Fumarole mineral

Fumarole formation of tazieffite  [ de ] 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, in this context called brimstone, 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] and possibly in a sample returned from the Moon by the probe Chang'e-5. ^[14]

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 ^[15] and coloured outcrops and mounds at the sites of former fumaroles. ^[16] Deposits at Tolbachik volcano have shapes likef crusts, small plates ^[17] and globules. ^[18]

Typical components of fumarole minerals are halides, oxides, sulfates and sulfides, ^[19] with the exact composition different between volcanoes, individual vents at volcanoes and different temperatures of the same vent. ^{[20] [21]} Fumarolic minerals are often unstable and are eroded or decompose, ^[22] in the Valley of Ten Thousand Smokes in Alaska it took less than a century for almost all fumarole mineral deposits to disappear ^[23] although others remained and were later used to identify former fumarole vents. ^[24] Thus, many fumarole minerals are rare and many rare minerals are fumarole minerals. ^[25] Some fumarolic minerals have been found in extinct Cenozoic volcanoes ^[26] and could exist in Archean rocks as well, however. ^[27] 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, ^[19] with detailed publications on Izalco in El Salvador, ^[28] Eldfell in Iceland, ^[29] Vesuvius ^[20] where research goes back to the early 19th century ^[30] and Vulcano in Italy, Mount Usu in Japan, Kudryavy and Tolbachik in Russia, Kilauea and Mount St. Helens in the United States. ^[19] Sulfur deposits containing fumarolic desublimates are found at Guallatiri and Lastarria volcanoes in the Central Volcanic Zone of the Andes. ^[31] Kudryavy volcano in the Kurils is particularly known for the numerous mineralizations its fumaroles have produced ^[32] and for the presence of rhenium-rich precipitates. ^[3] Among the elements found there are copper-gold-silver alloys. ^[33] Various sulfate-based minerals have been identified at the Salton Buttes in California. ^[34] Fumarolic minerals have also been reported from the Western Andes in Bolivia. ^[35]

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, ^[26] with a number of "endemic" minerals. ^[36] The high temperature and oxidizing regime of exhalations which transport the elements at Tolbachik facilitates mineral deposition. ^[37] A large assemblage of silicates ^[38] and a number of copper-zinc selenite chlorides ^[39] 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, ^[26] close to a record, ^[40] 40 of them only incompletely studied. ^[41] Elemental gold linked to chlorides at Tolbachik has been interpreted as gold transported by chlorine-rich oxidizing environments. ^[42] Specimens of fumarole minerals from Tolbachik and Kudryavy are hosted by the Fersman Mineralogical Museum in Moscow. ^[43]

Historical lava flows of Vesuvius volcano contain fumarolic minerals. ^[44] 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, ^[45] yielding increased sulfate and sulfur salt concentrations. ^[46] Fumarolic minerals have also been encountered in multiple mud volcanoes in Siberia. ^[47]

Minerals discovered in fumarole areas

Mineral	Formula	Location	Date described	Ref
Abramovite	Pb 2SnInBiS 7	Kudryavy, Russia	2008	[48]
Allochalcoselite	Cu+ Cu2+ 5PbO 2(SeO 3) 2Cl 5			[49]
Aluminocoquimbite	AlFe(SO 4)* 3H 2O	Grotta del' Alume, Vulcano, Italy	2010	[50]
Aluminopyracmonite	(NH 4) 3Al(SO 4) 3	La Fossa, Vulcano, Italy	2018	[51]
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	[52]
Baliczunicite	Bi 2O(SO 4) 2	La Fossa, Vulcano, Italy	2013	[46]
Belomarinaite	KNaSO 4	Toludskoe lava field, Tolbachik, Russia	2019	[53]
Belousovite	KZn(SO 4)Cl	Yadovitaya fumarole, Second Scoria Cone, Tolbachik, Russia	2018	[54]
Blossite	α‑Cu2+ 2V5+ 2O 7	Izalco, El Salvador	1987	[28]
Bubnovaite	K 2Na 8Ca(SO 4) 6	Naboko cone, Tolbachik, Russia		[55]
Burnsite	KCdCu 7O 2(SeO 3) 2Cl 9	Tolbachik	2002?	[56]
Cadmoindite	CdIn 2S 4	Kudryavy, Russia	2004	[57]
Calciolangbeinite	K 2Ca 2(SO 4) 3	Arsenatnaya fumarole, Tolbachik, Russia	2022	[58]
Campostriniite	(Bi3+ ,Na) 3(NH, 4K) 2Na 2(SO 4)· 6H 2O	La Fossa, Vulcano, Italy	2015	[59]
Cannizzarite	Pb 46Bi 54(S ,Se) 127	La Fossa, Vulcano, Italy		[60]
Cesiodymite	CsKCu 5O(SO 4) 5	Second Scoria Cone, Tolbachik, Russia	2018	[61]
Chubarovite	KZn 2(BO 3)Cl 2	Arsenatnaya fumarole, Tolbachik, Russia	2015	[62]
Cryptocalcite	K 2Cu 5O(SO 4) 5	Second Scoria Cone, Tolbachik, Russia	2018	[61]
Cuprodobrovolskyite	Na 4Cu(SO 4) 3	Second Scoria Cone, Tolbachik	2023	[63]
Cupromolybdite	Cu 3O(MoO 4) 2	New Tolbachik scoria cones, Tolbachik, Russia	2012	[64]
D'ansite	Na 21Mn2+ (SO 4) 10Cl	Vesuvius and Vulcano, Italy	2012	[65]
Demartinite	K 2SiF 6	La Fossa, Vulcano, Italy	2007	[66]
Demicheleite	BiSI and BiSBr	La Fossa, Vulcano, Italy	2010 and 2008	[67] [68]
Dobrovolskyite	Na 4Ca(SO 4) 3	Great Tolbachik fissure eruption, Kamchatka peninsula, Russia	2021	[69]
Elasmochloite	Na 3Cu 6BiO 4(SO 4)			[70]
Eldfellite	NaFe(SO 4) 2			[71]
Ermakovite	(NH 4)(As 2O 3) 2Br	Fan-Yagnob coal deposit, Tajikistan	2022	[72]
Grigorievite	Cu 3Fe3+ 2Al 2(VO 4)	Second Scoria Cone, Tolbachik, Russia	2015	[73]
Hermannjahnite	CuZn(SO 4) 2	Naboko scoria cone, Tolbachik, Russia	2018	[74]
Karpovite	Tl 2VO(SO 4) 2(H 2O)	First Cinder Cone, Tolbachik, Russia	2018	[75]
Knasibfite	K 3Na 4[SiF 6] 3[BF 4]	La Fossa, Vulcano, Italy	2008	[76]
Koksharovite	CaMg 2Fe3+ 4(VO 4) 6	Bezymyanny, Russia	2015	[73]
Kristjánite	KNa 2H(SO 4) 2	Fimmvörðuháls, Iceland	2010	[77]
Kudriavite	(Cd ,Pb)Bi 2S 4	Kudryavy, Russia	2004	[57]
Lehmannite	Na 18Cu2+ 12TiO 8(AsO 4) 8FCl 5	Arsenatnaya fumarole, Tolbachik	2020	[2]
Leonardsenite	MgAlF 5(H 2O) 2	Eldfell, Heimaey, Iceland	2015	[73]
Lesyukite	Al 2(OH) 5Cl20− *H 2O	First Cone, Tolbachik, Russia	2007 or earlier	[78]
Lucabindiite	(K ,NH 4)As 4O 6(Cl ,Br)	La Fossa, Vulcano, Italy	2010–2011	[79]
Majzlanite	K 2Na(ZnNa)Ca(SO 4) 4	Yadovitaya fumarole, Tolbachik, Russia	2019	[80]
Manuelarossiite	CaPbAlF 7	Vesuvius volcano, Italy	2024?	[81]
Medvedevite	KMnV 2O 6Cl *(H 2O) 2	Toludskoe lava field, Tolbachik, Russia	2020	[82]
Napoliite	Pb 2OFCl	Vesuvius, 1994 rocks	2010-2020	[83]
Nishanbaevite	KAl 2O(AsO 4)(SO 4)	Arsenatnaya fumarole, Tolbachik, Russia	2022	[84]
Oskarssonite	AlF 3	Eldfell, Iceland	2018	[29]
Ozerovaite	Na 2KAl 3(AsO 4) 4	Second Cinder Cone, Tolbachik, Russia	2019	[85]
Paradimorphite	As 4S 3	Solfatara, Campi Flegrei, Italy	2022	[86]
Parageorgbokiite	b- Cu 5O 2(SeO 3) 2Cl 2	Yadovitaya fumarole, Tolbachik, Russia	2007	[87]
Parascandolaite	KMgF 3	Vesuvius, Italy	2014	[88]
Parawulffite	K 5Na 3Cu 8O 4(SO 4) 8	Arsenatnaya fumarole, Tolbachik, Russia	2014	[89]
Petrovite	Na 10CaCu 2(SO 4) 8	Second Scoria Cone, Tolbachik, Russia	2020	[18]
Pliniusite	Ca 5(VO 4) 3F	Tolbachik, Russia	2022	[90]
Prewittite	KPb 1.5Cu 6Zn(SeO 3) 2O 2Cl 10	Second Scoria Cone, Tolbachik, Russia	2013	[39]
Pseudolyonsite	Cu 3(VO 4) 2	New Tolbachik scoria cones, Tolbachik, Russia	2011	[91]
Puninite	Na 2Cu 3O(SO 4) 3	Second scoria cone, Tolbachik, Russia	2017	[92]
Rhabdoborite	Mg 12(V ,Mo ,W) 4/3O 6[(BO 3) 6–x(PO 4) xF 2–x]	Arsenatnaya fumarole, Tolbachik, Russia	2020	[93]
Russoite	NH 4ClAs3+ 2O 3(H 2O) 0.5	Solfatara, Phlegrean Fields, Italy	2018	[94]
Ryabchikovite	CuMg(Si 2O 6)	Arsenatnaya, Tolbachik	2023	[95]
Sbacchiite	Ca 2AlF 7	Vesuvius, Italy	2019	[96]
Shcherbinaite	V 2O 5	Izalco, El Salvador	1983	[97]
Stoiberite	Cu 5V 2O 10	"Y fumarole", Izalco, El Salvador	1979	[98]
Therasiaite	(NH 4) 3KNa 2Fe2+ Fe3+ (SO 4) 3Cl 5	La Fossa, Vulcano, Italy	2014	[99]
Thermessaite	(NH 4) 2AlF 3(SO 4)	La Fossa, Vulcano, Italy	2021	[100]
Topsøeite	FeF 3(H 2O) 3	Hekla, Iceland	2018	[101]
Wulffite	K 3NaCu 4O 2(SO 4) 4	Arsenatnaya fumarole, Tolbachik, Russia	2014	[89]
Vasilseverginite	Cu 9O 4(AsO 4) 2(SO 4) 2	Arsenatnaya fumarole, Tolbachik, Russia	2021	[102]
Wrightite	K 2Al 2O(AsO 4) 2	Second Scoria Cone, Tolbachik, Russia	1983	[103]
Yavapaiite	KFe(SO 4) 2			[71]
Ziminaite	Fe3+ VO 4	Bezymyanny, Russia	2018	[104]
Zincobradaczekite	NaCuCuZn 2(AsO 4) 3	Yadovitaya fumarole, Tolbachik, Russia	2020	[105]

Gallery

• Scanning electron microscope images of fumarole minerals
• 
  Fumarole minerals in natural colours
• 
  Fumarole minerals in natural colours, Mutnovsky, Kamchatka
• 
  Fumarole minerals in natural colours, Tolbachik, Kamchatka

• Photos of fumarole minerals
• 
  Non-SEM photo of belomarinaite from Tolbachik, Kamchatka

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