GeolCarp_Vol50_No3_215

GEOLOGICA CARPATHICA, 50, 3, BRATISLAVA, JUNE 1999

215227

QUARTZ-APATITE-REE VEIN MINERALIZATION IN EARLY

PALEOZOIC ROCKS OF THE GEMERIC SUPERUNIT, SLOVAKIA

IGOR ROJKOVIÈ

, PATRIK KONEÈNÝ

, LADISLAV NOVOTNÝ

¼UBICA PUKELOVÁ

and VLADIMÍR STREKO

Faculty of Natural Sciences, Comenius University, Mlynská dolina, 842 15 Bratislava, Slovak Republic; rojkovic@fns.uniba.sk

Geological Survey, Mlynská dolina 1, 817 04 Bratislava, Slovak Republic

URANPRES, Fraòa Krá¾a 2, 052 80 Spiská Nová Ves, Slovak Republic

Geological Institute, Slovak Academy of Sciences, Dúbravská cesta 9, 842 26 Bratislava, Slovak Republic

(Manuscript received June 10, 1998; accepted in revised form March 17, 1999)

Abstract: Vein rare earth elements (REE) mineralization occurs in Early Paleozoic rocks of the Gemeric Superunit.

Quartz-apatite veins near Èuèma village contain a significant concentration of xenotime-(Y) accompanied by

monazite-(Ce), allanite-(Ce), goyazite, and plumbogummite. Less significant accumulation of disseminated xenotime

and its veinlets is also known near Betliar, Helcmanovce and Kociha villages. Near Kociha crandallite (?) was also

found with increased contents of REE. The REE mineralization is accompanied by apatite, uraninite, brannerite,

autunite, torbernite, quartz, pyrite, turmaline, rutile, titanite, marcasite and goethite. The content of REE and Y reaches

up to several tenths of one weight percent and rarely even more than 1 weight percent in veins near Èuèma. The other

occurrences show only moderately increased contents of REE and Y (from 0.1 to 0.8 weight percent). Phosphates

associated with metamorphosed black sediments are considered to be a source of the REE mineralization.

Key words: Gemeric Superunit, distribution of REE in minerals and rocks, REE minerals, veins.

Introduction

Quartz and quartz-apatite veins with uranium mineralization

accompanied by rare earth element minerals have been found

in the Early Paleozoic rocks of the Gemeric Superunit by the

former Uranium Survey (Fig. 1). The veins are often situated

in the vicinity of Gemeric granites. The uranium mineraliza-

tion was found in the quartz veins accompanied by apatite and

increased contents of REE near Èuèma village (váb et al.

1966; Tréger 1973). This association became an object of min-

eralogical studies by Pelymsky (1967 in Tréger 1973), Melnik-

ova (1973), Varèek (1975, 1977) and Rojkoviè (1993). Quartz,

apatite, xenotime, uraninite, pyrite and molybdenite were

found in quartz-apatite veins (Pelymskij 1967 in Tréger 1973).

Monazite was identified later as well as a younger generation

represented by younger quartz, siderite, Fe-dolomite, dolo-

mite, pyrite, arsenopyrite, pyrrhotite, marcasite, tetrahedrite,

chalcopyrite, sphalerite, jamesonite, etc. (Varèek 1977). The

younger stibnite mineralization in the area of Èuèma and

Betliar is represented by stibnite, chalcostibite, bournonite,

boulangerite, berthierite, jamesonite, antimony, accompanied

by pyrite, arsenopyrite, quartz, siderite, Fe-dolomite, pyrrho-

tite, sphalerite, chalcopyrite, galena and other minerals (Beòka

& Caòo 1992). Less increased contents of P, Y and REE were

found near Betliar, Helcmanovce and Kociha villages (Tréger

1973). Evansite was determined as the main phosphorus-bear-

ing mineral in Kociha locality according to chemical composi-

tion (in weight percent): 22.55 P

, 26.61 Al

, 13.66 SiO

0.56 Fe

and 0.39 CaO as well as according to differential

thermal analysis (Tréger 1973). Xenotime-(Y) together with

uraninite, brannerite, native gold and other minerals were

found in the Zimná voda Valley near Prakovce (Rojkoviè et al.

1997). An increased content of P

was found in the black

phyllite and lydite (Oruinský et al. 1989; Varèek et al. 1989;

Rojkoviè et al. 1995). The aim of this study was to identify

REE minerals and characterize the REE distribution in rocks.

Methods

Minerals were studied by polarizing microscope in both trans-

mitted and in reflected light and by scanning electron micro-

Fig. 1. Geological map of the eastern part of the Slovenské rudohorie

Mts. (adapted according to Biely et al. 1996). 1Tertiary sediments,

2Neogene volcanic rocks, 3Mesozoic rocks, 46Gemeric Su-

perunit, 4granite, 5Late Paleozoic rocks, 6Early Paleozoic

rocks, 7Paleozoic and Proterozoic ? rocks of Veporic Unit, 8

REE mineralization, BeBetliar, ÈuÈuèma, HuHelcmanovce,

KcKociha. The frame in the centre represents the area of Fig. 2.

216 ROJKOVIÈ et al.

scope (SEM). They were analysed by wave-dispersion X-ray

microanalysis (WDX), energy-dispersion X-ray microanalysis

(EDX) and by X-ray diffraction analysis (XRD). Micropobe

analyses were carried out on a JEOL-733 Superprobe X-ray mi-

croprobe equipped with KEVEX Delta IV+ energy dispersive

system (Geological Survey of the Slovak Republic). Monazite

and allanite were analysed with a JEOL-733 using 20 KV accel-

erating voltage, 20 nA beam current, 10 to 20 seconds counting

times according to the total number of counts. The obtained

counts were recalculated in oxides using PAP correction. Apa-

tite, titanite were analysed with KEVEX ED system. The elec-

tron beam was stabilized on 1.2 nA with 15 KV accelerating

voltage. Counts were acquired for 100 seconds and recalculated

using XPP quantitative correction. The electron beam was fo-

cused on 35 micrometers. Natural and synthetic standards were

applied to calibration of both systems: AlAl

, SiSiO

, P

apatite, Cawollastonite, Fehematite, YYAl garnet, LaLaB

CeCeO

, PrPrPO

, NdSmYbLuREE glass, ThThO

, U

and ClNaCl. Detection limits were better than 0.1 wt. %.

Relative standard deviation ranged from ±5 % (for 1 wt. %) to

±25 % (for 0.1 wt %).

The chemical composition of the rocks was determined by

chemical wet analysis and X-ray fluorescence analysis

(XFA) for major elements of the rocks and by colorimetry for

Major elements were analysed on the X-ray spectrome-

ter Philips PW 1410/20. Instrumental conditions: X-ray tube

with Rh anode (voltage 40 kV, current 40 mA), gas flow de-

tector with Ar/CH

=90/10 filling, crystal LiF 200 for Fe,

Mn, Ti, Ca, K and TlAP for Si, Al, Mg, Na. Samples (1.3 g)

were fused with Li

(5.5 g) at the temperature of

1050

C in Pt-crucible. The following standards were used:

GM granite, BM basalt, TS shale and their mix-

tures. Optical emission spectroscopy (OES) was used for

trace elements (including La, Yb and Y in some samples).

The spectra of samples were recorded by the grid spec-

trograph PGS-2 in UV and visual area, with 6 A power arch

as the activating source. The measuring time was 90 s. Stan-

dard: GM granite and TS shale.

Rare earth elements were analysed by atomic emission spec-

troscopy with induction coupled plasma (AES-ICP). The de-

composition procedure of samples by repeated treatment with

acid mixture (HNO

+ HF + HClO

) and following fusion of

the insoluble residue with NaBO

was used. REE were sepa-

rated by catex ion exchanger DOWEX AG 500W-X8. Sam-

ples were analysed by sequential atomic emission spectrome-

ter Plasmakon S 35. Detection limits ranged from 0.25 to 0.5

ppm. Relative standard deviation ranged from ±2 % (for 0.1

wt. %) to ±10 % (for 0.001 wt. %).

Geological setting and distribution

of REE mineralization

Èuèma

Quartz-apatite veins occur north of the village of Èuèma in

the Early Paleozoic rocks of the Bystrý Potok Formation (Ba-

janík et al. 1984). An adjacent rhyolite metatuff has been dated

by U/Pb dating at 403 Ma (Cambel et al. 1990). The veins are

accompanied by uranium mineralization and have increased

contents of REE (váb et al. 1966; Tréger 1973). The most im-

portant mineralization is bound to a vein structure 1.7 km long

(with segments of visible mineralization on the surface up to

25 m long), direction 6070

, inclination 65

to SSE and aver-

age thickness of 0.6 m (maximum up to 3 m). It occurs 200 m

north of a quartz vein with antimony mineralization exploited

in the past in Gabriela adit and shaft (Fig. 2). Short quartz-apa-

tite veins of direction 65

, inclination 35

to SE, length 50 m

and thickness from 0.1 to 0.3 m occur also in rhyolite metatuff

on the slopes of Majerská dolina Valley (Fig. 2). Sericite phyl-

lite and metamorphosed black shale in Majerská dolina Valley

contain lensoidal accumulations of apatite from 10 to 15 cm

long (váb et al. 1966).

Quartz-apatite veins are accompanied by U-REE mineral-

ization. Dominant quartz with apatite (up to more than 10

percent) are accompanied by xenotime, monazite, goyazite

and plumbogummite (Fig. 3). Xenotime is the most impor-

tant REE mineral of these veins reaching up to more than 1

percent, monazite ranges between 0.1 and 0.5 percent,

goyazite less than 0.01 percent and rare plumbogummite was

found in one sample only (Figs. 4, 5). The REE mineraliza-

Fig. 2. Geological map of the Èuèma and Betliar area (adapted ac-

cording to Bajaník et al. 1984). 1 Quaternary, 2 granite, 3

black phyllite, 4 lydite, 5 metarhyolite and its tuff, 6

quartz phyllite and metamorphosed quartz wacke, 7 chlorite-

sericite phyllite, 8 limestone, 9 occurrences of REE mineral-

ization, A Betliar, B Èuèma vein north of Gabriela shaft, C

Majerská dolina Valley, 10 mining dumps of abandoned an-

timony deposit Gabriela.

QUARTZ-APATITE-REE VEIN MINERALIZATION 217

tion is accompanied by uraninite, brannerite, autunite, torber-

nite, apatite, quartz, pyrite, tourmaline and goethite. Besides

the quartz-apatite veins the metatuff contains veinlets of

quartz with disseminated allanite (around 0.5 percent) ac-

companied by xenotime and monazite (Fig. 6). The younger

sulphide mineralization is associated with separated struc-

tures with dominant stibnite mineralization.

Regional rocks are represented by a rhyolite metatuff,

granite, chlorite sericite phyllite, quartz-sericite phyllite,

black phyllite and lydite. The metamorphosed rocks strike in

EW and NESW directions and dip 3040

to the S or SE.

The rhyolite metatuff is the wall rock of the veins. Sericitiza-

tion is the typical wall rock alteration (váb et al. 1966). The

Gemeric granite body was found by drilling underneath

quartz-apatite vein in depth of 220 m (váb et al. 1966,

Fig. 7). Frequent accessory minerals of the granite are tour-

Fig. 3. Tabular crystals of apatite (white) in brown quartz (grey).

Èuèma, Èu 10.

Fig. 4. Zonal xenotime (black) overgrows and in the form of thin

veinlet cuts apatite (grey) in quartz (white). Èuèma, Èu 5a, trans-

mitted light, 1 nicol.

Fig. 5. Monazite veinlet (mon) cuts apatite (ap). Grains and vein-

let of goyazite (go) occur at the contact of earlier minerals. Èuè-

ma, Èu 5a, SEM-BSE.

Fig. 6. Allanite aggregate of different brightness (all) reflecting a

varying REE content with small grains and veinlets of xenotime

(xe) and monazite (mon). Èuèma, Èu 15/4, SEM-BSE.

Fig. 7. Geological cross-section of quartz-apatite vein area near Èuè-

ma (adopted according to váb et al. 1966): 1 Quaternary gravel,

sand and clay, 2 granite, 3 metatuff of rhyolite and sericite phyl-

lite, 4 metarhyolite, 5 vein, 6 fault, 7 drilling.

218 ROJKOVIÈ et al.

maline, apatite and pyrite (Gbelský 1982), which are also

common minerals of the quartz-apatite veins.

Betliar

The REE mineralization occurs 6 km north of the village

of Betliar in the mountain crest at an altitude of 755 m, 400

m SW of hill 806.4 (Fig. 2). Rhyolite metatuff with veinlets

of quartz and iron hydroxides show increased radioactivity

(up to 600 imp./s). the accumulation of apatite, rutile and ti-

tanite accompanied by rare xenotime and monazite is similar

as that near Èuèma but it is not so extensive and abundant

(Fig. 8). The observed extent of mineralization is about 100

m with a direction of 80

, and inclination 50 to 60

towards

the south and thickness from 0.2 to 1 m.

Helcmanovce

The occurrence is situated in the mountain crest (altitude

815 m), 300 m NW from Ve¾ký hutný potok Stream and

Fig. 9. Aggregate of xenotime (white) in rhyolite metatuff with

abundant iron hydroxides (grey). Helcmanovce, Hu 3, SEM-BSE.

Fig. 10. Pyrite veinlet (py) enclosing apatite (ap) and xenotime

(xe). Kociha, Kc 2, SEM-BSE.

Fig. 8. Apatite crystals (grey) are accompanied by rutile (light

grey) and titanite (detail in Fig. 19). They are cut by iron hydrox-

ides (white). Betliar, Be 2, SEM-BSE.

2.6 km SW from the Helcmanovce village. U-REE mineral-

ization is bound to a zone with veinlets of quartz and iron hy-

droxides showing EW direction, length 200 m and thickness

around 1 m as revealed by technical works of the former Ura-

nium Survey. A mineralized tectonic zone contains accumula-

tion of xenotime ranging from 0.5 to 1 percent (Fig. 9). Wall

rock is represented by rhyolite metatuff and metarhyolite. It is

accompanied by black phyllite, lydite, quartz-sericite phyllite,

chlorite-sericite phyllite and small bodies of metabasalt and its

metatuff. The rocks show an EW direction of beds.

Kociha

The abandoned adit of the former Uranium Survey is 1 km

NE from the village of Kociha. The metamorphosed Early Pa-

leozoic black sediments are the dominant rocks of the area.

They are represented by black phyllite, lydite, carbonates and

intercalations of rhyolite metatuff (Tréger 1973). They are

covered by andesite tuff towards the east (Fig. 1). The shearing

zone has a NESW direction and inclination from 60 to 80

to-

wards the SE. It is intensively oxidized close to the surface

and shows increased contents of P and REE. Quartz and

quartz-carbonate veinlets several cm thick are bound to the

shearing zone (up to 1.5 m thick) and they are accompanied by

REE mineralization. Quartz-carbonate veinlets are accompa-

nied by pyrite, marcasite, apatite, xenotime and crandallite (?)

(Fig. 10). The wall rock is represented by lydite and limestone

of the Early Paleozoic Gelnica Group.

REE and accompanying minerals

Apatite Ca

[(F,OH)|(PO

)

] occurs as tabular crystals from

0.05 mm to 1 cm long with longitudinal cleavage forming

bands several millimetres thick (Fig. 3). It is accompanied by

close association of quartz and pyrite. It is rimmed and en-

closed by pyrite (Fig. 10). It is overgrown and cut by sericite,

quartz, xenotime, monazite and uraninite (Figs. 4, 5, 11).

Xenotime Y[PO

] shows high relief, a brownish tint and

distinct longitudinal cleavage (210) in transmitted light. It

QUARTZ-APATITE-REE VEIN MINERALIZATION 219

forms radial, zonal or irregular aggregates (0.2 mm rarely up

to 0.7 mm across) and clusters (rarely up to 1 mm across,

Fig. 9). Fan-like aggregates overgrow apatite and fill the in-

terstitial space of apatite grains (Fig. 4). The brown colour of

aggregates due to intergrowing with goethite covers some-

times even vivid colours in crossed nicols. The radial aggre-

gates often show cross zoning heightened by different tints of

brown colour due to enclosures of uraninite, autunite and go-

ethite. Xenotime crystals (up to 0.2 mm across) can be seen

in quartz as well as in thin quartz veinlets cutting apatite.

Small crystals from several

m up to 40

m are enclosed in

apatite, especially in its border and along fissures in apatite.

The distinct zoning reflecting different uranium contents in

xenotime can be observed in SEM (Fig. 12). Xenotime grains

(from 50 to 150

m across) were rarely found in pyrite-apa-

tite veinlets as well as in colloform zonal aggregates of cran-

dallite (?). Xenotime forms thin veinlets in apatite (Fig. 11).

The chemical composition of xenotime shows the presence

of uranium and HREE (Sm-Yb) as well as the main elements

(Y a P) (Table 1, Fig. 13).

Monazite Ce[PO

] accompanies xenotime in veinlets and

also forms separate veinlets in apatite (Fig. 5) and quartz

(Fig. 14). Monazite grains vary in size from 10

m to 0.2

mm across. Light rare earth elements (LREE) from La to Gd

with dominant Ce were confirmed in its chemical composi-

tion (Table 2, Fig. 13).

Allanite (Ca, Ce)

(Fe

,Fe

...

)Al

[O|OH|SiO

|Si

] forms

elongated crystals (2 to 4 mm long) and their aggregates

in quartz veinlets (Fig. 15). Some grains show distinct longi-

tudinal cleavage. It is accompanied by small grains and vein-

lets of monazite and xenotime in the intergranular space of

allanite. SEM, EDX and WDX confirm the variability of its

chemical composition as well as significant ratio of LREE

(Table 3, Fig. 13). Different REE content is displayed even

by back-scattered electron image in SEM. Darker domains

are accompanied along cracks by veinlets and grains of mon-

azite suggesting their secondary origin (Fig. 6). Darker do-

mains along cracks are explained as a result of oxidation

(Petrík et al. 1995). Allanite with low uranium content is,

however, accompanied by secondary uranium minerals autu-

nite and torbernite. Epidote was also found in some quartz

veinlets.

Goyazite SrAl

H[(OH)

(PO

)

] is a common minor miner-

al of the veins near Èuèma (Rojkoviè 1993). Small grains (up

to 30

m) or several

m thick veinlets fill fissures and intersti-

tial space of apatite mainly close to monazite (Figs. 5, 16). It

also occurs rarely in fissures of monazite. It was identified

only by the help of WDX analysis on the basis of dominant Sr

proportion partly replaced by LREE (Table 4, Figs. 13, 17).

Plumbogummite PbAl

H[(OH)

(PO

)

] was found only as a

rare mineral in the veins near Èuèma. Small grains (several

across) intergrown with goyazite replace apatite. It was identi-

fied only by WDX and EDX analysis according to the dominant

proportion of Pb (Table 4). However, it represents a transitional

member of the crandallite-goyazite series with significant pro-

portion of Ca and minor proportion of Sr (Fig. 17).

Crandallite (?) CaAl

H[(OH)

(PO

)

] was found in Ko-

ciha locality. Accumulation of iron hydroxides is accompanied

by yellowish-white coloured fine-grained hydrous phosphates.

Fig. 11. Grains and veinlet of xenotime (xe) fill fissure of apatite

(ap). Betliar, Be 2, SEM-BSE.

Fig. 12. Zonality of xenotime crystals due to different proportion

of uranium (light zones are uranium-bearing). Èuèma, Èu 1, back-

scattered electron image (SEM-BSE).

Fig. 13. Average REE distribution in the studied minerals.

220 ROJKOVIÈ et al.

They form colloform zonal aggregates mostly from 10 to 50

m across (Fig. 18). They can be distinguished only by

SEM. A high proportion of H

O and variability of chemical

composition in thin zones of colloform aggregates cause de-

viations from the formula of crandallite and a lower total in

chemical composition by WDX analysis (Table 4). However

the stable presence of Ca excludes evansite in the analysed

material. It contains increased contents of Sr, LREE (La-

Sm), Fe and Ba.

Uraninite UO

forms colloform zonal aggregates (up to 2

mm across) in quartz. Smaller grains and spheroids (from 1 to

m across) are abundant in xenotime. They often form thin

zones or bands several

m thick in xenotime. Uraninite shows

significant lead contents from 1.5 to 1.8 weight percent).

Brannerite UTi

or (U,Ca,Th,Y)[(Ti,Fe)

] is a rare

mineral of vein mineralization. Laths and rhombic sections

of brannerite from 15 to 50

m across were observed in the

quartz of quartz-apatite veins. The chemical composition of

brannerite corresponds to the formula (U,Ca)

0.99-1.07

(Ti,

Fe)

1.99-2.05

, where, besides the main elements (U and Ti), low

Weight percent

Sample

HfO

Total

Be 2.1

41.4

0.4

0.7

0.0

1.5

6.5

1.4

4.2

1.3

2.1

3.1

0.0

1.1

36.0

99.6

Be 2.2

37.8

0.0

2.3

1.5

6.5

1.4

4.2

1.3

4.5

0.2

0.1

0.0

40.4

100.1

Cu 1.1

43.4

1.0

4.3

1.6

7.3

0.0

2.5

5.1

1.6

32.8

99.7

Cu 1.2

47.0

0.8

3.7

0.0

6.4

0.0

2.7

4.7

1.4

33.0

99.7

Cu 1.3

49.4

0.8

2.4

0.0

4.0

0.0

2.3

6.0

1.0

33.9

99.9

Hu 3.2

43.8

0.4

0.5

0.0

1.3

5.4

1.8

4.2

1.6

1.5

1.8

0.0

0.9

34.6

97.8

Hu 3.3

43.4

0.2

0.3

0.0

1.3

5.4

1.8

4.2

1.6

2.6

0.0

1.0

32.2

96.6

Hu 3.4

40.1

0.0

1.7

1.3

5.4

1.8

4.2

1.6

4.5

2.1

0.0

37.5

100.1

Hu 3.6

39.3

0.0

2.4

1.6

5.7

1.4

4.3

1.4

3.2

2.3

0.0

38.5

100.1

Hu 3.7

40.5

0.4

0.6

0.0

1.2

6.1

0.0

4.9

1.5

3.0

3.2

0.0

0.8

36.6

98.7

Hu 3.8

37.5

0.0

2.4

1.2

6.1

0.0

4.9

1.5

6.1

3.4

0.0

36.9

100.0

Hu 3.9

40.5

0.2

0.8

0.0

1.2

6.0

1.9

4.8

1.9

2.9

3.4

0.0

1.0

34.1

98.7

Hu 3.10

37.5

0.0

1.9

1.2

6.0

1.9

4.8

1.9

5.5

2.7

0.0

36.8

100.0

Hu 3.11

35.8

0.0

1.8

1.2

6.2

1.9

5.3

2.2

5.4

2.7

0.0

37.3

99.9

Hu 3.12

43.8

0.6

0.9

0.2

1.5

5.8

1.4

3.8

1.7

1.5

2.2

0.0

0.5

38.7

102.4

Hu 3.13

42.8

0.0

2.8

1.5

5.8

1.4

3.8

1.7

3.6

1.8

0.0

35.1

100.1

Kc. 8.

36.8

0.0

3.6

1.7

6.2

1.9

3.7

1.5

4.9

0.0

0.1

0.0

39.7

100.1

Kc 95.1

36.3

0.0

3.8

1.6

5.7

1.8

3.7

1.9

4.9

0.6

0.1

0.0

39.7

100.1

Kc 95.2

36.2

0.0

3.7

1.6

6.1

2.0

3.5

1.6

5.0

1.2

0.1

0.0

39.3

100.1

Kc 95.6

45.6

0.0

3.8

0.0

6.2

0.0

4.7

0.8

3.7

1.1

0.0

34.3

100.2

Kc 95.7

42.1

0.0

4.9

0.0

6.9

0.0

5.1

0.9

5.1

1.5

0.0

33.6

100.1

Kc 95.8

38.2

0.0

4.7

0.0

6.8

0.0

4.9

2.0

4.8

1.8

0.0

37.0

100.1

Atomic proportion on 4 oxygens

UHf

Total

Be 2.1

0.736

0.004

0.008

0.000

0.016

0.069

0.015

0.044

0.014

0.021

0.031

0.000

0.010

1.017

1.985

Be 2.2

0.638

0.000

0.024

0.015

0.066

0.014

0.042

0.013

0.044

0.002

0.001

0.000

1.084

1.944

Cu 1.1

0.794

0.012

0.049

0.018

0.081

0.000

0.027

0.054

0.012

0.953

2.000

Cu 1.2

0.846

0.010

0.041

0.000

0.070

0.000

0.029

0.048

0.010

0.945

2.000

Cu 1.3

0.874

0.009

0.027

0.000

0.043

0.000

0.024

0.061

0.008

0.954

2.000

Hu 3.2

0.794

0.005

0.006

0.000

0.015

0.059

0.020

0.045

0.017

0.015

0.019

0.000

0.009

0.997

1.999

Hu 3.3

0.819

0.003

0.004

0.000

0.015

0.061

0.020

0.047

0.018

0.028

0.000

0.010

0.966

2.019

Hu 3.4

0.700

0.000

0.018

0.014

0.057

0.019

0.043

0.016

0.045

0.020

0.000

1.041

1.973

Hu 3.6

0.677

0.000

0.026

0.017

0.060

0.014

0.044

0.014

0.032

0.022

0.000

1.057

1.962

Hu 3.7

0.717

0.005

0.007

0.000

0.013

0.066

0.000

0.052

0.016

0.031

0.032

0.000

0.007

1.032

1.976

Hu 3.8

0.665

0.000

0.027

0.013

0.066

0.000

0.052

0.016

0.062

0.034

0.000

1.040

1.973

Hu 3.9

0.744

0.003

0.009

0.000

0.014

0.066

0.021

0.052

0.020

0.031

0.035

0.000

0.010

0.995

2.000

Hu 3.10

0.665

0.000

0.021

0.013

0.064

0.020

0.050

0.019

0.056

0.027

0.000

1.039

1.974

Hu 3.11

0.634

0.000

0.019

0.013

0.066

0.020

0.056

0.023

0.055

0.027

0.000

1.051

1.966

Hu 3.12

0.737

0.006

0.010

0.002

0.015

0.060

0.014

0.038

0.017

0.015

0.021

0.000

0.004

1.036

1.974

Hu 3.13

0.765

0.000

0.031

0.016

0.063

0.014

0.040

0.018

0.036

0.018

0.000

0.999

2.001

Kc. 8.

0.628

0.000

0.038

0.018

0.064

0.019

0.037

0.015

0.048

0.000

0.001

0.000

1.079

1.947

Kc 95.1

0.620

0.000

0.040

0.017

0.059

0.018

0.037

0.019

0.048

0.006

0.001

0.000

1.080

1.946

Kc 95.2

0.622

0.000

0.040

0.017

0.063

0.021

0.036

0.016

0.049

0.011

0.001

0.000

1.075

1.950

Kc 95.6

0.817

0.000

0.043

0.000

0.067

0.000

0.050

0.009

0.038

0.012

0.000

0.979

2.014

Kc 95.7

0.771

0.000

0.056

0.000

0.076

0.000

0.055

0.010

0.054

0.016

0.000

0.977

2.015

Kc 95.8

0.674

0.000

0.051

0.000

0.073

0.000

0.051

0.020

0.049

0.018

0.000

1.038

1.974

contents of Fe (up to 2.8 weight percent) and Ca (up to 1

weight percent) were observed.

Autunite Ca[UO

|PO

]

.10H

O forms tabular crystals

(from 0.1 to 0.5 mm across) and aggregates (up to 1.5 mm

across) with distinct cleavage and vivid colours in crossed

nicols in transmitted light. It fills fissures in vein minerals es-

pecially close to apatite. It overgrows apatite and intergrows

with goethite. Its identification was confirmed by EDX anal-

ysis.

Torbernite Cu[UO

|PO

]

.10(12-8)H

O forms aggregates

of tabular crystals up to 0.5 mm in quartz. Lamellae of green

colour form aggregates up to 1 mm across. Torbernite occurs

in close association with goethite. Its chemical composition

was confirmed by EDX analysis (Rojkoviè 1997).

Pyrite FeS

occurs as irregular grains as well as euhedral

crystals (pentagonal dodecahedrons and hexahedrons) from

m to 0.5 mm across (mostly around 0.1 mm). Their aggre-

gates usually reach around 2 mm across.

Rutile TiO

forms columnar crystals from 0.03 to 0.07 mm

long and their clusters (up to 0.5 mm across). It accompanies

Table 1: Chemical composition of xenotime.

QUARTZ-APATITE-REE VEIN MINERALIZATION 221

Weight percent

Sample

ThO

CaO

FeO

Total

Cu5.1

9.6

25.9

2.2

19.2

5.3

4.9

0.0

0.2

0.3

0.0

0.7

30.1

98.4

Cu5.2

8.9

26.2

2.2

19.2

4.8

4.7

0.0

0.2

0.0

0.5

29.5

96.4

Cu5.3

8.4

25.6

2.3

19.4

5.4

5.2

0.2

0.3

1.0

0.7

30.4

99.2

Atomic proportion on 4 oxygens

Sample

Total

Cu5.1

0.140

0.376

0.032

0.272

0.073

0.064

0.000

0.002

0.012

0.000

0.014

1.011

1.996

Cu5.2

0.133

0.389

0.032

0.278

0.067

0.063

0.000

0.002

0.010

0.000

0.012

1.011

1.996

Cu5.3

0.121

0.367

0.033

0.272

0.074

0.068

0.001

0.003

0.011

0.034

0.014

1.010

2.007

Weight percent

Sample

SiO

CaO

FeO

ThO

Total

Cu15.1

21.2

34.5

0.0

11.5

9.2

0.3

3.9

8.0

0.8

3.8

0.7

1.5

0.0

95.5

Cu15.2

19.9

32.9

0.1

12.9

9.9

0.0

4.9

9.4

0.7

3.5

0.5

1.3

0.0

96.1

Cu15.3

20.3

35.3

0.1

13.7

9.3

0.0

5.0

10.0

0.7

3.7

0.5

1.6

0.0

100.3

Cu15.4

20.5

34.9

0.1

9.5

8.9

0.0

4.7

10.4

0.9

4.4

0.5

1.4

0.0

0.1

96.2

Cu15.5

21.1

31.9

0.1

16.2

8.9

0.3

4.7

9.9

0.6

3.9

0.8

1.4

0.1

0.0

100.0

Cu12.1

19.2

33.1

0.1

10.6

12.1

0.3

3.0

10.3

0.8

5.1

0.8

2.0

0.0

0.1

97.5

Cu12.2

18.3

30.4

0.1

12.0

13.0

0.3

4.3

10.7

0.7

4.5

0.7

2.0

0.0

97.0

Cu12.3

18.5

32.1

0.1

9.1

12.9

0.0

4.6

11.3

0.7

4.8

0.8

2.1

0.0

97.1

Atomic proportion on 12 oxygens

Sample

Total

Cu15.1

2.190

3.020

0.003

1.080

0.673

0.016

0.126

0.257

0.026

0.118

0.021

0.044

0.001

0.000

7.575

Cu15.2

2.090

2.942

0.007

1.233

0.740

0.002

0.161

0.309

0.024

0.111

0.016

0.038

0.000

7.672

Cu15.3

2.038

3.009

0.007

1.250

0.661

0.000

0.158

0.311

0.022

0.112

0.016

0.045

0.000

7.629

Cu15.4

2.130

3.085

0.005

0.896

0.654

0.001

0.152

0.335

0.029

0.140

0.014

0.042

0.000

0.002

7.484

Cu15.5

2.159

2.775

0.010

1.507

0.644

0.012

0.152

0.315

0.020

0.121

0.025

0.042

0.002

0.000

7.784

Cu12.1

2.027

2.962

0.010

1.014

0.909

0.016

0.100

0.337

0.026

0.161

0.023

0.058

0.000

0.002

7.646

Cu12.2

1.994

2.811

0.007

1.191

1.007

0.016

0.147

0.363

0.025

0.149

0.022

0.061

0.000

7.791

Cu12.3

2.000

2.940

0.011

0.896

0.991

0.000

0.157

0.380

0.024

0.156

0.025

0.063

0.000

7.642

Table 2: Chemical composition of monazite.

Table 3: Chemical composition of allanite.

Weight percent

Sample *

CaO

SrO

PbO

BaO

Total

Cu 1.1 go

30.8

28.2

0.4

11.9

2.0

5.6

0.0

2.5

0.0

0.6

0.0

0.1

0.0

82.1

Cu 1.2 go

30.2

28.9

0.7

9.4

1.4

5.9

0.0

3.8

0.0

1.3

1.4

3.9

0.0

86.9

Cu 1.3 pg

27.8

26.8

2.4

2.6

1.2

3.3

0.0

2.2

0.0

14.0

3.9

0.0

84.2

Cu 5.1 go

33.2

26.4

0.9

11.5

2.4

6.5

0.0

2.7

0.0

0.7

0.4

0.9

0.0

85.6

Cu 5.2 go

29.3

24.1

1.0

9.9

3.0

6.5

0.0

2.3

0.0

0.7

0.2

4.2

0.0

81.2

Kc 95.1 cd

31.9

22.0

8.2

2.0

0.0

0.1

0.2

0.6

0.0

2.9

0.5

68.3

Kc 95.2 cd

31.9

25.4

9.5

1.3

0.0

0.3

0.0

2.6

0.3

71.5

Kc 95.3 cd

32.2

25.8

9.5

1.9

0.0

0.6

0.5

0.1

0.0

2.3

0.8

73.5

Kc 95.4 cd

31.3

24.9

8.3

1.6

0.0

0.3

0.6

0.4

0.0

2.6

0.5

70.4

Kc 95.5 cd

30.7

20.6

7.4

1.9

0.0

0.9

0.6

1.1

0.0

3.0

1.3

67.6

Kc 95.6 cd

31.1

24.4

8.5

2.0

0.2

0.3

0.4

0.7

0.2

0.0

3.4

0.7

71.9

Kc 95.7 cd

30.7

26.6

7.5

1.7

0.2

0.9

0.4

0.6

0.1

0.0

2.9

0.7

72.2

Atomic proportion on 6 atoms

Sample *

Total

Cu 1.1 go

3.048

2.004

0.036

0.579

0.062

0.172

0.000

0.075

0.000

0.017

0.000

0.007

0.000

6.000

Cu 1.2 go

2.885

1.983

0.061

0.442

0.042

0.175

0.000

0.110

0.000

0.035

0.031

0.238

0.000

6.000

Cu 1.3 pg

2.863

1.982

0.225

0.132

0.039

0.106

0.000

0.069

0.000

0.329

0.256

0.000

6.000

Cu 5.1 go

3.157

1.804

0.078

0.538

0.071

0.192

0.000

0.078

0.000

0.019

0.009

0.055

0.000

6.000

Cu 5.2 go

2.981

1.761

0.093

0.496

0.096

0.205

0.000

0.071

0.000

0.020

0.005

0.273

0.000

6.000

Kc 95.1 cd

3.275

1.627

0.768

0.099

0.000

0.002

0.006

0.019

0.000

0.188

0.017

6.000

Kc 95.2 cd

3.121

1.785

0.845

0.060

0.000

0.008

0.010

0.000

0.161

0.010

6.000

Kc 95.3 cd

3.101

1.784

0.830

0.088

0.000

0.017

0.014

0.002

0.000

0.139

0.026

6.000

Kc 95.4 cd

3.144

1.800

0.761

0.078

0.000

0.010

0.017

0.010

0.000

0.164

0.016

6.000

Kc 95.5 cd

3.271

1.578

0.714

0.102

0.000

0.029

0.021

0.036

0.000

0.203

0.048

6.000

Kc 95.6 cd

3.097

1.746

0.766

0.096

0.007

0.010

0.012

0.021

0.006

0.000

0.216

0.023

6.000

Kc 95.7 cd

3.060

1.903

0.681

0.082

0.007

0.027

0.012

0.017

0.002

0.000

0.186

0.023

6.000

* cd

crandallite (?), go

goyazite, pg

plumbogummite

Table 4: Chemical composition of crandallite series minerals.

apatite near Betliar village (Fig. 19). WDX microanalysis

confirmed Fe content up to 1.3 weight percent).

Titanite grains (up to 50

m across) are closely associated

and intergrown with rutile. It overgrows and encloses xeno-

time (Fig. 19).

Goethite

-FeOOH and limonite form aggregates up to

5 mm across filling fissures of apatite and quartz. It replaces py-

rite and forms pseudomorphs after pyrite in quartz (up to

0.7 mm across). Thin zones of goethite accumulation were ob-

served in xenotime aggregates. An increased content of uranium

was found in some grains of goethite (up to 3.7 weight percent).

Quartz is brown with different grain size showing a mosa-

ic structure and mostly direct extinction. A alternating layers

with different grain size were observed. Mostly fine-grained

222 ROJKOVIÈ et al.

Fig. 14. Thin monazite veinlet in quartz. Betliar, Be 2, SEM-BSE.

Fig. 15. Euhedral allanite (dark grey) in quartz. Èuèma, Èu 15/4,

transmitted light, 1 nicol.

Fig. 16. Goyazite (go) replacing apatite (ap) along grain bound-

aries close to monazite veinlet (mon). Èuèma, Èu 5b, SEM-BSE.

apatite, xenotime and crandallite (?). They occur rarely in

Èuèma veins.

Sericite KAl

[(OH,F)

AlSi

] lamellae (from 0.05 to

0.1 mm long) form aggregates (from 0.3 mm to several mm

in size) rimming apatite. It also forms veinlets (up to

0.01 mm thick) in quartz.

zones are in contact with apatite. Veinlets of coarse-grained

quartz (from 0.1 to 1 mm) cut carbonates and fine-grained

quartz (0.010.2) with apatite and pyrite.

Carbonate grains (mostly from 1 to 2 mm across) forming

mosaic structure are dominant only in Kociha locality in

quartz-carbonate veinlets accompanied by pyrite, marcasite,

Fig. 18. Aggregate of crandallite (?) (cn) in quartz (qz) encloses

xenotime (xe). Kociha, Kc 95/Z8, SEM-BSE.

Fig. 19. Rutile (ru) intergrows with titanite (ti), enclosing xenotime

(xe). Betliar, Be 2, SEM-BSE (detail of the upper part of Fig. 8).

Fig. 17. Atomic proportion of Sr, Pb and Ca in crandallite series

minerals (Èuèma and Kociha localities).

QUARTZ-APATITE-REE VEIN MINERALIZATION 223

Tourmaline Na(Mg, Fe, Mn, Li, Al)

(BO

)

(OH, F)

[Si

] is abundant in some samples of the veins. Prismatic

crystals with distinct pleochrosim (from 0.05 to 0.1 mm long)

sometimes form bands parallel to zones of quartz with a differ-

ent size of grains. It overgrows and rims apatite. It often inter-

grows with xenotime.

Geochemical characteristic

The contents of major and minor elements in rocks near the

Èuèma locality reflect their mineral composition. Metamor-

phosed shale-phyllite shows increased in the proportions of

alumina (Table 5), organic carbon, Ba, Cr, Mo and V. The

veins with studied mineralization show increased contents of

Ca and P, reflecting abundant apatite. The trace elements of

quartz and quartz-apatite veins are characterized by increased

contents of U, Pb, Mo, Au, Y and La (Table 6). Increased con-

tents of Co reflect abundant pyrite. The content of REE and Y

in veins attain up to several tenths of weight percent and rarely

even more than 1 weight percent (Table 7). The increased con-

tent of HREE reflects dominant xenotime in samples Cu 4a,

5a, 5b and 10 (Fig. 20).

The mineralized rhyolite metatuff near the Helcmanovce

village is enriched in Y, HREE and uranium (Tables 6, 7). In-

creased content of Fe

and loss of ignition (LOI) reflects the

presence of iron hydroxides in sample with abundant xenotime

(Hu 3, Table 5). The maximum content of Y 0.5 weight per-

cent with REE content 0.3 weight percent reaches in total 0.8

weight percent. The distribution of REE in metatuff with xe-

Sample

rock

SiO

TiO

FeO

MnO

MgO

CaO

LOI

O-

Total

Be 3

69.49

0.45

15.11

1.64

0.05

0.010

1.11

2.04

0.18

4.10

2.31

2.96

0.36

99.81

Be 7

74.93

0.06

13.97

0.73

0.18

0.030

0.42

0.68

3.13

4.14

0.19

0.89

0.23

99.58

Be 8

71.99

0.15

15.10

1.06

0.32

0.020

0.72

0.55

3.30

4.90

0.23

1.17

0.19

99.58

Cu 10

Iqa

52.48

0.27

4.19

3.41

0.30

0.013

6.14

21.37

0.48

1.90

5.62

1.29

0.25

97.71

Cu 15.4 R

74.82

0.43

9.77

1.37

0.04

0.010

0.82

6.75

0.14

2.19

0.94

2.18

0.33

99.79

Cu 26.2

Iqa

86.06

0.05

4.11

0.73

0.43

0.014

0.20

3.45

0.41

1.15

2.42

0.71

0.15

99.88

Cu 27.2

92.25

0.04

2.07

0.48

0.013

0.07

0.38

0.58

0.06

1.37

0.13

99.88

Cu 30

66.35

0.27

16.04

1.94

2.67

0.050

1.88

1.46

3.76

3.19

0.17

1.53

0.08

99.39

Cu 31

67.10

0.27

16.54

1.00

3.35

0.050

1.55

1.75

3.37

3.01

0.21

1.21

0.20

99.61

Cu 32

42.53

0.31

30.79

3.16

5.00

0.070

3.11

0.16

0.90

7.55

0.17

5.59

0.22

99.56

Cu 33

Bcq

77.95

0.07

10.50

0.52

2.61

0.030

1.69

0.15

0.90

2.67

0.10

2.37

0.06

99.62

Cu 34

73.21

0.12

15.56

0.13

0.76

0.020

0.39

0.23

3.49

4.19

0.26

0.90

0.06

99.32

Cu 35

53.50

0.25

25.08

1.27

3.56

0.060

1.46

0.20

0.94

7.46

0.21

5.45

0.10

99.54

Hu 1

76.35

0.09

11.74

0.76

0.32

0.006

0.34

0.02

0.21

8.71

0.06

0.88

0.06

99.48

Hu 3

77.29

0.06

11.96

2.06

0.14

0.024

0.80

0.04

1.56

3.51

0.09

2.06

0.02

99.53

Kc 8

66.36

0.11

5.10

13.82

0.15

0.008

0.08

1.03

0.12

0.27

8.49

8.10

4.39

99.54

Kc 66

Bcq

86.03

0.19

3.46

0.42

0.04

0.002

0.23

0.03

0.11

0.87

0.05

8.09

0.07

99.54

black phyllite, Bcq

lydite, G

granite, Iq

quartz vein, Iqa

quartz-apatite vein, R

metarhyolite, RT

metatuff of rhyolite

Table 5: Chemical composition of rocks (in weight percent).

Sample

rock

Be 2

0.5

617

16.6

100

1.5

4.8

89.0

48.0

26.3 2900

69.0

204

Be 3

35.0

776

16.1

363

3.2

5.1 3700.0

55.0

36.3 3900

85.0

269

400

Be 5

0.5

617

9.3

0.5

3.9

60.0

47.0

41.7 2950

78.0

177

Be 7

0.5

209

10.4

0.5

3.2

21.0

8.0

14.8

562

1.5

Be 8

0.5

437

6.9

0.5

3.8

10.0

15.0

20.4 1380

10.0

123

Cu 4 a Iqa

1.2 0.0250

296

47.0

212

47.0

Cu 4 b Iqa

1.6 0.0090

995

8.0

160

51.0

173

Cu 4 c Iqa

1.3 0.2000

127.0

214

40.0

150

Cu 10

Iqa

0.7

138

34.0

407

4.0

26.0

70.0

73.0

18.2 1180

370

27.0

49 6050

Cu 15.4 Iq

1.0

282

14.8

245

2.2

5.3 348.0

79.0

23.9 2700 1320

28.0

107

175

700

Cu 26.2 Iqa

2.1

101

260

28.0

165 279.0

17.0 103.0

73.0

19.3

463 1700

28.0

11 2487

Cu 27.2 Iq

0.7

70 182.0

2.8

62.0

52.0

5.0

2.0

381

6.0

Cu 30

0.5 0.0170

485

49.0

101

20.0

21.0

32.0

19.0

6.4 1110

1 569.0

Cu 31

0.5 0.0009

45 1430

36.0

2.4

21.0

65.0 157.0

8.2 3650

78.0

224

433

Cu 32

0.5 0.0020

152 1920

26.0

110

34 149.0

40.0

9.0

40.0

29.7 3270

24 284.0

Cu 33

0.5 0.0040

825

44.0

51 307.0

38.0

7.0

10.0

21.2 3100

3 377.0

189

Cu 34

0.5 0.0450

279

351

40.0

1.8

9.0

16.0

5.0

35.9

768

1.5

Cu 35

0.5 0.0008

130 2010

42.0

105

2.8

55.0

8.0

26.0

14.6 3400

4 230.0

Hu 1

0.5 0.0059

184

5.0

0.5

4.0

1.5

1.3

474

1.5

Hu 3

2.1 0.0005

196

10.0

123

0.5

16.0

74.0

1.5

15.6

381 1810

29.0

108 3100

Kc 1

Bcq

0.7 0.0150

950

26.0

53.0

Kc 7

1.8 0.0004

28 1930

45.0

290

160

225 124.0

96.0

56.0 1100.0

8.9 2310

105 472.0

189

574

Kc 8

0.5 0.0083

15 1850

12.0

188

106 1100 216.0

20.0 700.0 1100.0

4.1 1240

87 272.0

871

Kc 31

Bcq

0.5 0.0003

948

10.0

126

1.5

8.0

13.0

9.0

0.5 1940

1 137.0

Kc 66

Bcq

0.5 0.0004

472

7.0

34.0

9.0

8.0

5.0

1.0 1880

3 460.0

Kc 84

Bcq

0.5 0.0001

399

12.0

174

23.0

6.0

5.0

8.0

0.5

980

2 332.0

Kc 95.1 Bcq

0.5

146

3.9

330

158

9.1

7.5

13.0

54.0

1.5

146

161.0

black phyllite, Bcq

lydite, G

granite, Iq

quartz vein, Iqa

quartz-apatite vein, R

metarhyolite, RT

metatuff of rhyolite

Table 6: Trace elements in rocks (in ppm).

224 ROJKOVIÈ et al.

Fig. 20. Distribution of REE in quartz-apatite veins near Èuèma

(Cu-4, 5a, 5b a 10), in rhyolite metatuff (Cu 31) and in black

phyllite (Cu 32).

Fig. 21. Distribution of REE in rhyolite metatuff without (Hu 1)

and with xenotime accumulation (Hu 3, 4, 5 a 6) near Helcmanovce.

Fig. 22. Distribution of REE in mineralized metatuff of rhyolite near

Betliar (Be 3.4open square), in lydite (Kc 1asterix and Kc 66

full triangle) and in mineralized lydite (Kc 8full square) near Kociha.

Sample

rock

REE

REE+Y

Be 3.4

191.0 261.0

32.0 125.0

20.0

6.0

39.0

6.0

53.0

10.0

26.0

3.0

20.0

3.0

795.0

234.0 1029.0

Cu 4 a

Iqa

212.0 1050.0

12.0 750.0 291.0

44.0 315.0

56.0

58.5

21.8 126.0

15.4

2951.7

Cu 4 b

Iqa

160.0 1130.0

91.0 1050.0 435.0

50.0 565.0

87.0

65.5

47.0 263.0

35.5

3979.0

Cu 4 c

Iqa

214.0 1070.0

87.0 765.0 295.0

48.5 340.0

45.5

37.5

19.6 107.0

16.4

3045.5

Cu 5 a

Iqa

515.0 1330.0 200.0 857.0 505.0

75.3 580.0 161.0 955.0 165.0 451.0

59.2 365.0

38.6

6257.1 4630.0 10887.1

Cu 5 b

Iqa

586.0 1430.0 205.0 963.0 547.0

66.4 639.0 148.0 1040.0 154.0 476.0

55.9 399.0

41.3

6750.6 5040.0 11790.6

Cu 10

Iqa

407.0 972.0 163.0 1038.0 341.0

73.0 709.0 162.0 1142.0 214.0 566.0

74.0 410.0

25.0

6296.0 6050.0 12346.0

Cu 14.3

Iqa

254.0 465.0

70.0 330.0

68.0

14.0

54.0

6.0

52.0

6.0

16.0

3.0

12.0

3.0

1353.0

153.0 1506.0

Cu 15.4

146.0 261.0

35.0 213.0

74.0

26.0 136.0

26.0 172.0

30.0

78.0

9.0

60.0

3.0

1269.0

696.0 1965.0

Cu 21.1

Iqa

116.0 244.0

39.0 244.0

74.0

35.0

62.0

7.0

38.0

3.0

11.0

3.0

7.0

3.0

886.0

114.0 1000.0

Cu 26.2

Iqa

165.0 379.0

60.0 410.0 152.0

43.0 324.0

75.0 526.0

96.0 254.0

33.0 193.0

12.0

2722.0 2487.0 5209.0

Cu 31

43.5

90.4

10.7

40.2

9.0

1.3

7.5

1.0

6.4

1.2

2.6

0.4

2.9

0.4

217.5

30.7

248.2

Cu 32

50.4 114.0

12.9

45.1

9.9

1.8

7.8

1.2

5.6

1.1

1.9

0.4

2.9

0.4

255.4

26.0

281.4

Cu 34

5.4

10.7

3.0

5.1

1.3

0.9

3.2

0.2

2.2

0.5

1.0

0.3

1.3

0.2

35.4

14.2

49.6

Hu 1

25.7

50.4

7.1

28.5

8.1

0.4

8.1

1.2

9.0

1.8

3.0

0.6

5.5

0.5

149.9

46.7

196.6

Hu 3

11.1

40.8

9.5

50.1

95.1

4.0 330.0

82.5 735.0 163.0 283.0

46.4 288.0

34.5

2173.0 4530.0 6703.0

Hu 4

48.0 101.0

18.0 124.0

86.0

5.8 390.8 101.0 860.5 172.6 509.5

69.8 397.7

54.4

2939.1 5210.0 8149.1

Hu 5

38.0

86.0

12.0 111.0

80.0

5.0 341.8

82.0 657.9 127.7 369.3

50.4 289.0

40.0

2290.1 4071.0 6361.1

Hu 6

24.0

42.0

6.0

48.0

3.4 261.5

74.0 596.1 119.3 352.5

47.5 258.2

36.4

1916.9 3926.0 5842.9

Kc 1

Bcq

34.0

85.0

4.0

26.0

5.3

1.1

4.3

0.8

1.1

0.4

1.9

0.3

164.2

Kc 8

495.0 990.0 103.9 438.0 130.9

24.9 140.0

15.9

93.8

17.0

26.2

3.9

37.7

3.3

2520.4

417.0 2937.4

Kc 66

Bcq

11.6

22.7

3.1

13.2

4.0

0.2

4.0

0.9

5.8

1.3

2.2

0.5

4.0

0.5

73.8

55.0

128.8

black phyllite, Bcq

lydite, G

granite, Iq

quartz vein, Iqa

quartz-apatite vein, R

metarhyolite, RT

metatuff of rhyolite

Table 7: Rare earth elements in rocks (in ppm).

notime accumulation with dominant HREE is distinctly differ-

ent from non-mineralized metatuff with dominant LREE

(Fig. 21).

The chemical composition of the rhyolite metatuff with

quartz veinlets near Betliar shows increased contents of CaO

and P

(over 2 weight percent) reflecting accumulation of

apatite (Table 5). The content of REE and Y exceed

1000 ppm (Table 7). Chondrite normalized REE distribution

patterns confirm increased LREE as well as HREE in sample

Be 3.4 (Fig. 22). A mineralized sample with quartz veinlets

near the Kociha village (sample Kc. 8) shows P

content

over 8 weight percent and Fe

content over 13 weight per-

cent reflecting abundant presence of iron hydroxides and

crandallite (?) (Table 5). Crandallite (?) also increases the

contents of LREE and Ba (Tables 2 and 3, Fig. 22). The tran-

sitional composition of crandallite-goyazite series is reflect-

ed in increased contents of Sr (Table 6). The increased con-

QUARTZ-APATITE-REE VEIN MINERALIZATION 225

tent of Y is related to the confirmed xenotime (Tables 6, 7).

Maximal content of REE attains 2520 ppm and Y 417 ppm.

Discussion

The REE frequently accompany elements of uranium min-

eralization. REE, especially heavy rare earth elements

(HREE) and Y, can substitute uranium in the uraninite struc-

ture (Pagel et al. 1987; Bea 1996). Part of xenotime can be

formed by release and remobilization of Y and HREE from

the structure of uraninite and brannerite and by reactions

with mobile phosphates (Oberthür 1987; Rojkoviè et al.

1997). There are numerous studies confirming the mobility

of REE during metamorphism, hydrothermal alteration and

the formation of shear zones. However, large fluid versus

rock ratios are necessary to cause changes of REE distribu-

tion pattern during regional metamorphism of silicates. Ret-

rograde shear zones characterized by abundant hydrous min-

erals appear to be extremely favourable for REE

mobilization (Lottermoser 1992). The mobility of REE, es-

pecially that of HREE is often associated with uranium trans-

port as carbonate complexes, uranyl fluoride complexes and

uranyl phosphate complexes. Uranium and REE were trans-

ported mostly by carbonate complexes even in a low temper-

ature, alkaline and oxidizing solution in the Pine Creek Geo-

syncline (McLennan & Taylor 1979). HREE are leached

more easily in an environment close to neutral (pH from 6 to

7) and light rare earth elements (LREE) in a more acid envi-

ronment (Shmaryovich et al. 1989). Easier mobility of Y and

HREE is also suggested by rims of newly formed xenotime-

(Y) rims around zircon in metamorphosed rocks (Vocke et al.

1987; Rojkoviè et al. 1989). Hydrothermal xenotime-(Y),

monazite-(Ce) and rutile accompany silicification, carbonati-

zation, potassium matasomatism and chloritization at the

Kidd Creek deposit in Canada (Schandl & Gorton 1991).

Quartz veins with REE-U and U-REE±Au mineralization

cutting the Early Paleozoic sequences of the Gemeric Supe-

runit show significant increase of U, Au, Cu, Pb, Ca, Y, P,

Th, Ag, Co, Sr, La and Mo compared to metamorphosed host

black shales (Fig. 23). This enrichment reflects the presence

of apatite, xenotime, monazite, uraninite, torbernite, gold,

chalcopyrite and pyrite in these veins. The distribution of

REE in quartz-apatite veins mostly reflects the presence of

dominant xenotime with higher proportion of HREE (Figs.

13, 20, 21). Prevailing LREE in the veins of the Kociha lo-

cality may reflect the increased ratio of carbonates in this

gangue comparing to other localities. According to experi-

mental data LREE show easier solubility in fluids rich in

O and CO

(Mysen 1979; Wendlandt & Harrison 1979).

The chemical composition of the non-mineralized Early Pa-

leozoic metamorphosed black sediments (phyllite and lydite)

shows a similar association of elements to the above men-

tioned one in the veins. The contents of Mo, C

org

, U, Pb, V,

Au, Co, Sn, P, Ag, Ca, Y, La and Cu are increased compared to

quartz-(chlorite)-sericite phyllite with a low content of organic

matter. The distribution of elements in black phyllite and ly-

dite reflects their different lithological control. The C

org

, Au, P,

V, Ag, Sn, U, Mo, Y, Ca, Pb, La and Si contents are higher in

lydite than in black phyllite. The increased contents of K, Na,

Al, Th, Sr, Ti, Co, Ba, Cu, Cr and B in the black phyllite corre-

spond to the presence of these elements in clastic or clay min-

erals. Cluster analysis of non-mineralized metamorphosed

black sediments of the Gelnica Group also confirms two asso-

ciation of elements. U, Y, La, Au and V show a close correla-

tion to SiO

, organic carbon and phosphates (CaO and P

)

in lydite (Fig. 24 ). Th, B, Mo, Sn and Cu on the contrary are

bound to Al

in black phyllite with detritic quartz and abun-

dant sericite and chlorite. The different behaviour of U and Th

is confirmed by the close correlation of Th/Al

and U/P

(Rojkoviè 1997). The distribution of REE also reflects the dif-

ferent origins of the black sediments. The black phyllites rep-

resenting metamorphosed near-shore clastic sediments show a

distribution where LREE are dominant. The ratio of HREE is

higher in the lydites representing off-shore sediments (Rojk-

oviè et al. 1995).

The REE-U mineralization in Èuèma and Betliar as well as

the U-REE±Au mineralization in other localities in the Early

Paleozoic sequences of the Gemeric Superunit show an evi-

dent spatial and partly also material relationship to the Ge-

meric Granite. The granite near Èuèma shows the highest

uranium content of the Western Carpathians granites, with up

to 25.4 ppm (Tréger 1972) and 21.0 ppm (Kátlovský 1982).

Fig. 24. Cluster analysis of elements in black phyllites and lydites

(n = 54, Rojkoviè et al. 1995).

Fig. 23. Enrichment/depletion of elements in veins with REE-U

mineralization/metamorphosed black sediments (n = 57 for Fe,

Mn, P, Al, Si K, Ca, Na and n = 175 for the other elements).

226 ROJKOVIÈ et al.

According to our analyses, the Gemeric Granite is rich in U,

Sn, Th and B (Fig. 25). In spite of its large isotopic heteroge-

neity, Rb-Sr dating of this granite gives, the time of intrusion

from 270 to 223 Ma and the younger (Cretaceous) ages cor-

respond to later post-intrusive alteration (Kovách et al. 1986;

Cambel et al. 1990). As a reliable U-Pb dating of vein miner-

alization is missing the Permian age contemporaneous to the

Rb-Sr dating of the granite can be taken into account.

Sediments with increased content of organic matter and ore

elements are the probable source of the studied mineralization.

A similar origin of the U-Au vein mineralization is described

from Hoehensteinweg in Germany (Dill 1982). Phosphates as-

sociated with metamorphosed black sediments especially ly-

dites with abundant organic matter were a probable source of

REE in veins (Rojkoviè et al. 1995). During the Hercynian

metamorphism siderite-sulphidic veins were formed in the

eastern part of the Slovenské rudohorie Mts. by mobilization

of Cu, Zn, Ni, Co, Ba, Fe

and Sn from black metapelites

(Grecula & Radvanec 1988). During the metamorphism and

by the hydrothemal activity in proximity to the granite intru-

sion REE-U vein mineralization was also formed.

The temperature of the studied vein REE-U mineralization

is presumed to be 330 to 220

C according to decrepitation

temperatures (Varèek 1975). The homogenization temperature

of fluid inclusions in quartz associated with U-REE-Au miner-

alization at Zimná Voda gives T

hom

from 450 to 300

C and

hom

from 280 to 240

C for quartz associated with younger

sulphides (Kotúlová in Rojkoviè et al. 1997). The texture of

minerals suggests as a primary association of quartz accompa-

nied by apatite, xenotime and pyrite. During weathering pro-

cesses REE-bearing minerals of crandallite series (crandallite

(?), goyazite and plumbogummite) were formed reflecting a

low pH and high content of total dissolved phosphate (Nriagu

1976; Dill et al. 1995). The best bonding to crandallite (?) in

Kociha locality shows Ce as was also observed in phosphate

mineralization in the Nuba Mountains of Sudan (Dill et al.

1991). Similar zonal variations in the micrometer range of

Fig. 25. Enrichment/depletion of elements in metamorphosed

black sediments/Gemeric granites (n = 100 for Fe, Mn, P, Al, Si K,

Ca, Na and n = 199 for the other elements). Data on non-mineral-

ized rocks outside the mineralized areas by Rojkoviè et al. (1995)

including data of Vozárová & Ivanièka (1993), Cambel & Walzel

(1982) and Matula et al. (1983) were calculated.

REE contents of authigeneous arsenates of crandallite group

have been found in the uranium accumulations in Cenomanian

sandstones in the Czech Republic (Scharm et al. 1991). REE-

bearing minerals of crandallite series represent secondary

products of oxidation accompanied by secondary uranium

phosphates (torbernite and autunite) and iron hydroxides.

Conclusions

1) The most important REE mineralization in the Early Pa-

leozoic rocks of the Gemeric Superunit occurs in quartz-apa-

tite veins near the village of Èuèma. There are less significant

concentrations near Betliar, Helcmanovce and Kociha villages.

2) The REE mineralization is represented by accumulation

of xenotime, accompanied by monazite, allanite, goyazite,

plumbogummite and crandallite (?) with increased content of

LREE. The REE mineralization is accompanied by apatite,

uraninite, brannerite, autunite, torbernite, quartz, pyrite, tour-

malime, rutile, titanite, marcasite, scheelite and goethite.

3) The contents of REE and Y in range from 0.1 to 0.8

weight percent and rarely exceeds 1 weight percent. The in-

creased proportion of HREE is due to the dominant presence

of xenotime.

4) Phosphates associated with metamorphosed black sedi-

ments were a probable source of REE in veins. The hydrother-

mal mineralization was formed by mobilization of ore and

REE elements during the metamorphism and by hydrothermal

activity in proximity to the Hercynian Gemeric Granite.

Acknowledgements: The study was partly supported by

grant VEGA 2/4078/97 and is contribution to IGCP Project

No. 373: Correlation, anatomy and magmatic-hydrothermal

evolution of ore-bearing felsic igneous systems in Eurasia.

This manuscript benefited greatly by the reviews of Prof. F.

Bea, Dr. I. Broska, Dr. I. Petrík and Dr. B. Scharm.

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