Cadmium and Cadmium Compounds 1

Cadmium and Cadmium Compounds

Karl-Heinz Schulte-Schrepping, Degussa AG, Bonn, Federal Republic of Germany (Chaps. 1 – 6)

Magnus Piscator, Karolinska Institute, Stockholm, Sweden (Chap. 7)

1. Introduction . . . . . . . . . . . . . . . 1 3. Alloys . . . . . . . . . . . . . . . . . . . . 6
2. Cadmium Metal . . . . . . . . . . . . . 1 4. Cadmium Compounds and Com-
2.1. Physical Properties . . . . . . . . . . . 1 plexes . . . . . . . . . . . . . . . . . . . . 7
2.2. Chemical Properties . . . . . . . . . . 2 4.1. Properties . . . . . . . . . . . . . . . . . 7
2.3. Occurrence, Raw Materials . . . . . 2 4.2. Individual Compounds . . . . . . . . 7
2.4. Refining . . . . . . . . . . . . . . . . . . 2 4.3. Storage and Transportation . . . . . 9
2.4.1. The Starting Materials . . . . . . . . . . 2 5. Environmental Protection . . . . . . 9
2.4.2. Leaching of the Starting Materials and 5.1. Emission . . . . . . . . . . . . . . . . . . 9
Cementation . . . . . . . . . . . . . . . . 3
5.2. Waste Water . . . . . . . . . . . . . . . 9
2.4.3. Electrolytic Recovery . . . . . . . . . . 3
5.3. Air . . . . . . . . . . . . . . . . . . . . . . 10
2.4.4. Distillation . . . . . . . . . . . . . . . . . 4
2.4.5. Other Processes . . . . . . . . . . . . . . 4 5.4. Soil . . . . . . . . . . . . . . . . . . . . . 10
2.4.6. Recycling . . . . . . . . . . . . . . . . . . 5 6. Economic Aspects . . . . . . . . . . . . 11
2.5. Quality Specifications and Analysis 5 7. Toxicology and Occupational Health 11
2.6. Uses . . . . . . . . . . . . . . . . . . . . . 5 8. References . . . . . . . . . . . . . . . . . 15

1. Introduction and stabilizers for plastics. Publicity about the

toxicity of cadmium has affected the consump-
Cadmium [7440-43-9], Cd, atomic number 48, tion.
Ar 112.40, belongs to the zinc subgroup of the
periodictable along with mercury. In its com-
pounds it has an oxidation state of + 2. There
are eight natural isotopes, with mass numbers
2. Cadmium Metal
ranging from 106 – 116. The most abundant are
114
Cd (29 %) and 112 Cd (24 %). There are also 2.1. Physical Properties
a number of metastable isotopes.
Strohmeyer discovered cadmium in 1817 Cadmium is a soft, ductile, silver-white metal.
in the course of investigating zinc carbonate. He Like tin, it makes a grating sound when bent. The
recognized that the yellow color of a sample of most important physical properties are given be-
zinc oxide produced by roasting was due to the low.
presence of an unknown metal oxide. Because mp 320.9 ◦ C
this new element also occurred in the zinc ore bp 767 ± 2 ◦ C
Vapor pressure at 218 ◦ C 0.133 Pa
calamine, a name derived from the Latin word 302 ◦ C 6.666 Pa
“cadmia,” he named the new element cadmium. 392 ◦ C 133.32 Pa
485 ◦ C 1333.2 Pa
Unlike some other heavy metals, such as lead 611 ◦ C 13.332 kPa
or mercury, which have been used since an- 727 ◦ C 66.660 kPa
765 ◦ C 101.33 kPa
cient times, cadmium has been refined and uti-
lized only relatively recently. After its discovery Density 8.64 g/cm3
more than a century elapsed before the metal Specific heat at 20 ◦ C 0.230 J g−1 K−1
Heat of fusion 55 J/g
or its compounds were employed to any signif- Heat of vaporization at 767 ◦ C 890 J/g
icant extent. Only since the 1940’s production Thermal conductivity at 18 ◦ C 92 J m−1 s−1 K−1
and consumption have risen distinctly. The pri- Electrical resistivity at 18 ◦ C 7.5×10−6 Ω cm
Brinell hardness 22 – 24
mary uses are electroplated cadmium coatings,
nickel – cadmium storage batteries, pigments,

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a04 499
2 Cadmium and Cadmium Compounds
Coefficient of linear
expansion at 20 ◦ C 31×10−6 K−1
tion, with emphasis on the distillation process,
Ionization potential 8.96 V can be found in [3].
Electrochemical potential − 0.40 V
Cross section for thermal 2450 × 10−28 m2
neutrons

The crystal structure is distorted closest

packed hexagonal.

2.2. Chemical Properties

Cadmium is stable in air; only a slight loss in
luster occurs after an extended period of time in
air. When it is heated, initially yellow to brown
colors develop as a thin oxide layer forms. If the
metal is heated to volatilization, it burns with a
red-yellow flame to form brown cadmium oxide,
which is poisonous. Cadmium dissolves readily
in nitric acid but only slowly in hydrochloric or
sulfuric acid and not at all in bases. Zinc dis-
places it from solution.

2.3. Occurrence, Raw Materials

Cadmium is widely distributed. It occurs in the
earth’s crust with a content estimated to be be-
tween 0.08 and 0.5 ppm. In top soil cadmium
content usually lies between 0.1 and 1 ppm.
The best known cadmium mineral is
greenockite, cadmium sulfide (77.6 % Cd). One
mineral form of cadmium carbonate (61.5 % Cd)
was named otavite after its discovery site, the
Tsumeb Mine, in the Otavi deposit of South-
West Africa. In Sardinia, pure cadmium oxide
(87.5 % Cd) was found in a zinc deposit. How-
ever, none of these cadmium minerals is of in-
dustrial importance because the deposits are too
small.
Only zinc minerals in which cadmium is
found as an isomorphic component, with con-
centrations ranging from 0.05 to 0.8 %, aver-
aging about 0.2 %, have economic significance
for cadmium recovery [2]. In addition, lead and
copper ores contain small amounts of cadmium,
which can be separated during the roasting and
smelting processes.
2.4. Refining
Figure 1 summarizes the individual process
steps and their combination. Detailed descrip-
Figure 1. Processes for the production of cadmium metal
2.4.1. The Starting Materials
The flue dust on which the volatile cadmium col-
lects when zinc, copper, and lead ores are heated
in air are the primary starting material for cad-
mium recovery and refining. In many cases it is
necessary to recirculate this dust to obtain higher
cadmium concentrations [4].
In the Outokumpu Zinc Works in Finland,
roasting material contains 0.19 – 0.24 % Cd. The
cadmium content is extracted in the third step of
the zinc process and results in a cake consisting
of 90 % cadmium and 10 % zinc. This is the
starting material for further processing [5].
If the primary flue dust is reduced in a rotary
oven, lead and zinc remain in the oven, while
the cadmium is volatilized and enriched in the
secondary flue dust.
In the Berzelius Metal Works, Duisburg, Fed-
eral Republic of Germany, complex lead –zinc
ores are refined by the Imperial smelting pro-
cess. When the concentrate is roasted in the sin-
tering furnaces, cadmium-containing flue dust
 Cadmium and Cadmium Compounds
is produced. This is leached in an acid solution,
and the cadmium is subsequently precipitated as
cadmium carbonate. The cadmium in secondary
raw materials, such as steel mill dust, leaching
sediments, and sludge from water treatment, can
be processed at the same time. However, before
they are mixed with the concentrates they are
enriched in a rotating tube furnace (Waelz pro-
cess).
In hydrometallurgical zinc refining, the
cadmium-containing zinc concentrate is leached
with sulfuric acid. The cadmium is removed
from the solution together with copper by re-
duction with zinc dust to give a metallic sludge.
Similar cadmium sludges form in the purifica-
tion of zinc solutions used in the production of
zinc sulfide pigments or zinc carbonate. These
cadmium sludges are the most important starting
materials for cadmium refining today. The sec-
ondary starting materials mentioned above can
be added to the primary raw materials without
causing large alterations in the refining process.
Also of economic significance is the recy-
cling of used nickel – cadmium storage batter-
ies; cadmium-containing alloys, such as Sn – Cd
metallizing alloys from the manufacture of rec-
tifiers; defective industrial batches; residues
from the production of cadmium pigments; and
cadmium-containing fluorescent materials. Spe-
cial processes are usually necessary to convert
the cadmium content into a form that can be pro-
cessed normally. The most important processes
of this type are discussed in Section 2.4.6.
2.4.2. Leaching of the Starting Materials
and Cementation
Cadmium is extracted from the enriched starting
materials by oxidizing solutions. The extraction
must be carried out in such a way that all the
cadmium as well as the zinc dissolves. The pro-
cedure of Ruhr Zinc, Datteln, Federal Repub-
lic of Germany, is described here as an exam-
ple. The liquid from electrolytic baths, which
has a sulfuric acid concentration of 25 – 30 g/L,
is conveyed into 50 m3 tanks. In order to oxi-
dize the cadmium, either air is blown in or man-
ganese dioxide is added. Fresh cadmium sludge
or cadmium carbonate is added to decrease the
acidity of the solution, and a copper-containing
precipitate is removed with a filter press. Zinc,
3
cadmium, and thallium are almost completely
dissolved in the solution along with almost no
copper, cobalt, nickel, and arsenic [6].
Copper chloride mixed with other metal chlo-
rides or iron(III) chloride can be used as an oxi-
dant instead of air [7], [8]. Dust from the sinter-
ing process can also be roasted to give sulfates
and then be extracted in a similar fashion with
water [9].
Independent of the further processing of the
cadmium, it is precipitated from the solution as
a metal sponge by reduction with zinc. If neces-
sary the solution is purified first.
The cadmium raw solution resulting from the
leaching step at Ruhr Zinc contains about 30 g/L
of zinc and small amounts of cobalt, nickel, thal-
lium, and copper in addition to the 30 – 40 g/L
of cadmium. The cadmium is precipitated in a
50 m3 tank at a temperature of 60 ◦ C. In order
to avoid excess zinc in the cadmium sponge,
only 80 % of the stoichiometric amount of the
zinc is added initially. The remaining zinc dust
is added in small portions until the cadmium
concentration of the solution is below 0.1 g/L.
After decanting, the cadmium sponge is left in
the reaction container. The precipitation is car-
ried out three times, principally to reduce the
amount of zinc. After the final precipitation, the
sponge is washed, and the wash water is recy-
cled to the zinc plant. The precipitated sponge
contains 90 % cadmium and only 2.5 % zinc [6].
The procedure of the Outokumpu Zinc Works
starts with a purified cadmium solution because
of the nature of the succeeding metal recovery
(see Section 2.4.5). Copper is removed with zinc
powder, and lead is removed with barium car-
bonate. The separation of the cadmium sponge
from the solution, however, scarcely deviates
from the Ruhr Zinc processes. The greatest dif-
ference is that the cementation is interrupted at
cadmium concentrations of 3 – 5 g/L, and the so-
lution recirculated. Together with a very careful
wash, this reduces the residual content of zinc
in the compacted cadmium-sponge briquettes to
0.5 – 2.0 % [5].
2.4.3. Electrolytic Recovery
The largest amounts of cadmium are recov-
ered electrolytically. It is customary to extract
the cadmium sponge in the same tank with
4 Cadmium and Cadmium Compounds
the cadmium-containing electrolytic acid. Air is
supplied at a temperature of 80 ◦ C for 6 – 10 h.
Concentrated sulfuric acid is added to keep the
concentration of free sulfuric acid at 100 g/L.
Manganese dioxide can also be used as oxidant
[6].
The time required to dissolve the cadmium
sponge at room temperature can be reduced by
blowing air through special reactors. The rela-
tionship between solid and liquid, the amount
of air, and the pH are carefully controlled to re-
duce the time and temperature required for the
dissolution [10].
The electrolytic deposition of cadmium re-
quires that the impurities that cause problems
during the electrolysis or that are deposited as
impurity with cadmium be removed prior to
electrolysis. Traces of copper can be removed
by addition of small quantities of sodium sul-
fide in the form of copper sulfide or by cemen-
tation with zinc dust. Thallium is removed as
thallium dichromate by addition of potassium
dichromate. Thallium can also be removed as
thallium(III) hydroxide by addition of potassium
permanganate. Any arsenic is eliminated as iron
arsenate by oxidation with the potassium per-
manganate. The lead remaining in solution is
removed by adding strontium carbonate to oc-
clude lead carbonate [6].
The anode consists of lead, which does not
dissolve, and the cathode is sheet aluminum.
Today rotating cathodes, which allowed high
current density, have disappeared because cur-
rent densities of 100 A/m2 , permitting economic
electrolysis, can also be attained with fixed cath-
odes. However, the cathode deposit must be
stripped after 12-h intervals to avoid low yields
caused by short circuits between cathode and
anode. The current yield is ≈ 93 %; the energy
consumption is 1250 kWh per tonne of cadmium
cathode sheet deposited. Careful operation and
the use of hide glue and sodium silicate allow
cadmium of high purity to be produced. Typical
impurity levels in electrolytic cadmium sheet are
5 – 10 ppm Cu, 15 – 20 ppm Pb, 5 – 10 ppm Tl,
and 5 ppm Zn.
Some sheet is used as is. Otherwise, it is
melted under a cover of sodium hydroxide to
prevent oxidation and to reduce the amount of
zinc. The molten metal is poured into molds to
produce marketable shapes.
2.4.4. Distillation
After mixing with a reducing agent such as pul-
verized coke, the cadmium sponge can be bri-
quetted. The briquettes can be distilled under
atmospheric pressure to a raw metal still con-
taining thallium and zinc. These impurities can
be separated from the fused metal by addition of
ammonium chloride and caustic soda.
Distillation under reduced pressure avoids a
number of disadvantages of distillation at atmo-
spheric pressure. The differences between the
vapor pressure of cadmium and those of the
most important accompanying elements allows
Preussag (Federal Republic of Germany) to pro-
duce a 99.99 % pure metal in a single step. The
raw cadmium can contain up to 3 % lead and
thallium as well as 1 % copper [11]. Every hour,
100 kg of pure cadmium is produced at a distil-
lation pressure of 0.7 – 2.7 kPa and a tempera-
ture of 420 – 485 ◦ C. The presence of thallium,
the most volatile impurity, at a concentration ex-
ceeding 10 ppm in the distillate indicates that the
distillation is not functioning properly.
The cadmium distillation process of Hobo-
ken Overpelt, Belgium, allows the processing
of cadmium – zinc alloys containing 15 – 20 %
Zn. In a two-step distillation procedure, both
zinc and cadmium are obtained highly pure
(99.995 %) [12].
2.4.5. Other Processes
The cadmium sponge of the Outokumpu Zinc
Works contains 0.5 – 2 % zinc, 13 ppm lead, and
15 ppm copper. The briquettes pressed out of this
material are smelted with sodium hydroxide. In
seven hours 2.2 t of cadmium is obtained using a
110-kW furnace. The refined metal is drawn in
a continual casting machine to a cadmium wire,
which is then cut to rod. These cadmium rods
have a purity of at least 99.95 %; the impuri-
ties (max.) consisting of 20 ppm Cu, 10 ppm Zn,
5 ppm Tl, 5 ppm Fe, and 15 ppm Pb [5].
The removal of cadmium from solution by
ion-exchange has been described [13]. After
stripping, the cadmium is processed further by
cementation and smelting. Complexation of the
cations to give anionic cadmium species allows
selective separation of the cadmium even from
 Cadmium and Cadmium Compounds 5

copper and iron [14]. Aliphatic carboxylic acids
[15] and o-aminomethylphenols [16] selectively
extract cadmium from aqueous solution.
2.4.6. Recycling
the cadmium is distilled under a reducing atmo-
sphere at 850 ◦ C and returned to the production
department. Even sealed cells can be processed
by distillation after the plastic is destroyed by
pyrolytic pretreatment in a slightly oxidizing at-
mosphere [22].

The purpose of the recycling procedures de-

scribed here is the production of intermediate 2.5. Quality Specifications and Analysis
products – by special procedures – that can then
be fed into the normal cadmium production pro- The quality of the cadmium depends on the
cesses. production process. However, for 99.99 % cad-
The recovery of cadmium – tin alloys, about mium, the following maximum impurity levels
65 % Sn and 35 % Cd, usually begins by dissolv- are generally accepted [11]: 1 ppm Cu, 5 ppm
ing the scrap in nitric acid. The tin stays in the Pb, 5 ppm Tl, and 2 ppm Zn. For special pur-
residue as stannic acid. An impure carbonate is poses > 99.9998 % cadmium is available.
precipitated from the cadmium nitrate solution The maximum amounts of impurities and
with soda. the analysis procedures are given in ASTM C-
The residue and the rejected batches from 752. Although the classical analytical methods
the production of cadmium pigments contain- for impurities are still used, atomic absorption
ing cadmium sulfide and selenide are dissolved spectroscopy is the most common method [23].
in strongly oxidizing acid. The cadmium is re-
covered by cementation or as the carbonate. A
variation of this process is described in [17].
2.6. Uses
In order to recycle the cadmium from nickel –
cadmium batteries and similar production scrap,
Cadmium metal is used for cadmium coatings,
the parts are dissolved in agitated 2 wt % sul-
nickel – cadmium batteries, and to a limited ex-
furic acid. A reasonably good separation from
tent for reactor construction (see page 6).
the dissolved nickel can be attained by taking
advantage of the lower stability of the ammine
Electrodeposited Cadmium Coatings.
complexes of cadmium: cadmium can be pre-
Cadmium coatings are superior to other metal-
cipitated from ammonium hydroxide solution as
lic coatings because of their optimal combina-
carbonate, whereas nickel remains in solution
tion of properties: corrosion protection, ductil-
[18]. Alternatively, nickel can be extracted from
ity, frictional behavior, and soldering potential.
the ammonia solution with chelating reagents
Cadmium coatings have considerable signif-
before cadmium carbonate is precipitated [19].
icance in automotive construction, where disk
Sludge from the treatment of cadmium-
brake calipers, bearing races, screws, nuts, bolts,
containing waste water can often be injected di-
springs, tubing connectors, contacts, and steer-
rectly into the refinery process (Section 2.4.1).
ing parts are all cadmium plated. In machine
Preliminary, conventional wet chemical enrich-
construction and factory construction, the sur-
ment is possible but is usually omitted for eco-
face of fastening elements, especially screws,
nomic reasons [20]. Several methods for conver-
is coated. Although the corrosion protection is
sion of electroplating waste water to sludge not
most important, the frictional properties are also
requiring special handling can be found in [21].
important. For example, even screws that are
A plant was constructed by Sab-Nife in Swe-
extremely tight must last for years and then be
den for recycling used batteries and scrap at the
removable without difficulty. Precision screws
same location where nickel – cadmium batteries
and other connecting elements are subject to
are produced. Cadmium-containing waste and
similar requirements. In the machines of chem-
filter dust are leached with acid, and the cad-
ical plants they are subjected to corrosion in
mium is deposited by electrolysis. Used batter-
addition. Aircraft parts not made from stainless
ies are dismounted in a semiautomatic process.
steel are usually cadmium coated.
From the iron- and cadmium-containing plates,
6 Cadmium and Cadmium Compounds
For the often necessary attachment of differ-
ent metals, such as copper alloys, stainless steel,
and titanium alloys to aluminum or magnesium
alloys, cadmium coating is an absolute prereq-
uisite to avoid corrosion. Cadmium plating is of-
ten required in military procurement contracts to
ensure that the weapons and equipment function
reliably over many years.
Nickel – Cadmium Accumulators (→ Bat-
teries, Chap. 3.2.). The second most widely
used storage battery is based on cadmium and
nickel. In the charged state the negative electrode
consists of cadmium powder, and the positive
electrode consists of nickel(III) hydroxide. As
the battery discharges, cadmium hydroxide and
nickel(II) hydroxide form. Charging reestab-
lishes the original composition. The starting
material for the production of the negative elec-
trode is usually cadmium metal, which is dis-
solved in nitric acid and then precipitated as
cadmium hydroxide. In another technique, cad-
mium hydroxide is repeatedly precipitated into
the pores of sintered bodies, which become the
negative electrode. A further variation uses elec-
trodeposited cadmium powder, which is mixed
with an electrical conductor such as graphite.
A properly designed accumulating system does
not release gas, even when overcharged, and can
be sealed gastight. This development opened the
way for new applications, such as rechargeable
accumulators not larger than a single primary
cell for use in portable electronic products.
In addition to the general advantages of ac-
cumulators, nickel – cadmium cells have a long
life and are insensitive to low temperature and
storage in the uncharged condition. Nonsealed
nickel – cadmium accumulators are used in air-
planes; telephone, telegraph, and radar stations;
computer installations; and emergency power
stations. Gastight cells are used in transportable
pocket computers, razors, flashlights, etc.
Other Uses. Cadmium compounds, stabiliz-
ers for plastics, and pigments (→ Pigments, In-
organic) are generally produced from cadmium
metal. The metal is dissolved in a mineral acid,
usually sulfuric acid. Dissolution requires con-
siderable time even at high temperatures. In-
creasingly, cadmium sheets from electrodeposi-
tion are used because they, unlike metal blocks,
have a larger surface area and dissolve more
quickly. Because they do not have to be melted,
production costs are lower. In many cases, the
high purity of the sheet allows direct use of the
cadmium solution without additional purifica-
tion, especially as the noble impurities remain
as residue.
A small amount of cadmium is converted
into cadmium sulfide – copper sulfide solar
cells (→ Photoelectricity), which directly con-
vert light into electrical energy. The yield at
present is ≈ 10 %. A yield of 15 % is thought to
be attainable. It is expected that these cells can be
produced inexpensively. Other cadmium com-
pounds − cadmium telluride, cadmium selenide,
and the combination cadmium sulfide – indium
phosphide − have also been tested successfully.
The amounts of cadmium consumed for the
most important uses are given in Table 2.
3. Alloys
Numerous binary and tertiary cadmium alloys,
often with complicated phase diagrams, are
known. For practical purposes, cadmium does
not dissolve in molten iron or aluminum. A tabu-
lar summary of cadmium alloys is available [24],
and there is special literature about cadmium al-
loys [25]. A number of cadmium alloys, as a rule
produced simply by melting, are used industri-
ally. They can be divided by their principal use:
solder, electrical conductors, and other.
Solder. Cadmium forms alloys with silver,
copper, and zinc that have low melting points
and are widely applicable for the hard solder-
ing of metals. The cadmium lowers the melting
point. More than 80 % of the cadmium used in
alloys is used for this purpose.
Aluminum or aluminum alloys can be sol-
dered to copper, brass, or stainless steel by
lead alloys that contain antimony, tin, and
2.6 – 17 wt % cadmium [26], [27]. Similar al-
loys that contain between 0.6 and 60 % cad-
mium join glass and ceramics at temperatures
under 180 ◦ C [28]. For soldered connections
on gold-plated electrical conductors, cadmium-
containing zinc – lead – indium alloys are rec-
ommended [29], [30]. Occupational-medicine
aspects of cadmium-containing soldering are
treated in [31].
 Cadmium and Cadmium Compounds
Electrical Contacts and Conducting Wire.
The addition of cadmium or cadmium oxide to
silver, often the contact material in electrical
switches, reduces the metal loss due to sparking.
In addition, the welding tendency is decreased.
Cadmium (0.8 – 1 wt %) improves the mechan-
ical properties of copper wire without reducing
its electrical conductivity. This is especially use-
ful in the case of the overhead wires supplying
power to electrically powered locomotives [32],
[33].
Other Alloys. Cadmium is a component of a
few bearing alloys based on tin, copper, and alu-
minum, usually in amounts under 1 %. Wood’s
alloy and Lipowitz’s alloy, which contain be-
tween 6 and 14 % Cd, are used as fusible alloys
in automatic fire-protection sprinklers and other
devices. Cadmium in the form of a 5 % alloy
with silver and indium is put to use in the con-
trol rods of nuclear reactors because 113 Cd has
a particularly large neutron capture cross sec-
tion. A cadmium – selenium – indium alloy is an
important component of a white-light laser for
optical data processing systems [25].
4. Cadmium Compounds and
Complexes
4.1. Properties
Generally water-soluble cadmium compounds
are colorless. Aluminum and zinc can be used
to precipitate cadmium metal from solutions of
cadmium salts. From weakly acid or neutral so-
lutions, cadmium sulfide is precipitated by hy-
drogen sulfide, sodium sulfide, and sodium hy-
drogensulfides. The temperature, concentration,
and presence or absence of Cl− determine the
color of the precipitate: lemon yellow, orange,
or even red. Sodium selenide precipitates black
cadmium selenide. Mixed precipitates of cad-
mium sulfide and cadmium selenide are brown.
Sodium hydroxide gives white cadmium hy-
droxide, which is insoluble in excess hydrox-
ide. The precipitate formed by ammonia redis-
solves in excess reagent to form the complex
[Cd(NH3 )6 ]2+ . This complex also forms when
ammonia is added to precipitates such as the hy-
droxide or oxalate. Sodium carbonate produces
7
insoluble cadmium carbonate. Sodium cyanide
reacts with aqueous cadmium solutions to give
cadmium cyanide, which redissolves in excess
reagent to form [Cd(CN)4 ]2− . This complex is
weak enough that the cadmium can be com-
pletely precipitated with hydrogen sulfide. Cad-
mium solutions react with hexacyanoferrate(II)
to give a white precipitate, whereas they react
with hexacyanoferrate(III) to give a yellow pre-
cipitate. Cadmium sulfite is only slightly solu-
ble and can be precipitated from cadmium solu-
tion with sodium sulfite. All insoluble cadmium
compounds can be dissolved in mineral acids.
A few cadmium compounds fluoresce or phos-
phoresce, the silicate yellow to rose, the borate
rose. Silver- or copper-activated cadmium – zinc
sulfide gives colors spread over the entire spec-
trum.
4.2. Individual Compounds
The properties and uses of numerous cadmium
compounds are described in [24]. The following
text is limited to the most important industrial
cadmium compounds.
Cadmium oxide [1306-19-0] , CdO, M r
128.41. The amorphous formis yellow red,
brown red, or brown black, the color depend-
ing on the particle size and the stoichiometry.
It has a density of 6.95 g/cm3 . The amorphous
oxide is insoluble in water and bases but is read-
ily soluble in dilute acids, ammonia, ammonium
salt solutions, and sodium cyanide solutions.
The lustrous black cubic crystals of cadmium
oxide have a density of 8.15 g/cm3 . They sub-
lime at ≈ 700 ◦ C. The low specific resistance at
0 ◦ C, 5.5 × 10−3 Ω cm, is caused by an excess of
Cd2+ ions, which makes CdO a semiconductor.
Cadmium oxide is produced by evaporation
of cadmium metal and oxidation of the vapor. It
can also be obtained by thermal decomposition
of cadmium nitrate or carbonate or by oxidation
of molten cadmium by an oxidizing agent. Com-
mercial cadmium oxide should be completely
soluble in sodium cyanide solution and contain
no heavy-metal or sulfur impurities.
Cadmium oxide is used as a catalyst in
oxidation – reduction reactions, dehydrogena-
tion, cleavage, polymerization, the production of
multiply unsaturated alcohols, hydrogenation of
8 Cadmium and Cadmium Compounds
unsaturated fatty acids, and as a mixed catalyst
component to produce methanol from carbon
monoxide and water. Further uses include resis-
tant enamels, metal coatings for plastics, heat-
resistant plastics, selenium ruby glass, starting
material for other cadmium compounds, and sta-
bilizers for poly(vinyl chloride). Cadmium ox-
ide combined with an alkali-metal cyanide is the
salt mixture used in the baths for cadmium elec-
troplating. Cadmium oxide is a component of
batteries. It is temperature resistant and together
with silver useful in heavy-duty electrical con-
tacts. Cadmium oxide improves the behavior of
some high-temperature plastics.
Cadmium hydroxide [21041-95-2] ,
Cd(OH)2 , M r 146.43, isa colorless powder with
a hexagonal, layered lattice. The precipitation of
fine-grained cadmium hydroxide is only possi-
ble from nitric acid solution, basic salts often re-
sulting from precipitation from other solutions.
In the presence of halogenide ions, X− , the
complex [CdX4 ]2− forms. In fact, precipitation
of Cd (OH)2 can be prevented by a high con-
centration of alkali-metal chloride. Cadmium
hydroxide is a component of cadmium – nickel
accumulators and silver – cadmium batteries.
Cadmium hydroxide often replaces the oxide as
the starting material for other cadmium com-
pounds.
Cadmium carbonate [513-78-0] , CdCO3 ,
M r 172.42, has a density of 5.3 g/cm3 . (The den-
sity of CdCO3 · H2 O is 4.3 g/cm3 .) The white
crystalline powder with an orthorhombic lattice
of the calcite type decomposes above 360 ◦ C.
Often precipitation with sodium carbonate pro-
duces hydroxy products, which contain water
difficult to remove. Cadmium carbonate is a
starting material for the production of cadmium
pigments and other cadmium salts.
Cadmium chloride [10108-64-2] , CdCl2 ,
M r 183.32, has a density of 4.05 g/cm3 . The
colorless, lustrous orthorhombic crystals, which
melt at 568 ◦ C to a liquid that boils at 967 ◦ C,
are slightly soluble in water. The hydrates are
CdCl2 · H2 O, CdCl2 · 21/2 H2 O, and CdCl2 ·
4 H2 O. Cadmium chloride is produced by re-
action of molten cadmium and chlorine gas at
600 ◦ C or by dissolving cadmium metal or the
oxide in hydrochloric acid, subsequently vapor-
izing the solution. The salt is used in electro-
plating. An aqueous solution absorbs hydrogen
sulfide. Molten cadmium chloride dissolves cad-
mium metal. Upon cooling, the metal precipi-
tates.
The significance of cadmium chloride as
a commercial product is declining. It occurs,
however, as an intermediate in the produc-
tion of cadmium-containing stabilizers and pig-
ments, which are often obtained from a cadmium
chloride solution itself obtained from cadmium
metal, oxide, hydroxide, or carbonate.
Cadmium nitrate tetrahydrate
[10325-94-7] , Cd(NO3 )2 · 4 H2 O, M r 308.49,
has a density of 2.46 g/cm3 . The small colorless
deliquescing crystals readily dissolve in water.
They have a mp of 59.9 ◦ C, and the liquid has
a bp of 132 ◦ C. There are three hydrates, in-
cluding the tetrahydrate, and the anhydrous salt
(stability ranges):
Cd(NO3 )2 · 9 H2 O (−16 to 3.5 ◦ C)
Cd(NO3 )2 · 4 H2 O (3.5 to 48.7 ◦ C)
Cd(NO3 )2 · 2 H2 O (48.7 to 56.8 ◦ C)
Cd(NO3 )2 (> 56.8 ◦ C)
Cadmium nitrate is produced by dissolving
cadmium metal in nitric acid, purifying if neces-
sary, concentrating, and crystallizing. It is used
for the production of red lusters in glass and
porcelain and in cadmium – nickel sinter plates
of storage batteries.
Cadmium sulfate [10124-36-4] , CdSO4 ,
M r 208.46, 4.7 g/cm3 . The melting point of the
anhydrous salt is 1000 ◦ C. Anhydrous cadmium
sulfate is produced by melting cadmium with
ammonium or sodium peroxodisulfate. A satu-
rated aqueous solution contains 76 g CdSO4 per
100 g of water at 0 ◦ C, 77.2 g at 20 ◦ C, 69.4 g at
74.5 ◦ C, and 58.0 g at 100 ◦ C.
CdSO4 · 8/3 H2 O [7790-84-3], M r 256.52, 
3.09 g/cm3 . The colorless monoclinic crystals,
which effloresce in air, are soluble in water (see
above). This hydrate melts at 41.5 ◦ C in its own
water of crystallization, converting to the mono-
hydrate.
Cadmium sulfate monohydrate [13477-20-8],
CdSO4 · H2 O, M r 226.48,  3.79 g/cm3 , which
is the form usually marketed, is produced by
evaporating a cadmium sulfate solution above
41.5 ◦ C.
 Cadmium and Cadmium Compounds
Cadmium sulfate is used in electroplating and
as a starting material for pigments, stabilizers,
and other cadmium compounds that can be pre-
cipitated from aqueous solution. It is used to
produce fluorescent materials and in analysis.
A cadmium sulfate solution is a component of
the Weston cell, which has an almost constant
voltage of 1.0186 V.
Cadmium cyanide [542-83-6] , Cd(CN)2 ,
M r 164.448,  2.226 g/cm3 , is cubic and
isostructural with Zn(CN)2 . The solubility in
water is 17 g per liter at 15 ◦ C. The solubility in
sodium cyanide solution is greater because tri-
cyanocadmium ions, Cd(CN)− 3 , form. Cadmium
cyanide is produced from dilute cyanic acid and
cadmium hydroxide by evaporation or by precip-
itation from a concentrated solution of cadmium
salt and alkali-metal cyanide. Cadmium cyanide
and its mixtures with an alkali-metal cyanide are
used in electroplating. Cadmium cyanide baths
for the electroplating of cadmium metal coat-
ings have the advantage that they are easy to
work with. Metal removed from the solution as
electroplate is replaced by dissolution of the cad-
mium anode. These cadmium anodes should be
at least 99.95 % pure.
4.3. Storage and Transportation
The labeling for transport of cadmium com-
pounds in the Federal Republic of Germany and
the European Economic Community are similar
[34], [35]. The rules specify the use of certain
symbols and directions for safety precautions.
The international provisions for sea and air trans-
port have been made compatible in 1984 [36],
[37], although special regulations for individual
lands are often still very different. Frequently
there are even different provisions for the vari-
ous types of transportation or routes.
5. Environmental Protection
Cadmium has been ubiquitously distributed in
the natural environment for millions of years,
and information about this natural distribution in
soil and water can be found in general literature,
e.g., [24]. Industrial production of cadmium has
affected the total distribution in soil and water
9
only insignificantly, although in some restricted
areas environmental problems have developed.
More than 90 % of the total nonsmoker intake
of cadmium is reported to be through food (see
Chap. 7). All sources of cadmium that contami-
nate cultivated soil, whether by air, fertilizer, or
water, should be reduced as much as possible.
Cases of cadmium poisoning caused by the
contamination of the environment are described
in page 15.
5.1. Emission
Cadmium emission in the Federal Republic of
Germany is given in Table 1. Summaries for
the United Kingdom [38], the European Eco-
nomic Community [39], and the United States
[40] are difficult to compare because different
parameters have been selected. However, this
literature cites its sources, so comparison based
on tabulations in these sources is possible. Data
about industrial emission in the European Eco-
nomic Community and extensive discussion of
the technologies to reduce emissions have been
collected [41].
5.2. Waste Water
Cadmium ions are normally separated from
sewage by precipitation with an alkali-metal
hydroxide or carbonate, with subsequent sep-
aration of the sediment. The required limit of
1 mg/L, however, is only attainable when the
pH is adjusted to 9.5 or higher, and the pre-
cipitate is thoroughly separated from the solu-
tion. New regulations go even further and the
“Cadmium Guidelines” for the European Eco-
nomic Community require concentration lim-
its of 0.3 – 0.5 mg/L after 1986 and
0.2 mg/L
after 1989 [42]. These limits can only be met
by manufacturers and consumers with special
methods [41]. Especially useful for producers
of cadmium and cadmium compounds are the
coprecipitation of cadmium in so-called collec-
tors and subsequent filtration or special treat-
ment during production and before combination
with cadmium-free waste water. In special cases,
ion exchange, precipitation, for example, with a
sulfide compound, or electrolytic separation is
10 Cadmium and Cadmium Compounds
Table 1. Cadmium emission in the Federal Republic of Germany
Source (Year)
Production of Cd metal and
recycling (1980)
Pigments (1980)
Stabilizers (1980)
Electroplating (1981)
Batteries (1982)
Alloys (1982)
Glass (1982)
Fossile fuels (1982)<
Iron and steel (1982)
Cement (1982)
Fertilizer (1982)
Waste-water sludge (1982)
Man-made deposits (1982)
Waste burning (1982)
Automobile exhaust (1982)
Total, max.
∗ Maximum.
∗∗ Forty percent of the 1.8 × 10−6 t of waste water sludge produced each year, or 0.72 × 10−6 t, is used agriculturally. If the sludge
contains, on the average, 5 ppm Cd, this corresponds to the minimum estimate, 3.6 t Cd. Twenty ppm corresponds to the maximum
estimate, 14.4 t Cd.
used. Clearly the most important factor is the re-
duction of the amount of cadmium carried into
the waste water. Consequently the guidelines of
the European Community concentrate on reduc-
tion of the amount of cadmium in waste water.
The constant tightening of the standards for
waste water purification is intended to prevent
excessive concentrations of cadmium in the
sludge produced in biological waste-water treat-
ment. When the concentration of heavy metals
is too high, the sludge can no longer be used
in agriculture. In the Federal Republic of Ger-
many, maximum cadmium content in sludge is
restricted to 20 mg per kilogram of dry waste,
along with a limitation on the total amount of
waste [43]. Similar requirements are in prepara-
tion for the European Economic Community.
5.3. Air
Practically all cadmium emission sources are in
the form of the oxide because this compound is
formed in pyrometallurgical production, high-
temperature processing, and combustion, either
directly or via the metal. Initially the oxide is
finely divided, but these fine particles can be
made to agglomerate into coarse grains in suit-
able apparatus. However, this specialized appa-
ratus is often not practical, and other methods,
Emission, t/a
Air Soil Water Total ∗
5–7 − 62 69
0.17 − 1.2 1.4
0.05 − 0.18 0.23
− − 0.7 0.7
0.31 − 0.9 1.2
0.5 − − 0.5
3 − − 3
5 − − 5
5 − − 5
0.3 − − 0.3
− 35 0.5 35
0.1 3.6 – 14.4 ∗∗ − 14
− − − −
2.9 – 3.8 − − 3.8
< 0.5 − < 0.5 1.0
26 49 66 140
which also work well enough with fine particles,
must be used. The laws vary from land to land.
In TA-Luft (Technical Regulations for Air) the
Federal Republic of Germany requires that not
more than 0.2 mg Cd per m3 of air be released.
Larger gas effluents are usually subject to an
electrostatic purification, for example, the re-
moval of particles from gas exhausts of power
plants and garbage disposal plants. For low cad-
mium contents this separation suffices. For high
cadmium concentrations filtration is used. The
filters can be made from metal screen, ceramic,
or a variety of textiles. Regulations and gas re-
lease must be carefully adapted to conditions.
Washing, especially with Demisters, has proved
useful for removal of water-soluble aerosols
[44].
5.4. Soil
Cadmium reaches agricultural soil via airborne
particles; wastes, particularly sludge; and phos-
phate fertilizers. The importance of these three
has been summarized and described for the Fed-
eral Republic of Germany [45].
The normal content of an agricultural field
lies between 0.1 and 1 mg Cd per kilogram of soil
(0.1 – 1 ppm). Maximum 3 ppm in a 30-cm layer
 Cadmium and Cadmium Compounds
of top soil is thought allowable, corresponding
to 13.5 kg/ha. The contribution to this reservoir
per year is 7 g/ha from the air and 6 g/ha from
phosphate fertilizer. The removal by harvest is
about 4 g/ha. The annual increase is then 9 g/ha.
This means that a soil with a content of 4.5 kg/ha,
corresponding to 1 ppm, would reach the upper
limit after 1000 years.
A number of studies deal with the disposal of
sludge [46]. Even then there are still 265 years
until the upper limit is reached; therefore, there is
time to solve the problem of cadmium emissions.
The national regulations for the production of
waste-water sediment are tabulated in [47].
However, there are already problems associ-
ated with excessive cadmium contents in soil on
the grounds of old mining and smelting plants.
In the immediate vicinity of the sources of emis-
sion, the amount of cadmium in the soil exceeds
that thought allowable. Here the use of the adja-
cent agricultural land must be limited, but there
is no large-scale danger. Apparently man-made
waste deposits do not create a cadmium source
for plants since transfer of cadmium to the soil
does not take place.
In addition to concern about the amounts of
cadmium [48], the complicated mechanism of
transfer from the soil to the plant must be con-
sidered. A transport model, from soil into the
plant, has been proposed [39].
6. Economic Aspects
Since 1970 the production of the non-
communist countries has remained rather con-
stant, 12 – 15 kt/a. The increase in European pro-
duction was balanced by the decrease in North
America. Consumption has remained in equilib-
rium with production. The amounts of cadmium
for various uses have varied since 1970, affected
by technical, economic, and environmental fac-
tors [49]. The cadmium price from 1970 to the
beginning of the 1980s varied strongly, from
$ 0.50 to $ 4 per pound. The consumption in the
Western world between 1970 and 1982 is tab-
ulated in Table 2. The figures are totals of the
published statistics for the Federal Republic of
Germany, Japan, the United Kingdom, and the
United States, which together account for about
two thirds of non-communist consumption.
11
7. Toxicology and
Occupational Health
For more than a century there have been many
reports on acute poisoning caused by cadmium
compounds. Cadmium uptake occurred either
via inhalation during occupational exposures
or by oral poisoning due to ingestion of con-
taminated food or beverages [50]. In 1974 it
was established [51] that long-term inhalation
of cadmium oxide dust could cause a syndrome
characterized by damage to the pulmonary and
renal systems. Since then many studies have
been made in various countries, establishing that
occupational exposure to cadmium compounds
can cause adverse effects, especially in the kid-
neys.
During the last decades it was also recognized
that cadmium can cause renal effects in the gen-
eral population. In Japan, a large population is
exposed to cadmium via food, especially rice; in
one area this resulted in an epidemic of chronic
cadmium poisoning with severe bone damage,
called Itai-Itai disease.
Whereas the exposure levels were reduced
considerably in many industries, there is a grow-
ing concern about risks for the general popula-
tion around the world. This is not only caused
by emissions from industry. Waste disposal, es-
pecially by incineration, the increasing use of
phosphate fertilizers, and pH changes in soil and
water caused by acid rain are other factors of
concern. For more detailed information on dif-
ferent aspects of occurrence, metabolism, and
effects of cadmium, see [50], [52–56].
Exposure Levels. The average normal daily
intake via food is 10 – 20 µg in most countries;
considerably higher values, from 30 to above
200 µg/d, have been reported from certain areas
in Japan [50], [52], [54], [55]. The highest cad-
mium concentrations are found in some basic
foodstuffs such as wheat and rice and in liver,
kidney, and certain seafoods. Drinking water
generally is a minor source. Atmospheric levels
of cadmium in rural areas are less than 1 ng/m3 ,
in urban areas 1 – 10 ng/m3 , and in certain indus-
trialized areas a yearly average of up to 50 ng/m3
has been found [50]. Atmospheric exposure to
cadmium therefore is of minor importance.
12 Cadmium and Cadmium Compounds
Table 2. Consumption of cadmium, t
Use 1970 1973
Plating 3096 3273
Batteries 680 1580
Pigments 2021 3231
Stabilizers 1947 1892
Alloys 642 877
Total 8386 10853
Tobacco may contain 1 – 2 µg Cd per gram,
and smoking twenty cigarettes a day has been es-
timated to result in an inhalation of about 3 µg.
Because a large part of that dose will be ab-
sorbed, exposure via cigarette smoking may con-
tribute to the internal dose as much as that ab-
sorbed from food [50], [52], [55].
Metabolism. In order to understand the tox-
icity of cadmium some basic facts about the
metabolism of this metal must be known.
The fate of inhaled cadmium compounds de-
pends on particle size and solubility. Finely di-
vided cadmium oxides, especially fumes, de-
posit in the lower respiratory tract; because of
their relatively high solubility about 30 % of the
inhaled amount is absorbed. Cadmium sulfide
and sulfoselenide are relatively slightly soluble,
and they are not absorbed to the same extent.
(Mucociliary transport to the gut occurs, but the
absorption from the gut probably is only a few
percent.)
Ingested cadmium generally is absorbed to
a few percent [50], [57]. Nutritional deficien-
cies, e.g., in iron and calcium, will cause higher
absorption. Women with severe iron depletion
absorbed up to 20 % of the cadmium ingested
orally [57].
Cadmium absorbed from the lungs or the gut
initially is stored mainly in the liver. Exposure
to cadmium induces the synthesis of metalloth-
ionein, a low molecular mass, cysteine-rich pro-
tein, which strongly binds cadmium but also zinc
and copper [58]. The liver has a high capacity
to synthesize this protein, and even at very high
exposures most of the cadmium in the liver will
be bound to metallothionein. The protein breaks
down relatively fast, but continuous synthesis
ensures that cadmium does not escape to bind to
other structures.
In the blood, cadmium is found in the cells
and plasma, the concentrations being approx-
1976 1979 1982
3578 3326 2205
2106 2202 2180
2466 2578 1819
1195 1184 947
519 400 488
9864 9690 7639
imately equal. However, with increasing cad-
mium levels in the body more cadmium will be
found in the cells. In the red blood cells cad-
mium is bound to several proteins, a major part
to metallothionein. In plasma only a minor part
is bound to metallothionein. Plasma metalloth-
ionein easily passes the glomeruli, and as a pro-
tein it will be reabsorbed in the proximal tubules.
In the kidneys the protein then breaks down, and
cadmium is released. The kidney can also syn-
thesize metallothionein, which ensures that cad-
mium is trapped in an inert form. However, when
the synthesizing capacity is exceeded, cadmium
ions will be released and toxic effects may occur.
The cadmium excretion from the kidney is
very small. Long retention times in liver and kid-
ney, as well as in other tissue, lead to an accumu-
lation of cadmium in the kidneys from birth to
middle age. The newborn is virtually free from
cadmium because the placenta is an efficient bar-
rier. The gross biological half-life of cadmium in
the body has been estimated to be about twenty
years [50].
The average cadmium concentration in the
liver of adults is about 1 mg/kg wet weight;
the concentration in the renal cortex is about
20 mg/kg in most European countries and in
North America [55], [56], [59]. In Belgium
higher concentrations, on the average 40 mg/kg
in renal cortex, have been reported [60]. The
highest concentrations in members of the gen-
eral population have been found in Japan [55],
[56], [59], [60].
Smokers generally have about twice as high
cadmium concentrations in the renal cortex
(about 25 mg/kg wet weight) as compared with
nonsmokers [59], [60].
In the blood the cadmium concentrations
in nonsmokers are generally less than 1 µg/L,
whereas smokers have up to 5 µg/L [60]. The
difference between smokers and nonsmokers is
also obvious in the urine. Nonsmokers in Eu-
 Cadmium and Cadmium Compounds 13

rope and North America excrete about 0.4 µg/g in the 1940s [51], [64]. It has been concluded
creatinine, whereas smokers excrete about twice that to prevent any pulmonary effect of cadmium
as much [59], [61]. This urinary excretion is re- the time-weighted average concentration of res-
lated to the level of cadmium in the body and pirable dust in air should not exceed 20 µg/m3
is useful for monitoring general populations as [53].
well as most persons that are occupationally ex-
posed to cadmium. The total body burden in
adult nonsmokers generally is less than 10 mg
[59], whereas that of the newborn is only a few
micrograms.

Acute Toxicity. Acute cadmium poisoning

by inhalation has mainly been caused by acci-
dental exposure to cadmium fumes. The highest
risk is in welding, cutting, or soldering oper-
ations when cadmium-containing materials are
treated, especially if the worker is unaware cad-
mium is present. There may be a latent period of Figure 2. Concentration of cadmium in workroom air from
1946 to 1977
up to 24 h after exposure before symptoms oc- Arithmetic means of personal and stationary samples were
cur. Chemical pneumonitis occurs, which may obtained within seven subperiods. Data covering period IV,
lead to lung edema and general symptoms, in 1961 – 1964, are not available.
some cases with lethal outcome [50], [55], [62],
The critical effect of cadmium is renal tubu-
[63].
lar dysfunction. In 1950 it was discovered that
The concentration of cadmium in the air has
workers exposed to cadmium oxide dust in an al-
not been measured at the time of accidents.
kaline battery factory had an unusual type of pro-
Based on cadmium analysis of lung tissue from
teinuria [51]. The majority of the proteins were
people dying after acute exposure it has been
of low molecular mass. Studies of renal func-
estimated that the lethal dose corresponds to
tion showed that the glomerular filtration rate
1 mg/m3 as cadmium fume for eight hours. Con-
and the concentrating capacity were decreased.
centrations of 0.5 – 1 mg Cd/m3 for a couple of
The proteinuria in chronic cadmium poisoning
hours may cause pneumonitis [53]. A short-term
is a tubular proteinuria, caused by a decrease in
exposure limit for cadmium oxide fumes and
the reabsorption of filtered plasma proteins in
respirable dust of 0.25 mg Cd/m3 has been rec-
the proximal tubules [50].
ommended to prevent acute lung reactions [53].
The urinary excretion of protein was found
Single oral doses of about 10 – 15 mg may
to be related to exposure time [65]. The critical
cause gastrointestinal disturbances, but the
cadmium concentration in renal cortex was es-
lethal dose is probably several hundreds of mil-
timated to be 200 mg/kg wet weight [50]. This
ligrams [53], [55].
value was confirmed by further studies [66–68]
and is to be compared with the normal concentra-
Chronic Toxicity. The chronic effects after
tions reported in the previous section. A critical
long-term inhalation are mainly seen in lungs
urine concentration of about 10 µg of cadmium
and kidneys [50], [51], [55]. In earlier times ane-
per gram of creatinine has also been established,
mia, anosmia, and yellow lines on the teeth were
which generally is a good indicator of the body
common among cadmium workers but are un-
burden [50], [67–69].
common today. Emphysema was a major find-
The best dose – response relationship seems
ing in some earlier studies involving exposure
to be between cadmium concentration in the
to cadmium oxide fume and dust [50]. Because
liver, determined by in vivo neutron activation,
of the decrease in exposure, lung dysfunction is
and the degree of tubular dysfunction [67]. At
nowadays rare, and if it occurs the symptoms
liver concentrations above 30 mg/kg wet weight
are mild. Figure 2 shows how air concentrations
proteinuria appeared; this corresponds to a cad-
of cadmium have decreased during the years in
a Swedish factory, where emphysema was seen
14 Cadmium and Cadmium Compounds

mium concentration in renal cortex of about blood levels vary greatly. This is most obvious
200 mg/kg. with smokers. The natural cadmium content of
The increased excretion of low molecular cigarettes does not explain this finding, which
mass proteins is regarded as the first sign of renal is caused instead by contamination of cigarettes
tubular effects caused by cadmium. This is also or pipe tobacco during work and poor personal
consistent with the fact that cadmium primar- hygiene, as illustrated in Figure 4 [64].
ily is deposited in the proximal tubules, because
the cadmium-containing metallothionein is re-
absorbed.
At this early stage there are no measurable
changes in the excretion of other substances.
However, if exposure goes on and the renal lev-
els increase, other functions may be disturbed. In
advanced cases of chronic cadmium poisoning
the excretion of glucose, amino acids, and phos-
phate is increased (Fanconi syndrome). Distur-
bances in mineral metabolism may cause the for-
mation of renal stones. For detailed discussion,
see [70], [71].
The diagnosis of chronic cadmium poison-
ing must be based on occupational history, ex- Figure 3. Cadmium in blood vs. cadmium in air
posure levels in air, levels of cadmium in blood Arithmetic means of 4 – 5 samples of blood cadmium and
9 – 11 personal samples of airborne cadmium dust for 17
and urine, and protein analysis in urine. alkaline battery workers. Smokers are represented by the
The tubular damage is irreversible, and pre- solid circles; nonsmokers, by open circles.
vention is thus more important than diagnosis.
The determination of cadmium in whole blood
gives information about recent exposure, but is
not always a good indicator of the body burden
or risk for renal dysfunction, especially in smok-
ers. Cadmium in urine should be used to moni-
tor this risk. As long as the urinary excretion of
cadmium is below 5 µg per gram of creatinine
there should be no risk for the kidneys. At con-
centrations of 5 – 10 µg per gram of creatinine,
exposure should be minimized to prevent further
accumulation in the kidneys.
Monitoring is also necessary after exposure
has ceased. Intensive exposure during relatively
short periods may lead to a high cadmium con-
centration in the liver. Cadmium will then be Figure 4. Cadmium in blood in relation to the personal hy-
released from the liver and transported to the giene score
kidneys for a long time. The renal concentra- Arithmetic means of five samples of cadmium in blood from
tions may reach a critical level many years after nine smokers (solid circles) and of 4 – 5 samples from nine
the last exposure. nonsmokers (open circles).
The concentration of cadmium in air is sel- Therefore, it is imperative to prevent smok-
dom of help in evaluating risks. The long bi- ing in the workshops and the carrying of tobacco
ological half-life of cadmium will lead to a in work clothes; such measures will have much
continuous increase in renal levels over many more impact than small reductions of cadmium
years, and past exposure often is more important concentrations in air. Dust accumulation must
than present exposure. Changes in workplace be prevented in the workshop to minimize ex-
exposure during several decades are shown in posure caused by contamination of work clothes
Figure 2. Figure 3 demonstrates that cadmium
 Cadmium and Cadmium Compounds
and hand-to-mouth transfer. The latter may lead
to considerable gastrointestinal exposure [72].
The threshold limits for cadmium in air differ
among countries, varying from 10 µg Cd/m3 in
Finland to 100 µg/m3 (total dust) in East Euro-
pean countries. The low values, 10 –20 µg/m3 ,
should prevent renal damage, but as indicated
above, smoking and poor personal hygiene may
increase the internal exposure.
Carcinogenicity. Cadmium has been impli-
cated as a carcinogenic agent, especially with
regard to cancer of the prostate. The evidence
is weak and based on deaths from cancer of the
prostate. However, this cancer is extremely com-
mon among elderly men, and it often does not
give any symptoms [73], [74]. There is therefore
no evidence that cadmium induces this cancer;
diet and hormonal factors are more important
determinants. However, it cannot be excluded
that in heavily exposed workers cadmium might
have affected zinc metabolism in the prostate or
caused hormonal changes. It is extremely un-
likely that low exposures will have any effect on
the prostatic function.
According to animal experiments long-term
exposure to cadmium chloride aerosols causes
lung cancer in rats [75]. The concentrations
of cadmium in air were relatively low, 12.5 –
50 µg/m3 , but exposures were for 23 h a day.
Humans are generally not exposed to cadmium
chloride. In the Federal Republic of Germany
cadmium chloride has been listed as a carcin-
ogen. There have been a number of studies on
the occurrence of lung cancer among workers
exposed to cadmium oxide dust, but there are
no conclusive results indicating that cadmium
oxide causes lung cancer in humans [73].
Poisoning from Contamination of the Gen-
eral Environment. Contamination of the gen-
eral environment has caused cadmium poisoning
in certain areas of Japan [64]. Cadmium levels in
rice caused daily intakes of several hundreds of
micrograms, which should be compared to the
“normal” intake of 10 – 20 µg in most countries
in Europe and North America. The exposure in
Japan has caused renal tubular dysfunction of the
same type as described in the section on chronic
toxicity (page 13). In one area in the Toyama
prefecture the cadmium exposure resulted in the
development of severe bone damage, Itai-Itai
15
disease. Mainly multiparous women above 40
years of age were affected. The males in the
area had tubular dysfunction but generally did
not develop the bone disease. The women had
poor nutritional status with deficient intakes of
calcium, vitamin D, and protein, probably also
of iron. Cadmium alone can hardly cause such
severe bone changes, but combined with severe
calcium deficiency the result became disastrous.
It is not likely that Itai-Itai disease will occur
again, but as mentioned tubular dysfunction is
common in several other areas of Japan.
There are some contaminated areas in Eu-
rope, where signs of renal disease have been
sought [76], [77]. No definite conclusions can
yet be drawn, but the investigated populations
had higher cadmium levels than generally found
in Europe [77], [78].
Most domestic animals are not at risk for
cadmium poisoning. An exception is the horse.
Adult horses generally have about five times
higher cadmium concentrations in the renal cor-
tex than adult humans in the same area [79].
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