zinc

Zinc was shown to be essential in fungal growth of yeast by Jules Raulin in 1869. No proof for the need of zinc in human cells was shown until the late 1930s when its presence was demonstrated in carbonic anhydrase and the 1960s when it was identified as a necessary element for humans.

A trace element is a chemical element of a minute quantity, a trace amount, especially used to refer to a micronutrient . Trace element may also refer to minor elements in the composition of a rock or other chemical substance.

Zinc is currently considered an essential trace element for humans, animals, plants and microorganisms. Zinc is stored and transferred in metallothionein. It is the second most abundant trace metal in humans after iron and it is the only metal which appears in all enzyme classes. The non-magnetic character of zinc and its lack of color in solution delayed discovery of its importance to biochemistry and nutrition. This changed in 1940 when carbonic anhydrase, an enzyme that scrubs carbon dioxide from blood, was shown to have zinc in its active site. The digestive enzyme carboxypeptidase became the second known zinc-containing enzyme in 1955.

ADVERSE AGRICULTURE & ENVIRONMENT

Excessive absorption of zinc suppresses copper and iron absorption. The free zinc ion in solution is highly toxic to plants, invertebrates, and even vertebrate fish.

Zinc in rivers flowing through industrial and mining areas can be as high as 20 ppm. Concentrations of zinc as low as 2 ppm adversely affects the amount of oxygen that fish can carry in their blood.

Soils contaminated with zinc from mining, refining, or fertilizing with zinc-bearing sludge can contain several grams of zinc per kilogram of dry soil. Levels of zinc in excess of 500 ppm in soil interfere with the ability of plants to absorb other essential metals, such as iron and manganese. Zinc levels of 2000 ppm to 180,000 ppm (18%) have been recorded in some soil samples.

Zinc is added to the soil primarily through the weathering of rocks, but humans have added zinc through fossil fuel combustion, mine waste, phosphate fertilizers, pesticide (zinc phosphide), limestone, manure, sewage sludge, and particles from galvanized surfaces.

Calluna vulgaris, common heather, ling, or simply heather
Species of Calluna, Erica and Vaccinium can grow in zinc-metalliferous soils, because translocation of toxic ions is prevented by the action of ericoid mycorrhizal fungi.
An isolate of the ericoid mycorrhizal fungus, Gamarada debralockiae, isolated from Woollsia pungens
Species of Calluna, Erica and Vaccinium can grow in zinc-metalliferous soils, because translocation of toxic ions is prevented by the action of ericoid mycorrhizal fungi.

The ericoid mycorrhiza is a mutualistic relationship formed between members of the plant family Ericaceae and several lineages of mycorrhizal fungi. This symbiosis represents an important adaptation to acidic and nutrient poor soils that species in the Ericaceae typically inhabit, including boreal forests, bogs, and heathlands. Ericoid mycorrhizal fungi form symbioses with several crop and ornamental species, such as blueberries, cranberries and Rhododendron. Inoculation with ericoid mycorrhizal fungi can influence plant growth and nutrient uptake. However, much less agricultural and horticultural research has been conducted with ericoid mycorrhizal fungi relative to arbuscular mycorrhizal and ectomycorrhizal fungi.

Zeuterin is the trade name of a product containing zinc gluconate and the amino acid arginine which is used for STERILIZING young male dogs without the removal of the testicles

ZINC GLUCONATE DIETARY SUPPLEMENT
Zinc supplements (as zinc gluconate, 30 mg)

Zinc gluconate is the zinc salt of gluconic acid. It is an ionic compound consisting of two anions of gluconate for each zinc(II) cation. Zinc gluconate is a popular form for the delivery of zinc as a dietary supplement providing 14.35% elemental zinc by weight.

Zinc gluconate has been used in lozenges for treating the common cold. Zinc has also been administered nasally for treating the common cold, but has been reported to cause anosmia in some cases.

In September 2003, Zicam faced lawsuits from users who claimed that a nasal gel, containing zinc gluconate and several inactive ingredients, negatively affected their sense of smell and sometimes taste. Some plaintiffs alleged experiencing a strong and very painful burning sensation when they used the product. Matrixx Initiatives, Inc., the maker of Zicam, responded that only a small number of people experienced problems and that anosmia can be caused by the common cold itself. In January 2006, 340 lawsuits were settled for $12 million.

The U.S. Food and Drug Administration (FDA) considers zinc gluconate to be generally recognized as safe (GRAS) when used in accordance with good manufacturing practice, although this does not constitute a finding by the FDA that the substance is a useful dietary supplement. On 16 June 2009 the FDA "warned consumers to stop using and discard three zinc-containing Zicam intranasal products. The products may cause a loss of sense of smell. ... FDA is concerned that the loss of sense of smell may be permanent." In its warning, the FDA stated, "This warning does not involve oral zinc tablets and lozenges taken by mouth. Dietary zinc is also not subject to this warning."

Sphalerite is an important ore of zinc

From Greek word sphaleros, "deceiving", due to the difficulty of identifying the mineral. In pure form, it is a semiconductor, but transitions to a conductor as the iron content increases. Also known as zinc blende, black-jack, and ruby blende.

Marmatite

Marmatite or christophite is an opaque black variety of sphalerite with high iron content which can reach up to 25%. Marmatite is named after Marmato mining district in Colombia and christophite is named for the St. Christoph mine in Breitenbrunn, Saxony.

In addition to zinc, sphalerite is an ore of cadmium, gallium, germanium, and indium. It is found in association with galena, chalcopyrite, pyrite (and other sulfides), calcite, dolomite, quartz, rhodochrosite, and fluorite.

Sphalerite crystallizes in the face-centered cubic zincblende crystal structure, which is named after the mineral.

Minerals similar to sphalerite include those in the sphalerite group, consisting of sphalerite, colaradoite, hawleyite, metacinnabar, stilleite and tiemannite. The structure is closely related to the structure of diamond.

All natural sphalerite contains concentrations of various impurities, which generally substitute for zinc in the cation position in the lattice; the most common cation impurities are cadmium, mercury and manganese, but gallium, germanium and indium may also be present in relatively high concentrations (hundreds to thousands of ppm). Cadmium can replace up to 1% of zinc and manganese is generally found in sphalerite with high iron abundances. Sulfur in the anion position can be substituted for by selenium and tellurium. The abundances of these impurities are controlled by the conditions under which the sphalerite formed; formation temperature, pressure, element availability and fluid composition are important controls.

Depending on the impurities, sphalerite will fluoresce under ultraviolet light. Sphalerite can be triboluminescent. Sphalerite has a characteristic triboluminescence of yellow-orange.

Sphalerite fluorescing under ultraviolet light. (public display, Sternberg Museum of Natural History, Hays, Kansas, USA). Photo taken by James St. John.

Long Dong Silver
(and long dong gold)

Sphalerite has been found as a pseudomorph, taking the crystal structure of galena, tetrahedrite, barite and calcite. Sphalerite can have Spinel Law twins, where the twin axis is.

In mineralogy, a pseudomorph is a mineral or mineral compound that appears in an atypical form (crystal system), resulting from a substitution process in which the appearance and dimensions remain constant, but the original mineral is replaced by another. The name literally means "false form". Terminology for pseudomorphs is "replacer after original", as in brookite after rutile.

Ammonite with Pyrite pseudomorphs - Bully Calvados - France (4cm)
Ammonite with Pyrite pseudomorphs - Bully Calvados - France. Pyrite's metallic luster and pale brass-yellow hue give it a superficial resemblance to gold, hence the well-known nickname of fool's gold. The color has also led to the nicknames brass, brazzle, and brazil, primarily used to refer to pyrite found in coal Despite being nicknamed "fool's gold", pyrite is sometimes found in association with small quantities of gold. A substantial proportion of the gold is "invisible gold" incorporated into the pyrite (see Carlin-type gold deposit).

Calamine IS A HISTORIC NAME FOR AN ORE OF ZINC

German metallurgist Andreas Libavius received a quantity of what he called "calay" (from the Malay or Hindi word for tin) originating from Malabar off a cargo ship captured from the Portuguese in the year 1596. Libavius described the properties of the sample, which may have been zinc and which may or may not be connected to the name calamine. Zinc was regularly imported to Europe from the Orient in the 17th and early 18th centuries.

The name calamine was derived from lapis calaminaris, a Latin corruption of Greek cadmia (καδμία), the old name for zinc ores in general. The name of the Belgian town of Kelmis, La Calamine in French, which was home to a zinc mine, comes from this. In the 18th and 19th centuries large ore mines could be found near the German village of Breinigerberg. During the early 19th century it was discovered that what had been thought to be one ore was actually two distinct minerals:

Zinc carbonate ZnCO3 or smithsonite and
Zinc silicate Zn4Si2O7(OH)2·H2O or hemimorphite

Although chemically and crystallographically quite distinct, the two minerals exhibit similar massive or botryoidal external form and are not readily distinguished without detailed chemical or physical analysis. The first person to separate the minerals was the British chemist and mineralogist James Smithson in 1803. In the mining industry the term calamine has been historically used to refer to both minerals indiscriminately. In mineralogy calamine is no longer considered a valid term. It has been replaced by smithsonite and hemimorphite in order to distinguish it from the pinkish mixture of zinc oxide (ZnO) and iron(III) oxide (Fe2O3) used in calamine lotion.

Specimen of calamine from mine at Granby, Missouri. Hemimorphite, Smithsonite Locality: Granby Field, Tri-State District, Newton County, Missouri, USA (Locality at mindat.org) Size: 9.5 x 7.0 x 4.8 cm. Gemmy, honey-colored hemimorphite crystals richly cover the upper portion of the matrix and drusy hemimorphite covers the rest on this classic, old-time specimen from the Granby Field, Missouri of the famed Tri-State District. The matrix is comprised of tan "dry-bone" smithsonite and massive hemimorphite. Not pretty to look at, but certainly very highly desirable, old-time material from this well-known locality. Ex George Feist Collection and according to the accompanying label dates to 1925-27.

Calamine BRASS IS PRODUCED BY A PARTICULAR ALLYING TECHNIQUE USING THE ZINC ORE CALAMINE DIRECTLY RATHER THAN FIRST REFINING IT TO METALLIC ZINC

Direct zinc smelting appears to have been unknown in Europe until the mid-18th century, even though the alloyed calamine brass was in use for centuries, and metallic zinc was produced directly via reducing-atmosphere smelting in India and China from the 12th century CE onwards.

Calamine brass was produced using proportions of two-sevenths fine copper, four-sevenths calamine, and one-seventh shruff (old plate brass). Calamine brass was the first type of brass produced, probably starting during the 1st millennium BC, and was not replaced in Europe by other brass manufactures until the 18th century.

Brass is an alloy of copper and zinc and, when it was first developed, methods for producing metallic zinc were unknown. Metallurgists wishing to produce brass thus used calamine (actually a mixture of the virtually indistinguishable zinc ores smithsonite and hemimorphite) as the zinc component of brass. The resulting brasses, produced by heating a mixture of copper and calamine to a high temperature for several hours (allowing zinc vapor to distill from the ores and permeate the metallic copper), contained a significant amount of slag material resulting from the non-zinc components of calamine. The use of ore rather than metallic zinc also made it difficult to accurately produce the desired final proportion of copper to zinc. This process is known as cementation.

HEMIMORPHITE

Colorless prismatic crystals of hemimorphite on matrix (4.5 × 4.0 × 2.0 cm) with calcite. Found from Ojuela mine, Mapimí, Durango, Mexico.

Hemimorphite is the chemical compound Zn4(Si2O7)(OH)2·H2O, a component of mineral calamine. It is a silicate mineral which, together with smithsonite (ZnCO3), has been historically mined from the upper parts of zinc and lead ores. Both compounds were originally believed to be the same mineral and classified as calamine. In the second half of the 18th century, it was discovered that these two different compounds were both present in calamine. They closely resemble one another. The silicate was the rarer of the two and was named hemimorphite because of the hemimorph development of its crystals. This unusual form, which is typical of only a few minerals, means that the crystals are terminated by dissimilar faces. Hemimorphite most commonly forms crystalline crusts and layers, also massive, granular, rounded and reniform aggregates, concentrically striated, or finely needle-shaped, fibrous or stalactitic, and rarely fan-shaped clusters of crystals. Some specimens show strong green fluorescence in shortwave ultraviolet light (253.7 nm) and weak light pink fluorescence in longwave UV.
Hemimorphite most frequently occurs as the product of the oxidation of the upper parts of sphalerite bearing ore bodies, accompanied by other secondary minerals which form the so-called iron cap or gossan. Hemimorphite is an important ore of zinc and contains up to 54.2% of the metal, together with silicon, oxygen and hydrogen. The crystals are blunt at one end and sharp at the other.

SMITHSONITE

Smithsonite, Willemite Locality: Berg Aukas (Berg Aukus), Grootfontein District, Otjozondjupa Region, Namibia

Smithsonite, also known as zinc spar, is the mineral form of zinc carbonate (ZnCO3). Historically, smithsonite was identified with hemimorphite before it was realized that they were two different minerals. The two minerals are very similar in appearance and the term calamine has been used for both, leading to some confusion. Smithsonite is a variably colored trigonal mineral which only rarely is found in well formed crystals. The typical habit is as earthy botryoidal masses. It has a Mohs hardness of 4.5 and a specific gravity of 4.4 to 4.5. Smithsonite occurs as a secondary mineral in the weathering or oxidation zone of zinc-bearing ore deposits. It sometimes occurs as replacement bodies in carbonate rocks and as such may constitute zinc ore. It commonly occurs in association with hemimorphite, willemite, hydrozincite, cerussite, malachite, azurite, aurichalcite and anglesite. It forms two limited solid solution series, with substitution of manganese leading to rhodochrosite, and with iron, leading to siderite. A variety rich in cadmium, which gives it a bright yellow color, is sometimes called turkey fat ore.

Smithsonite (Var.: Cobaltoan Smithsonite) Locality: Tsumeb Mine (Tsumcorp Mine), Tsumeb, Otjikoto (Oshikoto) Region, Namibia
Smithsonite (Var.: Cobaltoan Smithsonite) Locality: Tsumeb Mine (Tsumcorp Mine), Tsumeb, Otjikoto (Oshikoto) Region, Namibia

LATTEN

Historically, the term "latten" referred loosely to the copper alloys such as brass or bronze that appeared in the Middle Ages and through to the late-18th and early-19th centuries. Such alloys were used for monumental brasses, in decorative effects on borders, rivets or other details of metalwork (particularly armour), in livery and pilgrim badges or funerary effigies. Latten commonly contained varying amounts of copper, tin, zinc and lead, giving it characteristics of both brass and bronze.

In the 16th century demand for latten (brass) in England came from the needs of wool-carding, for which brass-wire combs were preferred, and battery pieces (brassware formed by hammering sheet brass in a battery mill). The only known method for producing the alloy was by heating copper and calamine together in the cementation process and in 1568 a royal charter was granted to the Society of the Mineral and Battery Works to search for the mineral and produce brass, to reduce dependence on imported metal from Germany. By the late 17th century enough was known of metallic zinc to make brass solder directly by combining copper and spelter (zinc ingots).

Metalworkers commonly formed latten in thin sheets and used it to make church utensils. Brass of this period is made through the calamine brass process, from copper and zinc ore. (Later brass was made with zinc metal from Champion's smelting process and is not generally referred to as "latten".) This calamine brass was generally manufactured as hammered sheet or "battery brass" (hammered by a "battery" of water-powered trip hammers), and cast brass was rare.

"Latten" also refers to a type of tin plating on iron (or possibly some other base metal), which is known as white latten; and black latten refers to laten-brass, which is brass milled into thin plates or sheets. The term "latten" has also been used, rarely, to refer to lead alloys. In general, metal in thin sheets is characterised as "latten" - such as gold latten; and lattens (plural) refers to metal sheets between 1/64" and 1/32" in thickness.

Alchemical symbol for zinc
Alchemical symbol for zinc.

Alchemists burned zinc metal in air and collected the resulting zinc oxide on a condenser. Some alchemists called this zinc oxide lana philosophica, Latin for "philosopher's wool", because it collected in wooly tufts, whereas others thought it looked like white snow and named it nix album.

ZINC IN ANCIENT HISTORY

Metallic zinc was isolated in India by 1300 AD. Before it was isolated in Europe, it was imported from India in about 1600 CE. Postlewayt's Universal Dictionary, a contemporary source giving technological information in Europe, did not mention zinc before 1751 but the element was studied before then.

Brass, an alloy of copper and zinc in various proportions, was used as early as the third millennium BC in the Aegean area and the region which currently includes Iraq, the United Arab Emirates, Kalmykia, Turkmenistan and Georgia. In the second millennium BC it was used in the regions currently including West India, Uzbekistan, Iran, Syria, Iraq, and Israel. Zinc metal was not produced on a large scale until the 12th century in India, though it was known to the ancient Romans and Greeks. The mines of Rajasthan have given definite evidence of zinc production going back to the 6th century BC. To date, the oldest evidence of pure zinc comes from Zawar, in Rajasthan, as early as the 9th century AD when a distillation process was employed to make pure zinc.

Various isolated examples of the use of impure zinc in ancient times have been discovered. Zinc ores were used to make the zinc–copper alloy brass thousands of years prior to the discovery of zinc as a separate element. Judean brass from the 14th to 10th centuries BC contains 23% zinc.

Knowledge of how to produce brass spread to Ancient Greece by the 7th century BC, but few varieties were made. Ornaments made of alloys containing 80–90% zinc, with lead, iron, antimony, and other metals making up the remainder, have been found that are 2,500 years old. A possibly prehistoric statuette containing 87.5% zinc was found in a Dacian archaeological site.

Strabo writing in the 1st century BC (but quoting a now lost work of the 4th century BC historian Theopompus) mentions "drops of false silver" which when mixed with copper make brass. This may refer to small quantities of zinc that is a by-product of smelting sulfide ores. Zinc in such remnants in smelting ovens was usually discarded as it was thought to be worthless.

The manufacture of brass was known to the Romans by about 30 BC. They made brass by heating powdered calamine (zinc silicate or carbonate), charcoal and copper together in a crucible. The resulting calamine brass was then either cast or hammered into shape for use in weaponry. Some coins struck by Romans in the Christian era are made of what is probably calamine brass.

The oldest known pills were made of the zinc carbonates hydrozincite and smithsonite. The pills were used for sore eyes and were found aboard the Roman ship Relitto del Pozzino, wrecked in 140 BC.

The Berne zinc tablet is a votive plaque dating to Roman Gaul made of an alloy that is mostly zinc.

Bern zinc tablet in the Bern Historical Museum, 2019
The Bern zinc tablet or Gobannus tablet is a metal sheet found in 1984 in Bern, Switzerland. According to the scant information available, it was found in Thormenboden forest within what appears to be a Gallo-Roman context. It is inscribed with an apparently Gaulish inscription, consisting of four words, each on its own line, the letters formed by little dots impressed onto the metal: ΔΟΒΝΟΡΗΔΟ ΓΟΒΑΝΟ ΒΡΕΝΟΔΩΡ ΝΑΝΤΑΡΩΡ (Dobnoredo Gobano Brenodor Nantaror) The Bern Zinc Tablet is displayed in the Historisches Museum Bern

The Charaka Samhita, thought to have been written between 300 and 500 AD, mentions a metal which, when oxidized, produces pushpanjan, thought to be zinc oxide. Zinc mines at Zawar, near Udaipur in India, have been active since the Mauryan period (c. 322 and 187 BCE). The smelting of metallic zinc here, however, appears to have begun around the 12th century AD. One estimate is that this location produced an estimated million tonnes of metallic zinc and zinc oxide from the 12th to 16th centuries. Another estimate gives a total production of 60,000 tonnes of metallic zinc over this period.

The Rasaratna Samuccaya, written in approximately the 13th century AD, mentions two types of zinc-containing ores: one used for metal extraction and another used for medicinal purposes.

GALVANI

Portrait of Luigi Galvani (1737-1798), Italian physicist
Italian doctor Luigi Galvani discovered in 1780 that connecting the spinal cord of a freshly dissected frog to an iron rail attached by a brass hook caused the frog's leg to twitch. He incorrectly thought he had discovered an ability of nerves and muscles to create electricity and called the effect "animal electricity". The galvanic cell and the process of galvanization were both named for Luigi Galvani, and his discoveries paved the way for electrical batteries, galvanization, and cathodic protection.

VOLTA

Alessandro Giuseppe Antonio Anastasio Volta
Galvani's friend, Alessandro Volta, continued researching the effect and invented the Voltaic pile in 1800. Volta's pile consisted of a stack of simplified galvanic cells, each being one plate of copper and one of zinc connected by an electrolyte. By stacking these units in series, the Voltaic pile (or "battery") as a whole had a higher voltage, which could be used more easily than single cells. Electricity is produced because the Volta potential between the two metal plates makes electrons flow from the zinc to the copper and corrode the zinc.

PARACELSUS

Paracelsus
The name of the metal was probably first documented by Paracelsus, a Swiss-born German alchemist, who referred to the metal as "zincum" or "zinken" in his book Liber Mineralium II, in the 16th century. The word is probably derived from the German zinke, and supposedly meant "tooth-like, pointed or jagged" (metallic zinc crystals have a needle-like appearance). Zink could also imply "tin-like" because of its relation to German zinn meaning tin. Yet another possibility is that the word is derived from the Persian word سنگ seng meaning stone. The metal was also called Indian tin, tutanego, calamine, and spinter.

MARGGRAF

Andreas Sigismund Marggraf is given credit for first isolating pure zinc
German chemist Andreas Marggraf normally gets credit for isolating pure metallic zinc in the West, even though Swedish chemist Anton von Swab had distilled zinc from calamine four years previously. In his 1746 experiment, Marggraf heated a mixture of calamine and charcoal in a closed vessel without copper to obtain a metal. This procedure became commercially practical by 1752.

REFERENCES

GENERAL

ADVERSE AGRICULTURE & ENVIRONMENT

ZEUTERIN

ZINC GLUCONATE

HISTORY

CALAMINE AND CALAMINE BRASS

LATTEN

  • “latten”Oxford English Dictionary (Online ed.). Oxford University Press. (Subscription or participating institution membership required.) – “A mixed metal of yellow colour, either identical with, or closely resembling, brass; often hammered into thin sheets. Now only archaic and Historical.”
  • For example: Walesby, Thomas (1868). Notes and Queries. 4. Vol. 1. London. p. 20. Retrieved 22 June 2022[…] a compound metal called latten. It is a mixture of copper and tin, and therefore bronze.
  • Curl, James Stevens; Wilson, Susan (2016). Oxford Dictionary of Architecture. Oxford University Press. p. 429. ISBN 978-0-19-967499-2.
  • Brownsword, Roger (2003). Blair, John; Blair, W. John; Ramsay, Nigel (eds.). English Medieval Industries: Craftsmen, Techniques, Products. Hambledon & London. pp. 103–104. ISBN 978-0907628873.
  • Edge, David; Paddock, John Miles (1996) [1988]. Arms and Armour of the Medieval Knight. London: Saturn Books. ISBN 1862220018.
  • Day, Joan (1973). Bristol Brass. David & Charles. ISBN 0715360655.

HEMIMORPHITE AND SMITHSONITE

SPHALERITE, MARMATITE & PSEUDOMORPHS