Geo chem is try of tetrahedrite group min er als and as so ci ated sil ver paragenesis in the Boguszów baryte de posit, Po land
S³awomir MEDERSKI1, *, Jaroslav PREK1 and ¯aneta NIEMASZ1
1 AGH Uni ver sity of Sci ence and Tech nol ogy, al. A. Mickiewicza 30, 30-059 Kraków, Po land
Mederski, S., Prëek J., Niemasz, ¯., 2020. Geo chem is try of tetrahedrite group min er als and as so ci ated sil ver paragenesis in the Boguszów baryte de posit, Po land. Geo log i cal Quar terly, 64 (4): 958–968, doi: 10.7306/gq.1562
As so ci ate Ed i tor: Jacek Szczepañski
Pri mary ore min er al iza tion in the aban doned Boguszów baryte-polymetallic de posit, lo cated in the Intra-Sudetic De pres sion, was stud ied by re flected light mi cros copy and elec tron microprobe. Ore min er als, oc cur ring as veinlets, ir reg u lar ag gre gates and lenses in baryte veins are hosted by the Up per Car bon if er ous Che³miec rhyodacite laccolith. They are dom i nated by ga - lena, sphalerite (with Cd up to 0.04 apfu) and tetrahedrite group min er als (TGM). Four gen er a tions of the TGM were dis tin - guished ac cord ing to tex tural fea tures and Ag con tent: (1) low-Ag tetrahedrite-(Zn) (Ag: 0.22–0.6 apfu), (2) Ag-en riched tetrahedrite-(Zn) and Ag-en riched tetrahedrite-(Fe) (Ag: 0.71–1.45 apfu), (3) mem bers of the freibergite se ries:
“freibergite-(Fe)” and “freibergite-(Zn)” (Ag: 3.21–3.48 apfu; Hg: up to 0.75 apfu), (4) mem ber of the “freibergite-(Fe)” se ries (Ag: 5.32–5.78 apfu). Sev eral elon gated in clu sions of Ag-bear ing sulphosalts within ga lena crys tals were ob served (mem - bers of the se ries “freibergite-(Fe)” and “freibergite-(Zn)”, pyrargyrite and polybasite). These polymetallic sil ver-bear ing ores were mined in Boguszów from the 15th to the 19th cen tury. Ad di tion ally, small grains of co balt-en riched löllingite and gersdorffite were ob served, which were formed from flu ids sourced from the ultra mafic base ment. The tex tural char ac ter is - tics of the ore, the min eral paragenesis and the chem i cal com po si tion of in di vid ual ore min er als in di cate low-tem per a ture crys tal li za tion con di tions.
Key words: Boguszów, baryte veins, sil ver min er al iza tion, tetrahedrite.
INTRODUCTION
Sil ver min er al iza tion in the form of sil ver min er als, tetra - hedrite group min er als (TGM) or in the form of ad mix tures in ga lena or bornite is com mon in dif fer ent ge netic types of base metal de pos its. It oc curs pri mar ily in epi ther mal sys tems (e.g., Gemmell et al., 1989; Plumlee and Whitehouse-Veaux, 1994;
Cheilletz et al., 2002; Sack and Goodell, 2002; Sack et al., 2003; Bestemianova and Grinev, 2017). In these sys tems, baryte is a ma jor gangue min eral phase. The pres ence of sil - ver min er al iza tion is also re corded in other de posit types, in - clud ing skarn, volcanogenic mas sive sul phide, sed i men tary- ex ha la tive and sed i ment-hosted type de pos its (e.g., Grossou - - Valta et al., 1990; Höller and Gan dhi, 1995; Shalaby et al., 2004; Ko³o dziejczyk et al., 2016; Kozub-Budzyñ and Pies - trzyñski, 2018).
Oc cur rences of sil ver-bear ing min er al iza tion are quite com - mon in the area of Sudetes Moun tains in Po land (Lis and
Sylwestrzak, 1986). The Ag-min er al iza tion oc cur rences re cor - ded in the lit er a ture are shown in Ta ble 1. More Ag de pos its and oc cur rences, as well as op por tu ni ties for com par i son, can be ob served within the Bo he mian Mas sif in the Czech Re pub lic.
This area is fa mous for its nu mer ous sil ver de pos its mined in pre vi ous cen tu ries, some of which are sum ma rised in Ta ble 2.
In the Boguszów baryte de posit only proustite has been noted with out pre cise iden ti fi ca tion (Traube, 1888), as well as tetrahedrite with 3 wt.% Ag (Migaszewski, 1972). For many years sil ver ores were ex ploited in baryte veins in the Boguszów area. How ever, no quan ti ta tive re sults con cern ing the Ag-min - er al iza tion are avail able in the lit er a ture. This study de scribes the sil ver min er al iza tion in the baryte veins and to pro vide pre - cise chem i cal data on the sil ver min er als, es pe cially for the TGM from the Boguszów baryte de posit.
LOCALITY AND GEOLOGICAL SETTING
The Boguszów baryte vein de posit (Segen Gottes Mine) is lo cated on the south-west side of Che³miec Hill (Fig. 1A), ~6 km to the west of Wa³brzych, close to the town of Boguszów Gorce.
The baryte de posit is lo cated in the Wa³brzych De pres sion, which is part of the fault-bounded, NW–SE trending Intra- Sudetic De pres sion, at the north ern pe riph ery of the Bo he mian
* Corresponding author, e-mail: mederski@agh.edu.pl Received: June 1, 2020; accepted: September 8, 2020; first published online: October 14, 2020
Mas sif (¯elaŸniewicz et al., 2011). The de pres sion is filled with Car bon if er ous sed i ments: Culm fa cies (con glom er ates and grey wackes), Wa³brzych and Bia³y Kamieñ units (coal-bear ing lithostratigraphic units; Dziedzic, 1971; Mastalerz, 1996; Kuro - wski, 1998). The sed i men tary suc ces sion is di vided by the Up - per Car bon if er ous Che³miec rhyodacite laccolith of West - phalian B/C tran si tion age (310 ±4 Ma) (Gro cholski, 1965;
Mastalerz and Mastalerz, 2000; Awdankiewicz and Kryza, 2010). The Boguszów baryte de posit is closely re lated to the NW–SE trending (strike-slip) fault-zone ob served in the NW part of the Che³miec dome (Gruszczyk, 1952). Sev eral baryte veins (Fig. 1B) formed as a re sult of epi ther mal ac tiv ity at a late
stage of the subvolcanic ac tiv ity and these veins cut the Che³ miec laccolith and the sur round ing sed i men tary units (Gruszczyk et al., 1970).
In the Boguszów de posit, three main min eral as sem blages re lated to baryte veins are ob served: baryte-sulphides, baryte- flu o rite and baryte-quartz (Gruszczyk, 1952). How ever, Paulo (1994) dis tin guished five ore min er al iza tion stages there:
–quartz with Zn, Ag, Cu, Pb (mi nor As, Fe, Ni, Bi) sulphides;
–car bon ates and he ma tite (Cu, Pb sulphides);
–baryte and flu o rite (Pb, mi nor Cu and Zn sulphides);
–quartz, lo cally marcasite;
–flu o rite leach ing, ox i da tion, trans par ent baryte overgrowths.
T a b l e 1 Ag-min er al iza tion oc cur rences in the Sudetes Moun tains
Lo cal ity
(type of min er al iza tion) Sil ver min er al iza tion and Ag-en riched TGM Gen er al ized as so ci ated
min er al iza tion Ref er ences Grudno:
hy dro ther mal quartz- cal cite-sul phide vein
freibergite [Ag6(Cu4Fe2)Sb4S13], pyrargyrite [Ag3SbS3]
quartz, cal cite, ar seno py rite, py rite, sphalerite, TGM, chal co py rite, Cu,
Pb, Sb min er als
Paulo and Salamon (1974a) Radzimowice:
hy dro ther mal polymetallic veins
freibergite [Ag6(Cu4Fe2)Sb4S13], acanthite [Ag2S], gustavite [AgPbBi3S6], treasurite
[Ag7Pb6Bi15S32], hessite [Ag2Te], electrum [Au,Ag]
quartz, do lo mite, cal cite, sid er ite, an ker ite, baryte, py rite, ar seno py -
rite, chal co py rite, ga lena, sphalerite, TGM, dif fer ent sulphides
and sulphosalts
Manecki (1965);
Paulo and Salamon (1974b);
Mikulski (2005) Kletno:
polymetallic Cu-Ag-U-Se min er al iza tion
na tive sil ver, stromeyerite [AgCuS], miargyrite [AgSbS2], ar gen tite [Ag2S], matildite [AgBiS2], naumannite [Ag2Se],
bohdanowiczite [AgBiSe2]
quartz, baryte, flu o rite, cal cite, uraninite, Fe ox ides, Fe, Cu, Pb,
Zn, Hg sulphides, bis muth sulphosalts
Banaœ and Mochnacka (2000) Kowary:
magnetite-ura - nium-polymetallic min er al iza -
tion in veins and nests
na tive sil ver [Ag], stromeyerite [AgCuS], proustite [Ag3AsS3], ar gen tite [Ag2S], pyrargyrite [Ag3SbS3], matildite [AgBiS2]
cal cite, do lo mite, Fe ox ides, uraninite, Fe, Cu, Pb, Zn, Bi sulphides and sulphosalts
Mochnacka and Banaœ (2000) Rêdziny:
polymetallic min er al iza tion in quartz veins and dis sem i -
nated in schists and am phi bo lites
freibergite [Ag6(Cu4Fe2)Sb4S13], Ag-rich tetrahedrite (up to 15.9 wt.% Ag)
ar seno py rite, cas sit er ite, py rite, pyrrhotite, chal co py rite, cubanite,
ga lena, sphalerite, bis muth sulphides and sulphotellurides,
TGM, Ag(Cu)-Pb-Bi(Sb) sulphosalts, Sn-bear ing sulphides
Go³êbiowska et al.
(2012)
Czarnów:
polymetallic veins
ar gen tite [Ag2S], matildite [AgBiS2], treasurite [Ag7Pb6Bi15S32], hessite [Ag2Te],
Ag-Bi sulphotellurides
quartz, cal cite, do lo mite, ar seno py - rite, chal co py rite, pyrrhotite, py rite, ga lena, sphalerite, stibnite, cas sit - er ite and other Cu-Bi sulphides and
sulphosalts
Mikulski (2010)
Ciechanowice:
polymetallic veins
acanthite [Ag2S], Ag-amal gams, eugenite [Ag11Hg2], na tive Ag, stromeyerite [AgCuS],
ar gen tite [Ag2S], stephanite [Ag5SbS4], xanthoconite [Ag3AsS3], proustite [Ag3AsS3],
polybasite [Cu(Ag,Cu)6Ag9Sb2S11]
baryte, cal cite, an ker ite, löllingite,
safflorite, bornite, chalcocite, TGM Siuda (2012)
Przecznica, Gierczyn:
dis sem i nated and vein-type cas sit er ite-polymetallic
min er al iza tion in chlorite-mica-quartz schists
pyrargyrite [Ag3SbS3]: Gierczyn and Przecznica, Ag-rich tetrahedrite
(28–29 wt.% Ag): Przecznica
quartz, mica, chlorites, cas sit er ite, pyrrhotite, sphalerite, chal co py rite and dif fer ent sulphides, ar sen ides
and sulphosalts
Piestrzyñski and Mochnacka (2003) Dzieæmorowice – Stary
Julianów:
hy dro ther mal poly - metallic-baryte-quartz-
-cal cite veins
freibergite [Ag6(Cu4Fe2)Sb4S13], stephanite [Ag5SbS4]
baryte, quartz, cal cite, ga lena, sphalerite, TGM, nic co lite, smaltite,
cobaltite, py rite, chal co py rite, ar seno py rite, mag ne tite, uraninite
Petrascheck (1933) Zagórze Œl¹skie:
hy dro ther mal polymetallic-baryte veins
argentopentlandite [Ag(Fe,Ni)8S8] baryte, chal co py rite, ga lena,
sphalerite, pyrrhotite Piestrzyñski and Kowalik (2015)
Bystrzyca Górna:
hy dro ther mal Ag-rich baryte-quartz veins
pyrargyrite [Ag3SbS3], stephanite [Ag5SbS4], miargyrite [AgSbS2], ar gen tite [Ag2S], dyscrasite [Ag3Sb], Ag-rich tetrahedrite, freibergite [Ag6(Cu4Fe2)Sb4S13], zoubekite
[AgPb4Sb4S10], freiselbenite [AgPbSbS3], andorite VI [AgPbSb3S6]
baryte, quartz, ga lena, sphalerite, greenockite, chal co py rite, TGM,
bour no nite, na tive an ti mony, Pb-Sb sulphosalts
Pršek et al. (2019)
Boguszów:
hy dro ther mal Ag-rich baryte veins
Ag-en riched tetrahedrite-(Fe) and tetrahedrite-(Zn) (6.20 to 9.08 wt.% Ag),
mem ber of se ries “freibergite-(Fe)” and
“freibergite-(Zn)”, pyrargyrite [Ag3SbS3], polybasite [Cu(Ag,Cu)6Ag9Sb2S11]
baryte, quartz, car bon ates, ga lena, sphalerite, TGM, chal co py rite, py - rite, löllingite, gersdorffite, flu o rite
Traube (1888);
this study
Migaszewski (1972) stud ied and de scribed dif fer ent ore min er als from the hy dro ther mal veins (partly with baryte) and ore min er als lo cated in the hy dro ther mally al tered vol ca nic rocks: py rite, sphalerite, tetrahedrite, chal co py rite, ga lena, coba ltite and uraninite.
Min ing ac tiv ity in the Boguszów area dates back to the 15th cen tury, when sil ver-rich baryte-ga lena-tetrahedrite ores were ex ploited. Ini tially, the work was car ried out by open pit meth ods. The first un der ground mine was opened in 1530 (Gruszczyk, 1952). Min ing took place un til 1755, when the lo - Fig. 1A – sim pli fied geo log i cal map of the Boguszów area;
1B – cross-sec tion of baryte veins (mod i fied from Gruszczyk et al., 1970)
T a b l e 2 Se lected Ag-min er al iza tion oc cur rences in the Bo he mian Mas sif
Lo cal ity
(type of min er al iza tion) Sil ver min er al iza tion and Ag-en riched TGM Gen er al ized as so ci ated
min er al iza tion Ref er ences
Kutná Hora:
hy dro ther mal ore veins
ar gen tite [Ag2S], Ag-rich TGM, acanthite [Ag2S], dyscrasite [Ag3Sb], allargentum [Ag1-xSbx], polybasite [Cu(Ag,Cu)6Ag9Sb2S11],
proustite [Ag3AsS3], pyrargyrite [Ag3SbS3], pyrostilpnite [Ag3SbS3], stephanite [Ag5SbS4], var i ous Ag-Pb-Sb(Bi) sulphosalts,
na tive sil ver, uytenbogaardtite [Ag3AuS2]
quartz, kutnahorite, ga lena,
var i ous Ag-Pb-Sb(Bi) sulphosalts Pažout et al.
(2017, 2019)
Øepová near Mohelnice:
polymetallic baryte-car bon ate veins
tetrahedrite (up to 16.4 wt.% Ag), freibergite [Ag6(Cu4Fe2)Sb4S13], Ag-amal gams,
acanthite [Ag2S]
baryte, do lo mite, an ker ite, sid er ite, quartz, ga lena, sphalerite, cin na bar, chal co py rite, Ni-Co
phases, na tive Au
Dolníèek et al.
(2019a)
Horní Mìsto:
Ag min er al ized veins in a stratiform base metal de posit
na tive Ag, proustite [Ag3AsS3], pyrargyrite [Ag3SbS3], stephanite [Ag5SbS4], miargyrite
[AgSbS2], allargentum [Ag1-xSbx], Ag-rich ten nan tite (up to 14 wt.% Ag), Ag-rich tetrahedrite (up to 17.5 wt.% Ag)
K-feld spar, quartz, cal cite, ap a tite,
rutile, py rite, ar seno py rite Dolníèek et al.
(2019b)
Havlíèkùv Brod:
quartz-car bon ate veins
freibergite [Ag6(Cu4Fe2)Sb4S13], pyrargyrite [Ag3SbS3], miargyrite [AgSbS2], andorite VI [AgPbSb3S6], na tive Ag, ar gen tite [Ag2S]
quartz, car bon ates, ga lena, boulangerite, bour no nite,
ar seno py rite, sphalerite, berthierite, jamesonite
Sejkora et al.
(2015) Skalka near Kraslice:
quartz-sid er ite-Pb-Zn-Cu sul phide lenses
Ag-rich tetrahedrite (up to 18.2 wt.% Ag) quartz, sid er ite, jamesonite, sphalerite, bour no nite, boulangerite, ullmannite
Sejkora et al.
(2016) Komárovice:
baryte ± quartz-cal cite veins
pyrargyrite [Ag3SbS3],
freibergite [Ag6(Cu4Fe2)Sb4S13] baryte, quartz, cal cite, ga lena Hrazdil et al. (2012)
cal min ing au thor ity in Boguszów was closed. Be tween 1856 and 1865, lo cal min ing for sil ver ores was at tempted with no pos i tive re sult. How ever, at ten tion was drawn to the pres ence of baryte (Gruszczyk, 1952), which was mined from the Boguszów de posit un til 1997.
MATERIALS AND METHODS
Ore sam ples were col lected in the old dumps close to Segen Gottes Mine in Boguszów. Sam ples were care fully checked mac ro scop i cally and >20 ore tex tures were cho sen for mi cro scopic study. Only sam ples con tain ing sil ver min er al iza - tion were cho sen for EPMA anal y sis. Sil ver min er als, main sulphides and sulpharsenides, were ana lysed us ing the JEOL Super Probe 8230 in the Lab o ra tory of Crit i cal El e ments at the Fac ulty of Ge ol ogy Geo phys ics and En vi ron men tal Pro tec tion, AGH-UST, Kraków Po land. The fol low ing op er at ing con di tions and stan dards were used: ac cel er at ing volt age 20 kV, beam cur rent 20 nA (for sulphides and sulpharsenides) and beam cur rent 10 nA (for Ag min er als), peak time 10–20 s, back ground time 10 s (5 s for Ag min er als) and a beam di am e ter 5 µm. The fol low ing wave lengths (to omit in ter fer ences be tween the el e - ment spec tral lines) were used: CdLa, ZnKa, CuKa, SKa, SnLa, HgMa, FeKa, MnKa, AgLa, AsLa, SbLa, BiMa, TeLa, PbMa, SeLa, NiKa, CoKa (for sulphides and sulpharsenides);
SKa, CuKa, BiMa, AgLa, SbLa, SeLa, AsLa (for Ag min er als);
BiMa, SbLa, ZnKa, CuKa, SKa, HgMa, FeKa, AgLa, and AsLa for tetrahedrite. Nat u ral min eral stan dards (FeS2, ZnS, PbS) and syn thetic com pounds (CdS, InAs, MnS, HgTe, PbTe, Sb2S3, Cu, Ag, Bi, Ni, Co, Se) were used for cal i bra tion. All in ter - fer ences be tween the el e ment spec tral lines were cal cu lated us - ing autocorrections based on stan dards. The de tec tion lim its for ana lysed el e ments were as fol lows: for sulphides and sulpharsenides S – 0.01 wt.%, Zn – 0.03 wt.%, Fe – 0.03 wt.%, Cu – 0.02 wt.%, Ag – 0.02 wt.%, Cd – 0.02 wt.%, Hg – 0.02 wt.%, Co – 0.02 wt.%, for Ag min er als S – 0.02 wt.%, Sb – 0.09 wt.%, As – 0.12 wt.%, Cu – 0.05 wt.%, Ag – 0.35 wt.%, Bi – 0.06 wt.%, for tetrahedrite S – 0.02 wt.%, Sb – 0.07 wt.%, As – 0.01 wt.%, Cu – 0.04 wt.%, Ag – 0.02 wt.%, Zn – 0.04 wt.%, Fe – 0.03 wt.%, Hg – 0.06 wt.%, Bi – 0.05 wt.%.
RESULTS
The main ore min er als in the sam ples stud ied are ga lena, sphalerite, tetrahedrite, py rite and chal co py rite (Fig. 2). Ga lena and sphalerite form small veinlets up to 1 cm in lam i nated baryte, as well as ir reg u lar ag gre gates up to sev eral centi - metres across in baryte brec cia. Low-Ag tetrahedrite was also found as ag gre gates up to 1 cm in size dis sem i nated in highly al tered vol ca nic rocks or in baryte. Ag min er als and Ag-rich TGM mostly form in clu sions or veinlets in ga lena up to a few hun dreds of micrometres in size. Ad di tion ally, löllingite and gersdorffite oc cur as small, com monly zoned crys tals in ga lena and tetrahedrite ag gre gates.
GALENA PbS
Ga lena is the main ore min eral of the baryte-sul phide ore.
Ga lena forms ag gre gates up to sev eral centi metres across, se - ries of par al lel veinlets in baryte veins, as well as brec cia in fill -
ings ce ment ing baryte and quartz frag ments. Ga lena ag gre - gates are intergrown with sphalerite, Ag-tetrahedrite and chal - co py rite (Fig. 2A, C, G). Some ag gre gates in clude abun dant in - clu sions of sil ver-bear ing min eral phases [mem bers of the freibergite se ries: “freibergite-(Fe)” and “freibergite-(Zn)”, bour - no nite, pyrargyrite and polybasite; Fig. 2E]. Com monly, ga lena is re placed by var i ous sec ond ary min er als es pe cially cerussite, less so covel lite. Ga lena is chem i cally ho mo ge neous and has a low con tent of trace el e ments.
SPHALERITE ZnS
Sphalerite crys tals are ir reg u larly dis trib uted within baryte-quartz veins and are over grown by ga lena and chal co py - rite (Fig. 2A). Sphalerite forms two gen er a tions where sphalerite II usu ally grows over pri mary mas sive ag gre gates of sphalerite I (Fig. 2G). The sphalerite has a gen er ally low Fe con tent (up to 0.01 apfu) and is com par a tively Cd-rich (up to 0.04 apfu) (Ap pen dix 1*). In tense brown in ter nal re flec tions are ob served, which are prob a bly re lated to a lat tice sub sti tu tion of Cd for Zn. The high est Cd con tents (0.03–0.04 apfu) are ob - served in the sec ond gen er a tion of sphalerite. The Hg con cen - tra tion in sphalerite reaches up to 0.01 apfu, Cu reaches up to 0.01 apfu. The gen er al ized em pir i cal for mula is:
(Zn0.95-0.99Cd0.00-0.04Fe0.00-0.01)S=1S0.99-1.01.
TETRAHEDRITE GROUP MINERALS
At Boguszów, there are four gen er a tions of TGM de fined ac cord ing to tex tural char ac ter is tics and sil ver con tent (Fig. 3A).
The no men cla ture fol lows the new clas si fi ca tion of TGM (Biagioni et al., 2020a):
1 – low-Ag tetrahedrite-(Zn) (Ag: 0.22–0.6 apfu), 2 – Ag-en riched tetrahedrite-(Zn) and Ag-en riched tetra - hedrite-(Fe) (Ag: 0.71–1.45 apfu),
3 – mem bers of the freibergite se ries: “freibergite-(Fe)”
and “freibergite-(Zn)” (Ag: 3.21–3.48 apfu),
4 – mem ber of the freibergite se ries: “freibergite-(Fe)”
(Ag: 5.32–5.78 apfu).
LOW-Ag TETRAHEDRITE-(Zn)
Low-Ag tetrahedrite-(Zn) is ob served as idiomorphic crys - tals up to 5 mm in size with out any in clu sions and with out other sulphides as so ci a tion (Fig. 2B). Rep re sen ta tive anal y ses of the tetrahedrite-(Zn) are shown in Ap pen dix 2. The low-Ag tetrahedrite-(Zn) is char ac ter ized by small vari a tion in Cu and Ag con cen tra tions. In di vid ual re sults mostly vary in As con tent (from 0.57 to 1.74 apfu; Fig. 3B). This gen er a tion of TGM is the zinc mem ber of the tetrahedrite se ries (Fig. 4B). A gen er al ized for mula for low-Ag tetrahedrite-(Zn) based on 16 cat ions is:
(Cu9.37-9.80Ag0.22-0.60Zn1.16-1.72Fe0.22-0.77Hg0.02-0.05)S=11.95-12.01(Sb2.24 -3.47As0.57-1.74Bi0.01)S=3.99-4.05S13.02-13.11. Sim i lar low-Ag tetrahedrite with 3 wt.% of Ag was re ported by Migaszewski (1972) from veinlets criss-cross ing al tered vol ca nic rock.
Ag-ENRICHED TETRAHEDRITE-(Zn) + Ag-ENRICHED TETRAHEDRITE-(Fe)
Ag-en riched tetrahedrite-(Zn) and Ag-en riched tetrahedrite - -(Fe) are intergrown with ga lena and chal co py rite, as well as
* Supplementary data associated with this article can be found, in the online version, at doi: 10.7306/gq.1562
Fig. 2. Op ti cal (re flected light, 1P) (A–E) and BSE im ages (F–H) il lus trat ing the main fea tures of min eral as sem blages
A – ga lena – Ag-en riched tetrahedrite – sphalerite ag gre gate with chal co py rite; B – sin gle idiomorphic low-Ag tetrahedrite-(Zn) crys tal in baryte; C – ga lena – Ag-en riched tetrahedrite ag - gre gate with pyrargyrite and löllingite-gersdorffite in clu sions; D – pyrargyrite – chal co py rite ag - gre gate at the edge of ga lena; E – lin ear in clu sions of pyrargyrite and mem bers of the freibergite se ries in ga lena; F – zonation in Ag-en riched tetrahedrite crys tal re flect ing iron and zinc abun - dances; G – ga lena-sphalerite ag gre gate with some sec ond ary Cd-en riched zones in sphalerite;
H – löllingite-gersdorffite in clu sions in ga lena; Ag-Ttr – Ag-en riched tetrahedrite; Brt – baryte;
Ccp – chal co py rite; Frb – mem bers of the freibergite se ries; Gn – ga lena; Grd – gersdorffite; Lo – löllingite; Low-Ag Ttr – low-Ag tetrahedrite-(Zn); Prg – pyrargyrite; Sph – sphalerite
occuring as ir reg u lar ag gre gates up to 0.5 mm across (Fig. 2A, C, H). Some ag gre gates are en riched in tiny chal co py rite and löllingite in clu sions up to 20 mm in size (Fig. 2C). Re sults of chem i - cal anal y sis of this gen er a tion of TGM are shown in Ap pen dix 2.
As in the pre vi ous gen er a tion, a sim i lar trend of the As-Sb sub sti - tu tion is ob served (Fig. 3B). Microprobe anal y ses in di cate a wide range of Zn-Fe sub sti tu tion and a dom i nance of the zinc mem ber of the tetrahedrite se ries (Fig. 4B). El e ment ranges in the D po - si tion in the TGM are Fe – 0.26–1.15 apfu, and Zn – 0.8–1.79 apfu re spec tively. A gen er al ized for mula can be ex pressed as:
(Cu8.61-9.33Ag0.71-1.45Zn0.80-1.79Fe0.26-1.15Hg0.00-0.05)S=11.96-12.08(Sb2.75 -3.78As0.10-1.25Bi0.01-0.09)S=3.92-4.04S13.02-13.42.
MEM BERS OF THE FREIBERGITE SE RIES:
“FREIBERGITE-(Fe)” AND “FREIBERGITE-(Zn)”
Mem bers of the freibergite se ries, “freibergite-(Fe)” and
“freibergite-(Zn)”, oc cur as elon gated in clu sions up to 100 mm long along ga lena cleav age planes, as well as tiny ir reg u lar in - clu sions (Fig. 2E). The compositional vari a tion of this tetrahe - drite gen er a tion is shown in Ap pen dix 2. This gen er a tion tends to be As-poor, As – up to 0.002 apfu. Con se quently, Sb con - tent is rel a tively uni form and ranges be tween 3.98–4.12 apfu.
Most of the freibergites are “freibergite-(Zn)”, which is cur - rently not a de fined mem ber of the freibergite se ries (Biagioni et al., 2020a): Zn con cen tra tion ranges from 0.11 to 1.17 apfu, Fe con tent is gen er ally lower and reaches up to 0.98 apfu (Fig.
4B–D). More over, some of the EPMA anal y ses show rel a tively high mer cury con tents of up to 0.75 apfu. The high est Hg con - tent was mea sured in freibergite -(Fe), where Fe con tents ex - ceed Zn, Hg de creases with in creas ing Zn con tent. Ad di tion - ally, Hg-en riched freibergite has the low est sil ver con tent in this gen er a tion of freibergites (3.26–3.32 apfu). Com par a tive read ings of Zn ver sus Fe+Hg (Fig. 4B) and Zn ver sus Fe+Hg+(Cu+Ag-6) cross-plots (Fig. 4C) show that cop per in po si tion C is com mon in this TGM gen er a tion. The gen er al ized for mula for “freibergite-(Fe)” and “freibergite -(Zn)” is:
(Cu6.56-6.93Ag3.21-3.48Zn0.11-1.17Fe0.56-0.98Hg0.01-0.75)S=11.87-12.01(Sb3.98 -4.12Bi0.00-0.01)S=3.99-4.13S13.06-14.53.
MEMBER OF THE FREIBERGITE SERIES:
“FREIBERGITE-(Fe)”
One crys tal of “freibergite-(Fe)” was found in the sam ples.
This mem ber of the freibergite-(Fe) se ries has grown over the pyrargyrite and formed a 20 mm ir reg u lar ag gre gate. It is char ac ter ized by ho mo ge neous chem i cal com po si tion; the re sults are shown in Ap pen dix 2. A gen er al ized for mula based on 16 cat ions can be ex pressed as:
(Ag5.32-5.78Cu4.16-4.73Fe1.86-1.99Zn0.02-0.15Hg0.00-0.02)S=11.89-12.06(Sb3.82 -4.00As0.00-0.13Bi0.01)S=3.94-4.11S12.25-12.65.
PYRARGYRITE Ag3SbS3
The pyrargyrite in ves ti gated mostly oc curs as in clu sions up to 50 mm across in ga lena (Fig. 2E). Pyrargyrite inter - growths with chal co py rite (up to 100 mm across) are also pres - ent (Fig. 2D). They are char ac ter ized by uni form chem i cal com po si tion (Ap pen dix 1). Gen er ally, pyrargyrite is prac ti cally ar senic-free. Only iso lated pyrargyrite grains are char ac ter - ized by no ta bly higher As con cen tra tions (~2 wt.%). A gen er al - ized pyrargyrite for mula based on 4 cat ions is:
(Ag2.97-3.01Cu0.00-0.02)S=2.98-3.01(Sb0.82-1.02As0.00-0.17)S=0.99-1.02S3.09-3.14.
POLYBASITE Cu(Ag, Cu)6Ag9Sb2S11
This min eral oc curs as rounded in clu sions up to 20 mm across ran domly dis trib uted in ga lena crys tals. Polybasite is char ac ter ized by a ho mo ge neous chem i cal com po si tion (Ap - pen dix 1). The in clu sions in ves ti gated have more Cu, as well as less Sb and S than ideal, stoichiometric polybasite. The gen er - al ized em pir i cal polybasite for mula based on 18 cat ions is:
Cu(Ag5.68-5.80Cu0.20-0.32)S=6Ag9.08-9.23Sb1.76-1.90S10.15-10.62.
BOURNONITE PbCuSbS3
This min eral is a mi nor phase and oc curs as in clu sions re - lated to the cleav age planes in ga lena crys tals. Most of the bour no nite in clu sions in sam ples from Boguszów are too small Fig. 3. Compositional re la tion ships in the tetrahedrite se ries from Boguszów
A – di a gram of Ag-Cu sub sti tu tion in TGM; B – di a gram of Sb-As sub sti tu tion in TGM
to be quan ti ta tively ana lysed by EPMA due to their fine grain size (up to 1–3 mm). It was pos si ble to mea sure only some in - clu sions, the chem i cal com po si tion is close to the ideal for mula with out any sig nif i cant sub sti tu tions.
LÖLLINGITE FeAs2
Löllingite oc curs as idiomorphic crys tals up to 10 mm in size within ga lena and Ag-en riched tetrahedrite ag gre gates (Fig.
2C, H). A sum mary of the an a lyt i cal re sults avail able for
löllingite are shown in Ap pen dix 1. In com par i son with stoichio - metric löllingite, the löllingite from Boguszów is Fe-de pleted (0.67–0.91 apfu), be sides Co (0.03–0.24 apfu) and Ni (up to 0.16 apfu) en rich ment.
GERSDORFFITE NiAsS
Gersdorffite ap pears as thin rims (up to sev eral mm thick) around löllingite crys tals (Fig. 2C, H). The compositional vari - a tion of gersdorffite is shown in Ap pen dix 1. Gersdorffite is Fe Hg
Zn
Fig. 4. Compositional re la tion ships in the tetrahedrite se ries from Boguszów
A – di a gram of Ag ver sus Sb in TGM; B – di a gram of Zn vs Fe+Hg sub sti tu tion in TGM; C – vari a tion of Zn (apfu) as a func tion of Fe+Hg+(Cu+Ag-6) (apfu); D – ter nary di a gram, Zn ver sus Fe ver sus Hg (apfu) of the TGM
gen er ally en riched in Co (0.11–0.37 apfu), less in Fe (0.07–0.22 apfu). Com mon sub sti tu tions be tween co balt, nickel, and iron are ob served in the gersdorffite from the Boguszów. The gen er al ized em pir i cal gersdorffite for mula is:
(Ni0.53-0.81Co0.11-0.37Fe0.07-0.22)å=1As1.03-1.14S0.90-0.98. Tran si tion zo - nes be tween löllingite crys tals and gersdorffite rims are ob - served, but are too small to be mea sured by EPMA.
DISCUSSION
SILVER MINERALIZATION IN SUDETES AND BOHEMIAN MASSIF
The Sudetes in Po land in clude ~30 re corded baryte veins (Paulo, 1994), the high est rate of oc cur rence be ing ob served in the Sowie Moun tains and the Intra-Sudetic De pres sion.
Poly metallic Pb-Zn-Ag min er al iza tion is as so ci ated with a large part of these veins. Min ing, which goes back to me di eval times, was fo cused to wards the sil ver-rich ores. How ever, pre - vi ous re ports of sil ver min er als and Ag-rich TGM in the old lit - er a ture do not con tain re li able chem i cal data, in clud ing from Boguszów (Traube, 1888; Migaszewski, 1972) and Dzieæ - moro wice (Petra scheck, 1933). Di rect com par i son is pos si ble only with hy dro ther mal min er al iza tion from Zagórze Œl¹skie (Piestrzyñski and Kowalik, 2015) and Bystrzyca Górna (BG) (Pršek et al., 2019), which are lo cated within the Sowie Moun - tains. For ex am ple, polymetallic min er al iza tion in the baryte veins from Zagórze Œl¹skie is char ac ter ized by a higher abun - dance of Cu min er als. More min er al og i cal sim i lar i ties with the min er al iza tion stud ied can be found in polymetallic Ag-Sb - -Pb-(Cd) min er al iza tion re lated to baryte veins at BG. Pršek et al. (2019) re ported the pres ence of e.g. sil ver-en riched TGM, Ag-Sb-S, Ag-Pb-S and Pb-Sb sulphosalts (Ta ble 1). In con - trast to tex tures of Ag min er al iza tion from Boguszów (elon - gated in clu sions in ga lena), at BG sil ver min er al iza tion forms veinlets and dis sem i na tions in a fine- grained dark baryte - -quartz ma trix. In con trast to the Boguszów hy dro ther mal sys - tem, in BG ar senic is ab sent from the en tire paragenetic se - quence, the min er al iza tion be ing ex tremely Sb-rich. Ac cord ing to Pršek et al. (2019) a smoother tran si tion of Cu+-Ag+ sub sti - tu tion in TGM was rec og nized at BG. Chem i cal zonation re - gard ing the dis tri bu tion of Ag abun dances is ob served, freibergite-(Fe) rims around lower-Ag TGM be ing com mon at this lo cal ity. At Boguszów four par tic u lar TGM gen er a tions have been dis tin guished (Fig. 3A). As Pršek et al. (2019) state about BG, the for mer tetrahedrite (re lated to the early stage – base metal min er al iza tion) was dis solved by youn ger Ag-rich flu ids, which are re spon si ble for un usual Ag-Sb -Pb-(Cd) min - er al iza tion. In com par i son to the min er al iza tion from BG, tex - tural fea tures in ores from Boguszów in di cate an in crease in Ag-rich phases [freibergite-(Fe), pyrargyrite and polybasite]
dur ing the youn ger epi ther mal stages. As pre vi ously men - tioned, in the past, more sil ver mines were ac tive within the Bo he mian Mas sif (Ta ble 2). Sil ver was re cov ered mainly from Ag-rich TGM and Ag-Sb sulphosalts, which oc cur in baryte – quartz ± car bon ate veins. In gen eral, Ag-bear ing tetrahedrite or freibergite is one of the most im por tant sources of sil ver in these sil ver-bear ing min ing dis tricts in the Czech Re pub lic and Po land. The ac com pa ny ing sil ver min er als are vari able and the pres ence of in di vid ual min er als de pends on var i ous ore- form ing con di tions as well as the lo cal geo chem i cal source of min er al iza tion.
MERCURY IN TETRAHEDRITE GROUP MINERALS
The pres ence of mer cury in the TGM from Boguszów is re - stricted to few sam ples. The high est en rich ment is ob served in mem ber of the “freibergite-(Fe)” se ries, which is Sb-rich and Zn-de pleted – sim i larly to the hy brid mas sive sul phide-epi ther - mal Eskay Creek de posit in Can ada (Grammatikopoulos et al., 2005). Hg-Ag tetrahedrite from Eskay Creek (Hg: 0.12–1.54 apfu; Ag: 1.11–3.66 apfu – based on 16 cat ions) is as so ci ated with sphalerite-tetrahedrite, cin na bar, ga lena, stibnite and Pb-Sb sulphosalts. An other oc cur rence of Hg-Ag tetrahedrite from Chiprovtsi Ag-Pb (Bul garia) was re ported by Atanasov (1975). Ag-Hg rich tetrahedrite (Hg: 1.82–1.86 apfu; Ag:
2.88–3.13 apfu – based on 16 cat ions) is as so ci ated with the py rite-cin na bar stage and forms rims around cin na bar ag gre - gates. Mer cury-dom i nant tetrahedrite group min er als (Biagioni et al., 2020a) are com mon in the min er al iza tion rich in mer cury and have been re ported from many lo cal i ties (e.g., Mozgova et al., 1979; Arlt and Di a mond, 1998; Foit and Ulbricht, 2001; Karanoviæ et al., 2003; Krismer et al., 2011;
Velebil, 2014; Števko et al., 2015; Biagioni et al., 2020b).
Tetrahedrite en riched in Hg is gen er ally Ag-free or Ag-low and it is as so ci ated with Cu, Hg, As, Sb, Bi min er als in quartz or quartz-car bon ate-baryte veins as re ported world wide. Ex am - ples of the chem i cal com po si tion of Ag- and Hg-rich TGM are shown in the ter nary Ag ver sus Zn and Zn ver sus Fe ver sus Hg di a grams (Fig. 5). The most Ag-en riched Hg-rich TGM tend to be Zn-poor.
Ni-Co ASSOCIATION
Nickel and co balt min er als are pres ent in var i ous hy dro ther - mal oc cur rences and de pos its. Es pe cially char ac ter is tic is the
“five-el e ment vein type” min er al iza tion (“Ag-Co-Ni-As-Bi type”) (Kissin, 1992; Markl et al., 2016; Scharrer et al., 2019). Ni-Co en rich ment in hy dro ther mal min er al iza tion may also be re lated to leach ing of these el e ments by hy dro ther mal flu ids from the sur round ing ultra mafic rocks (Dolníèek et al., 2019a). In the Boguszów baryte de posit the Ni-Co as sem blage is rep re sented by tiny ag gre gates of Co-en riched löllingite and gersdorffite. Ad - di tion ally, small iso met ric in clu sions of cobaltite in tetrahedrite up to 15 mm in size were re ported by Migaszewski (1972). Met - als in this as sem blage were prob a bly sourced from the ultra - mafic base ment of the Intra-Sudetic Ophiolite, as was pro posed for hy dro ther mal veins in the Moravo-Silesian Culm from the Øepová – ultra mafic Zábøeh Crys tal line Com plex, where a Ni-Co as sem blage is as so ci ated with base metal +Ag-Hg-Au min er al iza tion (Dolníèek et al., 2019a).
CONCLUSIONS
1. Sil ver in the Boguszów baryte de posit oc curs in the form of its min er als: Ag-Sb sulphosalts (pyrargyrite, polybasite) and tetrahedrite group min er als (TGM). The com po si tion of these min er als, which form elon gated in clu sions in ga lena ag gre - gates, was de ter mined us ing an elec tron microprobe.
2. Other ore min er als found are ga lena, sphalerite, py rite chal co py rite, bour no nite, löllingite and gersdorffite.
3. Four gen er a tions of the TGM were dis tin guished ac cord - ing to tex tural char ac ter is tics and Ag con cen tra tions:
1 – low-Ag tetrahedrite-(Zn) (Ag: 0.22–0.6 apfu),
2 – Ag-en riched tetrahedrite-(Zn) and Ag-en riched tetra - hedrite-(Fe) (Ag: 0.71–1.45 apfu),
3 – mem bers of the freibergite se ries: “freibergite-(Fe)”
and “freibergite-(Zn)” (Ag: 3.21–3.48 apfu),
4 – mem ber of the “freibergite-(Fe)” se ries (Ag:
5.32–5.78 apfu).
4. Sim i lar Ag min er al iza tion oc cur rences re lated to Ag-Pb - -Sb min er als are known from sev eral lo cal i ties in the Sudetes and the Bo he mian Mas sif.
5. The Boguszów baryte de posit is one of the few lo cal i ties known in the world with Hg-rich mem bers of freibergite se ries.
6. The pres ence of co balt-en riched löllingite and gers - dorffite may in di cate leach ing of Ni and Co by hy dro ther mal flu - ids from the ultra mafic base ment.
Ac knowl edge ments. We are grate ful to G. Kozub-Budzyñ from the Lab o ra tory of Crit i cal El e ments at AGH-UST for help dur ing EPMA data col lec tion. We are also grate ful to the re view - ers, J. Sejkora and S. Mikulski, whose com ments helped us to im prove the manu script. This work is part of the re search pro - gram fi nanced by the AGH Uni ver sity of Sci ence and Tech nol - ogy stat u tory grant No. 11.11.140.320.
REFERENCES
Arlt, T., Di a mond, L.W., 1998. Com po si tion of tetrahedrite-ten nan - tite and schwazite in the Schwaz sil ver mines, North Tyrol, Aus - tria. Min er al og i cal Mag a zine, 62: 801–820.
Atanasov, V.A., 1975. Argentian mercurian tetrahedrite, a new va ri - ety, from the Chiprovtsi ore de posit, West ern Stara-Planina moun tains, Bul garia. Min er al og i cal Mag a zine, 40: 233–237.
Awdankiewicz, M., Kryza, R., 2010. The Che³miec subvolvanic in - tru sion (Intra-Sudetic Ba sin, SW Po land): pre lim i nary SHRIMP zir con age. Mineralogia – Spe cial Pa pers, 37: 69.
Banaœ, M., Mochnacka, K., 1986. The two ura nium de pos its in the Pol ish part of the Sudety Moun tains. In: Vein Type Ura nium De - pos its (ed. H. Fuchs): 335–357. In ter na tional Atomic En ergy Agency, Wien.
Bestemianova, K.V., Grinev, O.M., 2017. Bar ite-polymetallic min - er al iza tion of Zmeinogorsk ore dis trict and some ge netic as - pects of its for ma tion. In: IOP Con fer ence Se ries: Earth and En - vi ron men tal Sci ence, 110:1–7. IOP Pub lish ing.
Biagioni, C., George, L.L., Cook, N.J., Makovicky, E., Moëlo, Y., Pasero, M., Sejkora, J., Stan ley, C.J., Welch, M.D., Bosi, F., 2020a. The tetrahedrite group: No men cla ture and clas si fi ca tion.
Amer i can Min er al o gist, 105: 109–122.
Biagioni, C., Sejkora, J., Musetti, S., Velebil, D., Pasero, M., 2020b. Tetrahedrite-(Hg), a new “old” mem ber of the tetrahe - drite group. Min er al og i cal Mag a zine, 84: 584–592.
Cheilletz, A., Levresse, G., Gasquet, D., Azizi-Samir, M., Zyadi, R., Archibald, D.A, Farrar, E., 2002. The gi ant Imiter sil ver de - posit: Neoproterozoic epi ther mal min er al iza tion in the Anti-At - las, Mo rocco. Mineralium Deposita, 37: 772–781.
Dolníèek, Z., Nepejchal, M., Ulmanová, J., 2019a. Øepová near Mohelnice – min er al og i cally the most di verse ore vein min er al - iza tion in the Moravo-Silesian Culm (in Czech with Eng lish sum - mary). Bul le tin Mineralogie Petrologie, 27: 109–135.
Dolníèek, Z., Skácel, J., Nepejchal, M., 2019b. New find ings on sil - ver-rich vein min er al iza tion of the Zn-Pb de posit Horní Mìsto (Vrbno Group, Silesicum) (in Czech with Eng lish sum mary). Bul - le tin Mineralogie Petrologie, 27: 279–289.
Dziedzic, K., 1971. Sed i men ta tion and paleogeography of the Up - per Car bon if er ous de pos its in the Intrasudetic de pres sion.
Geologia Sudetica, 5: 65–75.
Foit Jr, F.F., Ulbricht, M.E., 2001. Compositional vari a tion in mercurian tetrahedrite–ten nan tite from the epi ther mal de pos its Fig. 5. Compositional re la tion ships in the Ag- and Hg-rich TGM from Boguszów (n = 13), Eskay Creek (n = 40)
(Grammatikopoulos et al., 2005) and Chiprovtsi (n = 3) (Atanasov, 1975); n – num ber of anal y ses A – di a gram of Ag ver sus Hg in TGM; B – ter nary di a gram Zn ver sus Fe ver sus Hg (apfu) in the TGM
of the Steens and Pueblo Moun tains, Harney County, Or e gon.
Ca na dian Min er al o gist, 39: 819–830.
Gemmell, J.B., Zantop, H., Birnie, R.W., 1989. Sil ver sulfosalts of the Santo Nino vein, Fresnillo Dis trict, Zacatecas, Mex ico. Ca - na dian Min er al o gist, 27: 401–418.
Go³êbiowska, B., Pieczka, A., Parafiniuk, J., 2012. Sub sti tu tion of Bi for Sb and As in min er als of the tetrahedrite se ries from Rêdziny, Lower Silesia, south west ern Po land. Ca na dian Min er - al o gist, 50: 267–279.
Grammatikopoulos, O., Roth, T., Valeyev, O., 2005. Compo si - tional vari a tion in Hg–Ag-rich tetrahedrite from the polymetallic Eskay Creek de posit, Brit ish Co lum bia, Can ada. Neues Jahrbuch für Mineralogie Abhandlungen, 181: 281–292.
Grocholski, A., 1965. The vol ca nic rocks in the Walbrzych Ba sin in the light of struc tural stud ies (in Pol ish with Eng lish sum mary).
Biuletyn Instytutu Geologicznego, 191: 5–67.
Grossou-Valta, M., Adam, K., Constantinides, D.C., Prevosteau, J.M., Dimou, E., 1990. Min er al ogy of and po ten tial ben efi ci ation pro cess for the Molai com plex sul phide orebody, Greece. In:
Sul phide De pos its – their Or i gin and Pro cess ing (eds. P.M.J.
Gray, G.J. Bowyer, J.F. Cas tle, D.J. Vaughan and N.A. Warner):
119–133. The In sti tu tion of Min ing and Met al lurgy, Dordrecht.
Gruszczyk, H., 1952. Z³o¿a barytu w Boguszowie I Jab³owie na Dolnym Œl¹sku (in Pol ish). Wyd. Geol., Warszawa.
Gruszczyk, H., Paulo, A., Smolarska, J., 1970. The pres ent knowl - edge on the baryte de posit at Boguszów, Lower Silesia (in Pol - ish with Eng lish sum mary). Prace Instytutu Geologicznego, 59:
69–84.
Höller, W., Gan dhi, S.M., 1995. Sil ver bear ing sulfosalts from the meta mor phosed Rampura Agucha Zn-Pb-(Ag) de posit, Rajasthhan, In dia. Ca na dian Min er al o gist, 33: 1047–1057.
Hrazdil, V., Škrdla, P., Houzar, S., Vokáè, M., 2012. His toric min ing of sil ver ore in Komárovice near Jihlava, west Moravia (in Czech with Eng lish sum mary). Acta re rum naturalium, 12: 137–144.
Karanoviæ, L., Cvetkoviæ, L., Poleti, D., Baliæ-Žuniæ, T., Mako - vicky, E., 2003. Struc tural and op ti cal prop er ties of schwazite from Dragodol (Ser bia). Neues Jahrbuch für Mineralogie Monatshefte, (11): 503–520.
Kissin, S.A., 1992. Five-el e ment (Ni-Co-As-Ag-Bi) veins.
Geoscience Can ada, 19: 113–124.
Ko³odziejczyk, J., Pršek, J., Asllani, B., Maliqi, F., 2016. The paragenesis of sil ver min er als in the Pb-Zn Stan Terg de posit, Kosovo: an ex am ple of pre cious metal epi ther mal min er al iza - tion. Ge ol ogy, Geo phys ics and En vi ron ment, 42: 19–29.
Kozub-Budzyñ, G.A., Piestrzyñski, A., 2018. The first oc cur rence of cupropearceite in the Kupferschiefer de posit, Lubin mine, SW Po land. Geo log i cal Quar terly, 62 (2): 319–326.
Krismer, M., Vavtar, F., Tropper, P., Kaindl, R., Sartory, B., 2011.
The chem i cal com po si tion of tetrahedrite-ten nan tite ores from the pre his toric and his toric Schwaz and Brixlegg min ing ar eas (North Tyrol, Aus tria). Eu ro pean Jour nal of Min er al ogy, 23:
925–936.
Kurowski, L., 1998. Flu vial sedimentology of the Bia³y Kamieñ For - ma tion (Up per Car bon if er ous, Sudetes, Po land). Geologia Sudetica, 31: 69–77.
Lis, J., Sylwestrzak, H., 1986. Minera³y Dolnego Œl¹ska (in Pol ish).
Wyd. Geol., War szawa.
Manecki, A., 1965. Min er al og i cal and pet ro graph i cal study of the polymetallic veins from the area of Wojcieszów (Lower Silesia) (in Pol ish with Eng lish sum mary). Prace Mineralogiczne, 2:
1–71.
Markl, G., Burisch, M., Neumann, U., 2016. Nat u ral fracking and the gen e sis of five-el e ment veins. Mineralium Deposita, 51:
703–712.
Mastalerz, K., 1996. Sed i men ta tion of the Zacler For ma tion (West - phalian) in the Walbrzych ba sin, SW Po land. Prace Geologiczno-Mineralogiczne, 52: 21–93.
Mastalerz, K., Mastalerz, M., 2000. Vol ca nic and post-vol ca nic hy - dro ther mal ac tiv ity in the Intrasudetic Ba sin, SW Po land: im pli -
ca tions for min er al iza tion. In: Or ganic Mat ter and Min er ali sa tion:
Ther mal Al ter ation, Hy dro car bon Gen er a tion and Role in Metallogenesis (eds. M. Glikson and M. Mastalerz): 185–202.
Springer, Dordrecht.
Migaszewski, Z., 1972. Mineralizacja kruszcowa w z³o¿u barytu w Boguszowie (in Pol ish). Rudy i Metale Nie¿elazne, 9: 425–428.
Mikulski, S., 2005. Geo log i cal, min er al og i cal and geo chem i cal char ac ter is tics of the Radzimowice Au-As-Cu de posit from the Kaczawa Mts. (West ern Sudetes, Po land) – an ex am ple of the tran si tion of por phyry and epi ther mal style. Mineralium Depo - sita, 39: 904–920.
Mikulski, S., 2010. The char ac ter is tic and gen e sis of the gold-bear - ing ar senic polymetallic min er al iza tion in the Czarnów de posit (West ern Sudetes) (in Pol ish with Eng lish sum mary). Biuletyn Pañstwowego Instytutu Geologicznego, 439: 303–320.
Mochnacka, K., Banaœ, M., 2000. Oc cur rence and ge netic re la tion - ships of ura nium and tho rium min er al iza tion in the Karkonosze Izera Block (the Sudety Mts, SW Po land). Annales Societatis Geologorum Poloniae, 70: 137–150.
Mozgova, N.N., Tsepin, A.I., Ozerova, N.N., Bortnikov, N.S., Tronieva, N.V., 1979. Mercuriferous grey cop per ores (in Rus - sian). Zapiski Vsesoyuznogo Mineralogicheskogo Obshche - stva, 108: 437–452.
Paulo, A., 1994. Ge ol ogy of bar ite Veins in the Pol ish Sudetes. In:
Metallogeny of Collisional Orogens (eds. R. Seltman, H. Kämpf and P. Möller): 383–390. Czech Geo log i cal Sur vey, Prague.
Paulo, A., Salamon, W., 1974a. A note on freibergite, pyrargyrite and bour no nite from Grudno, Lower Silesia (in Pol ish with Eng - lish sum mary). Mineralogia Polonica, 5: 83–86.
Paulo, A., Salamon, W., 1974b. Con tri bu tion to the knowl edge of a polymetallic de posit at Stara Góra (in Pol ish with Eng lish sum - mary). Geo log i cal Quar terly, 18 (2): 266–278.
Pažout, R., Šrein, V., Korbelová, Z., 2017. An un usual Ni-Sb-Ag-Au as so ci a tion of ullmannite, allargentum, Au-rich sil - ver and Au-bear ing dyscrasite from Oselské pásmo" sil ver"
Lode of Kutná Hora Pb-Zn-Ag ore dis trict (Czech Re pub lic).
Jour nal of Geosciences, 62: 247–252.
Pažout, R., Sejkora, J., Šrein, V., 2019. Ag-Pb-Sb sulfosalts and Se-rich min er al iza tion of An thony of Padua Mine near Polièany – model ex am ple of the min er al iza tion of Sil ver Lodes in the his - toric Kutná Hora Ag-Pb Ore Dis trict, Czech Re pub lic. Min er als, 9: 430.
Petrascheck, W.E., 1933. Die Erzlagerstätten des Schlesischen Gebirges. Archiv Lagerstättenforschung, Ger many.
Piestrzyñski, A., Kowalik, K., 2015. Argentopentlandite from bar ite vein in Zagórze Œl¹skie, Lower Silesia, a first oc cur rence in Po - land. Mineralogia, 45: 13–25.
Piestrzyñski, A., Mochnacka, K., 2003. Dis cus sion on the sul phide min er al iza tion re lated to the tin-bear ing zones of the Kamienica schists belt (West ern Sudety Moun tains, SW Po land) (in Pol ish with Eng lish sum mary). In: Sudety Zachodnie – od wendu do czwartorzêdu (eds. W. Ciê¿kowski, J. Wojewoda and A.
¯elaŸniewicz): 169–182. WIND, Wroc³aw.
Plumlee, G., Whitehouse-Veaux, P., 1994. Min er al ogy, para - genesis, and min eral zon ing of the Bull dog Moun tain vein sys - tem, Creede Dis trict, Col o rado. Eco nomic Ge ol ogy, 89:
1883–1905.
Pršek, J., Mederski, S., Kowalczyk, D., 2019. Ag-Sb-Pb-Cd min - eral paragenesis in the bar ite veins: ex am ple from the Sowie Moun tains, Po land. Life with Ore De pos its on Earth. 15th Bi en - nial SGA Meet ing, 27–30 Au gust 2019, Glas gow, 1: 455–458.
Sack, R.O., Goodell, P.C., 2002. Ret ro grade re ac tions in volv ing ga - lena and Ag-sulphosalts in a zoned ore de posit, Julcani, Peru.
Min er al og i cal Mag a zine, 66: 1043–1062.
Sack, R.O., Lynch, J.V.G., Foit, F., 2003. Fahlore as a petro gen etic in di ca tor: Keno Hill Ag-Pb-Zn Dis trict, Yu kon, Can ada. Min er al - og i cal Mag a zine, 67: 1023–1038.
Scharrer, M., Kreissl, S., Markl, G., 2019. The min er al og i cal vari - abil ity of hy dro ther mal na tive el e ment-ar se nide (five-el e ment)
as so ci a tions and the role of physicochemical and ki netic fac tors con cern ing sul fur and ar senic. Ore Ge ol ogy Re views, 113:
1–28.
Sejkora, J., Kopecký, S., Pauliš, P., 2015. New knowledges of pri - mary min er al iza tion in the ore dis trict Havlíèkùv Brod (Czech Re pub lic) (in Czech with Eng lish sum mary). Bul le tin Mineralo - gicko -petrologického oddìlení Národního Muzea v Praze, 23:
277–296.
Sejkora, J., Krištùfek, M., Pauliš, P., Jakobec, K., 2016. Sul fide min er al iza tion from Skalka near Kraslice (Czech Re pub lic) (in Czech with Eng lish sum mary). Bul le tin Mineralogicko -petrolo - gického oddìlení Národního Muzea v Praze, 24: 278–284.
Shalaby, I.M., Stumpfl, E., Helmy, H.M., El Mahallawi, M.M., Kamel, O.A., 2004. Sil ver and sil ver-bear ing min er als at the Um Samiuki volcanogenic mas sive sul phide de posit, East ern Desert, Egypt. Mineralium Deposita, 39: 608–621.
Siuda, R., 2012. Sil ver min er als from Friederike Juliane Mine at Ciechanowice (Sudety Mts, Po land) (in Pol ish with Eng lish sum -
mary). Biuletyn Pañstwowego Instytutu Geologicznego, 448:
315–324.
Števko, M., Sejkora, J., Peterec, D., 2015. Grumiplucite from the Rudnany de posit, Slovakia: a sec ond world-oc cur rence and new data. Jour nal of Geosciences, 60: 269–281.
Traube, H., 1888. Die Minerale Schlesiens. JU Kern, Wroc³aw.
Velebil, D., 2014. Con tri bu tion to knowl edge of chem is try of mer - curian tetrahedrites: lo cal i ties Jedová hora (Czech Re pub lic), Rudòany, Rožòava, Nižná Slaná, Slovinky (Slovakia) and Maškara (Bosnia and Herzegovina) (in Czech with Eng lish sum - mary). Bul le tin Mineralogicko-petrologického Oddìlení Náro - dního Muzea v Praze, 22: 131–143.
¯elaŸniewicz, A., Aleksandrowski, P., Bu³a, Z., Konon, A., Oszczypko, N., Œl¹czka, A., ¯aba, J., ¯ytko, K., 2011. Tec tonic regionalization of Po land (in Pol ish). Komitet Nauk Geolo - gicznych PAN, Wroc³aw.
Geo chem is try and geo chron ol ogy of the Jawornik granitoids, Orlica-Œnie¿nik Dome, Sudetes, Po land
Dawid BIA£EK1, *
1 Uni ver sity of Wroc³aw, In sti tute of Geo log i cal Sci ences, pl. M. Borna 9, 50-204 Wroc³aw, Po land
Bia³ek, D., 2020. Geo chem is try and geo chron ol ogy of the Jawornik granitoids, Orlica-Œnie¿nik Dome, Sudetes, Po land.
Geo log i cal Quar terly, 64 (4): 000–000, doi: 10.7306/gq.1567 As so ci ate Ed i tor: Leszek Krzemiñski
The Jawornik granitoids in trude, in vein-like form, a se quence of a polymetamorphic meta vol can ic and metapelitic rocks of the Orlica-Œnie¿nik Dome, Sudetes, Po land. This pa per pro vides whole-rock geo chem i cal data, sen si tive high-res o lu tion ion microprobe (SHRIMP) U-Pb zir con geo chron ol ogi cal data as well as 40Ar-39Ar age de ter mi na tions to con strain the ge netic and tem po ral re la tion ships of the dif fer ent rock types form ing these veins. Based on mac ro scop i cally vis i ble fea tures of the granitoids and their re la tion ship with tec tonic struc tures vis i ble in the coun try rocks, four va ri et ies of the Jawornik granitoids have been dis tin guished: am phi bole- and bi o tite-bear ing gran ites (HBG), bi o tite-bear ing gran ites (BG), bi o tite- and mus co - vite-bear ing gran ites (BMG) and mus co vite-bear ing gran ites (MG). The Jawornik granitoids as a whole show a lim ited but sig nif i cant vari a tion in ma jor el e ment chem i cal com po si tion, with SiO2 rang ing from 65 to 76 wt.% (av er age 69.16 wt.%, n = 24). They are subalkalic, peraluminous and calc-al ka line [av er age A/CNK = 1.07, av er age (Na2O + K2O) = 7.75, av er age (Fe2O3t
/(Fe2O3t
+ MgO) = 0.59]. Close in spec tion of their geo chem i cal pa ram e ters showed that the sam ples in ves ti gated can be sub di vided into two groups. The first group, the HBG, BG, and BMG va ri et ies, com pris ing most of the granitoids in the Z³oty Stok-Skrzynka Tec tonic Zone, were formed by melt ing of greywackes or/and am phi bo lites. The MG, be long ing to the sec ond group, were formed by par tial melt ing of a more fel sic source. The HBG yielded a zir con U-Pb age of 351 ±1.3 Ma and well-de fined 40Ar-39Ar pla teau ages for hornblende (351.1 ±3.9 Ma) and co ex ist ing bi o tite (349.6 ±3.8 Ma), in di cat ing prob a - bly the old est mag matic event in this re gion. Zir cons from the MG, the youn gest rock va ri ety on the ba sis of their re la tion ship with the tec tonic struc tures in the host rocks, yielded a U-Pb age of 336.3 ±2.4 Ma, though based on three points only. The biotites and mus co vites from the BMG have 40Ar-39Ar pla teau ages of 344.1 ±4.7 Ma and 344.6 ±3.8 Ma, re spec tively. These data, in com bi na tion with al ready pub lished iso to pic ages, sug gest that the Jawornik granitoids in truded host rocks of the Orlica-Œnie¿nik Dome in three stages, at ~350, ~344 and ~335 Ma.
Key words: Jawornik granitoids, geo chem is try, geo chron ol ogy, Sudetes, Variscan granitoids.
INTRODUCTION
The Sudetes, lo cated in south west ern Po land, north east ern Bo he mia and north ern Moravia, rep re sent a small por tion of the Variscan Orogenic Belt in Eu rope and form the NE part of the Bo he mian Mas sif (Fig. 1). Geo log i cal units, be long ing to all four ma jor lithotectonic do mains of the Bo he mian Mas sif (i.e.
Saxothuringian, Teplá-Barrandian, Moldanubian and Bruno - vistulian do mains), make up the com plex struc tural mo saic of the Sudetes (Matte et al., 1990; Cymerman et al., 1997;
Franke, 2000; Franke and ¯elaŸniewicz, 2002; Mazur et al., 2006, 2015; Schulmann et al., 2014). The as sem bly of these units oc curred dur ing Late De vo nian to Early Car bon if er ous terrane col li sions (e.g., Matte et al., 1990; Cymerman et al.,
1997; Aleksandrowski and Mazur, 2002); the Variscan granitoids form a por tion of the rock in ven tory in all of them.
They dif fer in age, com po si tion and their tec tonic con text. The Bo he mian Mas sif is an ex am ple of a hot orogen with nu mer ous compositionally di ver si fied granitoid plutons. The plutonism was ac tive for nearly 80 My, and on the ba sis of their tec tonic set - tings, age and petro gen esis, four groups of plutons have been dis tin guished (Žák et al., 2014). The old est (~375 Ma), vol u met - ri cally small, granitoid bod ies, are subduction-re lated, con - nected with early stages of plate col li sion. Plutons be long ing to the next two groups (354–346 Ma and 340–335 Ma) were emplaced dur ing con sec u tive phases of orogenic de for ma tion.
In the fourth group there are plutons emplaced dur ing fi nal stages of the Variscan orog eny (330–320 Ma) and post- orogenically (~300 Ma). The larg est Sudetic plutons – the Karkonosze Pluton, Strzegom-Sobótka Mas sif, Žulowá Pluton, and small in tru sions that crop out in the Strzelin Mas sif, emplaced on the pe riph ery of the Variscan orogen, can be clas - si fied as late- to post-tec tonic (Oberc-Dziedzic and Kryza, 2012;
Kryza et al., 2014; Laurent et al., 2014; Turniak et al., 2014).
Older and smaller granitoids of the cen tral Sudetes are spa tially
* E-mail: dawid.bialek@uwr.edu.pl
Received: March 6, 2020; accepted: July 30, 2020; first published online: October 30, 2020
