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Copper Compounds Toxicology
- Introduction :
metal is red, brownish, ductile and malleable, and has
excellent electrical and thermal conductivity. Copper
is an essential element; it is transported in the
serum linked to ceruloplasmin.
compounds used by potters are :
- -black copper oxide,
- -basic copper carbonate,
- -copper sulfate pentahydrate.
- Sources and Production
- I-Chemical Forms :
- Copper forms two (2) series of
- copper (I) (cuprous) and copper (II)
- Metallic copper is fairly resistant to
corrosion and is not attacked by dry air, water, or
- Copper I oxide (Cu2O) occurs naturally
as the reddish mineral cuprite.
- Copper II oxide is black and is
obtained by heating copper metal in air.
moist air, copper becomes coated with green basic
- II-Uses and Sources of Exposure
- Copper was the first metal used by
humans and appears to have been discovered on the
island of Cyprus around 2500 BC.
- Copper salts have been used
therapeutically for more than 2,000 years, copper
sulfate has clinically been used as an emetic, and it
was also a popular murder weapon and abortifacient in
France in the 19TH century.
- Chile, the USA, Canada, and Russia are
the principal producers.
ores of copper are concentrated by a flotation process
and then are refined. Smelting consists of applying
sufficient heat to concentrate the metal and fuse
remaining gangue (waste ore) into slag.
- A-Uses :
- Copper is used :
- - in
the production of a large variety of alloys having
multiple applications ;
- · brass: contains mainly copper
- · bronze: contains mainly copper
- · various alloys with silver,
cadmium, beryllium, nickel...
- - in
the electrical industry;
- - in
the construction industry: gas lines...
- - in
pigments such as emerald green, in ceramic glazes, and
salt in the lithographic process.
pesticides (seeds and vineyards) in the form of salts,
like the Bordeaux solution based
- -copper sulfate is also used in the
whitewashing and leather industry.
- B-Environmental exposure :
occurs primarily from ingestion of drinking water with
high copper concentrations and accidental or
intentional ingestion of copper salts.
- Clinical Toxicology :
- I-Routes of exposure :
- Copper is an essential element in
mammalian systems. Ilness occurs when diet is
deficient or intake is excessive.
principal route of exposure is through ingestion, but
inhalation of copper dust and fumes occurs in
- Toxicity has resulted from treatment
of burns using topical copper compounds.
- Copper has been reported to be
absorbed internally from prostheses, intrauterine
devices, hemodialysis units using copper-containing
equipment, and copper azide impregnation of the skin
after an explosion.
- II-Absorption, Metabolism, and
- A-Absorption :
daily copper requirement has been estimated at 30
micrograms/kg of body weight for an adult. After
ingestion, maximum absorption of copper occurs in the
stomach and jejunum.
- Copper is bound initially in the serum
to albumin and transcuprein, then later is bound more
firmly to ceruloplasmin, which binds more than 75% of
- Absorption is increased in copper
deficiency and is impaired in small-bowel
- Copper is distributed throughout the
body but is stored primarily in liver, muscle, and
normal concentration of copper in blood plasma is 1
all mammals, copper is an essential trace element
involved in :
- -fundamental cellular
- -connective tissue synthesis,
- B-Metabolism :
- Absorbed copper is initially bound to
albumin and is transported from the gastrointestinal
tract to the liver where it is transferred to
- Urinary excretion is enhanced by
increased molybdenum intake, cirrhosis, and biliary
- C-Elimination :
- Copper is eliminated principally
through the feces after excretion into the bile.
Urinary excretion of copper is low in humans.
- Healthy adults have urinary
concentrations of less than 100µg per 24
- III-Symptoms and Clinical Signs
- A-Acute Toxicity :
- 1-Gastrointestinal Tract :
- Because copper is an essential
element, toxicity is uncommon, as with all essential
reports of acute toxicity are from suicidal attempts
from ingesting copper sulfate. However, death is rare,
owing to copper sulfate's emetic properties :
- a-Mild forms
forms of poisoning produce only :
have been described in patients poisoned by eating or
drinking from copper-containing vessels or from a
- b-Severe poisoning :
- Copper sulfate ingestion produces a
severe inflammation of the gastrointestinal tract, an
amount of 10 g of the sulfate is sufficient to cause
these gastrointestinal symptoms :
the following are encountered :
- -liver and kidney necrosis.
- Patients who developed intense
jaundice from liver centrolobular necrosis after
massive acute copper sulfate poisonning had a more
fulminant course than did patients with milder
jaundice from intravascular hemolysis.
oxydule or the basic carbonate can also cause the
intoxication at the same dose.
ingestion, copper sulfate pentahydrate is only
moderately toxic to humans.
- Gastrointestinal effects, including
anorexia, nausea, and occasional diarrhea, have been
attributed to swallowing copper dust.
- Chalcosis corneae is the impregnation
of the eye with elemental copper or copper alloys.
This brownish or greenish-brown discoloration of the
cornea, lens, or iris may occur after penetrating
injuries with copper fragments.
- Copper sulfate, copper acetoarsenite,
and verdigris cause irritation and inflammation but no
- Copper chloride and copper cyanide
plating bath can cause severe reactions and permanent
- Transient irritation of the eyes has
followed exposure to a fine dust of oxidation products
of copper produced in an electric arc.
- 3-Respiratory Tract :
- Typical metal fume fever is
characterized by :
- -nasal congestion,
- -fever up to 39 C,
- -aching muscles,
- -dryness in the mouth and
- -shortness of breath,
- -leucocytosis up to 12,000 to
symptoms generally develop after repeated exposure
during the work week, tending to diminish toward the
end of the week, only to return more prominently on
reexposure after the weekend. This phenomenon has led
to the term Monday morning fever.
symptoms resolve after removal from exposure.
illness is postulated to result from immune
mechanisms, but no report of chronic toxicity.
- Inhalation of copper salts may cause
irritation of the respiratory tract.
- Inhalation of copper fumes may cause
nausea, metallic taste, and discoloration of the skin
- 4-Renal System :
- Kidney abnormalities have been
observed after copper sulfate ingestion.
- Hematuria, rising blood urea nitrogen,
and oliguria were frequently observed in a large
series of poisonnings. A picture of acute tubular
necrosis was observed on urinalysis and renal
- Intravascular hemolysis but not
hypertension, preceded developement of acute tubular
- 5-Neurologic System :
evidence substantiates neurologic injury from acquired
observed in acute copper sulfate poisoning probably
results from uremia.
- 6-Hematologic System :
- Hemolytic anemia accompanies severe
copper sulfate poisoning and additionally follows burn
treatment with copper sulfate and hemodialysis using
copper-containing dialyzing equipement.
- Hemolytic anemia also occurs
sporadically in Wilson's disease, the hemolysis is
precipitous in these situations.
- B-Chronic Toxicity :
rats, degenerative modifications in the liver and the
kidney have been described in animals receiving, in a
chronic manner, copper salts by ingestion (more than
4,000 ppm in foodstuffs).
man, the same modifications (eventually accompanied by
encephalopathy) have been described mainly in patients
suffering from Wilson's disease.
- Chronic disease from excessive copper
storage is epitomized by Wilson's disease, an
inherited, autosomal recessive error in copper
metabolism. This disease is characterized by excess
copper deposition in most organs, especially the
liver, kidneys, brain, and eyes.
- It is
characterized by a diminished capacity to eliminate
copper via bile.
- Wilson's disease also termed
hepatolenticular degeneration, owing to the prominent
effects on the liver (cirrhosis) and eye. Chelating
treatment with D-penicillamine gives excellent
therapeutic results while the preferred maintenance
treatment is 150 mg of zinc orally per day.
copper content in drinking water and food may
contribute to the development of severe liver damage
(cirrhosis) in infants.
- 1-Skin :
- Copper causes a greenish coloration of
skin, nails, hair and teeth.
- Contact dermatitis (copper itch) due
to copper is rare and its occurrence can be
substantiated by careful patch testing.
- Eczematous dermatitis and urticaria
have been associated with the use of copper
penetration of copper particles in the eye was
responsible for cataract.
- 3-Respiratory System :
- Chronic recurrent inhalation of copper
fumes and dust can lead to nasal septal
- Chronic exposure to copper dust and
fumes in the industrial setting can lead to upper
respiratory complaints and physical findings in
- Long-term exposure to dust in copper
refining was not associated with chronic obstructive
disease or small airway disease.
higher incidence of respiratory cancer reported in
copper smelters is due to the presence of arsenic in
- 4-Vineyard Sprayer's lung :
- Vineyard sprayer's lung disease
occurred when Bordeaux solution (1 to 2% solution of
copper sulfate neutralized with lime) was chronically
sprayed by Portuguese vineyard workers.
workers developed interstitial pulmonary disease
- -histiocytic granulomas,
- -associated nodular fibrohyaline scars
containing abundant copper.
clinical picture is characterized initially by general
loss of appetite,
loss of weight;
dyspnea and cough.
- Micronodular or reticulonodular lung
infiltration, especially in the lower fields, is the
most frequent radiological image encountered. The
evolution is variable: stabilization or regression or
evolution towards a pseudotumoral form as in
high incidence of adenocarcinoma, particularly
alveolar cell carcinoma, was observed.
- Extensive liver damage was also noted.
Biopsies revealed fibrosis, micronodular cirrhosis
angiosarcoma, and portal hypertension.
- C-Teratogenesis :
teratogenic effects attributed to copper have been
observed in humans.
- D-Carcinogenesis :
the exception of adenocarcinoma of the lung and
angiosarcoma of the liver seen in patients with
vineyard sprayer's lung, no evidence corroborates
carcinogenesis from copper exposure.
- IV-Management of Toxicity :
- A-Clinical Examination :
Careful history taking is essential to
diagnose copper poisoning in acutely ill
history should contain questions relevant to
intentional poisoning with copper salts and to
ingestion of food and drink, especially acidic
beverages or alcohol prepared in copper-containing
vessels. Persons acutely poisoned by copper
(especially copper sulfate) should be evaluated
initially for nausea, vomiting, and diarrhea.
Blue-green vomitus is diagnostic.
- Investigation for abnormal liver and
renal function and hemolytic anemia should be
signs and urine output should be conducted for
hypotension and oliguria.
medical history is also cornerstone of investigating
dermatits suspected to arise from copper. Inquiry as
to exposure to copper salts at work, use of
copper-containing jewelry, or use of copper
intrauterine device should be conducted. Patch testing
may be necessary to confirm the diagnosis.
history of delayed onset of fever, chills, shortness
of breath, and malaise after exposure to copper fumes
should lead to the suspicion of metal fume fever.
Fever, rigorous chills, diaphoresis, and wheezing may
be noted on physical examination.
- B-Laboratory Diagnosis :
- 1-Severe copper sulfate poisoning :
- Laboratory findings in severe copper
sulfate poisoning include :
- -abnormal hepatocellular
- -hyperbilirubinemia (both direct and
- -elevated blood urea nitrogen,
- -elevated creatinine,
- -hematuria and cellular casts on
- -positive stool guaiac,
- -elevated serum copper,
- -elevated ceruloplasmin.
- 2-Metal fume fever :
- Findings during episodes of metal fume
fever include :
- -abnormal pulmonary function study
- -small airway obstruction,
- -reduced lung volumes,
- -reduced carbon dioxide diffusing
- -abnormal chest X-ray :
- -peribronchiolar cuffing,
- -elevated urine copper levels.
- C-Treatment :
- Removal from exposure is often
sufficient to resolve most ilnesses associated with
- 1-Severe acute poisoning by ingestion
severe acute poisoning by ingestion, emesis should not
be induced and rarely is necessary, owing to
- Dilution with 4 to 8 ounces of milk or
water is indicated after ingestion or prior to gastric
lavage. After any seizure activity is controlled,
gastric lavage may be indicated.
necessary to prevent further absorption, activated
charcoal may be administered and followed by a
symptomatic patients, either intravenous calcium
disodium-ethylenediaminetetraacetic acid or
intramuscular dimercaprol should be given as soon as
- D-Penicillamine may be given after
initial treatment with dimercaprol. Hemodialysis alone
is not effective.
- Treatment of eye injuries includes
vigorous irrigation with normal salin. Ophthalmologic
referral is indicated for severe elemental copper,
copper chloride or copper cyanide plating bath
injuries to the eye.
- 3-Metal fume fever :
- Treatment is symptomatic and removal
from exposure may be sufficient.
- 4-Dermatitis :
- Removal from exposure may be
sufficient but application of topical corticosteroid
preparations may be required.
- 5-Green hair :
hair from exogenous copper can be treated effectively
with shampoos containing D-penicillamine.
- V-Biological Monitoring :
normal concentration of copper in blood plasma is 1
- Ninety-five percent (95%) of the
copper in plasma is in ceruloplasmin but, it is one of
the acute-phase reactant proteins and it increases in
acute and chronic inflammatory conditions. It is
elevated also in patients taking estrogens and birth
control pills and in those who are pregnant or have
cirrhosis, cancer, or thyrotoxicosis.
- Erythrocytes also contain a
significant portion of the copper found in blood in
the form of an enzyme, superoxide dismutase.
- Increased serum concentrations of
copper are found in individuals with such liver
diseases as primary cirrhosis and other cholestatic
air concentrations near current exposure limits,
biological monitoring is not warrented. Biological
limit values cannot be established, owing to lack of
reliable exposure dose, and effect relationship.
- VI-Occupational, Environmental
Regulations, and Dietary Recommendations :
- A-Occupational :
VEMP in Quebec for copper dust and mist is :
- 1mg/m3 expressed as copper
VEMP for copper fumes is :
- 0.2mg/m3 expressed as copper.
- B-Environmental :
EPA (USA) has determined that lake and stream water
should contain no more than 1 ppm, and drinking water
no more than 1.3 ppm.
- C-Dietary :
National Academy of Sciences (USA) recommends 2 to 3
mg of copper per day as a safe and adequate intake for
- VII-Environmental Fate and Transport
- Copper is found in the earth's crust
at approximately 70 ppm and in sea water at 0.001 to
0.002 ppm. Mining and smelting are the primary
- Acidic soil conditions contribute to
solubility and increased transport, although
appreciable mobilization occurs only at pH less than 3
in organic soils.
pH and the passage of soft water through copper pipes
can produce high levels in drinking water; however,
only 1% of U.S. drinking water samples exceed the U.S.
Environmental Protection Agency's standard.
- VIII-Environmental and Occupational
- Copper fume and dust levels should be
measured to ensure compliance with local
- Remonitoring should be performed after
any changes in work practices or plant processes that
could cause a rise in air concentrations.
patients suspected of having non-occupational
overexposure to copper, an environmental investigation
should be conducted including measuring copper
non-prescription remedies and supplements,
investigating dietary practices such as drinking
acidic beverages fron copper-containing
- Contact dermatitis due to copper is
rare. However, its occurrence can be substantiated by
careful patch testing. Exzematous dermatitis and
urticaria have been associated with the use of copper
- Greenish discoloration of the hair has
been seen in blond or lightly pigmented individuals
exposed to copper dust or copper-tainted water used
for shampooing or swimming.
- IX-Prevention :
- Copper compounds used by potters are
not considered much hazardous if there is no ingestion
of basic copper carbonate and/or the sulfate.
glazes, copper enhances lead leaching.
studio housekeeping is always good practice. Avoidance
- generating unnecessary dust is also
important and the wearing of an approved
mask when the exposure seems hazardous is also good
- References :
- 1-Occupational Medicine,Carl Zenz,
- 2-Occupational & Environmental
Medicine,Joseph Ladoue, last edition.
- 3-Clinical Environmental Health and
Toxic Exposures, Sullivan & Krieger; last
- 4-Sax's Dangerous Properties of
Industrial Materials, Lewis C., last
- 5-Toxicologie Industrielle et
Intoxications Professionnelles, Lauwerys R. last
- 6-Chemical Hazards of the Workplace,
Proctor & Hughes, 4th edition.
Out Bound Links
In Bound Links
- (Materials - General)
Copper Hydroxide - Cu(OH)2
Copper(II) hydroxide, Copper Hydrate, Cupric Hydroxide
- (Materials - General)
Copper Carbonate Basic - CuCO3.Cu(OH)2
Cupric Carbonate, Copper (II) Carbonate, Azurite
- (Materials - General)
Copper Carbonate - CuCO3
Synthetic Malachite, CuCO3
- (Materials - General)
Copper Oxide Black - CuO
Copper (II) Oxide, Black Copper Oxide, BCO, Cupric Oxide
- (Materials - General)
Copper Oxide Red - Cu2O
Cu2O, Red Copper, RCO, Copper (I) Oxide, Cuprous Oxide
Copper Oxide and Carbonate
The hazards of using copper oxide and carbonate in ceramics.
Edouard Bastarache M.D.
Occupational & Environmental Medicine
Author of "Substitutions for Raw Ceramic Materials"
Tracy, QuÃ©bec, CANADA