Characteristic Features of Skouries and Other Porphyry-Cu-Au+Pd±Pt Deposits

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This entry is adapted from the peer-reviewed paper 10.3390/min13111413

Many giant porphyry Cu-Au, Cu-Mo, and Mo-W deposits extend from the Pacific Rim to the Mediterranean and Carpathian system in Europe, the Himalayas, China, and Malaysia. However, only certain porphyry Cu-Au deposits, associated mostly with alkaline-type intrusions, are characterized by significant Pd and Pt contents, particularly in high-grade bornite–chalcopyrite and/or flotation concentrates. Such porphyry deposits include those in British Columbia, Colorado, in the Santo Tomas II deposit, the Philippines, the Skouries porphyry deposit, Greece, Elatsite, Bulgaria, the Kalmakyr deposit, Uzbekistan, the Grasberg deposit, Indonesia, Ok Tedi, Papua New Guinea, the Mamut deposit, Malaysia, and the Bajo de la Alumbrera, Argentina.

porphyry palladium platinum potential magnetite fertility

1. Geological Outline

The progressively collisional subduction of Tethys has led to mineralized ophiolitic slabs thrust over onto the Paleozoic continental margin of the Serbo-Macedonian massif (SMM) basement rocks and generated intra-continental syn-orogenic faults, which facilitated extensive Tertiary magmatic plutonic and sub-volcanic rocks, including porphyry Cu-Au intrusions ^[1]^[2]. The Skouries Vathi, Pontokerasia, and Gerakario porphyry-Cu intrusions belong to the Vertiskos unit of the SMM, extending to Serbia and Bulgaria (Figure 1; ^[3]^[4]^[5]^[6]).

The Vertiskos unit, at the central part of the SMM, is composed of an alternation of gneisses and schists, hosting mafic–ultramafic bodies (ophiolites) of Jurassic age, known as the Gomati–Therma–Volvi (GTV) complex, which has been metamorphosed to high-grade amphibolite facies ^[3]^[7]^[8]^[9]^[10]. Calc–alkaline magmatism started in the Early Miocene (22–17 Ma) is characterized by the intrusion of several subvolcanic rocks that host porphyry-style mineralization, including Vathi, Pontokerasia, Gerakario, and Skouries ^[11]^[12]. Based on whole-rock SiO₂ and alkali, the Skouries intrusion can be classified as a high K calc–alkaline type ^[9]^[13]^[14]. Also, although the contents of trace elements are scattered over a wide range, the high K/Rb and low Rb/Sr ratios from the Skouries porphyry stock are similar to PGE-fertile porphyry at the Allard stock, La Plata Mountains Colorado ^[13]^[15]^[16].

Figure 1. (a): Simplified geology of the Serbo−Macedonian Massif the studied part is marked by the red frame (modified after ^[5]^[6]); (b): schematic cross−section showing crosscutting successive monzonite porphyry intrusions; (c): the location of drill holes in the Skouries porphyry deposit ^[4]; (d): representative drill core sample, showing the presence of dark-green angular mafic fragments to a sharp contact with the host porphyry, and crosscutting relationships between successive quartz veins. Abbreviation: Cp = chalcopyrite, Py = pyrite, K-SPAR = K-feldspar.

Three major fault groups characterize the regional structures, which controlled the emplacement of the intrusions in the crystalline basement of the Vertiskos Unit. Based on crosscutting and overprinting relationships, at least four stages of mineralization have been described in the porphyry Cu-Au deposit of Skouries (Figure 1b): (1) the initial quartz monzonite porphyritic phase and (2) the main stage of porphyritic syenite, associated with the mineralization of defined reserves approximately 205 Mt at 0.5% Cu, and 0.53 ppm Au, (3) the porphyritic mela-syenite dykes, and (4) the late stage, which crosscuts all earlier phases ^[4]^[7]^[8]^[14]^[17]^[18]. According to these authors, magnetite–chalcopyrite (reaching up to 10 vol.%, average 6 vol.%) and bornite–chalcopyrite, linked to a pervasive potassic and propylitic alteration, crop outs in the central parts of the deposit, while chalcopyrite–pyrite dominates around the periphery of the deposit. Molybdenite is rare and occurs in pyrite–sericite–carbonate-bearing veinlets at the marginal parts of the deposit, with only a minor quantity of chalcopyrite.

The presence of isolated fragments of dark-green mafic fragments in drill core samples has been noted (Figure 1d) ^[19]^[20]. In addition, drill-hole samples from a depth of more than 300 m contain relatively large fragments of metamorphosed basic rocks, intruded by porphyry intrusions that affect the sulfide mineralization (Figure 2).

Figure 2. Photographs of dark-green biotite–amphibole metamorphic country rocks, which are dominant in drill cores as xenoliths in the Skouries porphyry. (a,b): Sulfide mineralization in those rocks intruded by porphyry intrusions are common. (c): layered amphibolite. Bar scale (a–c) = 1 cm.

A calc–alkaline syenite and a quartz granodiorite intrusion host the Vathi, Gerakario, and Pontokerasia porphyry deposits in SMZ are of Miocene age (18 Ma) too, with more than 258 Mt of ore at 0.40 wt.% Cu and 0.9 g/t Au ^[11].

2. Mineralogical Characteristics

New data presented here are combined with those available from previous detailed descriptions on the porphyry deposits hosted in the Vertiskos Formation ^[11]^[12]^[13]^[14]^[17]^[18]^[19]^[20]. Magnetite–chalcopyrite ± bornite, linked to pervasive potassic and propylitic alteration, is exposed in the central parts of the Skouries deposit, while pyrite, that is dominant around the periphery of the deposit, is characterized by a significant (Ni±Co) content, for example, those from the SOP76 drill-hole (Figure 1c) (Table 1). The hypogene mineralization at the Vathi occurs in the quartz monzonite, while the potassic alteration is associated with vein-type ore assemblage: pyrite + chalcopyrite + bornite + molybdenite + magnetite, the propylitic alteration is related to pyrite + chalcopyrite, and the sericitic alteration is associated with the assemblage pyrite + chalcopyrite + native gold ± tetradymite. The assemblage sphalerite + galena + arsenopyrite + pyrrhotite + pyrite ± stibnite ± tennantite is related to a subsequent epithermal overprinting event ^[11].

Table 1. Selected characteristics of the porphyry-Cu deposits from the Chalkidiki Peninsula.

Deposit	Setting	Age	Affinity	Drill Hole	Location of Drill Hole	Alteration	Mineralization	Mineralogy
Skouries							ccp-mgt±bn
				SOP06	Central part	Potassic	minor: native Au-mrk-hes-syl-zrn	qz-or-ab-an-bt-phl-ap
				SG6
				SOP18			ccp-mgt±bn
	Col	18 Ma	Monzonite	SOP1	Proximal to center	Potassic	minor: native Au-me-zrn-thr	qz-or-ab-an-bt-phl-ap
			syenite	SOP09
				SK8
				SOP39	Peripheral part	Potassic and clay	ccp-py-mol-mgt	qz-or-ab-bt-phl-ap-cal
				SOP43
				SOP46	Marginal part	Potassic and clay	ccp-py-cc-mol-mgt	qz-ab-ms-ser-cal
				SOP76			ccp-py-sp-gn
Vathi, Gerakario,
Pontokerasia	Col	18 Ma	Quartz monzonite	Surface samples		Potassic	py-ccp-mol-mgt
			syenite			Propylic	py-ccp-mol-cc-apy	qz-or-ab-an-bt-ser-cal
						Sericitic	py-ccp-cc-sp-gn

Abbreviations: SMM = Serbo-Macedonian Massif; Col = during or following collision; ccp = chalcopyrite, mgt = mgnetite, bn = bornite, mrk = merenskyite, hes = hessite, syl = sylvanite, zrn = zircon, thr = thorite, py = pyrite, mol = molybdenite, cc = chalcocite, sp = sphalerite, gn = galena, apy = arsenopyrite, qz = quartz, or = orthoclase, ab = albite, an = anortite, bt = biotite, phl = phlogopite, ap = apatite; cal = calcite, ms = muscovite.

Table 2. Representative electron microprobe analyses of minerals from porphyry-Cu deposits of the Balkan Peninsula, present research; (*) ^[21]^[22]; n.d. not detected.

Country

Greece

Bulgaria *

Deposit

Skouries

Elatsite

Medet

Drill-hole

SOP-76

SOP-46

SG-6

n = 4

Mineral

pyrite

linnaeite

siegenite

Pyrite

Carrolite

wt.%

45.6

46.5

42.6

45.6

46.2

43.4

1.4

3.4

38.2

33.8

1.8

n.d.

0.4

n.d.

16.3

3.3

0.1

15.9

0.9

1.1

4.2

1.9

0.7

n.d.

7.4

34.7

5.3

0.4

3.2

0.6

n.d.

0.5

n.d.

34.4

17.3

2.2

12.4

37.6

n.d.

0.9

n.d.

4.8

n.d.

52.6

53.3

52.2

52.5

51.9

50.7

41.3

41.5

53.9

53.2

41.6

Total

99.7

100.9

100.5

99.2

99.8

100.8

100.2

99.7

99.9

100.1

Drill-hole

SK8

SOP18

SG-6

SOP76

SOP18

SOP43

SOP18

SK8

Core

Rim

Cl-(OH)

Ti-

Cr-bearing

Mineral

Zircon

Apatite

Rutile

Thorite

U-thorite

Magnetite

SiO₂

32.6

31.3

31.7

n.d.

0.4

18.8

15.6

15.2

0.2

0.3

0.7

Al₂O₃

n.d.

0.3

n.d.

Cr₂O₃

n.d.

0.7

0.8

TiO₂

n.d.

95.5

n.d.

19.8

n.d.

FeO

0.6

0.4

n.d.

0.6

2.2

n.d.

0.6

4.3

49.4

31.0

30.9

Fe₂O₃

n.d.

30.8

68.2

67.6

MgO

n.d.

MnO

n.d.

CaO

n.d.

55.0

52.7

n.d.

P₂O₅

n.d.

43.9

42.5

n.d.

SO₃

n.d.

0.4

n.d.

ZrO₂

67.2

65.4

68.3

n.d.

67.2

n.d.

ThO₂

n.d.

3.2

n.d.

79.5

70.68

50.8

n.d.

HfO₂

n.d.

UO₃

n.d.

11.9

29.2

n.d.

Total

100.4

100.3

100.0

98.9

96.2

98.4

98.3

98.78

99.5

100.2

100

Disseminated magnetite as part of the quartz–bornite–chalcopyrite assemblages in the potassic alteration zones, proximal to the centers, is a characteristic feature in the Skouries and Elatsite deposits ^[14]^[20]^[21]^[23]^[24]. Merenskyite (the most common PGE-mineral) occurs commonly as inclusions or on the edge of hydrothermal chalcopyrite ^[12]^[14]^[20]. More attention was paid here on the texture and mineral chemistry of magnetite (Figure 3; Table 3) in order to define significant differences compared to PGE-poor porphyry-Cu intrusions.

Figure 3. Backscattered electron images from drill core samples at Skouries porphyry deposit. (a): clausthalite and bornite intergrowths with magnetite; (b): magnetite intergrowths with apatite; (c): association of rare accessory minerals with Ti-magnetite; (d): uranium-rich thorite and zircon associated with Ti-magnetite within a quartz matrix. Abbreviations: mt = magnetite; bn = bornite; qtz = quartz; ap = apatite; bi = biotite; rt = rutile; zr = zircon.

Magnetite in the Skouries porphyry Cu deposit results in the occurrence of intergrowths with Ti-magnetite, ilmenite, zircon, very fine Cu minerals (bornite and chalcopyrite), thorite, U-bearing thorite, rare earth element (REE) minerals (mostly monazite) and Cl,(OH)-apatite (Figure 3; ^[20]. Zircon often shows zoning, with Fe, Th, Hf, and S in the core in contrast to the rim (Table 3). Uranium-rich thorite is associated with Ti-magnetite hosted by quartz (Table 1).

Separates of disseminated magnetite, derived from large porphyry-Cu samples, were analyzed for major and trace elements. The Th contents ranging from 28 to 110 ppm (mean 65), U ranging from 5.3 to 31 (mean 15 ppm), and Zr ranging from 119 to 700 ppm (mean 323) in magnetite separates are much larger than in bulk analyses and confirm their association with magnetite (Figure 3c,d). In addition, a characteristic feature of the magnetite is the relatively high Cr (average 0.8 wt.% Cr₂O₃ (Table 1), reaching up to 2.3 wt.% Cr₂O₃) in SEM/EDS analyses, and in magnetite separates, the high Cr, Ni, and Co contents reach values up to 1060 Cr, 640 Ni, and 69 Co (all in ppm, Table 2). The average Cr content in magnetite from the Vathi porphyry ^[12] and Cr (16 ppm) from the Pagoni Rachi Cu-Mo-Re-Au porphyry prospect, northern Greece (Thrace), was 110 ppm and 16 ppm, respectively ^[25], meaning that they are much lower compared to that in magnetite from the Skouries deposit (Table 2 and Table 3).

Table 3. Composition of disseminated magnetite separates from the Skouries drill-holes. Present research.

		Skouries		Detection	Standard
				Limit	OREAS684	Vathi
ID		Porphyry-Cu
sample	SOP43/200	SOP6/363	Skou8/280
ppm
As	<5	<5	<5	5	<5	52
Bi	10	5.2	5.4	0.1	0.4
Cr	1060	560	280	0.01	13,000	240
Mn	560	430	360	0.01	1250	650
Ni	640	76	310	5	2250	300
Co	69	50	66	0.05	119	10
Cu	4850	1210	1310	0.1	960	28
Zn	61	37	68	5	95	70
V	670	920	690	1	165	3000
Ga	41	40	59	1		75
Ba	60	70	100	10	70
La	1.2	14	2.5	2	3.4
Ce	2.1	28	4.7	0.1	6.6
Pr	0.2	2.8	0.5	0.1	0.74
Nd	0.9	9.8	1.8	0.05	2.9
Sm	0.1	1.6	0.3	0.5	0.6
Eu	0.07	0.26	0.08	0.05	0.21
Gd	0.16	1.2	0.3	1	0.71
Tb	<0.05	0.16	<0.05	0.5	0.12
Dy	0.15	0.9	0.21	0.05	0.71
Ho	<0.05	0.2	<0.05	0.05	0.16
Er	0.15	0.7	0.18	0.1	0.5
Tm	<0.05	0.1	<0.05	0.05	0.08
Yb	0.2	1.1	0.3	0.1	0.5
Lu	<0.05	0.25	0.05	0.05	0.09
ΣREE	4.03	46.82	8.37
Ce/Ce*	0.95	0.98	0.96
Eu/Eu*	1.68	0.55	0.61
Tm/Tm*	0.19	0.79	0.47
Sc	8	8	9	5	19
Y	1.3	6.3	1.6	0.5	4.3
Hf	3	18	4	1	<1
Cs	0.7	0.2	0.2	0.1	0.2
In	<0.2	<0.2	<0.2	0.2	<0.2
Nb	1	7	1	1	<1
Pb	23	16	35	0.2	13
Rb	24	11	12	0.1	6.5
Sb	<0.1	<0.1	<0.1	0.1	<0.1
Sn	4	5	5	0.05	<1
Ta	<0.5	0.6	<0.5	0.5	<0.5
Mo	<2	<2	2	2	<2
Li	<10	<10	<10	10	<10
Sr	10	30	30	5	150
Th	28	110	56	0.1	0.6
U	5.3	31	9.3	0.5	0.2
Zr	119	700	150	0.5	14.7
W	74	39	52	0.1	<1
Tl	0.5	<0.5	<0.5	0.5	<0.5
wt%
Si	3.7	2.8	3.4	0.01	21.1
Al	0.58	0.54	0.6	0.01	5.75
Fe	>25	>25	>25	10	7.99
Ti	0.16	0.35	0.24	0.01	0.13
Ca	<0.1	<0.1	<0.1	0.1	4.2
Mg	0.24	0.07	<0.01	0.01	10.4
K	0.4	0.3	0.3	0.01	0.1
P	<0.01	<0.01	<0.01	0.01	<0.01

The rare earth element (REE) content of magnetite separates is relatively low, and the chondrite-normalized REE patterns (Figure 4a) are similar to those for porphyry (Figure 4b) in terms of highly fractionated LREE ^[26]. Mean ratios for Ce/Ce* = 0.96 and Eu/Eu* = 0.95 were calculated according to ^[27] (Table 3).

Figure 4. Chondrite normalized diagrams (a): for magnetite separates, data from Table 2; (b): for the Skouries porphyry after ^[26]. Chondrite values from ^[28].

3. Platinum-Group Minerals (PGMs) in the Porphyry-Cu-Au+Pd±Pt Deposits

Consistently with the geochemical data, the presence of discrete platinum-group minerals (PGMs) of Pd and, to a lesser extent, of Pt have been described in several porphyry-Cu-Au+Pd±Pt deposits, including the Skouries. In the Afton and Mt Milligan deposits of British Columbia, pyrite contains small amount of Pd ^[14]^[29]^[30]^[31]. In the Cu-sulfides associated with potassic alteration of the Skouries deposit, intergrowths of merenskyite [(Pd,Pt)(Te,Bi)₂], hessite (Ag₂Te), electrum, and Cu minerals (bornite and chalcopyrite) have been described ^[18]. More recently, the PGM identified in PGE-enriched porphyry deposits consist exclusively of Pd minerals such as merenskyite that rarely contains up to 3 wt% Pt ^[14]. Isomertierite (Pd₁₁Sb₂As₂), kotulskite [Pd(Te,Bi)], naldrettite (Pd₂Sb), sobolevskite (PdBi), sopcheite (Ag₄Pd₃Te₄), telargpalite [(Pd,Ag)₃Te)], and testibiopalladite [PdTe(SbTe)] are less abundant. The PGMs of Skouries have been identified to be enclosed or at the edge of sulfides, such as chalcopyrite and bornite, or associated with hydrothermally alternated silicates ^[14].

Moncheite [(Pt,Pd)(Te,Bi)₂], merenskyite, and kotulskite accompanied by Ag-tellurides and selenides have been described within the main magnetite–bornite–chalcopyrite assemblages of the potassic core at the Santo Tomas II (Philippines) porphyry-Cu intrusion ^[32], while stibiopalladinite [Pd₅Sb₂] and vysotskite [(Pd,Ni)S] have been identified in sulfide concentrates from the same deposit ^[33]. In addition to Ni-Co sulfides, the Elatsite deposit contains mostly mineral of the merenskyite–moncheite series accompanied by Ag-tellurides, selenides, and bismuthides ^[21]^[23]^[34]. In the Serbian deposit of Majdanpek, in the deposit of Mamut located in Malysia, in Mt Milligan B.C. and elsewhere the PGMs identified were merenskyite and sperrylite (PtAs₂) ^[35]^[36]^[37]^[38]^[39]. Sulfide concentrates from the Aksug deposit (Russia) contain only Merenskyite ^[36]. Several PGMs, such as arsenopalladinite [Pd₈(As,Sb)₃], kotulskite, merenskyite, naldrettite, and sopcheite, occur in the Malmyzh porphyry-Cu deposit of the Russian Far East ^[37].

4. Platinum and Palladium Distribution

Any systematic variation between the Pd and Pt contents with the drill-hole depth and the location of the drill-hole is not obvious. However, it seems likely that the maximum (Pd+Pt) contents were measured in the central part of the ore body (Figure 1c), for example, in the drill-hole labeled as SG6, whereas they are much lower in marginal drill-holes. In general, a common feature of the Skouries deposit and other (Pd, Pt, Au)-fertile porphyry-Cu deposits is the occurrence of the quartz–bornite–chalcopyrite assemblages in the potassic alteration zones, proximal to centers, during the primary hypogene mineralization event ^[13]^[14]^[19]^[20]^[21]^[23]^[32]^[35]^[38]^[40]^[41]. A relatively high PGE content in the Skouries porphyry-Cu deposits (up to 2.4 ppm Pd in chalcopyrite concentrates) measured in vein-type highly mineralized portions from drill-hole samples, covering deeper parts of the whole mineralized porphyry of Skouries (Figure 3), is consistent with the analyzed composite drill-hole sample (~15 kg), showing 75 ppb Pd at 0.5 wt.% Cu or 3300 ppb Pd (measured contents of Pd are normalized to 100% chalcopyrite or 33 wt.% Cu) ^[42].

The Vathi, Pontokerasia, Gerakario, and the Skouries porphyry deposits are all hosted in the Vertiskos Formation of SMM (Figure 1), but they display different geochemical data compared to the Skouries deposit, the Afton deposits, British Columbia, and other porphyry deposits. The Vahti, Pontokerasia, Gerakario, as well as the porphyry-Cu deposits of Russia and Mongolia exhibit larger Mo, Ba, Zr, and U and smaller Cr, Ni, Mg, Pd, Pt, and Au contents ^[14]^[20]^[21]^[23]^[43]^[44]^[45].

Although an overlapping may occur in the plots of the Pd and Pt contents, versus the (Ba+Sr) and (Cr+Ni) contents, the smaller (Ba+Sr) content and the maximum contents of Mg, Cr, Ni, and Co seem to be characteristic of the precious metal fertile intrusions (Figure 5).

Figure 5. (a): Plots of the Pd versus Pt content for whole rock and flotation concentrates: (b): plot of Pd versus Cu/Pd); (c,d): plots of the (Pd+Pt) content versus (Ba+Sr) and (Cr+Ni) contents for PGE-rich and PGE-poor, whole rock analyses. Data from Table 3, and ^[19]^[29]^[46]. PGE-rich and PGE-poor in the Figure 5b–d are presented as in Figure 5a.

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Subjects: Geochemistry & Geophysics

Contributors MDPI registered users' name will be linked to their SciProfiles pages. To register with us, please refer to https://encyclopedia.pub/register :

Maria Economou-Eliopoulos

Federica Zaccarini

Giorgio Garuti

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Update Date: 17 Nov 2023

Table of Contents

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1. Geological Outline

2. Mineralogical Characteristics

3. Platinum-Group Minerals (PGMs) in the Porphyry-Cu-Au+Pd±Pt Deposits

4. Platinum and Palladium Distribution

References