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AIR POLLUTION ASPECTS
OF
BERYLLIUM 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 Norman L. Durocher
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.
been identified, and available information has been summarized
Thirty such pollutants have
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
(NAPCA) by
for the National Air Pollution Control Administration
Litton Systems, Inc.
The complete listing is as follows:
Aeroallergens (pollens)
Aldehydes (includes acrolein
and formaldehyde)
Ammonia
Arsenic and Its Compounds
Asbestos
Barium and Its Compounds
Beryllium and Its Compounds
Biological Aerosols
(microorganisms)
Boron and Its Compounds
Cadmium and Its Compounds
Chlorine Gas
Chromium and Its Compounds
(includes chromic acid)
Ethylene
Hydrochloric Acid
Hydrogen SuI fide
Iron and Its Compounds
Manganese ang Its Compounds
Mercury and Its Compounds
Nickel and Its Compounds
Odorous Compounds
Organic Carcinogens
Pesticides
Phosphorus and Its Compounds
Radioactive Substances
Selenium and Its Compounds
Vanadium and Its Compounds
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 poll~tion 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, PhoD.
James L. Haynes
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The NAPCA project officer for the contract was Ronald C.
Campbell, assisted by Dr. Emanuel Landau and Gerald Chapman.
Appreciation is expressed to the many individuals both
outside and within NAPCA who provided information and reviewed
draft copies of these reports.
Appreciation is also expressed
to the NAPCA Office of Technical Information and Publications
for their support in providing a significant portion of the
technical literature.
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ABSTRACT
Inhalation of beryllium (Be) or its compounds by humans
or animals can cause a bOdy-wide systemic disease, with pulmonary
damage being of major concern.
The acute form occurs as a
chemical pneumonitis, with inflammation of the mucosa and sub-
mucosal tissues of the respiratory tract.
Chronic beryllium
disease, which differs clinically from the acute case, has
also caused severe respiratory damage.
As of 1965, 735 cases
of beryllium disease had been recorded in the Beryllium Case
Registry, with a fatality rate of approximately 26 percent.
Bone and lung cancers have been produced experimentally in
animals, and 20 malignant tumors have been recorded among the
735 cases of beryllium disease: however, the available evidence
is not considered sufficient to positively incriminate beryl-
lium as a carcinogen in humans.
There is some evidence that beryllium in soils is toxic
to plant life: no evidence has been found on the effects of
atmospheric beryllium on plants or materials.
The major sources of beryllium in the atmosphere are
the industrial processing plants engaged in the extraction,
refining, machining, and alloying of the metal.
The combustion
of coals containing small quantities of beryllium, and the pro-
posed use of beryllium as an additive in rocket fuels, are also
possible sources.
Conventional air-cleaning procedures have been generally
adopted by the beryllium industry, producing marked reductions
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in the amount of beryllium emitted to the atmosphere.
Data
on the costs of abatement are limited~ one study indicated
that costs for control amount to approximately 20 percent of
the cost of normal operation.
No data were found on the costs
of damage produced by beryllium air pollution~ however, legal
actions are currently in progress in Pennsylvania courts
which may provide data on values of health impairment result-
ing from beryllium exposure.
Methods for analysis of beryllium in the atmosphere are
available~ however, they do not discriminate between the vari-
ous compounds of beryllium.
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CONTENTS
FOREWORD
ABSTRACT
1. INTRODUCTION . . . . . . . . . . . 1
20 EFFECTS . . . . . . . . . . . . . . . 3
2.1 Effects on Humans . . o . . . . . . . . 3
2.1.1 Acute Beryllium Disease . . . . . 3
2.1.1.1 Respiratory Effects . . . 3
2.1.1.2 Other Physiological Effects . 8
2.1.2 Chronic Beryllium Disease . . . 10
2.1.2.1 Respiratory Effects . 10
2.1.2.2 Other Physiological Effects . . 13
2.1.2.3 Community Episodes . . . 14
2.1.3 Carcinogenicity . . . . . 16
2.2 Effects on Animals . . . . . . . 16
2.2.1 Commercial and Domestic Animals . . 16
2.2.2 Experimental Animals . . . . . . 0 17
2.2.2.1 Acute Beryllium Disease . . 17
2.2.2.2 Chronic Beryllium Disease a . 20
2.2.2.3 Carcinogencity . . . 21
2.3 Effects on Plants . . . 0 . . . a 21
2.4 Effects on Materials . . . . . . . . . .. 22
2.5 Environmental Air Standards o . . .. 22
3. SOURCES . . . . . . . . . . . . . 27
3.1 Natural Occurrence 0 .. 0 . . . a 27
3.2 Production Sources 0 . . . . . . . 28
3.2.1 Mining . . . . . . . . . . . . 28
3.2.2 Extraction and Refining . . . . . . . a 29
3.3 Product Sources . . . . . . . . 36
3.3.1 Beryllium-Copper Alloys . . . . . 37
3.3.2 Fluorescent Tubes . . . . . . . a 37
3.3.3 Rocket Fuels . . . . a . . . . 39
3.3.4 Coals . . . . . . . . . . . . . . 40
3.4 Other Sources . . . . . . . . . . . 40
3.5 Environmental Air Concentrations . . . . . . 41
4. ABATEMENT . . . . . . . . . . . . . 0 a 43
5. ECONOMICS . . . . . . . . . . . . . . 46
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6.
CONTENTS (Continued)
METHODS OF ANALYSIS. . . .
. . . . .
. . .
. . . . .
6.1
6.2
70
Sampling Methods. . . . . . . . . . . . . . . .
Quantitative Methods. . . . . . . . . . . . . .
6.2.1 Morin Fluorescent Method. . . . . . . .
6.2.2 Colorimetric Method. . . . . . . . . . .
6.2.3 Spectrographic Method. . . . . . . . . .
6.2.4 Other Methods. . . . . . . . . . . . . .
SUMMARY AND CONCLUSIONS. .
. . . . .
. . . .
. . . .
REFFERENCES
APPENDIX
48
48
48
48
49
49
50
52
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10.
11.
12.
13.
14.
15.
LIST OF TABLES
1.
Acute Respiratory Problems Resulting from
Beryllium Exposure. . . . . . . . . . . .
. . . . .
2.
Acute Skin Problems Resulting from Beryllium
Exposure. . . . . . . . . . . . . . . . . . 0 . .
3.
Results of Exposures of Beryllium Sulfate
Hexahydrate. . . . . . . . . . . . . . .
. . . .
4.
Theoretical Air Concentrations of Beryllium
Based on Vapor Pressures of Materials. . .
. . .
5.
Beryllium Oxide Production Lorain, Ohio
. . . . .
6.
Beryllium Metal Production Lorain, Ohio
. . . . .
7.
Beryllium Metal Powdering, Sintering, Machining
Lorain, Ohio, and Cleveland, Ohio. . . . . . . .
8.
Production of Beryl
. . . . .
. . .
. . . . . . .
9.
Mean, Median, and Range Values of Beryllium
Concentrations (2-Hour Averages) . . . . . .
. . .
Average Beryllium Concentrations for
Selected Areas. . . . . . . . . . .
. . . . . . .
Cleaners for Beryllium Handling Operations.
. . .
Properties, Toxicity, and Uses of Beryllium
and Some Beryllium Compounds. . . . . . . . . . .
Physiological Changes and Mortality Resulting
from Inhalation of Beryllium Fluoride, Beryllium
Oxide, and Beryllium Sulfate. . . . . . . . . . .
Physical Properties of Beryllium. .
. . . .
. . .
Concentration of Beryllium in the Air
. . .
. . .
7
9
19
32
33
34
35
36
38
42
44
65
70
77
78
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1
1.
INTRODUCTION
Beryllium and its compounds, when present in the enVl-
ronmental air, are of concern because of their effect on the
health of humans and animals, since beryllium is among the
most toxic and hazardous of the nonradioactive substances
being used in industry.
Beryllium is commonly found as an
atmospheric pollutant within the confines and in the proximity
of industrial plants producing or using beryllium substances.
Almost all the presently known beryllium compounds are
acknowledged to be toxic in both the soluble and insoluble
forms, depending on the amount of material inhaled and the
length of exposure.
Soluble beryllium compounds, such as
beryllium sulfate and beryllium chloride, commonly produce
acute pneumonitis; insoluble compounds, such as metallic
beryllium and beryllium oxide, can produce chronic pulmonary
2
disease (berylliosis).
However, it should be noted that the
toxic beryllium effect is not limited to berylliosis but
instead is a bOdy-wide systemic disease.
Expanded industrial use of beryllium in the 1930's,
particularly the large-scale production of fluorescent lamps
using phosphors of beryllium oxide, produced a number of cases
of pulmonary diseases which were initially attributed to
causes other than exposure to beryllium.
Recognition of the
toxic effects of beryllium, however, beginning in 1943,
resulted in establishment of the first Community Air Limit
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2
for metal substances, as well as in health safety procedures
which were exceptionally effective in controlling further
occurrences of the disease.
However,
increased use of beryl-
lium in the metallurgical industry, along with its proposed
use as a high-energy fuel for rocket motors, suggests that
study should-be made of the air pollution aspects of this
highly toxic material.
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3
2.
EFFECTS
Claims and counter-claims concerning the toxicity of
beryllium and its compounds have been made as early as the
latter part of the 19th century; however, serious study of
this problem did not commence until beryllium poisoning was
61
reported in humans by Weber and Englehardt in 1933.
Health
problems arising among workers engaged in the production and
manufacturing of beryllium and its products during the late
1930's and 1940's led to case studies and research which defi-
nitely established the toxic nature of beryllium in most of
its physical and chemical forms.
The properties, toxicity,
and uses of beryllium and certain of its compounds are listed
in Table 12 of the Appendix.
2.1
Effects on Humans
The major hazard from beryllium arises from the inhala-
. 52
tion of beryllium or ~ts compounds. Damage to the skin and
mucous membranes can occur from handling of the soluble salts
of beryllium.
These manifestations can be cured completely,
but may last for considerable periods of time.
The effects
of beryllium intoxication can be mild, moderate, or severe,
and can even prove fatal when severe damage to the pulmonary
system occurSo
201.1
Acute Beryllium Disease
201.1.1
Respiratory Effects
Acute chemical pneumonitis has been produced by inhala-
tion of virtually all beryllium compounds.
These include
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4
beryllium metal, beryllium oxide, beryllium sulfate, beryllium
fluoride, the hydroxide, and the chloride.
Responses to beryl-
lium exposure range from transient rhinitis, pharyngitis, or
tracheobronchitis to severe pulmonary reactiono
The degree of
response seems to be dependent upon the degree, duration, and
21
type of exposure.
Rapidly fatal cases have resulted from
exposure to large concentrations of soluble salts in beryllium-
processing industrial plants.
However, most commonly the ill-
ness is insidious in nature, developing as a dry cough and pro-
gressing to substernal discomfort and pain, general weakness
f . h 11,21,32,62
and fatigue, and loss 0 welg t. All regions of
the upper respiratory tract may be affected, with acute inflam-
. 14
mation of the mucosa and submucosal tlssues. Lung changes
may develop in 1 to 3 weeks, and are characterized by chest
X-ray haziness, progressing to appearance of discrete or con-
glomerate nodules.
Cases of acute pneumonitis are usually
hospitalized for observation and treatment, to include bed rest,
use of oxygen bronchodilators, antihistamines, antibiotics, and
. 32
cortlsone.
Other cases of a less severe nature, not requir-
ing hospitalization, may not receive medical attention, nor
will they be included in medical statistics.
According to Eisenbud, as reprinted in Reference 46
(1958), the disease runs its course in a matter of weeks, and
unless death occurs9 complete recovery results.
This state-
ment as to the course of the disease has been disputed by
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5
25
Hardy. who has stated that no medical fOllow-up was made of
workers discharged for having "any symptoms whatsoever of
toxic beryllium effect."
She also notes the long residence
of beryllium in the body and the possibility of chronic dis-
ease occurring at a much later period of time following
25 11
exposure. Cholak, et ale state that while some patients
with acute beryllium pneumonitis have also acquired the
chronic form, a sequential relationship between the two forms
of the disease has not been established.
This view is rein-
. 2 f
forced by the Committee on TOXlcology 0 the National Academy
of Sciences--National Research Council, which stated in 1966
that "As far as can be determined, there are no cases of
uninterrupted progression from acute chemical pneumonitis to
chronic beryllium disease from a single exposure." De Nardi
14
et ala reported in 1953 that in a large series of cases, 47
survivors of the acute disease were observed for as long as
12 years, with no occurrence of the chronic disease in any
person.
On the other hand, it has been stated that when these
survivors were studied further, a number of them were found to
have chronic disease.25
Hardy23 also reported in 1965 that on
the basis of data from the Beryllium Case Registry of June
1964, 46 cases out of 725 (6.3 percent) progressed from acute
to chronic and the mortality was high.
The toxicity of beryllium and its compounds is not
clearly defined;27,29,46 measurements of concentrations
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6
and particle size are not always available or adequate for
definite medical conclusions.
For instance, concentrations
of beryllium oxide of 30,000 ~g/m3 produced no acute cases
in exposed employees of one plant, whereas in a second plant,
exposure to 4,000 ~g/m3 produced a high incidence of acute
h . . , d f f ,. 46
disease, associated with a 19h lnCl ence 0 atalltles.
In this regard, laboratory studies have revealed that the
toxicity of beryllium oxides produced at 1,600oC is considera-
bly less than that produced at relatively low temperatures
(500oC).46 These findings were confirmed by laboratory tests
showing that animals were able to tolerate high exposures to
oxides formed at high temperatures but developed acute poison-
f' "d 52
ing when exposed to similar concentrations of low- lred OXl es.
Studies (1951) of the occurrence of the acute disease in beryl-
lium plants revealed that all cases had occurred after exposure
to concentrations in excess of 100 ~g/m3, and when concentra-
tions of the soluble beryllium compounds exceeded 1,000 ~g/m3,
acute disease 6ccurred in almost all personnel.19 Unfortunately;
the time period for exposure to these concentrations was not
known or specified.
The Panel on Toxicity of Beryllium of the Materials
Advisory Board, National Academy of Sciences--National Research
Council reported46 (1958) that no acute illnesses had occurred
when peak concentrations did not exceed 25 ~g/m3.
It was
further reported that inhalation of 40 ~g/m3 of beryllium
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7
sulfate by experimental animals produced typical lung damage
in some--but not all--animals; no damage was noted from expo-
sure to concentrations of 4 ~g/m3.
The extent of involvement of the respiratory tract,
the degree of severity, and the causative factors of acute
disease have" been tabulated by the Brush Beryllium company,63
based on observations on selected employees of this company.
These data are presented in Table 1.
TABLE 1
ACUTE RESPIRATORY PROBLEMS RESULTING
FROM BERYLLIUM EXPOSURE63
Tvpe
Degree of
Severity
Causation
1. Nose and
throat
(naso-
pharyn -
gitis)
Minor
Fumes, mists, and/
or dusts of soluble
salts of Be. Usu-
ally result of
minor-degree expo-
sure during massive
incident
2. Bronchial
tubes
(tracheo-
bronchitis)
Inter-
mediate
Usually the result
of relatively high
level of exposure
over prolonged
period of time (2
weeks +)
3. Lungs
(acute
beryllium
chemical
pneumo-
nopathy)
Major
Result of very
high level of
exposure in rela-
tively short time
Comments
BeF2 most reac-
tive of all
beryllium
compounds
More commonly
experienced with
BeS04 than with
other compounds
BeF2 more reac-
tive as to sever-
ity and morbidity
than other
compounds
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8
2.1.1.2
Other Phvsioloqical Effects
Acute beryllium poisoning can produce skin, eye, and
other limited physiological reactions.
Skin problems are
usually associated with contact exposure or implant of the
soluble salts of beryllium. Table 2 from data of the Brush
Beryllium Company 63 lists the principal types of skin prob-
lems, their causes, relative severity, and frequency (on a
scale of 0 to 4, with 4 representing the maximum intensity).
Lesions of the skin are similar to those produced by other
primary irritants! dermatitis occurs most frequently in the
exposed portions of the body, usually with symptoms of pruri-
tus and sensations of burning.
The affected areas usually
improve after termination of exposure.
Healing is assisted
by application of aluminum acetate soaks.
Mucous membranes of the conjunctiva, nose, nasopharynx,
trachea, and bronchi may be affected by the solUble salts of
beryllium.
Acute responses may occur as hyperemia, edema.
ulceration, hemorrhage, and such symptoms as itching, burning,
and rhinorrhea.ll
Tracheobronchitis may appear rapidly or
insidiously, with throat irritation, cough, tightness of chest,
and other symptoms difficult to distinguish from those of acute
't' 11
beryllium pneumon1 1S.
Hazard,26 as discussed by Vorwald,60 reported mild
thickening of the right ventricular wall of the heart in two
cases of acute beryllium diseaseo
Moderate inflammation of the
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9
TABLE 2
ACUTE SKIN PROBLEMS RESULTING FROM
BERYLLIUM EXPOSURE63
Causal
Frequency
Tvoe Cause and Severitv Conunents
1. Contact derma- Undue contact BeF4 4+ 4+ Gross aspect
titis (primary with soluble BeS04 2+ 2+ varies with the
irritant) salts of Be BeCla ? 2+ salt involved
Be(N03)a ? ?
Be (OH)2 0 0
2. "Allergic" Fumes, mists BeF2 1%
dermatosis and/or dusts BeS04 ?
(angioneurotic of BeF::1 Be(OH)2
edema with Equivocal
superimposed with BeS04
primary
irritant)
3. Chemical Contamination BeFa 4+ 4+ Most frequently
ulcer of neglected BeS04 2+ 2+ over bony struc-
minor cut Be ( OH) a 0 0 ture, e.g.,
with soluble knuckle
salts of Be
40 Ulcerating Implant of BeS04 4+ 2+ Existence of
granuloma soluble salt BeF::1 1+ 4+ granuloma not
of Be Be (OH)2 0 0 verified with
BeF2
liver was also noted
as well as some evidence of severe central
necrosis,
focal hemorrhage of the spleen, and mild edema of
the braino
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10
2.1.2
Chronic Bervllium Disease
Histopathologic lesions caused by chronic beryllium
disease occur in the skin, subcutaneous tissues, and the lungs.
Lesions in the skin and subcutaneous tissues can be cured by
minor surgery.
Granulomatous reactions in the lung can pro-
duce severe and permanent respiratory damage or death.ll
It
is believed that most all of the systems of the body can be
affected; there is evidence that beryllium affects enzyme sys-
terns, and is not limited to local effects in the lungs.
30
Johnson has pointed out that the granulomatous nodules are
a prominent histological feature but do not account for the
respiratory embarrassment responsible for much of the disability
associated with this disease.
Instead, there is a biochemical
lesion--a defect in the mechanism for transport of oxygen.
2.1.2.1
Respiratorv Effects
Although berylliosis and beryllium granulomatosis have
been widely used designations for chronic beryllium disease,
30
these are misnomers, according to Johnson, for what is basi-
cally a systemic disease, with recognizable beryllium injury
appearing in many tissues and organs.
Every organic system
would appear to be involved in response to beryllium inhalation,
except organs in the pelvic area.
Since beryllium has a long
residence time in the body. it may have a potential for cancer
induction, as has been suggested by animal experiments.
Attempts to correlate the chronic effects with exposure
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11
21
have been unsuccessful. The delay in onset of manifestations
2,32
can vary from months to as long as 23 years. The illness
is of long duration, with a high mortality rate.
Cases have
occurred in persons subject to exposure to beryllium in many
forms in a wide variety of occupations, and in persons not
connected with the processing of beryllium but residing in
the neighborhood of beryllium plants.
The evidence also indi-
cates that members of households of workmen employed in beryl-
lium plants have contracted this disease from exposure to dust
1 h' 12
carried home on c ot ~ngG
According to the National Academy of Sciences--National
Research Council,2 "The pathogenesis of chronic beryllium
disease is still unknown.
The fact that only a small percent-
age of the persons exposed develop the disease lends support
to the hypothesis advanced by several investigators that there
is an immunological abnormality associated with the disease,
or that the susceptibility is in some way related to an inborn
error of metabolism. II
However, a recent study (1968) would
appear not to support the immunologic view contained in this
report.
In this study by the Aerospace Medical Research Labo-
ratories, two beagle dogs were exposed for 20 minutes by
respiratory route to rocket exhaust products containing a
mixture of beryllium oxide, beryllium fluoride, and beryllium
chloride at an average beryllium concentration of 115,000
47
~g/m3. Robinson et ale concluded, "It appears that the
-------
12
lesions in these dog lungs are more typically the classical
reactions to a foreign body than immunologic in character."
The Council further states, "Among the factors asso-
ciated with the chronic disease that have complicated the
interpretation of the epidemiological studies are the follow-
ing:
the extremely small amounts of beryllium-containing
materials alleged to have produced the disease; the well-
documented fact that many persons have received severe exposures
to beryllium-containing compounds without developing the disease;
the latent period between exposure and symptoms; the occurrence
of illness in only a small percentage of the exposed population;
the similarity between chronic beryllium disease and other
chronic diffuse pulmonary diseases; the uncertainty as to the
identity of the physical-chemical properties of the beryllium
compounds involved; and the lack of any quantitative data on
the magnitude of the exposure and particle
size. "
This source also considers that the chronic form of the
disease is caused by exposure to the insoluble compounds of
beryllium, and that the few chronic cases alleged to have
resulted from exposure to soluble compounds could actually have
been due to either unknown exposure to insoluble compounds or
to hydrolysis in the tissues of beryllium hydroxide or oxideso
As of June 1966, 498 cases of chronic beryllium disease
had been recorded in the Beryllium Registry. An analysis of
460 of these cases2 noted that over 400 were industrial cases
-------
13
while 60 were nonindustrial.
Hall et al.,20 in an analysis
in 1959 of 382 cases from the Beryllium Case Registry, reported
the sYmptoms of chronic disease as dyspnea (69 percent), loss
of weight (61 percent), cough (78 percent), increased fatigue
(34 percent), pains in the chest (31 percent), loss of appetite
(26 percent); and general weakness (17 percent).
Little quantitative data are found in the literature
concerning atmospheric concentrations resulting in chronic
beryllium poisoning.
Qualitatively it is reported that chronic
cases have occurred as a result of single massive doses of
beryllium-contaminated air9 as well as from prolonged exposure
to concentrations of only a few micrograms per cubic metero52
. 52
Sterner and E1senbud have reported neighborhood cases in which
chronic disease occurred in approximately 1 percent of the popu-
lation exposed to concentrations of 1 ~g/m3 within one-fourth
mile of a beryllium plant.
However, among workers within this
same plant exposed to concentrations as much as 1,000 times
greater, only 0.5 percent contracted the disease.
Failure to
recognize the sYmptoms of beryllium poisoning may have con-
tributed to an underreporting of this disease.
2.1.2.2
Other Phvsioloqical Effects
Chronic disease of the skin as a result of beryllium
exposure is relatively rare, but highly publicized as a result
of fluorescent tube breakage and in-plant accidents.
It occurs
infrequently since the discontinuance, in 1949, of the use of
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14
b ' f . 63
erylllum phosphors in fluorescent tube manu acturlng. How-
ever, Breslin9 believes contact dermatitis to be a significant
disease problem still in the beryllium extraction industry,
where massive quantities of sulfate and fluoride compounds are
processed.
Soluble salts of beryllium cause contact dermatitis as
well as conjunctivitis.
The dermatitis can progress to ulcera-
tion.
Conjunctivitis, resulting from accidental splashes of
beryllium salts, is similar to inflammations caused by other
irritants.
2.1.2.3
Community Episodes
According to Lieben,36 "Beryllium disease is to date
(1961) the only generally accepted chronic disease entirely
due to air contamination of the community atmosphere 0 II (How-
ever, there are reported cases of manganese pneumonia in Scan-
I' . 25~
dinavia and other neighborhood cases of asbestos ma 19nancles. J'
Eisenbud et al.;6 Lieben,34 and Lieben et £1.56 reported on
the following cases of community contamination:
(1)
Northern Ohio, 1948-1949.16,36
A total of 11
chronic cases of berylli~ disease occurred in the neighbor-
hood of a beryllium extraction plant in northern Ohio.
The
persons involved resided in the area of the plant, but none
were employed in or near the plant.
Five of these persons
lived within one-fourth of a mile from the plant, three within
half a mile, two within three-fourths of a mile, and one within
-------
15
2 miles.
Since 500 persons lived within a quarter-mile of
the plant, the prevalence of disease within that distance
approximated 1 percent as of 1961.
Air sampling in the
vicinity of the plant showed concentrations ranging from 0.000
to 2,100 ~g/m3 at distances of 750 feet from the plant; aver-
age concentrations at the three-fourth mile radius ranged
from 20 to 40 ~g/m3.
(2)
Pennsylvania, 1947-1959.36,56
Twenty-six cases
of chronic poisoning occurred in the vicinity of a beryllium
refinery and alloy fabricating plant in Pennsylvania, with
onset of sYmptoms occurring over a period of 12 years.
This
particular plant, covering 15 acres, is located in a shallow
valley through which prevailing winds
are
channelled--from
the northeast 9 months of the year, and from the southeast the
remaining 3 months.
Most of the cases occurred in the downwind
sectors from the plant: one within 0.7 miles, eight within 2
miles, and the remainder within 3 to 6 miles.
Extensive sam-
pIing of the atmospheric concentrations, commenced in 1958,
revealed a mean concentration of 0.015 ~g/m3 in the area of
the plant.
Ten percent of the 500 samples showed concentra-
tions in excess of 0.035 ~g/m3.
Also noteworthy was the after-
math of a 2-week shutdown of the plant, which resulted in a
S 56 .
reduced mean concentration level of 0.0015 ~g/m3. ussman, ln
his comments about this reduced level, mentioned the possibility
that beryllium deposited on the ground and other surfaces in
-------
16
the area might become airborne.
Background levels of beryl-
lium, measured by Sussman elsewhere in the State, averaged
0.0002 I-Lg/m3.
Other neighborhood cases of less dramatic impact have
been reported earlier by Gelman18 and Hardy.22
2.1.3
Carcinoqenicitv
The Committee on Toxicology of the National Academy of
Sciences--National Research Counci12
reports
(1966):
"While
certain beryllium salts and oxides have been productive of
osteogenic sarcomas in rabbits following intravenous adminis-
tration and primary lung tumors in rats and monkeys following
inhalation, there is no evidence that community or industrial
exposure to beryllium compounds is associated with an increase
in the incidence of cancer in humans."
According to Hardy.23 there were (in 1966) 20 malignant
tumors recorded among the 735 Registry cases; five of these
are lung cancer, and one a bone tumor.
Without knowledge of
population at risk or more complete data, it is impossible to
incriminate beryllium as a carcinogen in human beings.
However,
beryllium has a long residence time in the body and therefore
may have a cancer-producing effect.
2.2
Effects on Animals
2.201
Commercial and Domestic Animals
No information has been found in the literature on the
effects of beryllium or its compounds on domestic or commercial
-------
17
animals.
It is possible that accidental poisoning of animals
has occurred simultaneously with the instances of 'neighborhood
cases" of beryllium poisoning in humans.
However, the promi-
nence accorded to human cases, and the volume of data attend-
ing these cases, undoubtedly so overshadowed the animal cases
that they received no mention in the literature.
The Community Air Quality Guide for Beryllium, estab-
lished by the American Industrial Hygiene Association,13
states that "no potential harmful effects are reported for
animal exposures at outdoor air concentrations."
2.2.2
Experimental Animals
Recognition of the toxic effects of beryllium and the
increasing incidence of beryllium disease in and around indus-
trial plants resulted in a vast program of experimental
research to identify and quantify the toxic characteristics of
beryllium and its various compounds.
A large amount of
research employing laboratory animals has been recorded in the
literaturei an excellent summarization of this work is con-
tained in the chapter entitled "Experimental Beryllium Toxi-
cOlogy,,,60 written by Vorwald, Reeves, and Urban for the text
Beryllium--Its Industrial Hygiene Aspects, edited by Stokinger.
Much of the following discussion is condensed therefrom, unless
otherwise noted.
2.2.2.1
Acute Bervllium Disease
In order to understand the nature of beryllium pneumo-
nitis in humans, many experiments were conducted with reference
-------
18
to the effect of beryllium poisoning on the respiratory sys-
37
tern. Marradi-Fabroni observed acute and subacute bronchio-
litis and pneumonitis in guinea pigs exposed to atmospheres
of beryllium carbonate.
From these observations he concluded
that beryllium was the cause of the disease he labelled
"berylliosis."
51
In 1947, Sprague et ale
reported on experiments with
56 anirnals--2 dogs, 3 rabbits, 10 rats, 14 guinea pigs, 20
mice, and 7 hamsters--exposed to beryllium sulfate dusts and
beryllium metal fumes.
In atmGspheric concentrations of
800,000 ~g/m3, mice died within 11 days, while dogs, rabbits,
and guinea pigs survived: however, acute damage was observed
in the lungs, liver, and kidneys.
High concentrations, in the
order of 24,000,000 ug-min/m3,* produced pulmonary hemorrhage
and death, but at low concentrations (4,000,000 ~g-min/m3J
mice survived exposures for 60-day periods and developed tol-
erance to 10 times the otherwise lethal dose.
. 54,55
Stok~nger ~ ~. reported on observations of
approximately 500 animals exposed to concentrations of 100,000,
50,000, 10,000, and 1,000 ~g/m3 of beryllium sulfate mist.
The general results of these experiments are tabulated in
Table 3.
In experiments designed to determine whether inhaled
insoluble compounds would produce acute pneumonitis, Hall
19
et ale in 1950 exposed six different species of animals to
*~g-min/m3 = microgram-minutes per cubic meter.
-------
19
TABLE 3
RESULTS OF EXPOSURES OF BERYLLIUM SULFATE HEXAHYDRATE54,55
Concentration
iuq/m3 }
Total
Exposure
(hours)
Species of Animal
Effects
100,000
66
Laboratory rodents
plus monkeys,
goats, dogs, cats,
and chickens
Lethal to majority
of animals
50,000
234
II
II
II
10,000
426
II
LDS0 for rats;
typical pneumoni-
tis in most species
1,000
426
II
Detectable injury
in some species
aerosols of different grades of beryllium oxide dust at mean
concentrations of 85,000 ~g/m3 over periods of 6 hours daily,
5 days per week, for 10 to 17 days.
All oxides produced acute
pneumonitis.
In one experiment, four female dogs were exposed
to 10,000 ~g/m3 of low-fired oxide for 40 days; this concentra-
tion also resulted in acute disease.
60
Vorwald et ale concluded in their reVlew that certain
forms of beryllium, even in extremely small amounts, are capable of
producing an acute and often lethal inflammatory reaction in
the lung.
Altman et sl.5 have compiled data on the physiological
changes and mortality occurring in mammals and birds from the
inhalation of beryllium fluoride and beryllium sulfate.
These
data are presented in Table 13, Appendix.
-------
20
2.2.2.2
Chronic Bervllium Disease
Efforts to produce symptoms of chronic beryllium poison-
ing in experimental animals were largely unsuccessful until
experimental procedures were followed which closely resembled
exposure conditions under which this disease was contracted by
humans.
This required an extensive experimental period involv-
ing low concentrations of the pollutant, principally the insolu-
ble oxide. Prine ~ al.44 reported on experiments inducing
chronic beryllium disease in dogs, using beryllium oxide and
metallic beryllium, and noted the interesting fact that two of
the six animals exposed for 30 to 36 months developed the
characteristic pulmonary granulomas.
. d d59
In a similarly lengthy experimental per10 , Vorwal
exposed a group of rhesus monkeys to an atmospheric concentra-
tion of 35 ~g/m3 of beryllium sulfate aerosol.
The experiments
were continued for many months, with only occasional periods of
respite from the beryllium atmosphere as necessary to insure the
continued survival of the animals.
Laboratory examinations
subsequent to the death of the animals revealed that the beryl-
lium compounds had produced symptoms of widespread chronic
beryllium pneumonitis with associated granulomas.
Also, the
animals had developed primary bronchopulmonary cancer. In a
comment on this experiment, Vorwald et al.60 state, "With
respect to the inflammatory pulmonary changes in both the rat
and the monkey, the response is judged to be the respective
-------
21
animal's counterpart of the chronic beryllium pneumonitis as
seen in some human subjects after their exposure to toxic
beryllium compounds."
2.2.2.3
Carcinoqenicitv
As mentioned briefly in the preceding section, pulmonary
60
cancer was developed in monkeys by Vorwald et ale Case histo-
ries include mention of cancerous growths created by intra-
broncheal injection of beryllium oxide and by inhalation of
beryllium sulfate aerosol.
Exposures to average concentrations
of 35 ~g/m3 intermittently over the course of more than 5 years
resulted in death in two of the 10 monkeys.
These experiments
were still in progress as of 1966.
In these experiments, conducted by the same authors
subsequent to their previous work with rats, proliferations of
pulmonary epithelial cells were induced by either the beryl-
lium oxide or the sulfate.
Primary pulmonary cancer appeared
as early as 8 months after intratracheal injection and 9 months
after inhalation. The incidence of cancer was nearly 100 percent
in a group of 150 rats exposed daily for 13 months to beryllium
sulfate aerosol in concentrations of 21 to 42 ug/m3.
Even at
the very low concentration of 2.8 ~g/m3, 13 of 21 rats devel-
45
oped pulmonary cancer.
2.3
Effects on Plants
There is some indication that beryllium is toxic to
48
plant life. Romney. Childress, and Alexander investigated
-------
22
the effects of beryllium on bush beans, concluding that it
was toxic in levels in excess of 1 ppm in soil solution.
This
conclusion was based on tests of bush-bean growth in nutrient
solutions containing 0.0, 0.5, 1.0, 2.0, 3.0, and 5.0 ppm of
beryllium.
Reduced growth rates were noted at the increased
beryllium concentrations.
Hopkins43 also noted the toxic nature of beryllium sul-
fate on the growth of seedling roots.
According to the Community Air Quality Guide for Beryl-
lium,13 no harmful effects to vegetation at outdoor air con-
centrations have been reported.
2.4
Effects on Materials
No harmful effects to materials were reported in the
literature resulting from beryllium or its compounds in the
atmosphere.
According to the Community Air Quality Guide for Beryl-
lium, no reports of permanent materials damage or soiling
effects due to beryllium air pollution at outdoor air concen-
trations are known.
2.5
Environmental Air Standards
Environmental Standards for atmospheric concentrations
of beryllium were first proposed in 1948 by a Beryllium
Advisory Committee of the U.S. Atomic Energy Commission.
In
1949, the AEC adopted these recommended standards, which are
. b 1 11
summar1zed e ow:
-------
23
( 1 )
The in-plant concentration of beryllium should
not exceed 2 ~g/m3 as an average concentration throughout an
8-hour day.
(2)
An absolute concentration limit of 25 ~g/m:' should
not be exceeded for any period of time, however short.
(3 )
Community air (outside of plants handling beryllium
compounds) averaged over monthly periods should not exceed 0.01
~g/m3.
(No absolute limit for peak periods was stipulated.)
Annual review of these standards was made by the AEC
for 7 years subsequent to their adoption in 1949, with no
cause for revision noted.
The value of 2 ~g/m3, as the average concentration to
which persons may safely be exposed over the course of a normal
workday,
was adopted by the Threshold Limits Committee of the
American Conference of Governmental Industrial Hygienists in
1959.
In 1956, the American Industrial Hygiene Association
published a Hygienic Guide on Beryllium which adopted the val-
ues set forth by the Atomic Energy Commission.
The New York State Air Pollution Control Board6 has set
a limit of 0.01 ~g/m3 for a 24-hour average as the ambient air
quality objective for all its regions. This same value was
adopted by the Pennsylvania Air Pollution Commission3 in 1967,
based on an extensive study conducted by the Pennsylvania
Department of Health in an area surrounding a beryllium plant.
In 1966, the Advisory Center on Toxicology of the National
2
Academy of Science--National Research Council reported
on a
-------
24
study of the toxicity and hazards of beryllium conducted in
behalf of the U.S. Public Health Service and the Department
of Defense.
This report recommended tentative Air Quality
Criteria.
(These values were considered by the National
Academy of Science--National Research Council to be interim
criteria, pending the results of additional research into
toxicities of beryllium compounds.)
These tentative criteria
are as follows:
(1)
For continuous exposure, a level of 0.01 ~g/m3,
averaged over a 30-day period, applies.
(2)
For intermittent exposure to beryllium compounds
arising from rocket motor firings, the following
limits apply:
A.
Soluble beryllium compounds:
7 5 ~g-min/m3
within the limits of 10-60 minutes, accumulated
during any two consecutive weeks.
B.
Beryllium oxide comparable to a product cal-
o
cined at temperatures around 400 C: 75 ~g-min/m3
within the limits of 10-60 minutes accumulated
during any two consecutive weeks.
C.
Beryllium oxide comparable to a product calcined
at temperatures in excess of 1,600oC:
1,500
~g-min/m3 within the limits of 10-60 minutes
accumulated during any two consecutive weeks.
The report continues, "In applying the above criteria
-------
25
for intermittent exposure to firing of a rocket motor, it
will be necessary to consider simultaneously the concentra-
tion of soluble beryllium compounds, the 'low-fired' beryl-
lium oxide and the 'high-fired' beryllium oxide, and adjust
the limits accordingly.
For example, if the rocket effluent
is composed of acid-soluble beryllium (36 percent HCl diluted
1:1) in amounts greater than 1 percent but less than 5 percent,
the 'high-fired' limit of 1,500 ~g-min/m3 should be reduced
by a factor of two; if greater than 5 percent, the limit for
'low-fired' beryllium should be used."
It must be emphasized that these proposed criteria are
tentative recommendations, subject to further research into
the toxicities of beryllium compounds.
These criteria have
been seriously questioned by recognized authorities in the
. . . ff 25
field of berylllum and ltS tOX1C e ects.
In the Soviet Union, hygienic regulations have set the
maximum concentration of beryllium in production facilities
33 .,. 40
at 1 ~g/m3. Mll nlkov recommends a value of 1 to 2 ~g/m3
for beryllium acetate, and a value of 10 to 20 ug/m3 for
finely dispersed beryllium oxide, as limiting concentrations
in factory facilities for a 6-hour day.
Imposition of the AEC limits of exposure has undoubtedly
resulted in effective control of beryllium disease in the
United States.
However, many instances are noted in the litera-
ture which suggest that these levels may be overly conserva-
tive,11,32,53 and that additional research is indicated
-------
26
concerning the toxicity of individual beryllium compounds,
maximum tolerance levels, and the severity of exposure as a
result of length of time exposed.
-------
27
3.
SOURCES
3.1
Natural Occurrence
Beryllium (Be), one of the lightest of metals, is widely
distributed geographically, but exists in relatively small
quantities, comprising less than 0.006 percent of the earth's
crust.
In concentrated form, it is found in relatively few
minerals, and these are basically compounds of beryllium oxide.
The most important such minerals are as follows, listed
alphabetically: 34
Beryl
3BeO.Al?,°s.6Si02
Beryllonite
NaBeP04
Bertrandite
Be4Si207 (OH)?,
Bromellite
BeO
Chrysoberyl
Be (AI02 )2
Euclase
BeHA1S iOs
Hambergite
Be?, (OH)BOs
Helvite
Mn4Be2 Sis 012 S
Herderite
CaBeP04(OH,F)
Leucophanite
(Ca,Na)2BeSi2(0,OH,F)
Phenacite
Be2 Si04
Physically, beryllium has a very high strength-to-weight
ratio, great stiffness (exceeding other metals, including
o
steels), high melting point (1,285 C), and valuable nuclear
properties.
Pure beryllium is quite stable and tarnishes
slightly at room temperatures in dry air and in pure oxygen.
-------
28
When finely ground it burns with brilliant scintillations.
Its physical properties are tabulated in Table 14, Appendix.
3.2
Production Sources
The processes of extracting, refining, and machining of
beryllium-containing material produce considerable quantities
of airborne beryllium, and are considered the principal
sources of beryllium illness and poisoningo
Dusts are created
in crushing, grinding, and cutting operations.
Fumes result
from condensation of vapors created during melting. pouring,
or welding processes: the fumes consist primarily of the
oxide.
Mists of soluble beryllium compounds occur from such
operations as wet grinding and pOlishing: use of coolant
liquids reduces the atmospheric concentration, but the contami-
nated liquid then becomes a hazard.
The open-pit mining of ores, the recovery of beryllium
as the oxide, and the reduction of the oxide have not been
. 'f . 21,24,62
accompanied by tOX1C man1 estat1ons. It is only where
finely divided metal, oxide, or compounds have been processed
that serious toxic effects have been experienced among beryl-
lium workers and others working or residing near plants from
. 7.41
which beryllium-containing dust or fumes have been eJected.
3.2.1
Mininq
Beryl has been the only commercial source of beryllium,
and as there is extremely little commercial-grade beryl pro-
duced in the United States, all beryl for consumption has been
. t d 41
1mpor e .
While beryl is widely distributed, it has never
-------
29
been found in quantities sufficient to permit the mining of
this material for itself.
Therefore, it is produced only as
a by-product of the mining of other minerals, such as mica,
feldspar,
etc.
There are no known cases of human berylliosis
caused by inhalation of beryl dust, and mining is not con-
. 11 t' 21,24,62
s~dered a significant factor in beryllium air po u ~on.
In the United States, the minerals bertrandite and
phenacite are considered possible sources of beryllium, despite
their low grade (0.1-3 percent).
constitute a hazard to health. 53
These minerals may possibly
3.2.2
Extraction and Refininq
Beryl is converted to beryllium oxide by one of the
following processes:?
( 1 ,
Joy-Windecker Process--Clifton Product, Inc.
In this process the ore is fused with soda ash and the
product treated with strong sulfuric acid to obtain silica in
insoluble and filterable form, and aluminum and beryllium in
the form of water-soluble sulfates.
The major portion of the aluminum sulfate is first
separated from the beryllium sulfate by adding ammonium sul-
fate to the mixed sulfates.
The ammonium alum crystals formed
by this addition are separated, leaving a filtrate of beryllium
sulfate contaminated mainly with aluminum and iron.
The iron
is oxidized to the ferric state, and the filtrate is diluted
and treated with sodium carbonate to a pH of about 5.5.
The
-------
30
precipitate, containing about 95 percent of the aluminum
and iron and about 10 percent of the beryllium present, is
filtered off and separated.
This crude hydroxide is then
redissolved in sulfuric acid, the beryllium sulfate solution
produced is diluted, and the pH of the solution is adjusted
with ammonia to 5.5 to 5.7 to precipitate the remaining alumi-
num and iron as hydroxides.
After separation of these impuri-
ties, the filtrate is completely precipitated with ammonia.
The pure beryllium hydroxide formed is separated by filtra-
tion, washed, dried, and ignited to beryllium oxide of high
purity.
(2)
Fluoride Process (Copaux-Kawecki)--The BerYllium
Corporation
The ore is first ground in a ball mill, either wet or
dry, until the particles are about 0.07 mm in diameter.
It
is then mixed with sodium ferric fluoride and made into wet
briquets, which are heated for about an hour at 750oC.
The
sodium ferric fluoride reacts selectively at 7500C with the
beryllium oxide in the beryl ore, forming sodium beryllium
fluoride and ferric oxide according to the equation:
3BeO.Al~Os.6SiO~ + 2NasFeFs =
3Na2BeF4 + Fe20s + A120s + 6SiO?
(3)
Sulfate Process (Sawver-Kiellqren Process)--Brush
Beryllium Co.
The beryl ore is first completely melted at approximately
1,6250C and then quenched in cold water.
The melted beryl is
-------
31
poured into water to obtain a frit, which is ground in a
ball mill.
This renders the ore susceptible to attack by
sulfuric acid at 27Soc.
The main reactions involved are:
3BeO.A120s.6Si02 + 6~S04 =
3BeS04 + A12(S04}s + 6SiO~ + 6~0
3BeS04 + A12(S04} + (NH4)2S04(excess) =
3BeS04 + 2AINH4(S04)~ + (NH4)2S04
6BeS04 = 6BeO + 6S02 + 302
Beryllium is produced as sOlid-lump metal by reducing
an excess amount of beryllium fluoride in solid form with
magnesium metal charged in a graphite-lined furnace at a cru-
cible temperature of about 900oC.
A slag of magnesium fluoride
and beryllium fluoride is produced.
Solid beryllium metal is
recovered after the reaction is completed by raising the
temperature to 1,300oC., somewhat above the melting point of
beryllium.
The molten beryllium, which floats on top of the
molten slag, is collected into a pool and then quickly solidi-
fied into a floating cake of solid beryllium.
This process is based on the following reactions:
BeO + 2NH4F.HF = (NH4)2BeF4 + H20
(NH4)2BeF4 = 2NH4F + BeF2
Eisenbud et al.16 estimated in a careful engineering
study that one extraction plant discharged 5 kg of beryllium
per day.
Hazardous concentrations can be expected whenever
-------
32
certain beryllium compounds are heated even to moderate tem-
peratures.
57
The following table (Table 4), from Tepper et ale
indicates the variation in emissions caused by increasing the
temperature of different compounds.
TABLE 4
THEORETICAL AIR CONCENTRATIONS OF BERYL~IUM
BASED ON VAPOR PRESSURES OF MATERIALS 7
(oC) Beryllium
Compound Temperature Concentration (UQ/m3)
Beryllium 885 2
1,060 200
Beryllium oxide 1,710 2
1,990 200
Beryllium oxide and
water vapor 1,400 0.68 x 106
Beryllium fluoride 420 2
525 200
Beryllium chloride, 108 2
iodide, bromide 158 200
Beryllium borohydride 20 4.35 x 106
Prior to recognition of the hazardous nature of this
metal, the dusts, mists, and fumes resulting from industrial
operations were permitted to pass into the atmosphere without
control.
In 1947-48, a period in which controls were just
corning into general use, the AEC conducted a survey of occu-
pational exposures within beryllium plants.
The following
tables present data on pollution concentrations in various
phases of the industry:
-------
33
TABLE 5
BERYLLIUM OXIDE PRODUCTION
LORAIN, OHI063
Process
Air Pollution Dataa
G.A.D B.Z.c G.A.-B.Z.d
Ore reduction
440; 212;
12 212;
380;
235;
318
1,350
267
102
Sulfating (hot mill) 173; 28; 96
Sludge repulp.
(wet process)
2
230; 20
176
150; 600
BeS04 crystallizing
(wet process)
22; 17; 2
15; 11; 24
1.4; 9; 42
45,200; 270
16.2; 31
247; 32; 18
12; 14; 55
28
1,135; 27
420; 18; 19
140
BeS04 calcining
6,450
83,000
76,000; 2,100
3,500
aAir pollution data recorded in ~g/m3, air samplings
taken between 10-23-47 and 2-26-48. Total: 50, listed in
chronological sequence.
bGA
= General air within the plant.
cBZ
= Breathing zone of a given worker on a specific
operation.
dGA-BZ = Transitionary exposure to both breathing zone
and general air conditions.
-------
34
Table 6 gives data for 1947-48 on the environmental
concentrations to which workers were exposed in the fluoride
process of producing metallic beryllium from the beryllium
oxide:
TABLE 6
BERYLLIUM METAL PRODUCTION
LORAIN, OHI063
Air Pollution Data
Process G.A.b B.Z.b G.A.-B.Z.D
(NH4 )2BeF4 180; 770
(wet process) 19,000; 200
16; 6.2
(NH4)2BeF4 decomp. 36; 746; 48 49; 184; 2,118 23
200; 97; 44 1,765; 8; 16
33; 110; 35 380
110; 35; 100
8; 10; 7; 21
BeF2 crushing 2,295; 550
BeF2 reduction 187; 146
Melts crushing 8; 23; 7; 76 2,470; 6,000 4,950
Pebble: leaching, 28.2; 177 1,320; 1,128
flotation (wet), 4.8
drying, sorting, 9,010; 883
screening (dry) 27; 196
aAir pollution
taken between 10-23-47
chronological order.
b
See footnotes
data recorded in ~g/m3, air samplings
and 2-26-48. Total: 48, listed in
for Table 5.
-------
35
Table 7 presents similar data for the powdering, sinter-
ing, and milling of beryllium:62
TABLE 7
BERYLLIUM METAL POWDERING, SINTERING, MACHINING
LORAIN, OHIO, AND CLEVELAND, OHI063
Air Pollution Dataa
Process b b D
G.A. B.Z. G.A.-B.Z.
Rolling Be chips 1,461; 324 35,890
11,914
Bottling chips 41 8,687
Attrition mill 1,227: 1,277
Powder drying 51
Sintering 32.7: 184.6
16: 7: 28: 37
65
Machining 461: 70: 35
45: 38: 32
aAir pollution
taken between 10-23-47
chronological order.
bSee footnotes
data recorded in ~g/m3, air samplings
and 2-26-48. Total: 23, listed in
for Table 5.
The major producers of beryllium in the United States
are:
The Beryllium Corporation, Reading and
Hazelton, Pa.
Brush Beryllium Company, Elmore, Ohio
The world and U.S. production of beryl for the years
1957 to 1966 are presented in Table 8.
-------
36
TABLE 8
53
PRODUCTION OF BERYL
Short Tons
1957-61 1962 1963 1964 1965 1966
World 11,080 11,000 7,700 5,200 4,900 3,600
United States Ua 978 751 vP vP vP
aU = Unknowno
bw = Withdrawn:
company confidential.
Research into new uses for beryllium, plus the impetus
of the aircraft and space industries' interest in this metal,
indicates increasing demand for beryllium production in the
future.
3.3
Product Sources
Beryllium has found a number of important uses in
industry.
These uses are of significance to air pollution
mainly during the initial processing period: however, in cer-
tain instances hazards to health continue to exist after the
production of the particular producto
The wide variety of
uses to which beryllium is being put may cause unintentional
worker exposure to levels of beryllium which may pose a threat
to healtho
This is particularly true of small machine shops
and foundries, which tend to have inadequate industrial health
practices.
An additional hazard is the possibility of neigh-
borhood contamination arising from small plants having
-------
37
inadequate pollution control devices.
3.3.1
BerVllium-Copper Allovs
A large part of the beryllium produced is used as a
hardening agent in alloys, the most common of which is beryl-
lium copper.
Depending upon the beryllium content, the alloy
can be high strength (high beryllium content) or high-
conductivity (low beryllium content).
This alloy is formed by
the direct reduction of beryllium oxide with carbon in the
presence of copper, resulting in a 2 to 4 percent beryllium
alloy.
Dusts and fumes of beryllium oxide can be emitted in
the alloying process and in the reduction process to refine
scrap alloy.
The proportion of beryllium to the basic metal
is not a reliable index of the degree of hazard attending the
57
manufacture of the alloy~ Tepper et ale reported on cases
of beryllium poisoning occurring from production of copper
alloy of 2.75 percent beryllium, during machining and surface
grinding, when no control procedures were used.
Air sampling
revealed 0.39 to 0.78 ~g/m3 during melting and pouring, 3.55
to 21.20 ~g/m3 during drossing and casting, and 87 to 144
~g/m3 during dry surface grindingo
Table 9 indicates the concentrations of beryllium in
the air at a number of locations within a beryllium-copper
alloy plant,12 in the year 1960, as observed by the Kettering
Laboratory, University of Cincinnati, Ohio.
3.3.2
Fluorescent Tubes
Beryllium oxide is no longer used in the manufacture
-------
38
TABLE 9
MEAN, MEDIAN, AND RANGE VALUES OF BERYLLIUM
CONCENTRATIONS (2-HOUR AVERAGES)12
Concentration ~n uq/m3
Location Hours Median Averaqe Ranqe
Oxide area 92 72.5 149.4 0.4 -1,050.0
Arc furnace area 92 50.0 87.6 22.1 -502.0
Mixing area 92 14.4 21.6 0.03-452.0
Cropping area 92 33.6 52.8 14.0 -399.0
Casting area 86 14.6 39.8 0.2 -535.0
Fischer furnace area 91 28.8 40.8 0.2 -340.0
Oliver saw area 90 21.1 25.6 <2.5 -92.5
All areas 635 28.4 60.3 0.3 -1,050
of fluorescent light tubes.
However, much of the history of
beryllium disease, and the controls upon the beryllium industry,
stem from this usage in the 1940's, and mention should there-
fore be made of this source of emission~.
In the manufacturing
process,
tube phosphors were prepared using beryllium oxides
(ranging from 4 to 13 percent), zinc, magnesium, and manganese,
fired at a high temperature.
Dusts and phosphor powders were
present in high concentrations, but largely unmeasuredo
The
prevalence-of-disease rate ran approximately 3 percent of the
1. . k 57
popu at~on at r~s. It was significantly higher in the
plant using 13 percent beryllium oxide than in the plants
using 4 percent beryllium oxide.
In 1949, the use of beryllium
-------
39
oxide in fluorescent tubes was discontinued.
3.3.3
Rocket Fuels
Finely powdered metallic beryllium may be used as an
additive in rocket fuels, to provide increased performance
h t. . 12
c arac erJ.stJ.cs.
Three separate air pollution hazards occur
from this usage:
handling of the beryllium metal prior to
launch; exhaust fumes resulting from firing; and the possible
dangers from accidental explosions or fires.
Exhaust fumes
are predominantly beryllium oxide, with other compounds pres-
ent depending upon the chemical formulation of the propellant
char ge .
For example, one analysis of rocket exhaust products
revealed that 50 percent of the total beryllium was beryllium
oxide, 40 percent beryllium fluoride, and the remainder was
mainly beryllium chloride.47
Analyses of residues from the burning of rocket pro-
pellants containing beryllium additives have been conducted
by the Hercules Powder Company and the Kettering Laboratory.12
These analyses revealed that a number of compounds of beryl-
lium,
including the chloride and the oxide, as well as metallic
beryllium, were present in the residue from the propellants.
Approximately 70 percent of the total metallic beryllium used
in the propellant was recovered in the residue, indicating
that 30 percent presumably escaped into the atmosphere.
The handling, storage, and use of beryllium metal as a
rocket fuel is obviously a localized problem.
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40
3.3.4
Coals
Beryllium is a constituent of most coals, in varying
concentrations.
The average contents in coal of the three major
coal-producing areas of the United States are:l
Area Averaqe Minimum Maximum
Northern Great Plains 1.5 ppm <0.1 9.1
Eastern Interior 2.5 ppm 0.5 12.0
Appalachian Region 2.5 ppm 0.1 31.0
Despite these low concentrations, the amount of beryl-
lium added to the atmosphere by the burning of coal may be
significant, in view of the quantity of coal consumed in the
United States.
304
Other Sources
The laundering of garments used by beryllium workers
can be a significant source of beryllium in the local air.
Eisenbud et alo16 reported that home laundering of clothes
contaminated with beryllium dusts could result in inhalation
57
Tepper et ale mention a
of 17 ~g of beryllium per day.
study of garments used by workers performing cylindrical
grinding of beryllium parts:
aprons contaminated by spatter-
ing of coolant and by the operators' hands produced a concen-
tration of 7.7 ~g/m3 of beryllium when shaken in a dust
chaniber.
As noted in Section 2, some "neighborhood" cases of
beryllium poisoning resulted from home laundry of workers'
garments.
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41
3.5
Environmental Air Concentrations
Beryllium is known to be present in the atmosphere,
and measurements have been made of its concentrations.
Beryl-
lium is now included in routine measurements of atmospheric
constituents from the National Air Sampling Networks.
Air
f" 4
Quality Data. 19ures of average and maximum concentrations
reveal that the daily average atmospheric concentration of
beryllium for 100 stations in the United States is less than
0.0005 ~g/m3, and the maximum value recorded for the 1964-65
period is 0.008 ~g/m3.
Tabular data for these 100 stations
are listed in Table 15, Appendix.
10
Chambers et ale analyzed
air samples collected from over 30 metropolitan areas, and
found a maximum value of 00003 ug/m3.
The variation of aver-
age atmospheric beryllium concentrations from urban areas
(over 2 million population) to small cities to rural areas is
demonstrated by the following data from Chambers et al.lO in
Table 10.
The authors acknowledge the limitations of this
work,
including the methods used, the selection of the loca-
tions, extent of coverage, and the inherent defects in analysis
of data based only on particulate samples; however, despite
these limitations, their work provides useful comparative data.
An air pollution study of atmospheric concentrations of
beryllium in the vicinity of a large beryllium plant near Read-
ing, Pa., was conducted in 1958.56 The average concentration
within one-half mile of the plant was 0.0281 ug/m3; concentra-
tions closer to the plant reached 0.0827 ~g/m3.
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42
TABLE 10
10
AVERAGE BERYLLIUM CONCENTRATIONS FOR SELECTED AREAS
Area
Concentration
(i-1g/m3 )
Cities over 2,000,000
Los Angeles
Detroit
Philadelphia
Chicago
New York
0.0001
0.0004
0.0005
0.0002
0.0003
Cities between 500,000-2,000,000
Cincinnati
Kansas City
Portland (Oreg.)
Atlanta
Houston
San Francisco
Minneapolis
0.0002
0.0003
0.0003
0.0002
0.0002
0.0001
0.0002
Rural (Suburban)
Boonsboro (Md.'
Salt Lake City
Atlanta
Cincinnati
Portland (Oreg.)
0.0001
0.0001
0.0002
0.0001
0.0001
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43
4.
ABATEMENT
Efforts to reduce concentrations of beryllium in the
atmosphere have generally centered on the problem of reducing
industrial concentrations of beryllium, where exceptional
success has been achieved.
Control activity has mainly sur-
rounded significant beryllium plants, where concentrations of
beryllium dust, produced within the plant, are discharged to
the outside atmosphere through intent or by accident.
Recog-
nition of beryllium as a cause of industrial disease in the
early 1940's has led to sweeping changes in manufacturing
processes and controls designed to reduce the concentration
of atmospheric beryllium, both in-plant and out-of-plant.
Conventional air-cleaning devices have been used.
For wet
chemical processes, scrubbers, venturi scrubbers, packed
towers, organic wet collectors, and wet cyclones have been
found to be effective.
For dry processes, conventional bag
collectors, reverse-jet bag collectors, electrostatic precipi-
tators, cyclones, and unit filters have been used.
Table 11
. 49
contains a listing by Sllverman of air-cleaning devices and
their expected efficiency.
The effectiveness of abatement activities can be
appreciated by comparing present-day industrial exposure con-
centrations with concentrations existing prior to recognition
of the significance of beryllium air pollution to industrial
health. Breslin9 states that current practices limit employees'
-------
TABLE 11
49
CLEANERS POR BERYLLIUM HANDLING OPERATIONS
44
Operation or
Process Phase
Ore handling, crushing,
etc.
Sinter furnace
Leaching and hydroxide
filter
Sodium fluoride
handling
Beryllium hydroxide,
dry
Beryllium hydroxide
drier and calciner
Beryllium fluoride
mixer
Beryllium fluoride
furnace
Reduction furnace
Ball mill
Machinery, powder,
metals handling
Welding, heat-treating
Miscellaneous labora-
tory hoods
Type Cleaner
Reverse-jet or shaking bag
filter
Wet cell or spray scrubber
Wet cell or spray scrubber
Wet cell or spray scrubber
Reverse-jet or shaking bag
filter
Wet spray for cooling, then
reverse~jet or shaking
bag filter
Wet cell or spray tower
Venturi or orifice scrubber
or packed tower and wet
Cottrell unit
Venturi or orifice scrubber
or packed tower and wet
Cottrell unit
Wet cell washer
Small cyclone units plus
bag filter with asbestos
filter aid
Bag filter with filter aid
and dilution air to bring
temperature to 1800p
Roughing filter plus high-
efficiency AEC-type
filter
Expected
Efficiency
by Weight
(Percent)
99
80
80
80
99
99
80
95
95
80
99.9
99.9
99.95
-------
45
exposure to beryllium dust to about 2 ~g/m3 or less, with
out-of-plant neighborhood concentrations limited to 0.01
~g/m3 .
U. . f h 35
By comparison, n1vers1ty 0 Roc ester samples
of beryllium concentration in a Cleveland factory in 1946
revealed concentrations as high as 4,710 ~g/m3.
Another form of control is exemplified by discontinu-
ance of the use of beryllium in fluorescent lamp tubes in
1949; this action eliminated an industrial exposure to beryl-
lium which had been responsible for approximately one-third
. . 17
of all beryllium resp1ratory 1l1nesses.
-------
46
5.
ECONOMICS
No losses resulting from damage to plants or materials
have been recorded from beryllium air pollution.
It is
difficult to assess the economic costs of loss of life or
illnesses resulting from beryllium disease, and no statisti-
cal data have been found on this subject.
However, court
cases are now pending in Pennsylvania that are based on
impairment of health resulting from beryllium exposure.
Schulte and Hyatt62 reported one particularly detailed
study on the economics of industrial hygiene control in a
beryllium machinery plant in the Los Alamos Scientific Labora-
tory (New Mexico) in 1958.
The cost figures produced by this
study are as follows:
Item
Cost/Year
Construction of shop area to incorporate
control facilities (1,000 sq. ft., at
$22.00/sq.ft. amortized over 20 years) . . 0 . 0 . $ 1,100.00
Ventilation system ($12,000 depreciated over
15 years at annual cost of $800) . . . . . .
.00
800.00
Clothing for four workers (coveralls, shirts,
shorts, socks, caps, and shoe covers} ......
274.00
Additional work-time required by hygienic
procedures necessary for beryllium control
. . . .
8,000.00
Air sampling equipment (amortized over 5 years). .
160.00
Air sampling operations
. . 0 . .
. . . . . . 0 .
250.00
Chemical analysis at $5.00/sample, 344 samples. .
1,720.00
Laundering of shop clothing
. .0. .
. . . . . .
1,000.00
(continued)
-------
47
Item
Cost/Year
Janitorial (no extra costs)
o . . . . . . .
. . .
$
Filter changing and ventilation maintenance
. . .
112.00
Trash disposal
. . . . . . . .
. . . . . .
. . .
150.00
Medical examinations ($25.00/man)
. . . . .
. . .
100.00
Total costs
$13,666.00
As the average cost of machine shop operation for the
four-man shop is $70,000 per year, the added costs for hazard
control run approximately 20 percent.
According to Tepper,57 in many instances the recovery
of valuable materials will significantly offset the costs of
abatement of beryllium air pollution.
Data on the production and consumption of beryllium
are presented in Section 3.
-------
48
6.
METHODS OF ANALYSIS
6.1
Samplinq Methods
The most common method of sampling beryllium concen-
trations in air employs a high-volume sampler which draws air
to be analyzed through a filter for the appropriate sampling
period.13 The Hi-Vol sampler--which samples at a rate of 1.5
to 1.7 m3/min when operated 24 hours--will provide an adequate
sample for the measurement of beryllium in ambient air in con-
centrations as low as 0.002 ug/m3.
Cellulose-fiber filter
paper with very low ash content is widely used~ cellulose
ester and fiberglass papers are also used, and are particularly
suitable for use when collecting contaminants are of very small
size.
Quantitative Methods
6.2
Atmospheric beryllium may be analyzed by colorimetric,
11
fluorimetric, or spectrographic procedures. These methods
are accurate and sensitive but do not discriminate between the
various compounds of beryllium.
6.2.1
Morin Fluorescent Method
The morin method is suitable for measuring quantities
of beryllium in the air surrounding beryllium plants~ its
b . 11
lower limit of detection is approximately 0.01 ~g of erylllum.
In this procedure, the beryllium is removed from the filter,
processed to remove interfering elements and to form an alka-
line solution, and fluorescent morin solution (C1sHl007-H20)
-------
49
is added.
Beryllium acts to reduce the fluorescent charac-
teristics of the morin solution, as a direct function of the
quantity of beryllium present.
Measurement of the fluorescence
by fluorimeter against standard samples indicates the quantity
of beryllium.
(Note:
Reference 31 states that the procedure
is sensitive to 0.00002 ~g/ml of the solution.
6.2.2
Colorimetric Method
This method, commonly called the Zenia method,
is
suitable for large concentrations from which at least 2 ~g
of beryllium can be obtained, and is used in monitoring the
atmospheres of industrial plants.
The procedure involves
removal from the filter paper, removal of interfering elements,
and addition of the Zenia (p-nitrobenzeneazoorcinol) solution.
Zenia solution added to a beryllium solution forms a reddish-
brown solution~ whose absorption of light is a function of its
beryllium content. Measurements can be made subjectively, to
15
give a quick spot-check, or by means of a spectrophotometer.
. 1. d 31
Sensitivity to 0.5 ~g/ml of solution 1S c a1me .
6.2.3 Spectroqraphic Methodll
This spectrographic method is considered suitable for
measuring concentrations in the general atmosphere, as it per-
11
mits detection of trace quantities down to 0.003 ~g.
Also,
automatic detectors are available that are capable of handling
large numbers of samples rapidly and accuratelyo
adds a thallium standard to the beryllium-zenia solution
This method
-------
50
produced in the colorimetric method, concentrates the solu-
tion, subjects it to an electric arc, and photographs its
spectra.
The ratio of the intensity of the beryllium line
at 2348.6R to that of the thallium line at 2379.7R is deter-
mined, giving a measure of the concentration of beryllium.
McCloskey38 reported on a variation of this method
using aluminon reagent in place of the Zenia solution that
was said to be more sensitive than the normal spectrographic
procedure.
6.2.4
Other Methods
Another method for automatic monitoring of beryllium
in air, under development by the U.S. Air Force, was reported
on in 1963 by Braman8 of the ITT Research Institute. This
device attempted to use the nuclear reaction of beryllium for
the detection of beryllium.
Design goals called for an alarm
signal at 25, 2, and 0.01 ~g/m3 of beryllium over sampling
periods of 30 seconds, 1 hour, and 24 hours respectively.
Emission spectroscopy has been used by the National
Air Pollution Control Administration for beryllium analysis
of samples from the National Air Sampling Network.58 The
samples are ashed and extracted to eliminate interfering ele-
ments.
The minimum detectable beryllium concentration by
emission spectroscopy is 0.0008 ~g/m3 for urban samples and
0000016 ~g/m3 for nonurban samples.
The different sensitivi-
ties result from the different extraction procedures required
-------
51
7
for urban samples.
The National Air Pollution Control Administration uses
atomic absorption to supplement analyses obtained by emission
spectroscopy. The method has a minimum detectable limit of
58
0.01 ~g/m3 based on a 2,000 m3 air sample.
-------
52
7.
SUMMARY AND CONCLUSIONS
Inhalation of beryllium or its compounds is highly
toxic to humans and animals, producing bOdy-wide systemic
disease commonly known as beryllium disease.
Both acute and
chronic manifestations of the disease are known.
The effects
of beryllium intoxication can be mild, moderate,
or severe,
and can prove fatal, depending on the duration and intensity
of exposure.
Acute beryllium disease is manifested by a chemical
pneumonitis ranging from transient pharyngitis or tracheo-
bronchitis to severe pulmonary reaction.
As of June 1966,
215 acute cases had been recorded in the Beryllium Case
Registry.
Chronic beryllium disease generally occurs as lesions
in the lung. producing serious respiratory damage and even
death.
However, every organ system may be involved in response
to beryllium exposure, except for the organs in the pelvic
area.
The chronic form is characterized by a delay in onset
of disease, which may occur weeks or even years after exposure.
In June 1966, 498 chronic cases had been recorded, plus 47
acute-to-chronic cases.
Of the total 760 cases recorded in the Beryllium Case
Registry, 210 fatalities, or 27.5 percent, had occurred by
June 1966.
Cancer has been produced experimentally in animals,
-------
53
and 20 cases of cancer have been found (as of 1966)
in humans
afflicted with beryllium disease.
However,
insufficient
information exists at this time to causally relate beryllium
poisoning to development of cancer in humans.
Beryllium and its compounds can produce dermatitis,
conjunctivities, and other contact effects; however, these
manifestations are rare.
There is some evidence that beryllium in soils is
toxic to plant life; no evidence was found on the effects of
atmospheric beryllium on plants or on materials.
The major potential sources of beryllium in the atmo-
sphere are industrial.
The processes of extraction, refining,
machining, and alloying of the metal produce toxic quantities
of beryllium, beryllium oxide, and beryllium chloride, which
if allowed to escape into the atmosphere would cause serious
contamination.
Recognition of the serious hazards to health
from these sources has led to adaptation of control procedures
minimizing this potential.
However, beryllium in limited
quantity is emitted from these industrial processes, and dan-
ger also exists from accidental discharges.
One major source
of beryllium contamination--the use of beryllium in fluores-
cent light tubes--was discontinued in 1949.
could be the use of metallic beryllium in rocket fuels, and
Other sources
the combustion of coals.
Rocket fuels could present a hazard
in the handling and storage of the powdered metallic beryllium
-------
54
used as an additive in the fuels.
Also, the exhaust fumes,
which contain oxidized beryllium as well as other compounds
of beryllium, would be of significance in local soil and air
pollution if not contained.
As beryllium is a normal constitu-
ent (above 2 ppm) of coals, the combustion of coal may add a
significant quantity of beryllium to the atmosphere.
Measurements are made of the beryllium concentration
at 100 stations in the United States.
The average 24-hour
concentration is less than 0.0005 ~g/m3; the maximum value
recorded during the 1964-65 period was 0.008 ~g/m3.
Abatement measures have been implemented industry-wide,
with a very high degree of success.
conventional air-cleaning
procedures have been employed, including the use of electro-
static precipitators, bag houses, scrubbers,
etc.
These pro-
cedures have enabled the beryllium industry to meet the indus-
trial hygiene standards established for beryllium.
Data on the economic losses resulting from beryllium
air pollution are not available.
Court cases are pending in
the State of Pennsylvania, however, which may provide data on
the economic values of impairment to health resulting from
exposure to beryllium.
Only one analysis of the costs for
abatement was found.
This study indicated that the added
costs for control amounted, in 1952, to approximately 20 per-
cent of the normal cost of operation for the particular plant
analyzed.
-------
55
Methods of analyzing beryllium in the atmosphere are
available, and are adequate for normal industrial processes.
The most common methods are the Zenia method, the morin fluo-
rescent method, and the spectrophotometric method.
The Zenia
method is relatively simple, works well with high concentra-
tions, and provides sensitivity on the order of 0.5 ~g/m3.
It can also be used subjectively, to provide a quick spot-
check for the presence of beryllium materials.
The morin
fluorescent method provides a higher sensitivity range (0.01
~g/m3) and is suitable for monitoring out-of-plant concentra-
tions in the vicinity of beryllium processing plants if a
large enough volume of air is sampled.
The spectrographic
process gives even higher sensitivities (0.003 ~g/m3} and is
suitable for monitoring concentrations in the general atmo-
sphere 0
However, none of the currently available procedures
provides for discrimination between the various compounds of
beryllium, or differentiation between the "low-fired" (highly-
toxic) and the "high-fired" (less toxic) forms of beryllium
oxide.
Based on the material presented in this report,
further studies are suggested in the following areas:
(1) Further research into the pathogenesis of beryl-
lium disease, with particular emphasis upon the
effects of protracted exposures to low
concentrations.
-------
56
(2) Further research into the carcinogenicity of
beryllium compounds.
(3) Analysis of the contribution of coal combustion
to beryllium pollution of the atmosphere.
(4) Development of procedures for analysis of differ-
ent compounds of beryllium present in the
atmosphere.
(5) Development of improved methods for characteriza-
tion of combustion products of rocket fuels con-
taining beryllium compounds.
-------
10.
11.
57
REFERENCES
1.
Abernethy, R. F., and F. N. Gibson, Rare Elements in
Coal, u.S. Bur. Mines Inform. Circ. IC8163 (1963).
2.
Air Quality Criteria for Beryllium and its Compounds,
Committee on Toxicology and the Advisory Center on Toxi-
cology, National Academy of Science--National Research
Council, Washington, D.C. (March 1966), in Hearinqs
before a Subcommittee on Air and Water Pollution of the
Committee on Public Works, United States Senate, 89th
Congress, u.S. Govt. Printing Office, Washington, D.C.
(1966) .
3.
Air Quality Criteria for Pennsylvania, J. Air Pollution
Control Assoc. (Jan. 1968).
4.
Air Quality Data from the National Air Sampling Networks,
1964-65, U.S. Dept. of Health, Education, and Welfare,
Public Health Service, Cincinnati, Ohio (1966).
5.
Altman, P. L., et al., Environmental Biology, Aerospace
Medical Research Laboratories, Wright-Patterson Air Force
Base, Ohio (Nov. 1966).
6.
Ambient Air Quality Objectives--Classification System,
New York State Pollution Control Board (1964).
7.
Beryllium, Actual and Potential Resources, Toxicity, and
Properties in Relation to its Use in Propellants and
Explosives, U.S. Naval Ordnance Laboratory, Bureau of
Naval Weapons Report 7346 (March 1961).
8.
Braman, R. S., Research and Development of an Automatic
Beryllium-in-Air Monitor, U.S. Air Force Systems Journal
Report RTD-TDR-63-1112 (1963).
9.
Breslin, A. J., "Exposures and Patterns of Disease in the
Beryllium Industry," Chapter 3 in Bervllium--Its Industrial
Hvqiene Aspects, H. E. Stokinger, Ed. (New York: Academic
Press, 1966).
Chambers, L. S., M. S. Foter, and J. Cholak, A Comparison
of Particulate Loadings in the Atmospheres of Certain
Cities, Proc. Nat. Air Pollution Symp., 3rd, Pasadena,
Calif. (1955).
Cholak, J., R. A. Kehoe, L. H. Miller, F. Princi, and L.
J. Schafer, Toxicity of Beryllium, U.S. Air Force Systems
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12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
58
Cholak, J., R. A. Kehoe, and L. J. Schafer, Toxic Hazards
of Beryllium Propellant Operations, Air Force Systems
Command Report AMRL-TDR-64-75 (Sept. 1964).
Community Air Quality Guide for Beryllium, Am. Ind. Hyq.
Assoc. J. 29 (1968).
DeNardi, J. M., H. S. Ordstrand, G. H. CUrtis, and J.
Zielinski, Berylliosis, Summary and Survey of All Clinical
Types Observed in a Twelve-Year Period, Arch. Ind. Med.
~: 1 (195'3).
Donaldson, H. M., R. A. Hiser, and C. W. Schwenzfeier,
A Rapid Method for Determination of Beryllium in Air
Samples, Am. Ind. Hyq. Assoc. J. 22:280 (1961).
Eisenbud, M., R. C. Wanta, D. Dustan, L. T. Steadman,
W. B. Harris, and B. S. Wolf, Non-Occupational Berylliosis,
J. Ind. Hyq. Toxicol. 31:282 (1949).
Fluorescent Lamp Makers stop Use, Beryllium-Industry
Hyqiene Newsletter 2 (1949).
Gelman, I. G., Beryllium Occupation and Health Supplement,
International Labor Office, Geneva (1938).
Hall, R. H., J. K. Scott, S. Laskin, C. A. Stroud, and
H. E. Stokinger, Acute Toxicity of Beryllium, III, A.M.A.
Arch. Ind. Hyq. Occupational Med. ~:25 (1950).
Hall, T. C., C. H. Wood, J. D. Stoeckle, and L. B. Tepper,
Case Data from the Beryllium Registry, A.M.A. Arch. Ind.
Health 19:100 (1959).
Hannan, J. W. G., et al., Beryllium Disease, Diseases of
the Chest 48(5):550 (1965).
Hardy, H. L., Delayed Chemical Pneumonitis in Workers
Exposed to Beryllium Compounds, Am. Rev. Tuberc. 57:547
(1948).
Hardy, H. L., Beryllium Poisoning----Lessons in Control of
Man-Made Disease, New Enql. J. Med. 273(22):1188 (1965).
Hardy, H. L., Statement in Hearinqs before a Sub-committee
on Air and Water Pollution of the Committee on Public
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-------
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,
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-------
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-------
63
OTHER REFERENCES
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-------
APPENDIX
-------
APPENDIX
TABLE 12.
PROPERTIES, TOXICITY, AND USES OF BERYLLIUM AND SOME BERYLLIUM COMPOUNDS38
Compound
Beryllium
Be
Beryllium
acetate
C4 Hs Be04
Beryllium
acetate,
basic
Be40(OCOCH3)s
Properties
mp 1,2840-
1,3000C
bp 2,9700C
gray metal
Decomposes
60-1000C
Crystals
o
mp 285-286 C
bp 330-3310C
Toxicitv
Death may result from
short exposure to incredi-
bly low concentrations of
the element and its salts.
Concomitant exposure to
acid fumes (hydrofluoric)
may increase toxic
effects. Contact derma-
titis, chemical conjuncti-
vitis, corneal burns, non-
healing ulceration at site
of injury, subcutaneous
nodules may occur follow-
ing exposure.
Acute: pneumonitis may
result from single expo-
sure to beryllium and
occasionally is fatal.
Chronic: pulmonary granu-
lomatous disease may
appear in 3 months to 15
years, often after short
exposure to low concentra-
tion. Uncertainty as to
complete recovery. Death
rate about 25%
See beryllium
See beryllium
Uses
As source of neutrons when
bombarded with alpha parti-
cles, according to the
equation
9 Be + 4 He -> 1 2 C + 1 n
4 :2 S 0 0
This yields about 30 neu-
trons per million alpha
particles. Also as neutron
reflector and neutron mod-
erator in nuclear reactors.
In beryllium copper and
beryllium aluminum alloys
(by direct reduction of
beryllium oxide with carbon
in the presence of Cu or
AI). In radio tube parts,
television tube phosphors,
fluorescent tubes
0"\
U1
,
- ,
-------
TABLE 12. PROPERTIES, TOXICITY, AND USES OF BERYLLIUM AND SOME BERYLLIUM COMPOUNDS (Continued)
Compounds
Beryllium
acetylace-
tonate
C1oH14Be04
Beryllium
borohydr ide
Be (BH4 )?,
Beryllium
bromide
BeBr"
Beryllium
carb ide
Be2C
Beryllium
chloride
BeC12
Properties
Monoclinic
crystals.
mp 10SoC
bp 270°C
Spontaneously
flammable
Sublimes at
91.30C
Decomposes
above 123°C
Crystals
mp 4SSoC
Sublimes at
473°C
bp S200C
Decomposes
°
above 2,100 C
Br ick-red or
yellow-red
octahedra
White to
faintly-yellow
crystals
mp 40SoC
bp 4SSoC
Toxicitv
Uses
See beryllium
See beryllium
See beryllium
See beryllium
In manufacture of beryllium.
Anhydrous form used as acid
catalyst ln organic reac-
tions similar to AIC1~
()\
()\
(continued)
-------
APPENDIX
TABLE 12. PROPERTIES, TOXICITY, AND USES OF BERYLLIUM AND SOME BERYLLIUM COMPOUNDS (Continued)
Comnounds Prouerties Toxicitv Uses
Beryllium Glassy hygro- See beryllium In manufacture of Be and
fluoride scopic mass Be alloys, manufacture of
BeF2 glass; in nuclear reactors
Beryllium Powder, decom- See beryllium
formate poses above
Be (OOCH) 2 250°c
Sublimes at
320°C
Beryllium White solid See beryllium
hydride
BeH2
Beryllium Amorphous powder See beryllium In manufacture of beryl-
hydroxide or crystals lium and beryllium oxide
Be (OH)2
Beryllium Needles See beryllium
iodide mp 480°C
BeI2 bp 488°C
Beryllium White to slight- See beryllium For stiffening mantles in
nitrate ly yellow gas and acetylene lamps
Be(N03)2 crystals
mp ",60oC
(continued)
0"1
--....J
-------
APPENDIX
TABLE 12. PROPERTIES, TOXICITY, AND USES OF BERYLLIUM AND SOME BERYLLIUM COMPOUNDS (Continued)
ComDound Properties Toxicitv Uses
Beryllium White crystals See beryllium
nitride to grayish-white
Be3 N2 powder
mp 2,200 ;I: 400C
Beryllium Light amorphous See beryllium In manufacture of beryllium
oxide powder oxide ceramics, glass; in
BeO 0 nuclear reactor fuels and
mp 2,530 C
moderators; as catalyst for
organic reactions
Beryllium Hygroscopic See beryllium
perchlorate crystals
Be(Cl04 )2
Beryllium Hard masses See beryllium
potassium
fluoride
K2BeF4
Beryllium Brilliant See beryllium In chromium and silver
potassium crystals plating
sulfate Soluble in water
K2Be(S04}2
Beryllium Orthorhombic See beryllium
selenate crystals
BeSe04 Anht;drous at
300 C
0'\
(X)
(continued)
-------
APPENDIX
TABLE 120 PROPERTIES, TOXICITY, AND USES OF BERYLLIUM AND SOME BERYLLIUM COMPOUNDS (Continued)
Comnounds Pronerties Toxicitv Uses
Beryllium Orthorhomic or See beryllium
sodium monoclinic
fluoride crystals
NaBeF4 mp ,,-,350oC
Beryllium Crystals at LDso in mice: 500 I-lg/kg
sulfate about 1000C Human toxicity: see
BeS04 Loses 2H20 beryllium
0'\
\.0
-------
A.PPENDIX
TABLE 13
PHYSIOLOGICAL CHANGES AND MORTALITY RESULTING FROM INHALATION50F
BERYLLIUM FLUORIDE, BERYLLIUM OXIDE, AND BERYLLIUM SULFATE
Particle
I Exposure size
'
. lbstance Animal Dose Duration u Effects
,
, ryllium 5 970 f..lg/m3 6 hr/day 0061(0033-
t cats, No deaths: lung damage
uoride young in H20 (207 days) 0.94)
adults
I 6 cats, 10,000 6 hr/day 0.63(0052- No deaths
young f..lg/m3 (3 wk) 0.74
I adults in H",O
I 14 dogs, 970 f..lg/m3 6 hr/day 0.61(0.33- 3 deaths: sus- " Consolidation, emphysema,
young in H?,O (207 days) 0.94) pected macro- and slight edema in lungs:
adults cvtic anemia Be tended to accumulate
6 dogs, 10,000 6 hr/day 1 death: 3 dogs in lungs, pulmonary lymph
young ~6m3 in (3 wk) in moribund con- nodes, liver, skeleton,
adults dition sacrificed; and bone marrow
6 dogs, 2,700 6 hr/day Decrease in RBC count and Hb levels: increase
young (2,000- (23 wk) in mean corpuscular volume consistent with
adults: 3 2,400 macrocytic anemia
rabbits f..lg/m3 in
~O
20 guinea 10,000 6 hr/day 0.63(0.52- 7 deaths
pigs, young f..lg/m3 in (3 wk) 0.74)
adults H~O
20 mice, 10,000 6 hr/day 0.63(0.52- 6 deaths
young f..lg/m3 in 5 days/wk 0.74)
adults ~O (3 wk)
10 rabbits, 970 flg/m3 6 hr/day 0.61(0.33- No deaths: suspected macrocytic anemia: lung
young in H",O (207 days) 0.94) damage
adults 10,000 6 hr/day, 0.63(0.52- 1 death: suspected macrocytic anemia: lung
f..lg/m3 in (3 wk} 0.74) damage
H",O
120 rats, 970 flg/m3 6 hr/day, 0.61(0033- 73 deaths: minimal lung lesions
young in H2 ° 5 days/wk 0094)
adults (207 davs)
-....]
o
(continued)
-------
APPENDIX
TABLE 13 (Continued)
PHYSIOLOGICAL CHANGES AND MORTALITY RESULTING FROM INHALATION50F
BERYLLIUM FLUORIDE, BERYLLIUM OXIDE, AND BERYLLIUM SULFATE
i Particle
I
Exposure Size
;. Substance Animal Dose Duration u Effects
Beryllium 40 rats, 10,000 6 hr/day, 0.63(0.52- 7 deaths; minimal lung lesions
fluoride young and j...lg/m3 5 days/wk 0.74)
old adults in H20 (3 wk)
~eryllium 65 rats 89.57 1-5 hr/day 0.285(0.11- Large amounts of the dust (~24,000 j...lg/IOO g
)xide j...lg/L 1. 25) of Be) in lungs more than a year after expo-
sure; little tendency for Be to be redis-
tributed from lungs to other tissues; fibrous
tissue proliferation from 35 days to more
than a year after exposure, but no granulo-
matous inflammation of lunas
90 rats, 10,000 & 6 hr/day, (0.47- Damage in lungs only; dust particles in
Wistar, 82,000 5 days/wk 0.59) peribronchial and perivascular tissues, as
young j...l g/m3 in (15-40 we 11 as in alveoli and phagocytes; inflamma-
adultsa ~ob days) tion, edema, and thickening of alveolar
83,000 6 hr/day, 1.13 walls; bronchial epithelial desquamation and
j...lg/m3 in 5 days/wk hyperplasia
H Oc (60 days)
I 2
(84,000- 6 hr/day, <1.0
86,000) 5 days/wk
j...lg/m3 in (10-1705
H Od days}
:?
88,000 6 hr/day, 0071
j...lg/m3 in 5 days/wk
H Oe (10 days)
?
Beryllium 4 cats 950 j...lg/m3 6 hr/day 0.25 No deaths; 2~/o body weight losso ug Be/g
sulfate young (40 j...lg Be) (100 days) fresh tissue from 4 sacrificed animals: lung,
adults in H?O 0.08; liver, 0002; kidney, 0.01; spleen, 0.01
5 cats, 10,000 6 hr/day 1.5 1 death; no change in body weight
young j...lg/m3 (430 (95 days)
adults j...lg Be) in
H20
-....J
I-'
(continued)
-------
r APPENDIX
Substance
Animal
3eryllium 5 cats,
:mlfate young
adults
12 dogs
5 dogs,
young
adults
1 goat
TABLE 13 (Continued)
PHYSIOLOGICAL CHANGES AND MORTALITY RESULTING FROM INHALATION50F
BERYLLIUM FLUORIDE, BERYLLIUM OXIDE, AND BERYLLIUM SULFATE
Dose
47,000
f.lg/m3
(2 ,000 f.lg
Be) in H;> 0
(3,600-
4,000) f.lg
f.lg/m3 in
~O
950 f.lg/m3
(40 f.lg Be)
in H2 0
10,000
f.lg/m3 (430
f.lg Be) in
H;:>O
47,000
ug/m3
(2,000 ug
Be) in H20
47,000
f.lg/m3
(2,000 ug
Be in ~ 0 I
Exposure
Duration
6 hr/day
(51 days)
6 hr/day
(2 mo)
6 hr/day
(100 days)
6 hr/day
(95 days)
6 hr/day
(51 days)
6 hr/day
(51 days)
Particle
Size
u
0.96
0.25
1.5
0.96
0.96
Effects
4 deaths: 43% body weight loss
Decrease in RBC count and Hb levels: increase
in mean corpuscular volume consistent with
macrocytic anemia: spontaneous recovery from
anemia after 3.5-4 mo
No deaths: 100/0 body weight\
loss. f.lg Be/g fresh tis-
sue from 5 sacrificed ani-
mals: lung, 0.6: pulmonary
lymph nodes, 0.7: liver
0001: kidney, 0.003:
spleen, 0.01
No deaths: 11% body weight
loss: leukocytosis. f.lg
Be/g fresh tissue from 4
sacrificed animals: lung,
4: pulmonary lymph nodes,
2 liver, 1.8: kidney, 0.8:
spleen, 0.004: femur, 0.8
4 deaths: 4% body weight
loss: leukocytosis
1 death: no change in body weight
J
Reversible macro-
cytic anemia
after 3 -8 wk:
significant
changes in phos-
pholipid and free
cholesterol of
whole RBC: ten-
>dency to hypoal-
buminemia and
hyperglobulinemia:
acute inflamma-
tory response in
lung, with ero-
sion and prolif-
eration of bron-
chial epithelium
......:J
rv
(continued)
-------
APPENDIX
TABLE 13 (Continued)
PHYSIOLOGICAL CHANGES AND MORTALITY RESULTING FROM INHALATION OF
BERYLLIUM FLUORIDE, BERYLLIUM OXIDE, AND BERYLLIUM SULFATES
Particle
Exposure Size
Substance Animal Dose Duration u Effects
Beryllium 20 guinea 950 ug/m3 6 hr/day 0.25 No deaths; 18"/0 body weight gain
sulfate pigs (400- (40 \-lg Be) (100 days)
600 g) in H20
34 guinea 10,000 6 hr/day 1.5 2 deaths; 10~1o body weight gain
pigs (400- \-lg/m3 (430 (95 days)
600 g) Ug Be in
H..,O
12 guinea 47,000 6 hr/day 0.96 7 deaths~ 37"/0 body weight gain
pigs (400- ug/m3 (51 days)
600 g) (2,000 \-lg
Be) in H2 °
10 guinea 100,000 6 hr/day 1.1 3 deaths; 2"/0 body weight loss
pigs (400- \-lg/m3 (14 days)
600 g) (4,300 \-lg
Be) in H20
83 hamsters 950 ug/m3 6 hr/day 0.25 No deaths~ no change in body weight
(40 \-lg Be) (100 days)
in ~O
10 hamsters 47,000 6 hr/day 0.96 5 deaths~ 1SOio body we ight loss
\-lg/m3 (51 days)
(2,000 \-lg
Be) in ~O
100,000 6 hr/day 101 2 deaths ~ SOlo body weight loss
\-lg/m3 (14 days)
(4,300 \-lg
Be in ~O
38 mice 47,000 6 hr/day 0.96 4 deaths; 6"/0 body weight loss
\-lg/m3 (51 days)
(2,000 \-lg
Be in H8 0
(continued)
-------
r--..
APPENDIX
TABLE 13 (Continued)
PHYSIOLOGICAL CHANGES AND MORTALITY RESULTING FROM INHALATION50F
BERYLLIUM FLUORIDE, BERYLLIUM OXIDE, AND BERYLLIUM SULFATE
Particle
Exposure Size
Substance Animal Dose Duration u Effects
Beryllium 38 mice 100,000 6 hr/day 1.1 No deaths: 13% body weight loss
sulfate ~g/m3 (14 days)
(4,300 ~g
Be) in H20
2 monkeys 950 ug/m3 6 hr/day 0.25 No deaths: l~/o body weight gain. ~g Be/g
(40 ~g Be) (100 days) fresh tissue from 2 sacrificed animals:
in H2 ° lung, 102: pulmonary lymph nodes: 1.3: liver,
0.5. kidnev. 0.01. spleen 0.1
5 monkeys 10,000 6 hr/day 1.5 No deaths: 31% body weight loss
~g/m3 (430 (95 days)
~g Be)
in H20
1 monkey 47,000 6 hr/day 0.96 1 death: 25% body weight loss
~g/m3 (51 days)
(2,000 ~g
Be) in H20
23 rabbits 950 ~g/m3 6 hr/day 0.25 No deaths: 15% body weight gain. Ug Be/g
(2.6-4.0 (40 ~g Be) (100 days) fresh tissue from 5 sacrificed animals: lung,
kg) in H20 1.6 pulmonary lymph nodes, 0: liver, 0.004:
kidnev. 0.003: spleen 0.01
24 rabbits 10,000 6 hr/day 1.5 2 deaths: no change in body weight;
(2.6-400 ~g/m3 (430 (95 days) leukocytosis
kg) ~g Be) in
H20
10 rabbits 47,000 6 hr/day 0.96 1 death: 7% body weight gain; leukocytosis
( 2 . 6 -4 . 0 ~g/m3 (51 days)
kg) (2,000 ~g
Be} in ~O
3 rabbits 100,000 6 hr/day 1.1 No deaths: no change in body weight;
(2.6-4.0 ~tg/m3 (14 days) leukocytosis
kg) (4, 300 ~g
Be) in ~O
-..JI
.s::.
(continued)
-------
APPENDIX
TABLE 13 (Continued)
PHYSIOLOGICAL CHANGES AND MORTALITY RESULTING FROM INHALATION50F
BERYLLIUM FLUORIDE, BERYLLIUM OXIDE, AND BERYLLIUM SULFATE
I Particle
I Exposure Size
. Substance Animal Dose Duration u Effects
~l Beryllium 40 rats 4,000 6 hr/day Decrease in RBC count; increase in mean
sulfate \-lg/m3 in (23 wk) corpuscular volume consistent with macro-
H~O cytic anemia
20 rats 950 \-lg/m3 6 hr/day, 0.25 No deaths; 20% body weight gain
(250- (40 \-lg Be) 5 days/wk
280 gJ in H20 (100 days)
15 rats 47,000 6 hr/day, 0.96 13 deaths; no change in body weight;
(250-280 g) ug/m3 5 days/wk leukocytosis
(2,000 \-lg (51 days)
Be) in H2 °
10 rats 100,000 6 hr/day 1.1 10 deaths; 2% body weight loss;
(250-280 g) \-lg/m3 '
5 days/wk leukocytosis
(43,000 \-lg (14 days)
Be) in H20
136 rats, 12 \-lg/ft3 8 hr/day, 46 deaths. Apparent effect on lung tissue:
wis tar & (1 \-lg Be) 5!z days/ stimulation of epithelial cell proliferation
Sherman 1% in ~ ° wk (6 mo) without provoking a connective tissue reac-
(140-210 g) tion; foam-cell clustering; focal mural
infiltration; lobular septal cell prolifera-
tion; peribronchial alveolar wall epitheliza-
tion- aranulomatosis and neoDlasia
47 rats!: 10,000 6 hr/day, 1.5 23 deaths; 28% body weight gain;
(250-280 g) \-lg/m3 5 days/wk leukocytosis
(430 \-lg (95 days)
Be) in ~O
(cont~nued)
-....J
lJ1
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APPENDIX
TABLE 13 (Continued)
PHYSIOLOGICAL CHANGES AND MORTALITY RESULTING FROM INHALATION OF
BERYLLIUM FLUORIDE, BERYLLIUM OXIDE, AND BERYLLIUM SULFATES
Particle
Exposure Size
Substance Animal Dose Duration u Effects
Beryllium 2 swine 47,000 6 hr/day 0.96 No deaths; 2SO,-b body weight loss
sulfate flg/m3 (51 days)
(2,000 flg I
Be) in ~O
4 ch ickens, 47,000 6 hr/day 0.96 No deaths; 11% body weight loss
young flg/m3 (51 days)
adults (2,000 ug
Be) in ~O
aData also apply to other young adult animals:
2 rhesus monkeys, and 9 New Zealand rabbits.
bSpecial grade of BeO; 6SO,-b of rats, exposed to 82,000 flg/m3 for 15 days, died; all other
treated animals survived.
2 cats, 10 dogs, 20 mixed English guinea pigs,
cRefractory grade GC of BeO; all animals survived.
dFluorescent grade of BeO; 5% of rats, exposed to 87,000 ug/m3 for 10 days, died; all other
treated animals survivedo
eRefractory grade SP of BeO; all animals survived.
fInhalation of HF vapor (8,000 flg/m3) doubles toxicity of BeS04 poisoning.
-------
77
TABLE 14
PHYSICAL PROPERTIES OF BERYLLIUM7
Density (specific gravity)---------
Hardness---------------------------
Tensile propertiesb
Ultimate strength-------------
Yield strength, annealed
(offset, 0.2 percent)-------
Elongation (in 2 inches)------
Reduction of area-------------
Young's.modulus of elasticity-
Compressive properties
Yield strength (offset,
0.2 percent)----------------
Young's modulus of
elasticity------------------
Shearing strength-------------
Electrical properties
Electrical conductivity-------
Electrical resistivity--------
Electrode potential-----------
Thermal properties
Melting point-----------------
Boiling point-----------------
Linear coefficient of
expan ion:
(20o-2000C)---------------
(20o-7000C)---------------
Thermal conductivity (at 20°C)
Specific heat (at 20o-100oC)--
Latent heat of fusion---------
Vapor pressure: (at 1,4000C)--
(at 3,0000C)--
Heat of oxidation-------------
Magnetic susceptibility-------
Reflectivity (white light)----
Velocity of sound-------------
a
1.846 to 1.816 g/cc
97-172 Brinell
35,000-95,000 Ib/inch2
30,000-45,000 Ib/inch2
2 - 20"/0%
2-20%
36,000,000-44,000,000
Ib/inch2
26,000-86,300 Ib/inch2
42,000,000-45,000,000
Ib/inch2
31,000-66,000 Ib/inch2
40-44% of Cu
3.9-4.3 microhms/cc
minus 1.69
1.2850C (2,3450F)
2,970oC (5,378oF)
13.3 X 10-6per °c
17.8 X 10-6per °c
0.385 cal/cm2/cm/sec/oC
or 42% of Cu
0.43-0.52 cal/g/oC
250-277 cal/g
0.001 rom Hg
760.0 rom H
140.15 calc
0.79 G/O
50-55%
12,600 m/sec
aTheoretical density reported by two different sources.
b" 'd d
TenS11e propert1es may vary over a W1 e range, accor -
ing to the method of fabrication employed.
cTemperature is not given.
in kilocalories.
Value is probably meant to be
-------
APPENDIX
4
TABLE 15. CONCENTRATION OF BERYLLIUMa IN THE AIR
(in ~g/m3)
1954-59IJ 1960 1961 1962 1963 1964
Location Max Ava Max Ava Max Ava Max Ava Max Ava Max Ava
Alabama
Birmingham .001 0000
Huntsville 0003
Arizona
Phoenix .000 .000 .001
Tucson .000
California
Los Angeles .000 .001 .000 .000 .000
Pasadena .000
San Francisco .000 .000 .000
Santa Barbara .000
Colorado
Denver .000 .000 .000 .000
Pueblo .000
Connecticut
Norwich .000
Waterbury .002
Delaware
Wilmington .000
District of Columbia
Washington .000 .000 .000
Florida
St. Petersburg .000
Tampa .000
Georgia
Atlanta .000 .000
Idaho
Boise .000 .000 .000
Illinois
Chicago .000 .001 . .000 .001
Cicero .001
East St. Louis .001
Joliet .000
North Chicago .000
Springfield 0000
(continued)
-....J
(X)
-------
APPENDIX
TABLE 15. CONCENTRATION OF BERYLLIUMa IN THE AIR4 (Continued)
(in \-lg/m3J
1954-59D 1960 1961 1962 1963 1964
Location Max Ava Max Avq Max Avq Max Ava Max Ava Max Ava
Indiana
E. Chicago .005
Gary .000
Indianapolis .000 .003 .000 .001
Muncie .000
Park County .000
Iowa
Cedar Rapids .000
Des Moines .000 .000 .000 .000
Kansas
wichita .000 .000
Louisiana
Lake Charles .000
New Orleans 0000 0000 .000
Maryland
Baltimore .000 .000 .000 .000 .001
Cumberland .000
New York
Buffalo .000
Glen Cove .000
Massena .000
Mount Vernon .000
New Rochelle .000
New York .000 .000 .000 .000
Rochester .000
Troy .000
North Carolina
Asheville .000
Charlotte .000 .000
Durham
Winston-Salem .000
North Dakota
Bismarck .000 I
.......
~
(continued)
-------
4Ho.~~.:c:o-:L""':LJ...LJ'i..-
TABLE 15. CONCENTRATION OF BERYLLIUMa IN THE AIR4 (Continued)
(in ~g/m3J
1954-59D 1960 1961 1962 1963 1964
Location Max AVG Max AVG Max Ava Max AVG Max Avq Max Ava
Ohio
Akron .001
Canton 0000
Cincinnati .002 .000 .000 .001 .001
Cleveland .000 .001 .002 0000
Columbus .002 .000
Dayton .002
Youngstown .000
Oklahoma
Oklahoma City .000 0000
Tulsa .000
Michigan
Detroit 0000 .002 .000 0001
Grand Rapids 0000
Minnesota
Minneapolis 0000 .000
St. Paul 0000
Missouri
St. Louis 0000 .000 0000 0000
Montana
Helena .000
Nebraska
Omaha 0000 .000 .000
Nevada
Las Vegas 0000 0000 .000 0000
Reno .000
New Hampshire
Manchester 0000
New Jersey
Bayonne .000
Camden 0000
G1assboro .000
Newark .001 0000 .000
Paterson .000
00
o
(contlnued)
-------
APPENDIX
4
TABLE 15. CONCENTRATION OF BERYLLIUMa IN THE AIR (Continued)
(in ~g/m3)
1954-59U 1960 1961 1962 1963 1964
Location Max Ava Max Ava Max Ava Max Ava Max Avq Max Ava
New Mexico
Albuquerque .000
Oregon
Eugene .000
Medford .000
Portland .000 0000
Pennsylvania
Allentown .003
Altoona .000
Bethlehem .000
Lancaster .000
Philadelphia .000 0001 .000 .000 .001 .000
Pittsburgh .000 .000 .001 .000
Scranton 0002
Rhode Island
East Providence .000
Tennessee
Chattanooga .000 .000
Nashville .000 0000
Texas
El Paso 0000 0000
Houston .000
Odessa .000
Tyler .000
Utah
Salt Lake City .000 0000
Washington
Seattle .000 .000 .000
Spokane .000
Tacoma .000
West Virginia
Charleston .004
Huntington .000
00
I-'
(contlnued)
-------
APPENDIX
TABLE 150 CONCENTRATION OF BERYLLIUMa IN THE AIR4 (Continued)
(in llg/m3)
1954-59JJ 1960 1961 1962 1963 1964
Max AVG Max Ava Max Ava Max AVG Max AVG Max AVG
Wisconsin
Milwaukee .000 .000
Racine .000
Wyoming
Cheyenne .000
aValues of 0.000 represent undetectable amounts.
bThe data in this column may include only 1 year or the average of all measurements
made during these yearso
co
rv
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