俄罗斯北堪察加Evevpenta金矿床玄武岩矿物次生蚀变特征及其成矿指示作用

doi:10.13745/j.esf.sf.2023.7.1

摘要/Abstract

摘要：

俄罗斯北堪察加地区Evevpenta金矿床玄武岩主岩青磐岩化蚀变的矿物学组成,是以英安岩中的石英、冰长石-石英、石英-碳酸岩岩脉和热液角砾岩组成的脉系为特征。脉状矿物是天然金、碲化物、硫化物、硒化物和金-银氯化物。青磐岩化蚀变发生在距浅成热液脉较远的地方。然而,它的特征矿物组合对重建成矿环境有重要研究意义。在青磐岩化带内可识别出氟磷灰石-氟铝钛矿、石英-方解石-斜绿泥石、石英-方解石-硬石-蒙脱石、方解石-丝光沸石4种不同的热液蚀变组合。最早的矿物组合形成于酸性富F的热液中。热液流体中氟化物浓度为0.2~1.2 g/L,流体温度约550 ℃。酸性热液与橄榄玄武岩寄主岩石长期相互作用,导致pH升高至接近中性并发生绿泥石化作用。绿泥石化阶段热液富集Fe和Mg,温度约175~210 ℃时形成第1阶段绿泥石, 120~140 ℃时形成第2阶段绿泥石。蚀变的最后阶段形成沸石群矿物,其在pH约为9、温度>135 ℃的热液中析出。热液流体的高pH值可能是由于碳酸氢盐和碳酸盐的存在以及溶液中铁盐的去除。根据青磐岩化带蚀变矿物组合特征,探讨了Evevpenta脉系形成的物理化学条件。在热液体系形成阶段,随着碱性氯化钠溶液的循环,贵金属Cl^-和OH^-络合物的形成导致了矿石元素的运移。高pH溶液也能转移硫。

关键词: 矿物学, 金, 丝光沸石, 斜绿泥石, 青磐岩化蚀变, Evevpenta, 堪察加

Abstract:

The mineralogy seen in propylitic alteration of basalt host rocks in the Evevpenta gold occurrence in North Kamchatka is based on a vein system consisting of quartz, adularia-quartz, quartz-carbonate veins, and, hydrothermal breccias hosted in dacite. Vein minerals are native gold, tellurides, sulfides, selenides, and Au-Ag chlorides. The propylitic alteration occurs at a distance from the epithermal veins; however, it contains characteristic mineral assemblages useful for the reconstruction of an ore-formation environment. Four distinct hydrothermal alteration assemblages are recognized within the propylitic zone: 1. fluorapatite-fluorine-aluminous titanite, 2. quartz-calcite-clinochlore, 3. quartz-calcite-stilbite-montmorillonite, and 4. calcite-mordenite. The earliest mineral assemblage was formed from an acid F-enriched hydrothermal fluid. The concentration of fluoride in fluid was 0.2-1.2 g/L, and temperature of about 550 ℃. The long-term interaction between the acid hydrothermal fluid and olivine basalt host rocks resulted in increasing pH to near neutral that caused a chloritization process. The chloritization stage hydrothermal fluid was enriched in Fe and Mg with temperatures of about 175-210 ℃, chlorite I, and 120-140 ℃, chlorite II. The final stage of alteration consists of zeolite group minerals, which were precipitated from the hydrothermal fluid of pH ~9 and temperature >135 ℃. The high pH of the hydrothermal fluid might be explained by the presence of bicarbonates and carbonates and removal of the iron salt from the solution. Based on the alteration mineral assemblages of the propylitic zone, the physical and chemical conditions of the Evevpenta vein system are discussed. The transport of ore elements took place due to the formation of precious metal Cl^- and OH^-complexes at the stage of hydrothermal system formation with circulation of alkaline sodium chloride solutions. Chalcogens were also transferred by high pH solutions.

Key words: mineralogy, gold, modernite, clinochlore, propylitic alteration, Evevpenta, Kamchatka

中图分类号:

Anastasiya SERGEEVA, Pavel ZHEGUNOV, Elena SKILSKAIA, Mariya NAZAROVA, Elena KARTASHEVA, Anna KUZMINA, Svetlana MOSKALEVA, Olesya ZOBENKO, Sharapat KUDAEVA, Ekaterina PLUTAKHINA, Kseniya SHISHKANOVA. 俄罗斯北堪察加Evevpenta金矿床玄武岩矿物次生蚀变特征及其成矿指示作用[J]. 地学前缘, 2023, 30(5): 450-468.

Anastasiya SERGEEVA, Pavel ZHEGUNOV, Elena SKILSKAIA, Mariya NAZAROVA, Elena KARTASHEVA, Anna KUZMINA, Svetlana MOSKALEVA, Olesya ZOBENKO, Sharapat KUDAEVA, Ekaterina PLUTAKHINA, Kseniya SHISHKANOVA. Secondary minerals in basalts of the Evevpenta gold occurrence (North Kamchatka, Russia) as indicators of ore forming processes[J]. Earth Science Frontiers, 2023, 30(5): 450-468.

图/表 13

Fig.1 Geological scheme of (a) the Evevpenta gold occurrence and (b) volcanic belts of the Kamchatka Peninsula (Tsukanov 2015) 1-proluvial Quaternary sediments; 2-lavas and pyroclastic rocks of the Tolyatovayam volcanic formation (Late Miocene-Early Pliocene); 3-lavas and pyroclastic rocks of the Umuvayam volcanic formation (Middle-Late Miocene); 4-subvolcanic bodies of andesites of the Tolyatovayam volcanic formation; 5-basalt dikes Tolyatovayam volcanic formation; 6-subvolcanicdacite bodies Umuvayam volcanic formation; 7-argillic alteration; 8-propylitic alteration; 9-adularia-quartz stockwork; 10-adularia-quartz veins; 11-faults; 12-faults covered by Quaternary sediments.

Fig.2 Specimen of olivine basalt from a geological exploration surface mine working in the study area with radiant sun aggregates of modernite (a), and core samples obtained as a result of core drilling (depth 112-1145 m) of the Evevpenta ore occurrence representing a zone of propylitic alterations with calcite veins in basalt (b)

Fig.3 X-ray diffraction (XRD) diffractograms for alteration mineral assemblages of I-IV microzones from which sample of olivine basalt (abbreviations given in Table 1).

Table 1 Mineral assemblages found in hydrothermally altered olivine basalt from the Evevpenta gold occurrence

Stage	Mineral assemblages
I (host rock)	Rock-forming minerals: plagioclase (labradorite-andesine)+monoclinic pyroxene relicts of olivine Secondary minerals: fluorapatite+aluminum- and fluorine-rich titanite
II (chloritization)	Secondary minerals: clinochlore+quartz+calcite
III (zeolitization)	Secondary minerals: calcite+stilbite+quartz+montmorillonite
IV (zeolitization)	Secondary minerals: calcite+mordenite

Table 2 Composition and unit-cell parameters of secondary minerals from the Evevpenta gold occurrence

Mineral name, Symmetry group	Chemical Formula	Unit-cell parameters/Å
Clinochlore, C₂	[Mg_3.29Al_1.30Fe_1.13Mn_0.04][Al_0.74Si_3.26]O₁₀(OH)₈	a: 5.36 b: 9.20 c: 14.24 β: 95.59
Calcite R-3/2c	CaCO₃	a: 4.99 c: 17.02
Mordenite, Cmcm	Na_0.47Ca_0.25K_0.05[Al_1.05Si_4.95]O₁₂·nH₂O	a: 18.13 b: 20.43 c: 7.52
Diopside, C2/c	[Mg_0.84Ca_0.83Fe_0.25Na_0.02Al_0.02Ti_0.02Mn_0.01]Al_0.12Si_1.88O₆	a:9.82 b:8.87 c: 5.23 β:105.79
Labradorite-andesine, C-1	A $n 0.660.48$	a:8.17 b: 12.85 c:7.10 α: 93.45 β: 116.04 γ: 90.12

Table 2 Composition and unit-cell parameters of secondary minerals from the Evevpenta gold occurrence

Mineral name, Symmetry group	Chemical Formula	Unit-cell parameters/Å
Clinochlore, C₂	[Mg_3.29Al_1.30Fe_1.13Mn_0.04][Al_0.74Si_3.26]O₁₀(OH)₈	a: 5.36 b: 9.20 c: 14.24 β: 95.59
Calcite R-3/2c	CaCO₃	a: 4.99 c: 17.02
Mordenite, Cmcm	Na_0.47Ca_0.25K_0.05[Al_1.05Si_4.95]O₁₂·nH₂O	a: 18.13 b: 20.43 c: 7.52
Diopside, C2/c	[Mg_0.84Ca_0.83Fe_0.25Na_0.02Al_0.02Ti_0.02Mn_0.01]Al_0.12Si_1.88O₆	a:9.82 b:8.87 c: 5.23 β:105.79
Labradorite-andesine, C-1	A $n 0.660.48$	a:8.17 b: 12.85 c:7.10 α: 93.45 β: 116.04 γ: 90.12

Table 3 Absorption bands of host rock and mordenite-calcite assemblages (T: Si Al)

Absorption bands/cm^-1		Assignment	Mineral
Chloritized basalt	Mordenite sample	Assignment	Mineral
	3596	ν(H₂O)	Mordenite
3561		ν(OH)	Clinochlore
	3448	ν(H₂O)	Mordenite
3422			Clinochlore
	3258	ν(H₂O)	Mordenite
1638	1646	δ(H₂O)	Mordenite Clinochlore
1440	1426	ν₃(CO₃)	Calcite
	1223	ν(SiO₄)_as	Mordenite
	1174	ν(SiO₄)_as	Mordenite
	1052	ν(SiO₄)_as	Mordenite
1022		ν(TO₄)_as	Plagioclase
	877	ν₂(CO₃)	Calcite
	794	ν(TO₄)_s	Mordenite
	714	ν(AlO₄)_s	Mordenite
776		ν(SiO₄)	Plagioclase
639		δ(O-T-O)	Plagioclase
	622	ν(TO₄) 5-rings (channel)	Mordenite
586		δ(O-T-O)	Plagioclase
540		δ(O-T-O)	Plagioclase
	550	ν(TO₄) 5-rings (channel)	Mordenite
	451	δ(O-T-O)	Mordenite
460		δ(O-T-O)	SiO₄-phase
439		δ(O-T-O)	Plagioclase
400		δ(O-T-O)	Plagioclase

Fig.4 Infrared spectra of altered basalt (1) and mordenite in association with calcite (2)

Fig.5 BSE-images showing mordenite enclosed in silica (a); Sr-bearing barite (b); and inclusion of Sb-bearing phase in mordenite (c) Abbreviations of minerals given according to Warr (2021): Mor-mordenite; Silicate-silica minerals; Sr-Brt-Sr-bearing barite.

Fig.6 Representative BSE images of hydrothermally altered basalts from the Evevpenta gold occurrence a-plagioclase phenocrysts are rimmed by several layers of secondary minerals; b-enlarged fragment of 6a showing details of a chlorite rim in plagioclase; c-plagioclase microlites overgrown by titanite and adularia; d-inclusion of fluorapatite in diopside; e-fluorapatite and silica minerals intergrown with clinochlore; f-amygdala filled with early (Chl I) and late (Chl II) chlorite; g-titanomagnetite in association with groundmass diopside and plagioclase; h-aluminum- and fluorine-rich titanite between plagioclase microlites in groundmass. Abbreviations of minerals given according to Warr (2021): Pl-plagioclase, Chl-chlorite, Tnt-titanite, Adl-adularia, Cpx-clinopyroxene, Ap-apatite, Mag-magnetite, Silicate-silica minerals, Ca-Pl-calcic plagioclase, Na-Pl-sodic plagioclase.

Table 4 EPMA data for minerals from altered basalt

Minerals	w_B/%
Minerals	Al₂O₃	CaO	F	TFeO	K₂O	MgO	MnO	Na₂O	P₂O₅	SiO₂	TiO₂	V₂O₅
Fluorapatite	0	53.45	3.71	0.65	0	0.52	0	0	40.19	0.49	0	0
Diopside	3.3	20.93	0	7.96	0	15.06	0.29	0.27	0	50.41	0.88	0
Clinochlore	16.71	1.02	0	12.74	0	21.63	0.63	0	0	33.22	0	0
Plagioclase	28.31-20.51	11.21-1.57	0	0.97-0.61	1.06-1.72	0.00-0.32	0	4.34-8.91	0	53.16-61.91	0	0
Sanidine	20.17	1.19	0	0.62	9.69	0	0	3.96	0	63.95	0	0
Titanite	6.16	27.04	1.67	1.39	0	0	0	0	0	32.81	27.17	1.09

Fig.7 Classification diagrams of chlorite from the Evevpenta gold occurrence, based on: a-Fe/(Fe+Mg) versus Si values (after Hey 1954); b-octahedral Al versus tetrahedral Al; c-Mg/(Fe+Mg) versus Al octahedral (after Bailey 1988); d-(Mg+Fe) versus Si values (Wiewióra and Weiss 1990; Ilalova and Gulbin 2019)

Fig.8 Scheme of geocrystallochemical classification of chlorites (Kotelnikov et al., 2009) 1-chlorites from kimberlites; 2-Mg-chlorites from serpentinites; 3-Mg-chlorites from halites and Mg-K-salts of high stages of salinization of basins; 4-Fe-Mg-chlorites of basic igneous rocks; 5-Fe-Mg-chlorites of clastogenic formations; 6-Fe-chlorites of iron ores; 7-ditrioctahedral Al-Fe-Mg-chlorites; 8-Mg-chlorites of evaporate chemogenic-terigenous formations; 9-chlorites of the Evevpenta gold occurrence.

Fig.9 Scheme of the stages of mineral formation of the Evevpenta ore occurrence based on alteration mineral assemblages I-fluorapatite aluminum- and fluorine-rich titanite mineral assemblages, the hydrothermal acidic fluid was accompanied by acid-volatile species such as HCl and HF; II-clinochlore quartz calcite mineral assemblages, the hydrothermal fluid was near-neutral containing NaCl, CO2, NaHCO3; III-calcite stilbite mordenite quartz montmorillonite mineral assemblages, the hydrothermal fluid was alkaline containing NaCl, NaHCO3, Na2CO3 and meteoric waters.

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