Goethite

goethite

cuprite

serpentine

chalcopyrite

Images

Formula: FeO(OH)
Hydroxide, diaspore group
Crystal System: Orthorhombic
Specific gravity: 4.27 to 4.29 measured, 4.18 calculated
Hardness: 5 to 5½
Streak: Brown to brownish yellow
Colour: Yellow, brown to dark brown and reddish brown
Solubility: Slightly soluble in hydrochloric acid
Common impurities: Mn
Environments:

Pegmatites
Carbonatites
Sedimentary environments
Hydrothermal environments

Goethite is a very common mineral, typically formed by the oxidation of iron-bearing minerals. It also forms as a direct inorganic or biogenic precipitate from water and it is widespread as a deposit in bogs and springs. Large quantities of goethite have resulted from the weathering of serpentine. It also occurs in vesicles in volcanic rocks, and in the oxidation zone of hypothermal (high temperature) hydrothermal veins.

Localities

At the Mount Kelly deposit, Gunpowder District, Queensland, Australia, the deposit has been mined for oxide and supergene copper ores, predominantly malachite, azurite and chrysocolla. The ores overlie primary zone mineralisation consisting of quartz-dolomite-sulphide veins hosted in dolomite-bearing siltstone and graphitic schist.
Goethite is common, coating fractures together with hematite and secondary copper minerals. Iridescent goethite occurs along the walls in the oxide zone (AJM 22.1.21).

At the Gascoyne River, Carnarvon Shire, Western Australia, Australia, goethite pseudomorphs after marcasite occur as nodules in white, fine-grained chalk along the river (AJM 22.2.5-12).
Goethite from the Gascoyne River - Image

At the Marron Volcanics of the Olalla Area, South-Central British Columbia, Canada, goethite has been found as two types: as limonitised pseudomorphs after pyrite and as radial sprays of golden brown acicular crystals to 3 mm on brewsterite and heulandite. The pseudomorphs and the unaltered pyrite are associated with one another. Goethite was found primarily near the pumphouse along the Yellow Lake road cut (R&M 96.6.522).

At the Blue Points mine, Thunder Bay, Ontario, Canada, goethite has been observed occasionally as microscopic acicular needles in quartz variety amethyst (R&M 94.4.318).

At Guangxi, China, goethite occurs as dark brown botryoidal aggregates with minor brassy yellow pyrite and steep pyramidal colourless calcite crystals up to 5 mm long, on a light coloured matrix (AESS).
Goethite from Guangxi - Image

At Devil's Peak, Sai Kung District, New Territories, Hong Kong, China, the mineralisation occurred in quartz veins in the contact zone between a granite intrusion and acid volcanic rocks. The mine is now closed, and inaccessible for collecting. Goethite occurred as pseudomorphs after pyrite (Hong Kong Minerals (1991). Peng, C J. Hong Kong Urban Council)

The Ma On Shan Mine, Ma On Shan, Sha Tin District, New Territories, Hong Kong, China, is an abandoned iron mine, with both underground and open cast workings. The iron ores contain magnetite as the ore mineral and occur predominantly as masses of all sizes enclosed in a large skarn body formed by contact metasomatism of dolomitic limestone at the margins of a granite intrusion. In parts of the underground workings magnetite is also found in marble in contact with the granite. The skarn rocks consist mainly of tremolite, actinolite, diopside and garnet.
Goethite occurs as botryoidal and stalactitic forms along fissures in the skarn (Hong Kong Minerals (1991). Peng, C J. Hong Kong Urban Council)

At Chessy, Lyon, Rhone-Alpes, France, goethite pseudomorphs after cuprite have been found (KL p142).
Goethite from Chessy - Image

At Chihuahua, Mexico, goethite pseudomorphs after gypsum have been found (KL p143).
Goethite from Chihuahua - Image

At the Mariquita Mine (Sultana Mine), Usagre, Badajoz, Extremadura, Spain, goethite, a product of the oxidation of iron-bearing sulphides in the primary mineralisation, is common. Occasionally it forms tiny golden brown crystals in cinnabar, baryte or quartz cavities. It also appears as pseudomorphs after small pyrite crystals (MinRec 55.4.502).

The San Valentín Mine, Sancti Spiritu, La Unión, Murcia, Spain is an open pit lead - zinc - iron mine. The deposit is a sub-volcanic, hydrothermal, late Tertiary (66 million to 2.6 million years ago) replacement of limestone. (Mindat).
Some beautiful and unusual specimens of goethite-coated quartz have been collected here. The otherwise routine clusters of quartz crystal points are covered entirely by films of goethite which render them vividly iridescent (Minrec 55.1.111).
Goethite from the San Valentín Mine - Image

The Sunnyside Deposit, Whitwell, Bolsover District, Derbyshire, England, UK, is hosted by late Permian (256 to 248 million years ago) dolostone that lies above a thick sequence of Carboniferous (354 to 290 million years ago) Coal Measures sediments.
Goethite replacements of marcasite are ubiquitous in vein baryte. The central cavities in the feeder veins are commonly lined with abundant millimetre-size pseudomorphs. Sharp replacements of goethite after marcasite are occasionally present in cavities in replacement baryte. Rare cubic pseudomorphs found in the same situation are almost certainly after pyrite (JRS 24.37-59).

At Old Ham mine, Clearwell, Gloucestershire, England, UK, goethite occurs with calcite in dolomitised rock (RES p153).
Goethite from Old Ham - Image

At Iron Acton, Gloucestershire, England, UK, goethite occurs with calcite in sandstone (RES p168).

At Croft Quarry, Croft, Blaby, Leicestershire, England, UK, microscopic spheroids of goethite have been found on quartz in association with calcite. A specimen has been found where rusty spots of goethite replacing pyrite were associated with a small cubo-octahedral galena crystal, with some cerussite alteration, on analcime (JRS 20.17).

At Cloud Hill quarry, Breedon on the Hill, Leicestershire, England, UK, goethite is associated with hematite, quartz and calcite (RES p206).

At Laverock Braes, Middleton Park, Aberdeen City, Scotland, UK, massive dark brown goethite is abundant. Specimens commonly contain cavities lined by distinctive chocolate-brown botryoidal crusts, with a characteristic radiating structure. Goethite forms along the edges of some iron- and manganese-bearing veins, where it may be shattered and criss-crossed by later manganite veinlets. Powdery brown limonite, which may be recent in origin, coats some specimens found loose in the till. Cavities in massive goethite are commonly infilled with white to red-stained baryte (JRS 22.19).

In Teller county, Colorado, USA, goethite pseudomorphs after siderite have been found with microcline (KL p145).
Goethite from Teller County - Image

At the Empire Mine, Palmer, Marquette County, Michigan, USA, goethite has been found with hematite on quartz (Mindat photo).
Goethite from the Empire Mine - Image

At Pelican Point, Utah, USA, goethite pseudomorphs after pyrite have been found (KL p144).
Goethite from Pelican Point - Image

Alteration

chalcopyrite to goethite
chalcopyrite + oxygen + water ⇌ cupric sulphate + goethite + sulphuric acid
4CuFeS2(solid) + 17O2(gaseous) + 6H2O(liquid) ⇌ 4Cu2+SO4(aqueous) + 4FeO(OH)(solid) + 4H2SO4(aqueous)
(JRS 18.12)

hematite and H2O to goethite
Fe2O3 + H2O ⇌ 2FeO(OH)
Both forward and reverse reactions are slow, but equilibrium in most natural environments is displaced to the left, favouring the formation of hematite (KB p362).

marcasite to goethite
Pseudomorphs of goethite after marcasite are fairly common in the Northern Pennine orefield, England, although unaltered marcasite is very rare there. The alteration takes place in three stages:
First each sulphur atom in the marcasite combines with four oxygen atoms to form sulphate groups (SO4)2-, resulting in ferrous (divalent iron) sulphate and sulphuric acid, as for the oxidation of pyrite, noted above:
marcasite + water + oxygen → ferrous sulphate + sulphuric acid
2FeS2 + 2H2O + 7O2 → 2Fe2+SO4 + 2H2SO4
Next the ferrous sulphate is oxidised to ferric (trivalent iron) sulphate:
ferrous sulphate + sulphuric acid + oxygen → ferric sulphate + water
4Fe2+SO4 + 2H2SO4 + O2 → 2Fe3+2(SO4)3 + 2H2O
Lastly ferric sulphate in solution is stable only at very low pH (very acid solution) and usually rapidly breaks down to form hydroxy iron oxides such as goethite, and sulphuric acid:
ferric sulphate + water → goethite + sulphuric acid
Fe3+2(SO4)3 + 4H2O → 2Fe3+O(OH) + 3H2SO4
(JRS 14.69-76)

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