I 3 K 2 I- :. L F E R E K C E MATERIAL
HAZARDS CF 2i::C I],' THE ENVIRONMENT
WITH F'ARTICULAP PE?EEi:"CE TO
THE AQUATIC r::!VIF.OI^ENT
Benjamin K. Lira
February 1972
-------
-------
TABLE OF CONTENTS
Page
I. Introduction ., 1
II. Zinc Content in United States Surface Waters 3
III. Zinc Content in United States Sea Water 5
IV. Safe Limits for Zinc 8
VV Toxicology of Zinc and Its Compounds -
Effects on Animals and Man 10
VI. Toxicology of Zinc and Its Compounds -
Effects on Fish 18
VII. The Antagonistic Effect of Calcium on the Toxicity
of Zinc on Fish 23
VIII. Relationship Betv/een the Toxic Effects of Zinc
and Dissolved Oxygen on Fish 32
IX. Uptake and Accumulation of Zinc by Aquatic Organisms . M
X. Toxic Effects of Some Specific Zinc Compounds . - . . 60
XI. Zinc Industry in the United States . 66
Bibliography
-------
V
-------
I. INTRODUCTION
Zinc and its compounds are generally considered to be
mildly toxic to man and animals in moderate doses; however,
high concentrations of certain compounds can produce harmful
effects on humans, animals, and plants. The element and its
compounds have their most pronounced toxic effects on aquatic
biota even at relatively low concentrations. These effects
will be discussed more fully in a separate section of this
paper.
The soluble zinc salts are astringent, corrosive, and
emetic. Where ingested in toxic doses, they produce severe
gastroenteric irritation and pain, nausea, vomiting, diarrhea.
Intoxications have resulted from drinking fruit juices or from
ingestion of sauerkraut kept in galvanized containers. Two
recent reports of intoxication indicate that galvanized pots
.or tubs should not be used for the preparation or storage of
food, especially foods with an acid pH, because of the possi-
bility of conversion of zinc metal into soluble zinc salts.
Zinc phosphide is a rodenticide which on ingestion
releases toxic hydrogen phosphide or phosphine. A dose of
5 gnu has caused death. There have been 25 deaths reported
Arch. Environ. Health 8, 657 (1964),
-------
-------
-2-
froru Europe. Besides gastroenteric symptoms, patients suffered
from excitement and tightness in the'chest. Patients alive
after three days recovered completely. Those that died suffered
2
severe hepatic, renal, and cardiac damage. Zinc dialkyldithio-
phosphate is irritating to the skin, eyes, and mucous membranes,
but it has a low order of systemic toxicity. The substance is
not a cholinesterase inhibitor. Zinc stearate is used in cos-
metics and as a constituent of baby powders. Upon ingestion,
it has a low order of toxicity, but repeated or prolonged
inhalation of this fine powder has produced pneumonitis as well
as fatal pneumonia in infants. Inhalation of zinc oxide vapors
has induced metal fume fever.
2J.B.P. Stephenson, Arch. Environ. Health 15, 83 (1967).
-------
-------
-3-
II. ZINC CONTENT IN UNITED STATES SURFACE WATERS
In the weathering process, soluble compounds of zinc are
formed and the presence of traces of zinc in surface water is
quite common. Zinc is absorbed to a considerable degree in
hydrolyzate sediments and in soils. High zinc concentrations
are found in waters having high acidity, such as in mine drain-
age* However, as the pH rises, the zinc concentration decreases.
At very high pH levels, zinc may form anion complexes, but such
conditions are not likely in natural waters.
Because of the excellent sensitivity for zinc with the
direct-reading spectrometer, microgram per liter concentrations
in waters are easily detected. Soluble zinc has been measured
,,. *- in over 76 percent of all samples at a mean value of 64 micro-
grams per liter. This overall mean concentration is exceeded
in five basins. Among these the highest is in the^Lake Erie
Basin where the mean is 205 micrograms per liter. The percent-
age occurrence is highest in the Southeastern Basin, where 96.7%
of all samples contain this element at measurable levels; however,
the mean zinc concentration is only 52 micrograms per liter. The
lowest mean value, 16 micrograms per liter, was observed in the
California Basin, where the frequency of detection is 72 percent.
Figure 1 depicts the quantities of zinc found in various
waters of this country.
-------
-------
-4-
O
H
-------
-------
-5-
III. ZINC CONTENT IN UNITED STATES
SEA WATER
Sea water is a solution of a large number of dissolved
chemicals containing small amounts of suspended matter of organic
or inorganic origin. The ratios of the more abundant elements
are very nearly constant, despite variations in absolute concen-
trations in different parts of the sea. Lower than average abso-
lute amounts are encountered in coastal areas and near river
mouths, while higher amounts are encountered in areas of high
evaporation, such as the Red Sea. Vertical variations are
usually small; in general, in the open ocean in mid-latitudes,
the quantity of dissolved materials, measured by the salinity,
first decreases slightly with depth, then increases slowly in
the deep water.
Table 1 shows the concentrations of some of the elements
in solution in sea water at a chlorinity of 19.0 percent, which
is near average for the sea, and the total amounts in the ocean
as a whole. The table also shows the total amounts and total
radioactivity of the principal naturally occurring radioisotopes.
In addition to the listed elements, there are variable amounts of
dissolved gases, including nitrogen, oxygen, and the noble gases.
A range of values is given for some elements present in small
quantities, such as nitrogen, phosphorus, silicon, iron, and
copper. Zinc content of sea water is reported to be 0.005 milli-
gram per 1 kilogram of sea water.
-------
-------
_ 6 -
n
w
rH
O
n
0)
u
S
,4
d
4)
10
O
v»
rH
O
CO
01
C
a>
rH
M
I
'm
o
rl
J:
u
m x~
r-( W
P C
H 0
H ^
p
U rH
< 0
rH O
0 H
p
d
d)
H
rH
U
&
^
w
c
o
p
0
c
0
ftl
o
c
rH
d
H
XP
tfs
tno
x.0%
tnrH
g II
U
.p
C
o
6
o
W
rH 00
O 0
rH rH
X X
VO IX
O
rH
o
rH
vo
X LO
CO
VO
o <
^J" rH
* o
vo vDinLO'^tT4'tYirOfOfN3c
rH rHrHrHrHrHrHrHrHiHr
oooooooooo
rHrHrHrHrHrHrHrHrHrH
xxxxxxxxxx
vo iX) CO 00
VO *^i" r*x 0*3 VO CO i 1 O\ CO ^t"
C^J irH^ rH r*4 l/"i ^O ON ^"O rH VQ
_
-
^
O rH C^l ^t" tO C^ LO CO CO ^j"
COvOr\COOCOvO(NrH
Q\ LO c^ co "xf ro
S. *S **
CO O rH
1 1
r t r-i
* * H 5 H *
C -H 6 -H C) « -H
H e M M 3 n c c -P
>-i 3 O 3 -H n -H Q C C
O-lHCV<(jr^g^T)QQ
rHtJ tjlrHrHP 0 M M Vl
rCO,D30O>-ia+-'U
O
rH
X
tj-
CO
rH
rH
o
rH
X
CO
rH
rH
tx
CO
i§
.
SI C<]/HrH iHrHrHO O<
H iHtHrH i i i 1 rH rH rH r
ooooooooo
rHrHrHiHrHiHrHrHrH
xxxxxxxxx
-
mc^ «rxc^rH «r*sN«
1 OV rH
CO 1 t
O rH rH
0
O O
O
in m
^- in N iH rH O O
M . O O O O O O
T}- O 1
1 1 ,M-H > d
CdrH'/JdrHOr-lrHC
H C Cl CJ r-l O ,C (U -H d
NrJWOD^HUiO>
LrT
CM CTv
^sh i i
rH
o
w d
s d
> OJ
to os
H (N
-------
-------
m
V
H
p
H
^
H
P
U
<£
fH
d
m
o
H
3
*~*-
v\
C
0
p
1
r-i
d
-p
o
E~"
o\
o
X
- 7 -
VD
1
H
t!
o
u
1
§
fc
O
ON
iH
II
i
»^1
U
ro
O
O
O
0
oo
O
O
o
0
-H
O
o
0
0
,00004
0
0
o
o
o
o
,000006
0
rH
1
CM
O
Element
«-:
Lanthanur
Yttrium. ,
Nickel . . ,
Scandium,
Mercury. ,
>-{
0
O
Radium. . ,
-------
-------
IV. SAFE LIMITS FOR ZINC
The U. S. Public Health Service Drinking Water Standards
of 1962 set a limit of 5 mg/1 of zinc in acceptable water supplies
when no alternate sources are available. From 1942 until 1962,
the limit had been 15.0 mg/1, but this standard was lowered because
the taste threshold for zinc occurs at about 5 mg/1. Furthermore,
the World Health Organization International and European standards
for drinking water prescribe a permissible or recommended limit of
5.0 mg/1.
Zinc has no known adverse physiological effects upon man
except at very high concentrations. An emetic concentration
requires 675 to 2,280 milligrams per liter. In fact, zinc in
small quantities is an essential and"beneficial element in human
nutrition. The normal human intake of zinc is estimated at 10-15
milligrams per day. A summary of 'literature relating to the
toxicity of zinc reveals that families and communities have used
waters containing 11.2, 17, 18.2, and 26.6 milligrams per liter
with no ill effects. One water supply containing 23.8 to 40.8
milligrams per liter of zinc gave no harmful effects to 200 per-
sons stationed at a depot. On the other hand, another supply
containing 30.8 milligrams per liter of zinc caused nausea and
fainting spells.
-------
-------
-9-
As conflicting as some of these reports' data may indi-
cate, high concentrations of zinc in domestic water supply are
undesirable. At a concentration of 30 milligrams per liter, zinc
gives water a milky appearance and causes a greasy film on boiling.
All readily soluble salts of zinc have an unpleasant,
astringent taste and can be detected in less-than-dangerous
amounts in drinking water. Taste thresholds have been reported at
40 milligrams per liter, 25 milligrams per liter, and as low as
2 milligrams per liter. In tests performed by a taste panel at
the R. A. Taft Sanitary Engineering Center with three zinc salts
in distilled water and in mineralized natural spring water, the
taste threshold was lower with zinc sulfate than with tne nitrate
'or chloride. In the case of zinc sulfate in distilled water the
estimated taste threshold of 50 percent of the panel was 17.6 milli-
grams per liter of zinc, but the most sensitive 5 percent of the
panel were able to detect zinc at 4.3 milligrams per liter. The
taste was less noticeable in spring water, the median threshold
being 27.2 milligrams per liter and the 5 percentile at about 6
milligrams per liter. These tests were partly instrumental in
changing the U. S. Public Health Service Drinking Water Standards
from 15 to 5 milligrams per liter of zinc.
-------
-------
-10-
V. TOXICOLOGY OF ZINC AND ITS COMPOUNDS
EFFECTS ON ANIMALS AND MAN
A brief review by Vallee touching on many of the salient
features of zinc and its biological significance to man appeared
1 2
in 1957. ' Sufficient evidence has accumulated to show that
zinc occurs in the body in two different protein combinations:
(a) as a metalloenzyme in which zinc is an inte-
gral part of an important enzyme system, such
as carbonic anhydrase for the regulation of
COo exchange, and
(b) as a metal-protein complex in which zinc is
loosely bound to a protein, which acts as its
.carrier and transports mechanisms in the body.
In general, zinc salts are astringent, corrosive to the
skin, and irritating to the gastrointestinal tract. Because of
the last, when ingested they act as emetics. Zinc ion, however,
is ordinarily too poorly absorbed to induce acute systemic
intoxication. After large doses have been ingested, fatal col-
lapse may occur as a result of serious damage to the buccal and
1B. L. Vallee, A.M.A. Arch. Ind. Health, 16, 147 (1957).
2B. L. Vallee, Physiol. Revs., 39, 443 (1959),
-------
-------
-11-
gastroenteric mucous membrane. Mass poisonings have been recorded
from drinking acidic beverages made in galvanized containers; fever,
nausea/ vomiting, stomach cramps, and diarrhea occurred in 3 to 12
hours following ingestion. The emetic concentration range in water
is from 675 to 2,280 parts per million; the threshold concentration
of taste for zinc salts is approximately 15 parts per million; 30
parts per million soluble zinc salts impart a milky appearance to
4
water; and 40 parts per million, a metallic taste. The lethal
dose of zinc ion administered orally to mice is 57 mg/kg. When
parentally administered, zinc depresses the central nervous system,
causing tremors and paralysis of the extremities; subcutaneous
injection of zinc lactate or valerute in a dose equivalent to 57 mg
of zinc per kilogram killed a cat after three days. Orally, soluble
zinc salts are more than 100 times less toxic than corresponding
cadmium salts, with which zinc is commonly contaminated.
3G. E. Callender and C. J. Geutkow, "Military Surgeon," 80, 67
(1939); J. W. Sale and C. H. Badger, "Ind. En.g. Chem." 16, 164
(1924); U. S. Natl. Office Vital Statist., "Communicable Diseases
Summary, for September 11, 1954".
4J. J. Hinman, "S. Am. Water Works Assoc.", 30, 484 (1938).
5H. Jaeger, "Arch. Exptl. Pathol. Pharmakol.," 159, 139 (1931).
-------
-------
-12-
Sorae research investigations" reported that the adminis-
tration of 175 to 1,000 rag of zinc oxide (ZnO) per day for
periods of from 3 to 53 weeks to dogs and cats was tolerated;
i.e., no occurrence of fatalities. However, glycosuria or
excessive excretion of glucose as in diabetes mellitus occurred
in the dogs. Fibrous degeneration of the pancreas'was found in
the cats at autopsy. No manifest injury occurred in rats from
administration of from 0.5 to 34.4 mg of ZnO per day for periods
of one month to one year. Similar lack of response from zinc
carbonate (Zn CO,) is reported. On the other hand, Waltner and
Waltner reported that feeding ZnCO? induced anemia and pores
o
in bones in rats. Sutton and Nelson found that 0.1 percent
metallic zinc was tolerated in the diet of rats, but that more
than 0.5 percent reduced their capacity to reproduce, and one
percent inhibited growth, caused severe anemia, and death.
The best known example of zinc, intoxication is called
"Metal-Fume Fever" resulting from the inhalation of zinc oxide
ftimes. The malaria-like symptoms of the illness start in a
6K. R. Kienker, P. K. Thompson, and M. March, "Am. J. Physiol.,"
80, 31, 65 (1927), 81, 284 (1927).
7K. Valtner and K. Waltner, "Arch, exptl. Pathol. Pharmakol.,"
141, 123 (1929); 146, 310 (1929).
&\rl. R. Sutton and D. E. Nelson, "Proc. Soc. Exptl. Biol. Med.,"
36, 211 (1937).
-------
-------
-13-
few hours after exposure. Metal-fume fever, however, is not
confined to the inhalation of zinc oxide but may follow expo-
sure to metal fumes of other heavy metals; such as, antimony,
arsenic, cadmium, cobalt, copper, iron, lead, manganese, mer-
cury, nickel, and tin. However, zinc oxide fume is the most
frequent cause. The symptoms include chills and fever, which
rarely exceeds 102 F., nausea and sometimes vomiting, dryness
.of the throat, cough, fatigue, yawning, weakness, and aching
of the head and body. After a few hours, the victim perspires
profusely, and the temperature begins to fall. The condition
lasts a day and is not fatal. Occasionally, excessive amounts
of glucose are found in the urine. Mental confusion and con-
vulsions may occur. The lungs' vital capacity may be impaired,
a condition which may persist for 15 hours. This condition may
recur weekly or more frequently. A marked increase of white
blood cells (12,000 to 16,000 per cubic millimeter) is found
9
for 12 hours after the temperature has returned to normal.
While the condition persists there is a measure of immunity.
A postulated mechanism for this immunity that seems most
9C. C. Sturgis, P. Drinker, and R. M. Thompson, "J. Ind. Hyg.,"
9, 88 (1927); P. Drinker, R. M. Thompson and J. L. Finn,
"J. Ind. Hyg.," 9, 98, 187, 331 (1927), 13 (1923).
-------
-------
-14-
reasonable today is that of Lehmann, who suggested that the
inhaled zinc-fume particles liberated modified protein from
the lung into the blood stream. The subsequent distribution and
absorption of the modified protein results in the characteristic
response resembling that from the injection of a foreign protein.
A recent review of the problem of metal-fume fever from inhaling
zinc oxide, with report of cases, is given by Rohrs.
10K. B. Lehmann, "Arch. Hyg.," 72, 358 (1910).
13-L. C0 Rohrs, "A.M.A. Arch. Int. Med.," 100, 44 (1957),
-------
-------
-15-
Traces of zinc are common in many foods. Milk contains
about 4 mg/1, hen eggs about 1 mg per egg. Zinc is almost
invariably present in oysters from the Atlantic Ocean.
Practically all of the zinc contained in the food is
excreted into the feces.
The excretion of zinc varies with the income. Little is
-retained. In man it amounts normally to 0.3 mg daily; in dogs,
to 5 to 25 rag per day. Nearly all of this, 94 to over 99 per-
cent, is in the feces. The normal urinary excretion in dogs
is 0.13 to 0.49 mg per day. The urinary excretion was but-
little increased by feeding zinc oxide to dogs and rats and
cats for three to 53 weeks and soluble zinc salts to rats. A
part is excreted by the bile. The excretion returns to the
normal level two weeks after the administration is discontinued.
The distribution of normal zinc in the tissues is some-
what peculiar. The total zinc of mice on normal diet averages
0.434 mg, which would correspond to about 1 Gm in a human
adult. The zinc content of whole human blood averages 124^
micrograms per 100 cc; about 75 percent of this is in the
plasma, 22 percent in the red cells, 3 percent in the white
cells. Part of the serum zinc is firmly bound to globulin,
-------
-------
-16-
part more loosely to several proteins. The latter is chiefly
changed in various diseases. It is decreased in febrile infec-
tions , pernicious anemia, leukeruias, malignant tumors, hepatitis
and nephritis; not in hemorrhagic or iron-deficiency anemias.
The zinc of the erythrocytes is within normal limits in anemias
other than pernicious anemia; in this it is increased, returning
to normal under liver therapy.
Spermatozoa have the highest zinc concentration of any
human tissue examined. High concentrations exist also in
prostatic acini and secretions of man and rats, and in the
crypts of Lieberkilhn in the small intestines. The prostatic
concentration is directly related to the alveolar tissue, and
is much less in cancerous prostate.
The pancreas has a relatively high concentration of
zinc, which probably forms part of the ordinary insulin mole-
cule; although zinc-freed insulin preparations are also active.
Pancreas rendered diabetic by alloxan appears to concentrate
peritoneally injected radio-zinc chloride considerably less
than in normal animals.
Hair and other epidermal structures, fingernails, toe-
nails and feathers, also have a high zinc content (80 to 450
ppm). The content is about the same in pigmented and unpig-
mented hair.
-------
-------
-17-
Zinc is an active component of carbonic anhydrase;
removal of zinc results in irreversible inactivation of the
enzyme, which is responsible for rapid exchange of carbon
dioxide. Zinc is also a component of carboxypeptidase that
splits terminal arxino groups from peptides; one atom of zinc
is combined to one molecule of enzyme. Four dehydrogenases
contain zinc that is essential for their action. They are:
alcohol dehydrogenase of yeast and liver, lactic acid
dehydrogenase, and glutamic dehydrogenase; two to four moles
of zinc are contained per enzyme molecule. Their presence
in liver and retina may explain the high concentration of
zinc at these sites. " '
-------
-------
-18-
VI. TOXICOLOGY OF ZINC AND ITS COMPOUNDS - EFFECTS ON FISH
It is toward fish and aquatic organism that zinc exhibits its
greatest toxicity, The lethal action of dissolved salts of heavy metals
on fish has been investigated by K. E. Carpenter, who in a series of
1 n O
papers J>J has shown that the death of fish placed in solutions of salts
of heavy metals results, not from internal poisoning but from an inter-
action between the metallic ion and the mucua secreted by the gills,
whereby a film of coagulated mucus is formed on the gill membranes
Impairing their respiratory efficiency to such a degree that the fish
is asphyxiated. This conclusion has been confirmed by B. Behrens in
1925 and later by M. M. Ellis in 1937-
J. R. E. Jones compared the relative toxicity to stickleback of a
few common heavy metal salts in a paper entitled, "Th" Relative Toxicity
of Salts of Lead, Zinc and Copper to the Stickleback (Gasterosteus
aculeatus L.) and the Effect of Calcium on the Toxicity of Lead and
Zinc Salts."
if *
Jones results are given in Tables I through IV.
K. E. Carpenter. "Annals of Applied Biology," vol. 12, No. 1, 1925
2
K. E. Carpenter. "British Journal of Experimental Biology,"
vol. k, No. k, 1927.
'K. E. Carpenter. "Journal of Experimental Biology," vol. 7>
No. It, 1930.
^
J. R. E. Jones. "Journal of Experimental Biology," vol. 15,1938.
-------
-------
-19-
Table I. Survival times of mature sticklebacks in lead nitrate solutions
Concentrations are g. lead per c.c. water. Temp. 14-17°C. pH of solutions 6.4-6.6,
Concentration
20 x 10'6
15
10
5
3
2
1
7 x 10-7
5
Average survival
time
6% hr.
8^" "
10 M
12 "
13 3A hr.
15% hr .
19 hr.
38^ "
81 "
Concentration
3 x 10-7
2
I 8
6 x ID'0
4
2
Average survival time
of 32 controls in tap
water
Average survival
time
4 3A
7
8^
11
10*5
11
lO1-^
days
ii
it
it
ii
ii
Table II. Survival times of small sticklebacks in lead nitrate solutions
Length of fish l8-20mm. Volume of each solution 500 c.c. Four fish were placed in
each solution and the solutions were renewed daily.
Concentrations are g. lead per c.c. water. Temp. 14-17°C. pH of solutions 6.4-6.6.
Concentration
3 x 10-6
2
1
7 x ID"7
5
3
2
1
Average survival time
of 8 controls in tap
water
Average survival time
days
2
2
- 5
10
101-3
12
14
30
-------
-------
-20-
* Table III. Survival times of mature sticklebacks in zinc sulphate solutions
Length of fish 45-50 mm. Volume of each solution 2000 c.c. Survival times are
means for four fish. All solutions v.cre renewed daily.
Concentrations arc g. zinc per c.c. water. Temp. 14-17 C. pH of solutions 6.4-6.6.
m
Concentration
3 x 10"^
. 2
15 X 10'r1
-u
1 x 10 >
7 x 10'5
5
3
* 2
1 -6
7 x 10 b
5
3
. 2
* 1
Average survival
time
109 min.
143 "
182 "
207 "
243 "
277 "
5k; "
5 3/4" min.
7 3/4 min.
10 min.
11 "
1 64 "
18 "
34 "
Concentration A
7 x 10"7
5
3
2
i
o
5x10"
Average survival time of
32 controls in tap water
verage survival
time
44 days
5 "
6 »
84 "
12 "
1 1% "
104 "
104 "
_
Table IV. Survival times of mature stickebacks in copper nitrate solutions
Length of fish 45-50 mm. Volume of each solution 2000 c.c. Survival times are means
for four fish. All solutions were renewed daily.
Concentrations are g. copper per c.c. water. Temp, of solutions 14-17 C. pH 6.4-6.6.
Concentrati on
5 x 10'6
3
2
15 x 10-7
. 1 x 10-6
7 x ID'7
5
3
2
1
8 x 10'8
Average survival
time
155 min.
216 "
270 "
327 "
6% hr.
10
11 3/4 hr.
214 hr.
- 321-a "
554 "
79 "
Concentration Av
6 x ID'8
4
2
1
Average survival time of
32 controls in tap water
erage survival
time
4^ days
51-i "
8 "
11 "
lO'-i "
-------
-------
-21-
Jones found that at high concentrations the toxicity of zinc salts
is very nearly equal to that of lead; thus, a 0.03 N solution of zinc
nitrate is fatal to gasterosteus in 160 minutes and an equimolar solution
of lead nitrate is fatal in 150 minutes. Experiments at low concentrations,
however, showed that the lethal limit of concentration for zinc is
definitely higher than that for lead. Jones' results with dilute solutions
of zinc sulfate are given in Table III above. It will be seen that the
lowest concentration at which definite lethal action is apparent was at
3 x 10~' g. per c.c.
A further experiment was made with zinc sulfate using 18 to 20 ram.
fish, and in this case a graded series of solutions was employed covering
the range 1X10~6 to IXlO-^g. per c.c. The results were sufficiently
consistent to be plotted as a survival curve which is given in Figure 1.
I
Average survival trae of control)
Xinc OHIO uli'ilion iti p-nit |>«r n-ii million
Tiq. 1.
Survival curve for Gasterosteus in dilute solutions of zinc sulfate
-------
-------
-22-
Here each plotted point represents the mean survival time of four
fish in 2,000 c.c. of solution. It will be seen that a sharp decline
in tcxicity is evident just belov; 3X10" , the survival curve rising
steeply to the limiting value given by the controls.
-------
-------
-23-
VII. THE ANTAGONISTIC EFFECT OF CALCIUM ON THE TOXICITY OF ZINC ON FISH
In 193^ J. R. E. Jones noticed that solutions of lead nitrate of
concentration 1X10" g. per c.c., or less, \.cro apparently harmless to
minnows and sticklebacks if made up with a hard tap water containing
approximately 50nig. per liter of calcium. This reduction in toxicity was
obviously related to the dissolved salts in the water, the chief of which
is calcium bicarbonate. He surmised that the calcium was the factor
responsible for the reduction in toxicity. This hypothesis was confirmed
by the treatment of fish with solutions of lead nitrate in soft water to
which were added varied quantities of calcium salts.
The survival time of sticklebacks in a 1X10 g. per c.c. solution
of lead was found to be 18-28 hours. However, the addition of 2 mg. per
liter of calcium, as calcium chloride, resulted in a considerable lengthening
of the survival time. Moreover, the addition of more and more calcium
still further prolonged the survival time until at 50 mg. per liter the
fish lived for over 10 days; that was, as long as the controls.
This antagonistic effect is depicted by Figure 1. On this graph,
each plotted point represents the mean survival time of five sticklebacks
in 2,000 c.c. of 1X10" g. per c.c. lead solution to which was added
quantities of calcium chloride as indicated by the horizontal scale. The
progressive lengthening of the survival time which results is sufficient
to annul the toxicity of the lead as the survival time reaches that of
the controls at a concentration a little above 30 mg. per liter.
-------
-------
0 2 5 10 20 30
mfr. cnlcium per litre
Pig. 1. Gasterosteus prolongation"of survival time
in lead solutions on addition of calcium chloride,
Jones noticed also that the fish in the solutions containing
50 mg. per liter of calcium did not display any of the symptoms
observed in the case of those treated with solutions of lead only;
in particular the respiratory distress displayed by the latter was
completely absent. The sticklebacks under normal conditions breathes
at a somewhat irregular rate, five to ten rapid opercular movements
-------
-------
-25-
alternating with periods of inertia lasting some 10-15 seconds, but on an
average the rate of breathing is about 120 opercular movements per minute
at 17°C., falling to about 100 per minute during periods of sluggishness,
and rising to about 140 per minute after periods of active swimming. A
stickleback placed in a 1X10 g. per c.c. lead solution soon shows signs
of uneasiness, making rapid darting movements, and the respiration rate
rises rapidly to reach 170 per minute in k hours «nd in 6 hours attains
over 200 per minute. The symptomatic effects of heavy metal poisoning
were, of course, present; e.g. the gills and body surface gradually become
coated with a whitish film of coagulated mucus and the opercular move-
ments become not only more rapid, but also greater in amplitude. Other-
wise, the fish becomes sluggish, occassionally swimming in a spasmodic
manner but for the most part resting on the bottom of the vessel,
propped on its tail and pelvic spines.
The respiration rate continues at 200-2^0 per minute for about
10 hours, rising slightly after the periods of swimming and falling
a little after the periods of rest. Then it begins to decline, in -
all probability because a point is eventually reached when the film
on the gills reduces their respiratory efficiency to such an extent
that even at the increased rate of breathing the fish fails to
obtain sufficient oxygen and begins to succumb. At this point the
fish loses its sense of balance and swims on one side or upside
down, and the pelvic spines become rigidly extended. Once begun,
the decline in respiration rate is rapid, in 2 hours it falls to 1^0
per minute and in the next hour to zero. The variation in respiration
-------
-------
.-26-
rate during the survival time is recorded in Figure 2 in which it is
plotted as ordinate against time as abscissa.
- 0 I 2 4 6 10 ,14
' Time (hours)
Fig. 2. Gctsterosteus; variation in respiration rate during
-survival time in 1 X i0-6 g, per c»c. lead nitrate.
Jones also observed that if 50 mg. per liter of calcium, as
chloride or nitrate, is added to the 1XI0" g. per c.c. lead solution
the respiration rate does not increase steeply but remains fluctuating
somewhat irregularly around the normal level, finally falling when
the fish eventually die, that is in about 10 days. Respiration is
not labored, the gills remain clear of mucous film and the body of the
fish remains clean and slimy.
-------
-------
-27-
The respiratory symptoms of the stickleback in zinc sulfate
solutions are essentially similar to those observed in the case of
lead, as vn 11 be seen from Figure 3? which records the respiration
rate variation of a fish in a 10X10 g. per c.c. solution of zinc. It
was by Carpenter in his works cited above that in the case of lead
solutions, if the fish were removed from the solution at a reasonable
time before death and placed in a supply of well-aerated water the
film of coagulated mucus was shed off and recovery took place.
Recovery takes place on removal from zinc solutions also, and the way
in which the respiration rate returns to normal is illustrated by
Figure 4.
Three sticklebacks were placed in a 2.X10 g. per c.c. solution
of zinc sulfate and the mean respiration rate recorded hourly. In 13'
hours this had risen to over 2^0 per minute and the fish were then
*.*
removed and placed in a frequently renewed supply of well-aerated soft
tap water. This point is indicated by the breaks in the graph (Figure k),
which shows that the respiration rate then fell, rapidly at first and
then more slowly, until in about 45 hours it settled down to the normal
level.
The effect of calcium on the toxicity of zinc salts is similar to
its effect on lead. In Figure 5 respiration rate graphs are given for
Gasterosteus in a 2X10 g. per c.c. solution of zinc sulfate and
2X10" g. per c.c. zinc sulfate plus 50 mg. per liter of calcium as
calcium nitrate. The latter shows that, in the presence of sufficient
calcium, the zinc fails to produce any symptoms of respiratory distress,
the fish surviving for over 10 days with their breathing rate below,
rather than above, the normal level.
-------
-------
-28-
240-
240
200
'f:
c.
«A
c
o
s
u
>
o
E
3 ico
u
o
c.
o
o
z;
2 -46 s
- - "Time"Cn'ours) . _ . _.l
Fig. 3. Gasterosteus; respiration
rate graph for 10XlO~^g.per c,c.
zinc sulphate.
230
70
50
30
to
0
Removal from solution
ci i
a 3
- 10
20
70
30 . 50
T;mc (hours)
Fig. 4. Gasterosteus; return of respiratio:
-rat'C--~vc. normal on transference to water af~
13 hr. immersion in 2X10"ug. per c.c. zinc
sulphate.
T::i:c (hours)
Fig. 5.
-6
Gasterosteus; respiration rate, graphs for 2X1CT" g. per c.c,
c.c. r.inc sulphate plus 50 rag. per 1. of calcium.
zinc sulpha;
The cxpcrimcr
-------
-------
-29- " ' -
The antagonistic properties of calcium to heavy metal poisoning
in fish have significant implications in water pollution abatement.
It is evident that pollution of a river with dissolved lead or zinc
will have far less serious effects on the fish if the river water
contains an adequate supply of calcium bicarbonate than if the water
is soft. An adequate calcium bicarbonate content would result in
the greater part of the lead and zinc being precipitated as insoluble
carbonatest and apparently what remained in solution would be rendered
innocuous.
Whether the treatment of effluents from lead and zinc workings
with calcium is possible is another question. Calcium carbonate,
unless very finely divided dissolves very slowly even in water contain-
ing much carbon dioxide, and the more readily soluble calcium hydroxide
could not be added without disturbing the pK of the water, while- in
all probability treatment with calcium nitrate or calcium chloride
"would not be economically feasible. However, the question is worthy
of further consideration, and it is clear that much work remains to
be done on the effect of calcium salts and salts of other metals on
the reactions that occur between heavy metal salts and the secretions
of the gills and body surface of fisru Kow far calcium salts can
reduce the toxicity of heavy metallic ions to invertebrate freshwater
animals is a further problem for study, in such animals the
mechanism of toxicity of metallic salts is essentially different
to that in fish.
-------
-------
-30-
The antagonistic effect of hardness toward zinc toxicity has been
confirmed by later investigators. The sensitivity of fish to zinc varies
with species, age, and condition of the fish, as well as with the physical
and chemical characteristics of the water. Some acclimatization to the
presence'of zinc is possible, and survivors from hatches of fish subjected
to dissolved zinc have been less susceptible to additional toxic concen-
trations than fish not previously exposed.
While calcium has an antagonistic effect on the toxicity of zinc,
the presence of copper appears to have a synergistic effect. It was
observed that test fish" in soft water could tolerate a concentration of
8 mg. per liter of zinc alone for 8 hours; however., most of the fish
died within eight hours when exposed to a solution containing only 1 mg.
per liter of zinc plus 0.025 mg. per liter of copper.
It was found that the zinc-cyanide complex, unlike nickel cyanide,
dissociated in very dilute solutions, which have been found to be even
more toxic than comparable solutions of cyanide without zinc, apparently
because of synergism.
The following concentrations of zinc have been
reported as lerhal to fish in the time specified:
Exposure
Time Fish
__ Trout on »-ic! youn;
___ You-; ral.-.baw treat
12-24 hrs Hi-'.bci S.-;crlln;s
-- C^ry
_ __ Sumon fry
__ Trout
___ MLtart f.sh
___ S-.lcklcbiclJ
_ Klvh
0 dar» Fl*1!
___ M.tcJ wsrn»nt*r r.u
Sdari Kir «::.-.; rilibo*
trout
3 cSr» Ituinbjw trout
i: hrs Kris
24 h.-j ?:i<-. :,'1nrx>
9C-hr TLm riuorii: su-.'.sh
IShn KI--I
CG-hr TL Bl. .>;.!! «ur.".«'i
8 hrt K.r.;rrl.r.; ri.!:.b--«
9£-i,r TL K.I...-I.
Concen-
tration
as Zi-.c,
mp/l
0.01
O.CZ-0.1
O.n
o.:3
0.15
0.15
0.3
0.3
0.3-0. 7
0.4
0.3
0.5
O.S
O.-'S
1.0
1.9-3.C
2 o
2.9-3.S
3.0
3.0
3 5
3.5
Type
of
T&aicr
-._
So:T
-.1
Sort
Sc'fl
s^t
Si.";
Svf:
s.-.':
S:f;
S>.':
Sc/t
S:d. dlL »i
rcn-.pcra-
Ture
'C
H^^
-i_-
M
-w-
55"
:o~
30"
Kef 20
-------
i
-------
- 31 -
' Concon-
tratitjH T'/pr Tempei'a-
my/I ' H'a.-er "C Time Fiih
{.(.I JlirJ ... S < Hil.i!.. v tf>i.t
4.; bcft 20 !'C-hr Ttm i::ui';U »UI.!L>|I
J.1S ... I Ml
CO -.- 4S l.rs YOJIIC truut
5.0 Soft ... i. l.r» K.-i,
f .02 S'c. dil. Vj'.er . 9^-!.r TLm I-.-i^ill sur.f^n
io.]-'.-: 5 f ";J Ii"i JO fj-l.r TLm K'o.-.'.l sur.'sh
Sft.O Soil <0 !-,-s KI.II
;;-JO 1-? 2 hrs Ka.i.bo*- xrout
200 So.'t ' 3.5 hrs FI.-I,
The following concentrations of zinc have been reported
not to have caused haru TO fish during the time specified:
T'ttc of Exposure
a Zii.c, 111311
0.063
O.ftOJ
0.13
1.0
** 0
J.&-3.5
3.0
4.0
8,o-n.o
Wufer
Hird
Hard
Hard
)!;rd
lli.'d
_«-_
1\me
CS d-,vs
Ju dj.s
21' dj>5
10 (Jj',a
- t!oj S
1-1 ('.C>i
10 li.AS
4:, l.u^rs
.-*-
FisJi <
Tialr.'jou a^eur.s
Uri.^n trcJt r;r^L'rJhgs
H.'uvi n tfuji tie 'crimes
SlicV'.el.iCM
K'lin.iou ;rout
KuCirlin: raii.bo* trout
\uuni; u. ut
Smiie iihlltliiiul trou;
It was reported that as little as 0.1 mg. per liter of zinc will cause
an effect upon biochemical oxygen demand and 62.5 mg. per liter of zinc
will cause a 50 percent drop in the 5-day BOD.
-------
-------
-32-
VIII. RELATIONSHIP BETWEEN THE TOXIC EFFECTS OF ZINC AND
DISSOLVED OMYC-EN OH FISH
Quantitative discrepancies have been reported on the toxicity
of zinc and other heavy metals on fish. These discrepancies may
stem fron oversights in not measuring the dissolved oxygen concen-
trations in the waters used. Low dissolved oxygen concentrations
have been shown to increase the toxicity of poisons to fish.
The dissolved oxygen concentration factor has great bearing
in establishing meaningful effluent water quality criteria because
it is characteristic of many polluted waters to have low dissolved
oxygen content. R. Lloyd indicates a common relation between the
dissolved oxygen concentration and the toxicity of poisons. I/
Briefly, the results of Lloyd's paper are tnat when the
logarithmic survival times of rainbow trout are plotted against the
corresponding logarithmic concentrations of phenols, zinc, lead,
and copper salts in well aerated water, a curvilinear relation is
obtained. At concentrations of these toxic substances in which
periods of survival are long, the line is nearly vertical, so that
a further slight decrease in concentration of these poisons is
associated with a prolonged period of survival. It is these
slightly toxic concentrations of poisons which are important for
predicting safe concentrations for a given water body. If the dis-
solved oxygen concentration of the water is reduced, the survival
I/ Lloyd, R. "Effect of Dissolved Oxygen Concentrations on the
Toxicity of Several Poisons to Rainbow Trout (Salno Gairdnerii
Richardson)." The Journal of Experimental Biology, Vol. 38, 1961.
-------
-------
-33-
tirae per concentration curve is displaced towards lower concentra-
tions of poison, and a value for this increase in toxicity can be
obtained by comparing concentrations of poison which are equitoxic
at prolonged periods of survival. This can be expressed as the
Xs
factor ^r-, where Xg is ^e concentration of poison at 100 percent
of the air-saturation value of oxygen, Cs, and X is the equitoxic
concentration at a lower value of dissolved oxygen, C. Values of
~ at different levels of dissolved oxygen concentration were derived
X
from the experimental data for these four toxic substances for
median periods of survival between 1,000 and 2,000 minutes. Values
of _ for these poisons are shown in figure 1, where it appears
J\
that the relation between increase toxicity and dissolved oxygen
concentration is similar for these substances.
I
1-..
1
O Zinc
V Lead
Copper
Phcnoli
Fig. I. Relation between the :"-iCtnr A",.'A" iVir several poisons and tlic dissolved ox\cn
concentrut.on o; the \\-:er. For cxplunanon of .\\'-V see text.
Source: Lloyd, R. "Effect of Dissolved Oxygen Concentrations on
the Toxicity of Several Poisons to Rainbow Trout (Salrao Gairdnerii
Richardson)." The.Journal of Experimental Biology, Vol. 38, 1961,
p. 448.
-------
-------
These facts led Lloyd to develop a theoretical relation
between heavy metal poisoning and oxygen uptake in fish. Lloyd's
discussion is, in part, as follows:
"Although the toxic actions of heavy metals ... are probably
dissimilar, the common effect on their toxicity resulting from a
reduction in the concentration of dissolved oxygen suggests that
this is a result of a physiological reaction by the fish to such a
change of the environment, and is independent of the nature of the
poison. The most obvious reaction of fish to a lowered oxygen
content of the water is to increase the volume of water passed over
the gills, and this may increase the amount of poison reaching the
surface of the gill epithelium, the site at which most poisons are
absorbed. It was shown that an increase in the oxygen uptake of'
."
several species of fish results in a decrease of their survival
times in toxic solutions; they found, however, that a reduction in
the dissolved oxygen concentration of the water reduced the oxygen
uptake of the fish, yet increased the toxicity of the solution,
and thought that this reduction in uptake was insufficient to
compensate for the reduced oxygen content of the solution and that
it was the increased rate of respiratory flow through the gills
which led to an increased toxicity of the poison. However, the
design of their experiments does not allow the results to be com-
pared in detail with those from the experiments described here.
Therefore, although there is some evidence that an increase in
respiratory flow increases the toxicity of poisons, there is no
evidence to show that this accounts for the whole of the increase
-------
-------
-35-
in the toxicity of poisons in water of low dissolved oxygen concen-
tration. The following hypothesis is suggested to explain the
relation between respiratory flew and the toxicity of poisons ...."
The structure of the teleost gill ... consists of a sieve
of fine plates which form long narrow channels through which the
respiratory water flows. It is assumed that in such a fine capil-
lary system, and over the normal range of respiratory flow rates,
the flow pattern will be laminar, even though the respiratory
current may not be continuous but intermittent. Since the walls of
this channel, (or) the respiratory epithelium, form an absorbing
surface for poisons, there will be a diffusion layer at this surface
in which a concentration gradient of toxic substances could exist.'
Although there are no da^a on the relation between velocity of flow
and the rate at which ions or molecules reach an absorbing surface
in capillary systems, Straielda L/ has shown that wider tubes, under
conditions of laminar flow and with a.constant concentration of
solute, the relation conforms to an equation which may be written
Xy = A + B VT'
where X'is the concentration of solute at the surface, v'is the
velocity of flow, A is the concentration of solute at the surface
when v' is zero, and B is a constant for the system. It is assumed
this equation can be applied to capillary systems of the same
I/ Strafelda, F., "Polargraphis im durchfliessenden Electrolyt.
I. Einf uhrur.gcnitteilung." Coll, Czechoslov. Chem. Commun. Vol. 25,
I960, pp. 862-70.
-------
-------
-36-
dimensions as those existing in a teleost gill; it is also assumed
that under conditions of zero flow, the diffusion layer would be
of infinite dapth and the solute would have to diffuse through the
capillary system from the bulk of the solution outside, so that
values of A would be very small when compared with the values of
x' obtained with a very thin diffusion layer at normal flow rates.
Therefore, the term A will be neglected, and the equation rewritten
as
x' = B Vv'
Thus, if xj_ is the concentration of solute at the surface when the
velocity of flow is v^ and x^ the concentration of solute at the
surface when the velocity of flow is v, and X2 the concentration
of solute at the surface when the velocity is increased to v^, the
factor for the increase in concentration of the solute at the surface,
"Xo/x^, is equal to V/y^/v '). Also, since it can be assumed that,
within the range of concentration of poisons used in these experi-
ments, the ratio between x and the concentration of solute in the
bulk of the solution is a constant for any given value of v', it
can be shown that if the flow is increased from v, to Vo and the
concentration X', is to remain at the level x,, the concentration
of solute in the bulk of the solution would have to be multiplied
by the factor X-,/X . Therefore, if the effect of low dissolved
* £i
oxygen concentrations on the toxicity of poisons is to increase
the rate of respiratory flow from v_ at the air-saturation level
s
of dissolved oxygen to v at a lower level, the decrease in concen-
tration in the bulk of the solution required to maintain constant
concentration of poison at the surface of the gill epithelium,
-------
-------
-37-
/Xs, should equal /V(v/v) or Xs/x ~ V(v/v )
It would be difficult to measure directly the velocity of water
flowing through the respiratory channels of the gills, but since
the dimensions of these channels presumably remain constant with
small differences in the flow rates, the velocity of flow will vary
directly with the volune of respiratory water passed through the
gills. Volumes of respiratory water passed in unit time can be
calculated from the oxygen uptake of the fish, the oxygen content
of the water and the percentage removal of oxygen from the water by
the fish, the equation being
QP ., 100
v* = c~ A P
s us s
where Vs is the volume of respiratory water (1/hr ), QS is the
oxygen uptake of the fish (mg/hr) , and P_ is the percentage removal
* S
of oxygen from the respired water when the dissolved oxygen con-
centration at the air-saturation value is Cs (mg/1). Similarly,
at a lower level of dissolved oxygen, C,
V= 100
CP
Where V, Q, and P are the velocity of flow, oxygen uptake of the fish
and percentage removal of oxygen from the respired water respectively
at the lower level of dissolved oxygen. Therefore, the increase in
the rate of respiratory flow when the dissolved oxygen concentra-
tion of the water is reduced from Cs to C is given by the equation
V - = C PQ
~"
-------
-------
-38-
Values of Qs and Q were obtained from respirometer experi-
ments with rainbow trout at two dissolved oxygen levels, Cs and C,
and are given in Table I; values for P and P have been given by
5
van Dam?-/for the sane species. (See Figure 3. ) These values were
used to calculate the factors for \/ (V/VS) shown in Figure 2,
where they are compared with the curve fitted to experimental data
for XS/X, shown in Figure 1.
TABLE I. Oxygen uptake of rainbow trout at different
levels of dissolved oxygen at 17.5° C.
Lower oxygen level
We fish
fe.)
0-99
1-05
2-10
3-04
IflO
too % air .
saturation.
Oxygen uptake
(mg. O.'hr.)
0-50
0-58
i-io
1-75
3-iS
saturation
48-0
63-0
42-0
40-8
47'5
Oxvgen uptake
(mg. Oshr.)
0-33
0-47
. 0-68
1-19
a-zz
O Theoretical vilues,
Experimental curve i
from Fir. 1 '
30 40 SO tO 70 80 53 100
Dissolved cx>j»n ('\, of air-saturation value)
Fig. 2. Relation between the curve fitted to the
experimental factors for X /X and theoretically
determined factors for V(V/V]_) based on
the increased rate of flow of respiratory water.
rj
__/van Dam, L. "On The Utilization of Oxygen and Regulation of
Breathing in Some Aquatic Animals." Dissertation, Gromingen.
-------
-------
-39-
o
*0
$ 70
o
. 20 30 40 SO 60
Dissolved oxvjen (*_, of a
£0 90 100
Fig. 3. Relation between the percentage removal of
oxygen fron the respiratory water by rainbow
trout and the dissolved, oxygen concentration of
the water.
The close relation between the points for V(V/VS) and the
curve for XS/X lends support to the hypothesis that the increased
toxicity of poisons at low dissolved oxygen concentrations Is the
result of an increased concentration of poison at the surface of
the gill epithelium, and that the concentration of poison in the
bulk of the solution has to be reduced from Xs to X to maintain
a constant concentration of poison at that surface."
In conclusion, Lloyd emphasized that: "...the close appoxi-
motion of the points given by the two theoretical methods to the
practical values obtained for XS/X suggests that the majority, if
not all, of the increase in toxicity of poisons in water of low
dissolved oxygen concentration is caused by the increase in the
rate of respiratory flow.
-------
-------
-4Q-
This is of fundamental importance in fish toxicology,
since it implies that any environmental or physiological
change which affects the rate of respiratory flow of a fish
will also affect the concentration of poison at the surface
of the gill epithelium, and that a known relation exists
between these two factors. It also implies that the relation
between the increase in toxicity of poisons to fish and a
reduced dissolved oxygen concentration of the water will be
the same for all poisons except those whose toxicities are
affected by the pH value of the water. Thus, the curve
obtained for the factor XS/X in Figure I. should apply to
the effect of dissolved oxygen concentration on the
toxicity of most heavy metal poisons to rainbow trout."
-------
-------
-41-
IX. UPTAKE AND ACCUMULATION OF ZINC BY AQUATIC ORGANISMS
A. General Considerations
Organises incorporate into their bodies those substances
from their environment and food required for their maintenance,
growth, and reproduction. The proportion of various substances
required by the organises are different from the proportions in the
environment, and this results in concentrations of some elements
in the biosphere. Some substances are accumulated because the
organisms have no means of getting rid of them.
In addition to the abundant elements carbon, oxygen and
hydrogen, the bodies of organisms contain a number of elements in
smaller amounts, such as nitrogen, phosphorus, calcium, strontium,,
copper, zinc, and iron, which are essential to the life processes.
These may be obtained by organisms above the plants in the food chain
either from their ingested food, or by direct uptake from the sea
water. Since the requirements for different elements are different
in different kinds of organisms, the energy fluxes of the various
elements are variable from one to another, and at different trophic
or nutritional levels.
The concentration factors of some of the more important
elements in different kinds of organisms are tabulated in Table 1.
Certain elements, for example, sodium, occur in some organisms at
lower concentrations than in the water/ they are selected against.
-------
-------
\J i
e
in
o
P
u
d
c
o
ri
P
d
P
c
.-H
d
p
41
rH
O
.y
CO
rH
fs.
O
4->
U .j
o
CO
O
in
(L>
P
0
to
o
p
o
C
M
1
^i
0
P
o
rH
O
V
CO
o
in
0*
p
0
CO
o
rH
o
o
rH
0 0
IT) O
o
cT
CO
rH 0
O
O
O
0
o
rH
O
0
O
O
o
o
m
o
o
o
o
o
o
rH
0
03
o
o
o
o
rH
o
rH
o
o
o
rH
o
rH
O
o
o
rH
O
O
o
o
o
0
in"
0
o
o
o
o
o
o"
o
i-H
0
o
o
o
o
O 0
0 0
CN] rH
o o
o o
rH O
O
O
O
V
O
O
O
K
CO
O
O
O
O
O
O
O
m
O
O
O
o
O
in
I
, rH s~*
d in
4> o 2
d « o
di c U 3 C" 0- C-
H 0> -H U
c o c
o j o
M H
6
0
M
in
0)
* 3
H ,H O -H fc
Z. $£. > H U
*
O O C
IV O ""
o
o^
o
o\
U 0
H -rl
c c
0 0
M H
A! CO
-------
-------
-43-
On the other hand, those elements, such as phosphorus,
that are essential to the organisms but occur in low concentra-
tion in the sea water are concentrated by several orders of
magnitude. In some parts of the sea, the phosphorus may be
nearly completely removed from the water by the organisms.
Such elements are often limiting constituents for further
increase of the populations of a particular part of the sea,
and any quantities added will be soaked up by the biosphere
very rapidly.
Both dissolved and particulate materials can be taken up
from the environment. Iron, for example, occurs in the sea
almost entirely in particulate form and is used in that form by
diatoms. Fishes can take up ionic calcium and strontium
directly from the sea water. Observations have shown that par-
ticulate feeders among the zoo plankton ingest particles of
inorganic compounds and retain them. - -
The uptakes of various elements by organisms are not en-
tirely independent of one another. Elements of similar chemical
properties tend to be taken up together very roughly in the same
proportions as they exist in the environment. This is true, for
example, of calcium and strontium. Sometimes one element has an
inhibiting effect on another in the uptake process. There can'
also be synergistic effects, such as the enhancement of phos-
phorus uptake of diatoms by increased concentrations of nitrogen.
-------
-------
-44-
Certain elements are deposited, in large part, in parti-
ular organs. Perhaps the best known examples are the deposition
of iodine in the thyroid glands of vertebrates, or the deposi-
tion of calcium and in the shells and other hard parts of
invertebrates.
The length of time an organism retains the average atom
of a given element varies greatly from one element to another.
This is sometimes measured as the biological half-life, although
the relative rate of loss is not a simple linear function of
time as in the case with radioactive decay. Much is known 'about
the retention times of different elements in man (see, for
example, Handbook 52 of the National Bureau of Sxandards, 1953),
"but there are few data for most marine- organisms. The rate of
excretion of an element and the amount ultimately retained, will
be quite different if the element is taken up quickly from a .
single dose or is taken up slowly over a long time.
B. The Uptake and Accumulation of Zinc
The definitive work on the subject was done by W. A.
*
' Chipman, T. R. Rice, and T. J. Price. The results of their
research are reported in a paper entitled, "Uptake and Accumula-
tion of Radioactive Zinc by Marine Plankton, Fish, and Shellfish."^/
3/Chipinan, V. A., T. R. Rice, and T. J. Price, "Uptake and Accu-
"~ mulation of Radioactive Zinc by Marine Plankton, Fish, and
Shellfish," Fishery Bulletin of the Fish and Wildlife Service,
Vol. 58, Fishery Bulletin 135, (1958).
-------
-------
-45-
The project's major findings were as follows:
1. The zinc content of sea-water samples collected from
inshore waters along the Atlantic and Gulf of Mexico coasts
averaged 10.6 micrograms per liter and ranged from a trace to
24.56 micrograms per liter; the higher values were for samples
from areas known to receive metal contamination.
2. There was a seasonal difference in the zinc content
of the sea water at Beaufort, North Carolina, the lower values
occurring during the winter months. The monthly averages
ranged from 2.8 to 14.6 micrograms per liter. The average of
all the observations was 9.6 micrograms per liter. See Table 2.
TABLE 2 -- Average of weekly observations of the zinc content of
the sea water at Beaufort, North Carolina.
Month
November
December
January
February
March
April
Zinc in mi-
crograms (x/.)
per liter
9.7
2.8
3.5
5.4
5.0
12.1
Month
May
June
July
August
September
October
Zinc in mi--
crograms (i{.
per liter
13.2
14.1
12.4
14.6*
12.1
11.6
*Before hurricane, 12.5; after hurricane, 19.6,
-------
-------
-46-
3. That oysters, clams, and scallops contain large
amounts of zinc, thousands of tines more than the sea water
per unit of weight, was confirmed. In these the greatest
accumulation is by oysters, less by hard-shell clams, and
least by bay scallops. See Tables 2 and 3. Table 4 gives
zinc concentrations by oysters and other shellfish reported
by other investigators.
TABLE 2 -- Zinc content of oysters and the surrounding sea water
(Winter and early spring samples)
Locality
Zinc in oysters Zinc in the
..(micrograms per water
gram of fresh (micrograms
tissue) per gram)
Milford, Connecticut
Upper Chesapeake Bay
Lower Chesapeake Bay:
York River, Virginia
James River, Virginia
Chincoteague Bay, Maryland
Beaufort, North Carolina
Brunswick, Georgia
Gulf of Mexico:
Pensacola, Florida
Galveston, Texas
3174
2933
1295
1484
778
1171
313
600
391
0.0188
.0240
.0079.
.0046
.0011
.0008
(Trace)
-------
-------
-47-
TA3LE 3 -- DISTRIBUTION OF ZINC IN THE OYSTER
(Based on dried tissue)
Tissue
Zinc content
(micrograms per
milligram)
Mantle
Gills
Labial palps...
Adductor muscle,
Remainder
6.91
8.02
9.58
.61
6.69
-------
-------
-48-
TABLE 4'-- Zinc in shellfish from Atlantic Coast waters (Maine through
North" Carolina) and the Pacific Oyster (Washington)
Species an d Location
I. Atlantic Coast (Maine through TT.C.):
A. Eastern Oyster (Crassostrea
virginica)
a. Pringle and Shuster^
b. KcFarren et al.3
c. Galtsoff4
d. Chipraan et al.
B. Northern Quahaug
(Mercenaria mercenaria)
C. Softshell Clam (Mya arenaria)
D. Surf Clam (Spisula solidissima)
E. Blue Mussel (Mytilus edulis)
(Narragansett Bay, R. I.)
F. Common Rangia (Rangia Cuneata)
(Pongo River, N. C.)
G. Channeled Whelk (Busycon
canaliculate)
(Narragansett Bay, R.I.)
Zinc concentration in tissue-*-
Average
180-4120
310-4000
710-2760
740-1332
11.50-40.20
9-28
12.39
21.34
16.90
81.75
1428
1641
1468
1018
20.6
17
II. . Pacific Coast (Washington)
A. Pacific Oyster (Crassostrea gigas) 86-344
229
Zinc values are given in parts'per million (ppra) of shellfish wet tissue
weights. The samples were shucked. The drained meats of shellfish were
homogc-nated, lyophilized, wet digested, diluted, and read on the atomic
absorption. Data other than that by Pringle and Shuster were determined
by methods other than via atomic absorption.
2 Pringle, B. H. and C. N. Shuster, Jr., "A Guide to Trace Metal Levels in
Shellfish," Public Health Service, Northeast Marine Health Sciences Labo-
ratory. December 1967.
3 McFarren, E. P., J. E. Campbell, and J. B. Engle, "The Occurrence of
Copper and Zinc in Shellfish." Proceedings, 1961 Shellfish Sanitation
Workshop: pp. 229-234.
^ Galtsoff, P. S. , "The- American Oyster Crassostera virginica Gmelin."
Dept. of the Interior, U.S. Fish and Wildlife Service, Fish Bulletin, 1964,
Vol. 64, pp. 1-480.
* Chipman, U. A., T. R. Rice, and T. J. Price, "Uptake and Accumulation of
Radioactive Zinc by Marine Plankton, Fiuh, and Shellfish." Dept. of the
Interior, U. S. Fish and Wildlife Service, Fish Bulletin, 1958, Vol. 58,
pp. 279-292.
-------
-------
4. Radioactive zinc present in the surrounding water is
rapidly taken up in great amounts by these shellfish, probably
because of the great difference between the zinc content of the
water and that in the tissues. Much of the zinc in the mollusks
is exchangeable with that of the water. See Tables 5 and 6.
TABLE 5 -- Uptake of zinc 65 by oysters immersed in sea
water containing the isotope
/Average of 15 oysters. Zinc 65 concentrations reported
in railliraicrocuries (mucj/
Hours of exoosure
Zinc 65 content
of oysters
(mu.c/giu. fresh
tissue)
Zinc 65 content of sea
water (muc/ml.)
Initially
At end
Test 1:
5...
24...
48.. .
Test 2:
42...
66...
90.. .
114...
138.. .
210.2
263.6
243.5
137.1
376.2
508.8
366.3
311.9
10.6
8.1
8.3
9.7
9.7
9.7
9.7
9.7
5.2
3.0
4.9
3.8
2.5
1.8
1.5
-------
i
-------
-50-
TABLi: _6 -- Uptake of zinc 65 by the separated gills of oysters
iranersed in sea v;ater containing the isotope and non-radio-
active zinc.
Hours of exposure
0
6
18
19 5
21 5
Radioactivity
of water
(counts per
minute ")
2,576
1,841
835
749
572
Hours of exposure
24
26
42
45
48
Radioactivity
of water
(counts per
minute
458
342
164
165
132
5. High concentrations of the zinc 65 injected into or
taken up by oysters and scallops occur in the gills. Consider-
able amounts accumulate in the kidney of scallops. There is also
accumulation in the hepatopancreas of the shellfish, but only
small amounts in the adductor muscle. See Tables 7 and 8.
TABLE 7 -- Uptake of zinc 65 by the separated gills of oysters immersed
in sea water containing the isotope, and loss of this isotope from
these gills when placed in non-radioactive sea water containing EDTA.
Hours of exposure
Radioactivity
of sea water
(counts per
minute)
Hours of exposure
Radioactivity
of sea water
(counts per
minute)
Sea water:
0
1
2
3
5
9
21.5
24
2,671
2,631
2,508
2,416
2,208
1,819
1,154
1,165
Sea water (cont.):
27
45.5
Sea water &. EDTA:
0
4
20
23
25
1,106
1,074
0
275
1,246
1,174
1,215
-------
-------
"51-
TABLE 8 -- Tissue distribution of zinc 65 in the bay scallop
after exposure for 2 hours to sea water containing 10 mnc
(millimicrocuries) zinc 65 per milliliter.
(Average of 10 scallops)
Organ
Gills
Testis and ovary
Foot
Heart
Mantle
Weight in
grams
0.595
2.085
3.924
1.401
.191
.070
.127
3.769
3.495
Zinc 65 content
iTjUc/gm.
1,384. 31
243.14
218.43
138.04
130.59
119.61
105.10
99.61
91.76
6. The marine diatom, Nitzchia closterium, takes up large
amounts of zinc 65 when it is present in the sea water. The zinc
very rapidly entered the cells, much of it within the first hour.
See Table 9.
-------
-------
-52-
TABLE 9 -- Uptake of zinc by Nitzschia cells from sea water
to which was added different caour.tc of zinc.
(Initial cell population: 7.2 x 107 per liter)
Gammas (micrograms) of zinc in cells
of liter culture
Time in hours
1
6
24
48
66
96
*Cell increase
**No increase in
Culture
containing
100 '(/liter
56
67
86
91
1 96
98*
ten fold.
cell numbers.
Culture
containing
lOOOVVliter
380
450
600
680
700
700*
Culture
containing
5000 Y/liter
1,000
1,250
2,500
2,550
2,200'
2.000**
When considerable amounts of zinc were present, more was
taken by the cells. The cells in the medium having 100 micrograms
of zinc per liter continued their divisions and growth. At the end
of 96 hours, the cell population had increased from 7.2 x 107 to
70 x 10/ cells per liter. Those in medium containing 1,000 micro-
grams and 5,000 micrograms per liter did not divide. The presence
of 5,000 rnicrograms of zinc per liter was sufficient to damage the
-------
-------
-S3-
cells, as indicated by a decrease in their zinc content after
48 hours. Because of the great uptake, there was a marked
change in the availability, carticularly in the culture con-
taining the lowest concentration, It seems likely that more
would have been taken by the cells if greater amounts were
still available. The amount of zinc per cell at the end of
96 hours was as follows:
-------
-------
Zinc in a liter
culture initially
100
1,000
5,000
Zinc per cell
after 96 hours
^(micrpgrams )
1,4 x KT6
96.0 x 10"6
361.0 x.10'6
Realizing that individual Nitzschia cells are small in
volume and in weight, it is apparent that they can take up tre-
mendous amounts of zinc if available in the sea water, more
being taken when the amount present is increased. It is evident
that, if zinc 65 is present in the sea water, the isotope will
be accumulated by the phytoplankton. Although the greater part
of the zinc of the cells is exchangeable with that of the water,
very little accumulated zinc 65 leaves the cell when they are
resuspended in nonradioactive sea water: See Table 10.
TABLE 10 -- Loss of zinc°-> from Nitzschia cells
filter-washed with distilled water and with
culture medium containing different amounts
of added zinc
Washing Medium
Distill*
Culture
Culture
Culture
Culture
Culture
Percentage
lost from
cells
2.80
14.64
15.42
30.55
34.27
42.28
This species of marine phytoplankton appears to accumu-
late considerable amounts of zinc.
-------
-------
-55-
7. Marine fish quickly take zinc into the body from the
digestive tract. See Table 11. Although the internal organs
TABLE 11 ~- Zinc65
its
Organ
Stomach
Intestines
content of diaostive tract of croakers
administration by mouth
Percentaae of
2 hours
50.2
8.7
Pyloric caeca 0.6
TOTAL
59.5
in gelatin
dose remainina
6 hours 12
8.4
11.3
0.9
20.6
following
after
hours
7.5
15.6
0.9
24.0
rapidly take up zinc in large amounts, they constitute only about
2 percent of the weight of the entire fish. The uptake and rate of
loss in these organs is usually rapid and much of the physiology
and metabolism of elements is explained in the changes in concen-
tration-s in these organs. See Table 12 and 13.
-------
-------
.-56-
Table 12 - Distribution of zinc 65 in croakers following
c5.T-.ettir.rj of the nuclide into the stomach
Distribution
Digestive tract:
Stomach
Intestines
Pyloric caeca
TOTAL
Fish Body
Unaccounted for
Percentage of dose remainina after
2 hour:;
59.7
20.4
6.9
87.0
3.6
9.4
'- hours
0.7
42.2
3.9
46.8
2.4
50.8
6 hours
0.7
42.6
11.4
54.7
7.9
37.4
12 hours
0.4
48.3
2.9
51.6
6.7
41.7
24 hours
9.8
6.3
2.9
19.0
9.7
71.3
43 hrr.
1.2
3,9
1.0
6.1
6.8
87.1
Table 13.- Changes in the zinc 65 content of the various organs and
tissues of croakers following its administration
/Dose: 1.55 nicrocuries per gram of fish. Values listed in
millimicrocuries per gram of fresh tissue/
Tissue or organ
Blood
Heart
Spleen
Gill filaments
Liver
Kidney
Gonads
Muscle
Bone
Integument
Zinc 65 content (muc/cm. ) af ter-
2 hours
0.93
0.02
0.09
0.11
1.50
0.05
0.01
0.02
**
4 hours
8.16
1.60
1.60
2.54
3.14
3.64
0.27
0.06
0.41
0.17
6 hour s
28.61
10.66
15.06
10.97
57.46
27.03
2.44
0.31
1.42
1.10
12 hours
7.21
3.72
6.97
4.48
20.64
10.09
1.61
0.21
1.27
1.21
24 hours
9.70
5.11
12.83
8.09
22.00
18.52
2.98
0.43
2.37
2.32
48 hours
3.49
3.91
3.86
4.52
11.72
12.26
2.57
2.21
1.19
1.06
While the rate of uptake in muscle and bone may be slow, these
tissues account -for 91 percent of the weight of the fish. The slow
accumulation of elements in these tissues is of considerable
importance.
-------
-------
In the croakers tests 12 hours after dosing, the greatest
amount of zinc 65 in the fish was in the muscles. The muscles and
bones had 66 percent of the total radioactive zinc present in the
fish. See Table 14.
Table 14.- Zinc 65 distribution in entire fish 12 nours after
inaestion of the isotope.
/Dose per fish: 6,000 millimicrocuriesy
Organ or tissue
Muscle
Bone
Gills
Liver
Gonads
Kidney
Heart
Spleen
Remainder
TOTAL
% of total
weight
80 -
11
2
0.8
0.4
0.3
0.2
0.1
5.2
MM MUM
Weight
grams
48.80
6.71
1.22
0.49
0.24
0.18
0.12
0.06
3.17
60.99
Zinc 65
muc/gm .
1.6
5.5
10.9
40.7
17.6
41.5
14.0
25.3
3 3.7
M_MM
Zinc 6i
muc per
tissue or
or a an
78.1
36.9
13.3
19.9
4.2
7.5 .
1.7
1.5
11.7
174.8
% of total
zinc 65
of body
44.7
21.1
7.6
11.4
2.4 -
4.3
1.0
0.9
6.7
,
Three percent of dose in tissues (178.8 muc); 24 percent in
digestive tract; 73 percent not accounted for, mostly excreted.
Skin, scales, digestive tract, blood, brain, eyes, and other parts
Based on skin and scales.
8. The retention of zinc 65 by fish was measured in experiments
using pinfish, Lagodon rhombaides, Following an exposure of the
fish for 4 days to sea water to which had been added zinc 65, they
were returned to a laboratory tank of flowing sea water.
The relative radioactivity of the fish during 25 days following
their return to nonradioactive flowing sea water is plotted in the
graph of figure 1. There was initially a marked loss of zinc 65
-------
-------
20
5 '0
-58-
_L
_L
J_
JL
J_
J_
J_
_L
J
-'.-:-- ... Z 4 6 8 10 12 14 16 18 20 22 24 26
; . . - . DAYS
TIOVRE 1.Loss of contained Zn" from the pinfish, Lagodon rhomboidts, following return to flowing sea water
from the fish when returned to a flowing sea water following the
exposure. However, 7 or 8 percent of that initially present was
retained throughout the 25 days of observation. It is apparent that
some zinc 65 containing compounds in the body of the fish have a
very slow rate of turnover. A part of any contained zinc 65 in
the fish will be present over very long periods of time since the
-------
-------
-59-
loss during 25 days was extremely slight, as shown by the line of
figure 1. The loss from the tissues cannot amount to much more
than that resulting from radiological decay. Because of the. long
half-life of zinc 65 (about 250 days) and the relatively great
fluctuations in individual samples, the observations reported were
not corrected for the radiological decay.
-------
-------
-60-
X. TOXIC EFFECTS OF SOME SPECIFIC ZINC COMPOUNDS
1. Zinc Chloride, ZnCl?
Zinc chloride is highly soluble in water, one gram dissolving
in 0.5 ml. of water. It is used as a deodorant, disinfecting,
and embalming material and in the manufacture of paper, dyes, glues,
and many other processes.
A dose of six grams of zinc chloride has been reported as fatal
to man. Practically all recorded cases of poisoning and deaths from
zinc have involved either the chloride or the sulfate.
Young carp were killed within 24 hours by 1.0 mg. per liter of
zinc chloride in tap water. The highest concentration of zinc chloride
tolerated by young eels for more than 50 hours was 0.14 mg. per liter.
Doudoroff and Katz reported that zinc chloride at a concentration of
0.65 g. per liter killed eels in about 12 hours. Caitns and Scheier
reported in their paper, "The Relationship of Bluegill Sunfish Body
Size to Tolerance for Some Common Chemicals," (Industrial Wastes,
Vol. 3:5, p. 126 (1958)), that for medium-sized bluegill sunfish in
standard dilution water at 20°c, the 96-hour TL for zinc chloride
' m
was 7.20 mg. per liter. Goodman reported in his article, "Toxicity
of Zinc for Rainbow Trout (Salmo gairdnerii)" (Cal. Fish and Game,
Vol. 37, p. 191 (1951)), that 15 mg. per liter of zinc chloride
killed fi&h within 8 hours.
According to Cairnsand Scheier in their paper, "The Effects of
Periodic Low Oxygen Upon the Toxicity of Various Chemicals to Aquatic
-------
-------
-61-
Organisras" (Proc. 12th Industrial Waste Cong., Purdue Univ.,
Engineering Bull., Vol. 42:3, p. 165 (1958)), the 96-hour TLm values
for bluegill sunfish exposed to zinc chloride were 8.02 mg. per liter
of zinc at normal oxygen tensions, but when the dissolved oxygen was
periodically lowered to 2.0 mg. per liter, the TLm was only 4.9 rag.
per liter as zinc.
Anderson in his paper, "The Apparent Thresholds of Toxicity of
Daphnia magna for Chlorides of Various Metals When Added to Lake Erie
Water" (Trans. Amer. Fish. Soc., Vol. 78, p.96 (1948)), quotes references
to the effect that 1.36 mg. per liter of zinc chloride in pond water
. killed Daphnia magna in less than 5 days, and in Lake Erie water at
25°C the threshold concentration for immobilization of Daphnia magna
was found to be very much less than 0.15 mg. per liter of zinc chloride.
Anderson also observed that the hardness of water appears to affect
markedly the toxicity of ^uch zinc salts.
2. Zinc Nitrate, 2n(KC-3)2
Zinc nitrate is a colorless, odorless salt used as a mordant in
dyeing. It is very soluble in water. In the paper, "Detection and
Measurement of Stream Pollution (Eelated Principally to Fish Life)",
(U. S. Dept. of Commerce, Bur. of Fisheries Bull. 22 (1937)), Ellis
quotes references to the effect that tadpoles survived a three-month
exposure of 1.89 mg. per liter of zinc nitrate but failed to develop
limb buds, that 5.7 nig. per liter killed most tadpoles, and that
94.7 mg. per liter killed tadpoles quickly. Anderson observed that a
-------
-------
-62-
zinc nitrate concentration of 189 mg per liter in well water
killed Daphnia rr.agna in 15 hours, but for stickleback fish the
toxic threshold was only 0.87 ing per liter.
3. Zinc Sulfate, ZnSC>4
Zinc sulfate is a colorless, odorless, crystalline or
amorphous substance. It is very soluble in water. Zinc sul-
fate is used extensively as a mordant in calico printing, for
preserving wood and skins, and for electroplating of zinc. It
has been used as an emetic, but 45 grams are reported to be
fatal.
The toxicity of zinc sulfate to fish has been well
established by numerous experiments. In general, 0.3 rag per
.liter of the compound as zinc has been found to be lethal to
sticklebacks. Depending on the concentrations, the average
survival times were as follows: four days at 0.7 mg per
liter and one week at 0.4 mg per liter as zinc.
The following concentrations of zinc sulfate, as the
salt or as zinc, have been reported lethal to fish in the
stated time of exposure:
-------
-------
-63-
Concentration
of Zinc Sulfate
na/1
0.13 (as Zn)
0.3 (as Zn)
0.4 (as Zn)
0.7 (as Zn)
0.8
1.5
3.6 (as Zn)
4.0
6.0 (as Zn)
8.1
10
10
10
16*
25
25-50 (as Zn)
100
400
1000
Type of
Water
_ __
Soft
Tap
Tap
..-
Fresh
Fresh
Distilled
Tap
Distilled
Hard
Time of
Exposure
_ __
Long terra
7 days
4 days
144 minutes
24 hours
48 hours
144 minutes
14 hours
72 minutes
?
30 hours
48 hours
20 hours
133 minutes
2 hours
5 days
200 minutes
1-4 hours
Fish
Guppy
Sticklebacks
Sticklebacks
Sticklebacks
Minnows
Sticklebacks
Young trout
Minnows
Trout fingerlings
Minnows
Fish
Trout
Minnows
Young eels
Rainbow trout
Rainbow trout
Goldfish
Minnows
Goldfish
*Approximately
-------
-------
The following concentrations have been reported as not
harmful in the time specified:
Concen-
tration
in raa/1
2.0
2.5-3.5
4.0
100
200
10CO
Reported
as
Zinc
Zinc
Zinc
Zinc sulfate
Zinc sulfate
Zinc sulfate
Type
of
Water
...
Hard
...
Hard
Sea
Time of
Expo-
sure
24 hours
14 days
24 hours
4 days
1 day
Fish
Young trout
Rainbow trout
Old trout
Fish
Minnows
Trout
Rudolfs, Barnes, et al. in their review paper, "Review of
Literature on Toxic Materials Affecting Sewage Treatment Processes,
Streams, and B.O.D. Determinations" /^Sewage and Industrial Wastes,
Vol. 22, p. 1157 (1950)_.7 reported that studies by different people
indicate the effects of zinc sulfate on plankton forms in scft water
were as follows: concentrations up to 500 mg per liter were tolerated
by larvae of stonefly, caddis, and water boatman. However, a con-
centration of 10 mg per liter killed many small Crustacea. Daphnia
in an Idaho lake were killed by 0.65 mg per liter in three days. A
concentration of 0.3 mg per liter was the minimum tolerance for
mayfly nymphs and 0.2 mg per liter for fresh-water snails and
shrimps. It was also found that a concentration as low as 0.1 mg
per liter of zinc sulfate as zinc was lethal to some of these organisms
after a longer period of exposure. Anderson also 'indicated in his
above cited paper that 0.024 rag per liter of zinc sulfate killed
Daphnia magna in hard water but a few survived a concentration as
-------
-------
high as 0.24 rag. per liter in soft water. In Lake Erie water at
25°C the threshold concentration for immobilization of Daphnia magna
was found to be less than 48 mg. per liter. Naumann claimed in his
paper, "The Effect of Some Salts and Mixtures of Salts on Daphnia
magna" (Physiog. Sallsk. Lund. Forh. Vol. 4, p. 11 (1935)), that
10 mg. per liter of zinc sulfate had no effect on Daphnia magna
during the first five hours of exposure, but thereafter signs of
poisoning appeared. The animals may live for some days but their
color fades and they lose their power of reproduction.
Using water of the River Havel from which the test organisms
were recovered, Bringmann and Kuhn in their papers, "Water Toxicology
Studies with Protozoans as Test Organisms" (Gesundheits-Ing. Vol. 80,
p. 239 (1959)) and "The Toxic Effects of Waste Water on Aquatic
Bacteria, Algae, and Small Crustaceans" (Gesundheits-Ing. Vol. 80,
p.115 (1959)) studied the threshold effects of zinc added as
ZnS04.7K20 on various species during an'exposure of 2-4 days. For
Daphnia the median threshold effect occurred at 1.8 mg. per liter
of zinc, for E. Coli at 1.4 - 2.3 mg. per liter, for Scenedesmus at
1.0 - 1.4 mg. per liter, and for Microregma at 0.33 mg. per liter.
Cleland in his article, "Heavy Metals Fertilization and Cleavage
in Eggs of Psammechinus miliavis" (Exp. Cell Research, Vol. 4, p. 246
(1953)) reported that various abnormalities in the fertilization and
cleavage of eggs of sea urchins when zinc sulfate was added to the
sea water at concentrations as low as 0.16 mg. per liter of zinc.
-------
-------
-66.
XI. ZINC INDUSTRY IN THE UNITED STATES
A. Physical Properties of Zinc
Zinc is a bluish-white metal with atomic weight of 65-3-
Characteristic properties are specific gravity of 7-13 grams
per cubic centimeter at 20 C, melting point of *i19° C, and
boiling point of 906 C. The properties of being chemically
active and alloying readily with other metals are utilized
industrially in preparing a large number of zinc-containing
alloys and compounds. The relatively high position of zinc
in the electromotive series largely accounts for the extensive
use of the metal to protect iron and steel products against
corrosion. Table A gives detailed physical properties of the
element, (next page)
-------
-------
-62-
Table A. Physical Properties of Zinc
Atomic number
Atomic weight
Atomic voiu.iie (cc/'g atom)
Mass numbers of stable isotopes
and percentage relative abundance
Oxidation states
Standard electrode potential
(M->M++ +2e-) at 25°C
Effective radius of bivalent ion (A)
Density (g/cc at 20°C)
Melting point (°Cj
Boiling point ( C)
Heat capacity (Cal/g/°C) (20°C)
Latent heat of fusion (Cal/g)
Latent heat of vaporization (Cal/g)
Coefficient of linear thermal
expansion X 10~b (per °C near 20°C)
Thermal conductivity (Cal/cec/cm/cm2/°C)(20°C)
Total emissivity of unoxidized metal
Electrical resistivity (microhm/cm at 20 C)
Temperature coefficient of electrical
resistivity (per °C at 0-100°C)
Magnetic susceptibility (18°C) * '
Crystal form
Hardness, Mohs scale
Modulus of elasticity (dynes/sq.cm x 10")
lonization potentials (in volts for 1st. 2nd.,
electrons)
6k
66
68
67
70
30
65.37
9.17
1*8.89%
27.81%
18
4
0
2
+0.762
57%
11%
62%
0.74
7.133
419.^6
906
0.0915
24.09
425.6
26.4
0.27
0.05(300°C)
5.8
0.00419 ,
0.l5X!0-6cgs
close-packed
hexagonal
7.8-10.2 (rolled)
9.40j 17-96; 39.66
B. The" Zinc Industry.
The zinc industry is an international basic industry with world-
wide influence in mining, smelting, and trade. In tonnage of
metal, zinc ranks fourth following steel, aluminum, and copper.
Some 47 nations, well distributed in all continental areas,
report zinc production in ore. Canada is the world's leading
producer with more than double the output of the U.S.S.R.,
estimated to be in second position followed by the United States.
Ten other countries are known or believed to exceed production
-------
-------
-68-
of 100,000 tons of zinc in ore annuallyAustralia, Peru, Mexico,
V
Japan, Poland, Italy, North Korea, West Germany, China, and
Yugoslavia. Smelting is accomplished in some 25 countries,
several of which depend totally or in part on imported concen-
trates. The United States leads by far in metal produced
followed by Japan and the U.S.S.R. Other major producers with
at least a ICO,000-ton output annually are Canada, Belgium,
Australia, France, United Kingdom, West Germany, and Italy.
/
The zinc industry is also closely associated with other nonferrous
metals in mining, smelting, and marketing, both internationally
and domestically. Some of the companies prominent in the U.S.
industry have substantial investments of control of important
zinc mines in Canada, Mexico, Bolivia, Argentina, Peru,
Australia, and Territory of South-West Africa. Among these are
American Metals Climax, Inc., American Smelting and Refining
Company, Pend Orielle Mines and Metals Co., and St. Joseph Lead Co.
Other important foreign zinc operations owned by U.S. corporations
are Peruvian mines and smelter by Cerro Corp., Mexican mines by
the Fresnillo Co., Canadian mines by Cyprus Corp., and African
mines by Newmont Mining Corp.
Zinc is recovered from ores showing wide variations in zinc content
as well as variations in the content of other metals recovered as
coproducts or byproducts. The ores range from the zinc ores of
the Eastern States through the virtually zinc-free ores of the
old Missouri lead belt to the complex lead-zinc ores of the
Western States. Essentially all ore is mined by subsurface methods
-------
-------
69-
and the ore beneficiated to a high-grade concentrate at the mine
site. The zinc concentrate is shipped to smelters for recovery
of byproduct metals, sulfuric acid production, and refining to
commercial grade of zinc metal or zinc oxide.
Domestic mines vary widely in output of ore from a few tons to
more than 10,000 tons per day. The mines are classified on the
basis of the recoverable metal of major value in the ore; that is
zinc ores, lead-zinc ores, and al1 other ores from which some zinc
is obtained. Zinc ores contribute more than 50 percent of the
total mine output; lead-zinc ores, more than 30 percent; lead ores,
2 percent; and a11 other ores, more than 10 percent. There are
23 mines classified zinc mines, 121 as lead-zinc mines, and 60 as lead
mines. Oklahoma has the largest number of mines, kl, followed by
Idaho with Jk and Colorado with 25. Tennessee, the leading zinc
producer, has six large mines. Twenty-one States produce zinc with
Tennessee producing more than 20 percent of the domestic mine output,
followed by New York, Idaho, Colorado, and Pennsylvania. These five
States contributed more than 60 percent of the 1968 domestic output.
Ores containing zinc are concentrated at mine plants and shipped to
a zinc plant for reduction to metal or manufacture of zinc oxide.
Domestic primary zinc plants are operated by nine companies:
American Zinc Co. with plants located at East St. Louis, 111., and
Dumas, Tex.; The Anaconda Company at Anaconda, Mont., and Great
Falls, Mont.; American Smelting and Refining Company at Amarillo,
Tex., and Corpus Christi, Tex.J Blackwell Zinc Co. at Blackwell, OUIa;
The Bunker Hill Co. at Kellogg, Idaho; Matthiessen & Hegeler Zinc Co.
-------
-------
-70-
at Meadow Brook, W. Va.; National Zinc Co. at Bartlesvi11e, Okla.;
The Hew Jersey Zinc Co. at Palmerton, Pa., and Depue, 111.; and
St. Joseph Lead Co. at Josephtown, Pa. In addition to the above
smelters treating concentrates of both domestic and foreign origin,
plants for recovering zinc by processing slag from lead smelters
are operated by American Smelting and Refining Company at Selby,
Calif., and El Paso, Tex.; The Anaconda Company at East Helena,
Mont.j The Bunker Hill Co. at Kellogg, Idaho; and International
Smelting & Refining Co. at Tooele, Utah. Domestic primary capacity
for refining slab zinc is approximately 1-3 million tons annually.
The primary zinc producing industry is essentially controlled by
a few large companies controlling mines and refineries. Major U.S.
operators of both mines and refineries are: American Zinc Co.,
The Anaconda Company, American Smelting and Refining Company,
American Metal Climax, Inc., The Bunker Hill Co., The New Jersey
Zinc Co., and St. Joseph Lead Co. These seven companies produce
more than 75 percent of the domestic slab zinc and more than 50
percent of the domestic mine output. In addition to the above
companies, the United States Steel Corp., Hecla Mining Co.,
Idarado Mining Co., United States Smelting, Refining and Mining Co.,
Ozark-Mahoning Mining Co., and Kennecott Copper Corp. operate
mines listed among the 25 leading zinc-producing mines in the United
States.
Zinc oxide is produced directly fra.i zinc concentrate at eight plants
in the United States. American Zinc Co., The Eagle-picher Industries,
Zinc Co., and St. Joseph Lead Co. are the principal
-------
-------
-71-
producers.
The recovery of zinc from old scrap, approximately one-half
from zinc-base alloys and the rest from copper-base alloys, is a
minor source of supply, accounting for less than 5 percent of the
total zinc supply. However, zinc recovered from new scrap accounts
for nearly 15 percent of the total zinc supply. Some 13 plants
are considered secondary zinc distillers. New scrap originating
in alloy manufacture is reused in alloys and zinc dust.
Consumption of slab zinc is distributed over k2 of the States with
Illinois, Michigan, Indiana, and Pennsylvania each using over
100,000 tons. The continuous galvanizing lines of the steel mills,
hot dip galvanizing pots of the job galvanizers, integrated die
cast shops of the automobile industry, and independent die casters
supplying the automotive and appliance industries make up the major
consumers.
C. Zinc Ores
Numerous minerals contain zinc but the principal ore is the cubic
sulfide. The mineral is known as sphalerite and the ore as blende,
sphalerite, or Black Jack. The hexagonal form of the sulfide known
as wurtzite is of infrequent occurrence. The sulfide is usually
associated with lead in amounts ranging from small percentages up
to the point where it constitutes the principal value in the ore.
Small amounts of cadmium sulfide are almost always present. Iron
sulfide is usually present in amounts varying from a small percen-
tage up to 10% or more, The zinc and iron sulfides may be
-------
-------
-72-
associated as in the mineral marmatite, in which case they cannot be
separated by milling. Important deposits of zinc-bearing ore occur
in which copper sulfidc constitutes one of the principal values, and
many complex ores are treated for the recovery of zinc, lead, and
copper. Many other metals may occur in small amounts in such ores.
The silicates are next in importance. Willemite occurs only in the
New Jersey deposits around Franklin while hemimorphi te (calamine) is
of rather widespread occurrence. The carbonates, smithsonite and
hydrozinci te, are important in Europe but not in the United States.
The oxide, zincite, is not common but is found in association with
willemite in the New Jersey deposits where it contains several
percent of manganese and is deep red in color. Also, found in
the New Jersey deposits is franklinite, a complex oxide of zinc,
iron, and manganese.
The composition of zinc ores is shown in Table 1.
Table 1 . Zinc Ores
Name Chemical Composition
Sphalerite ZnS (Cubic)
Wurtzite ZnS (Hexagonal)
Zincite ZnO
Smithsonite
Willemite Zn2SiO-
Hemimorphi te (Calamine) Zn^SiO.'HpO
Frankl ini te (Fe,Zn,Mn)0
Hydrozinci te ZnCO,-2Zn(OH)2
Goslarite
D. Mining Methods
Most zinc is mined using underground mining methods, principally
TS ooen shrinkoae, cut-and-f i 1 1 , or square-set stoping
-------
-------
-73-
methods. A few mines, particularly in their early stages of operation,
mine zinc by open pit methods. Open stopes with pillars (breast
stopes) are employed exclusively in mining the near-flat lying ores
of the Metaline, tri-State, Upper Mississippi Valley, Tennessee,
and Virginia mining districts. The large, single-level, open stopes
of the Tri-State, Tennessee, and Metaline districts have adopted
"trackless" mining in which huge, power loading equipment, and
/
haulage units are mounted on Crawler-type tread or pneumatic-tire nehicles.
The working speed and facility of movement from work face to work face
gives greater capacity with lower mining costs which in some cases
permit mining ore containing as little as 2 percent zinc. Tables 2 and
3 give, respectively, mine production of recoverable zinc in the
United States by States and by months through 1968. Table k gives the
major zinc mines in the United States. Table 5 gives the world
production of zinc ore by countries.
-------
-------
ZINC
Table 2.--Mine Production of Recoverable Zinc in the United States, by States
(Short tons)
State
Ar i zona.
California
Col or ^ do
Idaho
Illinois
Kansas
Kentucky
if *
Mai ne
Missouri
Montana
Nevada
New Jersey
New Mexico
New York
Oklahoma
*\
Pennsyl vania
Tennessee
Utah
Virginia...
Washington
Wi scons in
Total
1964
24,690
._ 143
53,682
59,298
13,800
4,665
2,063
1,501
29,059
582
._ 32,926
-. 29.833
- 60,75^
12,159
30,75*v
115,943
- 31,428
21,004
24,296
26,278
574,858
1965
21,757
225
53,870
58,034
18,314
6,508
5,654
4,312
38,786
3,858
38,297
36,460
69,830
12,715
27,635
122,387
27,747
20,491
22,230
26,993
611,153
1966
15,985
335
54,822
60,997
15,192
^,769
6,586
3,968
29,120
5,827
25,237
29,296
73,^54
11.237
28,080
103,117
37,323
17,666
24,772
24,775
572,558
1967
1^,330
441
52,442
56,528
20,416
^,765
6,317
7,^30
3,341
3,035
26,041
21,380
70,555
10,670
35,067
113,065
3^,251
18,846
21,540
28,953
549,413
1968
5,441
3,525
50,258
57,243
18,182
3,012
9,702
12,301
3,778
2,104
25,668
18,686
66,194
6,921
30,382
124,039
33,153
19,257
13,884
25,711
529,446
W Withheld to avoid disclosing individual company confidential data; excluded
from total.
IProduction of Kentucky and Maine combined to avoid disclosing individual
company confidential data.
-------
-------
-75- . ' <
Table 3Mine Production of Recovercble Zinc in tte United States, by Months
(Short tons)
Month
January
February
March
Apr i 1
May
June
July
126?
^3,1/3
- ^3,501
50,tf17
^49,528
- 50,U93
U7.967
. Ml, 700
1968
i*2, 3 J&
M,935
M,667
^3,723
^5,297
kk,k6k
^42,936
Month
Auqust
September
October
N ovembe r
December
Total
196?
1*8,821
^3,283
1*3,779
i*l,8li*
M,537
5^9,^13
1968
^6,679
k$, 03 1
^7,033
₯f,178
^3,25^4
529,^6
Source: Minerals Yearbook 1968, Bureau of Mines, U.S. Dept. of tho Interior.
Table **.- -Twenty- five leading zinc-producing mines in the. United States in 1968,
in order of output
Rank
1
2
3
k
5
6
7
B
9
10
11
'12
13
\k
15
Ib
17 '
18
19
20
21
22
23
2H
25
Mine
Balmat
Friedensvi 1 le
Sterling Hill
Young
Eagle
Bunker Hill
Zinc Mine Works
Austinville and
Ivanhoe
New Market
td wards
Jefferson City
.Star-Morning
Idaredo
U.S. and Lark
Mascot Ho. 2
Flat Gap
Shul 1 sburg
Burgin
Cal houn
Copperhi 1 1
Inrrsel
Page
Flrno No. 1
Fletcher
Oeardor i f Group
County and State
St. Lawrerce, N.Y.
Lehigh, Pa.
Sussex, N.J.
Jefferson, Tenn.
Eagle, Colo.
Shoshone, Idaho
*"
Jefferson, Tenn.
Wythe, Va.
Jefferson, fenn.
St. Lav/rence, N.Y.
Jefferson, Tenn.
Shoshone, Idaho
Ouray and San
Salt Lake, Utah
Knox, Tenn.
Hancock, Tenn.
Lafayette, Wis.
Utah, Utah
Stevens, Wash
Polk, Tenn.
Knox, Tenn.
Shoshone, Idaho
Grant, Wis.
Reynolds, Mo.
Hardin and Pope, 11
Operator
St. Joseph Lead Co. "
The New Jersey Zinc Co.
do
American Zinc Co,
The- New Jersey Zinc Co.
The Bunker Hill Co.
-
United States Steel. Corp.
The New Jersey Zinc Co.
New Market Zinc Co.
St. Joseph Lead Co.
The New Jersey Zinc Co.
Hecia Mining Co.
Idarado Mining Co,.
United States Smelting
Refining and Mining Co
American Zinc Co.
The New Jersey Zinc Co.
Eagle-Picher Indus., Inc
Kennccott Copper Corp.
American Zinc Co.
Tennessee Copper Co.
American Zinc Co.
Amcr . Smelt.. & Refin.Co.
The New Jersey Zinc Co.
St. Joseph Ler.d Co.
1 (hiark-Muhcning Co.
Source of zinc
Zinc ore.
'DO.
Do.
Do.
Zinc ore, si Iver
' . ore.
Lead-zinc, zinc
ores, silver
' tai 1 ings
Zinc ore.
Do.
.
Oo.
Do.
Do.
Lead-zinc ore.
Copper-lead-zir
Lead-zinc ore.
*
Zinc ore.
Do..
Do.
Lead-zinc ore.
Zinc ore.
Copper-zinc or
Zinc ere.
Lead-zinc ore.
Zinc ore.
Lead ore.
Fluorspar ore,
zinc ore.
-------
-------
-76-
Table 5<World ciinc production of zinc (content of ore), by countries
(Short U>r.s)
Country ' 1901 1965 195C 1SC7 1968 »
North A-rer ra:
Cirsdj 729.P39 910. 23 1,045,5:3 1,245,905 1,273,249
Guater.iU (ci;.=rts) ' ~-> '',-'5 '473 N'A
Horcu:^ S.4-15 12. 55 13.^51 14.4J5 15.295
Mex.co 259,70} 247. -3 24l,>;<14 «205.£91 264.575
UriUd >titea (:tct,Nt-»i.le). S74.65S 611. 53 672,55S 149,413 529.446
South A-. '.- "a:
Arr.ntna 25,257 S2. 13 '29,151 29,951 -30,000
Pol.via 10,523 14. :-3 17,CIS 18.4t,S 12.Sal
Eraul 5, 50 N'A NA « 6,300
Chile , . .. 1,105 1, ^4 '1,4^5 1,?3S 1,353
Colomt.i' 110 SO 330 . ' 6uO SOO
Ecuador 4''0 260 149 177 125
Peru 2C0.873 280,533 2S4.19G 'S35.9SO 340,720
Ur,y .................. 166.100 167. ..0 1S?..';0 1'^. 304
Pohnd ................... j A.C, 3,2c-4 t'X-n fi=i 1S1 83 359
Portui»l ................. gH.'i 43.2^3 '63.0,9 65. M £.
fc:::::::::::::::: -
.
101, it<3 lui.---' .j.--i
3S.932 42.334 .1380. -U ~0 .«.««
nS t« - 2 »,si i.
SSll -2.S3S 31.132 ..«.:iOO -66100
...^ j-j^ 7S:!S7o «:*« ".»»*
8;43S 8.579 ^7.000 -5.100 4 4»
110 c-,3 110. COO U°'., ^ i s'?0^ 7, oil
= «1 'IIS "ii "Ji ^
Phil.ppincs ............... J-^ 2:3C'3 -2.COO ...... ----- ...... -;j77
. Th»;.ar.d ................. J'S.-, 8. CCO o.-O 4 .7 5-" 463409
TurVcy. - .............. 34'5:,3 391.139 413. COD 4,7, u-.
Oceania: Austrai.a ............ "
Tpwl, .«.«0.3C9 '4.753.S57 M.^0.«3 5.330.5. 5.471.071
i TouU ne c! --.C : r--=» "ajy.
~* Ko:th Vtatn- nUo prod. -
thit lUted.
-------
-------
-77-
E. Hilling of Zinc Ores.
Milling consists of separating the desirable mineral constituents in
an ore from the unwanted impurities (gangue) by various mechanical processes
Simple ores, such as coarsely disseminated zinc or zinc-lead minerals
occurring with a low specific gravity gangue, are readily treated in
heavy-medium cones, jigs, and tables after being crushed and ground
in closed circuit with vibrating or trommel screens and classifiers
to give properly sized feed. Selective or differentia! flotation
of the slime producers or of a reground middling product completes the
flowsheet. Ores of this kind are common in the mines of the Mississippi
Valley and Eastern United States.
The more complex sulfide ores, such as those ir. the Western United
States, consist of disseminated mixtures of fine-grained lead and zinc
sulfide, usually accompanied by pyrite, some copper sulfides, and some
gold and silver in a country rock, quartz, or quartz-calcite gangue.
Concentrate of such ores may be complicated by partial oxidation of the
sulfides and the presence of high-density gangue minerals such as
barite, siderite or rhodochrosite. Such complex ores are crushed and
fine-ground in closed circuit to a size at which the ore minerals are
freed from the gangue. The ore is then selectively floated to yield
lead, zinc, and copper or copper-pyrite concentrates; middling
products are reground and recycled to complete the recovery.
The low capital and operating costs of the heavy-medium plant make it
very effective for producing a rough zinc concentrate and eliminating
a large fraction of the gangue minerals in simple ores. Such units,
-------
-------
-78-
using ferrosilicon as the heavy medium,have been used extensively
in eastern Tennessee and the Tri-State area (Kansas, Missouri and
Oklahoma) to treat ore.
A 1965 milling study showed that 10 plants operating on zinc ore produced
concentrates averaging 61.1 percent zinc with 95 percent recovery.
For 10 operations classed as lead-zinc ore, zinc concentrates averaged 58.5
percent zinc and represented 89 percent recovery. For 31 operations
classed as lead-zinc-silver ores, zinc concentrates averaged 5^
percent zinc and represented an 87 percent recovery. An additional
6 percent of the zinc was recovered in the lead concentrate.
F. Smelting and Refining of Zinc Ores.
The reduction of zinc ores and concentrates to zinc is accomplished
by electrolytic deposition from a solution or by distillation in
retorts or furnaces. For either method the zinc concentrate is roasted
to eliminate most of the sulfur ,and for conversion to impure zinc oxide
called roasted concentrates or "calcines."
At electrolytic zinc plants, the roasted zinc concentrate is leached
with dilute sulfuric acid to form a zinc sulfate solution. The
pregnant solution is then purified and piped to electrolytic cells,
where the zinc is electrodeposited on aluminum cathodes. This zinc
is either Special High Grade or High Grade. At intervals the cathodes
are lifted from the tanks and are stripped of the zinc, which is then
melted in a furnace and cast into slab form. The electrolysis of
the solution regenerates sulfuric acid, which is used in a succeeding
-------
-------
-79-
cyde of leaching. Inasmuch as zinc concentrates shipped to electrolytic
plants corrmonly contain lead, gold, and silver, the leach and electrolytic
tank residues become enriched in these metals by the extraction of the
zinc and are usually shipped to a lead smelter. There the lead, gold,
and silver content is recovered in lead bullion. Zinc adheres to the
lead furnace slag and is subsequently removed as an impure oxide by
a fuming operation. The zinc fume, after deleading and densifying in a
kiln, forms a suitable feed for return to a zinc reduction plant.
Distillation retort plants are classified as batch horizontal retorts,
continuous vertical retorts externally heated by fuel, and continuous
vertical retorts heated electrothermally. All employ coal or coke as
the reducing agent, quantities required range from about 0.5 to 0.8 ton
per ton of slab zinc output. The zinc vapor and carbon monoxide from
the retorts pass into condensers of various types where the zinc is
collected as liquid metal ready for casting into slab form. Zinc
produced by distillation, normally the lower commercial grade, may be
upgraded by refining to reduce the quantities of impurities. Refining
by redistillation is accomplished by vertical fractionating columns
which separate the impurities contained in the feed zinc and can produce
zinc of 99.995 plus purity.
The blast furnace process of producing zinc, also known as the Imperial
vertical-type smelter process, wasintroduced commercially in 1950 by
Imperial Smelting Corp., Ltd., Avenmouth, England. There are now a
number of such installations throughout the world. The normal blast
furnace practice of burning carbonaceous matter in intimate association
with the ore to be reduced is followed. However, as in other zinc
-------
-------
-80-
distillation processes, the zinc is released as a vapor and must be
condensed. An important advantage of the process is the ability to
treat a mixed zinc-lead concentrate and recover both metals as we'll
as any gold or silver present with no extra coke consumption and little
extra labor. Metal produced by the blast furnace conforms to Prime
Western grade, containing about 1.2 percent lead and 0.02 percent iron.
Metallurgical recoveries at zinc-reduction plants range from 89 to
97*5 percent, the range in recovery being governed by the nature of the
smelter feed, the treatment process, and the economics of recovery.
Zinc scrap is processed in a variety of ways. Some scrap .is vaporized
in a furnace and then converted to zinc oxide in a suitable combustion .
chamber. Other scrap is processed in a retort and condensed to either
dust or slab zinc dependent upon the type of condenser used. Much of
the scrap treated to produce slab zinc is part of the feed to primary
zinc smelters of the pyrometallurgical type. About half of the secon-
dary zinc recovered is from copper-base alloys, principally brass,
and recovery takes place simply by remelting for production of more
brass.
Tables 6 through 15 give the domestic and foreign zinc metal
production from 196^ through 19&8.
-------
-------
Table 6.Distilled and electrolytic zinc, primary and secondary,
produced in the United States, by grnues
(Short tons) . ...
Crcde
Special H.-;rr Grn^c ". ...
H -r G' :
Prlrr.e Y.«.;:.rn
Total
1904
<<;;;, 74s
m.cv-,
34 ;.;-..,
1 C2D £30
15Gi 1&S3
' <7« 7",-, 4c,2.7'22 '
r-2.4',1 1"?.C14
3:0. ,-',3 3-a.CO;
1 07S 021 I 103 329 1
19G7
435.M9
92 . r< "iS
'9l',073-
304.V23
196S
117 '.224; .
' ' o'j ,'/'>
4"! .347
1,100,755
. Table 7 ,-Primary slab zinc produced in the United States, by States where smelted
" (Short tons)
SUte
1364
1SS5
1956
19E7
1S68
Idaho
Illinois 114
Montana , 125,"
OV.hho-ra K.C.S
FennsyUania and West \ ir£.n,a ?'j2 ,9
Texss - COS. 7
91,761 91.000 90.9=3 92,
102.940
114.KM 9C.J-03 110,<"O9 119, C57
143 l.'J7 174.>21 lll.J'iS 142.929
r< j-'. i-;;,H2 i'-*i.^:.; 172,174
27-,i7U C?1,4'.'J 271.102 202.5-14
212.2;7 2v'5.-;^ l-.4,l-,o liJ.iOl
SSl.OSi 924,402 1.C25.0G3 «S, S30 1,020.»91
Table ' 8'"Primary s'-ab zinc plants Ly group capacity in the United States in 19&8
Type oJ pHnt
Ilant location
Slab rise
capacity
(short teas)
Corpus Christ!, Tel..
Svu-c-t, 111
An-ico^da. Mont
Grer.t T^'. = . Mon
Electrolytic pl^T.t-t "
Arr.crlcan i.r...U.;.i; a;.d "'"r.ing Company
The At.aco.ica Con-paay...
. Do
The Bur.V.cr H-.ll Co
Hori2on*..il-:i:c-i t '.:.-'..,
Anenc^r. S".'-/.:r.c- and Kff.r.-.ns Company. Amarillo, Tex
Black*ell 'i -c Co , An =x Lr;d ana 2:r.c, lac
The l.rsk-l'.c!-: i: ;.-;-,---. j;.=
Natior.il Z nc Co ... ..... .
Vertical-rf to-t } '. ir/..:
Matth t5s-n t :!' ( If r Z.r.c Co
The New vVr-.ov i'.:-c Co
Do
St. Joseph Lead Co
538,000
7S0.200
Mcadowt.rook, VT. Va.
DC-.U.-. ra ,
1 Plant dosed July 1, 1S51.
i '
TaV.e 9«~Sccor.f'.-vry slab /inc pbr.is by ^roup cr.paciry in tKc LJj.ited States in 19G8
Coinpsny l*Urtt locatiou
1),, . Yr.-ii'tin. .\.J
AT..TI.-...-, :' r,.~ i'\> II.l1 i.ur.i, 111
V, J i L',. , 1, r i .".. LI. AU
f u',' 1^1 ' it *. i. 1 u,' 'i, i Y. x
if. <*:.. ..-.- \ i i s .;.:.,! >, >'.,',!,
V r ic > - Co Y.v - ,i -i i ,,,r
i-»l..:,,v:.. .'. no i o .' .11..'.-. Jl. 1.1 '.
Siaii i.r.c
c.ipriciiy
(b^ori Ltr.s)
t5 900
-------
-------
-C?-
'"" ,. - .. - ' ' 17
Table 10 .-Production of zinc products fiorn 7inc-base scrap in the United Statw
(Short tcni)
Product ' JSG4 1905 1900 1957 1953
!:«o n n9 ^;.2n' -73..r03 7? *:?
7,'.r,r c..-- 'J ' ' :J 3 ','.2 3:..-"'; 32 . >1 3~/-"i
]:.!> . .- ".". '...'.'.'.....'.".'. ____ " ........ I .;.'-, o -.."-i :- 4.-.1 "..:)
' u ................. 129.774 144, C39 Uy c -ti'.btion:
ConpT-!.-.e.- ............ 101;.'"5,: 1^7.4.;,5 S,_-, z.r.c '.. .......... 72,595 IH.VH
Alun.r.u:. -b'Se ........... 2,jy5 3, I'D Zne-dj-t .......... ... 3J.;-'? 37,334
Total ................. . 219. CiC 271. 523 Total .................. lll.CTO 121, 4C3
Old scrap-. ' ' I" 7:rc-ba-p allovs 1... 17 2T3 17,:;2
Z.p.c-L-.-r 40.SC2 41.4TH In r---- -".;! i :^--~ 140.411 103.4'^J
Cc.j.l..r-i -.= 3o.H2 3J.3.-0 I-i -J\. ~. :. Ji-.-u .-. a.;.i. 5 6.145 6.041
Aluin.nu--i-k.i-e 3,105 2,SuO In r .-.^-.r-'un -i ^-jtio\5 -131 541
Wagnt-i.um-L.iie.. 140 99 In ci. .i..cal ;i-ocu?t--
7. .:- ov ! Ui.u-ir>c) 17.255 19,311!
Total S0,?09 79,797 7. -c ?u!: UP 9,5'i5 11.'00
===^== v nc cr!,irico 11,230 13,3i7
Grand total 319.S49 354.7J3 M^cciUr.i-ous 232 1.131
Total 20S.579 231.233
Crane1, total 319,8-19 3ii,722
1 Includes zinc content of rcd.^t.ilcd slab made from rericit die-cast slab.
Table 1 2 .Zinc dust produced in the United States
Value Value
Short Short
Year tons Total Average Year tons Total Averaje
(thousands) per (thousands) j-er
pound . pound
1904 45.979 $15.725 JO.171 1907 50.273 {IS 09« {0 1 = 0
1905 51.SCo 19.32.-> .las 19-J3 61,506 22.C41 .179
I960 55,4^5 20,41-S ,lb4
Table 1>3-Primary and redistilled secondary slab zinc produced in the United States
(Short tons)
Table 14--Di;tillcd and electrolytic ?inc, priir.nn. and secondary,
produced in the United States, by methods of reduction
(Short tor.s)
Method cf r,dj-'mn 1954 19C5 19CG 19C7 1963
Klcrtrcktic pn.T.ary 3i9.3^3 22.C2t>
Al I :.:.i-\ ^..'r.. -a 57.54C 70.300 71, :<> 5-S.3J1 67,101
At .rtCi-J..^ ir.'it-r. 14.U..J l.i.JU 11.7ul 15.1-^1 12.7^4
J9C
Primary:
r'roin dorrif sticorcs 531,
i'lor.; lc:>.c^ fris 4.'2,
Totil 9J1.
, Rcdistiuia ;i.coriC^.-> 71
' ! Total (O"»i-d'"--5 7 r.c rccov-
4
,957
,117
0-*4
,6-0
19G5 196S
5.J1.215 523. l-d
443.1^7 531.4--5
S?4 4<~2 l.Cj: C 0
1 0~? 021 1.103,329
19S7
43i. i53
5>.0,277
93-i..-30
73.:j5
1,012,335
19(
499
£21
l.CJO
79
1.100
;s
.491
.400
ittj
.si,5
.750
TcUl-. J.t.'i.CiJ J,C7»,li21
-------
-------
-83-
Table 15Y.'crld smoker ^reduction of zinc, by countries1
(Short t^r.;)
Cour.try ' '
North Am :.-ica:
Me. -co
U" »' d Statt-d
South .'..-.. ir:ca:
B.-^zil
P-.ru
Europe:
Austria .
Bo'~'i " *
France
Gerainy:
Enat
We "t
It.-xiy
2s"ct*it.'"l iudd
Norway.
Poland .
Sttln _ _.
L.S.S.K. Cpr.maryj*
U'Jtcd K r"Uoni
Yu^o iavla
Afr.'ca:
Zamoia
Asia:
Ir.d.a
Jaoa.i
Korea:
Xorth .,
South
Oceania: Au»;ralu
To-^l <
Est.'n.atc. > P.-vIImir.-iry.
1 Data d, rl vvd 11 p
-------
-------
-84-
G. Uses of Zinc.
Forecast growth rates for the range of possible zinc demand
in the United States are from a low of 1.1 percent to a high
of 3.1 percent to the year 2COO. Estimated rest-of-the-world
growth rates range from 2.5 to 3.3 percent per year. Quantities
are presented in Tables 16 and 17.
Table 16
Forecast range of demand for zinc
(thousand short tons')
United States:
High
United States:
Rest of the world:
High
1968
TOTAL
1,761
PRIMARY
1,406
4,000
2000
4,700
2,400
(3,580)
4,000
2,090
(3,015)
11,200
8 800
(10,000)
Estimate.
The following are made for zinc demand in each of the major
end uses during 1968-2000 and of the calculation of the
forecast range in the year 2000.
-------
-------
-84 a-
Tablo 17 - Contingency forecast of donand
(thouss
for zinc by end use, year 2000
Tid short "Tons) ___^__^___
Demand U.S.
Demand in year 2000
End use
Transportation ....
Electrical equipment
...and supplies. . . .
Plumbing and Heating
Industrial machinery,
excluding electrical
Pigments and
compounds
Boiled zinc, dry cells,
lithographic plates
Total 1
1968
340
400
210
240
160
220
50
141
,761
foi cccst
base
2000
530
670
730
400
260
370
80
230
«
Unit ad Star
Low
450
550
500
300
200
250
60
150
2,460
(Median
cs Rest
Hioh
750
.1,000
900
600
450
500
ICO
400
4,700
3,580)
of the v
Low
NA
NA
NA
NA
NA
NA
NA
NA
8,800 11
(Median
/arid
Kiah
NA
NA
NA
NA
NA
NA
NA
NA
,200
10,000;
NA Not available
-------
-------
-85-
t. Construction
Apprcxirr.a tel y 20 percent of the zinc consumed in the United States is consumed
by the heavy construction industries. Consumption in this area included galvanized
steel products and brass and bronze. In 1968, an estimated 310,000 tons of zinc
was consumed in this end use. A forecast base for the consumption of zinc in
construction in the year 2000 was obtained by relating the growth in zinc
consumption in this use to the forecast growth in steel production, 1.4- percent
per year. At present there is no completely satisfactory substitute for zinc
in protective coatings for iron and steel. Thus the high of the range, 750,000
tons annually in 2000, could be attained as a result of increased concern with
minimizing corrosion and lowering maintenance costs and by increased use of brass
and bronze articles for decorative purposes, reflecting the affluent society.
The low of the forecast range, 450,000 tons annually in 2000, is predicated on
the use of coatings other than galvanized, such as plastics, aluminum paint,
or widespread application of noncoated corrosion-resistant high-strength 1ow-
. alloy steel. Competition from prestressed concrete poses a threat to the zinc
galvanizing industry. A decrease in demand for brass hardware and trims could
curtail zinc consumption.
2. Transportation
t
The largest use of zinc is in the transportation industry where is is used in
numerous diccasting alloys and in galvanized steel alloys by the automobile in-
dustry, as hardware for ship construction , and in the form of plates and rods
for cathodic protection in marine and pipeline service. In this end use category,
the forecast bace is obtained by extending the 1968 estimated demand of ^00,000
-------
-------
-86-
tons at the same rate as estimated for total population, 1.6 percent annually.
This results in a forecast base in the year 2000 of 670,000 tons. It is estimate
that motor vehicle manufacturing consurr.es nearly 60 percent of the total consump-
tion of zinc diecastings. The high of the range, 1 million tons, would result if
'the production of automobiles, aircraft, and boats increased more rapidly than
population. In addition, the widespread use of sheet steel galvanized on
one or both sides for installation as splash guards and in other areas of motor
vehicles subject to the corrosive action of chemicals used on highways for snov;
and ice removal would contribute to the high demand. Increased use of trucks
for transporting freight, and the displacement by zinc of cadmium coatings,
aluminum, and plastics, also would contribute to the high demand in 2000.
\ - <
Or. the other hand, the exclusion of automobiles from city streets as an anti pol-
lution measure, establishment of rapid transit systems in major cities,
decreased use of decorative items, use of substitutes such as zinc-free plated
nuts and bolts, and loss of markets to aluminum and plastics could reduce demand
to a forecast low of 550,000 tons in 2000.
3.Electrical Equipment and Supplies
Zinc consumption in electrical power transmission and communication equipment,
household appliances, and wiring and electronic equipment is expected to grow
at the same rate as the GNP, k percent annually, resulting in a forecast base
of 730>000 tons in the year 2000. A number of contingencies could result in the
attainment of a high range of 900,000 tons for this end use in the year 2000.
These include the demands of a more affluent society for additional or new
appliances; improved standard of living for the presently underprivileged
-------
-87*
' classes also resulting in increased demands for appliances; increased use of
electricity resulting from lower energy costs; more use of lighting for
personal and property protection; and a high rate of growth in the commum'ca :i ons
-and computer fields. The low of the range, 500,000 tons of zinc in the year 200G,
would result through substitution of zinc by aluminum and plastics in appliances,
and the use of underground cable for electrical and communication uses which
eliminates the need for zinc-plated wire used as support for utility poles.
Increased use of communal systems whereby appliances would be centralized and the
widespread use of throwaway clothes and dishes would lessen the demand for appli-
ances and contribute to the low of the forecast range.
It,. Plumbing*and Heating
Zinc is consumed in 'plumbing and heati"hg applications primarily as brass alloys.
It is estimated that 2^0,000 tons was used in these end uses in 1968. Growth
of zinc consumption in this category to. the year 2000 is expected to parallel
the total population growth rate of 1.6 percent annually, resulting in a fore-
cast base of 400,000 tons in year 2000. The high of the range, 600,000 tons,
could result from an increase in the number of families owning two homes
requiring more plumbing and heating facilities. An improved standard of living
would lead to more plumbing per housing unit such as two or more baths. An
affluent society could afford home swimming facilities which would augment
the demand for zinc. A low demand of 300*000 tons annually in 2000 would resul
from the use of plastic tubing instead of copper in plumbing applications and
from the displacement of galvanized ducts by plastics in forced hot-air heating
or the elimination of such ducts by electrical-heating units.
-------
-------
/ -88-
5. Industrial Machinery, Excluding Electrical
Bearings and sheet metal and zinc diecastings account for a large part of the
estimated 160,000 tons of zinc consumed in household and commercial air conditicr
ing, farm machinery, and construction and metal working machinery in 1963.
Projecting at a growth rate of 1.6 percent annually, the growth anticipated
for total population, gives a forecast base of 260,000 tons in 2000. A
0
forecast high of A-50,000 tons would result from a rapid growth in air
conditioning, including climate control of shopping malls, stadiums, and possibU
small towns. Increased mechanization requiring less machining of castings
could contribute to the high of the range. The forecast low of 200,000 tons in
2000 would occur if alternate bear ings "such as nonbrass bearings, air, or
plastic bearings would be used, reducing the need for brass bearings. The ur.e
of aluminum sheet instead of galvanized sheet could reduce the demand for zinc
as cou.ld displacement of zinc diecastings by aluminum diecastings.
6, Pigments and Compounds ""' "
. More than 10 percent of the zinc consumption is used in zinc oxide production,
the principal zinc chemical. The 1968 consumption of 220,000 tons was projected
to the year 2000 by using the growth anticipated for total population, 1.6 per-
cent annually. This resulted in a forecast base of 370,000 tons. The high of
the range, 500,000 tons, would result from a high rate of growth of the rubber
industry where zinc oxide is utilized in natural and synthetic rubber, in incre:
use in animal nutrition and as a plant supplement in which zinc chemicals are
finding increasingly important applications. A reversal of the downward trend
in use of zinc oxide in paints and its continued use in medicinal ointments and
cilamine lotion would contribute to the high of the range. Alternate materials
-------
-------
-89- . .
such as fiberglass-containing tires for motor vehicles, titanium pigments,
and zinc-free water-based paints, and a decline in rayon manufacture could result
in a forecast low of 250,000 tons in the year 2000.
7> Rolled Zinc, Dry Cells, Lithographic Plates
Rolled zinc in the form of strips, sheet, wire, and rod accounts for less than
5 percent of the total zinc consumed. In 1968, SOjOOO tons of rolled zinc
were consumed in this area. Anticipating an annual growth rate of 1.6 percent,
equal to the forecast for total population, results in a forecast base of 80,000
tons in 2000. The high of the range, 100,000 tons, would result if there were
a sharp increase in the use of public and private surveillance equipment requirin
batteries. A more affluent society would lead to increased production of .
battery-operated toys and portable electrical equipment using batteries con-
taining zinc. The low of the range, 60,000 tons, is forecast upon the
substitution of nonzinc batteries such as .rechargeable batteries and mercury
batteries, and the elimination of the use of lithographic plates from new
printing techniques.
8. Other Uses
Consumption in other uses of zinc in 1968 was 1^1,000 tons. Growth at a rate
equal to that forecast for total population, 1.6 percent annually, results in
a forecast base of 230,000 tons in 2000. A high annual rate of ^00,000 tons in
2000 could result through needs of a more affluent society for more clothes,
instruments, jewelry, office equipment, and small mechanical devices. A high
demand v.'ould result if zinc consumption in the chemical industry paralleled th-
high growth rate expected for that industry. Consumption could be as low as
150,000 tons in the year 2000 if aluminum, plastics, or other materials were
-------
-------
-90-
substitutcd for zinc in these end areas.
Tables 18 through 28 give zinc consumption and import patterns in the
United States from 196*4- through 1S68.
-------
-------
Table l£LConiJuiptlon cf zinc in the United St.itcs
(Short to.-.b
19u3
5-.al,z.r.c ............................ 1.2C7.2,< 1,3V..,-,.! 1.410,137 1 .ISO. "OS 1.333 r.M
On: i -.-cox,.-, i.;. :.:..- <:..- i r.lr... ..... l.V..-> -J.VJ '.J',..,',0 1,4. -VI '-I.;1--;
&cur.(.u:>- ,;L....\, :-.!..,. i..-.c cocui.ij:.-. J-^.-.i J.^.i-.J ^--j.^O -Co.^S -.0.-),.-^
1.5C5.751 1, ;;_, CiT l.avC.J-;^ i.JOl.iOT l,7^d,<00
le 1$KSbb zir.c consurr.pticn la tr.e United States, by industry use
(Short tons)
Industry ir.d produce
Tuocs.ir.rt p.,- o
Fer.c'.r.^, v,* r,1 cioin, ur*Q r.oU
Total ...
Brass products:
S..rcl, strip, and pUtfc....
Tute
« ^
Other co;>pcr-'o.iso prooucus..
Total
Stusn ar.d s^nd c^tii*.; iilcy.
Total
Kolied 2 nc
Cthfr i. .". .1.
Toul. ... . .
Gr*nd total
1S04
gr" «o ^
4 -> '"<-}
Gli,; , J
\A
NA
XA
X A
44 r>:. '.
f,,,701
SJ3
135,095
517 351
604
6.0.M
--. cci
4 1 1 -, 1
19 I'll
;^ 753
" 0~!
.. 1, 207.20S
1S35
63, 2^',
'XA
XA
XA
XA
XA
31 Oil
4-. ' 4°1
ss.sc;
4 5 5 \ 0
10 CtO
3 050
1,^2
=J±:-1X==
- - -
7.^5
G37 r-70
vVr!
So " »0
1
I , J5 1 , 0 JJ I
1906
2(54 312
33.114
cs, ><;..
lo,: iu
4 2--*S
17 ,!;;*
ll.--.uO
15.S21
XA
59 v"i3
'
.";5 ru,7
97,0V,
60 079
12 I'.S
3 '.-.7ri
0 ^ T.I
3,500
550 371
495
9,170
--. ^.
in. 2 '.s
27 ,0 '.a
' 1 " 9°
'
,410,U7 1
1S67
236 ,135
01, i '.' 2
4 ' 1 37
1.x, 77!)
9.9S5
16,514
XA
67,237
40,759
S.f.vl
2,295
s I'M
4.241
131.5P.7
525,900
420
3,703
29.774
24 'MS
3u "3'
'
,236 ,60^
1SG8
23u,310
CO.OS9
o"3 ,021
.(,M5
20. 2:. S
9,050
'XA
5S 074
4S1 #17
8G.1S5
49 J-oS
9 . 818
i ,57G
KU.900
5M.K90
307
10.243
50° c '1
4S u '3
34 337
" 'J7.1
S.422
29 9J2
43 150
1,333,053
2CA Xot a%:iU<.r.'.o.
1 Induces z.oc L>> a ;a rr.^k.n;; zinc duit, bronze powder, t-iioys, chemicals, castings, and mibCeUaneoua uaoa
not cloe A'hcro rucni.o^isi.
Table 2QSlab zinc consumption in :hc Uriked States in 1963, by grades and industry use
(Short tons;
Gi;v
V..r.c
r. ...... 20 l' .0 2 5v*0 0*3 lw Lj7
Totil.. ub3,307 l-'2,ilG 7.i.7o 155,571
Pr r.-.c i
-i
aoliii
15.^15 .
;. . : ...I
379. C^j
R ,. ^^.^1
CrtiClb !Ob3L
2, .:'..! ii;i.',ii
i7ti tOJ.'. .
39 «.1i
o.-'.y i. jLij.Oj
u
i
3
-------
-------
-9Z-
ble 2 1-rS!aL zlr.c consumption in the United States in 1963, by industries and States
, (Short tons)
SUtc
Alfabs ma _.,..._......._.
^j.'.-, - ^- s
Ca'.:c-r.^
Co'or.uQ
Cor.r. ^:.cu:
V - - '
Id ho
irdiina
X o n * j r ; v
XjOU' i i*"* a
V.i.ne
"Vs*1 iid
Minnie;:. .
J.ionu-.a ^__ .
X'( dr.. La .
K*o .v } I ., ) i *c
VfA' Tf ' C'/
Kc'.v Yr :k
O>.;o
Oregon
K:.r.-y;v.m.2.
lihoce Jsl.ind ,
South Li;AoUi__
*i\ r " c>r -o
Tcx-is
Utih.
M ~ v. r ' tor.
V.'fot \ .r-:r,,3
^\ i^CO'^.Ii
Ucd^tr. bated
Total <
TV' T.'.tr.hcl'J to sv.-,:d c'-. ;
> Inc.-.i-'o., .-ra.^ r..'..:. ; -..
'li.cljd j p'ca-'-'-.-j, ^: ;.r
^S"
3'< OOS
W
3^(7J5
\V
3 C"4
W
\sr
46 -OJ
09 '^i'^
719
\V
^ o'-i
V,'
29. OSS
4 S32
0 510
\V
'
1.203
3,170
S2 701
C3.4S1
... . \V
-,.. v/
V.'
15,031
Vv'
frju
1,213
479, 54S
xc'nr :nciv,.\j:.l con-^r.r." con
, i-,:ot :r.; -.1--, ,:-.a ^. --^ .uJ
IC-L....I. a..jy x.- c. t,-..otir. ;,. t,:
I3rr;j!
W
2 , G < j
w
43,ir,3
\V
35 " Fj
W
V,'
W
w
\tr
15 731
W
\V
\v
w
6,r,.:9
11,307
V.'
w
V,'
w
nir
34
v,r
G.37'
153,513
f.c'nr.r.jl data
TlU'll ..
,. -.;<..- » c.ui,
Die
13,201
W
W
w
w
w
\\'
So.OOfi
45,834
W
" 13°~v'"
'
W
W
72.S79
W
86 425
W
\V .
25.CC4
\V
W
w -
9 , if.S
90,139
562,363
; mcladcd wi
acd rods.
Other >
\V
\V
W
2.41S
W
\V
\v.
\v
w
w
V,'
\v
\v
w
w
0 ^^^
w
w
1 COS
w
V,'
w
w
v:
1.139
V,'
10
119,054
126.551
th "Undj'r
Total
40,172
W
W
55,02t)
3.355
52.1'jO
1 , 4 r< S
W
M'
W
W
19G.715
152,409
1,300
\V
1S.S9J
f.a:,2
w
w
8 4^0
153 3-,S
W
18 214
\V
2,or.n
W
w
104,701
1 504
W
10.0S5
1,154'
144, S75
623
W
W
2,507
41.281 -
761
2 Co5
13,374
17, 504
2hl,371
1.32S, 42i
lauted."
1 J,r'c-;'<-c"* ^--*-> ^-i'''C u .^a m rotli.i Zinc ^ro-acu ana .a.^uic
* X^*C«Ui.Cii TvCit-.t Zkic.
Table 22-^Prorfuction ar.d shipn-.cnls of zir.c p:|^ncnts
Pigment or compound
Z.r.i- r..'. :.... ou- B «
'r _ , i . ,
and compounds * in ihc Unite
1907
s:..pm.-r,L.
i.o.i V_;LO »
tons) tons Tf.t.-.l Averaje
(II. OU- PI'."
sands) ton
r, ,, j j ..,
0 C 1) -i' - 'i " i -J L.'/'
,. v '7 Js j jO S '3" 1"3
d States
T.cn
LOUS)
w in
1", 1 '0
57,:) 14
57.1^1
IOCS
Sn.prncr.ts
\V.
tons Total
(thou-
«ar.d,)
,, c,. ..,. 0.,
5J.C47 10.C57
uC '
Average
per
ton
J"76
o- ,
W
174
W T.'.;': '*.( Ill to u\.- d ^ .-lo^.r * it.c v .uu il P.TT.; inv cor.i.u. :.t'.i! da*n.
» F'v.'lu^. j ;.;r.c;^ori . , /,.iL- w.^.r., ,u ;a wv^iw u.-c.osia^" ir.^iv .a« .1 company conudei.t.al dat*.
* Yu.Ui1 ~t ; ..' ..; ^ ^ ;,. r.-, ..: or . .. r». It ^u i c^.. ->''a m !. ac. J 7 rn ox.dr.
4 rr.L'luJoi tiLC cn.or.ui f:uiv«u*nt oi i.uc hi..iiiorjiu..t ci..ur,uc ai.a cl.rwntuU'd z*nc chloride.
-------
-------
Table 23- 7/:uc cor. lent of z'..ic ^merits1 and compounds
produced by uci~c:»:lc n*:i;;ufuciurcr*( by sources
(Short icn<
IOCS
cor.".;>ound
o.r.r in ;)..',t.,ojiu-* -inu i-om-
7jour.Ua ;.r(-uu(xci lr >r.\
Toi.il
zinc ~.n
^i .U or.i-.iry ar,c:
i. ic r...u«i- cn.u-
r*r»l pGu.-.-U
i,'. :\j oj.o .ry ar.a
"ur- line ni.ito- COM-
i,;n nul pour.cis
SO .CIS Ci,Cr>l SG,o4l 27.3C«3 iG7,77S
.i.ur.i ,;.s^: ............ 7.117
....
J/jJj _-..,_ lO.Tul 16,-iGIi
\V V.'.'hhdJ. 10 a\o!d di^clo ,rs jr.o.\.-'l-a', cor.;pa:t> co,. ".^ii.i..»i ii..f..
1 HxcluLts i.r.c buu.uy ai.a i.iii'>,.*..;io; :,,:^r(.j v. .ir.;*^^ u i.vo.« c.ici^^lt:^ individual company con^.dcatial
at&.
dwo £">nc couioni o[ L.nc air.n.oa.um caionde tnd caromaXC-d z.'iac chlor.de.
J
Table 2~fDfc.irji'u:iua' of zinc oxicc arid kauctl zinc oxide shipments, by Industries
(Short, tons)
Inilu-.try
1SJ5 1SOG 1537 13SS
Ziae o^;^t:
S3,cOS 101,057 104.W.3 Ol.T.F^ 111,707
0,;'.7 lu.OO'! l'J,1^7 &,.l<;0 10,'^Jti
XA !<7J 1,'i'y 5\->^> 5.f:'.
N'.'. - Vrr ll.'.iiS 14.('"J 21, or,.!
v\- \v \v \v \v
ibr,,s;o
l>»a--i.' ^ir.c cvce:
'P.'iir i.s .
Ot.-.or ir.il uusptcjf.cd.
Total
459
10.931 in,4C2 8,644 '6.C50
899 l.OOa l,6t;2 -1,633
IS.iViS ll.boO Il,5o7 lO.oOO .7,535
KA Not tvi.i.V,.,-.
W Vt i'viincla lu ivoic* a'.Nciosn\2 mdivic.ual cor.i^any ci,iir(ticntliil d:iUi, inclodeU with "Olhcr."
Distribution of zlr.c iu'.fme shipment., by industries
(Short tuiii)
Year
Tot.il
CJro.i Dry
D.-y
l',.C*.. ,
J^;^
:^ ov. ir, 103
1 T'.S ^ W7
^ v. .-i ^t- -''1
o -i'.j r. *L.>I
17 'Jli T 11 -»Jl
ir,
ui
*» ' i
.- -j
ax
l-U
. i -
-j'i
WitliWM 10 »vo.d 0*sclo-»ir.£ m
-------
-------
Tabic 2 r-Stocks ^r.d con.un.ption of new .,,,d old zinc >crnp in t!« United States in 1953
(Shore teas)
Con-.atnplion
Scocl;-. Rooeipu ~
J.n. 1 ' N«
Mock}
Total Due. 31
New (.:. ;>-';?---
O.d .v-.c
£',<:...::.-, J.'."'s
Sili...- n .r;^ -
,. , 7-5 77ii 100
.5S 5 o'-; ""i iii 5,in 4ts
7^ ^ S,,-; f.,n7a 5-..i9 I2..MJI
G.-.iv^r..-,-,-!' c,-o V I" I3,;,,j 7^.-''; 77..;:;u 77, Wo 'j.'j'.f
Life..,. i .-L.i 53,; j ii.o.-.n 4i.fou i!,fii;7
Kod i.!.u c...; sorap..1 1S7 i.M --- 1.1-1* l.H-> ,^2;
Fio-c'.i..t .- . l.tJ.2 5.-;'. 4,t-;i -t.ftii -',..7
ChtniL^i'rcsiiuci-.I C.GGJ l-,-;7 J.^^4 - -.- S.-iV. J.-^i
Total SG,^4u 2:f..u7a 1CJ.41."> CO.DT.i Cir. ,37S> ^37,S;3
Chcrn^-:rtl p'-..t5, .'^^..cr.cj ur.u
oih'T n.-'.j .ciurcTb:
''^
S::i:.--..'-.,-- .--i-o -^.i.-s ar7c,i;
5-.l.^......-...-.r- i.-W
D-.-cc ;..---. .,>
C.-.viSi-i.-^' u.-c^o -:
Dicc»-.-:r.,-j pj
Ko;!-.-,; ^.s s.cr^p.. " f~J
J". .^ f.' " ._ 0^1
Ch;r,iJc-l ru^jt.uC3 1..7.
48
11,031 l.&H
9,377 5,0'jJ
""5H 14
4J* -i^i:.,:.s
Oiu z.r.j
-i.il
C 50
rje .........
Ill 3.CIO 5,CIO
S.-.U-.i-.r. :r/, --'.-.^ -;>."' i
J)...n-l.- -in:- -'.-:-' '.'
«;,!v......-,.-.-.:.» i'.i.ui-. '.::.'..'.-
U:,-w.-i - ".--< -Hl.-.J
Itod ..i.kl cm scrip -i7 *-'
r!ujt.u.t -.'.^-J *. ;-.''
Chc.l.-cal if^:auo& 4.J4J o,,.^i
-'-'." ;. .',711 ^ ,.'iu7
'-"'!;.',(- nrr v«-ii-:i'. ~ «.';"«
..!l"..' -it.-''> 41,:-!> "';'!
""i'lM ''--- *''~l(>'' 2';'x"1
S4',5UiJ ".II".-- &!..''SO 7 '"'
2uJ,7£^ 46,071
-------
-------
Table26.U.S. i'.i'vcrts of vine, by countries
Country
S'oo.-t V^'.uo i'..ort V.'.v-f Short
tu:;.» (:ho.<..uiU) t.x-.-. (thuu-Ar.i-) tons
AI>r-:;a 50-
vV-. V"* '. '.'.'..'". i'.7"' c.'j f.'.c-7>', i.-;;o y'.ic? i.jio
c=n.^a."" ."..." 27-, A> co.;.-;, 2_-v.:.:7 42,wr, sin.;-; 4G.c-'j
C.r. ..i.., 'v.\-'. ;'.'0 i
n,v.-ir«i I HI/, ,'i, i.-;0;. a.72? i.a.iu lP-f--;'-! \-':'^
Nc'.'(.J.-:-.;,j^rr".III"I""".IIIIII si..", '3-0 '.- >'.'"''>
PH.. 7-..2.-.; ii.c-i 0^:7
£i,u'.i A;.-C.., i.';.j....c 01 :-.:,, 2.'.,1 8.-til
Yl.p,Uvi.. .<-' i".)
OU.iT >-'j i'"' i.r.JV
Tola! .r)21.r,J() Til.O'-.o .':!:.O'T
i:H
Ccr nar.v, V.'c ,t '3.Ur2 1,.""2 f1.,:) 25L^
X<..-*uy .l.ii.: i,'^7 ,,'J "''' r,. ,,
Po..-itQ_. ..... vi,i-i \ ,'*'~ lj ,'s*'\j 2,G'j7 'j.l^l 2,-j'j'
TJ'ji'.- K;r~don. -* ._ '2'S 7~3 1,110 2ol S.o^S 803
Yi,;0-Uv.a ZJl lit -If 4 330
Otbtr - 3,c4o Si7 3.250 7ft9 2,779 675
Total . 273,173 73,0-G 222,IIJ 57,ou2 COG,5^^ 7u,OCo
:. . ;U.S. iicpora for coiuurr.pi'on cf zinc, by ciisse1.
OK i
Year
Si.orl
tens
10C7 J^t.r.i.,
i Iti.d worn ou-. i^r^ s r.:ui . .c.r.-.Tr.-.i,:., 2.:.c du'jt To^al
v-xl.ua '
Sbwt V-.I.V Short ( V:. ua Short Va'.-;c
15',?;
::"U 2.-.9J ^ ,'! S.771
;-;l....I... V/o iiy ori '_:. s.ico
1 In cOUiLion, mnnufuctvjres o{ nr.c were ia.^orit-Ki as follows: l&Co, $343,COj; 1G67: 5318,2&7; IGG^: $446,6
jIe 27«U.S. ini;)orts for con^u^.^pl;o:1 of zinc pigments inJ compounds
Kind
" i' i ' f
v» , . /u
V . i t-
7ota!
1SS7 15oo>
Siiort ' V_'u,^ Short Value
tons (thouj«n£s) tons (tnouA^ndj}
2
"-" "'J7 S° "*t7 15 "51 3 0"""'
1 " t" " I r< "* "^ o " i *i i °
3 '".T - ' * 2*1'-'" " '5
' , -1 - ' . '>
iS/Jia 3.-:i4 UO.SJ8 <.li2
-------
-------
* IU?v;.-*u.
Table 2C.A\cra:^ n;on;My quoiccl prior-. 01 0-pcrcrnt nr.c conrcn:rc.te at Joplin,
ar.ti c&i.,.r.ju zir.c (r,io;»vi d<..i%try or spo'*/, Ilaj; Si. Louo s;ul London1
Month
zinc rc.n- c- .-.i ;.- r ;.C'i.nci j
C(.I.l-a",' ^
.'! l-i. ho r.r.c
t-nlj per POUDQ)
in in,- Ju -
V:1.!'-':" Sl
J..'iu v S'".n> 3
\; -. i, , in,
O ' ' "»
Xo-.t.-.,!.T .->:.,;
Dc^v;n.,.T a: ax
Avcfo\:u for yt-ur S7.UO
LO-.J London J '
.'0 j -.'.(;!
",.'i "> Til
J.iU U.t^
J.ki 1J.C7
l.'i r..
js:
.^ 1 .
s ;
bl
ii.
Si.
J op-
ton)
0,1
01)
ru
(MI
00
v.'0
GJ
uO
00
St. '
1"
1:1
13
13
l.i
ir>
13
13
lx>uu
. .""I
. .V)
!:,o
...0
.iO
. ;,o
.00
London * '
11
11
a
n
11
n
11
11
11
..ss
(''i
r,s
7 j
17
;.o
s.">
y;
Oi>
£3
! G:uv
cr^^c oi diily mean of bid u^d. 2si;i.>d CtuaUitioad a: Rio
it^ 01 cxcii:.r.^L- rcoorut-d by Fc
-------
-------
-97-
Major Zinc Compounds cr.i Their Uses. "
1. Zinc oxide, ZnO.
Zinc oxide is manufactured co~.rr.ercially by two methods.
(1) the French, or indirect, process which uses zinc metal, end
(2) the American, or direct, process which uses zinc ore. In
the indirect process zinc ir.etcl is charged into a special boiler,
such as a horizontal clay retort, externally heated, usually
with gas. The oxide from the burning zinc flame is sucked by
large fans through pipe lines to settling chambers and cloth
filters for collection. This method makes the puiest, whitest
zinc oxide. In the direct, or American, process for making
zinc oxide, zinc ore is mixed ^ith coal and is charged into
a furnace. The ore is usually roasted sulfide, silicate, or car-
bonate. The heat of combustion of the coal is sufficient to
reduce the zinc ore momentarily.to zinc vapor. The carbon
dioxide and excess oxygen over the charge oxidizes the vapor
to zinc oxide fume which is sucked out and collected as in
the direct process. Because the conversion of the ore to
oxide is performed in one operation, instead of two, the
direct process is more economical than the indirect, and can
often use ores not easily worked for the production of zinc
metal. However, the purity, brightness, and color of oxide
from ore are generally lower than those from metal, since the
-------
-------
-98-
combustion gases come in contact with the oxide fume,
leaving in the product traces of sulfur compounds, as well
as sone dust frora the ore and coal.
Zinc oxide is made and used on a larger .scale than any
other zinc compound. Its combination of bright whiteness,
fineness, range of shapes, ease of dispersion, chemical
activity, and fungistatic properties makes it valuable to
many industries. The leading uses for zinc oxide are in
the manufacture of tires, paints, ceramics, coated fabrics,
and floor coverings. Other uses of zinc oxide include the
manufacture of dental cement, soaps, perfume fixatives,
match heads,- viscose filament stabilizers, Portland cement,
plastics, coated paper, abrasive wheels, and agricultural
fertilizers and sprays.
2. Zinc Aluminate (Gahnite), AnAl?0,.
It is used as a white pigment in vitreous enamels.
3. Zinc Amide, Zn(HH2)2.
The amide is an amorphous white powder which decomposes
in water.
4. Zincammincs.
Zinc forms a series of complex cations as follows:
^Zn(irrl ),37t2 /Zn(HH) ~7,+2 and /Zn (NHJ ~7~!"2 which combine
~> <- o 4 o 6
with many onions to form compounds such as /_ Zn (NH..) ._/ SO .
-------
-------
-95-
5. Zinc Antimonate, Zn (SbO ) .
3 £
It is used as a bleach in ceramics. Because of the
presence of antimony, this substance has added toxicity.
6. Zinc Arsenic Compounds.
Zinc-arsenic compounds are poisonous and are used as
insecticides, fungicides, herbicides, wood preservatives, and
as toxic agents in antifouling marine paints.
-Metallic zinc and-arsenic form two intermettalic com-
pounds identified as Zn^As^" and ZhAs2 known as zinc arsenides.
Zinc arsenites have been prepared in the ortho and meta forms,
but the existence of the pyro forin_ds doubtful. Zinc ortho-
arsenite, Zn(AsO^)y, exists as the dihydrate, and as two
crystalline forms of the anhydrous salt. Zinc metarsenite,
Zn(As00) , can be precipitated by reacting solutions of
" 2
sodium arsenite and zinc sulfate in the presence of citric
acid or sodium carbonate.
Zinc arsenates are similarly formed. The ortho, pyro,
and meta forms have the respective formulas; Zn-,(AsO. ),
3 °r £
"Z.r\2^2^7 > an<^ Zn(AsO-J),). The orthoarsenate crystallized with
eight molecules of water is found in nature as ktfttigite.
Zinc fluoarsenate, 4 ZnO'ZnF^^S9°5/ ^s made by adding an
arsenic acid solution, then sodium fluoride, to a slurry of
Einc oxide. Many variations in the compound's composition
-------
-------
-100-
con be obtained. It is a very toxic compound and used as an
insecticide in places where the straight zinc arsenate burns
the folicge.
7. Zinc-Boron Compounds.
Zinc borate, 3ZnO*2B 0 , can be prepared by heating
<" 3
the component oxides together at about 600°C. Zinc borates
have found considerable use in formulations for fireproofing
textiles, as a fungistatic powder, as a flux in ceramics, as
a mildew inhibitor, and as an ingredient in pharmaceutical
*
ointments and powders.
«
8. Zinc Chroiaates.
Zinc tetroxychromate , ZnCrOx/ 4Zn(OH)? , and zinc
trioxychror.ate , ZnCrO^' 3Zn(OH)2 , are used in preparing metal
priming paint because of their excellent rust inhibiting pro-
perties. Zinc monoxychromate , ZnCrO,«Zn(OK) , is known, but
its use as a pigment is limited. Zinc chromate, ZnCrO , and
zinc dichrcmate ZnCr^O^'SH^) are also limited in their use as
pigments because of their high solubility.
Commercial zinc chromate, zinc yellow, is usually a zinc
potassium or zinc sodium chromate composed of 4ZnOK20«4Cr03« 3H2) ,
-------
-------
-101-
These alkali zinc chromates are chiefly used as pignents,
particularly for rust inhibitivc paints for iron, steel, and
light ir.etal alloys. Zinc chronite, ZnO'Cr^^, is a green
crystalline substance and used as fungicide.
Other industrial zinc compounds include:
Nome
9. Zinc Cobaltite
10. Zinc Cyanide
11. Zinc Ferrate (III)
Formula
ZnC°2°4
Zn(CN)2
ZnFe204
Use
qualitative zinc test
metal plating
rust prevention
12.. Zinc Hcxacyanoferrate(III) Zn/ Zn/ Fe(CN)g_/2_/ dry cells
13. Zinc Fluoride
14. Zinc Hydride
15. Zinc Hydrosulfite
16. Zinc Hydroxide
17. Zinc lodate
18. Zinc Iodide
19. Zinc Nitrate
20. Zinc Nitride
21. Zinc Nitrite
22. Zinc Permanganate
23. Zinc Peroxide
24. Zinc orthophosphate
25. Zinc pyrophosphatc
ZnF,
ZnH,
ZnS204
Zn(OH)2
Zn(I03)2-2H2)
ZnI2
Zn(N03)2
Zn(N02)2
Zn(Mn04)2-2H20
Zn02
Zn
wood preservative
bleaching agent
for the preparation of1
more complex zinc
compounds
Silver metallurgy
Zn2P2°7
antiseptic
dental cement
roofing granule;
-------
-------
-102-
Ncme
27. Zinc Phosphide
28. Zinc Selemide
29. Zinc Selenite
30. Zinc orthosilicate
31. Zinc Fluosilicate
32. Zinc Sulfornate
33. Zinc Sulfate
Formula
2n3P2
ZnSe
ZnSeO-
Zn2Si04
ZnSiF6-6H20
Use
rodenticide and explosive
primers
water-softening, waterproo;
paints
plastics, wood preserva-
tive, and fungicide
An(SO NH9)o*4H2° flameproofing textiles
3 /i "
ZnSo4'7H20 See Note 1
Lithopone, a white pigment, is made by coprecipating ZnS
and BaSO^ from equivalent solutions"of ZnSO and BaS. To obtain
the desired whiteness and brightness', both solutions must be
pure and especially free from iro'n, cadmium, manganese, and copper.
The titanium-base white pigments have caused a decline in the use
of lithopone.
34. Zinc Sulfide ZnS
Next to zinc oxide the most largely used zinc compound in
the sulfide. It is the main constituent of the commonest zinc ore,
known as sphalerite, Black Jack, or blende, when crystallized in
the cubic form; and as wurtzite when in the rare, high-temperature,
hexagonal form. Although the naturally occurring compound is
-------
-103-
variously colored, the pure compound is white and has a high
refractive index (2.37), making it a valuable pigment with
good color, brightness, and hiding power.
Name Formula Use
35. Zinc Sulfite 2nS03«2H 0
36. Zinc Tellurate Zn^TeOg
37. Zinc Telluride ZnTe
38. Zinc Thiocyanate Zn(SCN) «2H 0 quantitative analysis
£ 2
39. Zincates: See Note 3 See Note 3
Note 3. Strong alkaline solutions react with zinc oxide
or zinc hydroxide to form zincates. The formula of a particular
zincate varies with the conditions of solubilizing the ZnO in
base. The best known of the zincates are:
sodium zincate Na'Zn00
2 /
potassium zincate
barium zincate
These are white compounds, very soluble in water, but
'can be crystallized in several hydrated forms. Zincates may be
also prepared by heating zinc oxide with other oxides.
-------
-------
-10&-
Sodium zincate has been used as a water softening agent,
as a flocculating agent in water treatment, and as a treating
agent for paper or cloth to improve strength, to make a smoother
surface, and to prevent mildew. The soluble zincate can be
allowed to penetrate into the fibers of the paper or cloth, and
then by acid treatment or hydrolysis, zinc oxide or hydroxide
can be precipitated in the body of the treated material.
-------
-------
-105- '
_ZT_M_C
General References,,
Baker, R. A. Trace Inorganics in Water: Advances in Chemistry,
Series 73- WashTngTon, D.C.: anierican Chemical Society, 15o8.
Berg, G. G. and M. W. Miller. ChemJ£aT_j£n_gutj__Current Research on
Persistent Pcsticic'es. Springfield, Illinois: Charles C. Thomas,
Publisher, 1969
Brasted, R. C. and M. C. Sneed. Com p re he n s i ve_I_nor g a nj^c _C hem i s t r y ,
Vol. k. Princeton, N.J.: D. Van Nostrand Co., Inc., 1955-
Brov/ning, E. Toxj_ci t^ of Industri al _ Metal s. London, England:
Buttcrv.orth 5- Co., Ltd., 1 9oi .
Clark, R. L., D. B. Keyes and W. L. Faith. Industrial Chemicals.
2nd ed. New York, M.Y.: John Wiley & Sons, Inc., 1957-
Deichmann, W. B. and H.' W. Gerarde. Toxicology of Druos_an_d
Chemical s. New York, N.Y.: Academic Press, Inc., 19o9«
El kins, H, B. The Chemistry of Industrial Toxicology. 2nd. ed.
New York, N.Y.: John Wiley & Sons, Inc., 1959.
Jacobs, M. B. The Analytical Toxicology of Industrial Inorganic
Poisons. New York, M.Y.: In^erscierce Publishers, Division of
John V/fley & Sons, Inc., 1 9o7 .
Kaynard, J. L. and M. C. Sneed. General Inorganic Chemistry.
New York, N.Y.: D. Van Nostrand Co., Inc.,
Mineral Facts and Problems, 1 9^5 ed.. Washington, D.C.: Bureau of
Mines, Department of the Interior.
Mineral s Yearbook, 1968., Vol. I-II. Washington, D.C.: Bureau of
Mines, Department of the Interior.
Nemerow, N. L. Theories and Practices of Industrial Waste Treatment,
Reading, Mass.: Addi son-Wesley Publishing Co., Inc.
Patty, P. A. Industrial Hygiene and Toxicology, Vol. I and II, 2nd. ed.
New York, N . ~: liner science Puoiishers, Division of John Wiley &
Sons, Inc. , I 963
Sollmann, T. A__Mrnua_l of Pharmacology. 8th ed. Philadelphia, Pa.:
W. B. Saunders Company, 1957*
-------
-------
-106-
ZINC
Biblioarcrohv
_Per 1 od i c-3 i s
"The Merck Index of Chemicals and Drugs." 7th ed. (1960)
Browning, E., "Toxicity of Industrial Metals" Butterworths,
London, England (1961)
"Water Quality and Treatment." 2nd ed. A.W.W.A. (1950).
Hartman, B. J. , "Munitions." Sewage Wks. Eng. and Munic.
San. 15, 178 (1944);. Chem. Abs. 39, 5022 (1945).*
Sanborn, N.H., "Lethal Effect of Chemicals on Fresh Water
Fish." Food Packer 26, '41 (1945).
"Drinking Water Standards." Title 42 Public Health; Chapter 1
Public Health Service, Dept. of Health, Educ. , and Welfare;
Part 72 -- Interstate Quarantine Federal Register 2152 (Mar. 6, 1962)
"International Standards for Drinking Water." World Health Organiza-
'tion Geneva (1958).
"European Standards for Drinking Water." World Health Organization,
Geneva (1961).
Rothstein, Aser, "Toxicology of the Minor Metals" Univ. of
Rochester, AEC Project, UR-262, June 5, (1953).
Anderson, E.A., Reinhard, C. E., and Hammel, W. D., "The
Corrosion of Zinc in Various Waters." Jour. A.W.W.A. 26, 49
(1934).
Bartow, E. arid Weigle, A. M. , "Zinc in Water Supplies."
Ind. and Eng. Chem. 24, 463 (1932).
Hinrnan, J. J. , Jr. , "Desirable Characteristics of a Municipal
Water Supply." Jour. A.W.W.A. 30, 484 (1938).
Kehoe, R. A., Cholak, J., and Largent, E. J., "The Hygienic
Significance of the Contamination of Water With Certain Mineral
Constituents." Jour. A.W.W.A. 36, 645 (1944)
-------
-------
-107-
Nolte, A. G. and Kroner, W. A., "Zinc in Drinking Water."
Amsr. City 49, 4:63 (1934); Jour. A.W.W.A. 26, 1747 (1934).*
Howard, C. D. , "Zinc Contamination in Drinking Water."
Jour. A.W.W.A. 10, 411 (1923),
Drinker, C. K. and Fairhall, L. T., "Zinc in Relation to General
and Industrial Hygiene." Pub. Health Repts. 48, 32 (1933); Jour. A.W.W.A.
26, 796 (1934).*
Hegstedt, D., McKibben, J. and Drinker, C., "The Biological
Hygienic, and Medical Properties of Zinc Compounds." Pub.
Health Repts. 60, Supplement 179 (1945); Jour. AW.W.A. 52, 661 (1960).
Balavoine, P., "Sensibility of theTaste to Toxic Salts." Mitt.
Gebiete Lebensm. Hyg. (Ger.) 39, 27 (1948) Jour. A.W.W.A. 52,661
(I960).*
Cohen, J. M., Kamphake, L, J., Harris, E. K., and Woodward,
R. L. , "Taste Threshold Concentrations of Metals in Drinking Water."
Jour. A.W.W.A. 52, 660 (1950).
Negus, S.' S. , "The Physiological Aspects of Mineral Salts
in Public Water Supplies." Jour. A.W.W.A. 30, 242 (1938).
Kelley, W. P. and Brown, S. M., "Boron in the Soils and
Irrigation Waters of Southern California and Its Relation to
Citrus and Walnut Culture." Hilgardia 3, 445 (1938).
Lerou>:,D., "The Influence of Various Trace Elements on
the Fixation of Atmospheric N in the Course of Growth of a
Legume." Compt. rend 212:504 (1941). The Occurrence and
Biological Effects of Fluorine Compounds, Annotated Bibli-
ography, the Kettering Laboratory, Univ. of Cincinnati,
Cincinnati, Ohio, 107 (1958).
Wilson, C. C., "The Responses of Two Species of Pine to
Various Levels of Nutrient Zinc." Science 117, 231 (1953).
Hunter, J. H. and Vergano, 0., "Trace Element Toxicities in
Oat Plants." Ann. Applied Biology 40, 761, (1953).
-------
-------
-108-
Tomlinson, J.A., "Control of Watercress Crook Root Dis-
ease by Zinc-Fritted Giacs." Nature 173, 1301 (1956).
Billing, W. J., "Influence of Lecd and the Metallic Ions of
Copper, Zinc, Thorium, Ec-rylliun end Thallium on The Ger-
mination of Seeds." Annals of Applied Biol. 13, 160 (1926).
Anon., "Ohio River Valley Water Sanitation "Commission,
Subcommittee on Toxicities, natal Finishing Industries Action
Committee." Report No. 3 (1950).
Moxan, A. L. and Rhian, M., "Selenium Poisoning." Physiol.
Rev. 23, 305 (1943).
Sturkie, Paul D., "The Effects of Excess Zinc on Water
Consumption in Chickens." Poultry Science 35:5, 123 (1956).
.Perkins, R. W. and Nielsen, J. H., "Zinc-65 in Food and
People." Science 129, 94 (1959). "
Foster, R. F., Junkins, R. L. , and Lineroth, C. E., "Waste
Control at the Hanford Plutonium Production Plant." Jour. Water
Poln. Control Fed. 33, 511 (1961).
Palmer, R. F., "Radioisotopes in Rates Exposed to Reactor
Effluent Water." Hanford Biology Research Annual Report for 1957
pp. 189-190. Off. of Technical Services, U.S. Dept. Commerce, Wash.,B.C.,
228 pp. (1958).
Jones, J. R. E., "The Relative Toxicity of Salts of Lead,
Zinc, and Copper to the Stickleback." Jour. Expt. Biol 15, 394 (1938).
Cairns, J. Jr. and Schcier, A., "The Relationship of Bluegill
Sunfish Body Size to Tolerance for Some Common Chemicals."
Industrial Wastes 3:5, 126 (1958).
"The Sensitivity of Aquatic Life to Certain Chemicals Commonly
Found in Industrial Wastes." Acad. of Natural Sciences, Philadelphia(196C
Cairn, J., Jr. and Scheier, A., "The Effects of Temperature
and Hardness of Water Upon the Toxicity of Zinc to the Common Bluegill,
(Lepomis macrochirus Raf.)." Notulae Naturae 1:299, 12 (1957).
-------
-------
-109-
Cairns, J. Jr. and Scheier, A., "The Effects of Temperature and
Hardness of Water Upon the Toxicity of Zinc to the Pond Snail,
Physa hcterostrorha (Say).11 Kotulcs Ilaturae of
theAcadcr.ry of Natural Sciences of Phioa. 308 (1958).
Southgate, B., "Water Pollution.: Chem. and Ind., 1194 (1955)
Jones, J. R. E. , "Fish and River Pollution. " Chapter 7, of
"Aspects of River Pollution," L. Klein, Editor. Butterworth
Scientific Publ., London (1957).
Jones, J. R. E., "The Relation Between theElecrolytic
Solution Pressures of the Metals and Their Toxicity to the
Stickleback (Gasterosteus aculeatus L.)" Lour. Exp. Biol. 16, 425 (1939)
Lloyd, R., "The Toxicity of Zinc Sulfate to Rainbow Trout."
Ann. Appl. Biol. 48:1, 34 (1960)
"Water Pollution Research for 1957." Water Pollution Research Board, Dept.
of Scientific and Ind. Res., H. M. Stationary Office, London (1958).
"Effect on Fish-" Ind. Wastes 3:6 9A (1958).
Afflect, A. J, , "Zinc Poisoning in a .Trout Hatchery." Austr.
Jour, of Marine and Freshv;ater Res. 3, 142 (1952).
Goodman, J. R., "Toxicity of Zinc for Rainbow Trout (Salmo gairdnerii)."
Col. Fish andGarae 37, 191 (1951).
Doudorcff. P. and Katz, M., "Critical Review of Literature on the
Toxicity of Industrial V/astes and Their Components to Fish. II. The Meta
as Salts." Sewage and Industrial Wastes 25, 802 (1953).
Doudoroff, P., "Water Quality Requirements of Fishes and Effects of
Toxic Substances." Chapt. 9, in M. E. Brown, Vol. 2 (Behavior),
The Physiology of Fishes, 403 (1957).
Tarzwell, C. M., "The Use of Bio-Assays in Relation to the Disposal
of Toxic Wastes." Third Ontario Industrial Waste
Conference, Pollution Control Board of Ontario, 117 (1956).
Hayes, W. J,, Durham, W. P., and Cueto, C., Jr., "The
Effect of Known Repeated Oral Doses of Chlorophcnothane (DDT)
in Han." Jour. Am. Med. Assoc. 162, 9 (1956).
Doudoroff, P., "Some Recent Developments in theStudy of
Toxic Undustrial "wastes." Fourth Ann. Pac Northwest
t. Waste Conf. Proc. , Washington State College,
-------
-------
-110-
Lloyd, R., "The Toxicity of Mixtures of Zinc and Copper Sulphates
to Rair.bov.' Trout (Salmo gairdnerii Richardson)." Ann. Appl. Biol.
49, 535 (1961).
"Report of the Water Pollution Research Board, With the Report
of the Director of the Water Pollution Research Laboratory for the
Year 1959." Dept. of Scientific and Ind. Res., H. M. Stationery Office,
London (1960).
"Some Effects of Pollution on Fish." Notes on Water
Pollution No. 13, June (1961), Dept. of Scientific and Industrial
Research, England.
Lloyd, R., "Effect of Dissolved Oxygen Concentrations on the
Toxicity of Several Poisons to Rainbow Trout (Salmo gairdnerii
Richardson)." Jour. Exp. Biol. 39, 447 (1961).
"The Sensitivity of Aquatic Life to Certain Chemicals Commonly Found
in Industrial Wastes." Acad. of Natural Sciences, Philadelphia (1960).
Cairn, J., Jr. and Scheier, A., "The Effects of Temperature and
Hardness of Water Upon the Toxicity of Zinc to the Common Blue gill,
(Leporais macrochirus Raf.)." Notulae Naturae 1:299, 12 (1957).
Affleck, A.J., "Zinc Poisoning in a Trout Hatchery." Austr. Jour.
of Marine and Freshwater Res. 3, 142 (1952).
Goodman, J. R., "Toxicity of Zinc for Rainbow Trout (Salmo gairdnerii)."
Col. Fish and Game 37, 191 (1951).
Doudoroff, Peter, "Some Experiments on the Toxicity of
Complex Cyanides to Fish." Sewage and Industrial Wastes
28, 1020 (1956).
Doudoroff, P., "Sone Recent Developments in the Study of Toxic
Industrial Wastes." Fourth Ann. Pac. Northwest Indust. Waste
Conf. Proc., Washington State College, (1952).
Anon., "Aquatic Life Water Quality Criteria, Third Progress Report."
Aquatic Life Advisory Committee of the Ohio River Valley Water
Sanitation Commission (OHSAliCO). Jour, of the Water Pollution
Control Federation, 32:65, (1960).
-------
-------
-Ill-
Neil, J. H., "Toxicity of Cyanides to Fish." Third Ontario
Ind. Waste Conf., Pollution Control Beard of Ontario, 125 (1956).
Podubsky, V. and Stcdronsky, E., "Toxic Effects of Some Metals on
Fish and River Crabs." Ann. Acad. tehecosl. Agric. 21, 206 (1948);
Water Pollution Abs. 24 (Jan. 1951).*
Anon., Federation of Sewage and Industrial Wastes Associations,
Research Committee, Subcommittee on Toxicity of Industrial Wastes,
"Toxicity of Copper_and Zinc Ions in the Dilution EOD Test."
Sewage and Industrial Wastes 28, 1168 (1956).
Heukelekian, H. and Gellman, I., "Studies of Biochemical
Oxidation by Direct Methods. IV. Effect of Toxic Metal Ions
on Oxidation." Sewage and Industrial Wastes 27, 70 (1955).
Meinck, F«, Stooff, H., and Kohlschutter, H., "Industrial Waste
Waters (Industrie-Abwasser)." 2nd Edit. Gustav Fischer Verlag.
Stuttgart 536, 48 D.M. (1956).
Klein, L., "Aspects o^ River Pollution." Butterworth Scientific
Publications, London and Academic Press, Inc., New York (1957).
Anon., "Effluent Standards Proposed to be Adopted by the Mersey River
Board." (A Discussion) Jour. Inst. of Sewage Purification 4, (1953).
Speer, C. J., "Sanitary Engineering Aspects of Shellfish Pollution."
Bull. Maryland State Dept. of Health 1, No. 3 (April 1928).
Deschiens, R., Molinari, V., and Bartrand, D., "The Action of Zinc
Water as a Toxic Agent on Molluscs." Bull. Soc. Pat. Exot. 50:1,
59 (1957); Zbl. BakT. I, 16686 (1958).
Harry, K. W. and Aldrich, D. V., "The Ecology of Australorbis
glabratus in Puerto Rico." Bull, of the World Health Organization
18, No. 5-6, 819 (1958); Pub. Health Engineering Abs. 38,38 (1958).*
Gong, J. K., Shipman, W. H., and Cohn, S. H. , "Uptake of Fission
Products and Neutron-Induced Radionuclides by the Clan." Proc. of
the Soc. for Experimental Biology and Medicine 95, 451 (1951).
-------
-------
-.112-
Lockey, J. B., "Shellfish and Radioactivity." Eng. Progress 13,
Leaflet No. 11 (1959).
Waldichuk, M. , "Pollution." Excerpts from 1960-61 Annual Report
of the Biological Station, Kanairao , Brit. Col.
Silker, W. B., "Separation of Radioactive Zinc from Reactor
Cooling Water by an Isotope Exchange Method." Anal. Chem.
33, 233 (1961).
Saiki, M. and Mori, T., "Studies on the Distribution of Admistered
Radioactive Zinc in the Tissues of Fishes." Bull. Japan Soc. Sci.
Fisheries 21, 945 (1955); Biol. Abs. 31:23, 478 (1957).*
Boroughs, H. , Chapman,- W. A., and Rice, T. R., "Laboratory Experi-
ments on the Uotake, Accumulation, and Loss of Radicnuclid.es by
Marine Organisms." Nat'1. Acad. of Science, Nat'l, Res. Council,
Publication 551, 80 (1957).
'Chipman, W.A., Rice, T. R., and Price, T. J., "Uptake and Accumula-
tion of Radioactive Zinc by Marine Plankton, Fish, and Shellfish."
Fish. Bull., U.S. Fish and Wildlife Service 58, 279 (1958).
Morgan, G. B. , ''The Absorption of Radioisotopes by Certain
Microorganisms." Quarterly Journ. of the Florida Academy of
Sciences 24, 94, June (1961).
-------
-------
-113-
Anon., "Ohio River Valley Water Sanitation Commission, Sub-
committee on Toxicities, Metal Finishing Industries Action
Coiriaittee." Report Uo. 3 (1950).
Hov.-ard, C. D., "Zinc Contamination in Drinking Water." Jour.
A.W.W.A. 10, 411 (1923).
Cairns, J. Jr. and Scheier, A., "The Relationship of Bluegill
Sunfish Body Size to Tolerance for Some Common Chemicals."
Proc. 13th Industrial Waste Conf., Purdue Univ., Engineering
Bull, 43:3, 243 (1959).
Cairns, J. Jr. and Scheier, A., "The Relationship of Bluegill
Sunfish Body Size to Tolerance for Some Common Chemicals."
Industrial Wastes 3:5, 126 (1958).
Annon., "The Relationship of Body Size of the Bluegill Sunfisg to
the Acute Toxicity of Some Common Chemicals." PMladelphia
Academy of Sciences, Miiueo (1956).
Goodman, J. R., "Toxicity of Zinc for Rainbow Trout (Salmo
gairdnerii)." Cal. Fish and Game 37,.191 (1951).
Schaut, G. G., "Fish Catastrophes During Drought." Jour.
A.W.W.A. 31, 771 (1939).
Cairns, J. Jr. and Scheier, A., "The Effects of Periodic Low
Oxygen Upon the Toxicity of Various Chemicals to Aquatic Organisms."
Proc. 12th Industrial Waste Conf., Purdue Univ., Engineering
Bull. 42:3, 165 (1958).
Anderson, B. G., "The Apparent Thresholds of Toxicity of Daphnia
nagna for Chlorides of Various Metals When Added to Lake Erie Water."
Trans. Amer. Fish. Soc. 78, 96 (1948); Water Pollution Abs. 23
(Dec. 1950).-
-------
-------
-114-
Anon., "The Merck Index of Chemicals and Drugs." 7th ed. (1960)
Ellis, M. K., "Detection and Measurement of Stream Pollution
(Related Principally to Fish Life)." U.S. Dept. of Commerce,
Bur. of Fisheries Bull. 22 (1937).
Anderson, B. G., "The Apparent Thresholds of Toxicity of
Daphnia ir.agna for Chlorides of Various Metals When Added to Lake
Erie Water." Trans. Amer. Fish. Soc. 78, 96 (1948); Water Pollution
Abs. 23 (Dec. 1950).*
-------
-------
-115-
ZnO
Anon., "The Merck Index of Chemicals and Drugs." 7th ed. (1960).
Dilling, W. J., "Influence of Lead and the Metallic I0ns of
Copper, Zinc, Thorium, Beryllium ana Thallium on the Germination
of Seeds." Annals of Applied Biol. 13, 160 (1926).
Andorson, E. A., Reinhard, C. E., and Hammel, W. D., "The
Corrosion of Zinc in Various Waters." JOur. A.W.W.A. 26, 49 (1934).
Anon., "Ohio River Valley Water Sanitation Commission, Subcommittee
on Toxicities, Metal.Finishing Industries Action Committee."
Report No. 3 (1950).
-------
PROTECTION A@llf@₯
-j Region V
\ North Wackar Drive
-------
-116-
ZnSO,
Davies, G. N., "An Investigation of the Effect of Zinc Sulfate
on Plants." Ann. At;p. Biol~ 28, 81 (1941); Water Pollution
Ahs. 15 (Jan. 1942)'*.
Dilling, V7. J. , "Influence of Lead and the Metallic Ions of
Copper, Zinc, Thorium, Beryllium and Thallium on the Germination
of Seeds." Annals of Applied Biol. 13, 160 (1926).
Hunter, J. H. and Vergano, 0., "Trace Element Toxicities in Oat
Plants." Ann. Applied Biology 40, 761 (1953).
Murdock, H. R., "Industrial Wastes. Some Data on Toxicity of Metals
in Wastes to Fish Life are Presented." Ind. Eng. Chem. 45, 99A (153).
Jones, J.R. E., "The Reactions of Pygosteus pungitius L. to
Toxic Solutions." Jour. Exp. Biol. 24, 110 (1947); Water Pollution
Abs. 20 (Dec. 1947)*.
Rudolfs, W., Barnes, G. E., Edwards, G. P., Heukelekian, H., Hurwitz,
E., Renn, C. E., Steinberg, S., and Vaughan, W. F. , "Review of
Literature on Toxic Materials Affecting Sewage Treatment Processes
Streams, and B.O.D. Determinations." Sewage and Industrial V/astes
22, 1157 (1950).
Anderson, B. G. , "The Apparent Thresholds of Toxicity of
Daphbia magna for Chlorides of Various ;Metals When Added to Lake
Erie Water." Trans. Amer. Fish. Soc. 78, 96 (1948); Water Pollution
Abs. 23 (Dec. 1950)*.
Anderson, B. G., "The Th'e Toxicity Thresholds of Various Substances
Found in Industrial Wastes as Determined by the Use of Daphnia magna."
Sewage Work£3 Jour. 16, 1156 (1944).
Naumann, E., "The Effect of Some Salts and Mixtures of Salts on
Daphnia magna." Physiog. Sallsk. Lund Forh. 4, 11 (1935); Jour,
A.W.W.A. 30, 1418 (1933).*
-------
-------
-117-
ZnS04
^
Bringrr.onn, G. and Kuhn, R., "The Toxic Effects of Waste Water on
Aquatic Bacteria, Algae, and Snail Crustaceans." Gesundheits-Ing.
80, 115 (1959).
Bringnarm, G. and Kuhn, R., "Water Toxicology Studies with
Protozoans as Test Organisms." Gesundheits-Ing. GO, 239 (1959).
de-land, K. W. , "Heavy Metals, Fertilization and Clevage in
Eggs of Pscrr.mechinus miliavis." Exp. Cell. Research 4, 246 (1953).
Clemdennirig, K. A. end North, W.J., "Effect of Wastes on the
Giant Kelp, Macrocystis pyrifcra." Proc. 1st Int. Conf. on Waste
Disposal in the Marine Environment p. 82, Pergamon Press, N. Y.
(1960).
North, W. J. Clendenning, K.A,, The Effects of Waste Discharges on
Kelp." Annual Prog. Report, T st. Of Marine Resources, Univ. of
California, La Jolla IMR Reference 58-13 (1 July 1958).
, ,_,
ReSicr " " ' ' '":Ul-:-0i'i Agency
230 f>x-.; _y., ..
-------
-------
-------
------- |