Paramelaconite

{{Short description|Oxide mineral}} {{Infobox mineral | name = Paramelaconite | category = Oxide mineral | boxwidth = | boxbgcolor = | image = Paramelaconite-304492.jpg | imagesize = | caption = Paramelaconite from the Copper Queen Mine, Cochise County, Arizona, USA | formula = Cu{{su|b=2|p=I}}Cu{{su|b=2|p=II}}O₃<ref name="handbook" /> (or Cu₄O₃){{sfn|Morgan et al.|1996|p=33}} | IMAsymbol = Pml<ref>{{Cite journal|last=Warr|first=L.N.|date=2021|title=IMA–CNMNC approved mineral symbols|url=https://www.cambridge.org/core/journals/mineralogical-magazine/article/imacnmnc-approved-mineral-symbols/62311F45ED37831D78603C6E6B25EE0A|journal=Mineralogical Magazine|volume=85|issue=3 |pages=291–320|doi=10.1180/mgm.2021.43 |s2cid=235729616 |doi-access=free|url-access=subscription}}</ref> | molweight = | strunz = 4.AA.15 | dana = 4.6.4.1 | system = Tetragonal | class = Ditetragonal dipyramidal (4/mmm) <br />H-M group: (4/m 2/m 2/m) | symmetry = I4₁/amd {I4₁/a 2/m 2/d} | unit cell = a = 5.837&nbsp;Å, <br/>c = 9.932&nbsp;Å; Z&nbsp;=&nbsp;4<ref name="handbook" /> | color = Black to black with a slight purple tint<br />White with pinkish brown tint in reflected light | habit = Occurs as striated prismatic crystals; massive | twinning = | cleavage = None observed | fracture = Conchoidal | tenacity = Brittle | mohs = 4.5 | luster = Sub-adamantine, greasy, sub-metallic | polish = | refractive = | opticalprop = Uniaxial<ref name="handbook" /> | birefringence = | 2V = | dispersion = | pleochroism = Weak | fluorescence= Not fluorescent | absorption = | streak = Brown-black | gravity = 6.04–6.11 (measured) | density = | melt = | fusibility = | diagnostic = | solubility = Soluble in HCl and HNO₃{{sfn|Koenig|1892|p=287}} | diaphaneity = Opaque | other = | references =<ref name="mindat" /> }}

'''Paramelaconite''' is a rare, black-colored copper(I,II) oxide mineral with formula Cu{{su|b=2|p=I}}Cu{{su|b=2|p=II}}O₃ (or Cu₄O₃). It was discovered in the Copper Queen Mine in Bisbee, Arizona, about 1890. It was described in 1892 and more fully in 1941. Its name is derived from the Greek word for "near" and the similar mineral melaconite, now known as tenorite.

== Description and occurrence == [[File:Paramelaconite.jpg|left|thumb|Type material from the Copper Queen Mine held at the A. E. Seaman Mineral Museum]] Paramelaconite is black to black with a slight purple tint in color, and is white with a pinkish brown tint in reflected light. The mineral occurs with massive habit or as crystals up to {{convert|7.5|cm|in|0|abbr=on}}.<ref name="handbook" /> A yellow color is formed when the mineral is dissolved in hydrochloric acid, a blue color when dissolved in nitric acid, and a slightly brown precipitate when exposed to ammonium hydroxide.{{sfn|Koenig|1892|p=287}} When heated, paramelaconite breaks down into a mixture of tenorite and cuprite.{{sfn|Frondel|1941|pp=657–658}}

Paramelaconite is a very rare mineral; many specimens purported as such are in fact mixtures of cuprite and tenorite.{{sfn|O'Keeffe|Bovin|1978|p=180}} Paramelaconite forms as a secondary mineral in hydrothermal deposits of copper. It occurs in association with atacamite, chrysocolla, connellite, cuprite, dioptase, goethite, malachite, plancheite, and tenorite.<ref name="handbook" /> The mineral has been found in Cyprus, the United Kingdom, and the United States.<ref name="mindat" />

== Structure == Paramelaconite crystallizes in the tetragonal crystal system.<ref name="mindat" /> Its space group was correctly identified by Frondel as I4₁/amd. In 1978, O'Keeffe and Bovin determined the formula to be Cu₄O₃, specifically Cu{{su|b=2|p=I}}Cu{{su|b=2|p=II}}O₃. There has been misunderstanding and misreporting of the mineral's crystal structure, due in part to a typographical error in O'Keeffe and Bovin's paper and the commonality of choosing an incorrect origin for the I4₁/amd space group.{{sfn|Morgan et al.|1996|p=33}} At the same time as O'Keeffe and Bovin's report, a paper by Datta and Jeffery determined a structure for the mineral based on the incorrect formula Cu{{su|b=12|p=II}}Cu{{su|b=4|p=I}}O₁₄.{{sfn|Morgan et al.|1996|p=33}}{{sfn|Datta|Jeffery|1978|p=22}} The formula originated from incorrectly assuming that Frondel's analysis was of a homogeneous crystal of paramelaconite.{{sfn|Morgan et al.|1996|p=33}}

== Synthesis == The synthesis of microscopic paramelaconite was reported in 1986 as a product of the decomposition of CuO in an electron microscope. However, this method is not easily scaled up to produce samples large enough for study. Reduction of CuO and decomposition in a vacuum and controlled oxidation of Cu₂O failed to synthesize the mineral. Experiments at the National Bureau of Standards using aqueous solutions up to 250 °C produced only Cu₂O and CuO. Oxidation of copper or its alloys also does not produce paramelaconite, despite reports to the contrary.{{sfn|Morgan et al.|1996|p=35}}

The first unequivocal synthesis of the mineral was achieved in the 1990s and published in 1996. The material produced was 35% Cu₄O₃, 27% Cu₂O, and 38% CuO.{{sfn|Morgan et al.|1996|p=33}} The process consists of the leaching of copper or its oxides with concentrated aqueous ammonia in a Soxhlet extractor. The reaction forms a deep blue complex of cupric ammonium that is converted to a residue of black oxide in the apparatus.{{sfn|Morgan et al.|1996|p=35}}

== History == thumb|Drawing of a specimen found by Foote; the center pyramid is paramelaconite Albert E. Foote visited the Copper Queen Mine about 1890,{{sfn|Frondel|1941|p=658}} where he obtained two specimens containing unknown minerals. He could only associate them with anatase, but he thought it unlikely that the minerals were any form of titanium oxide.{{sfn|Koenig|1892|p=284}} The specimens were sold to Clarence M. Bement at fifty dollars apiece, and with his permission, were studied by George Augustus Koenig.{{sfn|Frondel|1941|p=658}}{{sfn|Koenig|1892|p=284}} Bement's collection, including the specimens of paramelaconite, were purchased by J. P. Morgan in 1900 and given to the American Museum of Natural History.{{sfn|Morgan et al.|1996|p=33}}{{sfn|Frondel|1941|p=658}}

Owing to its unique appearance, Koenig assigned the mineral as a new species.{{sfn|Koenig|1892|p=289}} His description of the mineral appeared in an 1892 publication of the Academy of Natural Sciences of Philadelphia.{{sfn|Koenig|1892|p=284}} He named the mineral ''paramelaconite'' from the Greek παρά, meaning "near", and the mineral melaconite (now known as tenorite), for its compositional similarity to melaconite.<ref name="mindat" />{{sfn|Koenig|1892|p=284}} At the time, however, the mineral was not recognized as a valid species.{{sfn|Frondel|1941|p=658}}

Clifford Frondel studied the mineral in more detail and published his results in the journal ''American Mineralogist'' in 1941.{{sfn|O'Keeffe|Bovin|1978|p=180}}{{sfn|Frondel|1941|p=657}} When the International Mineralogical Association was founded in 1959, paramelaconite was grandfathered as a valid mineral species.<ref name="mindat" /> In the early 1960s, the third known specimen of paramelaconite was discovered from the Copper Queen Mine; Koenig donated it to the A. E. Seaman Mineral Museum. Other specimens in the museum, labeled as originating from the Algomah Mine in Ontonagon County, Michigan, were also found to contain paramelaconite.{{sfn|Williams|1962|p=778}}

The type material is held at the A. E. Seaman Mineral Museum in Houghton, Michigan, the American Museum of Natural History in New York City, Harvard University in Cambridge, Massachusetts, the National Museum of Natural History in Washington, D.C., and the Natural History Museum in London.<ref name="handbook" />

== References == {{reflist | colwidth = 30em | refs = <ref name="handbook">{{cite encyclopedia | url = http://www.handbookofmineralogy.com/pdfs/paramelaconite.pdf | title = Paramelaconite | encyclopedia = Handbook of Mineralogy | editor1-first = John W. | editor1-last = Anthony | editor2-first = Richard A. | editor2-last = Bideaux | editor3-first = Kenneth W. | editor3-last = Bladh | editor4-first = Monte C. | editor4-last = Nichols | publisher = Mineralogical Society of America | location = Chantilly, VA | access-date = 2012-09-03 | archive-date = 2022-12-25 | archive-url = https://web.archive.org/web/20221225043111/https://www.handbookofmineralogy.com/pdfs/paramelaconite.pdf }}</ref> <ref name="mindat"> {{cite web | title = Paramelaconite | url = http://www.mindat.org/min-3098.html | publisher = Mindat | access-date = September 3, 2012 }} </ref> }}

=== Bibliography === * {{cite journal | last1=Datta|first1=N.|last2=Jeffery|first2=J. W.|title=The Crystal Structure of Paramelaconite, Cu{{su|b=12|p=2+}}Cu{{su|b=4|p=1+}}O₁₄|journal=Acta Crystallographica Section B|year=1978|volume=34|pages=22–26|doi=10.1107/S056774087800223X }} {{subscription required}} * {{cite journal | last=Frondel|first=Clifford|title=Paramelaconite, a tetragonal oxide of copper|journal=American Mineralogist|date=November 1941|volume=26|issue=11|pages=567–672|url=http://rruff.info/uploads/AM26_657.pdf}} * {{cite journal | last=Koenig|first=George Augustus|title=On paramelaconite, and the associated minerals|journal=Proceedings of the Academy of Natural Sciences of Philadelphia|year=1892|volume=43|pages=284–291|url=https://books.google.com/books?id=-MNLAAAAYAAJ&pg=PA284 }} * {{cite journal | last1=Morgan|first1=P. E. D.|last2=Partin|first2=D. E.|last3=Chamberland|first3=B. L.|last4=O'Keeffe|first4=M.|title=Synthesis of Paramelaconite: Cu₄O₃|journal=Journal of Solid State Chemistry|date=January 5, 1996|volume=121|issue=1|pages=33–37|doi=10.1006/jssc.1996.0005 | ref = {{sfnRef|Morgan et al.|1996}} |bibcode = 1996JSSCh.121...33M }} {{subscription required}} * {{cite journal | last1=O'Keeffe|first1=M.|last2=Bovin|first2=J.-O.|title=The crystal structure of paramelaconite Cu4O3|journal=American Mineralogist|date=January–February 1978|volume=63|issue=12|pages=180–185|url=http://www.minsocam.org/ammin/AM63/AM63_180.pdf}} * {{cite journal | last=Williams|first=Sidney A.|title=Paramelaconite and associated minerals from the Algomah mine, Ontonagon County, Michigan|journal=American Mineralogist|date=May–June 1962|volume=47|issue=5–6|pages=778–779|url=http://www.minsocam.org/ammin/AM47/AM47_778.pdf}}

=== Further reading === * {{cite journal|last1=Pinsard-Gaudart|first1=L.|last2=Rodríguez-Carvajal|first2=J.|last3=Gukasov|first3=A.|last4=Monod|first4=P.|title=Magnetic properties of paramelaconite (Cu₄O₃): A pyrochlore lattice with ''S'' = 1/2|journal=Physical Review B|date=1 March 2004|volume=69|issue=10|article-number=104408|doi=10.1103/PhysRevB.69.104408|bibcode = 2004PhRvB..69j4408P }} {{subscription required}}

== External links == {{Commonscat-inline|Paramelaconite}}

Category:Tetragonal minerals Category:Minerals in space group 141 Category:Copper(I,II) minerals Category:Oxide minerals Category:Minerals described in 1892