Botallackite

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Botallackite
Botallackite-rare08-2-27c.jpg
Aggregates of thin botallackite crystals from "Cligga Head" near Perranzabuloe, Cornwall, United Kingdom (step size: 10.5 cm × 7.0 cm × 3.8 cm)
General and classification
chemical formula Cu 2 (OH) 3 Cl
Mineral class
(and possibly department) 		Halides
System no. to Strunz
and to Dana 		3.DA.10b ( 8th edition : III / D.01)
01/10/03/01
Similar minerals Capellasite
Crystallographic Data
Crystal system monoclinic
Crystal class ; symbol monoclinic prismatic; 2 / m
Space group P 2 1 / m (No. 11)Template: room group / 11
Lattice parameters a  = 5.7155  Å ; b  = 6.1255 Å; c  = 5.6336 Å
β  = 93.090 °
Formula units Z  = 2
Frequent crystal faces {001}, {100}, {010}, {011}
Physical Properties
Mohs hardness 4.5, Vickers hardness VHN 25 = 310 ± 30 kg / mm 2
Density (g / cm 3 ) measured: ≈3.6; calculated: 3.60
Cleavage very completely parallel {100} or perpendicular to {001}
Break ; Tenacity uneven; brittle
colour mountain green, bluish green to green, emerald green
Line color white, greenish white
transparency translucent to translucent
shine Glass gloss to pearlescent gloss
Crystal optics
Refractive indices n α  = 1.775
n β  = 1.800
n γ  = 1.846
Birefringence δ = 0.071
Optical character biaxial positive
Axis angle 2V = 70 ° (measured), 74 ° (calculated)
Pleochroism faint in shades of bluish green tones
Other properties
Chemical behavior very sensitive to alkalis and ammonia, easily attacked by weak acids such as acetic acid, citric acid and formic acid

Botallackite is a very rare mineral from the mineral class of halides . It crystallizes in the monoclinic crystal system with the composition Cu 2 (OH) 3 Cl, so it is chemically a copper - chlorine oxyhalide.

Botallackite forms crusty aggregates of tiny and nested, rarely idiomorphic crystals , which are either tabular or blocky-prismatic. Their color is mountain green or bluish green to green. They typically occur in the oxidation zone of copper-rich deposits that either have high chlorine concentrations or were exposed to seawater during weathering.

Etymology and history

View of the Botallack Mine, after which the botallackite was named

Around 1865, the famous mineral dealer Richard Talling from Lostwithiel drew the attention of chemist and mineralogist Sir Arthur Herbert Church to a pale mountain-green mineral from the Botallack mine associated with atacamite and "tallingite" (later recognized as identical to connellite ) . Church described the mineral as botallackite in 1865, but admitted that his investigations were incomplete ("... my examination of it has been but imperfect ..."). Probably for this reason, the mineral does not appear in the 6th edition of "Dana's System of Mineralogy" or in Hintze's "Handbuch der Mineralogie" as an independent species, but rather was treated as a variety of atacamite. It was only through the X-ray diffraction and optical results of Clifford Frondel's work that it became clear that botallackite is an independent mineral. The crystal structure of the mineral was first clarified in 1958 and was refined again in 1985.

The name botallackite was given to the mineral in 1865 by Arthur Herbert Church, who named it after its first place of discovery, the botallack mine . However, it must be taken into account that the first location of the botallackite was almost certainly not the Botallack mine, but the upper levels (the 20-fathom level) of the neighboring mines of the “Wheal Cock” mine, which are located directly below sea level. The reason for the incorrect naming of the first place of discovery was obviously a too vague formulation by Richard Talling. It is interesting that the clarification of the exact first location for the botallackite is due to Arthur WG Kingsbury , of all people, whose false information about sites in Cornwall and allegedly found minerals had led to much confusion even among scientists.

Type material of the mineral is stored in the Natural History Museum , London , England (catalog number 36528) and at Harvard University, Cambridge, Massachusetts , USA (catalog number 100805, holotype, examined by Clifford Frondel).

classification

In the meanwhile outdated, but still in use 8th edition of the mineral classification according to Strunz , the botallackite belonged to the department of "oxyhalides", where together with the other members atacamite , anthonyite , belloit , bobkingite , calumetite , Gillardit , Haydeeit , Herbertsmithite , hibbingite , Kapellasit , Kempit , Klinoatacamit , Korshunovskit , Melanothallit , Nepskoeit and Paratacamit the "Atacamit series" with the system no. III / D.01 .

The 9th edition of Strunz's mineral systematics , which has been in effect since 2001 and is used by the International Mineralogical Association (IMA), classifies botallackite in the extended section of "Oxyhalides, hydroxyhalides and related double halides". This is further subdivided according to the predominant metals in the compound, so that the mineral can be found according to its composition in the sub-section "With Cu etc., without Pb", where it only has the "Belloit group" together with Belloit and Klinoatacamit the system no. 3.DA.10b forms.

The systematics of minerals according to Dana , which is mainly used in the English-speaking world , assigns botallackite to the “halides” class and there to the “oxyhalides and hydroxyhalides” division. Here he is to be found as the sole representative in the unnamed group 10.01.03 within the subdivision " Oxyhalides and hydroxyhalides with the formula A 2 (O, OH) 3 X q ".

Chemism

Botallackite from the “Levant Mine” has the measured composition Cu 1.99 Zn 0.01 (OH) 2.97 Cl 1.03 , while botallackite from the “Graf-Hohenthal-Schacht” has Cu 1.94 Co 0.04 Mn 0 , 02 Ca 0.01 (OH) 3.01 Cl 0.99 , which was idealized to Cu 2 (OH) 3 Cl and contents of 74.49% CuO, 16.60% Cl and 12.65% H 2 O requires.

Although botallackite is quite resistant to the incorporation of zinc , some botallackite have minor contents of Zn 2+ and to a lesser extent magnesium , but never reach the Zn: Cu ratio of kapellasite (1: 3). Botallackite from the Graf-Hohenthal-Schacht also has significant levels of cobalt , manganese and calcium . While Co 2+ and Mn 2+ enter the crystal lattice instead of Cu 2+ ( substitution ), the crystal-chemical nature of calcium is unknown.

An artificially produced substance formerly known as “bromatacamite” is the bromine-dominant analogue of botallackite, which is called “bromobotallackite”, Cu 2 Br (OH) 3 . However, since it is exclusively produced artificially, this substance is not a mineral in the sense of the definition.

Crystal structure

Crystal structure of botallackite projected onto the (a, c) plane. Red: copper, green: chlorine, blue: oxygen, gray: hydrogen.
Copper: coordination and bonding in botallackite

Botallackite crystallizes monoclinically in the space group P 2 1 / m (space group no. 11) with the lattice parameters a  = 5.7155  Å ; b  = 6.1255 Å; c  = 5.6336 Å and β = 93.090 ° as well as two formula units per unit cell . Template: room group / 11

In the structure of botallackite, as in atacamite, there are two crystallographically different copper positions. Both cases are octahedrally coordinated polyhedra that are heavily deformed by Jahn-Teller effects . Cu (1) is octahedrally coordinated by five hydroxide ions and one chlorine atom and forms [Cu (OH) 5 Cl] polyhedra, while Cu (2) is also octahedrally coordinated by four hydroxide ions and two chlorine atoms and [Cu (OH 4 ) Cl 2 ] Polyhedron. Each octahedron shares six edges with the surrounding octahedra and thus forms a two-dimensional brucite-like layer parallel {100} of edge-sharing [Cu 2 (OH) 3 Cl] octahedra. The adjacent layers are held together by hydrogen bonds between the hydroxide ions of one layer and the opposing chlorine atoms of the adjacent layer. The resulting weak bond between the layers is responsible for the very perfect cleavage according to {100} and the characteristic platy habit of botallackite crystals.

The new phase identified on a metallic mining artifact from the “Rowley Mine”, Maricopa County, Arizona / USA, with the idealized composition CuZn (OH) 3 Cl is isotypic (isostructural) with botallackite.

The thermal decomposition of botallackite takes place in two steps. Between 251 and 281 ° C., 12.65% by weight are released in the form of H 2 O, and between 413 and 437 ° C. another 12.83% by weight in the form of Cl.

properties

Costume and habitus of botallackite crystals
Botallackite tafelig.png
thin tabular crystal
Botallackite blockig.png
blocky isometric crystal

morphology

The first more extensive crystallographic description of botallackite crystals from "Wheal Cock" (as "Bottolackite" (sic!) In a work on atacamite) comes from Victor Leopold Ritter von Zepharovich . Although the surface forms are clearly not correctly indicated, the habitus of the crystals is described exactly.

“Some observations on atakamite crystals from two other localities, which I also owe to Mr. Brezina, may be mentioned here. (1) Cornwall. Tiny, emerald-green crystals of two-fold habit (Bottolackite). a) Tablets, no more than 1 mm long and 3/4 mm wide, predominantly of two parallel (101) surfaces and laterally bounded by very narrow surfaces of (100), (110) and (210). The (101), which here exceptionally determine the shape of the table, are made up of many linear steps in which (101) and (201) alternately reflect, or (101) appears matt and surrounded by a slightly protruding, strongly shiny edge ... "

- Victor Leopold Ritter von Zepharovich

Modern crystallographic characterizations of botallackite crystals were only made more than 130 years later. Thereafter botallackite forms crusty aggregates of tiny and nested, crystallographically mostly indistinct crystals up to 3 mm in size , whereby an exceptional find on the Cornish "Cligga Head" yielded crystals up to 9 mm in length. At different locations, the botallackite crystals also have different crystal dress and different crystal habit . Botallackite from the “Levant Mine” forms thin-tabular crystals with a rectangular outline that are slightly parallel [010]. Supporting and tracht determined form is the Basispinakoid {001}, to the front contact pinacoid {100}, which is usually only indistinctly formed pinacoid lateral {010} and the main kantenabstumpfend-emergent prism {011}. Botallackite crystals from the "Graf-Hohenthal-Schacht" are almost isometric and blocky-prismatic, stretched slightly parallel {100} and show the pinacoids {001}, {010} and {100} in their crystal costume. The different formation of the crystals in both deposits can be seen in the crystal drawings on the right. In addition, botallackite is found in leafy or scaly aggregates as well as coarse.

physical and chemical properties

The color of the crystals and aggregates of botallackite, depending on the size of the crystals, is mountain green, bluish green to green and emerald green or even blue-green to greenish blue. Its line color , on the other hand, is white or greenish-white. The surfaces of the translucent to transparent crystals, depending on size and color intensity, have a glass-like to mother-of-pearl-like sheen .

Botallackite has a very perfect cleavage parallel to {100} or perpendicular to the surfaces of the basic pinacoid {001}, but due to its brittleness it breaks similarly to amblygonite , whereby the fracture surfaces are uneven.

The measured Vickers hardness VHN 25 = 310 ± 30 kg / mm 2 corresponds to a Mohs hardness of 4.5. Botallackite is thus one of the medium-hard minerals that, like the reference minerals fluorite and apatite, can be scratched more or less easily with a pocket knife. The measured density for botallackite is ≈ 3.6 g / cm³, the calculated density is 3.60 g / cm³.

In the thin section the botallackite crystals and grain aggregates are pale bluish green. They have moderate relief and are weakly pleochroic in shades of bluish green tones. High birefringence and third-order interference colors can be seen under crossed polars. If the particles are thinner, first order anomalous interference colors slightly appear with blue-gray tones. When looking through a Chelsea filter, the appearance of the botallackite does not change.

Before the soldering tube and against acids and ammonia , botallackite behaves like atacamite. The latter gives water in front of the soldering tube in the flask and turns black. Melts on charcoal and even without being moistened with hydrochloric acid , the soldering tube flame turns a clear blue. There are two fittings in the oxidation flame, one brownish and one grayish-white, which evaporate when they come into contact with the reduction flame. Gives a ball of metallic copper when blowing for a long time. Soluble in acids as well as in ammonia, even more quickly in boiling potassium cyanide solution. In contrast, very resistant to water. Very sensitive to alkalis and ammonia, easily attacked by weak acids such as acetic acid , citric acid and formic acid .

Modifications and varieties

Three natural modifications of the compound Cu 2 (OH) 3 Cl are known so far . In addition to the monoclinically crystallizing botallackite, these are also monoclinically crystallizing Klinoatacamite and the orthorhombically crystallizing atacamite . Of all three Cu 2 (OH) 3 Cl polymorphs, atacamite is the most widespread in nature and botallackite the rarest modification. At room temperature, clinoatacamite is the most stable phase and botallackite is the least stable.

The trigonal paratacamite (Cu 3 (Cu, Zn) (OH) 6 C 12 ) is chemically similar, but not a polymorph. Belloite (Cu (OH) Cl) and claringbullite (Cu 4 [(OH) 6 Cl | (OH, Cl)]) are chemically similar . In addition, botallackite is the chlorine-dominant analogue of the two nitrate-dominated dimorphs Gerhardtite and Rouaite (Cu 2 (NO 3 ) (OH) 3 ).

Education and Locations

Close-up of a step from the "Levant Mine" near Trewellard north of St Just with countless botallackite crystals (step size: 3.5 cm × 2.3 cm × 1.0 cm)
Botallackite on quartz from the "Levant Mine" (step size: 7.4 cm × 4.5 cm × 3.4 cm)
Pale green botallackite crystals on slag from the "Herzog Julius" smelter near Astfeld not far from Goslar in the Harz Mountains (field of view: 4 mm)
Botallackite from Sounion Mine No. 19 ("Chloridstollen"), Lavrion, Attica, Greece (field of view: 4 mm)

Botallackite forms in the oxidation zone of sulphidic copper deposits that either primarily have high chlorine concentrations or were exposed to seawater during weathering. The chloride ions contained in the sea water percolate through the ores and supply the chlorine necessary for the formation of botallackite (and atacamite and paratacamite).

Botallackite is often also a secondary product of weathering in mostly medieval slag from former ore smelting . Strictly speaking, the phases found there are not minerals in the sense of the definition.

Finally, botallackite was also found in the so-called black smokers around the Mid-Atlantic Ridge . Botallackite was observed here ( coordinates of the Trans-Atlantic Geotraverse Hydrothermal Field (TAG) ) in a sample from the Trans-Atlantic Geotraverse Hydrothermal Field (TAG) in the Atlantic Ocean , where it forms the hollow interior of a Atacamite crust. The clear signs of etching and dissolution show that the mineral is only a metastable phase compared to its companions atacamite and paratacamite . Experimentally obtained botallackite recrystallizes very quickly, depending on the concentration of Cu 2+ (aq), to paratacamite (low concentration (several tens of ppm) of Cu 2+ in the solution) or atacamite (medium concentration (several hundreds of ppm) of Cu 2+ in the solution), whereby at even higher concentrations atacamite recrystallizes to paratacamite. Consequently, paratacamite is the most stable trimorph at normal temperature, the crystallization of the metastable atacamite and botallackite is mainly kinetically controlled.

As Begleitminerale were among other Atacamit , Brochantite , Chalkanthit , chalcocite , Connellit , cuprite , gypsum , goethite , native gold , hematite , Kröhnkit and Paratacamit identified.

As a rare mineral formation, botallackite has only been described in a few localities. So far (as of 2016) around 50 sites are known to be known. In the type locality applicable Botallack Mine in the St Just Mining District, Cornwall , and the mines in the immediate area, the mineral was found in several places. The correct type locality of the botallackite is the upper levels (the 20-fathom level, directly below sea level) of the “Wheal Cock” mines at St Just . In the late 1960s Richard Barstow and JR Knight succeeded in finding steps from the 24-fathom level (one thread equals 1.83 m) on the " Levant Mine " at Trewellard north of St Just (which was incorrectly attributed to the Botallack Mine has been). Further finds of well-formed crystals were reported from 1976 to 1987 in the submarine lode of the "Levant Mine" and from 1984 to 1986 in the Corpus Christi Load and on Allen's Shaft of the "Botallack Mine". After the submarine connection from the “Geevor Tin Mine” to the “Levant Mine” had been established, beautiful steps with botallackite on atakamite were recovered in the submarine lode of the “Levant Mine”. In 1988, emerald green crystals no longer than 4 mm long were found on the 235 m level of the South Lode in the "Levant Mine". Further finds from this mining area were found at “Loe Warren Zawn” and “West Wheal Owles” (“Cargodna Mine”), both near Botallack not far from St Just.

The second important Cornish discovery district for botallackite is the St Agnes mining district . After A. Kingsbury had found botallackite for the first time in 1952 at “Cligga Head” near Perranzabuloe and in 1985/86, elongated, flat-distorted botallackite crystals up to 2 mm long were recovered from “Hanover Cove” (Vugga Hayle) near St Agnes , the collector succeeded Michael Merry in April 2007 at Cligga Head an extraordinary new find with blue-green botallackite crystals up to 9 mm in length. T. sit in the cavities of dissolved potassium feldspars of a completely kaolinized granite . The steps were found right on the beach in the vicinity of mineralized veins . The copper required for the formation of botallackite comes from the weathering of the stannite in the corridors , the chlorine supplied the sea water. It is assumed that the crystallization of botallackite began in situ 4,000 to 5,000 years ago.

In addition, botallackite has been identified in a number of other locations in Cornwall. Other finds come from the "Penlee Quarry" at Paul , Mount's Bay , and from the "Cuddrabridge Mine" (also Padstow Consols) on "Gunver Head" in Padstow near Wadebridge in the former district North Cornwall .

In the United Kingdom also from the "Esgair Hir & Esgair Fraith Mines" in the area of ​​the Nant-y-Moch Reservoir , Talybont, Ceulanymaesmawr, Principal Area Ceredigion , from the "Mines Royal and Crown Copper Works", Principal Area Neath Port Talbot , dated Beach at Abersoch not far from Llanengan, Lleyn Peninsula , Principal Area Gwynedd , all Wales , as well as from the "Castletown Mine" at Lochgilphead , Strathclyde , Scotland . In Ireland from the “Dooneen Mine”, Allihies, Beara Peninsula , and the “Coosheen Mine”, Townland Coosheen, Schull , Mizen Peninsula , both in County Cork , and in crystals up to 2 mm from the “Stage Mine” Knockmahon, Bonmahon , County Waterford . From the "Cap Garonne Mine" at Le Pradet , Var , Region Provence-Alpes-Cote d'Azur , and the slag finds course "La Fonderie" at Poullaouen , Finistère department , Brittany , France .

In Germany , steps with beautiful botallackite crystals up to 0.3 mm in size come from the roof mountains of the "Graf-Hohenthal-Schachtes" ("Hans-Seidel-Schacht") near Eisleben , from slag from the Kupferkammerhütte near Hettstedt , both in the Mansfeld Basin in Saxony- Anhalt , as well as from the slag discovery site "Herzog Julius-Hütte" near Astfeld not far from Goslar in the Harz region of Lower Saxony . Also from slag heaps of the Richelsdorfer Hütte near Suss-Nentershausen in the Richelsdorf district , Hesse , and from the uranium test mining at Rudolfstein , Weißenstadt , Fichtelgebirge , Franconia , Bavaria .

In Austria , botallackite was only found on the heaps at Gratlspitz near Brixlegg-Rattenberg, Schwaz - Brixlegg area in the Inn Valley , Tyrol . Locations in Switzerland are unknown.

From the slag discovery sites "Carpenara", Val Varenna near Genoa , metropolitan city Genoa , Liguria region , and "Baratti" near Piombino , Livorno province , Tuscany region , both Italy . In Greece from the “Esperanza Mine”, the “Sounion Mine No. 19 ”(“ Chloridstollen ”) not far from Sounion and from the nearby slag discovery sites, all near Lavrion , Attica . From the west shaft of the “Polkowice Mine” near Polkowice in the copper mining district of Lubin, Lower Silesian Voivodeship (Dolnoslaskie), Poland .

From the "Mina Santo Domingo" near Gatico, Tocopilla Province , Antofagasta Region , Chile . In the United States from the "Southwest Mine" at Bisbee in the Mule Mts, from the "Gallagher Vanadium & Rare Minerals Corporation Mine" in the Tombstone Hills, both in Cochise County , and from the "Tonopah-Belmont Mine" at Belmont Mountain , Tonopah , Osborn District, Big Horn Mts, Maricopa County , all in Arizona . Also from "Balmat" in the Balmat-Edwards Zinc District, St. Lawrence County , New York , from the "Eagle Picher Mine", Creta in Jackson County , Oklahoma , and from the slag discovery site at the "ASARCO Smelter Site", Ruston , Tacoma , Pierce County , Washington .

Other locations are in Australia , the Isle of Man , Japan , Canada , Kazakhstan , South Africa and the United Kingdom .

use

Steps with botallackite crystals are primarily formations sought after by collectors. In addition, copper oxychlorides such as B. Botallackite plays a special role in the corrosion of copper alloys (bronzes), but also as pigments in wall painting, book illumination and on paintings. A number of the uses listed below do not explicitly apply to botallackite, but to the chemical compound copper oxychloride .

As a pigment

In the Mogao grottoes near Dunhuang in the Chinese province of Gansu , botallackite was found to be a green component of the wall paintings from the eighth century. For a long time it was unclear whether this was original pigments or degradation products from e.g. B. malachite . According to recent studies, pigments found on paintings, which were originally assumed to have been made from a copper trihydroxychloride (i.e. a Cu 2 (OH) 3 Cl polymorph), are conversion products of original pigments such as malachite. This is especially true for botallackite. Botallackite has also been identified in a Persian manuscript from the 15th century, but the spherical, zoned shape of the crystals suggests that this is a synthetic analogue of botallackite.

In chemistry

The presence of botallackite as a corrosion product in bronze objects has been known since 1950 . So is z. B. in the powdery, greenish- blue patina of an antique bronze statue of the cat goddess Bastet from the Fogg Art Museum Botallackit. Botallackite was also identified in an Egyptian censer in the Walters Art Museum , Baltimore . The formation of the Cu 2 (OH) 3 Cl polymorphs including botallackite takes place in connection with the so-called bronze disease ("bronze disease"), a corrosion of bronze artifacts. Cu 2 (OH) 3 Cl was used as a blue-green coloring agent in pyrotechnic products .

Cu 2 (OH) 3 Cl was also used in the production of catalysts and as a catalyst in halogenation or chlorination and / or oxidation . So Cu 2 (OH) 3 Cl is e.g. B. been used as a catalyst in the chlorination of ethylene .

In the medicine

Artificially produced dicopper trihydroxychlorides are used as micronutrients in animal feed mixes. In industrial production, equivalents of atacamite and paratacamite are made - and the formation of botallackite is avoided. However, a Chinese patent deals with the manufacture and use of botallackite for animal feed additives.

Copper oxychloride , Cu 2 (OH) 3 Cl, was used as a fungicidal spray ( contact fungicide ) to protect tea, oranges, wine, rubber, coffee, cardamom, cotton, etc.; also as a spray on rubber plants to prevent Phytophthora from attacking their leaves. In Germany, pesticides with this active ingredient are approved for growing pome fruit and strawberries. In Austria and Switzerland, copper oxychloride preparations are permitted in potatoes and grapevines as well as in a large number of fruits, berries and vegetables.

See also

literature

Web links

Commons : Botallackite  - collection of images, videos and audio files

Individual evidence

  1. ↑ a b c d e f g h i j k Werner Krause: X-ray powder diffraction data for botallackite . In: Powder Diffraction . tape 21 , 2006, p. 59-62 , doi : 10.1154 / 1.2104548 (English).
  2. ↑ a b c d e f Botallackite . In: John W. Anthony, Richard A. Bideaux, Kenneth W. Bladh, Monte C. Nichols (Eds.): Handbook of Mineralogy, Mineralogical Society of America . 2001 (English, handbookofmineralogy.org [PDF; 71  kB ; accessed on March 28, 2019]).
  3. ↑ a b c d Rupert Hochleitner, Stefan Weiß: Botallackite profile . In: Lapis . tape 25 (Issue 1), 2000, pp. 9-11 .
  4. ^ A b c d e Arthur Herbert Church : Notes on a Cornish mineral of the atacamite group . In: Journal of the Chemical Society . tape  18 , 1865, p. 212–214 ( available online at rruff.info [PDF; 127 kB ; accessed on March 28, 2019]).
  5. ↑ a b c d e f g h Clifford Frondel : On paratacamite and some related copper chlorides . In: The Mineralogical Magazine . tape  29 , 1950, pp. 34–45 (English, available online at rruff.info [PDF; 578 kB ; accessed on March 28, 2019]).
  6. ↑ a b Rudolf Duthaler, Stefan Weiß: Clean, prepare and store minerals. The workbook for the collector . 1st edition. Christian Weise Verlag, Munich 2008, ISBN 978-3-921656-70-9 , p. 138, 152 .
  7. ^ Edward Salisbury Dana: The system of mineralogy of James Dwight Dana. 1837-1868. Descriptive mineralogy . 6th edition. Wiley, New York 1892, pp. 1-1134 .
  8. ^ A b Carl Hintze : Handbook of Mineralogy . Section 2, 2nd half: Haloids: chlorides (as well as bromides, iodides, fluorides) and oxychlorides (as well as oxyfluorides). 1st edition. tape  1 . Veit & Co., Leipzig 1915, p. 2575 .
  9. ↑ Michael Fleischer : New Mineral Names . In: The American Mineralogist . tape  36 , 1951, pp. 384 (English, available online at minsocam.org [PDF; 274 kB ; accessed on March 28, 2019]).
  10. ↑ AA Voronova, BK Vainshtein: An electron diffraction study of CuCl 2 · 3 Cu (OH) 2 . In: Sov. Phys. Crystallogr. tape 3 , 1958, pp. 445-451 (English).
  11. ^ A b Frank C. Hawthorne: Refinement of the crystal structure of botallackite . In: The Mineralogical Magazine . tape 49 , 1985, pp. 87–89 (English, available online at rruff.info [PDF; 178 kB ; accessed on March 28, 2019]).
  12. ^ Arthur WG Kingsbury: Some minerals of special interest in southwest England . In: KFG Hosking, GJ Shrimpton (Ed.): Present Views of Some Aspects of the Geology of Cornwall and Devon . 1st edition. Royal Geological Society of Cornwall, Truro 1964, p. 247-266 (English).
  13. ↑ a b JR Knight: Botallackite - A locality correction . In: The Mineralogical Record . tape 33 , 2002, pp. 347-348 (English).
  14. ↑ The Mineralogical Record - Short biography of Arthur WG Kingsbury (English)
  15. ↑ John Leslie Jambor , John E. Dutrizac , Andrew C. Roberts , Joel D. Grice , Jan T. Szymański : Clinoatacamite, a new polymorph of Cu 2 (OH) 3 Cl, and its relationship to paratacamite and “anarakite” . In: The Canadian Mineralogist . tape  34 , 1996, pp. 61–72 (English, available online at rruff.info [PDF; 1,2 MB ; accessed on March 28, 2019]).
  16. ^ Richard SW Braithwaite, Kurt Mereiter, Werner H. Paar, AM Clark: Herbertsmithite, Cu 3 Zn (OH) 6 C l2 , a new species, and the definition of Paratacamite . In: Mineralogical Magazine . tape 68 , 2004, p. 527–539 (English, available online at rruff.info [PDF; 703 kB ; accessed on March 28, 2019]).
  17. ^ Claude H. Yoder, RW Schaeffer, PF McCaffrey, A. Rowand, X. Liu, J. Schaeffer: The synthesis of copper / zinc solid solutions of hydroxyl carbonates, sulphates, nitrates, chlorides and bromides . In: Mineralogical Magazine . tape 75 , 2011, p. 2573–2582 , doi : 10.1180 / minmag.2011.075.5.2573 (English, available online at rruff.info [PDF; 703 kB ]).
  18. ↑ Botallackite. In: mindat.org. Hudson Institute of Mineralogy, accessed March 28, 2019 .
  19. ↑ HR Oswald, Y. Iitaka, S. Locchi, A. Ludi: The crystal structures of Cu 2 (OH) 3 Br, and Cu 2 (OH) 3 J . In: Helvetica Chimica Acta . tape 44 , 1961, pp. 2103-2109 , doi : 10.1002 / hlca.19610440737 .
  20. ↑ a b Hexiong Yang, Isabel F. Barton, Marcelo B. Andrade, Robert T. Downs: Crystal structure of a new compound, CuZnCl (OH) 3 , botallackite isostructural with . In: The American Mineralogist . tape 101 , 2016, p. 986–990 , doi : 10.2138 / am-2016-5560 (English).
  21. ^ Andrew D. Butterworth: The utilization of layered hydroxysalts in the separation, immobilization and long term storage of long-lived radio-anions of nuclear power legacy waste origin . Loughborough University PhD thesis, Loughborough 2013, pp. 1–195 (English, available online at dspace.lboro.ac.uk [PDF; 5.2 MB ; accessed on March 28, 2019]).
  22. ↑ Victor Leopold Ritter von Zepharovich : The Atakamite Crystals from South Australia . In: Session reports of the mathematical and natural science class of the Imperial Academy of Sciences . tape  68 (born 1873). Verlag Carl Gerold's Sohn, Vienna 1874, p. 120–131 ( available online in the meeting reports of the mathematical and natural science class of the Imperial Academy of Sciences, pp. 130 f. In the Google book search).
  23. ^ A b Nicholas Eastaugh, Valentine Walsh, Tracey Chaplin, Ruth Siddall: Pigment compendium: optical microscopy of historical pigments . 1st edition. Elsevier, Butterworth-Heinemann, Amsterdam 2004, ISBN 0-7506-4553-9 , pp. 62-63 (English).
  24. ↑ a b AM Pollard, RG Thomas, Peter A. Williams: Synthesis and stabilities of the basic copper (II) chlorides atacamite, paratacamite and botallackite . In: The Mineralogical Magazine . tape 53 , 1950, pp. 557–563 (English, available online at rruff.info [PDF; 416 kB ; accessed on March 28, 2019]).
  25. ^ Hugo Strunz , Ernest H. Nickel : Strunz Mineralogical Tables. Chemical-structural Mineral Classification System . 9th edition. E. Schweizerbart'sche Verlagbuchhandlung (Nägele and Obermiller), Stuttgart 2001, ISBN 3-510-65188-X , p.  172 (English).
  26. ^ A b c Mark D. Hannington: The formation of atacamite during weathering of sulfides on the modern seafloor . In: The Canadian Mineralogist . tape 31 , 1993, pp. 945–956 (English, available online at rruff.info [PDF; 3.1 MB ; accessed on March 28, 2019]).
  27. ↑ Localities for Botallackite. In: mindat.org. Hudson Institute of Mineralogy, accessed March 28, 2019 .
  28. ↑ a b c List of locations where botallackite was found in the Mineralienatlas and Mindat
  29. ↑ a b Michael Merry, Stefan Weiß: Sensational new discovery: Botallackite from Cligga Head, Cornwall . In: Lapis . tape 32 , no. 9 , 2007, p. 33-36 .
  30. ↑ Stefan Weiss: The mining districts of St. Just and St. Ives in Cornwall . In: Lapis . tape 11 , no. 5 , 1986, pp. 9-32 .
  31. ^ P. Gay, PJ Wheatley: Conference Reports: Summarized proceedings of a conference on X-ray analysis - Cardiff, April, 1957 . In: British Journal of Applied Physics . tape 8 , 1957, pp. 433 (English).
  32. ^ Richard SW Braithwaite, J. Ike Wilson: Botallackite, including good crystals, from Ireland . In: Journal of the Russell Society . tape 7 , 2001, p. 96 (English, available online at mindat.org [PDF; 13.8 MB ; accessed on March 28, 2019]).
  33. ↑ Jürgen Siemroth, Thomas Witzke : The minerals of the Mansfeld copper slate . In: Series of the Mansfeld Museum New Series . tape 4 , 1999, p. 41 .
  34. ^ Ian NM Wainwright, Elizabeth A. Moffatt, P. Jane Sirois, Gregory S. Young: Analysis of Wall Painting Fragments from the Mogao and the Bingling Temple Grottoes . In: Neville Agnew (Ed.): Conservation of Ancient Sites on the Silk Road . Proceedings of an International Conference on the Conservation of Grotto Sites Mogao Grottoes, Dunhuang The People's Republic of China 3-8 October 1993. The Getty Conservation Institute, Los Angeles 1993, ISBN 0-89236-416-5 , pp. 334-340 (English, available online in Analysis of Wall Painting Fragments from the Mogao and the Bingling Temple Grottoes, p. 334 f. In the Google book search).
  35. ↑ a b David A. Scott: A review of copper chlorides and related salts in bronze corrosion and as painting pigments . In: Studies in Conservation . tape 45 , 2000, pp. 39-53 (English).
  36. ↑ Elizabeth West FitzHugh: Appendix 9: Study of pigments on selected paintings from the Verver Collection . In: Glenn D. Lowry, Milo Cleveland Beach (Ed.): An annotated and illustrated checklist of the Verver Collection . 1st edition. University of Washington Press, Washington, DC 1988, ISBN 0-295-96678-5 , pp. 425-432 (English).
  37. ↑ Rutherford John Gettens: The corrosion products of an ancient Chinese bronze . In: Journal of Chemical Education . tape 28 , 1951, pp. 67–71 , doi : 10.1021 / ed028p67 (English).
  38. ↑ Rutherford John Gettens, Clifford Frondel: Chalconatronite: an alteration product on some ancient Egyptian bronzes . In: Studies in Conservation . tape 2 , 1955, pp. 64-75 , doi : 10.2307 / 1504919 (English).
  39. ^ Clifford Frondel, Rutherford John Gettens: Chalconatronite, a new Mineral from Egypt . In: Science . tape 122 , no. 3158 , 1955, pp. 75–76 , doi : 10.1126 / science.122.3158.75 (English).
  40. ↑ Rutherford John Gettens: The corrosion products of metal antiquities . In: Annual Report of the Board of Regents of the Smithsonian Institution for 1963 . tape 1964 , 1964, pp. 547-568 (English).
  41. ^ H. Wayne Richardson (Ed.): Handbook of copper compounds and applications . 1st edition. Taylor & Francis, New York 1997, ISBN 0-8247-8998-9 , pp. 71 (English).
  42. ↑ Carlo Lamberti, Carmelo Prestipino, Francesca Bonino, Luciana Capello, Silvia Bordiga, Giuseppe Spoto, Adriano Zecchina, Sofia Diaz Moreno, Barbara Cremaschi, Marco Garilli, Andrea Marsella, Diego Carmello, Sandro Vidotto, Giuseppe Leofanti: The Chemistry of the Oxychlorination Catalyst : an In Situ, Time-Resolved XANES Study . In: Angewandte Chemie International Edition . tape 41 , 2002, p. 2341-2344 , doi : 10.1002 / 1521-3773 (20020703) 41:13 <2341 :: AID-ANIE2341> 3.0.CO; 2-P (English).
  43. ^ Andrej Lubej, Tine Koloini, Ciril Pohar: Industrial precipitation of cupric hydroxy salts . In: Acta Chim. Slov. tape 51 , 2004, p. 751–768 (English, available online at acta-arhiv.chem-soc.si [PDF; 314 kB ; accessed on March 28, 2019]).
  44. ↑ Commission Directive 2009/37 / EC of April 23, 2009 amending Council Directive 91/414 / EEC to include the active substances chlormequat, copper compounds, propaquizafop, quizalofop-P, teflubenzuron and zeta-cypermethrin (PDF)
  45. ↑ General Directorate Health and Food Safety of the European Commission: Entry on Copper oxychloride in the EU pesticide database ; Entry in the national registers of plant protection products in Switzerland , Austria and Germany ; accessed on February 23, 2016.