Fumarole formation of tazieffite acicular crystals (black) at Mutnovsky, Kamchatka. An electron micrograph, colour enhanced by optical microscopy, depicted width: 700 microns.

Fumarole minerals (or fumarolic minerals) are minerals which are deposited by fumarole exhalations. They form when gases and compounds desublimate or precipitate out of condensates, forming mineral deposits. They are mostly associated with volcanoes (as volcanic sublimate or fumarolic sublimate) following deposition from volcanic gas during an eruption or discharge from a volcanic vent or fumarole,[1] but have been encountered on burning coal deposits as well. They can be black or multicoloured and are often unstable upon exposure to the atmosphere.

Native sulfur is a common sublimate mineral and various halides, sulfides and sulfates occur in this environment associated with fumaroles and eruptions. A number of rare minerals are fumarole minerals, and at least 240 such minerals are known from Tolbachik volcano in Kamchatka, Russia. Other volcanoes where particular fumarole minerals have been discovered are Vulcano in Italy and Bezymyanny also in Russia.

Origin and appearance

Fumarole minerals in SEM images, from Mutnovsky volcano in Kamchatka. An electron micrograph, colour enhanced by optical microscopy, depicted width: 700 microns.

In fumaroles, minerals either form through desublimation from fumarole gases or through interactions of fumarole gases with country rock.[2] The former are known as sublimates and the latter as incrustations.[3] Some such deposits may also form through the interaction between liquid fumarole condensates and country rock[4] and are not always formed by desublimation.[5] Repeated cycles of primary deposition and secondary alteration may occur.[6] Volcanic gases such as hydrogen chloride, hydrogen fluoride, sulfur dioxide and water[7] can transport large amounts of elements, thus contributing to geochemical cycles on the surface and the formation of ore deposits at depth.[8] When these exhalations reach the atmosphere and cool, the minerals contained in them tend to precipitate out.[9]

Volcanic fumarole minerals (as volcanic sublimate or fumarolic sublimate) form following deposition from volcanic gas during an eruption or discharge from a volcanic vent or fumarole.[1] Burning coal produces enough heat to partially melt rocks and to generate exhalations of the mineral components embedded in coal.[10] Coal seam fires often deposit fumarolic minerals over areas of a few square metres which can be detected by airborne hyperspectral imagery.[11] Coal fires can mobilize toxic trace elements.[12] Fumarole minerals have also been found in Gusev crater on Mars.[13]

Fumarole deposits have been used to identify heat flow anomalies and to reconstruct ore genesis processes.[6]

Fumarole exhalations are often black or multicoloured, and tend to develop typical zonations. Common components are sulfur compounds and elemental sulfur.[9] In the Valley of Ten Thousand Smokes in Alaska the fumarole minerals form both thin crusts in the vents, mixtures with tephra deposits[14] and coloured outcrops and mounds at the sites of former fumaroles.[15] Deposits at Tolbachik volcano have shapes likef crusts, small plates[16] and globules.[17]

Typical components of fumarole minerals are halides, oxides, sulfates and sulfides,[18] with the exact composition different between volcanoes, individual vents at volcanoes and different temperatures of the same vent.[19] Fumarolic minerals are often unstable and are eroded or decompose,[20] in the Valley of Ten Thousand Smokes in Alaska it took less than a century for almost all fumarole mineral deposits to disappear[21] although others remained and were later used to identify former fumarole vents.[22] Thus, many fumarole minerals are rare and many rare minerals are fumarole minerals.[23] Some fumarolic minerals have been found in extinct Cenozoic volcanoes[24] and could exist in Archean rocks as well, however.[25] Unique textures occur such as bubble-like structures, which may form when the liquid that deposits the minerals evaporates.[4]

Volcanoes

Electron micrograph images of fumarolic minerals at Mutnovsky volcano, Kamchatka

Research on the mineralogy of fumarole minerals has been conducted in Central America, Russia and Europe,[18] with detailed publications on Izalco in El Salvador,[26] Eldfell in Iceland,[27] Vesuvius[19] where research goes back to the early 19th century[28] and Vulcano in Italy, Mount Usu in Japan, Kudryavy and Tolbachik in Russia, Kilauea and Mount St. Helens in the United States.[18] Sulfur deposits containing fumarolic desublimates are found at Guallatiri and Lastarria volcanoes in the Central Volcanic Zone of the Andes.[29] Kudryavy volcano in the Kurils is particularly known for the numerous mineralizations its fumaroles have produced[30] and for the presence of rhenium-rich precipitates.[3] Among the elements found there are copper-gold-silver alloys.[31] Various sulfate-based minerals have been identified at the Salton Buttes in California.[32] Fumarolic minerals have also been reported from the Western Andes in Bolivia.[33]

The most fumarolic minerals have been found at Tolbachik volcano in Kamchatka, Russia; Tolbachik also has one of the most diverse mineral assemblages in the world.[24] The high temperature and oxidizing regime of exhalations which transport the elements at Tolbachik facilitates mineral deposition.[34] A large assemblage of silicates[35] and a number of copper-zinc selenite chlorides[36] and copper-based fumarolic minerals were discovered at Tolbachik volcano, Kamchatka, Russia. Many of these include polymeric CuO
4 units.[2] About 240 minerals have been identified at Tolbachik,[24] close to a record,[37] 40 of them only incompletely studied.[38] Elemental gold linked to chlorides at Tolbachik has been interpreted as gold transported by chlorine-rich oxidizing environments.[39] Specimens of fumarole minerals from Tolbachik and Kudryavy are hosted by the Fersman Mineralogical Museum in Moscow.[40]

Historical lava flows of Vesuvius volcano contain fumarolic minerals.[41] Various fumarole minerals have been discovered at Vulcano volcano in Italy, where the mineralogy has changed since 1987 and 1990 due to hotter fumarole exhalations,[42] yielding increased sulfate and sulfur salt concentrations.[43] Fumarolic minerals have also been encountered in multiple mud volcanoes in Siberia.[44]

Minerals discovered in fumarole areas

Mineral Formula Location Date described Ref
Abramovite Pb
2SnInBiS
7		 Kudryavy, Russia 2008 [45]
Allochalcoselite Cu+
Cu2+
5PbO
2(SeO
3)
2Cl
5		 [46]
Aluminocoquimbite AlFe(SO
4)*
3H
2O		 Grotta del' Alume, Vulcano, Italy 2010 [47]
Aluminopyracmonite (NH
4)
3Al(SO
4)
3		 La Fossa, Vulcano, Italy 2018 [48]
Arsmirandite Na
18Cu2+
12Fe3+
O
8(AsO
4)
8Cl
5		 Arsenatnaya fumarole, Tolbachik, Russia 2020 [2]
Axelite Na
14Cu
7(AsO
4)
8F
2Cl
2		 Arsenatnaya fumarole, Tolbachik, Russia 2022 [49]
Baliczunicite Bi
2O(SO
4)
2		 La Fossa, Vulcano, Italy 2013 [43]
Belomarinaite KNaSO
4		 Toludskoe lava field, Tolbachik, Russia 2019 [50]
Belousovite KZn(SO
4)Cl		 Yadovitaya fumarole, Second Scoria Cone, Tolbachik, Russia 2018 [51]
Blossite a-
Cu2+
2V5+
2O
7		 Izalco, El Salvador 1987 [26]
Bubnovaite K
2Na
8Ca(SO
4)
6		 Naboko cone, Tolbachik, Russia [52]
Cadmoindite CdIn
2S
4		 Kudryavy, Russia 2004 [53]
Calciolangbeinite K
2Ca
2(SO
4)
3		 Arsenatnaya fumarole, Tolbachik, Russia 2022 [54]
Campostriniite (Bi3+
,Na)
3(NH,
4K)
2Na
2(SO
4)·
6H
2O		 La Fossa, Vulcano, Italy 2015 [55]
Cannizzarite Pb
46Bi
54(S
,Se)
127		 La Fossa, Vulcano, Italy [56]
Cesiodymite CsKCu
5O(SO
4)
5		 Second Scoria Cone, Tolbachik, Russia 2018 [57]
Chubarovite KZn
2(BO
3)Cl
2		 Arsenatnaya fumarole, Tolbachik, Russia 2015 [58]
Cryptocalcite K
2Cu
5O(SO
4)
5		 Second Scoria Cone, Tolbachik, Russia 2018 [57]
Cuprodobrovolskyite Na
4Cu(SO
4)
3		 Second Scoria Cone, Tolbachik 2023 [59]
Cupromolybdite Cu
3O(MoO
4)
2		 New Tolbachik scoria cones, Tolbachik, Russia 2012 [60]
D'ansite Na
21Mn2+
(SO
4)
10Cl		 Vesuvius and Vulcano, Italy 2012 [61]
Demartinite K
2SiF
6		 La Fossa, Vulcano, Italy 2007 [62]
Demicheleite BiSI and BiSBr La Fossa, Vulcano, Italy 2010 and 2008 [63][64]
Dobrovolskyite Na
4Ca(SO
4)
3		 Great Tolbachik fissure eruption, Kamchatka peninsula, Russia 2021 [65]
Elasmochloite Na
3Cu
6BiO
4(SO
4)		 [66]
Eldfellite NaFe(SO
4)
2		 [67]
Ermakovite (NH
4)(As
2O
3)
2Br		 Fan-Yagnob coal deposit, Tajikistan 2022 [68]
Grigorievite Cu
3Fe3+
2Al
2(VO
4)		 Second Scoria Cone, Tolbachik, Russia 2015 [69]
Hermannjahnite CuZn(SO
4)
2		 Naboko scoria cone, Tolbachik, Russia 2018 [70]
Karpovite Tl
2VO(SO
4)
2(H
2O)		 First Cinder Cone, Tolbachik, Russia 2018 [71]
Knasibfite K
3Na
4[SiF
6]
3[BF
4]		 La Fossa, Vulcano, Italy 2008 [72]
Koksharovite CaMg
2Fe3+
4(VO
4)
6		 Bezymyanny, Russia 2015 [69]
Kudriavite (Cd
,Pb)Bi
2S
4		 Kudryavy, Russia 2004 [53]
Lehmannite Na
18Cu2+
12TiO
8(AsO
4)
8FCl
5		 Arsenatnaya fumarole, Tolbachik 2020 [2]
Leonardsenite MgAlF
5(H
2O)
2		 Eldfell, Heimaey, Iceland 2015 [69]
Lesyukite Al
2(OH)
5Cl20−
*H
2O		 First Cone, Tolbachik, Russia 2007 or earlier [73]
Lucabindiite (K
,NH
4)As
4O
6(Cl
,Br)		 La Fossa, Vulcano, Italy 2010–2011 [74]
Majzlanite K
2Na(ZnNa)Ca(SO
4)
4		 Yadovitaya fumarole, Tolbachik, Russia 2019 [75]
Medvedevite KMnV
2O
6Cl
*(H
2O)
2		 Toludskoe lava field, Tolbachik, Russia 2020 [76]
Napoliite Pb
2OFCl		 Vesuvius, 1994 rocks 2010-2020 [77]
Nishanbaevite KAl
2O(AsO
4)(SO
4)		 Arsenatnaya fumarole, Tolbachik, Russia 2022 [78]
Oskarssonite AlF
3		 Eldfell, Iceland 2018 [27]
Ozerovaite Na
2KAl
3(AsO
4)
4		 Second Cinder Cone, Tolbachik, Russia 2019 [79]
Paradimorphite As
4S
3		 Solfatara, Campi Flegrei, Italy 2022 [80]
Parageorgbokiite b-
Cu
5O
2(SeO
3)
2Cl
2		 Yadovitaya fumarole, Tolbachik, Russia 2007 [81]
Parascandolaite KMgF
3		 Vesuvius, Italy 2014 [82]
Parawulffite K
5Na
3Cu
8O
4(SO
4)
8		 Arsenatnaya fumarole, Tolbachik, Russia 2014 [83]
Petrovite Na
10CaCu
2(SO
4)
8		 Second Scoria Cone, Tolbachik, Russia 2020 [17]
Pliniusite Ca
5(VO
4)
3F		 Tolbachik, Russia 2022 [84]
Prewittite KPb
1.5Cu
6Zn(SeO
3)
2O
2Cl
10		 Second Scoria Cone, Tolbachik, Russia 2013 [36]
Pseudolyonsite Cu
3(VO
4)
2		 New Tolbachik scoria cones, Tolbachik, Russia 2011 [85]
Puninite Na
2Cu
3O(SO
4)
3		 Second scoria cone, Tolbachik, Russia 2017 [86]
Rhabdoborite Mg
12(V
,Mo
,W)
4/3O
6[(BO
3)
6–x(PO
4)
xF
2–x]		 Arsenatnaya fumarole, Tolbachik, Russia 2020 [87]
Russoite NH
4ClAs3+
2O
3(H
2O)
0.5		 Solfatara, Phlegrean Fields, Italy 2018 [88]
Ryabchikovite CuMg(Si
2O
6)		 Arsenatnaya, Tolbachik 2023 [89]
Sbacchiite Ca
2AlF
7		 Vesuvius, Italy 2019 [90]
Shcherbinaite V
2O
5		 Izalco, El Salvador 1983 [91]
Stoiberite Cu
5V
2O
10		 "Y fumarole", Izalco, El Salvador 1979 [92]
Therasiaite (NH
4)
3KNa
2Fe2+
Fe3+
(SO
4)
3Cl
5		 La Fossa, Vulcano, Italy 2014 [93]
Thermessaite (NH
4)
2AlF
3(SO
4)		 La Fossa, Vulcano, Italy 2021 [94]
Topsøeite FeF
3(H
2O)
3		 Hekla, Iceland 2018 [95]
Wulffite K
3NaCu
4O
2(SO
4)
4		 Arsenatnaya fumarole, Tolbachik, Russia 2014 [83]
Vasilseverginite Cu
9O
4(AsO
4)
2(SO
4)
2		 Arsenatnaya fumarole, Tolbachik, Russia 2021 [96]
Wrightite K
2Al
2O(AsO
4)
2		 Second Scoria Cone, Tolbachik, Russia 1983 [97]
Yavapaiite KFe(SO
4)
2		 [67]
Ziminaite Fe3+
VO
4		 Bezymyanny, Russia 2018 [98]
Zincobradaczekite NaCuCuZn
2(AsO
4)
3		 Yadovitaya fumarole, Tolbachik, Russia 2020 [99]

References

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  46. ↑ Lykova, Inna; Rowe, Ralph; Poirier, Glenn; Friis, Henrik; Helwig, Kate (9 December 2022). "Bounahasite, Cu+Cu2+2(OH)3Cl2, a new mineral from the Bou Nahas Mine, Morocco". Mineralogical Magazine. 87 (2): 218–224. doi:10.1180/mgm.2022.133. hdl:10852/101312. S2CID 254532654.
  47. ↑ Demartin, Francesco; Castellano, Carlo; Gramaccioli, Carlo Maria; Campostrini, Italo (1 December 2010). "ALUMINOCOQUIMBITE, AlFe(SO4)3·9H2O, A NEW ALUMINUM IRON SULFATE FROM GROTTA DELL'ALLUME, VULCANO, AEOLIAN ISLANDS, ITALY". The Canadian Mineralogist. 48 (6): 1465. doi:10.3749/canmin.48.5.1465. ISSN 0008-4476.
  48. ↑ Demartin, F.; Castellano, C.; Campostrini, I. (2018). "Aluminopyracmonite, (NH4)3Al(SO4)3, a new ammonium aluminium sulfate from La Fossa crater, Vulcano, Aeolian Islands, Italy". Mineralogical Magazine. 77 (4): 443. doi:10.1180/minmag.2013.077.4.04. ISSN 0026-461X. S2CID 130573127.
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  50. ↑ Filatov, Stanislav K.; Shablinskii, Andrey P.; Vergasova, Lidiya P.; Saprikina, Olga U.; Bubnova, Rimma S.; Moskaleva, Svetlana V.; Belousov, Alexander B. (2019). "Belomarinaite KNa(SO4): A new sulfate from 2012–2013 Tolbachik Fissure eruption, Kamchatka Peninsula, Russia". Mineralogical Magazine. 83 (4): 569–575. Bibcode:2019MinM...83..569F. doi:10.1180/mgm.2018.170. ISSN 0026-461X. S2CID 133750327.
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