and cytochrome oxidase activities. These
effects were reversed by simultaneous administration of copper
sulfate. However, copper sulfate did not reverse the produced
4,-u • -u-^-4.- 16,60,61,64
growth inhibition. '
Studies of the relationship between zinc and calcium
have indicated that zinc decreases the normal deposition of
calcium and phosphorus in the bones of young rats. This effect
can be reversed by supplementary intake of the decreased
elements. Dietary intake of zinc can also cause an increase
in fecal and urinary elimination of calcium and phosphorus
and thus a reduction in retention of these elements. ' '
After administration of copper salts, normal rats and
rats intoxicated with zinc were found to have 27,000 Hg/kg
(dry weight) and 10,000 |ag/kg respectively of copper in the
heart.
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14
Glycosuria and albuminuria may develop in rabbits as
the result of prolonged and excessive zinc feeding or following
43
intravenous injection of zinc salts.
Duncan £jrt al.. , however, found that rats exposed to
diets with 0.4 percent zinc for 42 days became anemic after 4
days. The iron content of the liver dropped after 7 days, and
the copper content of the liver dropped consistently after 21
to 23 days, while the zinc content of the liver increased
12
rapidly after only one day on the diet.
12
Cox e_t al. report that rats fed 0.4 percent of the diet
as zinc in the form of zinc oxide were found to have reduced
iron, ferritin, hemosiderin, and hemoglobin in the liver. Of
the iron lost, 77 percent was from ferritin and 20 percent from
hemosiderin.
Data on zinc toxicity in experimental animals are
given in Table 1.
2.2.2.3 Injection
One group of 12 guinea pigs was injected with a single
dose of zinc silicate, and a comparable group with a single
dose of zinc beryllium silicate at concentrations of 0.75 ml
<49
of 1 percent salt suspension. Both groups developed lesions
consisting of histiocytes, lymphocytes, plasma cells, and
fibroblasts. In the group injected with zinc beryllium
silicate, these lesions were severe, reaching their maximum
level 2 weeks after the injection and progressing for 3 or 4
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TABLE 1
SELECTED DATA ON ACUTE ZINC TOXICITY
IN EXPERIMENTAL ANIMALS59
15
Zinc Compound
Sine acetate
Sine chloride
5ino diethyldithio-
carbamate
Sine ethylene-bis-
dithiocarbamate
Animala
Rabbit
Rat
Route
of
Admin.
or MLD
iv LD
Dosaqe p.q
976,000-1,
60,000-90,
966,000
000°
Rabbit
Rat
or
or
LD
50
600,000
>5,200,000
line phosphide Rat
Rat
line sulfate,6 ZnS04 = 7H9O Frog
^ Rat
Rat
Rat
Rabbit
Rabbit
Rabbit
Dog
Dog
Siram Mouse?
Rat
Ratcf
Rat?
Guinea pig
Guinea pig
Rabbit
Rabbit
Rabbit
or
or
sc
or
sc
iv
or
sc
iv
sc
iv
ip
or
ip
ip
or
ip
or
or
ip
LDSO
Lt>so
LD
LD
LD
LD
LD
LD
LD
LD
LD
LD50
LD50
LDso
LD50
LD50
LD50
LDS 0
LDSO
LD50
40,50012,900
46,700
149,000
2,200,000
330,000-440,000
49,300-61,000
1,914,000-2,200,000
>220, 000-440, 000
44,000
78,000
66,000-110,000
73,000*1,000
1,400,000*99,000
23,000*2,000
33,000*5,000
100,000-150,000
20,000-30,000
100,000-1,020,000
400,000
5,000-50,000
?: female;
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16
months. However, at 15 months only residual damage was
observed. During the second week, the respiratory epithelia
of bronchi and bronchioles were largely destroyed. In the
group injected with zinc silicate, less severe lesions
developed that reached their maximum level in 8 weeks. At 2
weeks the following symptoms were observed: (1) proliferation
of alveolar cells, (2) infiltration of alveolar walls by
histiocytes, (3) fusing of alveolar walls, and (4) oblitera-
tion of functional alveoli. At 4 weeks, proliferation increased,
and alveoli partitions greatly thickened. At 8 weeks, histio-
cytes became predominant, and some giant cells appeared.
Lesions were found to persist 3 months after the injection.
Subcutaneous injection of 0.5-1 g of finely powdered
13
zinc in rabbits resulted in intracapillary glomerulonephritis.
2.3 Effects on Plants
Although zinc is essential to living tissues of plants,
increasing the rate of photosynthesis in some instances,
excessive quantities of the metal may be expected to cause
7
adverse effects. For example, a Montana smelter discharged
daily into the atmosphere 3 tons of zinc, 2 tons of copper, and
2 tons of lead, in addition to 2,500 tons of sulfur oxides.
The resulting acidic condition of the atmosphere, acting to-
gether with the high concentrations of zinc and other metals,
has left the surrounding land barren and eroded. Studies have
been made of the adverse effects on plants resulting from
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17
excessive concentrations of a number of trace metals, such as
copper, cobalt, chromium, and nickel, but no study has been
17
found concerning the effects of zinc.
2.4 Effect on Materials
No information is available on the adverse effects on
materials of zinc in the environmental air. Actually, zinc
is used more than any other metal to protect materials from
20
corrosion by atmospheric pollutants.
2.5 Environmental Air Standards
Handbooks on the dangerous properties of industrial
materials list approximately 60 zinc compounds. Threshold
limit values (TLV) have been established only for zinc oxide
fumes. The 1967 American Conference of Government Industrial
Hygienists adopted the value of 5,000 (J.g/m3 for zinc oxide
fumes (averaged over the 8-hour workday) for those occupa-
tionally exposed. The value adopted is a revision of the
previously accepted value of 18,000 uxj/m3. This original TLV
was based on a study by a group of researchers who found no
acute or chronic illness in their examinations of 24 workers
exposed during working hours to zinc oxide fumes at levels of
about 3,000-15,000 Hg/m3 for periods of from 2 to 35 years.
A maximum allowable concentration for zinc oxide fumes
of 5,000 (-ig/m3 per 8-hour workday was established by 1965 in
28 55
both the Federal Republic of Germany and in the U.S.S.R.
-------
18
A tentative threshold limit value of 1,000 M-g/m3 was
set for those occupationally exposed to zinc chloride by the
American Conference of Governmental Industrial Hygienists in
1966.
-------
19
SOURCES
The primary sources of emissions of zinc compounds into
the atmosphere are zinc, lead, and copper smelting operations,
secondary processing to recover scrap zinc, and possibly the
incineration of zinc-bearing materials. Zinc oxide fumes are
the zinc compounds most commonly emitted from these sources.
3.1 Natural Occurrence
Zinc, widely distributed in the earth's crust, occurs
in small quantities in almost all igneous rocks. Sphalerite,
or zinc blende (ZnS)—the major zinc mineral—is commonly
associated with lead and iron sulfides. Most sphalerite has
cadmium associated as a coating or solid solution in quantities
ranging from traces to 2 percent.
Table 2 presents the zinc composition and content of
the economically important zinc minerals.
TABLE 2
30
CONTENT IN COMMERCIALLY IMPORTANT ZINC MINERALS
Zinc Minerals
Sphalerite (zinc blende)
Smithsonite (calamine)
Hemimorphite
Zincite
Willemite
Franklinite
Composition
ZnS
ZnCO3
(ZnOH)aSi03
ZnO
Zn8SiO4
(Fe,Zn,Mn)0:
(Fe,Mn)s03
Zinc %
67.0
52.0
54.2
80.3
58.5
15-20
Table 16 in the Appendix contains data on the physical
and chemical properties of zinc and its compounds.
-------
20
3.2 Production Sources
3.2.1 Mining
Mining methods vary with the type of ore body; however,
underground mining accounts for most of the production,
although some open-pit mining is done. Mining processes in-
clude size reduction, separation, and production of zinc
concentrates. No information was found on emissions or con-
centrations of zinc in the atmosphere in or around zinc mining
operations. While it is most probable that zinc dusts and/or
fumes are present, no instances were noted in the literature
of any illnesses connected with mining.
Table 3 lists the leading zinc-producing mines in the
United States. Table 4 presents data on the production of
zinc ore by state for the period. 1963-1967 .inclusive.
3.2.2 Smelting and Refining
3.2.2.1 Primary Zinc Production
The reduction of zinc ores and concentrates to zinc is
accomplished in primary reduction plants by the electrolytic
deposition of zinc from an ore solution, or by distillation in
retorts or furnaces. In either procedure the zinc concentrate
is roasted to eliminate most of the sulfur and to produce zinc
oxide.
The extraction of zinc from roasted concentrates involves
the heating of a mixture of roast and coke to about 1100°C.
Reduction of zinc from the oxide to the metal and distillation
-------
21
TABLE 3
LEADING ZINC-PRODUCING MINES IN THE UNITED STATES
IN 1967 IN ORDER OF OUTPUT32
Rank
Mine
State
County
Operator
Source of Zinc
(Ores)
1 Balmat N.Y.
2 Friedens-
ville Pa.
3 Sterling
Hill N.J.
4 Young Tenn.
5 Eagle Colo.
6 Bunker
Hill Idaho
7 Zinc Mine
Works Tenn.
8 Austinville
& Ivanhoe Va.
9 Star-
Morning Idaho
10 Ed.wards N.Y.
11 Idarad.o Colo.
12 New Market Tenn.
13 Jefferson
City Tenn.
14 Calhoun Wash.
15 U.S. and
Lark Utah
16 Flat Gap Tenn.
17 Mascot No.2 Tenn.
18 Shullsburg Wis.
19 Iron King Ariz.
20 Copperhill Tenn.
21 Deard.orff
Group 111.
22 Burgin Utah
23 Hanover N.Mex.
24 Oswaldo N.Mex.
25 Page Id.aho
St.Lawrence St. Joseph Lead Co,
Lehigh The N.J. Zinc Co.
Sussex
Jefferson
Eagle
Shoshone
Jefferson
Wythe
The N.J. Zinc Co.
American Zinc Co.
The N.J. Zinc Co.
The Bunker Hill Co.
U.S. Steel Corp.
The N.J. Zinc Co.
Shoshone Hecla Mining Co.
St.Lawrence St. Joseph Lead. Co.
Ouray and
San Miguel Idarado Mining Co.
Jefferson New Market Zinc Co.
Jefferson
Stevens
Salt Lake
Hancock
Knox
Lafayette
Yavapai
Polk
Hard.in and
Pope
Utah
Grant
Grant
Shoshone
The N.J. Zinc Co.
American Zinc Co.
U.S. Smelting, Refining,
and Mining Co.
The N.J. Zinc Co.
American Zinc Co.
Eagle-Picher Ind.. Inc.
Shattuck Denn Mining
Corp.
Tenn. Copper Co.
Ozark-Mahoning Mining Co.
Pb-Zn
Zn
Zn
Zn
Zn, Cu
Pb-Zn
Zn
Pb-Zn
Pb-Zn
Zn
Cu-Pb-Zn
Zn
Zn
Zn
Pb-Zn
Zn
Zn
Zn
Pb-Zn
Cu-Zn
F*-Pb-Zn
Kennecott Copper Corp. Pb-Zn
The N.J. Zinc Co. Zn
The N.J. Zinc Co. Zn
Am. Smelting and Ref. Co. Pb-Zn
*Fluorspar.
-------
22
TABLE 4
MINE PRODUCTION OF RECOVERABLE ZINC IN THE UNITED STATES,
09
BY STATES, LISTED BY ORDER OF THEIR 1967 PRODUCTION*3^
(Short Tons)
State
1963
1964
1965
1966
1967
Tennessee
New York
Idaho
Colorado
Pennsylvania
Utah
Wisconsin
New Jersey
Washington
New Mexico
Illinois
Virginia
Arizona
Oklahoma
Missouri
Kentucky
Kansas
Montana
Nevad.a
California
North Carolina
Oregon
95,847
53,495
63,267
48,109
27,389
36,179
15,114
32,738
22,270
12,938
20,337
23,988
25,419
13,245
321
1,461
3,508
32,941
571
101
13
3
115,943
60,754
59,298
53,682
30,754
31,428
26 ,278
32,926
24,296
29,833
13,800
21,004
24,690
12,159
1,501
2,063
4,665
29,059
582
143
*
122,387
69,880
58,034
53,870
27,635
27,747
26,993
38,297
22,230
36,460
18,314
20,491
21,757
12,715
4,312
5,654
6,508
33,786
3,858
225
*
103,117
73,454
60,997
54,822
28,080
37,323
24,775
25,237
24,772
29,296
15,192
17,666
15,985
11,237
3,968
6,586
4,769
29,120
5,827
335
113,065
70,555
56,528
52,442
35,067
34,251
28,953
26,041
21,540
21,380
20,416
18,846
14,330
10,670
7,430
6,317
4,765
3,341
3,035
441
Total
529,254 574,858 611,153 572,558 549,413
*Withheld to avoid, disclosing individual company confidential
data; excluded, from total.
-------
23
of the metal take place simultaneously. Zinc vapor passes
from the heated vessel into a condenser where it is converted
into liquid form and withdrawn. The reduction reaction of
zinc oxide can be summarized by the reaction
ZnO + C - Zn + CO
During the refining process, zinc fumes and dust are
discharged into the atmosphere. In spite of the fact that
hoods, baghouses, and Cottrell control equipment are employed,
a flag of white zinc oxide fume arising from the plant is a
47
distinctive characteristic of the zinc retort plant.
47 25
Stern and Johnson et al. state that the concentration of
zinc fume emitted is low; however, no quantitative information
was found.
The famous "Donora incident" of 1948 provides some
insight into the possible emissions of zinc from a zinc-
45
producing plant. Data from Schrenk are presented in Tables
5 and 6. It is significant to note that cyclone dust collectors,
Cottrell precipitators, and 125-foot-high stacks were in use at
this plant. In the sinter plant, the main gas stream passed
through Cottrell precipitators, and the effluent from these
units was vented to the atmosphere through two stacks 110 feet
high. Hot gases leaving the furnaces of the smelter plant
first passed through a waste heat boiler and then were dis-
charged to the atmosphere through a 125-foot stack. Despite
these precautions, emissions of zinc compounds were substantial.
Table 5 indicates emission concentrations from the roaster and
-------
24
the sinter plant; Table 6 provides estimates of the amount of
zinc pollution per day from a zinc-producing plant.
45
TABLE 5
ZINC CONCENTRATIONS AT EMISSION POINTS OF A ZINC PLANT
(DONORA AREA, 1948)
Zinc
Concentration
% of total
Emission Points
Sampling* Time
Start Min
j-ig/m particulate
Roaster (Hegeler),
charging platform
Normal operation
Raking Period
Sinter Plant
Cottrell Exhaust
Stacks
—
—
11:15
11:25
2:25
12:01
3:15
am
am
pm
pm
pm
13
5
5
5
10
5
5
4,800
19,400
62,200
26,900
26,300
64,000
45,700
52
43
17
10
9
8
8
*Sampling information:
Collection instrument: electrostatic precipitator.
Sampling rate: 2 ft3/min.
Temperature range (in sampled stacks): 135° to 1,000° F,
Method of determination: colorimetric: dithizone using
the Beckman DU spectrophotometer.
TABLE 6
ESTIMATED ATMOSPHERIC POLLUTION
(LOADS OF ZINC FROM A ZINC PLANT)
Sinter Plant Spelter Plant
(2 Stacksr 5 Cottrells) (9 boiler-stacks)
Total air flow from
stack (ft3x!06)/day
Estimated atmospheric
pollution load,
Ib of ZnO/day
ZnO as % of total
particulate
86.4
250.
25%
600
24,400
91.6%
-------
25
Data on the production and consumption of zinc in the
United States for the years 1963-67 inclusive are given in
Tables 17 and 18 in the Appendix. The major producers of slab
zinc are listed in Table 19, and the primary and secondary
slab zinc plants and their capacity in Tables 20 and 21 of the
Appendix.
The outlook for future demand in the United States is
one of continued growth with little change in the pattern of
32
present use. Figure 3 indicates the growth trends for U.S.
production and consumption of zinc; the continuous growth
record may be significant in relation to air pollution by zinc
materials.
3.2.2.2 Primary Production of Other Metals
Zinc, or zinc dusts and fumes, are produced as a by-
product in the refining of other metals, the most significant
of which are copper, lead, and steel. Commercial quantities
of zinc are produced in the refining of copper and lead; small
nonrecoverable quantities are produced in the production of steel,
In 1967, 33 percent of the zinc produced was obtained from lead-
zinc ores; 2 percent from lead ores; 6 percent from copper-lead,
copper-zinc, and copper-lead-zinc ores; and 6 percent from all
32
other combinations of metal ores. The balance (53 percent) of
zinc produced in 1963 was obtained from zinc ores. Therefore,
emissions of zinc from plants producing copper, lead, and steel
can be a source of air pollution if not controlled.
-------
26
SHORT TONS
X (103 )
AVERAGE PRODUCTION (SMOOTHEDI
1,400
1,200
1,000
O AVERAGE CONSUMPTION
• AVERAGE PRODUCTION
PRODUCTION (1881 - 1967) 10 YEAR AVERAGES (ANNUAL)
EXCEPT FOR 1961 -1967 PERIOD
CONSUMPTION 11941 - 19671 5 YEAR AVERAGES-EXCEPT
FOR 1966-1967 PERIOD
1881- 1891-
1890 1900
1901 -
1910
1911- 1921- 1931
1920 1930 1940
1941 -
1950
1951 - 1961 - 1971 - 1981 -
1960 (1967) 1980 1990
FIGURE 3
Trend Curves for Domestic Primary Zinc
Production and Slab Zinc Consumption's
-------
27
In the manufacture of steel from pig iron and scrap
steel, impurities are removed by oxidation. Open-hearth
furnaces, which accounted for over 85 percent of the steel
produced in the United States in I960, were found to emit a
particulate discharge containing a zinc concentration of 10
to 15 percent; the zinc content stems from the use of scrap
material containing galvanized steel. Zinc oxide comprised
39 percent of the discharge from electric-arc furnaces,
which produced 10 percent of the total steel capacity of
1960. Since typical discharges can average as much as 137
pounds of dust and fume per hour from a 50-ton open-hearth
furnace, the quantity of zinc emitted can be considerable.
Even when precipitators are used that are 98.98 percent
effective, a 63-ton open-hearth furnace emits 0.406 pounds of
dust per hour, which equals 0.04-0.06 pounds of zinc per
14
hour.
A steel strike provided the opportunity to study the
extent to which the iron, steel, and zinc industries are
contributing to zinc air pollution. The strike which
lasted for 2 weeks, affected the refinery industry in a
number of communities. Measurements of atmospheric concentra-
tions of air pollutants were made during the strike period and
again after the strike was settled. The results are
summarized in Table 7. It was found that of the many
pollutants sampled, only lead, zinc, and the sulfates showed
significant differences in concentrations at the two sampling
-------
28
TABLE 7
ZINC CONCENTRATIONS DURING STRIKE AND POST-STRIKE PERIODS
IN THE STEEL INDUSTRY IN FOUR COMMUNITIES
(U.S.A., 1956) AND CORRESPONDING PROBABILITY LEVELS53
Average Concentrations
Community ( M-g/m3 )
Post-Strike Strike Difference
Birmingham
Donora
East Chicago
Allegheny County
700
11,800
1,600
1,100
200
100
300
100
500
11,700
1,300
1,100
No . of Proba-
Samples bility"
9
15
9
8
0.028
0.001
0.002
0.039
a
Probability of obtaining the observed differences by
chance alone, limit of statistical significance: P=0.05.
The only community with a zinc plant (closed during
the strike).
times. Concentrations of iron and zinc during the strike
period were only a fraction of those observed after operations
were resumed. In Donora, the only community with a zinc plant,
the concentrations during and after the strike differ by two
orders of magnitude.
3.2.2.3 Secondary Zinc Refining
Scrap zinc may be converted into usable metal by the
use of refining methods similar to those for primary zinc, or
by melting the scraps in sweat furnaces. In the sweating
process, separation of the metals occurs as a result of their
differing melting temperatures. Air pollutants emitted from
a zinc-sweating plant primarily consist of zinc fumes, which
are negligible at low furnace temperatures, but become
-------
29
significant at high temperatures (above 900°F). Measurements
made at a zinc die-cast-sweating operation (using die-cast
products such as auto grilles, license plate frames, and zinc
skims and drosses) are shown in Table 8.
TABLE 8
DUST AND FUME EMISSIONS FROM A ZINC-SWEATING
FURNACE CONTROLLED BY A BAGHOUSE14
Type of furnace Reverbatory
Process weight, Ib/hr 2,800
Material sweated Zinc casting
Average gas temperature 180°F
Concentration (Ug/m3)
Baghouse inlet 700
Baghouse outlet 250
Dust and fums emission (Ib/hr)
Baghouse inlet 13.5
Baghouse outlet 0.5
3.2.2.4 Secondary Brass and Bronze-Melting Processes
The remelting of high-purity copper and bronze produces
only small amounts of volatilized metals. With good melting
practices, total emissions should not exceed 0.5 percent of the
process weight. However, brasses containing 15 to 40 percent
zinc are poured at about 2,200°F, and vaporization of zinc is
therefore inevitable. Emissions of zinc fumes may vary from
less than 0.5 percent to 6 percent or more of the total metal
charge and from 2 to 15 percent of the total zinc content of
the charge, depending on the composition of the alloy, the
14
type of furnace, and the procedures used.
-------
30
A recent study of a secondary metal smelter in
Baltimore, Md. (K. Hettlemans & Sons, subsidiary of Minerals
and Chemicals Philipp Corp.)/ revealed considerable emission
of zinc oxide dust. The input to this operation is raw scrap
of used brass or bronze (radiators, castings, plumbing
fixtures, valve bronzes, naval alloys, manganese-bronze ship
propellers, etc.). The output consists of (1) alloys for
plumbing and (2) zinc oxide dust (containing chlorine and
lead). The installation of proper air pollution control
devices (described under methods of abatement) appears to have
solved the emission problem.
3 . 3 Product Sources
Zinc and its compounds are emitted into the atmosphere
as a result of many different uses of these materials. The
most significant, from an air pollution view, seem to be the
use of zinc in galvanizing of iron or steel, and its use in
producing alloys of brass. Other possible sources of pollution
include incineration of zinc-bearing products.
3.3.1 Zinc Galvanizing
This process involves coating iron or steel with a
thin layer of zinc by immersion in molten zinc at temperatures
of 840° to 860°F.
-------
31
Ths subprocesses involved are:
1. Degreasing
2. Rinsing
3 . Pickling in acid, bath
4. Rinsing
5. Prefixing in zinc ammonium chloride
6. Immersing the article in molten zinc through
a molten flux cover
7. Finishing
The emissions from galvanizing kettles have been shown
14
to contain zinc, zinc oxide, and zinc chloride, among other
pollutants.
Results of the chemical analysis of the fumes collected
from zinc-galvanizing kettles by a baghouse and by an electric
precipitator are shown in Table 9.
TABLE 9
ANALYSIS OF FUMES FROM ZINC GALVANIZING KETTLES14
Baghouse Precipitator
(% wt) (Job-shop kettle) (Chain-link galv^J
Zinc 15.8 6.5
ZnO 3.6 15.2
ZnCl2 4.9
Total 24.3 21.7
Fumes discharged from continuous galvanizing of chain-
link fence were shown to have a different composition: 15.2
percent of zinc chloride and 6.5 percent of zinc oxide.
3.3.2 Brass Production
Brass is made by adding zinc to molten copper. The
properties of brass depend upon the zinc content, which ranges
-------
32
from 5 to 40 percent. Zinc fumes, a natural product of this
process, if uncontrolled will escape into the atmosphere.
Data on the emissions from different types of furnaces
producing brass are presented in Table 10.
TABLE 10
EMISSIONS FROM VARIOUS TYPES OF BRASS FURNACES14
Zinc
in Alloy
Produced
Typa of Furnace (%)
Rotary 5
Rotary 14.7
Rotary 5
Electric (induction) 38
Electric (induction) 23
Electric (induction) 23
Cyl . reverberatory 4
Crucible 2
Crucible 35
Crucible 37
Crucible 12
Pouring
Temperature
(°F)
No data
No data
No data
No data
No data
No data
No data
2,100
2,100
1,900-2,100
1,800
Process
Weight
Jlb/hr)
1,104
3,607
1,165
1,530
1,600
1,500
273
1,250
470
108
500
Fume
Emission
(Ib/hr)
22.5
25.
2.73
3.47
0.77
0.54
2.42
10.9
8.67
0.05
0.882
Particulate emissions from furnace stack gases in
copper-base alloy foundries may contain as much as 98 percent
of zinc oxide and/or lead. A series of tests in Los Angeles
County showed an average of 59 percent of zinc oxide in the
fumes from the manufacture of representative red and yellow
brass and a dust-and fume-loading at stack conditions of from
0.022 to 0.771 grain per cubic feet.
3.3.3 Incineration
Little is known about zinc pollution of the atmosphere
resulting from incineration of waste material. It is probable
-------
33
that small quantities of zinc are discharged into the air from
incineration of zinc-bearing materials, such as dry-cell
batteries, or reduction of old auto bodies.
3.4 Environmental Air Concentrations
Air quality data obtained from the National Air
Sampling Network are shown in Table 22 in the Appendix. The
national 24-hour average concentration of zinc in the atmosphere
was 0.67 (ag/m3 during the period 1960-64; the maximum value
recorded during that period was 58.00 |ag/m3 in 1963 at East
St. Louis, 111.
Measurements made in 1954 in seven major European
49
cities showed the following mean annual values for
atmospheric zinc concentrations:
Oslo 1.360 |ag/m3
Liverpool 0.279 "
Dublin 0.240
Helsinki 0.196
Belfast 0.160
N. Wales 0.107
Copenhagen 0.000 "
The high concentration of zinc in Oslo was attributed
to the large number of special industries located there.
-------
34
4. ABATEMENT
4.1 Primary Zinc-Smelting Operations
Following is a description of the system of air
pollution control equipment used at a major zinc-smelting
operation.
Sinter machine exhaust gases are preconditioned to
lower the electrical resistance of the gases. They are then
processed in electrostatic rod-curtain-type precipitators,
further treated in cyclone scrubbers, and then vented to the
atmosphere through a 402-foot chimney. Plant dusts and fumes
(other than from the sinter machine) are collected in a
275,000 CFM bag collector which discharges to a 168-foot
chimney.
Sinter machines, in the agglomeration of the roaster
calcines, produce large quantities of zinc fume. As zinc
fume has high electrical resistance, it must be preconditioned
prior to processing by the electrostatic precipitators. This
conditioning is achieved by treating the fumes with large
quantities of finely atomized water in conditioning chambers.
Water at a pressure of 500 psi and a flow of 350 gpm is used
to achieve the required atomization.
Following the preconditioning, the gases and fumes pass
to rod-curtain-type electrostatic precipitators, operating
with a collection efficiency of 90 percent, with an associated
dust loading in the exit gases of 0.05 grains per cubic foot.
-------
35
Two concrete cyclone scrubbers (25 feet in diameter by
50 feet high) further treat sintering gases before they are
vented to the atmosphere. Their collection efficiency is
approximately 50 percent, so that the overall removal of furae
from the sintering gases is of the order of 95 percent, with
a concentration in stack gases of approximately .02 grains
per cubic foot STP-*
For the control of dust and fume other than from the
sinter machines, a central cloth-bag collector system is used
with a capacity of 275,000 cubic feet per minute. The dust-
loading entering the collector is about 4 grains per cubic
foot, and the collector's efficiency is 99.9 percent. The
dust has approximately the same composition as sinter and is
returned to the sinter circuits.
The collector is a 56-section Dracco with 4,480 bags
(56 sections by 80 bags each, the bags measuring 8 inches by
10 feet). The discharge duct is 11 feet in diameter and leads
to the inlet of a No. 19 SOLD Buffalo exhauster discharging at
a 168-foot masonry chimney- The exhauster is operated at
225,000 cfm (total at high speed operation).
The above described system is in use in the Josephtown
zinc-smelting plant. No comparative data exist for the major
primary zinc-smelting operations identified elsewhere.
*STP: Standard temperature, pressure.
-------
36
The quantities of zinc dust emitted to the atmosphere
by a copper-smelting plant in Manitoba before installation of
o o
a filtration system are listed in Table 11. After
installation of an efficient filtration system, each day more
than 35 tons of dust with a zinc content of approximately 30
percent were recovered.
TABLE 11
SMELTING GAS STREAMS AND DUST BURDEN
BEFORE REVISION FOR FILTRATION OF GASES (1951) 38
Dust Burden
Flow CFM Temperature
Dryer gas
Roaster gas
Reverb gas
Combined flow
at Cottrells
Cottrell recovery
Cottrell loss
Converter gas
Cottrell recovery
Cottrell loss
at
18,
67,
100,
204,
100,
NTP
000
000
000
000
000
(UF)
325
350
1020
440
800
(tons/day)
Zinc
Zinc
% (tons/day)
550.62
4818.3
95
71
24
23
6
17
3
8
18
12
9
23
28
16
32
.7
. 1
.4
.7
.2
.0
.6
.7
.8
0.
4.
8.
12.
6.
5.
6.
1.
5.
037
45
83
06
53
53
58
00 ,
58
4.2 Secondary Zinc Melting Operations
When hoods of the proper type are used, they prove to
be very effective in all the three types of furnaces (Belgian,
distillation, and muffle). The hoods are usually placed
directly above the furnace or over the charge in doors of the
sweat chambers (muffle furnaces). Comparative data on hood
efficiency for the various types of furnaces are given in
Table 12.
-------
37
TABLE 12
COMPARATIVE DATA ON HOODS USED
IN VARIOUS TYPES OF FURNACES38
Type of furnace
Belgian retort
Distillation retort
Hood above the retort
Hood on "speise hold"
Muffle furnaces
Hood over charger door
Hood over discharger/screen
Hood over residue-tapping spout
Ventilation
(cfm)
2,000
200
3,200
5,500
8,700
Indraft Velocity
(fpm)
175
400
250
700
250
900
Baghouses and precipitators are the most commonly and
efficiently used control equipment in all the above-mentioned
types of furnaces. Relevant data on a few control systems in
use are given in Table 13.
TABLE 13
COMPARATIVE DATA ON AIR POLLUTION CONTROL EQUIPMENT
USED IN TWO SECONDARY-ZINC MELTING OPERATIONS38
Data
Case A
Case B
Output (product)
Type of furnace
Type of equipment
used
Type of baghouse
Cloth filtering
area (ft^)
Type of cloth
Filtering velocity
(fpm)
Efficiency, total
Baghouse
Cyclone
Zinc or ZnO
Muffle
Baghouse and
cyclone
6-section, pull-
through type
5,600
Glass
3
90%
5-lO%
ZnO
Muffle
Baghouse and cyclone
9-section, standard
16,848
Orion
1.8
100%
80%
20%
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38
4.3 Galvanizing Operations
In job shops it is necessary to use high-canopy or
room-type hoods. The amount of ventilation volume necessary
for use with high-canopy hoods as well as the size of the
collector required increases considerably with the height of
the hood. Low-canopy hoods can be used for a galvanizing kettle
when head room is not required.
Due to the fact that particles range from submicron to
2 microns in size, the only efficient control devices are
baghouses or high-efficiency electrostatic precipitators (used
in the presence of oil mists).
Cotton bags have proved effective as collectors in most
galvanizing operations. The tendency of fumes to coagulate
makes it difficult to clean the bags with mechanical shakers.
Because of high velocities (above 2 fpm) which also make
cleaning of the bags extremely difficult and because of the
large exhaust volumes required, large-sized baghouses are
needed.
4.4 Zinc-Alloy Sweating Operations
The types of hooding and ventilation mentioned in a
foregoing section on brass-melting operations are also used
with good results in zinc-alloy sweating operations. In low-
temperature operations, auxiliary hooding is usually necessary,
varying with the type of sweating operation. Normally, an
inlet velocity of 100 to 200 fpm is sufficient to prevent
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39
emissions to the atmosphere.
A baghouse together with an afterburner is used to
collect the dust and fumes. The maximum recommended baghouse
filter velocity is 3 fpm.
4.5 Secondary Brass Melting Operations
The collection of zinc oxide fumes in brass-melting
operations is a problem both economically and technically-
Most zinc oxide particles are of submicron size and can be
handled by precipitators; however, zinc oxide particles
emitted from brass furnaces are found in the 0.3-1.0 \j. range
(Figure 1, Page 7), where even the most efficient precipitators
operate at low efficiency ratios.
As already stated, zinc oxide fumes have been found to
represent, on the average, 59 percent of the stack emissions
from brass furnaces. The absolute amount of dust and fume
from these sources varies from 0.022 to 0.771 grains per
standard cubic foot at stack conditions.
The usual controls for the various types of furnaces
are slag (crushed glass) and flux (borax, soda ash, etc.)
covers. However, it is necessary to control the thickness of
slag covers in order to minimize emissions. in addition, if
the alloy contains more than 7 percent zinc, these covers do
not sufficiently suppress emissions. On the other hand, flux
covers usually destroy the furnace walls.
Of all the available types of air pollution control
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40
equipment, only baghouses have proved sufficiently economical
and efficient for secondary-brass-smelting operations.
Electric precipitators have not proven entirely satisfactory
for the control of zinc oxide fumes because of (1) the high
resistivity of the fumes, (2) the unavailability of small
high-voltage precipitators suitable for the average size of
the operations in question, and (3) the fact that at the
particle-size range below 0.5 micron the efficiency of
electrostatic precipitators drops considerably.
Scrubbers (dynamic) or washers (mechanical) have
proved (1) to be ineffective in the submicron range, (2) to
consume much power, (3) to be subject to mechanical wear, and
(4) usually to necessitate separation of the fumes and other
particulate matter.
Collectors (centrifugal) are also inefficient in the
submicron range. In one instance, a tested cyclone (wet) had
to be replaced by baghouses in the end.
4.6 Open-Hearth and Electric-Arc Furnaces, Steel Operations
Metal fumes and oxides from open-hearth and electric-
arc furnaces for making steel alloys amount to 99 and 75
percent (by weight) of the total emissions respectively. The
corresponding percentages of zinc are 15 and 37. in spite of
this, no air pollution control devices have been used or
recommended. The alleged reason is that the absolute amounts
of particulate emission have been found to be 0.00278 grain
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41
per standard cubic foot or 0.14 pound per hour (for a furnace
rated at 1,000 pounds capacity). This has been considered
"low."
4.7 Effectiveness
A measure of the effectiveness of pollutant-control
devices employed in the zinc and related industries can be
seen from Table 14, which presents data on the reduction of
emissions into the atmosphere of Los Angeles County during the
period 1950-1960.
TABLE 14
1
REDUCTION OF EMISSIONS FROM GALVANIZING AND BRASS-
MELTING OPERATIONS, LOS ANGELES COUNTY, 1950-1960
Reduction in Net Emissions
Melted Air Pollution to the
or Refined Due to Controls Atmosphere
(tons (tons (tons
Jdetal per month) per month) per month)
Zinc (except zinc
oxide production
and galvanizing)
Galvanizing (zinc)
Copper and Bronze
Red Brass
Semi -Red Brass
Yellow Brass
Totals (rounded'
3,000
600
1,500
2,000
2,000
1,200
) 10,300
24
12
4
3
18
33
124
2
4
1
1
2
2
12
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41
per standard cubic foot or 0.14 pound per hour (for a furnace
rated at 1,000 pounds capacity). This has been considered
"low."
4.7 Effectiveness
A measure of the effectiveness of pollutant-control
devices employed in the zinc and related industries can be
seen from Table 14, which presents data on the reduction of
emissions into the atmosphere of Los Angeles County during the
period 1950-1960.
TABLE 14
1
REDUCTION OF EMISSIONS FROM GALVANIZING AND BRASS-
MELTING OPERATIONS, LOS ANGELES COUNTY, 1950-1960
Reduction in Net Emissions
Melted Air Pollution to the
or Refined Due to Controls Atmosphere
(tons (tons (tons
Jdetal per month) per month) per month)
Zinc (except zinc
oxide production
and galvanizing)
Galvanizing (zinc)
Copper and Bronze
Red Brass
Semi -Red Brass
Yellow Brass
3,000
600
1,500
2,000
2,000
1,200
24
12
4
3
18
33
2
4
1
1
2
2
Totals (rounded) 10,300 124 12
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42
5. ECONOMICS
No information has been found on the economic costs of
zinc air pollution or on the costs of its abatement.
Data on the production and consumption of zinc are
presented in section 3.
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43
6. METHODS OF ANALYSIS
6.1 Sampling Methods
Dusts and fumes of zinc compounds may be collected by
any method suitable for collection of other dusts and fumes;
the impinger, electrostatic precipitator , and filters are
commonly used. The National Air Sampling Network uses a high
volume filtration sampler.
6 . 2 Quantitative Methods
The ring-oven technique of analysis has been adapted
to the determination of zinc in the range 0.05 to 1 l-Lg/m3 .
The reagent, 0-mercaptothenalaniline is used as coloring
agent. The method is specific for zinc and may be used in
air pollution studies. The limit of detection is 0.04 |ag,
although previous studies had suggested 0.1 |ag as the lower
limit.
A spectrophotometric method has been developed for the
determination of zinc; concentrations down to 0.1 [ig can be
26
measured using l-(2-thiazolylazo)-2-naphthol.
An instrument capable of monitoring and recording air
concentration of zinc sulfide pigment (a phosphorescing tracer)
on a real-time basis has been developed. The instrument has
a 35
a limit of detection of about 0.25
Emission spectroscopy has been used by the National Air
Pollution Control Administration for zinc analysis of samples
2
from the National Air Sampling Network. The samples are
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44
ashed and extracted to eliminate interfering elements. The
minimum detectable zinc concentration by emission spectroscopy
is 0.24 \lg/m3 for urban samples and 0.08 (-Lg/m3 for nonurban
samples. The difference in sensitivities results from the
3
different extraction procedures required for urban samples.
Thompson et al. have reported that the National Air
Pollution Control Administration uses atomic absorption to
supplement analyses obtained by emission spectroscopy- The
method has a minimum detectable limit of 0.0002 M.g/m3 based
on a 2,000 m3 air sample.
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45
7. SUMMARY AND CONCLUSIONS
It is not possible to assess fully the role of zinc and
its compounds as air pollutants. Despite the fact that specific
effects attributed to certain compounds of zinc have been noted,
the common association of zinc with other metals, and the
frequent presence of toxic contaminants (such as cadmium) in
zinc materials, raise questions Which have yet to be answered
concerning the synergistic effects of these metals.
The most common effects of zinc poisoning in humans are
nonfatal metal-fume fever, caused by inhalation of zinc oxide
fumes, and illnesses arising from the ingestion of acidic
foods prepared in zinc-galvanized containers. Zinc chloride
fumes, though only moderately toxic, have produced fatalities
in one instance of highly concentrated inhalation. Zinc
stearate has been mentioned as a possible cause of pneumonitis.
Zinc salts, particularly zinc chloride, produce dermatitis upon
contact with the skin.
Accidental poisoning of cattle and horses has occurred
from inhalation of a combination of lead- and zinc-contaminated
air. Zinc oxide concentrations of 400 to 600 |ag/m3 are toxic
to rats, producing damage to lung and liver, with death
resulting in approximately 10 percent of the cases. Although
dogs and cats were found to tolerate high concentrations
(up to 1,000,000 Hg/day) of zinc oxide for long periods, evidence
of glycosuria and damage to the pancreas became apparent.
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46
Concentrations of 40,000 to 50,000 M-g/m3 of zinc ammonium
sulfate produced no appreciable effects on cats.
Some evidence exists of damage to plants from high
concentrations of zinc in association with other metals. No
information was found on damage to materials from zinc or its
compounds in the atmosphere.
The primary sources of zinc compounds in the atmosphere
are the zinc-, lead-, and copper-smelting industries, secondary-
processing operations which recover zinc from scrap, brass-
alloy manufacturing and reclaiming, and galvanizing processing.
Average annual production and consumption of zinc in the
United States have increased steadily during this century, and
it is predicted that this trend will continue. As the
emission of zinc into the atmosphere in most of these operations
represents an economic loss of the zinc material, control
procedures are normally employed to prevent emission to the
atmosphere. In those industries where zinc is a by-product,
control procedures for zinc are not as effective, and greater
quantities of zinc therefore escape into the environment.
Measurements of the 24-hour average atmospheric
concentrations of zinc in primarily urban areas of the United
States reveal an average annual value of 0.67 |-lg/m3 for the
period 1960-1964; the highest value recorded during that period
was 58.00 |-ig/m3, measured in 1963 at East St. Louis, 111.
Extensive air pollution abatement methods are in general
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47
use by the zinc Industry. Control devices include precipitators,
scrubbers, baghouses, and collectors. The efficiency of the
various control methods varies widely. However, in many
instances air pollution control devices are not used in the
general metals industries. Thus it is very likely that
relatively large quantities of zinc or zinc compounds are
emitted into the atmosphere by industrial plants processing
zinc or other compounds containing zinc. No information has
been found on the economic costs of zinc air pollution or on
the costs of its abatement.
Limited means are available for the determination of
concentrations of zinc in the ambient air. These methods of
analyses, however, are not considered adequate for air pollution
monitoring purposes since they do not effectively discriminate
between the zinc and other metals and they lack sensitivity.
Based on the material presented in this report, further
studies are suggested in the following areas:
(1) Determination of whether zinc acts either as an
individual air pollutant exerting specific effects or as a
co-pollutant exerting synergistic effects, or has no adverse
effects.
(2) Determination of which zinc compounds are present
as pollutants in the environmental air, together with the
manner in which—and extent to which—these substances affect
human, animal, and plant health.
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48
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West, P. W., et al., Microdetermination of Caffeine by Using
the Ring-Oven Technique, Anal. Chim. Acta 30:227 (1964).
West, P. W., et al., Microdetermination of Selenium With 3,
3'-Diaminobenzidine by the Ring-Oven Technique and Its
Application to Air Pollution Studies, Anal. Chem. 36;2013
(1964).
Zaklady, C., Zinc From Scrap, Chem. Abstracts 67;35067
(1967).
-------
APPENDIX
-------
APPENDIX
TABLE 15.PROPERTIES, TOXICITY,AND USES OF SOME ZINC COMPOUNDS66
Compound
Properties
Toxicity
Uses
Zinc
Zn
mp 419.4°C
Inhalation of fumes may
result in sweet taste,
throat dryness, cough,
weakness, generalized
aching, chills, fever,
nausea, vomiting. Zinc
chloride fumes have
caused injury to mucous
membranes and skin irri-
tation. Ingestion of
sol. salts may cause
nausea, vomiting,
purging
For galvanizing sheet iron; as ingredient
of alloys such as bronze, brass, Babbitt
metal, German silver, and special alloys
for diecasting; as a protective coating
for other metals to prevent corrosion; for
electrical apparatus, especially dry-cell
batteries, for household utensils, castings
printing plates; as building materials,
railroad car linings, automotive equipment;
as reducing agent in organic chemistry;
for deoxidizing bronze; extracting gold by
cyanide process, purifying fats for soaps;
bleaching bone glue; in manufacture of
sodium hydrosulfite insulin zinc salts; as
reagent in analytical chemistry (e.g., the
March and Gutzeit test for arsenic); as a
reducer in the determination of iron
Zinc acetate
2H2O
35.6436
o,.
mp 237 C
Mildly irritating to
skin, mucous membranes
For preserving wood; as a mordant in
dyeing; in manufacturing glazes for
painting on porcelain. As a reagent in
testing for albumin, tannin, urobilin,
phosphate, blood. Mad. use: styptic,
astringent, emetic
Zinc arsenate
4H 0
2
34.8%
White,
odorless
powder
Poison!
Zinc
bacitracin
1%
Creamy
powder
containing
1-4% H2O
In ointments, tablets, implantation
pellets, suppositories, and troches,
either alone or in combination with other
antibiotics or therapeutic agents
(continued)
00
-------
APPENDIX
TABLE 15.PROPERTIES, TOXICITY,AND USES OF SOME ZINC COMPOUNDS (Continued)
Compound
Properties
Toxicitv
Uses
Zinc
benzoate
21 . 25%
Powder.
Soluble in
62 parts
water at
60° C
The dust can cause
respiratory irritation
Zinc
bromide
ZnBr2
29.0%
mp 394°C
bp 650°C
In making silver bromide collodion
emulsions for photography; in the shielding
of viewing windows for nuclear reactions
Zinc
caprylate
Zn(C3Hl502)2
18.2%
mp 136L
May liberate irritating
fumes of caprylic acid
As fungicide-like zinc propionate
Zinc carbonate
hydroxide
Odorless
powder.
Insoluble
in water
As pigment? in manufacture of porcelains and
pottery. Med. use: has been used topically
as antiseptic and astringent
56% Zn
Zinc
chromate( VI)
hydroxide
Zn2Cr04(OH)2-
H2°
44.0%
Yellow,
odorless,
fine powder
As pigment in paints, varnishes, oil
colors, linoleum, rubbers etc.
(Continued)
tn
-------
APPENDIX
TABLE 15.PROPERTIES, TOXICITY, AND USES OF SOME ZINC COMPOUNDS (Continued)
Compound
Properties
Toxicity
Uses
Zinc
chloride
mp 290°C
bp 732°C
Moderately irritating to
skin
47.97%
In deodorant, disinfecting and
embalming material; alone or with
phenol and other antiseptics for
preserving railway ties; for
fireproofing lumber; with
ammonium chloride as flux for
soldering; in etching metals;
in manufacture of parchment
paper, artificial silk, dyes,
activated carbon, cold-water
glues, vulcanized fiber; in
browning steel, galvanizing
iron, copperplating iron; in
magnesia cements; in petroleum
oil refining, cement for metals
and for facing stone; as a
mordant in printing and dyeing
textiles; in carbonizing woolen
goods; in producing crepe and
crimped fabrics; in mercerizing
cotton; in sizing and weighting
fabrics; in vulcanizing rubber;
in solvent for cellulose; for
preserving anatomical specimens;
in microscopy for separating
silk, wool, and plant fibers;
as dehydrating agent in chemical
syntheses. Med. use: topically
as antiseptic and astringent
(continued) o
-------
APPENDIX
TABLE 15-PROPERTIES, TOXICITY,AND USES OF SOME ZINC COMPOUNDS (Continued)
Compound
Properties
Toxicitv
Uses
Zinc citrate
2H2°
34.15%
Odorless
powder.
Slightly
soluble in
water
Low systemic toxicity.
Large doses orally may
cause gastrointestinal
irritation
Zinc cyanide
Zn(CN)
55.68%
White
powder.
Insoluble in
water
Poison!
In electroplating; for removing NH3 from
producer gas
Zinc
dichromate
(VI)
Orange-
yellow
powder.
Soluble in
hot water
19.49%
Zinc
ferrocyanide
Zn2Fe(CN)6-
2H20
32.96%
White, very
hygroscopic
leaflets.
Soluble in
water
No specific data.
Probably an irritant
Zinc
fluoride
ZnF2
63 . 24%
mp 872°C
bp 1500°C
In the fluorination of organic compounds,
in manufacture of phosphors for fluorescent
electric lights; in glazes and enamels
for porcelain; for preserving wood; in
electroplating baths
(continued)
-------
APPENDIX
TABLE 15. PROPERTIES, TOXICITY,AND USES OF SOME ZINC COMPOUNDS (Continued)
r
Compound
Properties
Toxicitv
Uses
Zinc formate
Zn(HCOO) -
2H2°
34.15%
Crystals.
Soluble
in water
No specific data.
Probably an irritant
Zinc glycero-
phosphate
(OH)7PO.
^ rr
27.77%
White
odorless
powder.
Water
soluble
No specific data
See Zinc
Zinc
hexafluoro-
silicate
ZnSiF -6H.,0
6 ~
20.72%
White
crystals.
Soluble
in water
Severe corrosive effect
on skin, mucous
membranes
As mothproofing agent; in laundry sour?
as hardeher for concrete
Zinc insulin
crystals
Contains not
less than
0.45% nor
more than
0.9% Zn
Decomposes
between
230-240°C
Med. use: as insulin zinc preparation for
diabetes mellitus
Zinc iodate
Zn(IO )
£
15.75%
White
crystalline
powder
Med use: has been used as topical
antiseptic
(continued)
-------
APPENDIX
TABLE 15.PROPERTIES, TOXICITY,AND USES OF SOME ZINC COMPOUNDS (Continued)
Compound
Properties
Toxicity
Uses
Zinc iodide
ZnI2
20.48%
mp 446UC
bp 625°C
Med. use: has been used as topical
astringent, antiseptic
Zinc iodide-
starch
A soln. pre-
pared by
heating 4
parts starch,
20 parts ZnCl_
and 2 Znl,
with 1 *
liter water
Deteriorates
with age and
acquires a
blue color
For detecting nitrites, free Cl, and
other oxidizing agents
Zinc lactate
Zn(C3H503)2-
3H2°
26.85%
Crystals
No specific data
See zinc
Zinc meta-
arsenite
White
powder
Poisonous
Used as a wood preservative; in
insecticide
23.42%
Zinc nitrate
Zn(N03)2-6H20
21.98%
mp 36 C
As a mordant in dyeing
(continued)
(Ti
CO
-------
APPENDIX
TABLE 15-PROPERNIES, TOXICITY,AND USES OF SOME ZINC COMPOUNDS (Continued)
Compound
Properties
Toxicity
Uses
Zinc nitride
87.50%
Blackish-
gray,
crystal
solid
Zinc oleate
Zn(C18H33°2'2
10.4%
dry
White,
greasy
powder.
Insoluble
in water
No specific data. A
case of pneumoconiosis
has been reported from
related compound, zinc
stearate
Zinc oxalate
ZnC 04«2H20
34.52%
Powder.
Very
slightly
soluble in
water
No specific data
Zinc oxide
ZnO
80.34%
Sublimes at
normal
pressure.
Practically
insoluble
in water
Freshly formed fumes, as
from welding, may cause
metal^fume fever with
chills, tightness in
chest, cough and
leukocytosis
As pigment in white paints instead of lead
carbonate; in cosmetics, driers, quick
setting cements; with syrupy phosphoric
acid or ZnCl^ in dental cements; in manu-
facture of opaque glass and certain types
of transparent glass; in manufacture of
enamels, in automobile tires, white glue,
matches, white printing inks, porcelains,
zinc green; as a reagent in analytical
chemistry. Med. use; as astringent, anti-
septic, protective in skin diseases,
formerly internally for diarrhea and as an
antispasmodic. Dose: ointment, 7.5-20%,
paste 25%. Vet use: dressing in moist
eczema and on wounds, otorrhea in dogs
(continued)
-------
APPENDIX
TABLE 15_.PROPERTIES, TOXICITY,AND USES OF SOME ZINC COMPOUNDS (Continued)
Compound
Properties
Toxicity
Uses
Zinc
perchlorate
Zn(C104)2-
6H20
17.56%
mp 106°C
Freely
soluble
in water
Zinc
permanga-
nate
Zn(Mn04)2'
6H20
15.90%
Violet-
brown
crystals.
Similar to
potassium
permanganate
in appearance
Soluble in
3 parts water
Med. uset 1:4000 soln. as antiseptic
and astringent for urethritis
Zinc peroxide
Zn02
67.14%
White to
yellowish-
white odor-
less powder.
Decomposes
above 150°C
In Pharmaceuticals. Med. uses as
medicinal zinc peroxide, topically as
antiseptic, astringent, deodorant; for
wounds and skin diseases. Dose: 40% aq.
suspension.
Zinc p-phenol-
sulfonate
Zn(HOC6H4S03)2 •
8H2°
15.88%
Crystals or
crystalline
powder.
Odorless
In insecticide formulations. Med« use;
as antiseptic and astringent; has been
used as intestinal antiseptic
(continued)
-------
APPENDIX
TABLE 15.PROPERTIES, TOXICITY/AND USES OF SOME ZINC COMPOUNDS (Continued)
Compound
Properties
Toxicity
Uses
Zinc phosphate
Zn(P04)2-4H20
42.81%
White, odor-
less powder
In dental cements
Zinc phosphide
75.99%
mp 420 C
bp 1100°C
May liberate phosphine
which is highly toxic
In rat and field mice poison preparations
Zinc phosphite
34.33%
White crystal
line powder.
Soluble in
cold water
Zinc
propionate
Zn(C3H502)2
30.91%
As fungicide on adhesive tape to reduce
plaster irritation caused by molds, fungi,
and bacterial action. Med. use: has
been used as antifungoid in dermatology
Zinc pyro-
phosphate
42.91%
White
crystalline
powder.
Insoluble
in water
•7.1
inc
salicylate
Zn(C6H4(OH)-
COO)2•3H20
19*25%
Needles or
crystalline
powder.
Soluble in
water
(continued)
-------
APPENDIX
TABLE 15.PROPERTIES, TOXICITY,AND USES OF SOME ZINC COMPOUNDS (Continued)
Compound
Properties
Toxicity
Uses
Zinc
selenate
ZnSeO
31.38%
Decomposes
above 50°C
Soluble in
water
Zinc selenide
ZnSe
45.30%
mp 1100°C
Decomposes
in air.
Insoluble
in water
Occupational exposure has
caused pallor, nervous-
ness, depression, garlic
odor of breath and sweat,
G.I. disturbances,
dermatitis
Zinc silicate
2ZnO*SiO2
58.68%
White powder
In television screens
Zinc stearate
10.34%
mp 120°C
Systemic toxicity negli
gible. Inhalation may
cause pneumonitis
In tablet manufacture; in cosmetic and
pharmaceutical powders and ointments; as
a flatting and sanding agent in lacquers,
as a drying lubricant and dusting agent
for rubber; as a plastic mold releasing
agent; as a waterproofing agent for con-
crete, rock wool, paper textiles. Med»
and vet. use: as water repellent, desi-
cant, protective agent
Zinc sulfate
40.50%
Powder or
granules.
Decomposes
above 500°C
Irritating to skin
mucous membranes
As a mordant in calico printing; for pre-
serving wood and skins; with hypochlorite
for bleaching paper; in manufacture of
lithopone and other zinc salts; for
clarifying glue, electrodepositing Zn;
also as a reagent in analytical chemistry.
Med. uses as emetic; externally as
astringent or styptic
(continued'
-------
APPENDIX
TABLE 15.PROPERTIES, TOXICITY/AND US3S OF SOME ZINC COMPOUNDS (Continued)
Compound
Properties
Toxicity
Uses
Zinc sulfide
ZnS03•2H 0
White crys-
talline pow-
der
Zinc tannate
Compound of
ZnO and tannin
in variable
proportions
Yellow, odor-
less powder
Med. use: formerly as astringent and
antiseptic
Zinc tartrate
ZnC
46
26.21%
2H2O
Crystalline
powder
No specific data
Zinc telluride
ZnTe
33.88%
mp 1239°C
May cause nausea,
vomiting, central nervous
system depression
In semiconductor research, as a photocon-
duetor
Zinc thio-
cyanate
Zn(SCN)2
36.02%
White
crystals
Zinc valerate
2H20
24.43%
Lustrous
scales or
powder
No specific data
Vitamin B,
tannate
complex
Practically
insoluble
in water
Med. use: long-acting injectable vitamin
B preparation
(continued)
(Tv
oo
-------
APPENDIX
TABLE 15.PROPERTIES, TOXICITY,AND USES OF SOME ZINC COMPOUNDS (Continued)
Compound
Properties
Toxicity
Uses
Undecylenic
acid, zinc
salt
Amorphous
white powder
Med. use: as topical fungistatic agent,
Has been given orally. Vet. use: in
cutaneous fungus infections, such as
ringworm
CTi
-------
70
TABLE 16
PHYSICOCHEMICAL PROPERTIES OF ZINC30
Atomic weight: 65.37
Atomic number: 30
Valence: +2
Specific gravity: 7.13 g/cm3
Melting point: 419.5°C
Boiling point: 906 C
Grades of Slab Zinc % Pure Zinc
Special high grade 99.99
High grade 99.90 -
Intermediate 99.50
Brass special 99.00
Selected 98.75
Prime western 98.30
-------
TABLE 17
PRIMARY AND REDISTILLED SECONDARY SLAB
ZINC PRODUCED IN THE UNITED STATES32
(Short Tons)
71
Type ,-)f Zinc
Primary :
From domestic ores
From foreign ores
Total
Redistilled secondary
Total*
1963
474,
418,
892,
60,
952,
007
577
584
303
887
1964
531,
422,
954,
71,
1,025,
967
117
084
596
680
1965
551,
443,
994,
83,
1,078,
215
187
402
619
021
1966
523
501
1,025
83
1,108
,580
,486
,066
,263
,329
1967
438,
500,
938,
73,
1,012,
553
277
830
505
335
*Excludes zinc recovered, by remelting.
-------
72
TABLE 18
CONSUMPTION OF ZINC IN THE UNITED STATES32
(Short Tons)
Type of Zinc 1963 1964 1965 1966 1967
Slab zinc 1,105,113 1,207,268 1,354,092 1,410,197 1,236,808
Ores (recoverable
zinc content) 104,705a 105,948a 122,892a 126,696a 114,301a
Secondary
(recoverable
zinc content)b 204,398 222,535 265,083 269,650 240,888
Total 1,414,216 1,535,751 1,742,067 1,806,543 1,591,997
alncludes ore used directly in galvanizing.
^Excludes redistilled, slab and remelt zinc.
-------
73
TABLE 19
MANUFACTURERS OF ZINC SLAB IN THE UNITED STATES, 1968
Company Location
54
Aluminum Smelters Inc.
American Metal Climax Inc.
American Smelting and Refining Co,
Federated Metals Div.
American Zinc
Anaconda Company
Anchor Alloys Inc.
Arco Die Cast & Metals Inc.
Associated Metals .& Minerals Corp.
Bay State Smelting Corp.
Behr, Joseph & Sons, Inc.
Belmont Smelting & Refining Works
Bullock, W. J., Inc.
Car-Mor Metal Co.
Cassell, Adam A., Metal Co.
Certified Metals Mfg. Co.
City Metals Refining Co.
Combined Metals Reduction Co.
Eagle-Picher Industries Inc.
Empire Metal Co.
General Smelting Co.
Hayman, Michael, & Co., Inc.
Henning Bros. & Smith Inc.
Illinois Smelting & Refining Co.
International Minerals & Metals
Jordan Company
Kahn Bros. Smelting Corp.
Kirk, Morris P., & Son
Lapides Metals Corp.
Matthiessen & Hegeler Zinc Co.
Metal Corrosion Control
Metallurgical Products Co.
Michigan Standard Alloys Inc.
National Lead Co., Metal Div.
National Zinc Co.
New England Smelting Works Inc.
New Jersey Zinc Co.
Ney Metals Inc.
North American Smelting Co.
Pacific Smelting Corp.
Pitt Metals Co.
Republic Metal Co.
St. Joseph Lead Co.
Sandoval Zinc Co.
Seitzinger's Inc.
Smith & McCrorken
Star Refining Co.
United States Smelting Works
Viener, Hyman & Sons
New Haven, Conn.
New York, N.Y.
New York, N.Y.
St. Louis, Mo.
New York, N.Y.
Brooklyn, N.Y.
Detroit, Mich.
New York, N.Y.
Somerville, Mass.
Rockford, 111.
Brooklyn, N.Y.
Fairfield, Ala.
Wilmington, Del.
Milwaukee, Wis.
Cincinnati, Ohio
Detroit, Mich.
Salt Lake City, Utah
Cincinnati, Ohio
Syracuse, N.Y.
Philadelphia, Pa.
Buffalo, N.Y.
N.Y.
111.
. N.Y.
111.
Brooklyn, N.Y".
Los Angeles, Calif.
New Haven, Conn.
La Salle, 111.
Plainfield, N.J.
Philadelphia, Pa.
Benton Harbor, Mich.
New York, N.Y.
New York, N.Y.
West Springfield, Mass,
New York, N.Y.
Long Island City, N.Y.
Wilmington, Del.
Torrance, Calif.
Pittsburgh, Pa.
Brooklyn, N.Y.
New York, N.Y.
Chicago, 111.
Atlanta, Ga.
New York, N.Y.
Boston, Mass.
Philadelphia, Pa.
Richmond, Va.
Brooklyn,
Chicago,
New York,
Chicago,
-------
TABLE 20
PRIMARY SLAB ZINC PLANTS BY GROUP CAPACITY IN THE UNITED STATES IN 196732
Type of Plant
Plant Location
Slab Zinc
Capacity
(Short Tons)
Electrolytic plants:
American Smelting and Refining Company
American Zinc Company of Illinois
The Anaconda Company
The Anaconda Company
The Bunker Hill Company
Horizontal-retort plants :
American Smelting and Refining Company
American Zinc Company of Illinois
Blackwell Zinc Company, Division of American
Metal Climax, Inc.
Eagle-Picher Industries, Inc.
Matthiessen & Hegeler Zinc Company
National Zinc Company
Vertical-retort plants:
Matthiessen & Hegeler Zinc Company
The New Jersey Zinc Company
The New Jersey Zinc Company
St. Joseph Lead Company
Corpus Christi, Tex.
Sauget, 111.
Anaconda, Mont.
Great Falls, Mont.
Kellogg, Idaho
Amarillo, Tex.
Dumas, Tex.
Blackwell, Okla.
Henryetta, Okla.
LaSalle, 111.
Bartlesville, Okla,
Meadowbrook, W. Va.
Depue, 111.
Palmerton, Pa.
Josephtown, Pa.
525,000
742,500
*Plant closed July 1, 1961
-------
TABLE 21
SECONDARY SLAB ZINC PLANTS BY GROUP CAPACITY IN THE UNITED STATES IN 196732
Company
Plant Location
Slab Zinc
Capacity
(Short Tons)
American Smelting and Refining Company
American Smelting and Refining Company
American Zinc Company of Illinois
Apex Smelting Company
Arco Die Cast Metals Company
W. J. Bullock, Inc.
General Smelting Company
Gulf Reduction Company
H. Kramer Company
Pacific Smelting Company
Sandoval Zinc Company
Superior Zinc Corporation
Wheeling Steel Corporation
Sand. Springs, Okla.
Trenton, N.J.
Hillsboro, 111.
Chicago, 111.
Detroit, Mich.
Fairfield., Ala.
Bristol, Pa.
Houston, Texas
El Segund.o, Calif.
Torrance, Calif.
Sandoval, 111.
Bristol, Pa.
Martins Ferry, Ohio
55,900
U1
-------
TABLE 22
CONCENTRATION OF ZINC IN THE AIR67"69
Location
Alabama
Birmingham
Arizona
Phoenix
California
Los Angeles
San Francisco
Colorado
Denver
D.C.
Washington
Georgia
Atlanta
Idaho
Boise
Illinois
Chicago
Cicero
E. St .Louis
Micrograms per cubic meter ^
1954-59^
Max Avg
8.40
2. 00
1.40
7.90
2.40
1.29
0.72
0.30
0.88
0.93
1
Indiana i
E. Chicago
Indianapolis 1.10 0.18
1960
Max Avq
0.43
0.14
1
1961
Max Avq
1.50
7.20
1.00
0.59
1.56
0.52
1962
Max
1.60
1.80
2.10
1.40
1.40
b
12.00
0.33
b
4.00
4.60
1.20
Avq
0.55
0.67
0.34
0.53
0.26
b
3.52
0.01
b
0.95
1.16
0.28
1963
Max
1.80
1.10
1.50
0.65
6.40
5.50
58.00
Avq
0.39
0.15
0.52
0.26
1.28
1.52
5.52
1964
Max
8.60
1.50
1.90
0.65
0.23
3.80
Avq
1.00
0.33
0.22
0.05
0.01
0.95
12-00 i 2.57
i L
-------
TABLE 22 (Continued)
CONCENTRATION OF ZINC IN THE AIR
Location
Iowa
Des Moines
Louisiana
New Orleans
Maryland
Baltimore
Massachusetts
Boston
Michigan
Detroit
Missouri
St. Louis
Montana
Helena
Nevada
Las Vegas
New Jersey
Newark
New York
Buffalo
New York
Microqrams per cubic meter
1954-59a
Max
0.79
0.65
2.00
6.90
1.80
8.20
Avq
0.04
0.09
0.63
0.73
0.50
1.61
1960
Max
1.60
Avq
0.57
1961 _J
Max
2.20
4.50
Avq
0.59
0.70
1962
Max
0.82
0.36
1.60
1.80
5.50
0.00
4.60
1.90
2.80
Avq
0.16
0.03
0.41
0.72
1.53
Oe82
0.38
0.86
1963
Max
b
0.00
1.70
3.00
0.31
b
1.80
2.10
Avq
0.41
0.69
0.01
b
0.43
0.78
1964
Max
0.00
2.50
0.79
4.30
4.10
0.43
0.00
3.30
1.80
Avq
0.61
0.33
0.83
0.67
0.05
0.64
0.49
-------
TABLE 22 (Continued)
CONCENTRATION OF ZINC IN THE AIR
Location
No. Carolina
Charlotte
Winston-
Salem
Ohio
Cincinnati
Cleveland
Columbus
Dayton
Pennsylvania
Allentown
Philadelphia
Pittsburgh
Scranton
Tennessee
Chattanooga
Nashville
Texas
El Paso
Houston
Washington
Seattle
Tacoma
Micrograms per cubic meter
1954-59^
Max
0.92
2.70
1.60
1.40
4.50
1.00
2.50
1.70
0.75
Avq
0.23
0.81
0.56
0.63
1.09
0.25
0.28
0.81
0.11
1960
Max
17.00
8.20
Avq
2.56
1.95
1961
Max
5.90
0.99
Avq
1.17
0.42
1962
Max
0.75
15.00
4.20
0.32
7.00
7.30
2.90
0.57
0.47
Avq
0.27
2.05
0.85
0.02
1.47
1.12
1.12
0.15
0.08
1963
Max
8.00
2.60
5.00
20.00
3.60
0.71
0.00
Avq
1.62
0.95
1.14
2.22
1.21
0.11
1964
Max
0.46
14.00
2.10
6.10
8.00
2.10
3.60
0.71
0.47
Avq
0.08
2.87
0.65
1.41
1.06
0.57
1.16
0,13
0.04
00
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TABLE 22 (Continued)
CONCENTRATION OF ZINC IN THE AIR
Location
West Virginia
Charleston
Wisconsin
Milwaukee
Wyoming
Cheyenne
Nebraska
Omaha
Florida
Tampa
Kansas
Wichita
New Hampshire
Manchester
North Dakota
Bismarck
Oregon
Portland
Utah
Salt Lake
City
Microqrams per cubic meter
1954^59^
Max Avq
1.40
0.86
1.70
0.96
1.10
0.69
0.48
4.10
0.90
0.40
0.03
0.47
0.14
0.64
0.08
0.01
0.67
0.03
1960
Max
Avq
1961
Max
Avq
1962
Max
0.83
Avq
0.13
1963
Max
Avq
1964
Max
0.62
1.00
0.00
Avq
0.07
0.16
aData for 1954-59 include the averages for all measurements during this period, or
only one-year values, as available.
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