Mineral Inventory of the Algares 30-Level Adit, Aljustrel Mine, Iberian Pyrite Belt, Portugal

Mining activity in Algares (Aljustrel Mine, Portuguese sector of the Iberian Pyrite Belt, IPB) stems prior to Roman times. As the orebody is vertical and relatively thin, mining was carried out mainly along underground adits (galleries). Nowadays, the deposit is considered exhausted and the area is being rehabilitated for a different use. The Algares +30 level adit intersects two volcanic units of the IPB Volcano-Sedimentary Complex. The massive sulphide and related stockwork zone are hosted by the Mine Tuff volcanic unit and are exposed in the walls of the gallery, showing intense hydrothermal alteration. Along the mine adit, the geological sequence is affected by strong oxidation and supergene alteration, giving rise to the formation of secondary minerals through the oxidation of the sulphides. The most common minerals found were melanterite (FeSO4·7H2O) and chalcanthite (CuSO4·5H2O), forming essentially massive or crystalline aggregates, ranging from greenish to bluish colours. Melanterite from the walls revealed to be Cu-rich by opposition to that from stalactites/stalagmites formed below the old ore storage silo revealing the low-copper-grade ores exploited underground. The mineralogy of the efflorescent salts was used to ascertain the processes involved in their formation, and moreover, the inventory of minerals is presented, as well as their principal characteristics.


Introduction
With more than 90 deposits of massive polymetallic sulphide ores, the Iberian Pyrite Belt (IPB) is one of the most important European metallogenic provinces [1,2]. Ten deposits (located in Portugal) can be considered large-sized with regards to their Cu-Zn-Pb contents, including the operating Neves-Corvo and Aljustrel mines. Pyrite (FeS 2 ) is the most common ore mineral. Roman mining practice focused on the exploitation of secondary ores (oxidation zone-iron cap and supergene alteration zone) and, in addition, of primary pyrite ore. The ore was roasted in place to extract the metals for export. Some of the Roman mines were very big endeavours and caused the first events of acid mine drainage (AMD) known in Portugal [3].
Mining activity in Algares (Aljustrel mine) occurred prior to the Roman Empire's occupation of the Iberian Peninsula. Vipasca Mine, as it was known when exploited during the Empire, was considered deposits, capped by a set of jaspers unit, black, siliceous and purple shales and volcanogenic sediments of the Paraíso Formation (all defining the Volcano-sedimentary Complex, VSC), and subsequently overlain by a flysch sedimentary sequence (Mértola Formation) [15,16,[19][20][21]. Minor mafic volcanism occurred in a submarine environment and the presence of ignimbritic flows suggests transient subaerial or extremely shallow water conditions [1]. The VSC in Aljustrel defines a NW-SE trending anticlinorium structure with subvertical rock and an ore lenses distribution. Above the aforementioned Palaeozoic stratigraphic sequence, a succession of Cenozoic-age fluvial and continental sediments mainly composed of sandstones, mudstones, conglomerates and carbonates were deposited, forming the Alvalade/Sado Basin [19].
The Algares adit intersects, from E to W, two volcanic units of the IPB's VSC, the Megacrystal Tuff unit (Vap in Figure 1) and the MT unit (Tufo da Mina-Mine Tuff ) [15,16,[19][20][21] (see the geological map in Figure 1). The massive sulphide and related stockwork zone are hosted by the Mine Tuff volcanic unit (Va in Figure 1) and are exposed on the walls of the underground adit, showing intense sericitic and chloritic hydrothermal alteration. Along the mine adit, this geological sequence is affected by intense weathering, giving rise to the formation of a natural mineralogical laboratory where secondary minerals are precipitated through the oxidation of the sulphides.
Minerals 2020, 10, x FOR PEER REVIEW 3 of 18 sediments of the Paraíso Formation (all defining the Volcano-sedimentary Complex, VSC), and subsequently overlain by a flysch sedimentary sequence (Mértola Formation) [15,16,[19][20][21]. Minor mafic volcanism occurred in a submarine environment and the presence of ignimbritic flows suggests transient subaerial or extremely shallow water conditions [1]. The VSC in Aljustrel defines a NW-SE trending anticlinorium structure with subvertical rock and an ore lenses distribution. Above the aforementioned Palaeozoic stratigraphic sequence, a succession of Cenozoic-age fluvial and continental sediments mainly composed of sandstones, mudstones, conglomerates and carbonates were deposited, forming the Alvalade/Sado Basin [19]. The Algares adit intersects, from E to W, two volcanic units of the IPB's VSC, the Megacrystal Tuff unit (Vap in Figure 1) and the MT unit (Tufo da Mina-Mine Tuff) [15,16,[19][20][21] (see the geological map in Figure 1). The massive sulphide and related stockwork zone are hosted by the Mine Tuff volcanic unit (Va in Figure 1) and are exposed on the walls of the underground adit, showing intense sericitic and chloritic hydrothermal alteration. Along the mine adit, this geological sequence is affected by intense weathering, giving rise to the formation of a natural mineralogical laboratory where secondary minerals are precipitated through the oxidation of the sulphides. Two gossans were intersected: Algares East, located in the SW of the Megacrystal Tuff unit (tectonic shear zone contact), and Algares West, located near the Vipasca main shaft in the central sector of the Mine Tuff volcanic unit. Large stockwork zones outcrop in both sides of this ore lens. Each gossan was developed above the two massive sulphide ore lenses. The location of these structures and surface mapping [9,15] suggest that the Algares West ore lens is compressed, probably in a narrow synform (Figure 1). Two gossans were intersected: Algares East, located in the SW of the Megacrystal Tuff unit (tectonic shear zone contact), and Algares West, located near the Vipasca main shaft in the central sector of the Mine Tuff volcanic unit. Large stockwork zones outcrop in both sides of this ore lens. Each gossan was developed above the two massive sulphide ore lenses. The location of these structures and surface mapping [9,15] suggest that the Algares West ore lens is compressed, probably in a narrow synform ( Figure 1).

Materials and Methods
More than 100 georeferenced efflorescent samples were collected from the walls and roof of the Algares +30 level adit along its entire length, considering both colour and crystal morphology (Figures 1 and 2). Sampling was performed in September 2018 with a temperature of about 20 • C inside the adit. To prevent mineralogical changes of some unstable minerals, samples were preserved in closed containers and quickly analysed as soon as they reached the laboratory. Fragments for X-ray diffraction (XRD) were selected (approx. 200) using the stereomicroscope (Stemi SV-11, Zeiss, Jena, Germany), and images were collected with a digital Zeiss camera (Axio-Cam Mrc). Several images were mustered from the same fragment with the focus set at different levels, all of which were compiled together in Adobe Photoshop TM using the focus stacking method.

Materials and Methods
More than 100 georeferenced efflorescent samples were collected from the walls and roof of the Algares +30 level adit along its entire length, considering both colour and crystal morphology (Figures 1 and 2). Sampling was performed in September 2018 with a temperature of about 20 °C inside the adit. To prevent mineralogical changes of some unstable minerals, samples were preserved in closed containers and quickly analysed as soon as they reached the laboratory. Fragments for X-ray diffraction (XRD) were selected (approx. 200) using the stereomicroscope (Stemi SV-11, Zeiss, Jena, Germany), and images were collected with a digital Zeiss camera (Axio-Cam Mrc). Several images were mustered from the same fragment with the focus set at different levels, all of which were compiled together in Adobe Photoshop TM using the focus stacking method.
Two XRD equipment were used, due to the large number of powdered (roughly comminuted, to avoid mineralogical changes) samples: 1) A Philips PW 1500 powder diffractometer with Bragg-Brentano geometry, equipped with a large-anode copper tube operating at 50 kV-40 mA and a curved graphite crystal monochromator; 2) a Rigaku Dmax III-C 3kW powder diffractometer with a Bragg-Brentano geometry, using Cu Kα radiation at 40 kV and 30 mA settings with a 20° to 65° 2θ range, an acquisition time of 1 s and a 2θ increment of 0.04°. To corroborate XRD crystalline phase identification, thermo-analytical techniques-simultaneous differential thermal analysis (DTA) and thermogravimetry (TG)-were occasionally used, using a SETARAM 92-16.18 apparatus, incorporating a microbalance with a controlled argon gas flow (inert atmosphere). About 70-80 mg of milled sample was deposited in an alumina (α-Al2O3) crucible. The reference material was alumina powder. Therefore, a DTA-TG assay was performed in one sample of supposedly chalcanthite, and the heating temperature ranged from ambient to 1000 °C at a heating rate of 10 °C min -1 . For the supposedly melanterite samples, the temperature interval was the same but at a heating rate of 17 °C min -1 . Two XRD equipment were used, due to the large number of powdered (roughly comminuted, to avoid mineralogical changes) samples: (1) A Philips PW 1500 powder diffractometer with Bragg-Brentano geometry, equipped with a large-anode copper tube operating at 50 kV-40 mA and a curved graphite crystal monochromator; (2) a Rigaku Dmax III-C 3kW powder diffractometer with a Bragg-Brentano geometry, using Cu Kα radiation at 40 kV and 30 mA settings with a 20 • to 65 • 2θ range, an acquisition time of 1 s and a 2θ increment of 0.04 • .
To corroborate XRD crystalline phase identification, thermo-analytical techniques-simultaneous differential thermal analysis (DTA) and thermogravimetry (TG)-were occasionally used, using a SETARAM 92-16.18 apparatus, incorporating a microbalance with a controlled argon gas flow (inert atmosphere). About 70-80 mg of milled sample was deposited in an alumina (α-Al 2 O 3 ) crucible.
The reference material was alumina powder. Therefore, a DTA-TG assay was performed in one sample of supposedly chalcanthite, and the heating temperature ranged from ambient to 1000 • C at a heating rate of 10 • C min −1 . For the supposedly melanterite samples, the temperature interval was the same but at a heating rate of 17 • C min −1 .
The identification of some mineralogical phases proved to be difficult due to the solid solution between end-members of the sulphate-mineral groups or to the overlapping of peaks. For that reason, a portable X-ray fluorescence (p-XRF) equipment (Genius 9000 + 7000 from Skyray Instrument) was also used at the laboratory for a rapid chemical characterisation (elements below K could not be measured) of the powdered samples to help in the XRD identification, whenever necessary. Occasionally, for crucial magnesium content determination, a semi-quantitative chemical analysis was performed through X-ray fluorescence spectrometry with a wavelength-dispersive system (XRF-WDS), using a PANalytical 4.0 AXIOS sequential spectrometer (Rh X-ray tube) under He flow.

Mineral Inventory of the Algares Adit
The mineralogical phases identified in efflorescence samples are listed in Table 1, in alphabetical order for easier reading, constituting a mineral inventory of the Algares adit. The mineral characterisation of secondary minerals revealed the presence of alunogen, antlerite, atacamite, chalcanthite, copiapite, fibroferrite, gypsum, halotrichite, melanterite and pickeringite, being chemically aluminium sulphates, hydrated sulphates of iron aluminium and magnesium aluminium, hydrated copper sulphates, copper hydroxide sulphates and hydroxide chlorides, hydrated iron sulphates, iron hydroxide sulphates with various degrees of hydration and hydrated calcium sulphates. However, some phases such as pyrite, chalcopyrite, quartz, chlorite/clinochlore, mica group minerals, kaolinite, alunite, jarosite and hematite are considered here as substrates due to their presence beneath the previous ones (examples in Figure 3). The identification of some mineralogical phases proved to be difficult due to the solid solution between end-members of the sulphate-mineral groups or to the overlapping of peaks. For that reason, a portable X-ray fluorescence (p-XRF) equipment (Genius 9000 + 7000 from Skyray Instrument) was also used at the laboratory for a rapid chemical characterisation (elements below K could not be measured) of the powdered samples to help in the XRD identification, whenever necessary. Occasionally, for crucial magnesium content determination, a semi-quantitative chemical analysis was performed through X-ray fluorescence spectrometry with a wavelength-dispersive system (XRF-WDS), using a PANalytical 4.0 AXIOS sequential spectrometer (Rh X-ray tube) under He flow.

Alunogen
Alunogen, Al2(SO4)3·17H2O, was frequently found as white crystalline aggregates ( Figure 5), occasionally associated with chalcanthite (blue) or with halotrichite/pickeringite, jarosite and melanterite. The translucent crystals appear over quartz, chlorite/clinochlore + quartz or kaolinite + hematite + quartz. In opposition to the common accepted value of 18 water molecules, studies performed by Fang and Robinson [24] showed that the maximum H2O content in the alunogen formula is 17 molecules.

Antlerite
The pale green antlerite ( Figure 6), Cu3(SO4)(OH)4, is a rare mineral in the adit walls and appears associated with chalcanthite. The massive aggregates of antlerite crystals seem to be associated with an intermediate zone between the reddish substrate (chlorite/clinochlore + hematite

Alunogen
Alunogen, Al 2 (SO 4 ) 3 ·17H 2 O, was frequently found as white crystalline aggregates ( Figure 5), occasionally associated with chalcanthite (blue) or with halotrichite/pickeringite, jarosite and melanterite. The translucent crystals appear over quartz, chlorite/clinochlore + quartz or kaolinite + hematite + quartz. In opposition to the common accepted value of 18 water molecules, studies performed by Fang and Robinson [24] showed that the maximum H 2 O content in the alunogen formula is 17 molecules.

Alunogen
Alunogen, Al2(SO4)3·17H2O, was frequently found as white crystalline aggregates ( Figure 5), occasionally associated with chalcanthite (blue) or with halotrichite/pickeringite, jarosite and melanterite. The translucent crystals appear over quartz, chlorite/clinochlore + quartz or kaolinite + hematite + quartz. In opposition to the common accepted value of 18 water molecules, studies performed by Fang and Robinson [24] showed that the maximum H2O content in the alunogen formula is 17 molecules.

Antlerite
The pale green antlerite ( Figure 6), Cu3(SO4)(OH)4, is a rare mineral in the adit walls and appears associated with chalcanthite. The massive aggregates of antlerite crystals seem to be associated with an intermediate zone between the reddish substrate (chlorite/clinochlore + hematite

Antlerite
The pale green antlerite ( Figure 6), Cu 3 (SO 4 )(OH) 4 , is a rare mineral in the adit walls and appears associated with chalcanthite. The massive aggregates of antlerite crystals seem to be associated with an intermediate zone between the reddish substrate (chlorite/clinochlore + hematite + quartz) and the chalcanthite (the presence of chalcanthite probably resulted from the precipitation of later fluids over antlerite).

Chalcanthite
Of the blue coloured samples, chalcanthite (CuSO4·5H2O) is the most common mineral found in the adit, changing from vitreous deep blue masses to light blue crystals to fibrous columnar crystalline or crusts, as shown by the stereomicroscope images ( Figure 8). The DTA-TG curve performed in one sample of supposedly chalcanthite was compared to published data [25] (p. 122), and the phase constitution of heated material was monitored by XRD. Four endothermic peaks were obtained at about 155, 275, 775 and 830 °C and the resulting material was a mixture of tenorite (CuO) plus cuprite (Cu2O). These results reflect the chalcanthite decomposition under inert atmosphere.

Chalcanthite
Of the blue coloured samples, chalcanthite (CuSO4·5H2O) is the most common mineral found in the adit, changing from vitreous deep blue masses to light blue crystals to fibrous columnar crystalline or crusts, as shown by the stereomicroscope images ( Figure 8). The DTA-TG curve performed in one sample of supposedly chalcanthite was compared to published data [25] (p. 122), and the phase constitution of heated material was monitored by XRD. Four endothermic peaks were obtained at about 155, 275, 775 and 830 °C and the resulting material was a mixture of tenorite (CuO) plus cuprite (Cu2O). These results reflect the chalcanthite decomposition under inert atmosphere.

Chalcanthite
Of the blue coloured samples, chalcanthite (CuSO 4 ·5H 2 O) is the most common mineral found in the adit, changing from vitreous deep blue masses to light blue crystals to fibrous columnar crystalline or crusts, as shown by the stereomicroscope images ( Figure 8). The DTA-TG curve performed in one sample of supposedly chalcanthite was compared to published data [25] (p. 122), and the phase constitution of heated material was monitored by XRD. Four endothermic peaks were obtained at about 155, 275, 775 and 830 • C and the resulting material was a mixture of tenorite (CuO) plus cuprite (Cu 2 O). These results reflect the chalcanthite decomposition under inert atmosphere.

Gypsum
White or greyish aggregates and crystals of gypsum ( Figure 11), CaSO4·2H2O, were frequently found, associated with atacamite or melanterite and sometimes with chalcanthite. The thin and elongated (up to 2 cm) efflorescences of hyaline crystals have a radial shape. The adit sector located SW of the Algares East gossan is full of microcrystalline aggregates of gypsum. These sulphates are present in fine crusts in rock surface of the Mine Tuff volcanic rocks which present disseminated sulphide mineralisation. These crystals can show a dark grey colour interpreted as a consequence of dust deposition due to the rehabilitation works performed inside the adit.

Gypsum
White or greyish aggregates and crystals of gypsum ( Figure 11), CaSO 4 ·2H 2 O, were frequently found, associated with atacamite or melanterite and sometimes with chalcanthite. The thin and elongated (up to 2 cm) efflorescences of hyaline crystals have a radial shape. The adit sector located SW of the Algares East gossan is full of microcrystalline aggregates of gypsum. These sulphates are present in fine crusts in rock surface of the Mine Tuff volcanic rocks which present disseminated sulphide mineralisation. These crystals can show a dark grey colour interpreted as a consequence of dust deposition due to the rehabilitation works performed inside the adit.

Gypsum
White or greyish aggregates and crystals of gypsum ( Figure 11), CaSO4·2H2O, were frequently found, associated with atacamite or melanterite and sometimes with chalcanthite. The thin and elongated (up to 2 cm) efflorescences of hyaline crystals have a radial shape. The adit sector located SW of the Algares East gossan is full of microcrystalline aggregates of gypsum. These sulphates are present in fine crusts in rock surface of the Mine Tuff volcanic rocks which present disseminated sulphide mineralisation. These crystals can show a dark grey colour interpreted as a consequence of dust deposition due to the rehabilitation works performed inside the adit.

Melanterite
Melanterite, the heptahydrate iron (II) sulphate, is readily soluble in water and, when exposed to air, tends to lose hydration water and alters to rozenite (FeSO4·4H2O) or to siderotil (FeSO4·5H2O); if melanterite is Cu-rich, it tends to dehydrate to siderotil [22]. From the iron minerals, melanterite (FeSO4·7H2O) is the most common with colours from greenish yellow to bluish ( Figure 13) and variable contents of iron/copper/zinc. Although not well-established, it seems that the blue colour is related to copper and, visually, cuprian melanterite can be confused with chalcanthite [31]; the yellow/brownish colouration ( Figure 13) could be related to the presence of ferric oxide [22]. Indeed, the general formula of melanterite is M 2+ SO4·7H2O, where M represents a divalent cation such as Co, Cu, Fe, Mg, Mn and Zn [31]. The crystal structure of melanterite is formed by a SO4 tetrahedron, two independent M(H2O)6 octahedra, and one interstitial H2O group which is not directly bonded to M 2+ cations (e.g., [32,33]).
The green melanterite stalactites/stalagmites in Algares revealed a high content of Fe (>20%), no copper and a small amount of Zn (1-2%); in crusts from the walls, the Cu content increases (5-9%), and one sample presents even 15% Cu. These values are presented in the ternary diagram of Figure  14, although being only indicative due to the equipment used (portable XRF) and to the presence of vestigial phases. Stalactites were formed closer to an old ore shoot structure inside the adit with percolation of water (see Figure 2). With a cylindrical shape, some tubes are up to 3 cm in length and 0.5 cm in diameter. Below these structures, on the ground, stalagmites with a botryoidal habit have formed, being green outside and yellow inside (due to minute amounts of Fe 3+ ? e.g., [31]). The XRD identification showed only melanterite in both colours of minerals. Melanterite from the walls occurs associated to gypsum, pickeringite, alunogen or chalcanthite, mainly over quartz + pyrite, quartz + chlorite/clinochlore, pyrite + kaolinite. Rozenite and siderotil were not identified in Algares adit, although melanterite is highly soluble in water and tends to lose hydration water.
DTA-TG assays were also performed in three samples of supposedly melanterite, one without copper and the remainder being copper-rich. The sample free of Cu showed endothermic peaks at about 120, 170, 325, 355, 530 (small peak) and 770 °C, in accordance to published data [25] (p. 123). The decomposition under inert atmosphere gave rise to magnetite (Fe3O4) and hematite, reflecting the previous existence of melanterite. The DTA-TG curves of the two samples with Cu were similar,

Melanterite
Melanterite, the heptahydrate iron (II) sulphate, is readily soluble in water and, when exposed to air, tends to lose hydration water and alters to rozenite (FeSO 4 ·4H 2 O) or to siderotil (FeSO 4 ·5H 2 O); if melanterite is Cu-rich, it tends to dehydrate to siderotil [22]. From the iron minerals, melanterite (FeSO 4 ·7H 2 O) is the most common with colours from greenish yellow to bluish ( Figure 13) and variable contents of iron/copper/zinc. Although not well-established, it seems that the blue colour is related to copper and, visually, cuprian melanterite can be confused with chalcanthite [31]; the yellow/brownish colouration ( Figure 13) could be related to the presence of ferric oxide [22]. Indeed, the general formula of melanterite is M 2+ SO 4 ·7H 2 O, where M represents a divalent cation such as Co, Cu, Fe, Mg, Mn and Zn [31]. The crystal structure of melanterite is formed by a SO 4 tetrahedron, two independent M(H 2 O) 6 octahedra, and one interstitial H 2 O group which is not directly bonded to M 2+ cations (e.g., [32,33]).   The green melanterite stalactites/stalagmites in Algares revealed a high content of Fe (>20%), no copper and a small amount of Zn (1-2%); in crusts from the walls, the Cu content increases (5-9%), and one sample presents even 15% Cu. These values are presented in the ternary diagram of Figure 14, although being only indicative due to the equipment used (portable XRF) and to the presence of vestigial phases. Stalactites were formed closer to an old ore shoot structure inside the adit with percolation of water (see Figure 2). With a cylindrical shape, some tubes are up to 3 cm in length and 0.5 cm in diameter. Below these structures, on the ground, stalagmites with a botryoidal habit have formed, being green outside and yellow inside (due to minute amounts of Fe 3+ ? e.g., [31]). The XRD identification showed only melanterite in both colours of minerals. Melanterite from the walls occurs associated to gypsum, pickeringite, alunogen or chalcanthite, mainly over quartz + pyrite, quartz + chlorite/clinochlore, pyrite + kaolinite. Rozenite and siderotil were not identified in Algares adit, although melanterite is highly soluble in water and tends to lose hydration water.  As an historical reference, a pigment, known as "Azul de Aljustrel" (Aljustrel Blue), was described in a document from King John III (16th century) and referred to as being produced in Aljustrel by a regal functionary, refined and sold to artists [34]. The use of "Azul de Aljustrel" pigment is thought to have been an episode lasting only a few years, as no other references are known [35]. Concerning its nature, it is supposed that it might have been a pigment based on copper sulphates or basic copper carbonates existing in the sulphur deposits of the Aljustrel region [36]. In similar deposits in the Spanish IPB, ancient references about the collection of materials in pits for making paint and for medicinal use (probably in Rio Tinto) led Rebollar [37] to consider that these materials were sulphates and melanterite rather than chalcanthite.
In the case of the Algares adit, melanterite stalactites and stalagmites are located below the old ore silo opening on the roof of the adit. In fact, above the gallery, crushed massive sulphide ore is still present, and through the air flow and rainwater percolation, the precipitation of sulphates occurs in the mine adit roof and floor. DTA-TG assays were also performed in three samples of supposedly melanterite, one without copper and the remainder being copper-rich. The sample free of Cu showed endothermic peaks at about 120, 170, 325, 355, 530 (small peak) and 770 • C, in accordance to published data [25] (p. 123). The decomposition under inert atmosphere gave rise to magnetite (Fe 3 O 4 ) and hematite, reflecting the previous existence of melanterite. The DTA-TG curves of the two samples with Cu were similar, with endothermic peaks at about 100, 160, 350, 720, 775 and 815 • C, and the formation of magnetite plus tenorite, compatible with a former Cu-rich melanterite.
As an historical reference, a pigment, known as "Azul de Aljustrel" (Aljustrel Blue), was described in a document from King John III (16th century) and referred to as being produced in Aljustrel by a regal functionary, refined and sold to artists [34]. The use of "Azul de Aljustrel" pigment is thought to have been an episode lasting only a few years, as no other references are known [35]. Concerning its nature, it is supposed that it might have been a pigment based on copper sulphates or basic copper carbonates existing in the sulphur deposits of the Aljustrel region [36]. In similar deposits in the Spanish IPB, ancient references about the collection of materials in pits for making paint and for medicinal use (probably in Rio Tinto) led Rebollar [37] to consider that these materials were sulphates and melanterite rather than chalcanthite.
In the case of the Algares adit, melanterite stalactites and stalagmites are located below the old ore silo opening on the roof of the adit. In fact, above the gallery, crushed massive sulphide ore is still present, and through the air flow and rainwater percolation, the precipitation of sulphates occurs in the mine adit roof and floor.

Discussion
Indeed, the great majority of the minerals identified (Table 1) are frequently found in acid mine drainage (AMD) environments (e.g., [38][39][40][41][42]) and, depending on their solubility and environmental conditions, could be visible on the ground. Some of them are already mentioned as occurring in mill tailings impoundments from Algares [43]. Other authors also refer their presence as a coating of the gallery walls (e.g., [37,[44][45][46]), being long preserved from dissolution.
Melanterite (FeSO 4 ·7H 2 O) and chalcanthite (CuSO 4 ·5H 2 O) are the most common minerals found in the Algares adit; covering the walls, they appear associated with almost all secondary minerals and over the majority of substrates. Melanterite from the walls revealed to be Cu-rich by opposition to that from stalactites/stalagmites formed below the old ore storage silo (see Section 4.1.10). This can be explained by the expected Cu supergene enrichment observed in the mine adit and the presence of low-copper-grade ores exploited underground and stored in the mine silo. Dehydration of melanterite was not observed, as the species rozenite and siderotil were not identified, revealing that the temperature and humidity of the adit favour melanterite stability. On the other hand, copiapite [Fe 2+ Fe 3+ 4 (SO 4 ) 6 (OH) 2 ·20H 2 O] was found only in one efflorescent sample, representing an advanced stage in the oxidation sequence.
Indeed, the oxidation of primary Fe and Cu sulphide minerals (pyrite, FeS 2 and chalcopyrite, CuFeS 2 )-see the possible reaction pathways in Hammarstrom [22], Parafiniuk [47], Bigham and Nordstrom [48]-give rise to the formation of Fe 2+ and Cu 2+ salts (secondary sulphate minerals), namely melanterite and chalcanthite, respectively, or even hematite (depending on relative humidity and time [49]). Occurrences of melanterite have been reported, for example, at Rio Tinto (Spain) [38]; Falun (Sweden) [26]; Apuan Alps, Tuscany (Italy) [32]; or even at Genna Luas, Sardinia (Italy). In the last locality, melanterite was pointed out not only as the result of pyrite weathering, but also the precursor of copiapite [50]. Chalcanthite is commonly found in the late stage oxidation zones of copper deposits or on mine walls by the action of acidic surface waters on copper veins (e.g., as in Rio Tinto, Spain [37]). Due to its ready solubility in water, it tends to crystallise, dissolve and recrystallise as crusts depending on the humidity conditions. Copiapite forms from the precipitation of iron salts in mixed valence (2+, 3+), is frequently found with other sulphates and was considered one of the earliest basic minerals originating from the oxidation of pyrite ores [51].
Furthermore, an aqueous solution of Fe 2+ /Mg 2+ combined with Al 3+ from silicates give rise to halotrichite [FeAl 2 (SO 4 ) 4 ·22H 2 O]/pickeringite [MgAl 2 (SO 4 ) 4 ·22H 2 O]. In the Algares adit, these sulphates occur as white (mainly) or orange aggregates of crystals. According to the ratio Mg/Fe obtained (see Section 4.1.9), the orange colour in pickeringite can be due to the substitution of Al 3+ by Fe 3+ [30]. Pickeringite crystals (white, creamy or light pink) were found as efflorescences on the surface of weathered schists, associated with the decomposition of chlorite (Mg source) through acidic solutions derived from the oxidation of pyrite [52]. Halotrichite/pickeringite minerals were identified in the adit in mixtures, sometimes with another aluminium sulphate, the alunogen [Al 2 (SO 4 ) 3 ·17H 2 O] (this one frequently found as white crystalline aggregates along the walls). Alunogen is formed by the actions of sulphate solutions resulting from the oxidation of the sulphides on aluminous minerals and is found in the wall rock of pyritic ore deposits [26] or in salt efflorescence from AMD (e.g., [53]).
Besides chalcanthite, other copper minerals identified were antlerite [Cu 3 (SO 4 )(OH) 4 ] (rarely found in the adit walls) and atacamite [Cu 2 Cl(OH) 3 ] (occurring associated with gypsum or with halotrichite/pickeringite). Antlerite usually appears in the oxidised zones of copper ore veins in the arid areas such as Chuquicamata Mine in Chile, and in several deposits in Arizona, USA [26,54]. The crystallisation of antlerite from solution probably occurs at 30-35 • C, as shown by experiments concerning antlerite stability [54]. Atacamite and paratacamite are polymorphs; while the first one seems to be more stable at room temperature, the second one is formed in solutions of relatively low CuCl 2 concentration [55]. Atacamite is an important constituent of supergene oxide zones of copper deposits in the Atacama Desert of northern Chile, and its formation is related to gypsum-saturated saline groundwaters [56,57].
White or greyish aggregates and crystals with a radial shape of gypsum (CaSO 4 ·2H 2 O) were frequently found in the Algares gallery, while fibroferrite [Fe 3+ (OH)SO 4 ·5H 2 O] is not abundant and found over hematite. The occurrence of both minerals in pyrite-bearing schists has been described by, e.g., Parafiniuk [47,52].
Alunite [(K,Na)Al 3 (SO 4 ) 2 (OH) 6 ]/jarosite [KFe 3 (SO 4 ) 2 (OH) 6 ] forms in extremely acidic environments by the hydrolysis of Al 3+ /Fe 3+ when combined with K + from silicates. Alunite veins from the Algares deposit were already studied and correlated with the kaolinite [Al 2 Si 2 O 5 (OH) 4 ] supergene alteration along the gossan [9][10][11]. In the Algares adit, alunite veins are present in small late fractures over the stockwork veins areas. They are located near the Algares West gossan, close to the old roman galleries that occur in the upper part of the gallery. In consequence of the great geotechnical instability observed in the gallery, some sections near the gossans developed above the massive ore are protected by concrete walls. These protections do not allow observation near gossan oxides and sulphate mineral assemblages.
Kaolinite [Al 2 Si 2 O 5 (OH) 4 ], from the kaolin group, and illite [(K,H 3 O)Al 2 Si 3 AlO 10 (OH) 2 ], the general term used here for mica group, are clay minerals formed by the chemical weathering of aluminium-bearing silicate minerals. They occur as substrates of sulphate minerals. The occurrence of the kaolinite/halloysite supergene alteration is referred to the Algares gossan, showing a clear zonation and high intensity near the ore lenses [9][10][11]. This clay alteration zoning is related to supergene processes and can achieve up to >40 m depth. According to these authors, the same alteration occurs in the IPB Lagoa Salgada, Lousal, Caveira and São Domingos deposits.

Conclusions
The massive sulphides and stockwork mineralisation hosted by the Mine Tuff volcanic rocks unit in the Algares adit show intense supergene alteration, but the sheltered environment of this underground mine gallery provides the preservation of water-soluble minerals. The continuous air flow and constant humidity are favourable conditions for mineral precipitation occurring as complex mineral assemblages. The abundance, variety and chemical composition of minerals (mostly sulphates) are essentially linked with the chemical composition of the ores (mainly pyrite and chalcopyrite). In that way, melanterite (FeSO 4 ·7H 2 O) and chalcanthite (CuSO 4 ·5H 2 O) were the most commonly observed minerals on the multi-coloured aggregates, resulting from the weathering through acidic waters; these minerals were found essentially as massive or crystalline aggregates, with colours ranging from greenish to bluish. The difference observed in copper content of melanterite samples collected on stalactites/stalagmites (copper-free) and adit walls (up to 15% Cu) can be explained by the expected Cu supergene enrichment observed in the walls and the presence of low-copper-grade ores exploited underground and stored in the old Algares mine silo. Although the species rozenite and siderotil were not identified, revealing that the temperature and humidity favour melanterite stability, copiapite [Fe 5 (SO 4 ) 6 (OH) 2 3 ], whose presence is indicative of the percolation of saline fluids. These minerals intercalated/over chlorite/clinochlore (grey) or hematite (reddish) give the adit a rainbow colour effect, making this an attractive mining heritage site to visit.