Investigation of fluorite from the Slavyanka deposit, Bulgaria as a material for application in the...

Investigation of fl uorite from the Slavyanka deposit Bulgaria as a material for application in the optics

Bogdana Zidarova

With 14 fi gures and 15 tables

Abstract From a geodynamic point of view the Slavyanka deposit belongs to a region of autonomous Alpine tectono-magmatic acti-vation namely the Ograzdenian block of Serbo-Macedonian massif It is a result of the activity of a paleohydrothermal gradient sys-tem Its spatial development has been controlled by the local structure-deformational pattern and the lithological situation determining the morphogenetic type of the deposit This is a case of vein-type deposit formation which is due to the presence of strike-slip faults (Central and Mikhaletz) as ore-bearing structures and tensile stresses The temporal evolution of the system has been controlled by the generation of discrete impulse post-volcanic hydrothermal activity fi xed by a four-stage release of the mineral-forming impulses The paleohydrothermal activity has been organized in convective cells of several orders hierarchically Temperature gradient the orienta-tion of the heat fl ow and the inhomogeneities in the local thermal fi elds determine the convective mass-heat transport which appear as zonality in the distribution of the fl uorite formation temperature and as regular variation of its constitutive peculiarities thus leading to a direction-dependent change of the fl uorite properties Inverse temperature zoning is caused by an upward heat fl ow in the deposit which had been shielded by Tertiary sediments while the strong fracturing of the underlying gneissic massif makes it a heat collector producing an inverse temperature gradient Directed and non-reversible variations in temperature concentration pH and Peq are the indicators of zone variation in the constitutional peculiarities of the fl uorite The mechanism of formation of fl uorite bodies depends on local peculiarities of the hydrothermal system namely the m ineral composition of the host rocks and the degree of their tectonic pre-treatment the degree of opening of the system chemistry of solution thermal gradient between the front of crystallization and the solution The hydrothermal solutions depositing fl uorite in this deposit have low salinity (below 1 NaCl-equivalent) pH ~ 6 rela-tively constant Eh Th100 ndash 200 degC (5 degC) and Peq from 1 to 20 MPa Most probably the fl uorite in this case came from a complex form Complexes of the type AlFn

3ndash play an important role as intermediate form for the fl uorine transport in an acid medium Their destruction in the presence of SiF6

2ndash and Ca2+ and in the solutions with pH ~ 6 leads to deposition of fl uorite alkalization of the solutions and subsequent deposition of montmorillonite and quartz The mechanism of growth of fl uorite crystals and aggregates on a microscale depends on the degree of opening of the hydrothermal system and on the equilibrium state in the crystal-solution system If the tem-perature gradient between the front of crystallization and the solution in an open system far for equilibrium exceeds certain extreme values (eg 22 degC as is the case in the Slavyanka deposit) synergetic effects are effective ie self-organization of the medium through dissipation originating from convective mass-heat transport in dissipative cells with polygonal cross-section of the front of crystalliza-tion (instability of Benar) These are revealed in the anatomy of growing fl uorite aggregates through specifi c dissipative structures The model proposed for the formation of fl uorite aggregates from the deposit is an alternative possibility to the mineralogical concepts for the growth of mineral aggregates which relates their structure with the dynamics of the forming medium In open hydrothermal sys-tems local variations in the concentration of Ca2+ and Fndash ions take also place along the front of crystallization The ratio of their activi-ties and the product of solubility determine the processes of dissolution (1) and regeneration (1) of fl uo-rite crystals and aggregates and refl ect in their zonal structure One can assume the zoned deposition of montmorillonite on the pyramids of crystal growth or along the front of crystallization of dissipative cells has resulted from self-vibration reactions of the solu-tion In a closed hydrothermal system under stagnant conditions taking place in some caverns due to gravity stratifi cation of hydro-thermal solutions local fl uctuations in their concentration have originated leading to the occurrence of aggregates of banded structure (the region Mikhaletz) Under such conditions though on rare occasions one can observe growth of fl uorite spherolites in colloidal media eg montmorillonite gels or water saturated masses of montmorillonite

This paper presents optical transmission spectra (OTS) of the main fl uorite varieties (I and II) from the Slavyanka fl uorite deposit and the single crystals grown there from by the method of Stockbarger These results are the basis for an examination and the express evaluation of the quality and homogeneity of natural raw fl uorite for the optical industry The zonal change of the constitutional pecu-liarities of the fl uorite is revealed by its indicator properties Most informative among them are the optical ones ndash photoluminescence (PLS) X-ray luminescence (XRLS) thermoluminescence (TLS) optical transmission spectra (OTS) as a consequence of the directed pass of the mineral-forming processes in the epithermal hydrothermal deposits It refl ects the directed and nonreversible change of temperature concentration рН and partial pressure of the dissolved in these gasses

Key words fl uorite fl uid-inclusion data rare-earth elements optical characteristics applications

2+ 2

2CaFCa F

[(a ) (a ) Ksp 1]

N Jb Miner Abh 1893 223 ndash 262 ArticlePublished online May 2012

copy 2012 E Schweizerbartrsquosche Verlagsbuchhandlung Stuttgart Germany wwwschweizerbartdeDOI 1011270077-775720120221 0077-775720120221 $ 1000

224 B Zidarova

1 Introduction

The Slavyanka fl uorite deposit is located in the crystal-line basement of SW Bulgaria and is a typical hydrother-mal vein deposit It was exploited for a period of about 50 years throughout the second part of XX century and was one of the most important industrial fl uorite depos-its in SE Europe Its geological structure and peculiarities of mineralization concerning some particular questions mainly in the Bulgarian language (ALEKSIEV amp PAVLOVA 1967 NECEV 1979 BONEV 1979 YUSHKIN 2002) and thus is practically unknown to the western scientists Fluorite from both the Slavyanka and the Mikhalkovo deposits (ZIDAROVA 2010 2011) are the topic of the present con-tribution

The present paper is an attempt to generalize the infor-mation on fl uorite from the Slavyanka deposit It aims to solve two linked problems 1) establishment of a theoreti-cal model for the dynamics of the mineral-forming pro-cesses within the whole deposit parts of it or separate bodies of a defi nite mineralogical variety 2) prognosis on the potential fl uorite reserves of the deposit according to the quantity of raw material which has been applied for traditional purposes as well as some of its genetically implanted properties with application in new high techno-logical industries as the optical industry (ZIDAROVA 2008) The interrelations between the indicator peculiarities and the optical properties of fl uorite allow a prognosis of the quality of synthetic CaF2 monocrystals as well as estima-tion of the crystal chemistry of the fl uorite as raw material according to its optical indicators The study gives an idea for the application of a defi nite type of natural raw mate-rial with preliminary given genetic properties during the later growth of synthetic optical quality crystals

2 Methodology

Mineralogical mapping on a large scale (about 550 m in the vertical interval between levels535 m and40 m) was carried out in the Slavyanka mine The texture of the veins their mineral composition and the spatial relations of fl uorite and its varieties have been marked on geologi-cal and mineralogical plans scaled 150 and on detailed cross profi les scaled 150 with an average distance of 10 m The fl uorite is divided into three main mineralogical varieties and each variety ndash into subvarieties and mac-roscopic typomorphic features that can undergo mapping have been studied namely texture anatomical crystal and morphological specifi cities colour paragenesis and disposition in the ore veins (ZIDAROV et al 1987) The pre-sent study is based on more than one thousand samples of

fl uorite from the Slavyanka deposit (ZIDAROV amp ZIDAROVA 2002) Fluid inclusions REE and optical spectra have been studied in the samples

480 measurements were carried out with a Reichert microscope complete with a Koumlfl er-type heating stage for fl uid-inclusion investigations The measurements were made on thin platelets polished on both sides were about 1 or 2 mm thick of fl uorite crystals sampled from various hypsometric levels (Table 1) The preliminary investiga-tion has shown that the volatiles in the inclusions are Н2О and СО2 (Table 2)

Some structural impurities of all the fl uorite varieties from all sites and mining levels of the Slavyanka deposit Rb Ва Sr (X-ray spectral analyses) and some REE (La Ce Sm Eu Tb Yb Lu with 60 and Dy with 26 samples ndash neutron-activation analysis) and Y Mn (semiquantitative spectral analyses) are determined

The dominance of REE2+ or REE3+ in the studied varie-ties of fl uorite is specifi ed according to the application of the following optical spectra obtained by photolumines-cence (PLS) X-ray luminescence (XRLS) thermolumi-nescence (TLS) optical (OS) and infrared (IRS) spectra of fl uorites from the Slavyanka deposit The analysis of the spectral results makes it possible to evaluate the phys-ical and chemical conditions of formation of crystals and aggregates All the spectral bands in the PLS XRLS and ТLS as well as ОS and IRS are due to an elevated content of RЕЕ U and Th which was determined by neutron-activation analysis

The photoluminescence spectra (PLS) of 150 fl uorite samples from various hypsometric levels and fl uorite va-rieties were investigated upon excitation by a mercury lamp Fluotest-universal in 254 and 366 nm (Table 7)

The X-ray luminescence (XRLS) of 200 samples from various hypsometric levels and fl uorite varieties was stud-ied in the range 250 ndash 800 nm (ZIDAROVA et al 1984) The results and reviews of KRASILlsquoSHCHIKOVA amp POVARENNIKH (1970) MARFUNIN (1975) TARASHCHAN et al (1975) PLA-TONOV (1976 ab) TARASHCHAN (1978) KRASILlsquoSHCHIKOVA et al (1980 1981) SMOLYANSKY (2002) were used in the interpretation of these curves

Thermoluminescence (TLS) of 200 fl uorite samples of fl uorite varieties I and II with the corresponding subvarie-ties from various hypsometric levels was studied in the temperature between 20 and 400 degC (ZIDAROVA et al 1984 ZIDAROVA 1989 1992 b) The curves of non-irradiated and of irradiated fl uorites were obtained (with Mo-anticatode 55 kw 18 ma and Cs137 radioactive isotope) which al-lowed the activation of a low-temperature maximum typical of fl uorite from hydrothermal deposits (Table 10) The papers of VASILrsquoKOVA amp SOLOMKINA (1965) TARASH-CHAN et al (1974) TARASHCHAN (1978) KRASILrsquoSHCHIKOVA

225Investigation of fl uorite from the Slavyanka deposit Bulgaria

et al (1986) were used in the interpretation of the thermo-luminescence curves

Optical spectra of transmission (OTS) and absorp-tion (OAS) of 60 parallel polished platelets of differently coloured fl uorite varieties were carried out by a Specord UV-VIS spectrometer in the 200 ndash 800 nm spectral range A microscope NU-2 E equipped with a special attachment was used in the spectral range of 400 ndash700 nm (ZIDAROVA et al 1984) in order to study in detail the optical spectra of single as well as of polychrome-zoned fl uorites (Table 12)

Optical density was also studied with microphoto-metric studies in selected zonal fl uorite samples in the

direction from the salband to the center of the vein cor-responding to the growth direction with a graphic im-age representation of the zonality (ZIDAROVA et al 1984 ndash Fig 2 ZIDAROVA 1995 b ndash Fig 2) The measurements are done using a scanning semiautomatic densitometer with additional treatment of the obtained microphotograms with the help of an EVM ES-1022 (programme ldquoZon-ingrdquo) according to the methodology described by KALIKOV (1982) Both mineral slices and their photo images were applied to photometry

Sixty fl uorite samples from various hypsometric levels and fl uorite varieties were studied by infrared spectrosco-py (IRS) both in two different manners ndash on thin platelets

Fig 1 Geological map of the Slavyanka fl uorite deposit (after N Zidarov unpubl) 1 ndash Quaternary (Alluvium) 2 ndash 4 Delchevo Formation (Middle Miocene) 2 ndash sandstones 3 ndash hydrothermally altered argillaceous sandstones and clays 4 ndash argillaceous sandstones clays conglo-merates 5 ndash7 Ograzden Supergroup Maleshevska Group (Precambrian) 5 ndash two-mica gneisses 6 ndash biotite gneisses 7 ndash amphibolites 8 ndash11 Faults 8 ndash observed 9 ndash observed only in the metamorphic basement 10 ndash with industrial fl uorite (already out of exploitation) 11 ndash with probably industrial fl uorite 12 ndash sites with fl uorite veinlets

226 B Zidarova

polished on both sides and on settled down suspension on a pad (КBr or CsJ) depending on the studied region of the spectrum The investigations were made on a Carl Zeiss UR-20 (in range 200 ndash 4000 cmndash1) (ZIDAROVA et al 1984)

3 Geological setting

The Slavyanka deposit is situated on the eastern slopes of the Maleshevska mountain in SW Bulgaria From the structural point of view the region belongs to the Ograzh-den block of the Serbo-Macedonian massif which lies to the eastern part of the Struma depression (ZAGORCEV 2001) The block consists of migmatised two-mica bio-tite and muscovite gneisses (metagranites) in alternation with amphibolites and amphibole schists covered by Miocene sediments (Fig 1) Slavyanka is a hydrothermal quartz-fl uorite deposit of vein type and is a representative for the so-called Fluorite Formation The veins intersect metamorphic rocks and sediments thus dating them to be younger than the Middle Miocene

4 Results

41 Fluorite mineralization

The fl uorite mineralization in the deposit is localized along the Central and Mikhaletz faults (Fig 1) The mor-phology and texture of the quartz-fl uorite veins embedded have been described in detail by NECHEV (1979) ZIDAROVA amp KOSTOV (1979) ZIDAROV et al (1987) ZIDAROVA (1989) ZIDAROVA amp ZIDAROV (1995 b)

The quartz-fl uorite mineralization is represented as non-uniform veins nests and lenses which are located in a large tectonic zone (Central ore-bearing fault) includ-ing a series of subparallel and oblique fi ssures The tec-tonic movements in the zone have been pre-ore intra-ore and post-ore which result in its complex morphology and non-uniform distribution of the mineralization Open fi s-sures (caverns) formed by upthrow and strike-slip fault movements in the plane of the S-shaped bended salbands are typical Frequent are veins with asymmetric structure caused by the several openings of the tectonic fi ssures from the direction of the upper salband (ZIDAROV et al 1987) The maximum number of detected caverns during the mapping is 78 with a length from 05 to 19 m and a width from 05 to 20 m dipping from 60deg to 90deg

The asymmetric fabric of the vein salbands has been controlled by the reopening of the faults and the succes-sive deposition of minerals

The hydrothermal mineralization products are of rela-tively simple composition namely fl uorite quartz mont-

morillonite and rarely calcite Small amounts of pyrite pyrrhotite graphite hydromica barite and adularia have been sporadically observed

The recently formed minerals from vadose water cir-culating along the ore veins and tectonic fractures consist of fi ne-needle gypsum marcasite pyrite iron hydroxides and rarely calcite (YUSHKIN 2002)

For the detailed study of the structure of the quartz-fl uorite veins in the mine and for the characterisation of the mineralogical fl uorite varieties a profi ling with a step of about 10 m across the elongation of the veins was per-formed The veins were sampled and described between the two salbands along the walls and the top of the galler-ies as well as in some accessible chimneys (Fig 2) The structure mineral composition and the relationships be-tween different minerals and their varieties (ZIDAROV et al 1987 ZIDAROV amp ZIDAROVA 1989 ZIDAROVA et al 1992) have been described in detail and sketched in a scale 110 (Fig 2) Lateral variation in the mineralization was con-trolled by additional profi ling and sampling with a dis-tance of 2 m

Technologic semi-industrial and laboratory samples were collected in the region of the profi les of the sepa-rated monomineral fl uorite bodies The profi les are instru-mentally related to the mine plane scaled 150 that was used as a basis for the mapping

According to the mineral composition and structural peculiarities the deposit belongs to the quartz-fl uorite type of the Fluorite Formation (IVANOVA 1981 IVANOVA et al 1986 ZIDAROVA amp ZIDAROV 2004)

42 Mineral-forming process

The mineralization process has developed during four distinct impulses of hydrothermal activity ndash one type of pre-ore (hydrothermal alteration of the rock around the faults) and three types of ore (with separate mapped fl uorite varieties I IIа IIb and IIc) (ZIDAROVA amp ZIDAROV 1995 а b 2006)

I impulse (pre-ore stage) ndash alteration of the embedding rocksndash in biotite gneisses and amphibolites ndash chloritization

muscovitization sericitization silifi cation andsporadic pyritization (more intense in the lying wall and in the proximity of the fractures)

ndash in the clastic sediments with quartz-adularia impregna-tion and large-fl ake muscovite

II impulse (fl uorite stage) ndash the hydrothermal solutions possessed a different composition Preliminary deposition


of scalenohedral calcite in quartz (negative forms) and then montmorillonite (indication of the alkalinity of the medium) indicate high concentrations of Ca2+ and H2CO3 or products of its dissociation In addition complexes of the type MeFn

3ndashn (MeAl Si) in the solution probably ex-isted being formed during the dissolution of plagioclases and amphiboles If the pH6 it will follow the paths

AlF2+OHndash rarr AlOH2+Fndash (1)

SiF62ndash4OHndash rarr SiO26Fndash2H2O (2)

The interaction of these compounds resulted in depo-sition of montmorillonite Calcite had dissolved due to an increase in the solution acidity With increasing of the

concentration of Ca2+ ndash the fl uorite mineralogical variety I has been deposited as follows

3CaCO3Na2SiF62HClnH2O rarr 3CaF2 SiO22NaClH2CO3nH2O (3)

A1F+2 Ca2+ rarr CaF2Al3+ (4)

III impulse (fl uorite stage) after tectonic movements and brecciation montmorillonite enclosed in grey to black chalcedony quartz has been deposited

2NaAlSi3O82FndashnH2O rarr Al2[Si4O10]xnH2Oalbite montmorillonite 2NaF2SiO2 (5)

Fig 2 Geological and mineralogical plan of fragments from the Central fault (A and B) from Mikhaletz fault (C and D) and correspondi-ng geological sections of the fl uorite zone (E and F) Legend Mineralogical varieties of fl uorite 1 ndash I 2 ndash II 3 ndash III quartz 4 ndash combed replacing calcite 5 ndash dark-grey chalcedony-like 6 ndash white and greyish-white 7 ndash montmorillonite tectonic breccia of hydrothermally altered gneiss with 8 ndash quartz-fl uorite cement 9 ndash quartz-fl uorite-montmorillonite cement hydrothermally altered 10 ndash biotite muscovite and two-mica gneisses 11 ndash cavity elements of 12 ndash faults and fl uorite veins 13 ndash crystalline schistosity 14 ndash main cross-section number 15 ndash section thickness of the sampled wall

228 B Zidarova

Sporadically deposited calcite is the result of the in-crease in the concentration of Ca2+ and H2CO3 The NaF formed in (5) has led then to the dissolution of quartz

SiO2 6NaF4HClnH2O rarr Na2SiF6 4NaClnH2O (6)

Na2SiF6 has interacted with CaCO3 (3) thus producing the main amount of fl uorite in the deposit (fl uorite miner-alogical variety II)

IV impulse (fl uorite stage) ndash after an interruption the last evidence of hydrothermal activity is deposited montmo-

Fig 3 Textures of fl uorite aggregate (andashf) ndash polished sections


Fig 4 Fluorite from the Slavyanka deposit I ndash variety IIc 2 ndash variety I 3 ndash variety IIIa 4 ndash variety IIb 5 ndash variety IIc 6 ndash variety III

230 B Zidarova

rillonite followed by white granular fl uorite The hydro-thermal activity in the deposit has been terminated by the deposition of masses of gelous montmorillonite into the empty caverns

The fl uorite mineralization is distributed into two main fl uorite varieties with subvarieties The fl uorite from the productive parts of the deposit is divided into fl uo-rite varieties according the following criteria sequence of deposition (Fig 3a c d) crystal-morphological and anatomical peculiarities colour mineral paragenesis and spacial localization in the deposit (ZIDAROV et al 1987 ZIDAROVA 1989)

Mineralogical variety I It is represented by green to grey-ish-green fl uorite which builds dense aggregates with oc-tahedral crystals in their cavities (Fig 4-2) The surface of these crystals shows a mosaic structure This type is related to the earliest mineral-forming impulse of the hydrothermal activity and is always deposited in the sal-bands of the ore vein as a band exceeding 2 ndash 3 cm thick-ness (Fig 4-3) Dark grey chalcedony-like quartz (band 2 ndash 3 mm thick) is as underlying fl uorite variety I White fi ne-grained quartz replacing platy aggregates of calcite is very often observed in the zone between chalcedony quartz and the host hydrothermally altered wall rocks At the end of the fi rst mineral-forming impulse platy aggre-

gates of calcite which are partially replaced by quartz are deposited

Mineralogical variety II This fl uorite variety represents the main volume of the fl uorite mineralization in the ldquoVodena skalardquo site (Fig 4-3 4 5) and is deposited dur-ing the second mineral-forming impulse It is found upon the green fl uorite variety I (Fig 4-3) or directly upon the altered rock or upon the chalcedony quartz (Fig 4-3 4) Its colour varies from dark-violet through violet (purple) pale violet up to rose and white The change in colour is observed both along the vein and its cross-section Usu-ally fl uorite is darker in the salbands compared to that in the central parts This variety is subdivided into 3 subva-rieties according to its colour intensity and structural fea-tures The fl uorite subvarieties IIа is dark-violet forming aggregates with striped texture and fl at surface Fluorite subvariety IIb is violet to purple semi-transparent with pronounced zonality with a cellular structure ndash smalls and thickly situated or narrow and high cells which are unifi cated in V-shaped individuals terminated with small comparatively fl at domeins The fl uorite subvariety IIc is violet pale violet to colourless semi-transparent ho-mogeneous compact with poorly developed zoning The growth continued without a break from fl uorite subvariety IIb or is independently deposited

Table 1 Distribution of average Th o C in fl uorite varieties from the Slavyanka deposit

Fault Site Level m Th degC of the fl uorite varietiesIa Ib IIa IIb IIc

Central Vodena skala 40 1695 1475 1423 1205 985 80 1725 1505 1453 1235 1015110 1745 1525 1473 1255 1035145 1775 1555 1503 1285 1065370 1955 1735 1683 1465 1245

Baba 500 2065 1845 1783 1575 1355Mikhaletz Venetza 350 1985 1765 1713 1495 1275

Mikhaletz 385 2015 1795 1743 1525 1305

Table 2 Results from the analysis of fl uid inclusions in the fl uorite varieties from the Slavyanka deposit

Variety I IIa IIb IIc

Level m 145 145 350 500 110 145 80 110 145 385 370Colour green green green green dark-violet dark-violet violet violet violet violet violetNumber 91 52 128 65 19 1 19 1 1 5 2Тh

о С 156 177 195 186 147 153 123 126 135 152 114Н2О mgg 634 835 18320 10010 81 81 121 151 101 121 35CO2 mlg 045010 048010 025005 0500100 031007 035010 028005 023005 024005 019005 01CO2 molкg 032 026 006 011 170 190 100 068 110 075 13Peq МРа 37 32 1 15 ~50 ~100 15 9 18 10 18Рhydr МРа 35 35 15 01 40 35 45 40 35 14 13


The fl uorite variety II is deposited as layers in lying salband (Fig 3e) or as aggregates with dissipative tex-tures in hanging salband (Fig 3f) It is deposited at the time of the third mineral-forming impulse

Mineralogical variety III The fl uorite from this variety is yellow-white coarse-grained (Fig 4-6) Its aggregates are constituted by fi ne idiomorphic transparent and colour-less cubic crystals which have formed small clusters It occurs sporadically usually as thin 2 ndash 3 mm crust depos-ited upon fl uorite variety II It is deposited at the time of the fourth mineral-forming impulse

Similar textures of the fl uorite variety I (Fig 3a-d) are observed and described by other authors (Strong et al 1984 ndash Fig 3a-d)

43 Fluid inclusion data

In order to investigate the changes in temperature and composition of the mineral-forming fl uids the tempera-ture of homogenization (Th degC) and the composition of fl uid inclusions in various fl uorite varieties in the Slavy-anka deposit were determined (Table 1 and 2)

The fl uid inclusions in fl uorites are inhomogeneously distributed the inclusion-richest being the early green fl uorites (variety I) Most of the inclusions are primary tetrahedral or cubic in form 10 ndash 30 m sometimes up to 100 m in size and contain a water phase and gas bubble Th degC are reported previously and they are in the range 100 ndash 200 degС (5 degС) (ZIDAROVA amp KOSTOV 1979 ZIDARO-VA 1989) In the violet fl uorites inclusions are very scarce and this turns out to be a very serious obstacle in their study Reverse spatial and direct temporal temperature zonalities has been observed ndash the Тh degС variation of crys-tallization of fl uorite from the upper level (level 500 m) to the lower level (level 40 m) in the deposits (Table 1) and from the salband to the centre of the vein (ZIDAROVA 1989 ZIDAROVA amp PIPEROV 1995)

Temperature pulses occurred with a step of about 225 degС between the separate portions of mineral-form-ing solutions In each pulse they correspond to a temporal pulsation in their entrance and thus control the mechanism of the fl uorite growth The vertical temperature gradient (T) of fl uorite deposition in the deposit is 01 degСm

Such a reverse zoning is most frequently observed in the fl uorite deposits so that is should be regarded rather as a direct one (ARKHIPCHUK amp LOKERMAN 1966 ARKHIPCHUK et al 1968 KOPLUS et al 1968 KORYTOV 1972 PUZANOV 1972 ZIDAROVA 2011) Therefore the richest parts of the deposits are in the lover levels when the temperature zon-ing is reverse in the sections of highest temperature of homogenizations (KOPLUS et al 1968)

431 Reconstruction of the temperature regime and composition of the mineral-forming fl uids

The spatial distribution of Th degC compared to the relative-ly small depth of formation of the deposit (50 ndash 500 m) displays a signifi cant discrepancy with the temperature of the hydrothermal solutions calculated by the geothermal gradient with values corresponding to the contemporary thermal fl ow with high intensities ndash74 ndash 83 mWmndash 2 (VE-LINOV 1986) It can not depend only on the temperature of the hydrothermal solutions Without a preliminary or si-multaneously warming up of the rock massive a relatively constant temperature of the solutions along the structure with the size of the Central fault can not be supported It can be caused by the late Alpine magmatism related to the intrusion of dykes and subvolcanic bodies in the re-gion (IVANOV amp ZIDAROV 1968 PECSKAY et al 2001) or by thermal transfer along the faults in this active tectonic re-gion and especially on the sides of the Struma depression Indirect proof for the later is the abnormal temperature in part of the deposit (NECHEV 1979)

The total salinity of mineral-forming solutions in the 29 fl uid inclusions has been evaluated by microcryometry using a home made freezing stage (PIPEROV et al 1979 1986) A single solid phase (ice) is obtained in all cases and this phase melts at Тf from ndash 04 degС to ndash10 degС corre-sponding to a total salinity12 wt equiv NaCl

To extract the volatiles both heating and grinding in vacuum were used by the one of the variants of the ther-mal analysis (EGA) described in detail by PIPEROV (1984) The preliminary investigation has shown that at 550 degС the volatiles in the inclusions are represented only by Н2О and СО2 with some СО N2 and lighter hydrocarbons (mainly СН4) The results for СО2 include the free СО2 as well as СО2 from the destruction of HCO3

ndash and the experi-ments show that only Н2О and СО2 are defi nite composite parts of the fl uid inclusions while the rest of the volatile components are by-products (ZIDAROVA amp PIPEROV 1995)

The obtained low salinity and the calculated absolute values of СО2 make it diffi cult to estimate of the atti-tude СО2HCO3

ndash and the existence of free СО2 cannot be proved (PIPEROV et al 1986)

If it is assumed that all the СО2 is free the comparison of the equilibrium pressures (ZIDAROVA amp PIPEROV 1995 ndash Peq in Table 2) calculated from the solubility of СО2 in water at the corresponding Тh degC (by data of TAKENOUCHI amp KENNEDY 1964) and the hypsometric levels of the stud-ied fl uorites indicate that solution is saturated in СО2 for most samples of the fl uorite variety I These data show a good concurrence with the calculated hydrostatic pressure (Рhydr) (ZIDAROVA amp PIPEROV 1995 ndash Рhydr in Table 2) when it is assumed that the palaeorelief has not undergone sig-nifi cant changes Fluorite varieties II are relatively poor

232 B Zidarova

in inclusions and that is why the data for them are uncer-tain They show even higher СО2Н2О relations and give the opportunity for the possible existence of a free gas phase in the upper horizons (Table 2)

Some geological and mineralоgical observations are also indicative for relatively high СО2 concentrations and for the existence in the high horizons of a СО2-bearing gas phase (degassing effervescence) Thus for example the argillitization of the host rocks caused by the penetra-tion of aggressive hydrothermal fl uids in the tectonic fi s-sures has infl uenced selectively the hanging salband (NE-CHEV 1979) which can be explained with the asymmetric movement of gas bubbles along the veins

On the basis of the data obtained for the composition of the mineral-forming fl uids it was found that the fl uor-ites had been formed from solutions saturated with СО2

This allows the supposition of the existence of a free gas phase in the uppermost levels Their composition indi-cates a formation under the strong infl uence of the embed-ding rock The transport of the various compounds in the solutions depends mainly on their temperature pH and concentration

During a high degree of open hydrothermal system (as in the case with the Slavyanka deposit) and at a sup-ply of heat and substance in it the ore-conducting struc-ture has been relatively uniformly and well heated As a result the deposition of fl uorite from each portion of the solution during its movement towards the surface will take place close to the isothermal conditions If their con-dition is far from the equilibrium and in case of diffi cult thermal mass transfer on the front of crystallization (heat release) characteristic dissipative structures can form in the solution being sealed in the growing aggregate (ZIDAROVA 1989 ndash Fig 9 1995 b) As a result an increase of the alkalinity of the solutions can be expected espe-cially if the СО2 has been separated by degassing ndash a phenomenon which has been already described (ZIDARO-VA amp PIPEROV 1995) The accumulation of volatiles in the upper part of the Central fault with a more or less stockwerk character as reported also by VASILrsquoKOVA et al (1980) can be one of the causes for additional heating of the upper parts of the deposit shielded by Neogene clays and sandstones with a low thermal conductivity In such an environment the conditions are favourable for heat transfer along the faults and its evolutionary deposition in slightly lithifi ed covering sediments (VELINOV 1986) It must also be taken into account that the coeffi cient of thermal supply of the hydrothermal system in the host rocks is linked to the area and the form of the horizontal section of the hydrothermal fl ow with the thermal sup-ply оf the system with a larger area of horizontal section taking place slower than in the case of a system with a

smaller crosswise section (KAZANSKY et al 1978 MA-LINOVSKY 1982) In the present case this is refl ected in the additional and continuous heating of the upper part of the hydrothermal system where numerous apophyses and fi ssures are formed along the Central fault (ZIDAROV et al 1987 ZIDAROVA 1989)

The heat-mass-transport in the formed thermal-gradi-ent hydrothermal system have been probably realized by a convective mechanism The pulsations in the fl uid tem-perature has been probably controlled by the periodic var-iations in the system drainage basis related to the stages of tectonic activity and respectively to rise of the block with an accompanying decrease of the heat fl ow energy

432 Composition of the contemporary underground waters

The mineral waters which have sources nearby and in the deposit (Table 3) as well as the waters circulating in the its region despite of their mixed character (meteoric and juvenile solutions which have been identifi ed by the isotopic content of the noble gases in them (PIPEROV et al 1987 1994) can be accepted approximately as a model for the ionic composition of the hydrothermal solutions As seen from Table 3 the difference between these waters and the hydrothermal solutions is mainly in the T pH andPCO2

but as hydrocarbon-sodium they correspond to the composition found in the fl uid inclusions of the fl uorites in the deposit (ZIDAROVA amp PIPEROV 1995)

The calculated relation between the activities of the fl uorine and carbonate ions (ZHOVINSKY 1985) (Table 3) shows that at present fl uorite is also de-posited from some of the waters because of the high con-tent of fl uorine ions in them These data correspond to the necessary condition for fl uorite deposition

The relation of the solubility products (Ksp) cal-culated after the data of ZHOVINSKY (1985) is KspCaF2KspCaCO3 4010 ndash118710 ndash 9 4610 ndash 3 calcite or aragonite (from Kozuh) is deposited from waters where the equilibrium is shifted to carbonate formation (ZIDARO-VA amp PIPEROV 1995)

The processes do not depend on P (1ndash 500 bars) but increase of their velocity and are proportional to T (up to 200 degС) and the concentration of fl uorite in the solu-tion (ZHOVINSKY 1979) As is evident in Table 3 in de-pendence that whether the relation between the activities of CO3

2ndash and Fndash is4610 ndash 3 ndash fl uorite will form and if it is4610 ndash 3 ndash calcite it will deposit The same case was observed in the Mikhalkovo deposit (ZIDAROVA 1989 2010)

23

2F CO

(a ) a

3 2 3

2 2CO CaF CaCOF

(a ) (a ) Ksp Ksp


The hydrothermal solutions depositing fl uorite in the deposit have been of low salinity (below 1 NaCl equivalent) pH ~ 6 relatively constant Eh Рeq from 1 to 20 МРа Тh100 ndash 200 degС (5 degC) They are comparable to the major physical and chemical parameters of natu-rally forming fl uids described in database information for 21 minerals including fl uorite (NAUMOV et al 2009) Most probably the fl uorite therein has been in a complex form Most probably the complex of the type A1Fn

3ndashn plays an important role as an intermediate form Their destruc-tion in the presence of SiF6

2ndash and Ca2+ in the solution at pH ~ 6 (ZIDAROVA 2010) leads to deposition of fl uorite alkalization of the solution and subsequent deposition of montmorillonite and quartz

44 REE geochemistry

Besides the main components ndash Ca and F other trace ele-ments are distinguished in natural fl uorites their compo-sition and distribution infl uenced by the host rocks as well as by their formation mechanisms

The non structural impurities determining the chem-istry of the fl uorite from the Slavyanka deposit are these with a composition linked to incorporation of microscop-ic particles of foreign mineral phases fl uid inclusions and sorption ions in the defect parts of the fl uorite structure

In the studies of several authors (ALEKSIYEV amp PAV-LOVA 1967 ZIDAROVA amp KOSTOV 1979 KRASILrsquoSHCHIKOVA

et al 1986 ZIDAROVA 1989) Rb Sr Ва Mn U Th Y and RЕЕ have been proven in fl uorite as structural impurities Their composition and type of incorporation has signifi -cant infl uence on some of the physical properties of fl uo-rite They are determined in order to fi nd the most effec-tive industrial application of fl uorite

The Rb contents in all fl uorite varieties and each levels is almost one and the same and within limits from 29 to 37 gt The Ba contents in fl uorite variety I is lower (from 88 to 142 gt) than fl uorite variety II (from 208 to 322 gt) The same trend is observed for the Sr (Table 4) Similar regularity also in the others fl uorite deposits was observed (RENTZCH 1958) Simultaneously the content of the Sr is almost one and the same in each fl uorite subvarieties ir-respective at the levels

Table 3 Temperature pH and chemical composition of waters fl owing in gneisses around and into the Slavyanka deposit and the products deposited

Location of the water source

Type of waterndashbearing rocks

Т degС рН Ion composition equiv

F mgl References Deposition product

Kozuh gneisses 62ndash77 710 350 Petrov 1964 18310 ndash 3 carbonate

Slavyanka gneisses 20ndash25 709 580 Nechev 1979 103010 ndash 3 fl uorite


Slavyanka gneisses 22 805 249 Zidarova 1989 23910 ndash 3 carbonate



23

2F

CO

(a )a

3 486 10 4

90 7 3

HCO SO Cl

(Na+K) Ca Mg

3 474 19 6

64 24 7

HCO SO Cl

(Na+K) Ca Mg

3 478 16 5

64 27 10

HCO SO Cl

(Na+K) Ca Mg

3 475 17 5

94 4 2

HCO SO Cl

(Na+K) Ca Mg

3 3 419 573

90 9 1

+CO )(HCO SO Cl

(Na+K) Ca Mg3 478 15 5

91 8 1

HCO SO Cl

(Na+K) Ca Mg

Table 4 Content of Sr (gt) in fl uorite varieties from the Slavyanka deposit

Site Level m Ia Ib IIa IIb IIc

Vodenaskala

110 88 230 255145 90 215 260 276

253258

190 ndash 240 142 240Venetza 350 121 230Vodena skala 370 208 243 322Mikhaletz 385 90 213 275

234 B Zidarova

Tabl

e 5

REE

dat

a of

the fl u

orite

var

ietie

s fro

m th

e Sl

avya

nka

depo

sit

No

Site

Loca

tion

Leve

lm

Varie

tyC

olou

rC

onte

nts

ppm

LaC

eSm

EuTb

Yb

LuR

EЕLa

Yb

TbY

bEu

Eu

Ce

Ce

3Vo

dena

skal

am

ain

lode

80

Igr

een

6

51 1

104

3

41

146

2

18 3

03

07

5 2

838

21

50

720

830

63 6

mai

n lo

de 8

0I

gree

n

937

16

85

524

1

91

351

42

6 0

92

42

06 2

20

082

069

067

8ap

ophy

sis

80

Igr

een

8

90 1

499

4

72

224

2

85 4

56

126

6 5

092

19

50

630

940

6411

apop

hysi

s 8

0I

gree

n 1

318

25

71

531

3

17

297

53

211

75

67

41 2

48

056

121

073

13m

ain

lode

80

Igr

een

9

66 1

829

3

55

272

2

55 3

65

07

7 4

119

26

50

701

430

7722

extr

chu

te11

0I

gree

n

625

11

53

356

1

82

265

39

2 1

25

30

98 1

59

068

094

069

28m

ain

lode

110

Igr

een

17

25 2

696

5

08

192

0

60 3

73

04

8 5

602

46

20

161

300

6837

mai

n lo

de14

5I

gree

n

602

3

38

315

1

16

134

09

5 0

51

16

51 6

34

141

080

021

38lo

de 1

90-

Igr

een

18

68 3

982

6

38

285

3

04 4

01

12

7 7

605

46

60

760

960

8739

fi llin

g24

0I

gree

n 3

044

40

60 1

220

3

34

156

62

0 1

20

95

57 4

91

025

094

054

42Ve

netz

am

ain

lode

350

Igr

een

49

70 7

433

8

62

319

1

55 4

92

08

114

312

101

00

321

100

7047

Vode

na sk

ala

mai

n lo

de38

5I

gray

ish-

gree

n

219

5

03

264

0

90

249

55

9 1

76

20

60 0

39

045

057

073

49m

ain

lode

385

Igr

ayis

h-gr

een

6

30 1

278

6

36

215

5

5412

47

44

6 5

000

05

10

440

430

6955

Mik

hale

tz38

5I

gree

n

980

10

75

027

0

20

069

20

7 0

34

24

12 4

73

033

088

076

59B

aba

500

Ida

rk-g

reen

14

80 1

858

5

80

150

2

74 3

03

05

2 4

697

48

80

900

550

5060

500

Ipa

le g

reen

23

10 2

138

3

80

054

0

77 1

74

05

4 5

187

132

70

440

400

4416

Vode

nask

ala

mai

n lo

de 8

0II

ada

rk-v

iole

t

522

12

40

857

1

60

292

115

0 1

87

44

08 0

45

025

045

070

25m

ain

lode

110

IIa

dark

-vio

let

8

20 1

735

10

42

365

10

3617

41

13

4 6

873

04

70

600

590

6629

mai

n lo

de11

0II

ada

rk-v

iole

t

654

20

60 1

005

2

20

480

198

0 2

12

66

11 0

33

024

047

094

36m

ain

lode

145

IIa

viol

et

115

5

06

146

0

40

080

57

0 1

05

15

62 0

20

014

055

145

57M

ikha

letz

385

IIa

dark

-vio

let

5

30 1

430

6

40

139

8

1315

06

24

0 5

298

03

50

540

340

86 9

Vode

nask

ala

apop

hysi

s 8

0II

bvi

olet

1

56

320

2

61

104

2

81 5

77

178

0 3

479

02

70

490

640

6212

apop

hysi

s 8

0II

bvi

olet

4

48 1

224

4

41

180

3

76 5

24

13

7 3

330

08

50

720

690

9020

mai

n lo

de 8

0II

bpa

le v

iole

t

033

1

03

032

ndash

038

09

6 0

27

3

29 0

34

040

ndash1

0530

mai

n lo

de11

0II

bvi

olet

1

60

307

1

70

020

0

55 3

66

04

7 1

125

04

40

150

290

6443

Vene

tza

350

IIb

viol

et

324

4

88

142

0

27

139

41

1 0

77

16

08 0

79

034

031

059

48Vo

dena

skal

am

ain

lode

385

IIb

viol

et

672

13

43

649

2

02

490

93

6 3

26

46

18 0

72

052

063

066

50m

ain

lode

385

IIb

viol

etis

h-bl

ue

398

7

16

266

1

70

181

40

0 1

33

22

64 0

99

045

123

065

51m

ain

lode

385

IIb

viol

et

205

9

52

501

1

40

542

114

0 3

73

38

53 0

18

048

045

132

53m

ain

lode

385

IIb

pale

vio

let

0

79 ndash

1

99

091

2

32 4

52

20

2 1

255

01

70

510

73ndash

54m

ain

lode

385

IIb

pale

vio

let

4

55

999

2

37

134

1

97 3

23

11

2 2

457

14

10

611

010

8156

Mik

hale

tz38

5II

bpa

le v

iole

t

048

0

88

077

0

54

047

18

0 0

23

5

17 0

27

026

134

055

5838

5II

bpa

le v

iole

t

031

10

25

034

0

20

012

03

2 0

13

11

67 0

97

038

138

150


The Y contents in fl uorite variety I reach 300 gt while in fl uorite variety II the minimum content is 00005 and higher average content -00033 ie a trend for augmentation of the content of the Y from earlier to later subvarie-ties of the fl uorite variety II is observed In the fl uorite of Mikhaletz zone the Y contents is higher to considerably (ZIDAROV et al 1987) This result is well correlated with data by laser mi-croscopy analysis (ZIDAROVA 1995 b)

The Mn content spans from 10 to 60 gt and is higher in the fl uorite va-rieties II

The REE content ndash La Ce Sm Eu Tb Yb Lu in 60 fl uorite samples and Dy in 26 fl uorite samples from the de-posit is determined (Table 5) The data on the absolute and relative concentra-tions of REE may be used for genetic reconstructions The obtained data tes-tify that the REE of fl uorite variety I is more than REE of fl uorite variety II The fl uorite from the Slavyanka de-posit shows considerable variation in REE content with the concentration ranging from 001 to 14312 ppm This variation is not unexpected even ex-hibits considerable variation in REE composition from hydrothermal de-posits Using the criterion of Vilkokson (in GMURMAN 1977) it was proven that both the main fl uorite varieties belong to different classes (ZIDAROVA amp KOS-TOV 1979 ZIDAROVA 1989)

The content and statistical param-eters of the REE in the fl uorite varie-ties (Table 6) shows that the range (хmin ndash xmax) is bigger in fl uorite varieties I and the square medium mistakes on the arithmetic medium and interval confi de on the general medium are considera-ble less and narrow towards the fl uorite varieties II

Histograms for the distribution of the studied REE have been made (ZIDAROVA amp KOSTOV 1979 ndash Fig 3 ZIDAROVA 1989 ndash Fig 15) with a wide-ness of the interval determined by Ste-gerrsquos formula

KXmax ndash Xmin132 lgn1Vo

dena

skal

am

ain

lode

40

IIc

viol

et

003

ndash

012

ndash

015

03

2 0

07

0

70 0

09

047

ndashndash

2m

ain

lode

40

IIc

viol

et ndash

ndash

001

ndash ndash

ndash ndash

0

01 ndash

ndashndash

ndash4

mai

n lo

de 8

0II

cvi

olet

ndash ndash

0

10 ndash

ndash 0

10

00

4

024

01

25ndash

ndashndash

5m

ain

lode

80

IIc

viol

et

015

ndash

013

ndash

012

06

4 0

26

1

30 0

23

019

ndashndash

7m

ain

lode

80

IIc

viol

et ndash

ndash

011

0

04

007

01

4 ndash

0

36 ndash

050

071

ndash10

apop

hysi

s 8

0II

cvi

olet

1

00 ndash

1

55

068

1

60 3

42

110

1 1

926

02

80

470

72ndash

14m

ain

lode

80

IIc

viol

et

014

ndash

013

ndash

010

02

5 0

04

0

66 0

56

040

ndashndash

15m

ain

lode

80

IIc

pale

vio

let

0

20 ndash

0

35

010

0

45 0

81

01

1

202

02

20

560

44ndash

17m

ain

lode

80

IIc

pale

vio

let

0

30

001

0

24

012

0

01 0

49

00

1

118

06

10

022

230

0118

mai

n lo

de 8

0II

cpa

le v

iole

t

192

2

30

030

0

01

020

06

2 0

01

5

36 3

10

032

006

058

19m

ain

lode

80

IIc

pale

vio

let

ndash ndash

0

10 ndash

ndash 0

15

ndash

025

ndashndash

ndashndash

21na

rrow

80

IIc

pale

vio

let

0

35 ndash

0

47

011

0

41 1

25

41

4

673

02

80

330

41ndash

23ex

tract

ion

110

IIc

viol

et

021

ndash

020

ndash

018

03

9 0

10

1

08 0

54

046

ndashndash

24ch

ute

110

IIc

viol

et ndash

ndash

001

ndash ndash

ndash ndash

0

01 ndash

ndashndash

ndash26

mai

n lo

de11

0II

cpa

le v

iole

t

022

ndash

013

ndash

011

02

3 0

02

0

71 0

96

048

ndashndash

27m

ain

lode

110

IIc

pale

vio

let

ndash ndash

0

06 ndash

ndash 0

15

ndash

021

10

0ndash

ndashndash

31m

ain

lode

110

IIc

pale

vio

let

0

43

086

0

40

001

0

01 0

79

02

4

274

05

40

010

140

6732

mai

n lo

de14

5II

cpa

le v

iole

t

010

01

01

01

01 0

01

00

1

016

100

01

001

750

0533

mai

n lo

de14

5II

cpa

le v

iole

t

012

01

011

01

01 0

01

00

1

028

120

01

001

520

0434

mai

n lo

de14

5II

cpa

le v

iole

t

01

01

01

01

01 0

01

00

1

007

10

01

001

750

3035

mai

n lo

de14

5II

cvi

olet

0

16

065

0

59

017

0

32 1

28

01

6

333

01

250

250

581

0640

lode

fi lli

ng21

5II

cpa

le v

iole

t

080

0

01

029

0

01

022

05

5 0

01

1

89 1

45

040

006

000

541

Mik

hale

tz33

5II

cpa

le v

iole

t

036

ndash

016

ndash

020

03

0 0

17

1

19 1

20

067

ndashndash

44Vo

dena

skal

am

ain

lode

370

IIc

pale

vio

let

0

36

01

017

01

01 0

86

01

0

152

04

20

011

120

015

45m

ain

lode

370

IIc

pale

vio

let

5

67

001

0

14

001

0

01 0

41

00

1

626

138

30

020

280

001

46m

ain

lode

370

IIc

pale

vio

let

0

46

078

0

57

020

0

01 0

96

01

8

316

04

80

012

640

5452

mai

n lo

de38

5II

cpa

le v

iole

t ndash

ndash

019

ndash

012

05

5 0

15

1

04 0

02

022

ndashndash

236 B Zidarova

From the performed calculations and the construction of histograms asymmetric distribution of the content of the REE for fl uorite varieties II (predominately low con-tents) are determined while for fl uorite varieties I a sym-metric distribution was observed in the whole interval (with exception of Lu)

A cluster diagram based on Spearmanrsquos rank correla-tion coeffi cient was made (ZIDAROVA amp KOSTOV 1979 ZIDAROVA 1989) The results obtained show that for the fl uorite variety II all bonds are of importance and have

high values whereas with those of fl uorite variety I only a part of the bonds are signifi cant (between La-Ce Sm-Eu Sm-Eu-Yb) while the others below a thresh-old value can be assumed only as a variant (Fig 5) It both kinds of fl uorite there have been pair-correlations between the content of lanthanides (La-Ce Sm-Eu Yb-Lu) (Fig 6)

A tendency is noticed for concentration of the LREE in the earlier fl uorite varieties and the HREE ndash of the later fl uorite varieties For example the fl uorite variety I is en-

Table 6 Contents and statistical parameters of the REE of fl uorite varieties from the Slavyanka deposit

REE Variety Numberanalysis

Range ppm(хmin ndash xmax)

x SxG V x

La I 17 2188 ndash 4970 1392 1141 277 8197 1392543II 43 001ndash 8195 151 210 032 13907 151063

Ce I 17 338 ndash 7433 2129 1672 405 7853 2129794II 43 001ndash 2060 326 506 077 15521 326150

Sm I 17 027ndash 1220 485 261 063 5381 485123II 43 001ndash 10416 166 274 042 16506 166082

Eu I 17 020 ndash 337 190 091 022 4789 190043II 43 001ndash 3654 048 074 011 15416 048021

Tb I 17 060 ndash 5541 229 118 029 5153 229057II 43 001ndash 10362 129 225 034 17442 129066

Dy I 7 374 ndash 2172 1057 520 196 4919 1057380II 19 006 ndash 6151 1101 1892 288 17200 1101564

Yb I 17 095 ndash 12412 427 243 059 5690 427115II 43 001ndash 1980 314 483 074 15382 314145

Lu I 17 034 ndash 1266 242 369 089 15248 242174II 43 001ndash 1780 133 313 048 23534 133094

ndash arithmetic medium value S ndash square medium divert (decline) V ndash factor of the variety ndash square medium mistake on the arithme-tic medium x ndash interval confi de on the general mediumx xG

Fig 5 Cluster diagram based on Spearmanrsquos rank correlation coeffi cient A ndash fl uorite variety II B ndash fl uorite variety I


riched by of La Ce Sm Eu which in the fl uorite variety II are on a lower order The contents of the others REE of the fl uorite varieties I and IIb is compatible while in fl uorite subvariety IIc ndash on order lower A tendency was observed in the upper levels of the deposit for increasing of the contents of the REE (ZIDAROVA amp KOSTOV 1979) which was later confi rmed (ZIDAROVA 1989) The chon-drite-normalized REE patterns of fl uorites (HASKIN et al 1966) was made for every fl uorite variety and at total for the fl uorite from the deposit is illustrated (Fig 7)

As shown on Fig 7 and Table 5 each fl uorite variety along the Central and Mikhaletz faults is distinguished not only by the chondrite normalization but also by the

EuEu and CeCe relations Fluorite variety I is charac-terized by Cemin Eumin and Ybmin fl uorite varieties IIa and IIb ndash only by Eumin fl uorite variety IIc ndash partly by Cemin and Eumin in the upper mining levels (145 ndash 370 m) The calculated CeCe values range from 000 to 150 ndash cor-respondingly 021ndash 087 (fl uorite variety I) 066 ndash145 (fl uorite variety IIa) 000 ndash150 (fl uorite variety IIb) and 000 ndash106 (fl uorite variety IIc) The EuEu values vary from 000 to 264 ndash correspondingly 040 ndash143 (fl uorite variety I) 034 ndash 059 (fl uorite variety IIa) 000 ndash138 (fl u-orite variety IIb) and 000 ndash 264 (fl uorite variety IIc)

Positive Eu anomalies indicate the release of Eu2+ dur-ing feldspar destruction oxidation to Eu3+ at the depo-sition site and subsequent incorporation in the fl uorite Samples with negative Eu anomalies indicate the pres-ence of Eu2+ (CONSTANTOPOULOS 1988) The anomaly be-haviour of Eu in the geochemical processes is known and is frequently linked to the oxidation-reduction conditions of the mineral-forming medium As a result of carried out experiments KOLONIN amp SHIRONOSOVA (2006 2007) found that Eu transfers entirely from the solid state into the solu-tion forming a minimum in dependence of the tempera-ture which corresponds to its maximum concentration in the solution The authors suggest that of importance is the higher solubility even of its three-valence complex forms compared to the similar such forms among the other REE

The fl uorites exhibit a small negative Ce and a posi-tive or negative Eu anomaly which are indicative of low temperatures and low or high fCO2 conditions Plots of TbCa-TbLa (Fig 8) is consistent with a hydrothermal origin for the mineralizing solutions

45 Optical characteristics of fl uorite

Fluorite is a mineral with composition coding with impor-tant information about the mineral-forming environment Especially informative in this respect are the structural impurities such as REE On the basis of their quantitative relationships and the position in the lattice of natural fl uo-rite crystals one can determine various physical-chemical parameters of the mineral-forming environment Spec-tral methods are especially sensitive for determining the structural position of REE Depending on the excitation energy suitable are the X-ray luminescence (XRLS) thermoluminescence (TLS) photoluminescence (PLS) optical (OS) and infrared (IRS) spectra The luminescent method allows to conclude about the possible varieties for combining the microimpurities and structural defects ex-isting in the natural crystals and in particular the REE their valence the peculiarities of their incorporation into the fl uorite crystal lattice and studying their geochemical behavior during the postmagmatic processes

Fig 6 Correlation between coupled REE in fl uorites from the Sla-vyanka deposit A) fl uorite variety I B) fl uorite variety II

238 B Zidarova

Fig 7 Chondrite-normalized REE patterns of the fl uorites in the Slavyanka deposit a) variety I b) variety IIa c) variety IIb d) variety IIc e) varieties I II IIa IIb IIc


The application of REE as indicators for the hydrother-mal processes is made because of the suitable fractiona-tion of the different REE in the different fl uorite depos-its the infl uence of the main factors on their distribution the change in valence state and the crystal chemical and chemical properties The differentiation of the REE as demonstrated experimentally mainly through connec-tion to the change of the mineral-forming fl uid solution (KOLONIN amp SHIRONOSOVA 2009 MORGUNOV amp BYKOVA 2009) Different types of luminescent centers have been studied by PLS cathodoluminescence and XRLS tech-niques For natural fl uorites luminescence spectra have been ascribed to the REE ions Ce3+ Nd3+ Sm3+ Sm2+ Eu3+ Eu2+ Gd3+ Tb3+ Dy3+ Ho3+ Er3+ Tm3+ and Yb2+ (AIERKEN et al 2003 GAFT et al 2005) These lumines-cent properties have found many applications eg in the detection and identifi cation of minerals in rocks and ores (BODYL 2009)

The dominance of REE2+ or REE3+ in the studied vari-eties of fl uorite is specifi ed according to the application of the following spectroscopic methods

The luminescence and the colour of fl uorite have been used of specifying the genetic features the zoning and the size of fl uorite deposit (KRASILlsquoSHCHIKOVA amp NECHAYEV

1984) as an element of the mineralogical mapping and prognosis of both the amount (VYBOROV et al 1984) and quality (ZIDAROV amp ZIDAROVA 1993) of the fl uorite raw material

The spectroscopic characteristics of the fl uorite from the Slavyanka deposit (ZIDAROVA amp ZIDAROV 1995 a) are indicative of the state of the mineral-forming environ-ment and the content and the type of REE

451 Photoluminescence

The data of 254 nm was uninformative Only data of 360 nm for fl uorite varieties I and IIb have been il-lustrated (Table 7) The obtained spectra are with clearly defi ned luminescence bands from Eu2+ (~413 nm) and Yb2+ (~530 nm) incorporated into the fl uorite structure The bands are better exposed in the spectra of fl uo-rite variety I and are weaker and not well expressed in the spectra of fl uorite subvariety IIb The fl uorites from the Slavyanka deposit can be attributed accord-ing to VASILrsquoKOVA amp SOLOMKINA (1965) to fl uorites with well exposed Eu2+ and Yb2+ bands in the spectra the observed blue (fl uorite variety I) and blue-violet band (fl uorite subvariety IIa) linked to the presence of Eu2+ and the red-violet band (fl uorite subvariety IIb) ndash to Sm2+ (PSHIBRAM 1947 1959 VASILrsquoKOVA amp SOLOMKINA 1965) which is confi rmed by the results obtained from neutron-activation analyses for fl uorites from the same deposit (ZIDAROVA 1989 ndash Table 8)

452 X-ray luminescence

Representative spectra (ZIDAROVA et al 1986 ZIDAROV amp ZIDAROVA 1989 ZIDAROVA 1989) are of the Sm-Dy-type Dy-type fl uorite and in partly in pure fl uorite (Fig 9)

The fl uorites from the Slavyanka deposit are character-ized by capture and radiation centres caused by internal defects in the fl uorite structure (Vk(296)- and F2(744)-centres) impurity ions (centres with local cubic symmetry) ndash Ce3+ Pr3+ Sm3+ Eu3+ Gd3+ Dy3+ Tb3+ and more complicated centres of non-cubic symmetry for which a local compen-sation take place of the excess change of Na+ O2 ndash and Fi

ndash ions replacing isomorphically Ca2+ and Fndash ions in sites or in interstitials of the fl uorite lattice (Еr3+-Na+

(540) Dy3+-O2

(674754) Er3+-O2 ndash(553) Sm3+-Fi

ndash(578))

Fig 8 TbCa ndash TbLa variation diagram of the crystallization fi elds of fl uorites of varieties I (A) and II (B) in the Slavyanka deposit A ndash redeposited fl uorite (tg044) B ndash primary fl uorite (tg122)

Table 7 PLS of fl uorite varieties from the Slavyanka deposit

Variety Colour of the fl uorite Colour of the PLS in 366 nmI green blue

IIa dark-violet blue-violetIIb violet red-violetIIc pale violet rose-violet (cyclamen) to a

scarcely perceptible

240 B Zidarova

The correlation between the total sum of REE (REE) and the sum of the intensities of the four most prominent curves (REE) in the XRLS spectra ndash Dy3+

(480)Sm3+(567)

Dy3+(572)Sm3+ ndash Fi

ndash(578) (Fig 10) shown here are practi-

cally full correspondence of these two indicators which allow a simplifi cation of the operations of analysis of the fl uorites from the deposit taking into consideration only the REE (ZIDAROVA et al 1986 YUSHKIN et al 1986)

Control through the criterion of VILKOKSON was ap-plied and determined that the fl uorite of the fl uorite varie-ties I (green) and fl uorite variety II (violet) represented

separates unity for all REE with exception of the Yb (ZIDAROVA amp KOSTOV 1979) also substantiated and with ХRLS (ZIDAROVA 1989)

The identity in the composition of emission centres in fl uorite from a certain deposit gives evidence for a single source of the ore-generating fl uids and the variability in the composition of the capture centres ndash as a result of mul-tistage repeat transfi guration of the structure of the me-dium during the mineral deposition in the ore vein and the growth zones (KRASILrsquoSHCHIKOVA amp POPOVA 1984)

In order to trace the evolution of the centres composi-tion not only a qualitative comparison of the spectra is required but also calculation of the parameters refl ecting the change of the composition of the most characteristic REE and their combinations which bear in their content and structure information for the mineral-forming medi-um (ZIDAROVA et al 1984)

The parameters (KRASILlsquoSHCHIKOVA et al 1981) reveal-ing the variations of the content of the most characteris-tic defects and their combinations are A IDy3+

cub(572)IFndash

2(296) refl ecting the concentration ratio for activation centers and centers of own defects in the fl uorite struc-ture BIDy3+ ndash O2 ndash

(754)IDy3+cub(572) refl ecting the degree

of inclusion of oxygen ions in the fl uorite structures CIREEYIREECe presenting the ratio of the integral intensity of lines corresponding to centers of ions of Y- and Ce-subgroup D ISm3+ ndash O2 ndash

(605)ISm3+cub(567) has the same

meaning as the parameter B E IEr3+ ndashNa+(540)IEr3+ ndash

O2 ndash(533) is a measure of the degree of inclusion of Na+ and

O2 ndash ions in the fl uorite structureThe results show that the parameters A B C D E

(Table 8) are determined from the relationships in the se-lective inclusion of various groups REE3+ into the fl uorite structure depending on the geochemical peculiarities and the thermo-dynamical parameters of the mineral-forming environment Their variations are usually related not only with the geochemical and genetic specifi city of fl uorite but also with the regional and local temporal variations in the thermal-barometric-geo-chemical parameters of the environment

ndash The earlier fl uorite varieties (I and IIa) are enriched and the later ones (IIb and IIc) are depleted in REE A ten-dency of enrichment is observed for the LREE in the ear-lier varieties and for the HREE ndash in the genetically later fl uorite varieties An increase in the content of REE is also observed in the upper levels of the examined sites of the deposit during one and the same fl uorite variety on account of the centers of own defects (parameter А) (ZIDAROVA 2003 ndash Fig 1 А) This tendency is also pre-served for the temporal evolution of the mineral-forming process (ZIDAROVA et al 1984 ndash Fig 1) The ratio between the concentrations of active centers and centers of own

Fig 9 XRLS in fl uorite of the Slavyanka deposit 1 ndash Sm-Dy type (fl uorite variety I) 2 ndash Dy type (fl uorite variety IIa) 3 ndash Dy type (fl uorite variety IIb) 4 ndash pure fl uorite (variety IIc)


defects in the fl uorite structures shows that in fl uorites formed fl uorite varieties I IIa and IIb parameter A 1 ndash activation centers are dominant while in fl uorite subva-riety IIc parameter А1 ndash the own defects are dominant (Table 8)

ndash The parameter С (domination of ions of Y- or of Ce-group) in the Slavyanka deposit is smaller for the fl uo-rite varieties I than for fl uorite varieties II (ZIDAROVA 2003 ndash Fig 1 С) This is may be due to an initial neutralization of the solutions when reacting with the host rocks As far this ratio is indicative for the relative change of pH of the medium while the increased content of Се3+ is charac-teristic of fl uorites crystallized from more alkaline solu-tions One can conclude that the acidity of the medium is increased with the fl uorite formation process progressing (ZIDAROVA 2003 ndash Fig 2 and Fig 4 ZIDAROVA amp PIPEROV 1995 PIPEROV et al 1986)

ndash The parameters В and D in the frames of fl uorite variety I do not undergo certain changes which allows to presume that the oxygen potential (resp Еh) of the fl uids during the II impulse has been stable In the fl uorites from the III impulse the values of these parameters vary irregu-larly even among fl uorites from one of the subvarieties deposited symmetrically in both salbands of the ore vein which can be an indicator for local variations in the oxy-reduction regime of the environment The parameters В and D are also informative for the inclusion of oxygen ions in the fl uorite structures realized for B through REE from the Y-group (ZIDAROVA 2003 ndash Fig 1 В) while for D ndash through REE from the Се-group (ZIDAROVA 2003 ndash Fig 1 D) This explains the nearly mirror-behaviour of the two graphs depending on the predominant group These parameters are related with рН-Еh of the medium i e with its oxidation-reduction potential which is de-

Table 8 XRLS parameters of fl uorite varieties from the Slavyanka deposit

Level m Site Variety А B C D E 80 Vodena

skalaI 515 043 194 053 088I 418 037 202 042 086I 673 051 200 059 090I 778 033 213 046 087

110 I 928 085 200 034 112145 I 284 124 157 042 089350 Venetza I 1027 063 173 049 100385 Vodena skala I 755 051 234 035 079500 Baba I 344 127 167 041 118145 Vodena

skala IIa 4345 022 3061 000 092 IIa 1533 033 1495 100 087

385 Mikhaletz IIa 3270 032 1355 100 107 80 Vodena

skala IIb 378 035 826 100 082

385 IIb 1316 054 223 039 081 IIb 1158 038 255 030 081 IIb 2083 033 245 027 075 IIb 400 050 237 034 077 IIb 580 034 270 020 075

385 Mikhaletz IIb 712 030 1251 100 095 IIb 335 024 1592 133 088

40 Vodenaskala

IIc 010 100 286 033 400 IIc 024 080 247 033 071

80 IIc 382 023 277 0125 075 IIc 061 055 247 019 052 IIc 003 100 350 033 100 IIc 1241 026 278 021 078 IIc 043 062 261 018 086 IIc 081 050 233 028 072 IIc 378 035 826 100 082

110 IIc 023 212 248 025 090 IIc 041 045 527 150 040

145 IIc 107 048 587 080 075 IIc 013 333 302 000 075

370 IIc 035 046 1370 000 085

242 B Zidarova

Fig 10 Correlation between the amount REE (REE) in arbitrary units and amount Dy3(480)Sm3

(567)Dy3(572)Sm3ndash Fi

ndash(578) (REE)

in arbitrary units of XRLS in the fl uorite from the Slavyanka deposit а) for 200 samples b) for 35 samples


termined by the process of mineral formation under vein condition The value of the parameters B and D always is1 (with exception to parameter B ndash level 40 80 110 145 500 and D ndash level 80 110 145 385)

ndash The charge compensation of REE3+ (e g for Er3+) not only proceeds through О2 ndash and Fndash ions but also by Na+-ions (parameter Е) (ZIDAROVA 2003 ndash Fig 1 Е) var-ying in narrow limits for all fl uorite varieties (with excep-tion to parameter E ndash level 40 IIc) (Table 8)

453 Thermoluminescence

Most intense are the maxima on the curves corresponding to the primarily deposited fl uorite at highest temperature in the Slavyanka deposit (Table 9)

Only high-temperature maximum at 280 degС (Y2+) cu-bic center and at 320 degС (REEO2)deg center was present on the TLS curves of non-irradiated fl uorite varieties from deposit

After irradiation the maxima listed below appeared on the TLS curves 130 ndash150 degС ndash dipole centre REE2+ ndash Оndash 180 degС ndash defective (YO2)deg centre 220 degC ndash REE2+

cub centre 280 degC ndash Y2+

cub centre 320 degС ndash defective (REEO2)deg centre and 380 degС ndash Sm2+ ndash Ce4+ centre Very

weak maxima were fi xed in certain fl uorite varieties at 50 ndash70 degС ndash defective Fdeg centre and at 100 ndash120 degС ndash M centre (ZIDAROVA 1989 1992 b) (Fig 11) The abundance of REE2+ indicates a suffi ciently low oxidation-reduction potential of the solutions from which the early high-tem-perature fl uorites in the deposit (fl uorite varieties I and IIa) had crystallized For the fl uorite subvariety IIb and IIc characteristic are higher values of the oxidation-reduction potential and lower temperatures (most probably with a charge compensation of the type O2 ndash rarr Fndash) as well as a very low content or even absence of REE2+

There is a relation between the conditions of the fl uo-rite formation and the position of the TLS maxima The high-temperature fl uorite varieties are characterized by domination of shallow capturing levels (low-temperature peaks Tdeg160 ndash 320 degС) and are typical of fl uorites crys-tallized under relatively low values of the reduction po-tential of the medium On the contrary the low-tempera-ture fl uorite varieties characterized with deeper capturing levels (high-temperature peaks Tdeg350 ndash 370 degС) have been crystallized under conditions of elevated values of the oxidation potential of medium

Low-temperature maximum (up to 100 degС) was re-ferred to incorporating levels conditioned by thermal mi-cro-defects while the higher-temperature ones act as an

Table 9 Intensity of the peaks (arb units) and capture centers of fl uorite varieties from the Slavyanka deposit

Level m Variety Spot Temperature position of peaks and nature of the capture centers130-150 degCREE2+-Ondash

180 degC(YO2)o

220 degCREE2+

280 degCY2+

320 degC(REEO2)o

380 degCSm2+-Ce4+

80 I main lode ndash 2500 ndash 53500 30000 9500 80 I main lode ndash 2500 ndash 33500 28700 10500 80 I apophisis ndash 6000 ndash 56500 36000 9000 80 I apophisis ndash 3000 ndash 35000 23250 14750210 I lode fi lling ndash 2500 ndash 53500 30000 9500385 I main lode ndash 2500 ndash 33500 28700 10500110 IIa main lode 4900 ndash ndash 3800 3300 2400 80 IIb main lode ndash ndash 310 ndash 900 360 80 IIb apophisis ndash 120 490 ndash 1390 740 80 IIb narrow ndash 015 ndash 775 770 ndash110 IIb main lode 2340 ndash 240 300 400 190385 IIb main lode ndash 300 ndash 4550 2700 1625385 IIb main lode ndash 210 ndash 1700 ndash 1900385 IIb main lode ndash ndash ndash 150 225 490385 IIb main lode ndash 095 065 565 480 1060385 IIb main lode ndash 050 075 480 410 325385 IIb main lode ndash ndash 150 ndash 560 175 40 IIc main lode ndash ndash ndash 085 085 030 40 IIc main lode ndash 003 ndash 069 ndash 097 40 IIc main lode ndash ndash ndash 045 035 ndash 80 IIc main lode ndash ndash ndash 015 015 015 80 IIc main lode ndash 005 ndash 025 035 ndash 80 IIc apophisis ndash ndash 130 210 280 ndash

244 B Zidarova

ldquoactivatingrdquo levels of incorporation In the maxima found on the TLS (Fig 11) it is seen that the fl uorites from the Slavyanka deposit are characteristic both as centres with-out local compensators (REE2+ and Y2+) cavities (YO2)deg and (REEO2)deg ndash an oxygen type compensation and as do-nor-acceptor couples Dy2+ ndash Ce4+ and Sm2+ ndash Ce4+ where the admixtures of Dy3+ and Sm3+ are acceptor ones while the Ce3+ is a donor one (TARASHCHAN et al 1974)

454 Optical spectra and colour

The following absorption bands have been observed in the ultraviolet spectral region (200 ndash 400 nm) only in fl uo-rite varieties I and IIa at 265 nm (corresponding to Sm2+ and Yb2+) at 300 ndash 315 nm (to Ce3+ Sm2+ and Yb2+) In the visible spectral range (400 ndash 800 nm) there are lines at 410 and 580 nm (corresponding to internal defects Fi

ndash and

Fig 11 TLS in fl uorite from main lode (Central fault) of the Slavyanka deposit 1 ndash mining level 40 m 2 ndash mining level 80 m 2 a ndash apophysis to main lode 2 b ndash extr chute 3 ndash mining level 110 m 4 ndash fi ling between mining levels 190 ndash 240 m 5 ndash mining level 385 m


2Findash) in the fl uorite lattice at 420 and 600 ndash 650 nm (to

Sm2+) at 500 nm [to (Y REE)O2] and at 560 nm (to MO2 ndash) The results and reviews of MARFUNIN (1975) PLA-TONOV (1976 ab) YUSHKIN et al (1983) KRASILrsquoSHCHIKOVA et al (1986) ZIDAROVA (1989 1993) were used in the in-terpretation of these curves It has been observed that all of the absorption bands depend on the REE content in natural fl uorites (Table 10)

Using optical spectra of transmission (OTS) and ab-sorption (OAS) it was found that in the course of pro-gression of the fl uorite formation the content of REE de-creases This makes possible to use some of the fl uorites in the deposit as raw material for growing single crystals of optical grade or directly to prepare elements for optics (ZIDAROVA 1992 a ZIDAROVA et al 1992)

The occurrence of characteristic absorption bands in the spectra of different fl uorite varieties depends on the type and concentration of REE (Table 10) (ZIDAROVA 1989 ZIDAROVA et al 1992 ZIDAROVA 1993) The variety of colour nuances is caused by impurity ions and electron-hole centres as well as by their combinations only the most stable of these (Table 12) being preserved depending on the conditions of crystallization

The colour of fl uorite is an important indication of its quality In the fl uorite from the Slavyanka deposit the abundance of REE2+ ions indicates a lower reduction po-tential (Eh) of the hydrothermal solutions from which the higher-temperature fl uorite varieties (I and IIа) have been deposited A charge compensation of the type О2 ndash rarr Fndash seems most probable for the lower-temperature fl uorite

subvarieties (IIb and IIc) In this case REE2+ ions are of very low concentration or are missing at all (Table 10) and the process of crystallization has proceeded at higher values of Eh

The absorption bands are an indicator for irregular-ity in the optical density of fl uorite The latter is caused by the irregularity in colouration of the different fl uorite varieties as well as by the change of this density caused by the dispersion of light from the presence of defects in the fl uorite structure because of the zonal distribution of the trace elements identifi ed by local laser microchemical analysis (ZIDAROVA et al 1984 ZIDAROVA 1989 1995 b) This fact demonstrates the complex character of the chemical inhomogeneity in each part of the ore vein

The optical spectra studied in detail were represented in the spectral range 400 ndash700 nm (Table 11 Fig 12) The change in the value of light transmission (Т ) from one to another of the fl uorite varieties takes place at a leap and among a single fl uorite variety ndash gradually (ZIDAROVA et al 1984 ndash Fig 3) The deviations are the result of the al-ternation of different colour hues in a single sample Only the last sample (fl uorite subvariety IIc) where an alterna-tion of transparent and milky white zones is observed and the fl uctuations of light permeance (Т ) for the different zones reach high values are the exception

The variation in the colour of fl uorite is caused by presence of colour centres which can be identifi ed by optical spectra The most informative in this respect is the spectral region from 200 to 800 nm where the lines of REE2+ and REE3+ dominate the spectrum (ZIDAROVA 1993) According to published data (BILL amp CALAS 1978 SCHMETZER et al 1980 KRASILrsquoSHCHIKOVA et al 1986 KEMPE 2006 DILL amp WEBER 2010) the change in the posi-tion of such centers in the fl uorite structure leads to an evolution in the colour of natural fl uorite (ZIDAROVA 1993 ndash Table 1)

Both the luminescence and the colour are sensitive to variations in the thermodynamic parameters of the miner-al-forming medium

Several authors (ERMAKOV 1948 1950 YAKZHIN 1962 IVANOVA 1974) link the sequence in deposition of the dif-ferent coloured fl uorite varieties with evolution in the temperature regime of the medium which in turn geneti-cally is determined by the change of the colour centers

The zonal distribution in the colouring of fl uorite crys-tals and aggregates results when impurity ions (REE) are embedded in the structure from the hydrothermal solu-tions The change in their composition and concentration during the mineral-forming process in each individual pulse depending on the physic-chemical parameters of the medium ndash T P pH chemistry etc (ZIDAROVA 1995 b) Upon the occurrence of essential variations leading to

Table 10 Characteristic absorption bands in different fl uorite varieties from the Slavyanka deposit

Variety REE Concentration interval(хminndashxmax) ррm

Absorption bands

I CeSmYb

338 ndash7433027ndash1220095 ndash1241

Yb2+ndash 260 270 nmCe3+ndash 306 nmYb2+ndash 365 nmFi

ndashndash 400 nmSm2+ndash 425 nm2Fi

ndashndash 580 nm IIa Ce

SmYb

065 ndash 2060059 ndash1042128 ndash1980

Yb2+ndash 260 270 nmCe3+ndash 306 nmSm2+ndash 340 nmYb2+ndash 365 nm2Findash 580 nm

IIb Ce 088 ndash1343 Yb2+ndash 247 nmSm 032 ndash 649 Yb2+ndash 308 310 nmYb 032 ndash1140 2Findash 580 nm

IIc Ce 001ndash 320 Yb2+ndash 308 310 nmSm 001ndash 261 Fi

ndashndash 400 nmYb 001ndash 577 2Fi

ndashndash 580 nm

246 B Zidarova

a change in the crystal habit the zoning in the colour (mainly the polychrome zoned) is controlled by the habit (ZIDAROVA 1993) In many cases described in the special literature the evolution in the fl uorite crystal forms during the growth is revealed namely through the colour zoning As a rule the crystals with the octahedral habit (the case valid for the examined deposit) are more deeply coloured than those with the cubic habit

The investigation of differently coloured fl uorites re-vealed that a change in the composition of colour centres occurs which refl ects the variations in the physico-chem-ical parameters of the crystallization medium The factors which have given rise to such a zoning are either external resulting from the pulsed supply of hydrothermal solution or internal on account of the crystallization processes in the specifi c physic-chemical systems (ZIDAROVA 1993) Enrichment or depletion in REE of the investigated fl uo-rite samples to their chondrite normalized contents the appearance of Eu andor Ce anomalies and the SmCe ratio (ZIDAROVA 2003 ndash Fig 2) are typical of each fl uorite varieties in the deposit The total REE content as well as the content of LREE and HREE in the fl uorite depend on T degC (ZIDAROVA 2003 ndash Fig 3) pH (ZIDAROVA 2003 ndash Fig 4) and Eh of the mineral-forming hydrothermal solu-tions

Two types of zoned fl uorite are characteristic for the Slavyanka deposit (Table 12 B and Fig 13)

ndash monochrome zoned ndash the colour is formed by a single spectral tone (violet or green) and its intensity var-ies gradually forming different zones

ndash polychrome zoned ndash the different zones are with different colours the transfer between them being also gradual

The zoning observed in the fl uorite of the deposit is as growth zoning ndash primary of a fi rst degree as a refl ection of the change in the physical and chemical parameters of the mineral-forming medium (GRIGORIEV amp ZHABIN 1975) It can be realized when the growth takes place in open spaces (cavities) with an observed rhythmic colouration (from the pulsation of the solutions) parallel to the octa-hedral or cubic face depending on the crystals character-istic for such conditions Similar studies on the sectoral growth of fl uorites crystal have been carried out by BOSZE amp RAKOVAN (2002)

It has been observed from the obtained OAS (Fig 13 Table 12 B) for the different coloured zones that

ndash monochrome zoned fl uorites ndash with a very specifi c maxima from Sm2+

(420) O3 ndash(440) (YO2)deg(520) and a weaker

Sm2+(620) and the weakest MO2 ndash

(560) The appearance of oxygen-bearing centers is rare has been previously men-tioned

Table 11 OTS (Т ) at different levels of zonal fl uorite varieties from the Slavyanka deposit

Levelm

Variety Colour inthe zones

ZoneNо

Thickness of platelets mm

Т K cmndash1 T K cmndash1

400 nm 600 nm 80 I smoky 1 400 323 857 500 748

white 2 484 756 666 676green 3 1613 456 2333 363green 4 2742 323 4000 229green 5 4032 227 5166 165violet 6 1613 456 2333 363green 7 4355 207 5666 142

110 IIa dark-violet 1 400 484 756 833 621dark-violet 2 484 756 666 676dark-violet 3 484 756 500 748dark-violet 4 322 858 333 849

IIb violet 5 806 629 1000 575violet 6 1129 545 1333 503violet 7 2258 372 3500 262violet 8 2903 309 3833 239

IIc pale violet 9 5645 143 6833 095pale violet 10 6290 116 7333 077

110 IIc pale violet 1 400 6451 109 7666 066milk-white 2 3387 270 4166 219pale violet 3 6451 109 7333 077milk-white 4 2742 323 3500 262pale violet 5 6129 122 7333 077

Kcm-123dcm-1 x lg100T


Fig

12

OTS

of fl

uor

ites

from

diff

eren

t lev

els

and

min

eral

ogic

al v

arie

ties

from

the

Slav

yank

a de

posi

t Le

gend

key

1 ndash

em

bedd

ing

rock

s 2

ndash v

arie

ty I

3 ndash

var

iety

IIa

4 ndash

varie

ty II

b 5

ndash va

riety

IIc

6 ndash

suga

r-gra

ined

qua

rtz

248 B Zidarova

ndash polychrome zoned fl uorites ndash there is also a very specifi c maxima from Sm2+

(420) O3 ndash(440) (YO2)deg(520) and a

weaker one also of Sm2+(620) and Sm2+

(660) and the weakest MO2 ndash

(560)Some authors consider that the optical absorption of

the yellow fl uorites is attributed to the presence of O3 ndash

center in the structure and the O3 molecules were incorpo-rated during crystallization (TRINKLER et al 2005 DILL amp WEBER 2010) Our investigations show that the O3

ndash cent-ers take place not only in the yellow colouration but also in the polychrome and some monochrome fl uorite zones (Table 12 B)

The zoning in the colour distribution is quite charac-teristic of fl uorite and provides valuable genetic informa-tion on the character and the direction of the change in the conditions during the crystallization process These changes are responsible for the formation of zones of dif-ferent colour optical absorption Th degC chemistry etc (Fig 13) The factor which has given rise to such zon-ing are either external resulting from the pulsed supply of hydrothermal solutions or internal on account of the

crystallization processes in a specifi c physical-chemical system

According to the results obtained the fl uorites from the Slavyanka deposit are attributed to the fl uorites with oxy-gen-rare earth composition of optic active centres follow-ing the classifi cation of KRASILlsquoSHCHIKOVA et al (1986)

The optical density is also studied for determination of the main tendencies in the change of the optical prop-erties of the fl uorite in the mineral-forming process In such way each stage in the process of fl uorite formation respectively for each fl uorite variety can be determined ndash the dynamic in the change of such parameters as quantity and width of zones (the frequency of changeability in the conditions of crystallization) amplitude of fl uctuations (intensity of changeability of factors particularly the in-tensity in capturing the gas phase or impurity) character of growth (activation) and sequent drop (relaxation) of such fl uctuations in each rhythm The obtained results are re-viewed and described in detail by ZIDAROVA (1989 ndash Table 17 Fig 26 1995 b ndash Table 3 Fig 2 3) First order fl uc-tuation corresponding to the coarse (macro) zoning in the

Fig 13 OAS of zoned fl uorites from different levels and mineralogical va-rieties from the Slavyanka deposit a) variety I ndash zones 3 ndash7 b) variety II variety IIa ndash zones 1ndash 4 variety IIb ndash zones 5 ndash 6 variety IIc ndash zones 7ndash 9 c) variety IIc ndash1 3 and 5 The legend key follows Fig 12 The platelets are scan-ned from the salband to the vein center


investigated plates is related to variations in the minero-genesis physical and chemical parameters external with respect to the growing crystals and aggregates The sepa-ration between the zones in this case is from 23 to 49 mm Third order fl uctuations corresponding to the fi ne zoning and related to the structure of the crystallizing medium (GRIGORIEV amp ZHABIN 1975) ie to the process of crystal growth The separation lengths in this case are between 032 and 041 mm and are uniformly distributed through-out the different mineralogical varieties Fluctuations of I and II order are applied to determine those of order III

The fl uctuations of I order correspond to the coarse zoning and refl ect the changes in the external conditions which take place during the crystalrsquos growth According to them one can assume that there is a change of the phys-ical and chemical parameters of the crystallization me-dium in an open pulsating hydrothermal system in which the evolution of solutions is from relatively more alkaline towards more acid The zonal distribution of the coloura-tion is caused not only to colour centres and defects of the fl uorite structure but also to the incorporation of non-structural (ZIDAROVA 1989 ndash Table 6 Fig 14bc 1995 b ndash Table 2 Fig 2ab) and isomorphic impurities It depends on their presence in each portion of the pulsating solution and to the non adequate reaction of the growing crystal to such impurities The isomorphic substitutions depend on to a signifi cant degree the thermodynamic param-eters of the medium ndash the hotter solutions bring a larger quantity of isomorphic impurities The separate portions of hydrothermal solution composition and form of pres-ence and concentration of impurities can be changed as they depend on the рН of the medium which in its turn is

linked to the temperature and thus ndash their differentiation (ZIDAROVA 1989 2010) The intensities of the amplitudes of capture of impurities (Ā1) by the growing crystals and aggregates decreases correspondingly from 720 to 192 arb units (ZIDAROVA 1995 b ndash Table 3) because the hot-ter solutions capture a larger quantity of impurities and at the end of each impulse their concentration decreases Namely the regular change in the colour of fl uorite re-fl ects the change in their impurity composition of the fl uo-rite during the evolution of the solutions parameters giv-ing origin to a certain rhythm This is illustrated very well by ZIDAROVA (1989 ndash Fig 14а) where for fl uorite varieties I the quantity of fl uctuations is 3 and for fl uorite varieties II ndash 5 (ZIDAROVA 1989 ndash Fig 14b 1995 b ndash Fig 2а)

Confi rmation of the amazing repeat of the forms and morphological details on the surface of the fl uorite varie-ties II probably is linked to the formation in the close crystal space of cell structures as a result of dissipa-tive processes taking place in the solution with stable T225 degC Probably this is the main reason for the similarity in the microphotograms of fl uorite varieties II (ZIDAROVA 1995 b ndash Fig 3) The dissipative effect in this space is determined by the parameters of the medium The width of the zones at third order fl uctuations (ZIDAROVA 1995 b ndash Table 3) for the different fl uorite varieties is con-stant while the concentration gradient will be the higher as the growth velocity is higher The intensity of impurity capture is constant for fl uorite varieties I and II with ex-ception of fl uorite subvarieties IIc (site 110) and IIb (site 335 ndash a little different mechanism of mineral deposition) The incorporation of inclusions refl ects the optical den-sity (ZIDAROVA 1992 a ZIDAROVA et al 1992) The fl uc-

Table 12 Characteristic absorption bands in different coloured fl uorite varieties from the Slavyanka deposit

АVariety Colour Absorption bands

I green Yb2+(265365) Ce3+

(306) Sm2+(425) Fi

ndash(400) 2Fi

ndash(580)

IIa dark-violet Yb2+(265365) Ce3+

(306) Sm2+(340) 2Fi

ndash(580)

IIb violet Yb2+(247310) 2Fi

ndash(580)

IIc pale violet Yb2+(310) Fi

ndash(400) 2Fi

ndash(580)

BType zoned Colour Absorption bands

Main Secondarymonochrome green Sm2+

(420) MO2 ndash(565) Sm2+

(620)

dark-violet Sm2+(420) (YO2)o

(480) MO2 ndash(560) Sm2+

(620)

violet Sm2+(420) O3 ndash

(440) (YO2)o(520)

pale violet Sm2+(420) O3 ndash

(440) MO2 ndash(560)

polychrome green Sm2+(420) O3 ndash

(440) (YO2)o(520) Sm2+

(660)

green Sm2+(420) MO2 ndash

(560) Sm2+(620)


(440) MO2 ndash(560)

250 B Zidarova

tuations in their distribution cause the complex character of the chemical unhomogeneity in the fl uorite from the Slavyanka deposit

It is shown in detail (ZIDAROVA 1989 1995 b) that the fl uorite crystals and aggregates with zoned distribution of colour are those in which the information on both the dy-namics of the growth and geochemical as well as thermo-dynamical characteristics of the medium are chronologi-cally recorded

455 Infrared spectra

Bands at 1400 ndash1500 cmndash1 were observed by infrared spec-troscopy (IRS) in thin platelets polished on both sides (Table 13) They originated from the presence of CO3

2ndash at 1630 cmndash1 corresponding to deformation vibrations and at 3400 cmndash1 corresponding to stretching vibrations of OH-groups These are namely the main phases observed in the analysed fl uid inclusions (PIPEROV et al 1986 ZIDAROVA 1989) In the same samples with milk-white zones rich of the fl uid inclusions and clay minerals intensity of these bands grow

46 Estimation of fl uorite from the Slavyanka deposit as a material for growing optical grade single crystals

One of the applications of the natural raw fl uorite is as a material for growing synthetic single crystals for the optical industry Already the creators of the fl uorite crys-talrsquos industrial technology (STOCKBARGER 1949 STEPANOV amp FEOFILOV 1957) used to accentuate the presence of a relation between the natural raw material and the crys-talrsquos quality Today there is no doubt that the crystals of quite different optical quality grow from different va-rieties of raw fl uorite Thus a specifi ed kind of fl uorite

crystals for the optical purpose has to be grown It is necessary that a suitable raw material had to be selected from mineralogical viewpoint even since the geologi-cal examination and exploration (ZIDAROV et al 1987 ZIDAROV amp ZIDAROVA 1989) In such a manner the optical quality of crystal growth from a given variety of raw material can be prognosticated The spectral parameters of the impurities in raw fl uorite depend on both the con-dition of its formation and the variety of the deposit It is known that inclusions to a great extent can be removed technologically while the structural defects are totally inherited during the growth of the crystals deteriorating their optical properties namely the luminescence effi -ciency light scattering and transparency That is the rea-son why simultaneous studies of the optical properties of the raw materials and the crystals grown therefrom are of a particular interest and can serve to develop methods for determining the quality of natural raw fl uorite in terms of objective criteria such as those based on the meas-urement of the intensity of characteristic lines of REE in XRLS of natural raw fl uorite (ZIDAROVA et al 1986 1992 ZIDAROVA 1990)

This paper presents results on the OTS on both the main fl uorite varieties (I and II) from the Slavyanka fl uo-rite deposit and the single crystals grown therefrom by the method of Stockbarger These results are the basis for ex-press evaluation of the quality and homogeneity of natural raw fl uorite for the optical industry

Calcium fl uoride is commonly used as a window able to transmit ultraviolet radiation with photon energies of up to 10 eV (Hodby 1974)

The OTS of the raw fl uorite used and of the correspond-ing synthetic crystals was studied in the spectral region 200 ndash 800 nm by means of the Specord UV-VIS spectrom-eter As shown in Fig 12 all the fl uorite varieties under consideration are characterized by strong absorption in UV 200 ndash 400 nm Apparent bands due to impurity absorp-

Table 13 IRS of different coloured fl uorite varieties from the Slavyanka deposit

Site Level m Variety Colour Thickness ofplatelets cm

Light transmission degree

Absorption coeffi cient Ксm-1

7500 nm 9300 nm 7500 nm 9300 nmVodena

skala

40 IIb pale violet 100 34 3 108 350 80 I green 100 84 26 017 134

IIb violet 100 32 3 114 350110 IIb pale violet 120 46 3 077 350

190 ndash 240 I green 080 66 18 052 214I green 080 67 24 050 178

385 IIb violet 150 64 6 029 187 IIb violet 500 9 3 481 700 IIb violet 100 35 3 105 350 IIb violet 160 28 3 079 219


tion are present only in the spectra of the fl uorite varieties I and IIa at about 265 nm (Sm2+ and Yb2+) 300 ndash 315 nm (existing in the raw material structure defects inclusions phase boundaries impurities and inhomogeneities) which are responsible for the scattering and absorption of light

As can be easily seen from Table 10 and Fig 13 (ZIDAROVA 1989 ndash Table 15 Fig 75 ZIDAROVA 1992 a ndash Table 1 Fig 1) the optical spectra are dominated mainly by the absorption bands of Ce2+ Sm2+ and Yb2+ due to their higher concentration in the natural raw fl uorite used This fact is also supported by the performed control neu-tron-activation analyses (see Table 10) An increased con-tent of these elements was observed as well in the XRLS of the particular fl uorite varieties and subvarieties of raw fl uorite (ZIDAROV amp ZIDAROVA 1989 ZIDAROVA et al 1986 ZIDAROVA 1989 1990)

In order to provide responsible and stable optical pa-rameters one should standardize the natural raw fl uorite and the synthetic crystals grown therefrom as specifi ed in Fig 14 This was necessary as fragments of various fl uorite varieties and subvarieties came into being during different impulses of the deposit formation so they could get into the separate lots of raw fl uorite (ZIDAROV et al 1987)

The similarity of the OAS of raw fl uorite with the standard spectrum shown in Fig 13 can serve as an indi-cation for the homogeneity of the initial lot of raw mate-rial This approach makes it possible to classify and to control objectively and with a high degree of confi dence the raw fl uorite from which under optimal technologi-cal conditions of crystal growth only the REE impurities specifi c for each fl uorite varieties and subvarieties (Table 15) are included in the synthetic crystals

In this respect the complex comparison of the typo-morphic compositions of the optically active centres from the initial fl uorite raw materials with those obtained cor-respondingly from them synthetic monocrystals is espe-cially perspective for determination of the indicator role of the different centres and their characteristic combina-tions The solving of this important from a theoretical and practical view task is possible only with the systematic on a unifi ed methodological base on a large experimental material upon the optical properties of fl uorite of different fl uorite varieties represented in a separate deposit and the grown from them monocrystals as it was made for the Slavyanka and the Mikhalkovo deposits

Especially fruitful in the process of research has been the comparative analysis between the optical properties of natural fl uorite and those of the grown from it monocrys-tals On Table 14 15 and in the works of ZIDAROVA (1989 ndash Fig 69 ndash73 2008 ndash Fig 2 2011 ndash Table 10 11 Fig 11) are listed the results for 18 samples from different fl uorite Ta

ble

14 I

nfl u

ence

of t

he R

EE o

n th

e co

lour

and

lum

ines

cenc

e of

fl uo

rite

varie

ties f

rom

the

Slav

yank

a de

posi

t

Varie

tyI

IIa

IIb

IIc

T h degC

153 ndash 20

2(f

requ

ently

155 ndash1

97)

140 ndash

178

(fre

quen

tly 1

45 ndash1

72)

120 ndash

157

(fre

quen

tly 1

26 ndash1

53)

103 ndash

119

(fre

quen

tly 1

10 ndash1

15)

REE

ppm

165

1ndash14

312

333 ndash

687

33

30 ndash

461

80

07ndash 3

479

colo

urgr

een

dark

-vio

let

viol

et p

ale

viol

etvi

olet

pal

e vi

olet

PLS

gree

nda

rk-v

iole

tvi

olet

pale

vio

let

XR

LSD

y-Sm

type

spec

traD

y ty

pe sp

ectra

Dy

type

spec

traU

nallo

yed

type

spec

traTL

S18

0 degС

ndash (Y

O2)deg

def

ectiv

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

130-

150

degС ndash

REE

O2+

- Ondash d

ipol

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

180

degС ndash

(YO

2)deg d

efec

tive

cent

er22

0 degC

ndash R

EE2+

cubi

c ce

nter

28

0 degС

ndash Y

2+ cu

bic

cent

er

320

degС ndash

(REE

O2)deg

def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

OA

SY

b2+(2

653

65)

Ce3+

(306

) Sm

2+(4

25)

F indash (4

00)

2Findash (5

80)

Yb2+

(265

365

) C

e3+(3

06)

Sm2+

(340

) 2F

indash (580

)Y

b2+(2

473

10)

2Findash (5

80)

Yb2+

(310

) F i

ndash (400

) 2F

indash (580

)

252 B Zidarova

Fig

14

Spe

ctro

scop

ic c

hara

cter

istic

s (X

RLS

TLS

OTS

IR

S) o

n ra

w (

__)

and

synt

hetic

(---

) fl u

orite

s fro

m th

e Sla

vyan

ka d

epos

it an

d ar

ea o

f the

thei

r app

licat

ion

(UV

ndash u

ltrav

iole

t V

ndash v

isib

le I

R ndash

infr

ared

)


varieties and their synthetic analogues from the Slavyanka and the Mikhalkovo deposits with chemical and neutron-activation analyses ХRLS TLS OTS OAS IRS as well as their fi eld of application

The zonal change of the constitutional peculiarities of the fl uorite revealed by its indicator properties (most in-formative among them are the optical ones ndash PLS XRLS TLS OTS) is a consequence of the directed change of the mineral-forming processes in the epithermal hydro-thermal deposits It refl ects the directed and nonrevers-ible change of temperature concentration рН and partial pressure of the dissolved in them gasses (ZIDAROVA 2010 ndash Fig 11) As a result the natural fl uorite frees its impurities progressively respectively REE with their fractionation and relatively enrichment of HREE (increase of the TbLa ratio) This process refl ects also in the change of the relation between the TLS activation centers smoothing of XRLS increase of the light absorption in the UV region of the optical spectra etc (ZIDAROVA 2011 ndash Table 10)

This way the study of the fl uorite structure and its ge-netic properties provides a possibility to defi ne and envis-age some new properties that could fi nd effi cient applica-tion in the future (Table 15)

The studied fl uorites include a wide range of impu-rities whose composition depends on the physical and chemical conditions and the rate of crystallization as well as of their formation mechanism If the nonstructural impurities in natural fl uorite can be subjected in a high

degree to purifi cation with the application of different technologies the structural impurities can not be puri-fi ed and they are inherited in the synthetic monocrystals from the initial natural raw material worsening their optic characteristics That is why always during the synthesis of fl uorite monocrystals from natural raw material are studied beside the structural impurities together with the non-structural impurities In some cases the natural raw material is preferred (YONEZAWA et al 2003)

Most informative is the estimation according to ХRLS which refl ects the total action of all the REE upon the optical quality and in the case the granulometry of the material is not of importance The method can be applied for study on the ready material for growth as well as for prognosis of the quality of the monocrystals obtained from assembled samples of initial raw material (ZIDAROVA 2011 ndash Table 11)

This can be illustrated best by comparing the ХRLS ndash one and the same characteristic lines with equal in-tensity are displayed attributed to REE Among them as most important are the four bands related to Dy3+

480 Sm3+

567 Dy3+572Sm3+ ndash Fi

ndash578 with a total sum of intensi-

ties (REE) correlating to the total sum of the intensities of REE (REE) (Fig 10) This was initially developed on natural fl uorite and its synthetic analogues from the Slavyanka deposit and is applied in practice (ZIDAROVA et al 1986 YUSHKIN et al 1986 ZIDAROVA 1989 ZIDAROVA 2008)

Table 15 Concentration of structural and non-structural impurities in natural fl uorite from the Slavyanka deposit and its application

Variety andit application

Non-structural impurities ppm Structural impurities ppmMg Si Al Fe Be Mn Y La Ce Sm Eu Tb Yb Lu

I(V IR)

002 0001 001 0003 ndash 00006 001 1868 3982 638 285 304 401 127

IIa

(IR)003 006 001 0003 0006 002 003 820 1735 1042 365 1036 1741 134

IIb

(V IR)0001 0003 001 002 0006 0003 0003 013 ndash 010 ndash 008 010 004

IIb

(IR)0001 0001 001 001 00003 0006 ndash 021 ndash 017 ndash 018 039 010

IIb

(V IR)0001 0001 001 0003 00001 0003 ndash ndash ndash 001 ndash ndash ndash ndash

IIb

(IR)0006 010 003 0005 00001 0003 ndash 398 716 266 170 181 400 133

IIb

(IR)002 010 006 0001 00003 0006 ndash ndash ndash 019 ndash 012 055 015

IIc

(UVV IR)001 0006 0006 0002 0006 0003 0001 ndash ndash 009 ndash 006 ndash 002

IIc

(UVV IR)001 001 0008 0005 0006 0006 0003 018 ndash 035 010 045 081 011

IIc

(UVV IR)002 003 003 0005 0006 0006 ndash 036 ndash 016 ndash 020 030 017

254 B Zidarova

The character of ХRLS can be used as an element of mineral mapping in fl uorite deposits according to which can be determined the contours of the geological bodies build up by different technological types fl uorite raw ma-terial suitable for the optic industry (ZIDAROV amp ZIDAROVA 1989 1993)

According to the character of TLS the fl uorite vari-eties from the Slavyanka and the Mikhalkovo deposits differ from each other and according to the composi-tion of the molecular centres (Table 14) they belong to the rare earth-oxygen and oxygen-vacancy group (after KRASILrsquoSHCHIKOVA et al 1986) and ZIDAROVA (2011 ndash Ta-ble 10)

A specifi c peculiarity for the fl uorite subvariety IIc (Slavyanka deposit) is almost the total absence of TLS due to the lack of U and Th activation centres with which is linked its stability to radioactive irradiation (VASILrsquoKOVA amp SOLOMKINA 1965) Тhus according to TLS one can also predict the radiation stability of the synthetic monocrys-tals

The optical spectra of natural fl uorite are very inform-ative for the determination of the quality of the grown crystals All the absorption bands attributed to Ce3+ Sm2+ and Yb2+ appear in the absorption bands of the grown sin-gle crystals because of their inheritance but with more clear manifestation as the growth defects in natural fl uo-rite have been eliminated Only the absorption bands at-tributed to Fi

ndash(400) and 2Fi

ndash(580) that are related to defects in

the fl uorite structure are lacking

5 Discussion

It is known that the deposition of hydrothermal fl uorite takes place either from concentrated high-temperature chloride (ZIDAROVA 1978) or from more low-temperature diluted hydrogen-carbonate solutions (CADEK et al 1982 ARKHIPCHUK et al 1989) The investigations display that the Slavyanka deposit belongs to the second group The genesis of the mineral-forming fl uids most probably takes part under the infl uence of СО2 which attacks the host rocks The transportation of Са2+ and Fndash is in the form of complexes (MALININ 1979 CADEK et al 1982 HOLLAND amp MALININ 1979 1982) and the fl uorite deposition is con-trolled mostly by the changes of Т degС and рН near the surface The active role of СО2 partly explains the reverse temperature zoning as well as the rhythm in the mineral deposition

The temperature gradient (T) the orientation of the heat fl ow and the inhomogeneities in the local thermal fi elds are those determining the convective mass-heat transport which appears as zoning in the distribution of

the temperature of fl uorite formation and as regular vari-ation of its constitutive peculiarities thus leading to a di-rection-dependent change of the fl uorite properties

The inverse temperature zoning is due to the fact that the upward heat fl owing in the deposit had been shielded by Tertiary sediments while the strong fracturing of the underlying gneissic massif makes it a heat collector pro-ducing an inverse T A possible pathway is when the circulating hydrothermal solutions (heat carriers) in the cell of the fi rst order fl owed upwards along the Central fault discharging the main part of their thermal energy However the solution of this problem is ambiguous as one can hardly estimate the thermal situation in Mikha-letz zone

The zoned variation in the constitutional peculiarities of fl uorite manifested in its indicator properties the most informative among which are PLS XRLS and TLS as well as OTS result from the evolution of mineral-forming processes It is refl ected in the directed and non-reversible variations and T C pH and Рeq

Slavyanka fl uorites seem to have been deposited at a small depth (40 ndash 500 m) and the comparison between the hypsometric level of deposition and the pressures cal-culated from СО2 solubility in water shows СО2 saturated solutions for most of the fl uorite variety I The data for the fl uorite variety II which data are not quite reliable represent even higher СО2 to water ratios

The rather low salinity of the inclusion water the high СО2 content as well as the presence of calcite in the min-eral paragenesis suggest the hydrogen-carbonate (HCO3

ndash) nature of the ore-forming solutions Contemporary waters that fi ll the fl uorite vein chambers though subthermal are also of NaHCO3 ndash type (Table 3) and they spontaneously release small amounts of СО2 These waters may be as-sumed to have been the last evolution stage of mineral-forming solutions

A rough reconstruction of mineral formation in the Slavyanka deposit can be proposed on the basis of geo-logical data and the results obtained emphasizing the role of СО2 as a main pH regulator The beginning of every impulse seems to be marked by a СО2 infl ux and hence a decrease in the pH-values of solutions This has led to the total dissolution of earlier calcite and deposition of quartz Later the СО2 water ratio decreased and pH reached near to neutral values when fl uorite crystallized The exhaus-tion of СО2 and the decrease in the acidity of solutions made possible crystallization of calcite in the end of every impulse

The mechanism of formation of fl uorite bodies de-pends on local peculiarities of the hydrothermal system such as the mineral composition of embedding rocks and the degree of their tectonic pretreatment the degree of


opening of the system chemistry of solutions the T be-tween the front of crystallization and the solution

The epithermal character of fl uorite formation (KO-PLUS 1988) has been related to the processes of hydro-thermal argillitization of the embedding rocks ie to the intense formation of montmorillonite from the alteration of gneisses schists and amphibolites The process has contributed to increasing the impermeability of the walls of penetrating faults along which the hydrothermal solu-tion have fl own and has promoted their increasingly inert behavior with respect to circulating solutions This type of hydrothermal variations is of a regional character in the Ograzhden massif and characterizes pre-ore hydrothermal processes which have been possibly synchronous with the formation of the volcanic massifs in the region

The mechanism of growth of fl uorite crystals and ag-gregates on a microscale depends on the degree of open-ing of the hydrothermal system and on the equilibrium state in crystal-solution system

If the T between the front of crystallization and the solution in an open system far from equilibrium exceeds certain extreme values (eg 22 degС as is case in the Slavy-anka deposit) synergetic effects would have come into play ie self-organization of the medium through dissi-pation originating from convective mass-heat transport in dissipative cells with polygonal cross-section of the front of crystallization (instability of Benar) These are revealed in the anatomy of growing fl uorite aggregates through specifi c dissipative structures The aggregate growth in each dissipative cell has proceeded individually and in competition between aggregates and geometric se-lection has been observed similarly to that in group crystal growth (ZIDAROVA 1989 ZIDAROVA et al 2002) Account-ing for the approximations in the model (ZIDAROVA et al 2002) the obtained value for the growth rate of fl uorite is comparable to that measured in laboratory experiments (ZIDAROVA 1978) The same correspondence has been ob-served for the growing time of quartz crystals in nature and in laboratory autoclave (ASKHABOV 1993) The model proposed for the formation of fl uorite aggregates from the Slavyanka deposit is an alternative possibility to the min-eralogical concepts for the growth of mineral aggregates (GRIGORIEV amp ZHABIN 1975 MALEEV 1971) which relates their structure with the dynamics of the forming medium

In open hydrothermal systems local variations in the concentration of Ca2+ and Fndash ions take also place along the front of crystallization The ratio of their activities and product of solubility deter-mine the processes of dissolution (1) and regeneration (1) of fl uorite crystals and aggregates and refl ect in their zoned structure One can assume that zoned deposition on montmorillonite on the pyramid of crystal growth or

2+ 2

2CaFCa F

[(a ) (a ) Ksp 1]

along the front of crystallization of dissipative cells has resulted from self-vibrational reactions of the solution

In a closed hydrothermal system under stagnant condi-tions taking place in some caverns due to gravity strati-fi cation of hydrothermal solutions local fl uctuations in their concentration have originated leading to the occur-rence of aggregates of banded structure (the Mikhaletz region)

Under such conditions though on rare occasions one can observe growth of fl uorite spherolites in colloidal me-dia e g montmorillonite gels or water saturated masses of montmorillonite

The statistical treatment of the content of REE has revealed that the two main from a viewpoint of their amount and distribution fl uorite varieties in the deposit which differ in morphology colour and temperature of formation also differ considerably in the distribution of REE Thus there is a tendency for the LREE to be con-centrated in earlier whereas the HREE in the later fl uorite varieties as well as an increase on their content in the up-permost levels of the deposit

According to МOumlLLER (1983) МOumlLLER et al (1976 1981) DILL et al (1986) the change in the relative con-centrations of the end-members of the series La-Lu is most marked in fl uorites and calcites and the atomic ratios TbCa-TbLa can also be used for obtaining genetic con-clusions It has been suggested that the solutions would be initially enriched with LREE while relatively poor in HREE provided that they are not entirely bonded in clus-ters with fl uorine ions As the crystallization progresses an additional fractioning of REE would take place in the solution resulting in an increase of the atomic ratios TbCa-TbLa which can serve as an indication for primary crystallization (ZIDAROVA 1989 ndash Fig 19 ZIDAROVA 1995 a ndash Fig 1) In a TbCa-TbLa diagram (Fig 8) the fl uorites of the Slavyanka deposit plot in the hydrothermal fi eld (МOumlLLER et al 1976)

If the primary fl uorite is the remobilized during its redeposition it would be crystallizing from solutions of approximately the same activity of Ca2+ and Fndash ions and the HREE would remain in the solution in the form of complexes Thus ion exchange would take place only between LREE in the solution and the embedding rocks resulting in an increase of the ratio TbLa

The neutron-activation data for fl uorites of the fl uo-rite varieties I and II (Table 5) are presented in Fig 8 It is seen that the fl uorite variety II can be classifi ed as a primary since for the tilt angle of the least-square linear approximation tg122

The small tilt angle (tg044) for the fl uorite va-riety I speaks in favour of the presence of points in its fi eld belonging to primary and redeposited fl uorite forms

256 B Zidarova

which could be classifi ed to fl uorite subvarieties Iа and Ib respectively formed under differing thermal condition (ZIDAROVA 1989)

The (TbYb)n-(LaYb)n ratios indicated the order of crystallization (МOumlLLER et al 1976 HILL et al 2000 RON-CHI et al 1993 SASMAZ et al 2005 ab) In the Slavyanka deposit octahedral fl uorites (fl uorite variety I) preferen-tially concentrated LREE as a result of high (LaYb)n and low (TbYb)n ratio (Table 5) have crystallized too early Similar to all low-temperature hydrothermal deposits the fl uorites from the Slavyanka deposit also indicate a LREE enrichment positive to negative Eu anomalies (Fig 7)

The increase of the Sr content is in contrast to the con-tent of Eu and the EuEu relation from the earlier fl uor-ites towards the later fl uorite varieties This can be linked to the decomposition of feldspars from the host rocks and their assimilation from the hydrothermal solution Similar cases are also observed by researchers of fl uorite deposits related to Tertiary acid and medium volcanic rocks (EP-PINGER amp GRAHAM Closs 1990)

The data for the arbitrary content of REE in the stud-ied fl uorites calculated after the intensities of the lines in the XRLS spectra are compared to their content which have been quantitatively determined with neutron-activa-tion analyses The obtained results are the base for the following conclusions

ndash XRLS of fl uorite varieties I are highly complicat-ed and with most intensive lines of REE with their sta-ble confi guration the most characteristic is the doublet Dy3+

(572) ndash Sm3+(567)

ndash XRLS of fl uorite subvarieties IIa and IIb are with close confi gurations but sharply differ according to the intensity of the corresponding lines and fl uorite subvari-ety IIc has a spectrum without structure characteristic for fl uorite with extremely low REE content Among these three types of spectra there is some sort of similarity con-fi rmed by the occurrence of transfer types The grouping of the samples among the main types is an evidence for the existence of discretion in the mineral-forming process from the III impulse caused by the change of the char-acteristics of the mineral-forming medium correspond-ing to a progressive decrease of the REE content from an earlier fl uorites toward later fl uorite varieties from this impulse

An impression is obtained that the samples of the same type according to their REE composition in most cases are similar and according to the relation of the ХRLS pa-rameters As the results display the ХRLS parameters are determined by the regularities in the selective incorpora-tion of different groups of REE3+ in the fl uorite cell de-pending on of the geochemical peculiarities and the ther-modynamic parameter of the mineral-forming medium

Their variations are regularly connected not only to the geochemical and genetic specifi cation of fl uorite but also with the regional and local changes in the thermobaromet-ric and geochemical parameters of the medium in time

The appearance of REE as luminescence centres in fl uorite is indicative of the following conditions of fl uo-rite formation low temperatures of formation ndash upon fast cooling excess of F OH-groups in the mineral-forming medium and under the presence of reduction condition (KRASILlsquoSHCHIKOVA amp POVARENNIKH 1970)

The comparison of the ХRLS parameters reviewed in the case of fl uorite from the Slavyanka deposit gives the opportunity to detect the similarity and difference be-tween the different fl uorite varieties as well as the char-acter of change (continuous or discrete) in the physical and chemical conditions of crystallization of fl uorite at the individual ndash mineral body ndash deposit levels

Higher-temperature peaks of TLS are more charac-teristic for the higher-temperature fl uorite varieties than those for the lower-temperature ones Besides a stronger TLS is observed in the green coloured fl uorite varieties I The presence of TLS is an indication for the presence of U and Th in the fl uorite lattice (ZIDAROVA 1992 b)

The fl uorites with octahedral habit are formed under more oxidation conditions ndash a defective (REEO2)deg centre is prevalent in comparison with these with a cubic one In the other fl uorite varieties the peaks on the TLS curves are of lover intensity

In the various fl uorite varieties the above listed centres are in different combinations depending both on the con-tents of REE U Th and Th degC and on the compositions of the centers and their electron structure

In IRS the weaker expressive band also are observed at 3000 ndash 4000 сmndash1 and 1650 cmndash1 Probably they corre-sponding with Н2О and CO3

2ndash in fl uid inclusions as es-tablished with gas analyses (ZIDAROVA amp PIPEROV 1995) Indication of that are the decreasing intensities in grindcrush samples in which they fully disappeared

The character of XRLS can be applied as an element of the mineralogical mapping of fl uorite deposits according to which the contour of the geological bodies are deter-mined as built up by different technological types of fl uo-rite raw material suitable for the optic industry (ZIDAROV amp ZIDAROVA 1989 1993)

The fl uorite varieties from the Slavyanka and the Mikhalkovo deposits differ according to the character of the TLS and according to the composition of their molecu-lar centres (Table 14) they belong to the rare earth-oxygen and oxygen-vacancy group (after KRASILrsquoSHCHIKOVA et al 1986) and ZIDAROVA (2011 ndash Table 10) Specifi c peculiar-ity of the fl uorite subvariety IIc (the Slavyanka deposit) is almost the total absence of TLS due to the absence of U


and Th activation centers with which is linked to its sta-bility to radioactive irradiation (VASILrsquoKOVA amp SOLOMKINA 1965) Thus according to TLS the radiation stability of synthetic monocrystals can be predicted

The optical spectra of natural fl uorite are very in-formative for determination of the quality of the grown of the single crystals All the absorption bands attributed to Ce3+ Sm2+ and Yb2+ appear in the absorption bands of the grown single crystals as also reported in a study (SILS et al 2009) because of their inheritance but with more clear manifestation as the growth defects in natural fl uorite have been eliminated Only the absorption bands attributed to Fi

ndash(400) and 2Fi

ndash(580) which are related to defects

in the fl uorite structure are lackingThe estimation of the Ce content in the primary sample

also does not depend on its condition and the absorption band in the synthetic monocrystals determines in a large degree their permeability and application in optics A cor-relation link has been established between the Ce content determined according to neutron-activation method and the coeffi cient of absorption of Се3+

306 calculated from the OAS (ZIDAROVA 1989 1992 а 2008) Such correlative link can be applied as an express method for estimation of the quality of the future synthetic crystals according to analytical data of the raw material

Characteristic for the fl uorites from the Slavyanka de-posit is the same confi guration of OTS for each fl uorite variety and their synthetic analogue Only in the fl uorite subvariety IIb and its synthetic analogues two types of curves are observed in the fi rst one appears an absorp-tion band Yb2+

308 and in the second one ndash Yb2+365 (with

a higher content of Yb2+ according to neutron-activation analyses data another confi guration of TLS and a higher intensity of the peaks) (Table 10 12 A 14) The shift of the Yb2+ absorption band towards the short wave region is regular explained by the decrease of the temperature of crystallization and an indication of lower energy of inter-action of the Yb2+-ions in the crystal fi eld of the fl uorite cell In this manner by the position of the Yb2+ absorption band in the ОТS one can also judge the relative change of the temperature of formation of fl uorite

The weak TLS in fl uorite subvarieties IIb and IIс as well as its absence in some fl uorite subvarieties IIс is an indicator for the infl uence of Yb2+-ions on the fl uorite cell directly from the hydrothermal solution аnd not as a result of the reduction of Yb3+ under radioactive irradia-tion (DANIELS et al 1953 a b) This gives the explanation for the increased content of Yb2+ observed by ILIEV et al (1988) and it is an indication for a low oxidation-reduc-tion potential of the mineral-forming medium

According to IRS data each fl uorite variety is char-acterized by a typical spectrum Absorption bands in the

region of stretching (3400 cmndash1) and deformation vibra-tions (1630 cmndash1) ОН-groups have also been observed at 1400 ndash1500 cmndash1 due to CO3

2ndash in all of them In the grown monocrystals such bands are absent because since the be-ginning of crushing of the raw material the СО2 comes out from the fl uid inclusions аnd the Н2О evaporates

The optical spectra are with the most reduced applica-tion as one can predict with them with confi dence only the appearance of absorption bands in the UV-region the degree of light transmission not being able to be detected correctly If special facilities and methods are not used their application is only for estimation of fl uorite from which thin slices can be produced During the study of zonal crystals and aggregates even during the measure-ment of the light transmittance in each of the zones prog-nosis on their total infl uence on the quality of the future crystal could not be made but only the cause for the col-our may be determined

The suggested methods for estimation of the optic quality of the synthetic fl uorite monocrystals are with a different level of information and correspondingly the reliability of the prognostic estimation is also different It also depends on the technical possibilities of the research laboratory

According to the investigations on a large number of experimental materials it was determined that one part of fl uorite subvariety IIc from the Slavyanka deposit can be applied directly for growth of non-defect details for the optic industry with diameter up to 20 mm with ap-plication in the IR- and even in the V-area It has a high chemical purity (Table 5 No2 IIc) and is of a non-impuri-ty type ХRLS with specifi c OTS and IRS (ZIDAROVA 1989 ndash Fig 77 2008 ndash Fig 4)

All these studies and results show that for the esti-mation of defi nite natural fl uorite raw material in gen-eral and for its future application for example in optics a detailed mineral sampling is required as already done (ZIDAROV et al 1987) The quantity of the impurities is different along the vein in the upper and lower salband in its narrow sites apophyses as well as at the different hypsometric levels (Table 5) This cannot be done with random sampling in the deposits or by the use of samples from museums In such a case they only can give some idea about their quality (content) but not for future ap-plication

6 Conclusions

The studies on the mineralоgical peculiarities of fl uo-rite from the Mikhalkovo (ZIDAROVA 2010 2011) and the Slavyanka deposits aimed to solve two important prob-

258 B Zidarova

lems The fi rst one is to create a concrete theoretical model for the dynamics of the mineral-forming processes in the geological space where the deposits are located with their areas and separate bodies of specifi c fl uorite varieties The second one is the prognostics of the potential of the de-posit according to the quantity of fl uorite raw material ap-plied for traditional uses as well as for some of its genetic properties predetermining its application in advanced and more effective industries as the optic industry

Observing the dynamics of the hydrothermal process it was established that the temperature of homogeniza-tion of the fl uid inclusions the mineral composition of the primary and altered host rocks as well as the texture peculiarities of the fl uorite aggregates (origin of dissipa-tive structures) are the most informative for deciphering of the thermal regime of fl uorite formation Element com-position the composition of the fl uid inclusions as well as the composition of contemporary underground waters in the region of the deposits are the most informative for the chemistry of the processes The mechanism of forma-tion of fl uorite crystals and aggregates and their mineral assemblage points to their structural-textural peculiarities and sequence of deposition as well as the whole com-plex of typomorphic features according to which natural bodies built up by defi nite fl uorite varieties and can be separated and individualized in depth Additional infor-mation for the genesis of the deposits can be obtained by the study of the constitutional peculiarities of fl uorite which refl ect in its optical properties The established evolutionary habit row of fl uorite varieties focuses on the evolution of the mineral-forming medium and variety of its parameters A synthesis of this natural regularity is the crystallоgenetic diagram (ZIDAROVA 1989 ndash Fig 65 2010 ndash Fig 11) composed for the fl uorite from the Mikhalkovo deposit which is also confi rmed for the Slavyanka depos-it and is probably valid for all the deposits of the Fluorite formation

The established regularities in the distribution of the temperature of formation and the corresponding habit fl u-orite varieties can be used for determination of the width of the ore interval in horizontal sections of the ore bod-ies Such zoning confi rmed in the distribution of fl uorite varieties also in the Slavyanka deposit also linked with temperature zoning allows an exact determination of the asymmetrical spatial distribution of the fl uorite bodies for each of them indicating as perspective the Vodena Skala site in depth (ZIDAROV et al 1987) According to extensive mineralоgical mapping in the Slavyanka deposit it be-came possible to separate industrial bodies from a defi nite mineral-genetic type with fl uorite raw material of specifi c quality for selective production (ZIDAROV amp ZIDAROVA 1989 1993)

The mutual link between the constitutional peculiari-ties and the optical properties of fl uorite allows a progno-sis of the quality of the future synthetic calcium fl uoride monocrystals as well as to judge according to their opti-cal indicators upon the crystal chemistry of the fl uorite from the initial raw material

The correlation between the contents of Ce in the raw fl uorite and the coeffi cient of absorption of Се3+

360nm in the synthetic monocrystals could be used as an express method for preliminary determination of their quality The variety of methods that could be used for determi-nation of the optical quality of the synthetic fl uorite monocrystals (XRLS TLS OTS and IRS) show differ-ent informative degrees resulting in varying reliability of the prognostic estimation One important characteristic of the fl uorite subvariety IIc is the very low content of the REE which are sometimes even absent It could be explained by the observation that parallel to the progress of the mineral-forming process the solutions purify them-selves of REE Thus it could be demonstrated that from that variety ready optical details suitable for the infrared and visible spectra without further recrystallization could be taken In this way the study of the fl uorite structure and its genetic properties provides a possibility to defi ne and envisage some new properties that could fi nd effi cient application on the future (ZIDAROVA 2008)

Acknowledgements

The author wishes to thank Acad DSc N P YUSHKIN PhD G A MARKOVA A I VYBOROV and N B VOLKOVA for research facilities kindly offered and for their help during the spectroscopic experiments at the Geological Institute Komi Scientifi c Center of the Ural Branch of the Russian Academy of Sciences as well as for their fruitful coopera-tion The referees to Prof H-G DILL (Federal Institute for Geosciences and Natural Resources Hannover Germany) and Acad N P YUSHKIN (Geological Institute Komi Sci-entifi c Center of the Ural Branch of the Russian Academy of Sciences) are greatly acknowledged for their construc-tive comments and suggestions I extend my gratitude also to Prof H-G Stosch (University Karlsruhe Germa-ny) and to Prof R KLEMD (Institute for Mineralogy and University Erlangen-Nuumlrnberg Germany) for editorial handling of my manuscript


References

AIERKEN S KUSACHI I amp YAMASHITA N (2003) Natural fl uo-rite emitting yellow fl uorescence under UV light ndash Physics and Chemistry of Minerals 30 8 478 ndash 485

ALEKSIYEV E amp PAVLOVA M (1967) Rare earths in many of the Bulgarian fl uorite deposits ndash Bulgarska Akademiya na Naukite Geologicheski Institut Izvestiya Seriya Geokhimiya Mineral-ogiya i Petrografi ya 16 17ndash 23 (in Bulgarian)

ARKHIPCHUK R Z GALABURDA Y A amp GORBACHEVA L Y (1989) Fluorite forming hydrotherms in deposits from Central Asia ndash Mineral Rev Lvovsk Univ 43 1 35 ndash 41 (in Russian)

ARKHIPCHUK R Z KOVALrsquoSKIY F I LOKERMAN A A amp ROSIKHINA A I (1968) Mineral-thermometry characterization and tem-perature zonality in the fl uorite deposits of the Khurai Ore Field (Western Zabaikalye) ndash In Mineralogical Thermometry and Ba-rometry I Nauka Press Moscow 261ndash 268 (in Russian)

ARKHIPCHUK R Z amp LOKERMAN A A (1966) New data on the dependence of the morphology of fl uorite crystals on the condi-tions of formation ndash Mineral Rev Lvovsk Univ 20 4 602 ndash 605 (in Russian)

ASKHABOV A M (1993) Crystallogenesis and Evolution of the Crystal-Medium System ndash Nauka St Petersburg 155 pp (in Russian)

BILL H amp CALAS G (1978) Color centers associated rare-earth ions and the origin of coloration in natural fl uorites ndash Phys and Chem Miner 3 2 117ndash131

BODYL S (2009) Luminescence properties of Ce3+ and Eu2+ in fl uorites and apatites ndash Mineralogia 40 1ndash 4 85 ndash 94

BONEV I (1979) Fibrous montmorillonite and ldquofl uorite gelsrdquo from the Slavyanka deposit district of Blagoevgradndash Geochem Min-eral and Petrol 11 66 ndash78 (in Bulgarian)

BONZE S amp RAKOVAN J (2002) Surface-structure-controlled sec-toral zoning of rare earth elements in fl uorite from Long Lake New York and Bingham New Mexico USA ndash Geochim et Cosmochim Acta 66 6 997ndash1009

CADEK I VESELI I amp MAJER V (1982) Transport of fl uorine in low temperature hydrothermal brines ndash In Geologiya Rudnykh Mestorozhdenii Proc VI symp IAGOD Tbilisi p 235

CONSTANTOPOULOS J (1988) Fluid inclusions and rare earth ele-ment geochemistry of fl uorite from South-Central Idaho ndash Eco-nomic Geology 83 3 326 ndash 636

DANIELS F BOYD C amp SAUNDERS D (1953 a) Thermolumines-cence as a research tool ndash In Advances in Physical Sciences 51 2 271ndash 286 (in Russian)

DANIELS F BOYD C amp SAUNDERS D (1953 b) Thermolumines-cence as a research tool ndash Science 117 343 ndash 349

DILL H G DULSKI P amp МOumlLLER P (1986) Fluorite mineraliza-tion and REE patterns in vein-type deposits from the N Bavarian Basement (Germany) ndash N Jb Miner Abh 154 141ndash151

DILL H G amp WEBER B (2010) Variation of color structure and morphology of fl uorite and the origin of the hydrothermal F-Ba deposits at Nabburg-Woumllsendorf SE Germany ndash N Jb Miner Abh 187 2 113 ndash132

EPPINGER R amp GRAHAM CLOSS L (1990) Variation of trace ele-ments and rare earth elements in fl uorite a possible tool for ex-ploration ndash Economic Geology 85 1896 ndash1907

ERMAKOV N P (1948) Use of defects in fl uorite crystals for inves-tigating mineral natural history ndash Miner Collected Papers Lvov Geol Soc 2 93 ndash112 (in Russian)

ERMAKOV N P (1950) Research on mineral-forming solutions ndash Kharkov Univ Press 460 pp (in Russian)

GAFT M REISFELD R amp PANCZER G (2005) Luminescence Spec-troscopy of Minerals and Materials ndash Springer-Verlag Heidel-berg Berlin 361 pp

GRIGORIEV D P amp ZHABIN A G (1975) Ontogeny of Minerals Individuals ndash Nauka Moscow Leningrad 339 pp (in Russian)

GMURMAN V E (1977) Theory of Probability and Mathematical Statistics ndash Vysshaya Shkola Moscow p 328 ndash 330 (in Russian)

HASKIN L A FREY F A SCHMITT R A amp SMITH R H (1966) Meteoritic solar and terrestrial rare-earth distributions ndash In AH-RENS L H PRESS F RUNCORN S K amp UREY H C (eds) Phys-ics and Chemistry of Space vol VII Pergamon Press Oxford 167 pp

HILL G T CAMPBELL A R amp KYLE P R (2000) Geochemistry of southwestern New Mexico fl uorite occurrences implications for precious metals exploration in fl uorite-bearing systems ndash J Geo-chem Expl 68 1ndash 20

HODBY J W (1974) The optical properties of the fl uorite com-pounds ndash In HAYES W (ed) Crystals with the fl uorite structure Electronic vibrational and defect properties Clarendon press Oxford 24 ndash 29

HOLLAND H D amp MALININ S D (1979) The solubility and occur-rence of non-ore minerals ndash In BARNES H E (Ed) Geochem-istry of hydrothermal ore deposits John Wiley New York 2nd edition 46 1ndash 508

HOLLAND H D amp MALININ S D (1982) The solubility and occur-rence of non-ore minerals ndash In Geochemistry of hydrothermal ore deposits Mir Moscow 370 ndash 404 (in Russian)

ILIEV M LIAROKAPIS E amp SENDOVA M (1988) Laser excited lu-minescence of rare earth impurities in natural and synthetic CaF2 ndash Phys Chem Minerals 15 597ndash 600

IVANOV R amp ZIDAROV N (1968) On the Petrochemistry of the Ter-tiary Volcanism in the Mountains of Ograzden Malesevska and Vlahina SW Bulgaria ndash Bull of the Geol Inst ser Geochem Miner and Petrogr 17 295 ndash 309 (in Bulgarian)

IVANOVA A A (1974) Fluorite deposits of Eastern Transbaikal ndash Nedra Moscow 208 pp (in Russian)

IVANOVA A A (1981) Forecasting criteria and methodology in the fl uorite and barite deposits in development zones of postorogenic magmatism and in the regions of tectonic-magmatic activity ndash In RUNDKVIST D amp EROFEEV B (eds) Forecasting Criteria and Methodology in the Deposits for Metallic and Nonmetallic Use-ful Minerals Moscow chapter III 104 ndash148 (in Russian)

IVANOVA A A MIKHAILOVA Y I amp NOVOLINSKAYA S A (1986) Industrial Raw Materials Fluorite ndash Criteria of Predicting Valua-tion of the Territories for Solid Useful Materials Chapter 4 Len-ingrad Nedra 610 ndash 629 (in Russian)

KALIKOV V N (1982) Analysis of the graphic images in crystal zoning ndash In Crystallogenesis Papers of the Geology Institute Republic Komi Branch AS USSR 39 72 ndash 80 (in Russian)

KAZANSKY V I MALINOVSKY E P NAUMOV G B PEK А А amp SAFONOV Y G (1978) Infl uence of structural factors on the hydrothermal ore deposition ndash In Geological Structures of En-dogenous Ore Deposits Nauka Мoskow 21ndash 40 (in Russian)

KEMPE U (2006) On violet coloration of natural fl uorite ndash Fedor-ov Session 2006 Abstracts of the Internal Scientifi c Conference Saint-Petersburg Russia 162 ndash164

KOLONIN G R amp SHIRONOSOVA G P (2006) Peculiarities of REE distribution between fl uorite and ore-forming fl uid (thermody-namic modeling) ndash Vestnik Otdelenia nauk o zemle Akademii Nauk Russii 1 24 1ndash 3 (in Russian)

KOLONIN G R amp SHIRONOSOVA G P (2007) REE distribution be-tween fl uorite and ore-forming fl uid based on results of thermo-dynamic modeling ndash Doklady Akademii Nauk 414 4 535 ndash 539 (in Russian)

260 B Zidarova

KOLONIN G R amp SHIRONOSOVA G P (2009) Fluorite as a marker of REE behavior during hydrothermal ore-forming processes ndash Geochimica and Cosmochimica Acta Supplement 73 p A677

KOPLUS A V (1988) Model of formation of ores of the epithermal fl uorite formation genetic type ndash In Ore Genesis and Genetic Models of Endogenous Ore Formations Nauka Novosibirsk SO 323 ndash 334 (in Russian)

KOPLUS A V KORITOV F Y amp PUZANOV L S (1968) New data on the vertical temperature zonality in the deposits of the Fluo-rite formation ndash Reports at the 3rd All-Union Meeting on the Mineralogical Thermometry and Geochemistry of the Abyssal Mineral-forming Solutions Moscow 198 ndash 200 (in Russian)

KORYTOV F Y (1972) Form and colour of fl uorite crystals from the fl uorite deposits of the Zabaikalie ndash In Typomorphism of Miner-als and Its Practical Signifi cance Nedra Moscow 129 ndash131 (in Russian)

KRASILlsquoSHCHIKOVA O A IVANOVA G F amp TARASHCHAN A N (1981) Compositional evolution of luminescence centers in fl uorites at different stages of mineral deposition evidence from the Yugodzyr molybdenum-tungsten deposit (Mongoliya MNR) ndash Mineralogicheskiy Zhurnal 5 11ndash 20 (in Russian)

KRASILlsquoSHCHIKOVA O A amp NECHAYEV S B (1984) Mapping geo-chemical barriers by means of the luminescence properties of fl uorite ndash Mineralogicheskiy Zhurnal 6 1 37ndash 42 (in Russian)

KRASILlsquoSHCHIKOVA O A amp POPOVA V I (1984) Topographic study of luminescence of the fl uorites from the Hingansk tin-bearing deposit ndash In Crystal Chemistry and Spectroscopy of Minerals Naukova Dumka Kiev 101ndash109 (in Russian)

KRASILlsquoSHCHIKOVA O A amp POVARENNIKH O S (1970) Lumines-cence spectra of fl uorite mineralogy and geochemistry ndash Geo-logicheskiy Zhurnal Kiev 30 5 28 ndash 38 (in Russian)

KRASILlsquoSHCHIKOVA O A TARASHCHAN A N amp PLATONOV A N (1980) Color centers and luminescence of fl uorite as geochemi-cal and genetic indicators ndash In Sedimentary Rocks and Ores Naukova Dumka Kiev 55 ndash 61 (in Russian)

KRASILlsquoSHCHIKOVA O A TARASHCHAN A N amp PLATONOV A N (1986) Coloration and Luminescence of Natural Fluorite ndash Kiev Naukova Dumka 224 pp (in Russian)

MALEEV M N (1971) Properties and Genesis of Natural Whiskers and Their Aggregates ndash Nauka Moscow 200 pp (in Russian)

MALININ S D (1979) Physical Chemistry of Hydrothermal Sys-tems Containing Carbonic Acid ndash Nauka Moscow 111 pp (in Russian)

MALINOVSKY E P (1982) Structural open-close system as factor for the intensity of ore-formation ndash In Geological Environment and Structural Conditions for Hydrothermal Ore Genesis Nauka Moscow 203 ndash 207 (in Russian)

MARFUNIN A S (1975) Spectroscopy Luminescence and Radia-tion Centers in Minerals ndash Nedra Moscow 327 pp (in Russian)

MORGUNOV K G amp BYKOVA V G (2009) Thermodynamic mod-eling of the REE distribution among fl uorite and oreforming fl uid in postmagmatic deposits in Western Transbaikalia ndash Geologia and Geophizika 50 7 778 ndash785 (in Russian)

МOumlLLER P (1983) Lanthanides as a geochemical probe and prob-lems in lanthanide geochemistry Distribution and behavior of lanthanides in nonmagmatic-phases ndash Systematic and Properties of the Lanthanides Berlin Reidel Publ Comp 561ndash 616

МOumlLLER P DULSKI P SCHLEY F LUCK J amp ZACKI W (1981) A new way of interpreting trace element concentrations with re-spect to modes of mineral formation ndash J of Geochemical Explo-ration 15 271ndash 284

МOumlLLER P PAREKH P P amp SCHNEIDER H J (1976) The applica-tion of TbCa-TbLa abundance ratios to problems of fl uorspar genesis ndash Mineralium Deposita 11 111ndash116

NAUMOV V B DOROFEEVA V A amp MIRONOVA O F (2009) Prin-cipal physicochemical parameters of natural mineralforming fl u-ids ndash Geochemistry international 47 8 777ndash 802

NECEV D (1979) The Slavyanka fl uorite deposit village of Palat Blagoevgrad district ndash Geochem Miner and Petrol 11 35 ndash 50 (in Bulgarian)

PECSKAY Z HARKOVSKA A ZIDAROV N ZAGORCHEV I POPOV M amp PANTEVA V (2001) K-Ar dating of the Tertiary volcanic rocks from Ograzden and Maleshevska Mountains South-Western Bulgaria ndash Compt rend Acad bulg Sci 54 4 71ndash76

PIPEROV N B (1984) A concise review of the up-to-date methods for chemical analysis of the fl uid inclusions in minerals ndash In Proc of the 27th Intern Geol Congress Mineralogy Moscow 10 165 ndash184

PIPEROV N B KAMENSKY I L amp TOLSTIKHIN I N (1987) Isotopes of the light noble gases in thermal source in Bulgaria ndash Geo-chemiya 2 1712 ndash1721 (in Russian)

PIPEROV N B KAMENSKY I L amp TOLSTIKHIN I N (1994) Isotopes of the light noble gases in mineral waters in the eastern part of the Balkan Peninsula Bulgaria ndash Geochimica and Cosmochimica Acta 58 8 1889 ndash1898

PIPEROV N B PENCHEV N P amp ZIDAROVA B P (1979) The analy-sis of the volatiles from fl uid inclusions in hydrothermal fl uorite ndash Chem Geol 27 215 ndash 231

PIPEROV N B PENCHEV N P amp ZIDAROVA B P (1986) Evidence for the chemical nature of fl uorite-depositing solutions based on the fl uid inclusion studies (Palat Bulgaria) ndash In Conditions of the forming on the ore deposits (6th IAGOD Symposium Sep-tember 6 ndash12 1982 Tbilisi USSR) Moscow 1 354 ndash 365

PLATONOV A N (1976 a) Nature of Coloring of Minerals ndash Nau-kova Dumka Kiev 264 pp (in Russian)

PLATONOV A N (1976 b) Typomorphic signifi cance of the colour of minerals ndash In Minerals All-Union Conference ldquoPhysics of Minerals and Problem of Typomorphismrdquo Leningrad 31ndash 39 (in Russian)

PSHIBRAM K (1947) On the fl uorescence of fl uorite and two-va-lence rare earths ndash Dokladi Academii Nauk SSSR IV 56 4 31ndash 35 (in Russian)

PSHIBRAM K (1959) Color and Luminescence of Minerals ndash IL Moscow 458 pp (in Russian)

PUZANOV L S (1972) Temperatures of formation and temperature zonality of fl uorite mineralization ndash Geol Rudn Mestorozhdenii (Geology of Ore Deposits) 4 66 ndash75 (in Russian)

RENTSCH J (1958) Beitraumlge zur geochemie der Fluoritvorkommen des Thuumlringer Waldes ndash Geologie 7 924 ndash 934

RONCHI L H TAURAY J C MICHARD A amp DARDENE M A (1993) The Ribeira fl uorite district Southern Brasil geological and geochemical (REE Sm-Nd isotopes) characteristics ndash Min-eral Deposita 28 240 ndash 250

SASMAZ A OumlNAL A SAGIROGLU OumlNAL M amp AKGUL B (2005 a) Origin and nature of the mineralising fl uids of thrust zone fl uor-ites in Ccedilelikhan (Adiyaman Eastern Turkey) A geochemical ap-proach ndash Geochem Journal 39 131ndash139

SASMAZ A YAVUZ F SAGIROGLU A amp AKGUL B (2005 b) Geo-chemical patterns of the Akdagmadeni (Yozgat Central Turkey) fl uorite deposits and implications ndash Journal of Asian Earth Sci-ences 24 469 ndash 479

SCHMETZER K BANK H amp GUBELIN E (1980) The alexandrite ef-fect in minerals chrysoberyl garnet corundum fl uorite ndash N Jb Miner Abh 138 2 147ndash164

SILS J HAUSFELD S CLAUSS W PAHL U LINDER R amp REICH-LING M (2009) Impurities in synthetic fl uorite for deep ultravio-let optical applications ndash Journal of Applied Physics 1061ndash 8


SMOLYANSKY P L (2002) Principles of typifi cation and interpreta-tion of the X-ray excited optical luminescence spectra of natural fl uorite ndash Zapiski Vsesoyuznogo Mineralogicheskogo obsh-chestva 3 97ndash105 (in Russian)

STEPANOV I V amp FEOFILOV P P (1957) Crystal Growth ndash Mos-cow AS USSR 229 ndash 241

STOCKBARGER D C (1949) Artifi cial fl uorite ndash Opt Soc Amer 39 731ndash740

STRONG D F FRYER B J amp KERRICH R (1984) Genesis of the St Lawrence fl uorspar deposits as indicated by fl uid inclusion rare earth element and isotopic data ndash Economic Geology 79 1142 ndash1158

TAKENOUCHI S amp KENNEDY G C (1964) The binary system H2O-CO2 at high temperatures and pressures ndash Amer J Sci 262 1055 ndash1074

TARASHCHAN A N (1978) The Luminescence of Minerals ndash Nau-kova Dumka Kiev 292 pp (in Russian)

TARASHCHAN A N KRASILlsquoSHCHIKOVA O A amp PLATONOV A N (1975) X-ray luminescence of natural fl uorite ndash Konstitutsiya i Svoystva Mineralov 9 111ndash120 (in Russian)

TARASHCHAN A N KRASILlsquoSHCHIKOVA O A PLATONOV A N amp POVARENNYKH A S (1974) Thermoluminescence in natural fl uo-rite ndash Mineralogicheskiy Sbornik (Lvov) 28 1 8 ndash17 (in Rus-sian)

TRINKLER M MONECKE T amp THOMAS R (2005) Constraints on the genesis of yellow fl uorite in hydrothermal barite fl uorite veins of the Erzgebirge Eastern Germany evidence from optical absorption spectroscopy rare-earth-element data and fl uid inclu-sion investigation ndash Canadian Mineralogist 43 883 ndash 898

VASILrsquoKOVA N N KARTENKO P F amp KUKUSHKINA O A (1972) Connection between the fl uoritersquos properties and the trace ele-ment composition ndash Trudy VNIIMS 4 158 pp (in Russian)

VASILrsquoKOVA N N KUKUSHKINA O A PETROPAVLOV M V amp KU-PRIANOVA I N (1980) Тypomorphic signs of fl uorite and their importance for the study of zonality and depth of deposits es-timation ndash In New Data on Mineralrsquos Typomorphism Nauka Moscow 130 ndash145 (in Russian)

VASILrsquoKOVA N N amp SOLOMKINA S G (1965) Tipomorphic Char-acteristics of Fluorite and Quartz ndash Nedra Moscow 134 pp (in Russian)

VELINOV T (1986) Geothermal Field in Bulgaria ndash RevBulg GeolSoc 47 1 1ndash 8 (in Bulgarian)

VYBOROV A I SILAEV V I amp ROMASHKIN Y N (1984) X-ray lu-minescence of fl uorite as an element of mineralogical mapping ndash Mineralogicheskiy Zhurnal 6 1 32 ndash 38 (in Russian)

YAKZHIN A A (1962) Relationships in Formation and Distribution of Fluorite Deposits in Zabaykalrsquoya ndash Gosgeoltekhizdat Mos-cow 250 pp (in Russian)

YONEZAWA T MATSUO K NAKAYAMA J amp KAWAMOTO Y (2003) Behaviors of metal-oxide impurities in CaF2 and BaF2 single-crystals growth with PbF2 scavenger by Stockbargerrsquos method ndash J Crystal Growth 258 2 ndash 4 385 ndash 393

YUSHKIN N P (2002) Calcite oolites from fl uorite mine near Palat vilage Bulgaria ndash Works in the Geology Institute Syktyvkar Republic Komi Scientifi c Center Ural Department RAS 110 79 ndash 98 (in Russian)

YUSHKIN N P MARKOVA G A VOLKOVA N B ZIDAROVA B P amp MALEEV M N (1986) Method for evaluation of the quality of raw fl uorite ndash Certifi cate No127607811081986 URSS (in Russian)

YUSHKIN N P VOLKOVA N V amp MARKOVA G A (1983) Optical Fluorite ndash Nauka Moscow 136 pp (in Russian)

ZAGORCHEV I (2001) Geology of SW Bulgaria an overview ndash Geologica Balcanica 21 1ndash 2 3 ndash 52

ZHOVINSKY E Y (1979) Geochemistry of Fluorine in the Sedimen-tary Formations of the SW Eastern European Platform ndash Nau-kova Dumka Press Kiev 200 pp (in Russian)

ZHOVINSKY E Y (1985) Fluorine-metric Methods on Searching ndash Naukova Dumka Press Kiev 161 pp (in Russian)

ZIDAROV N amp ZIDAROVA B (2002) The collection bdquoFluorite miner-alization in the Slavyanka deposit SW Bulgarialdquo of the Central Laboratory of Mineralogy and Crystallography BAS ndash an exam-ple for ex-situ preservation of the mineral diversity ndash In Mineral diversity I International Symposium-2000 ldquoMineral diversity ndash research and preservationrdquo October 6 ndash 9 Sofi a Earth and Man National Museum р 31

ZIDAROV N ZIDAROVA B SEKIRANOV A amp KLIMOV I (1987) To-pomineralogical study of the ldquoSlavyankardquo mine fl uorite minerali-zation in the district of Blagoevgrad ndash Oreforming Processes and Mineral Deposits 26 20 ndash 32 (in Вulgarian)

ZIDAROV N G amp ZIDAROVA B P (1989) Geology-mineralogy cri-terions for the separating in the earthlsquos bowels fl uorite raw ma-terials suitable for production of optical fl uorite ndash In Extended abstracts of the XIV Congress KGBA IV September 20 ndash 23 Sofi a Bulgaria 1266 ndash1269 (in Russian)

ZIDAROV N G amp ZIDAROVA B P (1993) Method for separation of industrial bodies consisting fl uorite raw materials in the earthrsquos crust suitable for production of optical fl uorite ndash Certifi cate No5178830091993 Bulgaria (in Bulgarian)

ZIDAROVA B (1978) Hydrothermal synthesis of fl uorite ndash Geo-chem Mineral and Petrol 8 27ndash 40 (in Russian)

ZIDAROVA B (2003) Rare earth elements in natural fl uorite as in-dicators of mineral-forming environment ndash Compt rend Acad bulg Sci 56 11 19 ndash 26

ZIDAROVA B (2010) Hydrothermal fl uorite-forming processes in the Mikhalkovo deposit (Central Rhodopes Bulgaria) ndash fi eld ob-servation and experimental confi rmations ndash N Jb Miner Abh 187 2 133 ndash157

ZIDAROVA B (2011) Formation temperature REE contents and optical spectra of fl uorite from the Mikhalkovo deposit (Central Rhodopes Bulgaria) genetical implication and practical signifi -cation ndash N Jb Miner Abh 188 3 257ndash 283

ZIDAROVA B amp KOSTOV I (1979) Peculiarities of the fl uorite from the Palat deposit district of Blagoevgrad ndash Geochem Mineral and Petrol 11 51ndash 65 (in Bulgarian)

ZIDAROVA B MARINOV M amp ZIDAROV N (2002) Mathematical model for the growth of fl uorite aggregates in caverns in Slavy-anka deposit ndash Compt rend Acad bulg Sci 55 3 59 ndash 64

ZIDAROVA B amp ZIDAROV N (1995 a) Main еlements of the local geogenetic model for Fluorite Formation I Slavyanka deposit ndash Compt rend Acad bulg Sci 48 8 33 ndash 36

ZIDAROVA B amp ZIDAROV N (2004) Main elements of the common geogenetic model for deposits of the Fluorite Ore Formation in Bulgaria ndash Rev Bulg Geol Soc 65 1ndash 3 55 ndash 66 (in Bulgarian)

ZIDAROVA B amp ZIDAROV N (2006) Application of topographic mineralogy in the creation of geological-genetic models for the Fluorite Mineral Formation in Bulgaria ndash In Theory History Philosophy and Practice of the Mineralogy (Proc of IV Interna-tional Mineralogical Seminar) Syktyvkar Republic Komi Rus-sian May 17ndash 20 114 ndash116

ZIDAROVA B P (1978) Hydrothermal synthesis of fl uorite ndash Geo-chem Miner and Petrol 8 27ndash 36 (in Russian)

ZIDAROVA B P (1989) Mineralogical Peculiarities and Genesis on Fluorite in the Industrial Deposits in Bulgaria ndash Bulgarian Academy of Sciences Sofi a DSc Thesis 287 pp (unpublished in Bulgarian)

262 B Zidarova

ZIDAROVA B P (1990) X-ray luminescence-method of the estimate on the quality of natural fl uorite ndash In Methods and Technolo-gies of Research for Mineral Raw Materials I Technique Sofi a 136 ndash140 (in Bulgarian)

ZIDAROVA B P (1992 a) The effect of cerium in raw fl uorite on the optical quality of synthetic single crystals ndash Compt rend Acad bulg Sci 45 3 73 ndash74

ZIDAROVA B P (1992 b) Thermoluminescence characterization of fl uorites in the Slavyanka Mikhalkovo and Ciprovci deposits ndash Compt rend Acad bulg Sci 45 8 67ndash70

ZIDAROVA B P (1993) The origin of color in fl uorite from Bulgar-ian deposits ndash Compt rend Acad bulg Sci 46 9 69 ndash72

ZIDAROVA B P (1995 a) The distribution of La and Tb in hydro-thermal fl uorite from the Slavyanka deposit as an indication for the processes of rearrangement and redeposition ndash Compt rend Acad bulg Sci 48 3 37ndash 40

ZIDAROVA B P (1995 b) Type and distribution of the fl uorite chem-ical inhomogeneity in Slavyanka deposit ndash Geochem Mineral and Petrol 30 99 ndash106 (in Bulgarian)

ZIDAROVA B P (2008) Application of the spectroscopic methods for prospection and evaluation of raw fl uorite ndash In YUSHKIN N P amp RAKIN V I (eds) The World of Minerals Crystals and Na-nostructures GEOPRINT issue of the Geology Institute Sykty-

vkar Republic Komi Scientifi c Center Ural Department RAS 244 ndash 250 (in Russian)

ZIDAROVA B P MALEEV M N YUSHKIN N P MARKOVA G A amp VOLKOVA N B (1986) Method for evaluation of the quality of raw fl uorite suitable for growing synthetic single crystals of calcium fl uoride ndash Certifi cat No3936427061986 Bulgaria (in Bulgarian)

ZIDAROVA B P MARKOVA G A amp KALIKOV V N (1984) Zonal-ity and dynamics of fl uorite formation in the Palat Deposit (Bul-garia) ndash In Topomineralogy and minerals ore bearing regions (Works in the Geology Institute) Syktyvkar 45 113 ndash125 (in Russian)

ZIDAROVA B P amp PIPEROV N B (1995) Temperature and molecu-lar composition of the mineral-forming fl uids in Slavyanka fl uo-rite deposit ndash Rev Bulg Geol Soc 56 2 9 ndash18 (in Bulgarian)

ZIDAROVA B P amp ZIDAROV N G (1995 b) Processes of fl uorite formation in the Slavyanka deposit South-Western Bulgaria ndash Geol Soc Greece (XV Congress of KBGA September 17ndash 20 1995) Sp Publ 4 869 ndash 872

ZIDAROVA B P ZIDAROV N G MARKOVA G A amp YUSHKIN N P (1992) Infl uence of the Natural Raw Material on the Quality of Synthetic Fluorite Single Crystals ndash Compt rend Acad bulg Sci 45 3 69 ndash72

Manuscript received July 19 2011 accepted Februiary 2 2012Responsible editor R Klemd

Authorrsquos addressB ZIDAROVA Bulgarian Academy of Sciences ldquoAcad Ivan Kostovrdquo Institute of Mineralogy and Crystallography Bl 107 ldquoAcad Georgi Bonchevrdquo Str BG-1113 Sofia Bulgaria E-mail zidarovainterbgccom bzidarovagmailcom

224 B Zidarova

1 Introduction

The Slavyanka fl uorite deposit is located in the crystal-line basement of SW Bulgaria and is a typical hydrother-mal vein deposit It was exploited for a period of about 50 years throughout the second part of XX century and was one of the most important industrial fl uorite depos-its in SE Europe Its geological structure and peculiarities of mineralization concerning some particular questions mainly in the Bulgarian language (ALEKSIEV amp PAVLOVA 1967 NECEV 1979 BONEV 1979 YUSHKIN 2002) and thus is practically unknown to the western scientists Fluorite from both the Slavyanka and the Mikhalkovo deposits (ZIDAROVA 2010 2011) are the topic of the present con-tribution

The present paper is an attempt to generalize the infor-mation on fl uorite from the Slavyanka deposit It aims to solve two linked problems 1) establishment of a theoreti-cal model for the dynamics of the mineral-forming pro-cesses within the whole deposit parts of it or separate bodies of a defi nite mineralogical variety 2) prognosis on the potential fl uorite reserves of the deposit according to the quantity of raw material which has been applied for traditional purposes as well as some of its genetically implanted properties with application in new high techno-logical industries as the optical industry (ZIDAROVA 2008) The interrelations between the indicator peculiarities and the optical properties of fl uorite allow a prognosis of the quality of synthetic CaF2 monocrystals as well as estima-tion of the crystal chemistry of the fl uorite as raw material according to its optical indicators The study gives an idea for the application of a defi nite type of natural raw mate-rial with preliminary given genetic properties during the later growth of synthetic optical quality crystals

2 Methodology

Mineralogical mapping on a large scale (about 550 m in the vertical interval between levels535 m and40 m) was carried out in the Slavyanka mine The texture of the veins their mineral composition and the spatial relations of fl uorite and its varieties have been marked on geologi-cal and mineralogical plans scaled 150 and on detailed cross profi les scaled 150 with an average distance of 10 m The fl uorite is divided into three main mineralogical varieties and each variety ndash into subvarieties and mac-roscopic typomorphic features that can undergo mapping have been studied namely texture anatomical crystal and morphological specifi cities colour paragenesis and disposition in the ore veins (ZIDAROV et al 1987) The pre-sent study is based on more than one thousand samples of

fl uorite from the Slavyanka deposit (ZIDAROV amp ZIDAROVA 2002) Fluid inclusions REE and optical spectra have been studied in the samples

480 measurements were carried out with a Reichert microscope complete with a Koumlfl er-type heating stage for fl uid-inclusion investigations The measurements were made on thin platelets polished on both sides were about 1 or 2 mm thick of fl uorite crystals sampled from various hypsometric levels (Table 1) The preliminary investiga-tion has shown that the volatiles in the inclusions are Н2О and СО2 (Table 2)

Some structural impurities of all the fl uorite varieties from all sites and mining levels of the Slavyanka deposit Rb Ва Sr (X-ray spectral analyses) and some REE (La Ce Sm Eu Tb Yb Lu with 60 and Dy with 26 samples ndash neutron-activation analysis) and Y Mn (semiquantitative spectral analyses) are determined

The dominance of REE2+ or REE3+ in the studied varie-ties of fl uorite is specifi ed according to the application of the following optical spectra obtained by photolumines-cence (PLS) X-ray luminescence (XRLS) thermolumi-nescence (TLS) optical (OS) and infrared (IRS) spectra of fl uorites from the Slavyanka deposit The analysis of the spectral results makes it possible to evaluate the phys-ical and chemical conditions of formation of crystals and aggregates All the spectral bands in the PLS XRLS and ТLS as well as ОS and IRS are due to an elevated content of RЕЕ U and Th which was determined by neutron-activation analysis

The photoluminescence spectra (PLS) of 150 fl uorite samples from various hypsometric levels and fl uorite va-rieties were investigated upon excitation by a mercury lamp Fluotest-universal in 254 and 366 nm (Table 7)

The X-ray luminescence (XRLS) of 200 samples from various hypsometric levels and fl uorite varieties was stud-ied in the range 250 ndash 800 nm (ZIDAROVA et al 1984) The results and reviews of KRASILlsquoSHCHIKOVA amp POVARENNIKH (1970) MARFUNIN (1975) TARASHCHAN et al (1975) PLA-TONOV (1976 ab) TARASHCHAN (1978) KRASILlsquoSHCHIKOVA et al (1980 1981) SMOLYANSKY (2002) were used in the interpretation of these curves

Thermoluminescence (TLS) of 200 fl uorite samples of fl uorite varieties I and II with the corresponding subvarie-ties from various hypsometric levels was studied in the temperature between 20 and 400 degC (ZIDAROVA et al 1984 ZIDAROVA 1989 1992 b) The curves of non-irradiated and of irradiated fl uorites were obtained (with Mo-anticatode 55 kw 18 ma and Cs137 radioactive isotope) which al-lowed the activation of a low-temperature maximum typical of fl uorite from hydrothermal deposits (Table 10) The papers of VASILrsquoKOVA amp SOLOMKINA (1965) TARASH-CHAN et al (1974) TARASHCHAN (1978) KRASILrsquoSHCHIKOVA








226 B Zidarova




4 Results





























228 B Zidarova








230 B Zidarova










Mikhaletz 385 2015 1795 1743 1525 1305






















232 B Zidarova















23

2F CO

(a ) a

3 2 3

2 2CO CaF CaCOF

(a ) (a ) Ksp Ksp





44 REE geochemistry

















23

2F

CO

(a )a

3 486 10 4

90 7 3

HCO SO Cl

(Na+K) Ca Mg

3 474 19 6

64 24 7

HCO SO Cl

(Na+K) Ca Mg

3 478 16 5

64 27 10

HCO SO Cl

(Na+K) Ca Mg

3 475 17 5

94 4 2

HCO SO Cl

(Na+K) Ca Mg

3 3 419 573

90 9 1

+CO )(HCO SO Cl

(Na+K) Ca Mg3 478 15 5

91 8 1

HCO SO Cl

(Na+K) Ca Mg



Vodenaskala

110 88 230 255145 90 215 260 276

253258


234 B Zidarova

Tabl

e 5

REE

dat

a of

the fl u

orite

var

ietie

s fro

m th

e Sl

avya

nka

depo

sit

No

Site

Loca

tion

Leve

lm

Varie

tyC

olou

rC

onte

nts

ppm

LaC

eSm

EuTb

Yb

LuR

EЕLa

Yb

TbY

bEu

Eu

Ce

Ce

3Vo

dena

skal

am

ain

lode

80

Igr

een

6

51 1

104

3

41

146

2

18 3

03

07

5 2

838

21

50

720

830

63 6

mai

n lo

de 8

0I

gree

n

937

16

85

524

1

91

351

42

6 0

92

42

06 2

20

082

069

067

8ap

ophy

sis

80

Igr

een

8

90 1

499

4

72

224

2

85 4

56

126

6 5

092

19

50

630

940

6411

apop

hysi

s 8

0I

gree

n 1

318

25

71

531

3

17

297

53

211

75

67

41 2

48

056

121

073

13m

ain

lode

80

Igr

een

9

66 1

829

3

55

272

2

55 3

65

07

7 4

119

26

50

701

430

7722

extr

chu

te11

0I

gree

n

625

11

53

356

1

82

265

39

2 1

25

30

98 1

59

068

094

069

28m

ain

lode

110

Igr

een

17

25 2

696

5

08

192

0

60 3

73

04

8 5

602

46

20

161

300

6837

mai

n lo

de14

5I

gree

n

602

3

38

315

1

16

134

09

5 0

51

16

51 6

34

141

080

021

38lo

de 1

90-

Igr

een

18

68 3

982

6

38

285

3

04 4

01

12

7 7

605

46

60

760

960

8739

fi llin

g24

0I

gree

n 3

044

40

60 1

220

3

34

156

62

0 1

20

95

57 4

91

025

094

054

42Ve

netz

am

ain

lode

350

Igr

een

49

70 7

433

8

62

319

1

55 4

92

08

114

312

101

00

321

100

7047

Vode

na sk

ala

mai

n lo

de38

5I

gray

ish-

gree

n

219

5

03

264

0

90

249

55

9 1

76

20

60 0

39

045

057

073

49m

ain

lode

385

Igr

ayis

h-gr

een

6

30 1

278

6

36

215

5

5412

47

44

6 5

000

05

10

440

430

6955

Mik

hale

tz38

5I

gree

n

980

10

75

027

0

20

069

20

7 0

34

24

12 4

73

033

088

076

59B

aba

500

Ida

rk-g

reen

14

80 1

858

5

80

150

2

74 3

03

05

2 4

697

48

80

900

550

5060

500

Ipa

le g

reen

23

10 2

138

3

80

054

0

77 1

74

05

4 5

187

132

70

440

400

4416

Vode

nask

ala

mai

n lo

de 8

0II

ada

rk-v

iole

t

522

12

40

857

1

60

292

115

0 1

87

44

08 0

45

025

045

070

25m

ain

lode

110

IIa

dark

-vio

let

8

20 1

735

10

42

365

10

3617

41

13

4 6

873

04

70

600

590

6629

mai

n lo

de11

0II

ada

rk-v

iole

t

654

20

60 1

005

2

20

480

198

0 2

12

66

11 0

33

024

047

094

36m

ain

lode

145

IIa

viol

et

115

5

06

146

0

40

080

57

0 1

05

15

62 0

20

014

055

145

57M

ikha

letz

385

IIa

dark

-vio

let

5

30 1

430

6

40

139

8

1315

06

24

0 5

298

03

50

540

340

86 9

Vode

nask

ala

apop

hysi

s 8

0II

bvi

olet

1

56

320

2

61

104

2

81 5

77

178

0 3

479

02

70

490

640

6212

apop

hysi

s 8

0II

bvi

olet

4

48 1

224

4

41

180

3

76 5

24

13

7 3

330

08

50

720

690

9020

mai

n lo

de 8

0II

bpa

le v

iole

t

033

1

03

032

ndash

038

09

6 0

27

3

29 0

34

040

ndash1

0530

mai

n lo

de11

0II

bvi

olet

1

60

307

1

70

020

0

55 3

66

04

7 1

125

04

40

150

290

6443

Vene

tza

350

IIb

viol

et

324

4

88

142

0

27

139

41

1 0

77

16

08 0

79

034

031

059

48Vo

dena

skal

am

ain

lode

385

IIb

viol

et

672

13

43

649

2

02

490

93

6 3

26

46

18 0

72

052

063

066

50m

ain

lode

385

IIb

viol

etis

h-bl

ue

398

7

16

266

1

70

181

40

0 1

33

22

64 0

99

045

123

065

51m

ain

lode

385

IIb

viol

et

205

9

52

501

1

40

542

114

0 3

73

38

53 0

18

048

045

132

53m

ain

lode

385

IIb

pale

vio

let

0

79 ndash

1

99

091

2

32 4

52

20

2 1

255

01

70

510

73ndash

54m

ain

lode

385

IIb

pale

vio

let

4

55

999

2

37

134

1

97 3

23

11

2 2

457

14

10

611

010

8156

Mik

hale

tz38

5II

bpa

le v

iole

t

048

0

88

077

0

54

047

18

0 0

23

5

17 0

27

026

134

055

5838

5II

bpa

le v

iole

t

031

10

25

034

0

20

012

03

2 0

13

11

67 0

97

038

138

150








dena

skal

am

ain

lode

40

IIc

viol

et

003

ndash

012

ndash

015

03

2 0

07

0

70 0

09

047

ndashndash

2m

ain

lode

40

IIc

viol

et ndash

ndash

001

ndash ndash

ndash ndash

0

01 ndash

ndashndash

ndash4

mai

n lo

de 8

0II

cvi

olet

ndash ndash

0

10 ndash

ndash 0

10

00

4

024

01

25ndash

ndashndash

5m

ain

lode

80

IIc

viol

et

015

ndash

013

ndash

012

06

4 0

26

1

30 0

23

019

ndashndash

7m

ain

lode

80

IIc

viol

et ndash

ndash

011

0

04

007

01

4 ndash

0

36 ndash

050

071

ndash10

apop

hysi

s 8

0II

cvi

olet

1

00 ndash

1

55

068

1

60 3

42

110

1 1

926

02

80

470

72ndash

14m

ain

lode

80

IIc

viol

et

014

ndash

013

ndash

010

02

5 0

04

0

66 0

56

040

ndashndash

15m

ain

lode

80

IIc

pale

vio

let

0

20 ndash

0

35

010

0

45 0

81

01

1

202

02

20

560

44ndash

17m

ain

lode

80

IIc

pale

vio

let

0

30

001

0

24

012

0

01 0

49

00

1

118

06

10

022

230

0118

mai

n lo

de 8

0II

cpa

le v

iole

t

192

2

30

030

0

01

020

06

2 0

01

5

36 3

10

032

006

058

19m

ain

lode

80

IIc

pale

vio

let

ndash ndash

0

10 ndash

ndash 0

15

ndash

025

ndashndash

ndashndash

21na

rrow

80

IIc

pale

vio

let

0

35 ndash

0

47

011

0

41 1

25

41

4

673

02

80

330

41ndash

23ex

tract

ion

110

IIc

viol

et

021

ndash

020

ndash

018

03

9 0

10

1

08 0

54

046

ndashndash

24ch

ute

110

IIc

viol

et ndash

ndash

001

ndash ndash

ndash ndash

0

01 ndash

ndashndash

ndash26

mai

n lo

de11

0II

cpa

le v

iole

t

022

ndash

013

ndash

011

02

3 0

02

0

71 0

96

048

ndashndash

27m

ain

lode

110

IIc

pale

vio

let

ndash ndash

0

06 ndash

ndash 0

15

ndash

021

10

0ndash

ndashndash

31m

ain

lode

110

IIc

pale

vio

let

0

43

086

0

40

001

0

01 0

79

02

4

274

05

40

010

140

6732

mai

n lo

de14

5II

cpa

le v

iole

t

010

01

01

01

01 0

01

00

1

016

100

01

001

750

0533

mai

n lo

de14

5II

cpa

le v

iole

t

012

01

011

01

01 0

01

00

1

028

120

01

001

520

0434

mai

n lo

de14

5II

cpa

le v

iole

t

01

01

01

01

01 0

01

00

1

007

10

01

001

750

3035

mai

n lo

de14

5II

cvi

olet

0

16

065

0

59

017

0

32 1

28

01

6

333

01

250

250

581

0640

lode

fi lli

ng21

5II

cpa

le v

iole

t

080

0

01

029

0

01

022

05

5 0

01

1

89 1

45

040

006

000

541

Mik

hale

tz33

5II

cpa

le v

iole

t

036

ndash

016

ndash

020

03

0 0

17

1

19 1

20

067

ndashndash

44Vo

dena

skal

am

ain

lode

370

IIc

pale

vio

let

0

36

01

017

01

01 0

86

01

0

152

04

20

011

120

015

45m

ain

lode

370

IIc

pale

vio

let

5

67

001

0

14

001

0

01 0

41

00

1

626

138

30

020

280

001

46m

ain

lode

370

IIc

pale

vio

let

0

46

078

0

57

020

0

01 0

96

01

8

316

04

80

012

640

5452

mai

n lo

de38

5II

cpa

le v

iole

t ndash

ndash

019

ndash

012

05

5 0

15

1

04 0

02

022

ndashndash

236 B Zidarova








x SxG V x




















238 B Zidarova














(540) Dy3+-O2

(674754) Er3+-O2 ndash(553) Sm3+-Fi

ndash(578))






240 B Zidarova


(480)Sm3+(567)









cub(572)IFndash

















skalaI 515 043 194 053 088I 418 037 202 042 086I 673 051 200 059 090I 778 033 213 046 087


skala IIa 4345 022 3061 000 092 IIa 1533 033 1495 100 087


skala IIb 378 035 826 100 082



40 Vodenaskala

IIc 010 100 286 033 400 IIc 024 080 247 033 071


110 IIc 023 212 248 025 090 IIc 041 045 527 150 040

145 IIc 107 048 587 080 075 IIc 013 333 302 000 075

370 IIc 035 046 1370 000 085

242 B Zidarova



ndash(578) (REE)
















180 degC(YO2)o

220 degCREE2+

280 degCY2+

320 degC(REEO2)o

380 degCSm2+-Ce4+


244 B Zidarova




ndash and

















Absorption bands

I CeSmYb





SmYb






ndashndash 580 nm

246 B Zidarova













Levelm


ZoneNо



400 nm 600 nm 80 I smoky 1 400 323 857 500 748








Fig

12

OTS

of fl

uor

ites

from

diff

eren

t lev

els

and

min

eral

ogic

al v

arie

ties

from

the

Slav

yank

a de

posi

t Le

gend

key

1 ndash

em

bedd

ing

rock

s 2

ndash v

arie

ty I

3 ndash

var

iety

IIa

4 ndash

varie

ty II

b 5

ndash va

riety

IIc

6 ndash

suga

r-gra

ined

qua

rtz

248 B Zidarova






















(306) Sm2+(425) Fi

ndash(400) 2Fi

ndash(580)


(306) Sm2+(340) 2Fi

ndash(580)


ndash(580)


ndash(400) 2Fi

ndash(580)



(420) MO2 ndash(565) Sm2+

(620)


(480) MO2 ndash(560) Sm2+

(620)


(440) (YO2)o(520)


(440) MO2 ndash(560)


(440) (YO2)o(520) Sm2+

(660)


(560) Sm2+(620)


(440) MO2 ndash(560)

250 B Zidarova
















7500 nm 9300 nm 7500 nm 9300 nmVodena

skala












ble

14 I

nfl u

ence

of t

he R

EE o

n th

e co

lour

and

lum

ines

cenc

e of

fl uo

rite

varie

ties f

rom

the

Slav

yank

a de

posi

t

Varie

tyI

IIa

IIb

IIc

T h degC

153 ndash 20

2(f

requ

ently

155 ndash1

97)

140 ndash

178

(fre

quen

tly 1

45 ndash1

72)

120 ndash

157

(fre

quen

tly 1

26 ndash1

53)

103 ndash

119

(fre

quen

tly 1

10 ndash1

15)

REE

ppm

165

1ndash14

312

333 ndash

687

33

30 ndash

461

80

07ndash 3

479

colo

urgr

een

dark

-vio

let

viol

et p

ale

viol

etvi

olet

pal

e vi

olet

PLS

gree

nda

rk-v

iole

tvi

olet

pale

vio

let

XR

LSD

y-Sm

type

spec

traD

y ty

pe sp

ectra

Dy

type

spec

traU

nallo

yed

type

spec

traTL

S18

0 degС

ndash (Y

O2)deg

def

ectiv

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

130-

150

degС ndash

REE

O2+

- Ondash d

ipol

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

180

degС ndash

(YO

2)deg d

efec

tive

cent

er22

0 degC

ndash R

EE2+

cubi

c ce

nter

28

0 degС

ndash Y

2+ cu

bic

cent

er

320

degС ndash

(REE

O2)deg

def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

OA

SY

b2+(2

653

65)

Ce3+

(306

) Sm

2+(4

25)

F indash (4

00)

2Findash (5

80)

Yb2+

(265

365

) C

e3+(3

06)

Sm2+

(340

) 2F

indash (580

)Y

b2+(2

473

10)

2Findash (5

80)

Yb2+

(310

) F i

ndash (400

) 2F

indash (580

)

252 B Zidarova

Fig

14

Spe

ctro

scop

ic c

hara

cter

istic

s (X

RLS

TLS

OTS

IR

S) o

n ra

w (

__)

and

synt

hetic

(---

) fl u

orite

s fro

m th

e Sla

vyan

ka d

epos

it an

d ar

ea o

f the

thei

r app

licat

ion

(UV

ndash u

ltrav

iole

t V

ndash v

isib

le I

R ndash

infr

ared

)









480 Sm3+







I(V IR)

002 0001 001 0003 ndash 00006 001 1868 3982 638 285 304 401 127

IIa

(IR)003 006 001 0003 0006 002 003 820 1735 1042 365 1036 1741 134

IIb

(V IR)0001 0003 001 002 0006 0003 0003 013 ndash 010 ndash 008 010 004

IIb


IIb


IIb

(IR)0006 010 003 0005 00001 0003 ndash 398 716 266 170 181 400 133

IIb


IIc


IIc

(UVV IR)001 001 0008 0005 0006 0006 0003 018 ndash 035 010 045 081 011

IIc


254 B Zidarova





ndash(400) and 2Fi



5 Discussion

















2+ 2

2CaFCa F

[(a ) (a ) Ksp 1]









256 B Zidarova






(572) ndash Sm3+(567)
















ndash(400) and 2Fi
















6 Conclusions


258 B Zidarova







Acknowledgements



References






































260 B Zidarova












































































262 B Zidarova























226 B Zidarova




4 Results





























228 B Zidarova








230 B Zidarova










Mikhaletz 385 2015 1795 1743 1525 1305






















232 B Zidarova















23

2F CO

(a ) a

3 2 3

2 2CO CaF CaCOF

(a ) (a ) Ksp Ksp





44 REE geochemistry

















23

2F

CO

(a )a

3 486 10 4

90 7 3

HCO SO Cl

(Na+K) Ca Mg

3 474 19 6

64 24 7

HCO SO Cl

(Na+K) Ca Mg

3 478 16 5

64 27 10

HCO SO Cl

(Na+K) Ca Mg

3 475 17 5

94 4 2

HCO SO Cl

(Na+K) Ca Mg

3 3 419 573

90 9 1

+CO )(HCO SO Cl

(Na+K) Ca Mg3 478 15 5

91 8 1

HCO SO Cl

(Na+K) Ca Mg



Vodenaskala

110 88 230 255145 90 215 260 276

253258


234 B Zidarova

Tabl

e 5

REE

dat

a of

the fl u

orite

var

ietie

s fro

m th

e Sl

avya

nka

depo

sit

No

Site

Loca

tion

Leve

lm

Varie

tyC

olou

rC

onte

nts

ppm

LaC

eSm

EuTb

Yb

LuR

EЕLa

Yb

TbY

bEu

Eu

Ce

Ce

3Vo

dena

skal

am

ain

lode

80

Igr

een

6

51 1

104

3

41

146

2

18 3

03

07

5 2

838

21

50

720

830

63 6

mai

n lo

de 8

0I

gree

n

937

16

85

524

1

91

351

42

6 0

92

42

06 2

20

082

069

067

8ap

ophy

sis

80

Igr

een

8

90 1

499

4

72

224

2

85 4

56

126

6 5

092

19

50

630

940

6411

apop

hysi

s 8

0I

gree

n 1

318

25

71

531

3

17

297

53

211

75

67

41 2

48

056

121

073

13m

ain

lode

80

Igr

een

9

66 1

829

3

55

272

2

55 3

65

07

7 4

119

26

50

701

430

7722

extr

chu

te11

0I

gree

n

625

11

53

356

1

82

265

39

2 1

25

30

98 1

59

068

094

069

28m

ain

lode

110

Igr

een

17

25 2

696

5

08

192

0

60 3

73

04

8 5

602

46

20

161

300

6837

mai

n lo

de14

5I

gree

n

602

3

38

315

1

16

134

09

5 0

51

16

51 6

34

141

080

021

38lo

de 1

90-

Igr

een

18

68 3

982

6

38

285

3

04 4

01

12

7 7

605

46

60

760

960

8739

fi llin

g24

0I

gree

n 3

044

40

60 1

220

3

34

156

62

0 1

20

95

57 4

91

025

094

054

42Ve

netz

am

ain

lode

350

Igr

een

49

70 7

433

8

62

319

1

55 4

92

08

114

312

101

00

321

100

7047

Vode

na sk

ala

mai

n lo

de38

5I

gray

ish-

gree

n

219

5

03

264

0

90

249

55

9 1

76

20

60 0

39

045

057

073

49m

ain

lode

385

Igr

ayis

h-gr

een

6

30 1

278

6

36

215

5

5412

47

44

6 5

000

05

10

440

430

6955

Mik

hale

tz38

5I

gree

n

980

10

75

027

0

20

069

20

7 0

34

24

12 4

73

033

088

076

59B

aba

500

Ida

rk-g

reen

14

80 1

858

5

80

150

2

74 3

03

05

2 4

697

48

80

900

550

5060

500

Ipa

le g

reen

23

10 2

138

3

80

054

0

77 1

74

05

4 5

187

132

70

440

400

4416

Vode

nask

ala

mai

n lo

de 8

0II

ada

rk-v

iole

t

522

12

40

857

1

60

292

115

0 1

87

44

08 0

45

025

045

070

25m

ain

lode

110

IIa

dark

-vio

let

8

20 1

735

10

42

365

10

3617

41

13

4 6

873

04

70

600

590

6629

mai

n lo

de11

0II

ada

rk-v

iole

t

654

20

60 1

005

2

20

480

198

0 2

12

66

11 0

33

024

047

094

36m

ain

lode

145

IIa

viol

et

115

5

06

146

0

40

080

57

0 1

05

15

62 0

20

014

055

145

57M

ikha

letz

385

IIa

dark

-vio

let

5

30 1

430

6

40

139

8

1315

06

24

0 5

298

03

50

540

340

86 9

Vode

nask

ala

apop

hysi

s 8

0II

bvi

olet

1

56

320

2

61

104

2

81 5

77

178

0 3

479

02

70

490

640

6212

apop

hysi

s 8

0II

bvi

olet

4

48 1

224

4

41

180

3

76 5

24

13

7 3

330

08

50

720

690

9020

mai

n lo

de 8

0II

bpa

le v

iole

t

033

1

03

032

ndash

038

09

6 0

27

3

29 0

34

040

ndash1

0530

mai

n lo

de11

0II

bvi

olet

1

60

307

1

70

020

0

55 3

66

04

7 1

125

04

40

150

290

6443

Vene

tza

350

IIb

viol

et

324

4

88

142

0

27

139

41

1 0

77

16

08 0

79

034

031

059

48Vo

dena

skal

am

ain

lode

385

IIb

viol

et

672

13

43

649

2

02

490

93

6 3

26

46

18 0

72

052

063

066

50m

ain

lode

385

IIb

viol

etis

h-bl

ue

398

7

16

266

1

70

181

40

0 1

33

22

64 0

99

045

123

065

51m

ain

lode

385

IIb

viol

et

205

9

52

501

1

40

542

114

0 3

73

38

53 0

18

048

045

132

53m

ain

lode

385

IIb

pale

vio

let

0

79 ndash

1

99

091

2

32 4

52

20

2 1

255

01

70

510

73ndash

54m

ain

lode

385

IIb

pale

vio

let

4

55

999

2

37

134

1

97 3

23

11

2 2

457

14

10

611

010

8156

Mik

hale

tz38

5II

bpa

le v

iole

t

048

0

88

077

0

54

047

18

0 0

23

5

17 0

27

026

134

055

5838

5II

bpa

le v

iole

t

031

10

25

034

0

20

012

03

2 0

13

11

67 0

97

038

138

150








dena

skal

am

ain

lode

40

IIc

viol

et

003

ndash

012

ndash

015

03

2 0

07

0

70 0

09

047

ndashndash

2m

ain

lode

40

IIc

viol

et ndash

ndash

001

ndash ndash

ndash ndash

0

01 ndash

ndashndash

ndash4

mai

n lo

de 8

0II

cvi

olet

ndash ndash

0

10 ndash

ndash 0

10

00

4

024

01

25ndash

ndashndash

5m

ain

lode

80

IIc

viol

et

015

ndash

013

ndash

012

06

4 0

26

1

30 0

23

019

ndashndash

7m

ain

lode

80

IIc

viol

et ndash

ndash

011

0

04

007

01

4 ndash

0

36 ndash

050

071

ndash10

apop

hysi

s 8

0II

cvi

olet

1

00 ndash

1

55

068

1

60 3

42

110

1 1

926

02

80

470

72ndash

14m

ain

lode

80

IIc

viol

et

014

ndash

013

ndash

010

02

5 0

04

0

66 0

56

040

ndashndash

15m

ain

lode

80

IIc

pale

vio

let

0

20 ndash

0

35

010

0

45 0

81

01

1

202

02

20

560

44ndash

17m

ain

lode

80

IIc

pale

vio

let

0

30

001

0

24

012

0

01 0

49

00

1

118

06

10

022

230

0118

mai

n lo

de 8

0II

cpa

le v

iole

t

192

2

30

030

0

01

020

06

2 0

01

5

36 3

10

032

006

058

19m

ain

lode

80

IIc

pale

vio

let

ndash ndash

0

10 ndash

ndash 0

15

ndash

025

ndashndash

ndashndash

21na

rrow

80

IIc

pale

vio

let

0

35 ndash

0

47

011

0

41 1

25

41

4

673

02

80

330

41ndash

23ex

tract

ion

110

IIc

viol

et

021

ndash

020

ndash

018

03

9 0

10

1

08 0

54

046

ndashndash

24ch

ute

110

IIc

viol

et ndash

ndash

001

ndash ndash

ndash ndash

0

01 ndash

ndashndash

ndash26

mai

n lo

de11

0II

cpa

le v

iole

t

022

ndash

013

ndash

011

02

3 0

02

0

71 0

96

048

ndashndash

27m

ain

lode

110

IIc

pale

vio

let

ndash ndash

0

06 ndash

ndash 0

15

ndash

021

10

0ndash

ndashndash

31m

ain

lode

110

IIc

pale

vio

let

0

43

086

0

40

001

0

01 0

79

02

4

274

05

40

010

140

6732

mai

n lo

de14

5II

cpa

le v

iole

t

010

01

01

01

01 0

01

00

1

016

100

01

001

750

0533

mai

n lo

de14

5II

cpa

le v

iole

t

012

01

011

01

01 0

01

00

1

028

120

01

001

520

0434

mai

n lo

de14

5II

cpa

le v

iole

t

01

01

01

01

01 0

01

00

1

007

10

01

001

750

3035

mai

n lo

de14

5II

cvi

olet

0

16

065

0

59

017

0

32 1

28

01

6

333

01

250

250

581

0640

lode

fi lli

ng21

5II

cpa

le v

iole

t

080

0

01

029

0

01

022

05

5 0

01

1

89 1

45

040

006

000

541

Mik

hale

tz33

5II

cpa

le v

iole

t

036

ndash

016

ndash

020

03

0 0

17

1

19 1

20

067

ndashndash

44Vo

dena

skal

am

ain

lode

370

IIc

pale

vio

let

0

36

01

017

01

01 0

86

01

0

152

04

20

011

120

015

45m

ain

lode

370

IIc

pale

vio

let

5

67

001

0

14

001

0

01 0

41

00

1

626

138

30

020

280

001

46m

ain

lode

370

IIc

pale

vio

let

0

46

078

0

57

020

0

01 0

96

01

8

316

04

80

012

640

5452

mai

n lo

de38

5II

cpa

le v

iole

t ndash

ndash

019

ndash

012

05

5 0

15

1

04 0

02

022

ndashndash

236 B Zidarova








x SxG V x




















238 B Zidarova














(540) Dy3+-O2

(674754) Er3+-O2 ndash(553) Sm3+-Fi

ndash(578))






240 B Zidarova


(480)Sm3+(567)









cub(572)IFndash

















skalaI 515 043 194 053 088I 418 037 202 042 086I 673 051 200 059 090I 778 033 213 046 087


skala IIa 4345 022 3061 000 092 IIa 1533 033 1495 100 087


skala IIb 378 035 826 100 082



40 Vodenaskala

IIc 010 100 286 033 400 IIc 024 080 247 033 071


110 IIc 023 212 248 025 090 IIc 041 045 527 150 040

145 IIc 107 048 587 080 075 IIc 013 333 302 000 075

370 IIc 035 046 1370 000 085

242 B Zidarova



ndash(578) (REE)
















180 degC(YO2)o

220 degCREE2+

280 degCY2+

320 degC(REEO2)o

380 degCSm2+-Ce4+


244 B Zidarova




ndash and

















Absorption bands

I CeSmYb





SmYb






ndashndash 580 nm

246 B Zidarova













Levelm


ZoneNо



400 nm 600 nm 80 I smoky 1 400 323 857 500 748








Fig

12

OTS

of fl

uor

ites

from

diff

eren

t lev

els

and

min

eral

ogic

al v

arie

ties

from

the

Slav

yank

a de

posi

t Le

gend

key

1 ndash

em

bedd

ing

rock

s 2

ndash v

arie

ty I

3 ndash

var

iety

IIa

4 ndash

varie

ty II

b 5

ndash va

riety

IIc

6 ndash

suga

r-gra

ined

qua

rtz

248 B Zidarova






















(306) Sm2+(425) Fi

ndash(400) 2Fi

ndash(580)


(306) Sm2+(340) 2Fi

ndash(580)


ndash(580)


ndash(400) 2Fi

ndash(580)



(420) MO2 ndash(565) Sm2+

(620)


(480) MO2 ndash(560) Sm2+

(620)


(440) (YO2)o(520)


(440) MO2 ndash(560)


(440) (YO2)o(520) Sm2+

(660)


(560) Sm2+(620)


(440) MO2 ndash(560)

250 B Zidarova
















7500 nm 9300 nm 7500 nm 9300 nmVodena

skala












ble

14 I

nfl u

ence

of t

he R

EE o

n th

e co

lour

and

lum

ines

cenc

e of

fl uo

rite

varie

ties f

rom

the

Slav

yank

a de

posi

t

Varie

tyI

IIa

IIb

IIc

T h degC

153 ndash 20

2(f

requ

ently

155 ndash1

97)

140 ndash

178

(fre

quen

tly 1

45 ndash1

72)

120 ndash

157

(fre

quen

tly 1

26 ndash1

53)

103 ndash

119

(fre

quen

tly 1

10 ndash1

15)

REE

ppm

165

1ndash14

312

333 ndash

687

33

30 ndash

461

80

07ndash 3

479

colo

urgr

een

dark

-vio

let

viol

et p

ale

viol

etvi

olet

pal

e vi

olet

PLS

gree

nda

rk-v

iole

tvi

olet

pale

vio

let

XR

LSD

y-Sm

type

spec

traD

y ty

pe sp

ectra

Dy

type

spec

traU

nallo

yed

type

spec

traTL

S18

0 degС

ndash (Y

O2)deg

def

ectiv

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

130-

150

degС ndash

REE

O2+

- Ondash d

ipol

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

180

degС ndash

(YO

2)deg d

efec

tive

cent

er22

0 degC

ndash R

EE2+

cubi

c ce

nter

28

0 degС

ndash Y

2+ cu

bic

cent

er

320

degС ndash

(REE

O2)deg

def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

OA

SY

b2+(2

653

65)

Ce3+

(306

) Sm

2+(4

25)

F indash (4

00)

2Findash (5

80)

Yb2+

(265

365

) C

e3+(3

06)

Sm2+

(340

) 2F

indash (580

)Y

b2+(2

473

10)

2Findash (5

80)

Yb2+

(310

) F i

ndash (400

) 2F

indash (580

)

252 B Zidarova

Fig

14

Spe

ctro

scop

ic c

hara

cter

istic

s (X

RLS

TLS

OTS

IR

S) o

n ra

w (

__)

and

synt

hetic

(---

) fl u

orite

s fro

m th

e Sla

vyan

ka d

epos

it an

d ar

ea o

f the

thei

r app

licat

ion

(UV

ndash u

ltrav

iole

t V

ndash v

isib

le I

R ndash

infr

ared

)









480 Sm3+







I(V IR)

002 0001 001 0003 ndash 00006 001 1868 3982 638 285 304 401 127

IIa

(IR)003 006 001 0003 0006 002 003 820 1735 1042 365 1036 1741 134

IIb

(V IR)0001 0003 001 002 0006 0003 0003 013 ndash 010 ndash 008 010 004

IIb


IIb


IIb

(IR)0006 010 003 0005 00001 0003 ndash 398 716 266 170 181 400 133

IIb


IIc


IIc

(UVV IR)001 001 0008 0005 0006 0006 0003 018 ndash 035 010 045 081 011

IIc


254 B Zidarova





ndash(400) and 2Fi



5 Discussion

















2+ 2

2CaFCa F

[(a ) (a ) Ksp 1]









256 B Zidarova






(572) ndash Sm3+(567)
















ndash(400) and 2Fi
















6 Conclusions


258 B Zidarova







Acknowledgements



References






































260 B Zidarova












































































262 B Zidarova




























228 B Zidarova








230 B Zidarova










Mikhaletz 385 2015 1795 1743 1525 1305






















232 B Zidarova















23

2F CO

(a ) a

3 2 3

2 2CO CaF CaCOF

(a ) (a ) Ksp Ksp





44 REE geochemistry

















23

2F

CO

(a )a

3 486 10 4

90 7 3

HCO SO Cl

(Na+K) Ca Mg

3 474 19 6

64 24 7

HCO SO Cl

(Na+K) Ca Mg

3 478 16 5

64 27 10

HCO SO Cl

(Na+K) Ca Mg

3 475 17 5

94 4 2

HCO SO Cl

(Na+K) Ca Mg

3 3 419 573

90 9 1

+CO )(HCO SO Cl

(Na+K) Ca Mg3 478 15 5

91 8 1

HCO SO Cl

(Na+K) Ca Mg



Vodenaskala

110 88 230 255145 90 215 260 276

253258


234 B Zidarova

Tabl

e 5

REE

dat

a of

the fl u

orite

var

ietie

s fro

m th

e Sl

avya

nka

depo

sit

No

Site

Loca

tion

Leve

lm

Varie

tyC

olou

rC

onte

nts

ppm

LaC

eSm

EuTb

Yb

LuR

EЕLa

Yb

TbY

bEu

Eu

Ce

Ce

3Vo

dena

skal

am

ain

lode

80

Igr

een

6

51 1

104

3

41

146

2

18 3

03

07

5 2

838

21

50

720

830

63 6

mai

n lo

de 8

0I

gree

n

937

16

85

524

1

91

351

42

6 0

92

42

06 2

20

082

069

067

8ap

ophy

sis

80

Igr

een

8

90 1

499

4

72

224

2

85 4

56

126

6 5

092

19

50

630

940

6411

apop

hysi

s 8

0I

gree

n 1

318

25

71

531

3

17

297

53

211

75

67

41 2

48

056

121

073

13m

ain

lode

80

Igr

een

9

66 1

829

3

55

272

2

55 3

65

07

7 4

119

26

50

701

430

7722

extr

chu

te11

0I

gree

n

625

11

53

356

1

82

265

39

2 1

25

30

98 1

59

068

094

069

28m

ain

lode

110

Igr

een

17

25 2

696

5

08

192

0

60 3

73

04

8 5

602

46

20

161

300

6837

mai

n lo

de14

5I

gree

n

602

3

38

315

1

16

134

09

5 0

51

16

51 6

34

141

080

021

38lo

de 1

90-

Igr

een

18

68 3

982

6

38

285

3

04 4

01

12

7 7

605

46

60

760

960

8739

fi llin

g24

0I

gree

n 3

044

40

60 1

220

3

34

156

62

0 1

20

95

57 4

91

025

094

054

42Ve

netz

am

ain

lode

350

Igr

een

49

70 7

433

8

62

319

1

55 4

92

08

114

312

101

00

321

100

7047

Vode

na sk

ala

mai

n lo

de38

5I

gray

ish-

gree

n

219

5

03

264

0

90

249

55

9 1

76

20

60 0

39

045

057

073

49m

ain

lode

385

Igr

ayis

h-gr

een

6

30 1

278

6

36

215

5

5412

47

44

6 5

000

05

10

440

430

6955

Mik

hale

tz38

5I

gree

n

980

10

75

027

0

20

069

20

7 0

34

24

12 4

73

033

088

076

59B

aba

500

Ida

rk-g

reen

14

80 1

858

5

80

150

2

74 3

03

05

2 4

697

48

80

900

550

5060

500

Ipa

le g

reen

23

10 2

138

3

80

054

0

77 1

74

05

4 5

187

132

70

440

400

4416

Vode

nask

ala

mai

n lo

de 8

0II

ada

rk-v

iole

t

522

12

40

857

1

60

292

115

0 1

87

44

08 0

45

025

045

070

25m

ain

lode

110

IIa

dark

-vio

let

8

20 1

735

10

42

365

10

3617

41

13

4 6

873

04

70

600

590

6629

mai

n lo

de11

0II

ada

rk-v

iole

t

654

20

60 1

005

2

20

480

198

0 2

12

66

11 0

33

024

047

094

36m

ain

lode

145

IIa

viol

et

115

5

06

146

0

40

080

57

0 1

05

15

62 0

20

014

055

145

57M

ikha

letz

385

IIa

dark

-vio

let

5

30 1

430

6

40

139

8

1315

06

24

0 5

298

03

50

540

340

86 9

Vode

nask

ala

apop

hysi

s 8

0II

bvi

olet

1

56

320

2

61

104

2

81 5

77

178

0 3

479

02

70

490

640

6212

apop

hysi

s 8

0II

bvi

olet

4

48 1

224

4

41

180

3

76 5

24

13

7 3

330

08

50

720

690

9020

mai

n lo

de 8

0II

bpa

le v

iole

t

033

1

03

032

ndash

038

09

6 0

27

3

29 0

34

040

ndash1

0530

mai

n lo

de11

0II

bvi

olet

1

60

307

1

70

020

0

55 3

66

04

7 1

125

04

40

150

290

6443

Vene

tza

350

IIb

viol

et

324

4

88

142

0

27

139

41

1 0

77

16

08 0

79

034

031

059

48Vo

dena

skal

am

ain

lode

385

IIb

viol

et

672

13

43

649

2

02

490

93

6 3

26

46

18 0

72

052

063

066

50m

ain

lode

385

IIb

viol

etis

h-bl

ue

398

7

16

266

1

70

181

40

0 1

33

22

64 0

99

045

123

065

51m

ain

lode

385

IIb

viol

et

205

9

52

501

1

40

542

114

0 3

73

38

53 0

18

048

045

132

53m

ain

lode

385

IIb

pale

vio

let

0

79 ndash

1

99

091

2

32 4

52

20

2 1

255

01

70

510

73ndash

54m

ain

lode

385

IIb

pale

vio

let

4

55

999

2

37

134

1

97 3

23

11

2 2

457

14

10

611

010

8156

Mik

hale

tz38

5II

bpa

le v

iole

t

048

0

88

077

0

54

047

18

0 0

23

5

17 0

27

026

134

055

5838

5II

bpa

le v

iole

t

031

10

25

034

0

20

012

03

2 0

13

11

67 0

97

038

138

150








dena

skal

am

ain

lode

40

IIc

viol

et

003

ndash

012

ndash

015

03

2 0

07

0

70 0

09

047

ndashndash

2m

ain

lode

40

IIc

viol

et ndash

ndash

001

ndash ndash

ndash ndash

0

01 ndash

ndashndash

ndash4

mai

n lo

de 8

0II

cvi

olet

ndash ndash

0

10 ndash

ndash 0

10

00

4

024

01

25ndash

ndashndash

5m

ain

lode

80

IIc

viol

et

015

ndash

013

ndash

012

06

4 0

26

1

30 0

23

019

ndashndash

7m

ain

lode

80

IIc

viol

et ndash

ndash

011

0

04

007

01

4 ndash

0

36 ndash

050

071

ndash10

apop

hysi

s 8

0II

cvi

olet

1

00 ndash

1

55

068

1

60 3

42

110

1 1

926

02

80

470

72ndash

14m

ain

lode

80

IIc

viol

et

014

ndash

013

ndash

010

02

5 0

04

0

66 0

56

040

ndashndash

15m

ain

lode

80

IIc

pale

vio

let

0

20 ndash

0

35

010

0

45 0

81

01

1

202

02

20

560

44ndash

17m

ain

lode

80

IIc

pale

vio

let

0

30

001

0

24

012

0

01 0

49

00

1

118

06

10

022

230

0118

mai

n lo

de 8

0II

cpa

le v

iole

t

192

2

30

030

0

01

020

06

2 0

01

5

36 3

10

032

006

058

19m

ain

lode

80

IIc

pale

vio

let

ndash ndash

0

10 ndash

ndash 0

15

ndash

025

ndashndash

ndashndash

21na

rrow

80

IIc

pale

vio

let

0

35 ndash

0

47

011

0

41 1

25

41

4

673

02

80

330

41ndash

23ex

tract

ion

110

IIc

viol

et

021

ndash

020

ndash

018

03

9 0

10

1

08 0

54

046

ndashndash

24ch

ute

110

IIc

viol

et ndash

ndash

001

ndash ndash

ndash ndash

0

01 ndash

ndashndash

ndash26

mai

n lo

de11

0II

cpa

le v

iole

t

022

ndash

013

ndash

011

02

3 0

02

0

71 0

96

048

ndashndash

27m

ain

lode

110

IIc

pale

vio

let

ndash ndash

0

06 ndash

ndash 0

15

ndash

021

10

0ndash

ndashndash

31m

ain

lode

110

IIc

pale

vio

let

0

43

086

0

40

001

0

01 0

79

02

4

274

05

40

010

140

6732

mai

n lo

de14

5II

cpa

le v

iole

t

010

01

01

01

01 0

01

00

1

016

100

01

001

750

0533

mai

n lo

de14

5II

cpa

le v

iole

t

012

01

011

01

01 0

01

00

1

028

120

01

001

520

0434

mai

n lo

de14

5II

cpa

le v

iole

t

01

01

01

01

01 0

01

00

1

007

10

01

001

750

3035

mai

n lo

de14

5II

cvi

olet

0

16

065

0

59

017

0

32 1

28

01

6

333

01

250

250

581

0640

lode

fi lli

ng21

5II

cpa

le v

iole

t

080

0

01

029

0

01

022

05

5 0

01

1

89 1

45

040

006

000

541

Mik

hale

tz33

5II

cpa

le v

iole

t

036

ndash

016

ndash

020

03

0 0

17

1

19 1

20

067

ndashndash

44Vo

dena

skal

am

ain

lode

370

IIc

pale

vio

let

0

36

01

017

01

01 0

86

01

0

152

04

20

011

120

015

45m

ain

lode

370

IIc

pale

vio

let

5

67

001

0

14

001

0

01 0

41

00

1

626

138

30

020

280

001

46m

ain

lode

370

IIc

pale

vio

let

0

46

078

0

57

020

0

01 0

96

01

8

316

04

80

012

640

5452

mai

n lo

de38

5II

cpa

le v

iole

t ndash

ndash

019

ndash

012

05

5 0

15

1

04 0

02

022

ndashndash

236 B Zidarova








x SxG V x




















238 B Zidarova














(540) Dy3+-O2

(674754) Er3+-O2 ndash(553) Sm3+-Fi

ndash(578))






240 B Zidarova


(480)Sm3+(567)









cub(572)IFndash

















skalaI 515 043 194 053 088I 418 037 202 042 086I 673 051 200 059 090I 778 033 213 046 087


skala IIa 4345 022 3061 000 092 IIa 1533 033 1495 100 087


skala IIb 378 035 826 100 082



40 Vodenaskala

IIc 010 100 286 033 400 IIc 024 080 247 033 071


110 IIc 023 212 248 025 090 IIc 041 045 527 150 040

145 IIc 107 048 587 080 075 IIc 013 333 302 000 075

370 IIc 035 046 1370 000 085

242 B Zidarova



ndash(578) (REE)
















180 degC(YO2)o

220 degCREE2+

280 degCY2+

320 degC(REEO2)o

380 degCSm2+-Ce4+


244 B Zidarova




ndash and

















Absorption bands

I CeSmYb





SmYb






ndashndash 580 nm

246 B Zidarova













Levelm


ZoneNо



400 nm 600 nm 80 I smoky 1 400 323 857 500 748








Fig

12

OTS

of fl

uor

ites

from

diff

eren

t lev

els

and

min

eral

ogic

al v

arie

ties

from

the

Slav

yank

a de

posi

t Le

gend

key

1 ndash

em

bedd

ing

rock

s 2

ndash v

arie

ty I

3 ndash

var

iety

IIa

4 ndash

varie

ty II

b 5

ndash va

riety

IIc

6 ndash

suga

r-gra

ined

qua

rtz

248 B Zidarova






















(306) Sm2+(425) Fi

ndash(400) 2Fi

ndash(580)


(306) Sm2+(340) 2Fi

ndash(580)


ndash(580)


ndash(400) 2Fi

ndash(580)



(420) MO2 ndash(565) Sm2+

(620)


(480) MO2 ndash(560) Sm2+

(620)


(440) (YO2)o(520)


(440) MO2 ndash(560)


(440) (YO2)o(520) Sm2+

(660)


(560) Sm2+(620)


(440) MO2 ndash(560)

250 B Zidarova
















7500 nm 9300 nm 7500 nm 9300 nmVodena

skala












ble

14 I

nfl u

ence

of t

he R

EE o

n th

e co

lour

and

lum

ines

cenc

e of

fl uo

rite

varie

ties f

rom

the

Slav

yank

a de

posi

t

Varie

tyI

IIa

IIb

IIc

T h degC

153 ndash 20

2(f

requ

ently

155 ndash1

97)

140 ndash

178

(fre

quen

tly 1

45 ndash1

72)

120 ndash

157

(fre

quen

tly 1

26 ndash1

53)

103 ndash

119

(fre

quen

tly 1

10 ndash1

15)

REE

ppm

165

1ndash14

312

333 ndash

687

33

30 ndash

461

80

07ndash 3

479

colo

urgr

een

dark

-vio

let

viol

et p

ale

viol

etvi

olet

pal

e vi

olet

PLS

gree

nda

rk-v

iole

tvi

olet

pale

vio

let

XR

LSD

y-Sm

type

spec

traD

y ty

pe sp

ectra

Dy

type

spec

traU

nallo

yed

type

spec

traTL

S18

0 degС

ndash (Y

O2)deg

def

ectiv

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

130-

150

degС ndash

REE

O2+

- Ondash d

ipol

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

180

degС ndash

(YO

2)deg d

efec

tive

cent

er22

0 degC

ndash R

EE2+

cubi

c ce

nter

28

0 degС

ndash Y

2+ cu

bic

cent

er

320

degС ndash

(REE

O2)deg

def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

OA

SY

b2+(2

653

65)

Ce3+

(306

) Sm

2+(4

25)

F indash (4

00)

2Findash (5

80)

Yb2+

(265

365

) C

e3+(3

06)

Sm2+

(340

) 2F

indash (580

)Y

b2+(2

473

10)

2Findash (5

80)

Yb2+

(310

) F i

ndash (400

) 2F

indash (580

)

252 B Zidarova

Fig

14

Spe

ctro

scop

ic c

hara

cter

istic

s (X

RLS

TLS

OTS

IR

S) o

n ra

w (

__)

and

synt

hetic

(---

) fl u

orite

s fro

m th

e Sla

vyan

ka d

epos

it an

d ar

ea o

f the

thei

r app

licat

ion

(UV

ndash u

ltrav

iole

t V

ndash v

isib

le I

R ndash

infr

ared

)









480 Sm3+







I(V IR)

002 0001 001 0003 ndash 00006 001 1868 3982 638 285 304 401 127

IIa

(IR)003 006 001 0003 0006 002 003 820 1735 1042 365 1036 1741 134

IIb

(V IR)0001 0003 001 002 0006 0003 0003 013 ndash 010 ndash 008 010 004

IIb


IIb


IIb

(IR)0006 010 003 0005 00001 0003 ndash 398 716 266 170 181 400 133

IIb


IIc


IIc

(UVV IR)001 001 0008 0005 0006 0006 0003 018 ndash 035 010 045 081 011

IIc


254 B Zidarova





ndash(400) and 2Fi



5 Discussion

















2+ 2

2CaFCa F

[(a ) (a ) Ksp 1]









256 B Zidarova






(572) ndash Sm3+(567)
















ndash(400) and 2Fi
















6 Conclusions


258 B Zidarova







Acknowledgements



References






































260 B Zidarova












































































262 B Zidarova


















230 B Zidarova










Mikhaletz 385 2015 1795 1743 1525 1305






















232 B Zidarova















23

2F CO

(a ) a

3 2 3

2 2CO CaF CaCOF

(a ) (a ) Ksp Ksp





44 REE geochemistry

















23

2F

CO

(a )a

3 486 10 4

90 7 3

HCO SO Cl

(Na+K) Ca Mg

3 474 19 6

64 24 7

HCO SO Cl

(Na+K) Ca Mg

3 478 16 5

64 27 10

HCO SO Cl

(Na+K) Ca Mg

3 475 17 5

94 4 2

HCO SO Cl

(Na+K) Ca Mg

3 3 419 573

90 9 1

+CO )(HCO SO Cl

(Na+K) Ca Mg3 478 15 5

91 8 1

HCO SO Cl

(Na+K) Ca Mg



Vodenaskala

110 88 230 255145 90 215 260 276

253258


234 B Zidarova

Tabl

e 5

REE

dat

a of

the fl u

orite

var

ietie

s fro

m th

e Sl

avya

nka

depo

sit

No

Site

Loca

tion

Leve

lm

Varie

tyC

olou

rC

onte

nts

ppm

LaC

eSm

EuTb

Yb

LuR

EЕLa

Yb

TbY

bEu

Eu

Ce

Ce

3Vo

dena

skal

am

ain

lode

80

Igr

een

6

51 1

104

3

41

146

2

18 3

03

07

5 2

838

21

50

720

830

63 6

mai

n lo

de 8

0I

gree

n

937

16

85

524

1

91

351

42

6 0

92

42

06 2

20

082

069

067

8ap

ophy

sis

80

Igr

een

8

90 1

499

4

72

224

2

85 4

56

126

6 5

092

19

50

630

940

6411

apop

hysi

s 8

0I

gree

n 1

318

25

71

531

3

17

297

53

211

75

67

41 2

48

056

121

073

13m

ain

lode

80

Igr

een

9

66 1

829

3

55

272

2

55 3

65

07

7 4

119

26

50

701

430

7722

extr

chu

te11

0I

gree

n

625

11

53

356

1

82

265

39

2 1

25

30

98 1

59

068

094

069

28m

ain

lode

110

Igr

een

17

25 2

696

5

08

192

0

60 3

73

04

8 5

602

46

20

161

300

6837

mai

n lo

de14

5I

gree

n

602

3

38

315

1

16

134

09

5 0

51

16

51 6

34

141

080

021

38lo

de 1

90-

Igr

een

18

68 3

982

6

38

285

3

04 4

01

12

7 7

605

46

60

760

960

8739

fi llin

g24

0I

gree

n 3

044

40

60 1

220

3

34

156

62

0 1

20

95

57 4

91

025

094

054

42Ve

netz

am

ain

lode

350

Igr

een

49

70 7

433

8

62

319

1

55 4

92

08

114

312

101

00

321

100

7047

Vode

na sk

ala

mai

n lo

de38

5I

gray

ish-

gree

n

219

5

03

264

0

90

249

55

9 1

76

20

60 0

39

045

057

073

49m

ain

lode

385

Igr

ayis

h-gr

een

6

30 1

278

6

36

215

5

5412

47

44

6 5

000

05

10

440

430

6955

Mik

hale

tz38

5I

gree

n

980

10

75

027

0

20

069

20

7 0

34

24

12 4

73

033

088

076

59B

aba

500

Ida

rk-g

reen

14

80 1

858

5

80

150

2

74 3

03

05

2 4

697

48

80

900

550

5060

500

Ipa

le g

reen

23

10 2

138

3

80

054

0

77 1

74

05

4 5

187

132

70

440

400

4416

Vode

nask

ala

mai

n lo

de 8

0II

ada

rk-v

iole

t

522

12

40

857

1

60

292

115

0 1

87

44

08 0

45

025

045

070

25m

ain

lode

110

IIa

dark

-vio

let

8

20 1

735

10

42

365

10

3617

41

13

4 6

873

04

70

600

590

6629

mai

n lo

de11

0II

ada

rk-v

iole

t

654

20

60 1

005

2

20

480

198

0 2

12

66

11 0

33

024

047

094

36m

ain

lode

145

IIa

viol

et

115

5

06

146

0

40

080

57

0 1

05

15

62 0

20

014

055

145

57M

ikha

letz

385

IIa

dark

-vio

let

5

30 1

430

6

40

139

8

1315

06

24

0 5

298

03

50

540

340

86 9

Vode

nask

ala

apop

hysi

s 8

0II

bvi

olet

1

56

320

2

61

104

2

81 5

77

178

0 3

479

02

70

490

640

6212

apop

hysi

s 8

0II

bvi

olet

4

48 1

224

4

41

180

3

76 5

24

13

7 3

330

08

50

720

690

9020

mai

n lo

de 8

0II

bpa

le v

iole

t

033

1

03

032

ndash

038

09

6 0

27

3

29 0

34

040

ndash1

0530

mai

n lo

de11

0II

bvi

olet

1

60

307

1

70

020

0

55 3

66

04

7 1

125

04

40

150

290

6443

Vene

tza

350

IIb

viol

et

324

4

88

142

0

27

139

41

1 0

77

16

08 0

79

034

031

059

48Vo

dena

skal

am

ain

lode

385

IIb

viol

et

672

13

43

649

2

02

490

93

6 3

26

46

18 0

72

052

063

066

50m

ain

lode

385

IIb

viol

etis

h-bl

ue

398

7

16

266

1

70

181

40

0 1

33

22

64 0

99

045

123

065

51m

ain

lode

385

IIb

viol

et

205

9

52

501

1

40

542

114

0 3

73

38

53 0

18

048

045

132

53m

ain

lode

385

IIb

pale

vio

let

0

79 ndash

1

99

091

2

32 4

52

20

2 1

255

01

70

510

73ndash

54m

ain

lode

385

IIb

pale

vio

let

4

55

999

2

37

134

1

97 3

23

11

2 2

457

14

10

611

010

8156

Mik

hale

tz38

5II

bpa

le v

iole

t

048

0

88

077

0

54

047

18

0 0

23

5

17 0

27

026

134

055

5838

5II

bpa

le v

iole

t

031

10

25

034

0

20

012

03

2 0

13

11

67 0

97

038

138

150








dena

skal

am

ain

lode

40

IIc

viol

et

003

ndash

012

ndash

015

03

2 0

07

0

70 0

09

047

ndashndash

2m

ain

lode

40

IIc

viol

et ndash

ndash

001

ndash ndash

ndash ndash

0

01 ndash

ndashndash

ndash4

mai

n lo

de 8

0II

cvi

olet

ndash ndash

0

10 ndash

ndash 0

10

00

4

024

01

25ndash

ndashndash

5m

ain

lode

80

IIc

viol

et

015

ndash

013

ndash

012

06

4 0

26

1

30 0

23

019

ndashndash

7m

ain

lode

80

IIc

viol

et ndash

ndash

011

0

04

007

01

4 ndash

0

36 ndash

050

071

ndash10

apop

hysi

s 8

0II

cvi

olet

1

00 ndash

1

55

068

1

60 3

42

110

1 1

926

02

80

470

72ndash

14m

ain

lode

80

IIc

viol

et

014

ndash

013

ndash

010

02

5 0

04

0

66 0

56

040

ndashndash

15m

ain

lode

80

IIc

pale

vio

let

0

20 ndash

0

35

010

0

45 0

81

01

1

202

02

20

560

44ndash

17m

ain

lode

80

IIc

pale

vio

let

0

30

001

0

24

012

0

01 0

49

00

1

118

06

10

022

230

0118

mai

n lo

de 8

0II

cpa

le v

iole

t

192

2

30

030

0

01

020

06

2 0

01

5

36 3

10

032

006

058

19m

ain

lode

80

IIc

pale

vio

let

ndash ndash

0

10 ndash

ndash 0

15

ndash

025

ndashndash

ndashndash

21na

rrow

80

IIc

pale

vio

let

0

35 ndash

0

47

011

0

41 1

25

41

4

673

02

80

330

41ndash

23ex

tract

ion

110

IIc

viol

et

021

ndash

020

ndash

018

03

9 0

10

1

08 0

54

046

ndashndash

24ch

ute

110

IIc

viol

et ndash

ndash

001

ndash ndash

ndash ndash

0

01 ndash

ndashndash

ndash26

mai

n lo

de11

0II

cpa

le v

iole

t

022

ndash

013

ndash

011

02

3 0

02

0

71 0

96

048

ndashndash

27m

ain

lode

110

IIc

pale

vio

let

ndash ndash

0

06 ndash

ndash 0

15

ndash

021

10

0ndash

ndashndash

31m

ain

lode

110

IIc

pale

vio

let

0

43

086

0

40

001

0

01 0

79

02

4

274

05

40

010

140

6732

mai

n lo

de14

5II

cpa

le v

iole

t

010

01

01

01

01 0

01

00

1

016

100

01

001

750

0533

mai

n lo

de14

5II

cpa

le v

iole

t

012

01

011

01

01 0

01

00

1

028

120

01

001

520

0434

mai

n lo

de14

5II

cpa

le v

iole

t

01

01

01

01

01 0

01

00

1

007

10

01

001

750

3035

mai

n lo

de14

5II

cvi

olet

0

16

065

0

59

017

0

32 1

28

01

6

333

01

250

250

581

0640

lode

fi lli

ng21

5II

cpa

le v

iole

t

080

0

01

029

0

01

022

05

5 0

01

1

89 1

45

040

006

000

541

Mik

hale

tz33

5II

cpa

le v

iole

t

036

ndash

016

ndash

020

03

0 0

17

1

19 1

20

067

ndashndash

44Vo

dena

skal

am

ain

lode

370

IIc

pale

vio

let

0

36

01

017

01

01 0

86

01

0

152

04

20

011

120

015

45m

ain

lode

370

IIc

pale

vio

let

5

67

001

0

14

001

0

01 0

41

00

1

626

138

30

020

280

001

46m

ain

lode

370

IIc

pale

vio

let

0

46

078

0

57

020

0

01 0

96

01

8

316

04

80

012

640

5452

mai

n lo

de38

5II

cpa

le v

iole

t ndash

ndash

019

ndash

012

05

5 0

15

1

04 0

02

022

ndashndash

236 B Zidarova








x SxG V x




















238 B Zidarova














(540) Dy3+-O2

(674754) Er3+-O2 ndash(553) Sm3+-Fi

ndash(578))






240 B Zidarova


(480)Sm3+(567)









cub(572)IFndash

















skalaI 515 043 194 053 088I 418 037 202 042 086I 673 051 200 059 090I 778 033 213 046 087


skala IIa 4345 022 3061 000 092 IIa 1533 033 1495 100 087


skala IIb 378 035 826 100 082



40 Vodenaskala

IIc 010 100 286 033 400 IIc 024 080 247 033 071


110 IIc 023 212 248 025 090 IIc 041 045 527 150 040

145 IIc 107 048 587 080 075 IIc 013 333 302 000 075

370 IIc 035 046 1370 000 085

242 B Zidarova



ndash(578) (REE)
















180 degC(YO2)o

220 degCREE2+

280 degCY2+

320 degC(REEO2)o

380 degCSm2+-Ce4+


244 B Zidarova




ndash and

















Absorption bands

I CeSmYb





SmYb






ndashndash 580 nm

246 B Zidarova













Levelm


ZoneNо



400 nm 600 nm 80 I smoky 1 400 323 857 500 748








Fig

12

OTS

of fl

uor

ites

from

diff

eren

t lev

els

and

min

eral

ogic

al v

arie

ties

from

the

Slav

yank

a de

posi

t Le

gend

key

1 ndash

em

bedd

ing

rock

s 2

ndash v

arie

ty I

3 ndash

var

iety

IIa

4 ndash

varie

ty II

b 5

ndash va

riety

IIc

6 ndash

suga

r-gra

ined

qua

rtz

248 B Zidarova






















(306) Sm2+(425) Fi

ndash(400) 2Fi

ndash(580)


(306) Sm2+(340) 2Fi

ndash(580)


ndash(580)


ndash(400) 2Fi

ndash(580)



(420) MO2 ndash(565) Sm2+

(620)


(480) MO2 ndash(560) Sm2+

(620)


(440) (YO2)o(520)


(440) MO2 ndash(560)


(440) (YO2)o(520) Sm2+

(660)


(560) Sm2+(620)


(440) MO2 ndash(560)

250 B Zidarova
















7500 nm 9300 nm 7500 nm 9300 nmVodena

skala












ble

14 I

nfl u

ence

of t

he R

EE o

n th

e co

lour

and

lum

ines

cenc

e of

fl uo

rite

varie

ties f

rom

the

Slav

yank

a de

posi

t

Varie

tyI

IIa

IIb

IIc

T h degC

153 ndash 20

2(f

requ

ently

155 ndash1

97)

140 ndash

178

(fre

quen

tly 1

45 ndash1

72)

120 ndash

157

(fre

quen

tly 1

26 ndash1

53)

103 ndash

119

(fre

quen

tly 1

10 ndash1

15)

REE

ppm

165

1ndash14

312

333 ndash

687

33

30 ndash

461

80

07ndash 3

479

colo

urgr

een

dark

-vio

let

viol

et p

ale

viol

etvi

olet

pal

e vi

olet

PLS

gree

nda

rk-v

iole

tvi

olet

pale

vio

let

XR

LSD

y-Sm

type

spec

traD

y ty

pe sp

ectra

Dy

type

spec

traU

nallo

yed

type

spec

traTL

S18

0 degС

ndash (Y

O2)deg

def

ectiv

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

130-

150

degС ndash

REE

O2+

- Ondash d

ipol

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

180

degС ndash

(YO

2)deg d

efec

tive

cent

er22

0 degC

ndash R

EE2+

cubi

c ce

nter

28

0 degС

ndash Y

2+ cu

bic

cent

er

320

degС ndash

(REE

O2)deg

def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

OA

SY

b2+(2

653

65)

Ce3+

(306

) Sm

2+(4

25)

F indash (4

00)

2Findash (5

80)

Yb2+

(265

365

) C

e3+(3

06)

Sm2+

(340

) 2F

indash (580

)Y

b2+(2

473

10)

2Findash (5

80)

Yb2+

(310

) F i

ndash (400

) 2F

indash (580

)

252 B Zidarova

Fig

14

Spe

ctro

scop

ic c

hara

cter

istic

s (X

RLS

TLS

OTS

IR

S) o

n ra

w (

__)

and

synt

hetic

(---

) fl u

orite

s fro

m th

e Sla

vyan

ka d

epos

it an

d ar

ea o

f the

thei

r app

licat

ion

(UV

ndash u

ltrav

iole

t V

ndash v

isib

le I

R ndash

infr

ared

)









480 Sm3+







I(V IR)

002 0001 001 0003 ndash 00006 001 1868 3982 638 285 304 401 127

IIa

(IR)003 006 001 0003 0006 002 003 820 1735 1042 365 1036 1741 134

IIb

(V IR)0001 0003 001 002 0006 0003 0003 013 ndash 010 ndash 008 010 004

IIb


IIb


IIb

(IR)0006 010 003 0005 00001 0003 ndash 398 716 266 170 181 400 133

IIb


IIc


IIc

(UVV IR)001 001 0008 0005 0006 0006 0003 018 ndash 035 010 045 081 011

IIc


254 B Zidarova





ndash(400) and 2Fi



5 Discussion

















2+ 2

2CaFCa F

[(a ) (a ) Ksp 1]









256 B Zidarova






(572) ndash Sm3+(567)
















ndash(400) and 2Fi
















6 Conclusions


258 B Zidarova







Acknowledgements



References






































260 B Zidarova












































































262 B Zidarova

































232 B Zidarova















23

2F CO

(a ) a

3 2 3

2 2CO CaF CaCOF

(a ) (a ) Ksp Ksp





44 REE geochemistry

















23

2F

CO

(a )a

3 486 10 4

90 7 3

HCO SO Cl

(Na+K) Ca Mg

3 474 19 6

64 24 7

HCO SO Cl

(Na+K) Ca Mg

3 478 16 5

64 27 10

HCO SO Cl

(Na+K) Ca Mg

3 475 17 5

94 4 2

HCO SO Cl

(Na+K) Ca Mg

3 3 419 573

90 9 1

+CO )(HCO SO Cl

(Na+K) Ca Mg3 478 15 5

91 8 1

HCO SO Cl

(Na+K) Ca Mg



Vodenaskala

110 88 230 255145 90 215 260 276

253258


234 B Zidarova

Tabl

e 5

REE

dat

a of

the fl u

orite

var

ietie

s fro

m th

e Sl

avya

nka

depo

sit

No

Site

Loca

tion

Leve

lm

Varie

tyC

olou

rC

onte

nts

ppm

LaC

eSm

EuTb

Yb

LuR

EЕLa

Yb

TbY

bEu

Eu

Ce

Ce

3Vo

dena

skal

am

ain

lode

80

Igr

een

6

51 1

104

3

41

146

2

18 3

03

07

5 2

838

21

50

720

830

63 6

mai

n lo

de 8

0I

gree

n

937

16

85

524

1

91

351

42

6 0

92

42

06 2

20

082

069

067

8ap

ophy

sis

80

Igr

een

8

90 1

499

4

72

224

2

85 4

56

126

6 5

092

19

50

630

940

6411

apop

hysi

s 8

0I

gree

n 1

318

25

71

531

3

17

297

53

211

75

67

41 2

48

056

121

073

13m

ain

lode

80

Igr

een

9

66 1

829

3

55

272

2

55 3

65

07

7 4

119

26

50

701

430

7722

extr

chu

te11

0I

gree

n

625

11

53

356

1

82

265

39

2 1

25

30

98 1

59

068

094

069

28m

ain

lode

110

Igr

een

17

25 2

696

5

08

192

0

60 3

73

04

8 5

602

46

20

161

300

6837

mai

n lo

de14

5I

gree

n

602

3

38

315

1

16

134

09

5 0

51

16

51 6

34

141

080

021

38lo

de 1

90-

Igr

een

18

68 3

982

6

38

285

3

04 4

01

12

7 7

605

46

60

760

960

8739

fi llin

g24

0I

gree

n 3

044

40

60 1

220

3

34

156

62

0 1

20

95

57 4

91

025

094

054

42Ve

netz

am

ain

lode

350

Igr

een

49

70 7

433

8

62

319

1

55 4

92

08

114

312

101

00

321

100

7047

Vode

na sk

ala

mai

n lo

de38

5I

gray

ish-

gree

n

219

5

03

264

0

90

249

55

9 1

76

20

60 0

39

045

057

073

49m

ain

lode

385

Igr

ayis

h-gr

een

6

30 1

278

6

36

215

5

5412

47

44

6 5

000

05

10

440

430

6955

Mik

hale

tz38

5I

gree

n

980

10

75

027

0

20

069

20

7 0

34

24

12 4

73

033

088

076

59B

aba

500

Ida

rk-g

reen

14

80 1

858

5

80

150

2

74 3

03

05

2 4

697

48

80

900

550

5060

500

Ipa

le g

reen

23

10 2

138

3

80

054

0

77 1

74

05

4 5

187

132

70

440

400

4416

Vode

nask

ala

mai

n lo

de 8

0II

ada

rk-v

iole

t

522

12

40

857

1

60

292

115

0 1

87

44

08 0

45

025

045

070

25m

ain

lode

110

IIa

dark

-vio

let

8

20 1

735

10

42

365

10

3617

41

13

4 6

873

04

70

600

590

6629

mai

n lo

de11

0II

ada

rk-v

iole

t

654

20

60 1

005

2

20

480

198

0 2

12

66

11 0

33

024

047

094

36m

ain

lode

145

IIa

viol

et

115

5

06

146

0

40

080

57

0 1

05

15

62 0

20

014

055

145

57M

ikha

letz

385

IIa

dark

-vio

let

5

30 1

430

6

40

139

8

1315

06

24

0 5

298

03

50

540

340

86 9

Vode

nask

ala

apop

hysi

s 8

0II

bvi

olet

1

56

320

2

61

104

2

81 5

77

178

0 3

479

02

70

490

640

6212

apop

hysi

s 8

0II

bvi

olet

4

48 1

224

4

41

180

3

76 5

24

13

7 3

330

08

50

720

690

9020

mai

n lo

de 8

0II

bpa

le v

iole

t

033

1

03

032

ndash

038

09

6 0

27

3

29 0

34

040

ndash1

0530

mai

n lo

de11

0II

bvi

olet

1

60

307

1

70

020

0

55 3

66

04

7 1

125

04

40

150

290

6443

Vene

tza

350

IIb

viol

et

324

4

88

142

0

27

139

41

1 0

77

16

08 0

79

034

031

059

48Vo

dena

skal

am

ain

lode

385

IIb

viol

et

672

13

43

649

2

02

490

93

6 3

26

46

18 0

72

052

063

066

50m

ain

lode

385

IIb

viol

etis

h-bl

ue

398

7

16

266

1

70

181

40

0 1

33

22

64 0

99

045

123

065

51m

ain

lode

385

IIb

viol

et

205

9

52

501

1

40

542

114

0 3

73

38

53 0

18

048

045

132

53m

ain

lode

385

IIb

pale

vio

let

0

79 ndash

1

99

091

2

32 4

52

20

2 1

255

01

70

510

73ndash

54m

ain

lode

385

IIb

pale

vio

let

4

55

999

2

37

134

1

97 3

23

11

2 2

457

14

10

611

010

8156

Mik

hale

tz38

5II

bpa

le v

iole

t

048

0

88

077

0

54

047

18

0 0

23

5

17 0

27

026

134

055

5838

5II

bpa

le v

iole

t

031

10

25

034

0

20

012

03

2 0

13

11

67 0

97

038

138

150








dena

skal

am

ain

lode

40

IIc

viol

et

003

ndash

012

ndash

015

03

2 0

07

0

70 0

09

047

ndashndash

2m

ain

lode

40

IIc

viol

et ndash

ndash

001

ndash ndash

ndash ndash

0

01 ndash

ndashndash

ndash4

mai

n lo

de 8

0II

cvi

olet

ndash ndash

0

10 ndash

ndash 0

10

00

4

024

01

25ndash

ndashndash

5m

ain

lode

80

IIc

viol

et

015

ndash

013

ndash

012

06

4 0

26

1

30 0

23

019

ndashndash

7m

ain

lode

80

IIc

viol

et ndash

ndash

011

0

04

007

01

4 ndash

0

36 ndash

050

071

ndash10

apop

hysi

s 8

0II

cvi

olet

1

00 ndash

1

55

068

1

60 3

42

110

1 1

926

02

80

470

72ndash

14m

ain

lode

80

IIc

viol

et

014

ndash

013

ndash

010

02

5 0

04

0

66 0

56

040

ndashndash

15m

ain

lode

80

IIc

pale

vio

let

0

20 ndash

0

35

010

0

45 0

81

01

1

202

02

20

560

44ndash

17m

ain

lode

80

IIc

pale

vio

let

0

30

001

0

24

012

0

01 0

49

00

1

118

06

10

022

230

0118

mai

n lo

de 8

0II

cpa

le v

iole

t

192

2

30

030

0

01

020

06

2 0

01

5

36 3

10

032

006

058

19m

ain

lode

80

IIc

pale

vio

let

ndash ndash

0

10 ndash

ndash 0

15

ndash

025

ndashndash

ndashndash

21na

rrow

80

IIc

pale

vio

let

0

35 ndash

0

47

011

0

41 1

25

41

4

673

02

80

330

41ndash

23ex

tract

ion

110

IIc

viol

et

021

ndash

020

ndash

018

03

9 0

10

1

08 0

54

046

ndashndash

24ch

ute

110

IIc

viol

et ndash

ndash

001

ndash ndash

ndash ndash

0

01 ndash

ndashndash

ndash26

mai

n lo

de11

0II

cpa

le v

iole

t

022

ndash

013

ndash

011

02

3 0

02

0

71 0

96

048

ndashndash

27m

ain

lode

110

IIc

pale

vio

let

ndash ndash

0

06 ndash

ndash 0

15

ndash

021

10

0ndash

ndashndash

31m

ain

lode

110

IIc

pale

vio

let

0

43

086

0

40

001

0

01 0

79

02

4

274

05

40

010

140

6732

mai

n lo

de14

5II

cpa

le v

iole

t

010

01

01

01

01 0

01

00

1

016

100

01

001

750

0533

mai

n lo

de14

5II

cpa

le v

iole

t

012

01

011

01

01 0

01

00

1

028

120

01

001

520

0434

mai

n lo

de14

5II

cpa

le v

iole

t

01

01

01

01

01 0

01

00

1

007

10

01

001

750

3035

mai

n lo

de14

5II

cvi

olet

0

16

065

0

59

017

0

32 1

28

01

6

333

01

250

250

581

0640

lode

fi lli

ng21

5II

cpa

le v

iole

t

080

0

01

029

0

01

022

05

5 0

01

1

89 1

45

040

006

000

541

Mik

hale

tz33

5II

cpa

le v

iole

t

036

ndash

016

ndash

020

03

0 0

17

1

19 1

20

067

ndashndash

44Vo

dena

skal

am

ain

lode

370

IIc

pale

vio

let

0

36

01

017

01

01 0

86

01

0

152

04

20

011

120

015

45m

ain

lode

370

IIc

pale

vio

let

5

67

001

0

14

001

0

01 0

41

00

1

626

138

30

020

280

001

46m

ain

lode

370

IIc

pale

vio

let

0

46

078

0

57

020

0

01 0

96

01

8

316

04

80

012

640

5452

mai

n lo

de38

5II

cpa

le v

iole

t ndash

ndash

019

ndash

012

05

5 0

15

1

04 0

02

022

ndashndash

236 B Zidarova








x SxG V x




















238 B Zidarova














(540) Dy3+-O2

(674754) Er3+-O2 ndash(553) Sm3+-Fi

ndash(578))






240 B Zidarova


(480)Sm3+(567)









cub(572)IFndash

















skalaI 515 043 194 053 088I 418 037 202 042 086I 673 051 200 059 090I 778 033 213 046 087


skala IIa 4345 022 3061 000 092 IIa 1533 033 1495 100 087


skala IIb 378 035 826 100 082



40 Vodenaskala

IIc 010 100 286 033 400 IIc 024 080 247 033 071


110 IIc 023 212 248 025 090 IIc 041 045 527 150 040

145 IIc 107 048 587 080 075 IIc 013 333 302 000 075

370 IIc 035 046 1370 000 085

242 B Zidarova



ndash(578) (REE)
















180 degC(YO2)o

220 degCREE2+

280 degCY2+

320 degC(REEO2)o

380 degCSm2+-Ce4+


244 B Zidarova




ndash and

















Absorption bands

I CeSmYb





SmYb






ndashndash 580 nm

246 B Zidarova













Levelm


ZoneNо



400 nm 600 nm 80 I smoky 1 400 323 857 500 748








Fig

12

OTS

of fl

uor

ites

from

diff

eren

t lev

els

and

min

eral

ogic

al v

arie

ties

from

the

Slav

yank

a de

posi

t Le

gend

key

1 ndash

em

bedd

ing

rock

s 2

ndash v

arie

ty I

3 ndash

var

iety

IIa

4 ndash

varie

ty II

b 5

ndash va

riety

IIc

6 ndash

suga

r-gra

ined

qua

rtz

248 B Zidarova






















(306) Sm2+(425) Fi

ndash(400) 2Fi

ndash(580)


(306) Sm2+(340) 2Fi

ndash(580)


ndash(580)


ndash(400) 2Fi

ndash(580)



(420) MO2 ndash(565) Sm2+

(620)


(480) MO2 ndash(560) Sm2+

(620)


(440) (YO2)o(520)


(440) MO2 ndash(560)


(440) (YO2)o(520) Sm2+

(660)


(560) Sm2+(620)


(440) MO2 ndash(560)

250 B Zidarova
















7500 nm 9300 nm 7500 nm 9300 nmVodena

skala












ble

14 I

nfl u

ence

of t

he R

EE o

n th

e co

lour

and

lum

ines

cenc

e of

fl uo

rite

varie

ties f

rom

the

Slav

yank

a de

posi

t

Varie

tyI

IIa

IIb

IIc

T h degC

153 ndash 20

2(f

requ

ently

155 ndash1

97)

140 ndash

178

(fre

quen

tly 1

45 ndash1

72)

120 ndash

157

(fre

quen

tly 1

26 ndash1

53)

103 ndash

119

(fre

quen

tly 1

10 ndash1

15)

REE

ppm

165

1ndash14

312

333 ndash

687

33

30 ndash

461

80

07ndash 3

479

colo

urgr

een

dark

-vio

let

viol

et p

ale

viol

etvi

olet

pal

e vi

olet

PLS

gree

nda

rk-v

iole

tvi

olet

pale

vio

let

XR

LSD

y-Sm

type

spec

traD

y ty

pe sp

ectra

Dy

type

spec

traU

nallo

yed

type

spec

traTL

S18

0 degС

ndash (Y

O2)deg

def

ectiv

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

130-

150

degС ndash

REE

O2+

- Ondash d

ipol

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

180

degС ndash

(YO

2)deg d

efec

tive

cent

er22

0 degC

ndash R

EE2+

cubi

c ce

nter

28

0 degС

ndash Y

2+ cu

bic

cent

er

320

degС ndash

(REE

O2)deg

def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

OA

SY

b2+(2

653

65)

Ce3+

(306

) Sm

2+(4

25)

F indash (4

00)

2Findash (5

80)

Yb2+

(265

365

) C

e3+(3

06)

Sm2+

(340

) 2F

indash (580

)Y

b2+(2

473

10)

2Findash (5

80)

Yb2+

(310

) F i

ndash (400

) 2F

indash (580

)

252 B Zidarova

Fig

14

Spe

ctro

scop

ic c

hara

cter

istic

s (X

RLS

TLS

OTS

IR

S) o

n ra

w (

__)

and

synt

hetic

(---

) fl u

orite

s fro

m th

e Sla

vyan

ka d

epos

it an

d ar

ea o

f the

thei

r app

licat

ion

(UV

ndash u

ltrav

iole

t V

ndash v

isib

le I

R ndash

infr

ared

)









480 Sm3+







I(V IR)

002 0001 001 0003 ndash 00006 001 1868 3982 638 285 304 401 127

IIa

(IR)003 006 001 0003 0006 002 003 820 1735 1042 365 1036 1741 134

IIb

(V IR)0001 0003 001 002 0006 0003 0003 013 ndash 010 ndash 008 010 004

IIb


IIb


IIb

(IR)0006 010 003 0005 00001 0003 ndash 398 716 266 170 181 400 133

IIb


IIc


IIc

(UVV IR)001 001 0008 0005 0006 0006 0003 018 ndash 035 010 045 081 011

IIc


254 B Zidarova





ndash(400) and 2Fi



5 Discussion

















2+ 2

2CaFCa F

[(a ) (a ) Ksp 1]









256 B Zidarova






(572) ndash Sm3+(567)
















ndash(400) and 2Fi
















6 Conclusions


258 B Zidarova







Acknowledgements



References






































260 B Zidarova












































































262 B Zidarova




















44 REE geochemistry

















23

2F

CO

(a )a

3 486 10 4

90 7 3

HCO SO Cl

(Na+K) Ca Mg

3 474 19 6

64 24 7

HCO SO Cl

(Na+K) Ca Mg

3 478 16 5

64 27 10

HCO SO Cl

(Na+K) Ca Mg

3 475 17 5

94 4 2

HCO SO Cl

(Na+K) Ca Mg

3 3 419 573

90 9 1

+CO )(HCO SO Cl

(Na+K) Ca Mg3 478 15 5

91 8 1

HCO SO Cl

(Na+K) Ca Mg



Vodenaskala

110 88 230 255145 90 215 260 276

253258


234 B Zidarova

Tabl

e 5

REE

dat

a of

the fl u

orite

var

ietie

s fro

m th

e Sl

avya

nka

depo

sit

No

Site

Loca

tion

Leve

lm

Varie

tyC

olou

rC

onte

nts

ppm

LaC

eSm

EuTb

Yb

LuR

EЕLa

Yb

TbY

bEu

Eu

Ce

Ce

3Vo

dena

skal

am

ain

lode

80

Igr

een

6

51 1

104

3

41

146

2

18 3

03

07

5 2

838

21

50

720

830

63 6

mai

n lo

de 8

0I

gree

n

937

16

85

524

1

91

351

42

6 0

92

42

06 2

20

082

069

067

8ap

ophy

sis

80

Igr

een

8

90 1

499

4

72

224

2

85 4

56

126

6 5

092

19

50

630

940

6411

apop

hysi

s 8

0I

gree

n 1

318

25

71

531

3

17

297

53

211

75

67

41 2

48

056

121

073

13m

ain

lode

80

Igr

een

9

66 1

829

3

55

272

2

55 3

65

07

7 4

119

26

50

701

430

7722

extr

chu

te11

0I

gree

n

625

11

53

356

1

82

265

39

2 1

25

30

98 1

59

068

094

069

28m

ain

lode

110

Igr

een

17

25 2

696

5

08

192

0

60 3

73

04

8 5

602

46

20

161

300

6837

mai

n lo

de14

5I

gree

n

602

3

38

315

1

16

134

09

5 0

51

16

51 6

34

141

080

021

38lo

de 1

90-

Igr

een

18

68 3

982

6

38

285

3

04 4

01

12

7 7

605

46

60

760

960

8739

fi llin

g24

0I

gree

n 3

044

40

60 1

220

3

34

156

62

0 1

20

95

57 4

91

025

094

054

42Ve

netz

am

ain

lode

350

Igr

een

49

70 7

433

8

62

319

1

55 4

92

08

114

312

101

00

321

100

7047

Vode

na sk

ala

mai

n lo

de38

5I

gray

ish-

gree

n

219

5

03

264

0

90

249

55

9 1

76

20

60 0

39

045

057

073

49m

ain

lode

385

Igr

ayis

h-gr

een

6

30 1

278

6

36

215

5

5412

47

44

6 5

000

05

10

440

430

6955

Mik

hale

tz38

5I

gree

n

980

10

75

027

0

20

069

20

7 0

34

24

12 4

73

033

088

076

59B

aba

500

Ida

rk-g

reen

14

80 1

858

5

80

150

2

74 3

03

05

2 4

697

48

80

900

550

5060

500

Ipa

le g

reen

23

10 2

138

3

80

054

0

77 1

74

05

4 5

187

132

70

440

400

4416

Vode

nask

ala

mai

n lo

de 8

0II

ada

rk-v

iole

t

522

12

40

857

1

60

292

115

0 1

87

44

08 0

45

025

045

070

25m

ain

lode

110

IIa

dark

-vio

let

8

20 1

735

10

42

365

10

3617

41

13

4 6

873

04

70

600

590

6629

mai

n lo

de11

0II

ada

rk-v

iole

t

654

20

60 1

005

2

20

480

198

0 2

12

66

11 0

33

024

047

094

36m

ain

lode

145

IIa

viol

et

115

5

06

146

0

40

080

57

0 1

05

15

62 0

20

014

055

145

57M

ikha

letz

385

IIa

dark

-vio

let

5

30 1

430

6

40

139

8

1315

06

24

0 5

298

03

50

540

340

86 9

Vode

nask

ala

apop

hysi

s 8

0II

bvi

olet

1

56

320

2

61

104

2

81 5

77

178

0 3

479

02

70

490

640

6212

apop

hysi

s 8

0II

bvi

olet

4

48 1

224

4

41

180

3

76 5

24

13

7 3

330

08

50

720

690

9020

mai

n lo

de 8

0II

bpa

le v

iole

t

033

1

03

032

ndash

038

09

6 0

27

3

29 0

34

040

ndash1

0530

mai

n lo

de11

0II

bvi

olet

1

60

307

1

70

020

0

55 3

66

04

7 1

125

04

40

150

290

6443

Vene

tza

350

IIb

viol

et

324

4

88

142

0

27

139

41

1 0

77

16

08 0

79

034

031

059

48Vo

dena

skal

am

ain

lode

385

IIb

viol

et

672

13

43

649

2

02

490

93

6 3

26

46

18 0

72

052

063

066

50m

ain

lode

385

IIb

viol

etis

h-bl

ue

398

7

16

266

1

70

181

40

0 1

33

22

64 0

99

045

123

065

51m

ain

lode

385

IIb

viol

et

205

9

52

501

1

40

542

114

0 3

73

38

53 0

18

048

045

132

53m

ain

lode

385

IIb

pale

vio

let

0

79 ndash

1

99

091

2

32 4

52

20

2 1

255

01

70

510

73ndash

54m

ain

lode

385

IIb

pale

vio

let

4

55

999

2

37

134

1

97 3

23

11

2 2

457

14

10

611

010

8156

Mik

hale

tz38

5II

bpa

le v

iole

t

048

0

88

077

0

54

047

18

0 0

23

5

17 0

27

026

134

055

5838

5II

bpa

le v

iole

t

031

10

25

034

0

20

012

03

2 0

13

11

67 0

97

038

138

150








dena

skal

am

ain

lode

40

IIc

viol

et

003

ndash

012

ndash

015

03

2 0

07

0

70 0

09

047

ndashndash

2m

ain

lode

40

IIc

viol

et ndash

ndash

001

ndash ndash

ndash ndash

0

01 ndash

ndashndash

ndash4

mai

n lo

de 8

0II

cvi

olet

ndash ndash

0

10 ndash

ndash 0

10

00

4

024

01

25ndash

ndashndash

5m

ain

lode

80

IIc

viol

et

015

ndash

013

ndash

012

06

4 0

26

1

30 0

23

019

ndashndash

7m

ain

lode

80

IIc

viol

et ndash

ndash

011

0

04

007

01

4 ndash

0

36 ndash

050

071

ndash10

apop

hysi

s 8

0II

cvi

olet

1

00 ndash

1

55

068

1

60 3

42

110

1 1

926

02

80

470

72ndash

14m

ain

lode

80

IIc

viol

et

014

ndash

013

ndash

010

02

5 0

04

0

66 0

56

040

ndashndash

15m

ain

lode

80

IIc

pale

vio

let

0

20 ndash

0

35

010

0

45 0

81

01

1

202

02

20

560

44ndash

17m

ain

lode

80

IIc

pale

vio

let

0

30

001

0

24

012

0

01 0

49

00

1

118

06

10

022

230

0118

mai

n lo

de 8

0II

cpa

le v

iole

t

192

2

30

030

0

01

020

06

2 0

01

5

36 3

10

032

006

058

19m

ain

lode

80

IIc

pale

vio

let

ndash ndash

0

10 ndash

ndash 0

15

ndash

025

ndashndash

ndashndash

21na

rrow

80

IIc

pale

vio

let

0

35 ndash

0

47

011

0

41 1

25

41

4

673

02

80

330

41ndash

23ex

tract

ion

110

IIc

viol

et

021

ndash

020

ndash

018

03

9 0

10

1

08 0

54

046

ndashndash

24ch

ute

110

IIc

viol

et ndash

ndash

001

ndash ndash

ndash ndash

0

01 ndash

ndashndash

ndash26

mai

n lo

de11

0II

cpa

le v

iole

t

022

ndash

013

ndash

011

02

3 0

02

0

71 0

96

048

ndashndash

27m

ain

lode

110

IIc

pale

vio

let

ndash ndash

0

06 ndash

ndash 0

15

ndash

021

10

0ndash

ndashndash

31m

ain

lode

110

IIc

pale

vio

let

0

43

086

0

40

001

0

01 0

79

02

4

274

05

40

010

140

6732

mai

n lo

de14

5II

cpa

le v

iole

t

010

01

01

01

01 0

01

00

1

016

100

01

001

750

0533

mai

n lo

de14

5II

cpa

le v

iole

t

012

01

011

01

01 0

01

00

1

028

120

01

001

520

0434

mai

n lo

de14

5II

cpa

le v

iole

t

01

01

01

01

01 0

01

00

1

007

10

01

001

750

3035

mai

n lo

de14

5II

cvi

olet

0

16

065

0

59

017

0

32 1

28

01

6

333

01

250

250

581

0640

lode

fi lli

ng21

5II

cpa

le v

iole

t

080

0

01

029

0

01

022

05

5 0

01

1

89 1

45

040

006

000

541

Mik

hale

tz33

5II

cpa

le v

iole

t

036

ndash

016

ndash

020

03

0 0

17

1

19 1

20

067

ndashndash

44Vo

dena

skal

am

ain

lode

370

IIc

pale

vio

let

0

36

01

017

01

01 0

86

01

0

152

04

20

011

120

015

45m

ain

lode

370

IIc

pale

vio

let

5

67

001

0

14

001

0

01 0

41

00

1

626

138

30

020

280

001

46m

ain

lode

370

IIc

pale

vio

let

0

46

078

0

57

020

0

01 0

96

01

8

316

04

80

012

640

5452

mai

n lo

de38

5II

cpa

le v

iole

t ndash

ndash

019

ndash

012

05

5 0

15

1

04 0

02

022

ndashndash

236 B Zidarova








x SxG V x




















238 B Zidarova














(540) Dy3+-O2

(674754) Er3+-O2 ndash(553) Sm3+-Fi

ndash(578))






240 B Zidarova


(480)Sm3+(567)









cub(572)IFndash

















skalaI 515 043 194 053 088I 418 037 202 042 086I 673 051 200 059 090I 778 033 213 046 087


skala IIa 4345 022 3061 000 092 IIa 1533 033 1495 100 087


skala IIb 378 035 826 100 082



40 Vodenaskala

IIc 010 100 286 033 400 IIc 024 080 247 033 071


110 IIc 023 212 248 025 090 IIc 041 045 527 150 040

145 IIc 107 048 587 080 075 IIc 013 333 302 000 075

370 IIc 035 046 1370 000 085

242 B Zidarova



ndash(578) (REE)
















180 degC(YO2)o

220 degCREE2+

280 degCY2+

320 degC(REEO2)o

380 degCSm2+-Ce4+


244 B Zidarova




ndash and

















Absorption bands

I CeSmYb





SmYb






ndashndash 580 nm

246 B Zidarova













Levelm


ZoneNо



400 nm 600 nm 80 I smoky 1 400 323 857 500 748








Fig

12

OTS

of fl

uor

ites

from

diff

eren

t lev

els

and

min

eral

ogic

al v

arie

ties

from

the

Slav

yank

a de

posi

t Le

gend

key

1 ndash

em

bedd

ing

rock

s 2

ndash v

arie

ty I

3 ndash

var

iety

IIa

4 ndash

varie

ty II

b 5

ndash va

riety

IIc

6 ndash

suga

r-gra

ined

qua

rtz

248 B Zidarova






















(306) Sm2+(425) Fi

ndash(400) 2Fi

ndash(580)


(306) Sm2+(340) 2Fi

ndash(580)


ndash(580)


ndash(400) 2Fi

ndash(580)



(420) MO2 ndash(565) Sm2+

(620)


(480) MO2 ndash(560) Sm2+

(620)


(440) (YO2)o(520)


(440) MO2 ndash(560)


(440) (YO2)o(520) Sm2+

(660)


(560) Sm2+(620)


(440) MO2 ndash(560)

250 B Zidarova
















7500 nm 9300 nm 7500 nm 9300 nmVodena

skala












ble

14 I

nfl u

ence

of t

he R

EE o

n th

e co

lour

and

lum

ines

cenc

e of

fl uo

rite

varie

ties f

rom

the

Slav

yank

a de

posi

t

Varie

tyI

IIa

IIb

IIc

T h degC

153 ndash 20

2(f

requ

ently

155 ndash1

97)

140 ndash

178

(fre

quen

tly 1

45 ndash1

72)

120 ndash

157

(fre

quen

tly 1

26 ndash1

53)

103 ndash

119

(fre

quen

tly 1

10 ndash1

15)

REE

ppm

165

1ndash14

312

333 ndash

687

33

30 ndash

461

80

07ndash 3

479

colo

urgr

een

dark

-vio

let

viol

et p

ale

viol

etvi

olet

pal

e vi

olet

PLS

gree

nda

rk-v

iole

tvi

olet

pale

vio

let

XR

LSD

y-Sm

type

spec

traD

y ty

pe sp

ectra

Dy

type

spec

traU

nallo

yed

type

spec

traTL

S18

0 degС

ndash (Y

O2)deg

def

ectiv

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

130-

150

degС ndash

REE

O2+

- Ondash d

ipol

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

180

degС ndash

(YO

2)deg d

efec

tive

cent

er22

0 degC

ndash R

EE2+

cubi

c ce

nter

28

0 degС

ndash Y

2+ cu

bic

cent

er

320

degС ndash

(REE

O2)deg

def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

OA

SY

b2+(2

653

65)

Ce3+

(306

) Sm

2+(4

25)

F indash (4

00)

2Findash (5

80)

Yb2+

(265

365

) C

e3+(3

06)

Sm2+

(340

) 2F

indash (580

)Y

b2+(2

473

10)

2Findash (5

80)

Yb2+

(310

) F i

ndash (400

) 2F

indash (580

)

252 B Zidarova

Fig

14

Spe

ctro

scop

ic c

hara

cter

istic

s (X

RLS

TLS

OTS

IR

S) o

n ra

w (

__)

and

synt

hetic

(---

) fl u

orite

s fro

m th

e Sla

vyan

ka d

epos

it an

d ar

ea o

f the

thei

r app

licat

ion

(UV

ndash u

ltrav

iole

t V

ndash v

isib

le I

R ndash

infr

ared

)









480 Sm3+







I(V IR)

002 0001 001 0003 ndash 00006 001 1868 3982 638 285 304 401 127

IIa

(IR)003 006 001 0003 0006 002 003 820 1735 1042 365 1036 1741 134

IIb

(V IR)0001 0003 001 002 0006 0003 0003 013 ndash 010 ndash 008 010 004

IIb


IIb


IIb

(IR)0006 010 003 0005 00001 0003 ndash 398 716 266 170 181 400 133

IIb


IIc


IIc

(UVV IR)001 001 0008 0005 0006 0006 0003 018 ndash 035 010 045 081 011

IIc


254 B Zidarova





ndash(400) and 2Fi



5 Discussion

















2+ 2

2CaFCa F

[(a ) (a ) Ksp 1]









256 B Zidarova






(572) ndash Sm3+(567)
















ndash(400) and 2Fi
















6 Conclusions


258 B Zidarova







Acknowledgements



References






































260 B Zidarova












































































262 B Zidarova
















234 B Zidarova

Tabl

e 5

REE

dat

a of

the fl u

orite

var

ietie

s fro

m th

e Sl

avya

nka

depo

sit

No

Site

Loca

tion

Leve

lm

Varie

tyC

olou

rC

onte

nts

ppm

LaC

eSm

EuTb

Yb

LuR

EЕLa

Yb

TbY

bEu

Eu

Ce

Ce

3Vo

dena

skal

am

ain

lode

80

Igr

een

6

51 1

104

3

41

146

2

18 3

03

07

5 2

838

21

50

720

830

63 6

mai

n lo

de 8

0I

gree

n

937

16

85

524

1

91

351

42

6 0

92

42

06 2

20

082

069

067

8ap

ophy

sis

80

Igr

een

8

90 1

499

4

72

224

2

85 4

56

126

6 5

092

19

50

630

940

6411

apop

hysi

s 8

0I

gree

n 1

318

25

71

531

3

17

297

53

211

75

67

41 2

48

056

121

073

13m

ain

lode

80

Igr

een

9

66 1

829

3

55

272

2

55 3

65

07

7 4

119

26

50

701

430

7722

extr

chu

te11

0I

gree

n

625

11

53

356

1

82

265

39

2 1

25

30

98 1

59

068

094

069

28m

ain

lode

110

Igr

een

17

25 2

696

5

08

192

0

60 3

73

04

8 5

602

46

20

161

300

6837

mai

n lo

de14

5I

gree

n

602

3

38

315

1

16

134

09

5 0

51

16

51 6

34

141

080

021

38lo

de 1

90-

Igr

een

18

68 3

982

6

38

285

3

04 4

01

12

7 7

605

46

60

760

960

8739

fi llin

g24

0I

gree

n 3

044

40

60 1

220

3

34

156

62

0 1

20

95

57 4

91

025

094

054

42Ve

netz

am

ain

lode

350

Igr

een

49

70 7

433

8

62

319

1

55 4

92

08

114

312

101

00

321

100

7047

Vode

na sk

ala

mai

n lo

de38

5I

gray

ish-

gree

n

219

5

03

264

0

90

249

55

9 1

76

20

60 0

39

045

057

073

49m

ain

lode

385

Igr

ayis

h-gr

een

6

30 1

278

6

36

215

5

5412

47

44

6 5

000

05

10

440

430

6955

Mik

hale

tz38

5I

gree

n

980

10

75

027

0

20

069

20

7 0

34

24

12 4

73

033

088

076

59B

aba

500

Ida

rk-g

reen

14

80 1

858

5

80

150

2

74 3

03

05

2 4

697

48

80

900

550

5060

500

Ipa

le g

reen

23

10 2

138

3

80

054

0

77 1

74

05

4 5

187

132

70

440

400

4416

Vode

nask

ala

mai

n lo

de 8

0II

ada

rk-v

iole

t

522

12

40

857

1

60

292

115

0 1

87

44

08 0

45

025

045

070

25m

ain

lode

110

IIa

dark

-vio

let

8

20 1

735

10

42

365

10

3617

41

13

4 6

873

04

70

600

590

6629

mai

n lo

de11

0II

ada

rk-v

iole

t

654

20

60 1

005

2

20

480

198

0 2

12

66

11 0

33

024

047

094

36m

ain

lode

145

IIa

viol

et

115

5

06

146

0

40

080

57

0 1

05

15

62 0

20

014

055

145

57M

ikha

letz

385

IIa

dark

-vio

let

5

30 1

430

6

40

139

8

1315

06

24

0 5

298

03

50

540

340

86 9

Vode

nask

ala

apop

hysi

s 8

0II

bvi

olet

1

56

320

2

61

104

2

81 5

77

178

0 3

479

02

70

490

640

6212

apop

hysi

s 8

0II

bvi

olet

4

48 1

224

4

41

180

3

76 5

24

13

7 3

330

08

50

720

690

9020

mai

n lo

de 8

0II

bpa

le v

iole

t

033

1

03

032

ndash

038

09

6 0

27

3

29 0

34

040

ndash1

0530

mai

n lo

de11

0II

bvi

olet

1

60

307

1

70

020

0

55 3

66

04

7 1

125

04

40

150

290

6443

Vene

tza

350

IIb

viol

et

324

4

88

142

0

27

139

41

1 0

77

16

08 0

79

034

031

059

48Vo

dena

skal

am

ain

lode

385

IIb

viol

et

672

13

43

649

2

02

490

93

6 3

26

46

18 0

72

052

063

066

50m

ain

lode

385

IIb

viol

etis

h-bl

ue

398

7

16

266

1

70

181

40

0 1

33

22

64 0

99

045

123

065

51m

ain

lode

385

IIb

viol

et

205

9

52

501

1

40

542

114

0 3

73

38

53 0

18

048

045

132

53m

ain

lode

385

IIb

pale

vio

let

0

79 ndash

1

99

091

2

32 4

52

20

2 1

255

01

70

510

73ndash

54m

ain

lode

385

IIb

pale

vio

let

4

55

999

2

37

134

1

97 3

23

11

2 2

457

14

10

611

010

8156

Mik

hale

tz38

5II

bpa

le v

iole

t

048

0

88

077

0

54

047

18

0 0

23

5

17 0

27

026

134

055

5838

5II

bpa

le v

iole

t

031

10

25

034

0

20

012

03

2 0

13

11

67 0

97

038

138

150








dena

skal

am

ain

lode

40

IIc

viol

et

003

ndash

012

ndash

015

03

2 0

07

0

70 0

09

047

ndashndash

2m

ain

lode

40

IIc

viol

et ndash

ndash

001

ndash ndash

ndash ndash

0

01 ndash

ndashndash

ndash4

mai

n lo

de 8

0II

cvi

olet

ndash ndash

0

10 ndash

ndash 0

10

00

4

024

01

25ndash

ndashndash

5m

ain

lode

80

IIc

viol

et

015

ndash

013

ndash

012

06

4 0

26

1

30 0

23

019

ndashndash

7m

ain

lode

80

IIc

viol

et ndash

ndash

011

0

04

007

01

4 ndash

0

36 ndash

050

071

ndash10

apop

hysi

s 8

0II

cvi

olet

1

00 ndash

1

55

068

1

60 3

42

110

1 1

926

02

80

470

72ndash

14m

ain

lode

80

IIc

viol

et

014

ndash

013

ndash

010

02

5 0

04

0

66 0

56

040

ndashndash

15m

ain

lode

80

IIc

pale

vio

let

0

20 ndash

0

35

010

0

45 0

81

01

1

202

02

20

560

44ndash

17m

ain

lode

80

IIc

pale

vio

let

0

30

001

0

24

012

0

01 0

49

00

1

118

06

10

022

230

0118

mai

n lo

de 8

0II

cpa

le v

iole

t

192

2

30

030

0

01

020

06

2 0

01

5

36 3

10

032

006

058

19m

ain

lode

80

IIc

pale

vio

let

ndash ndash

0

10 ndash

ndash 0

15

ndash

025

ndashndash

ndashndash

21na

rrow

80

IIc

pale

vio

let

0

35 ndash

0

47

011

0

41 1

25

41

4

673

02

80

330

41ndash

23ex

tract

ion

110

IIc

viol

et

021

ndash

020

ndash

018

03

9 0

10

1

08 0

54

046

ndashndash

24ch

ute

110

IIc

viol

et ndash

ndash

001

ndash ndash

ndash ndash

0

01 ndash

ndashndash

ndash26

mai

n lo

de11

0II

cpa

le v

iole

t

022

ndash

013

ndash

011

02

3 0

02

0

71 0

96

048

ndashndash

27m

ain

lode

110

IIc

pale

vio

let

ndash ndash

0

06 ndash

ndash 0

15

ndash

021

10

0ndash

ndashndash

31m

ain

lode

110

IIc

pale

vio

let

0

43

086

0

40

001

0

01 0

79

02

4

274

05

40

010

140

6732

mai

n lo

de14

5II

cpa

le v

iole

t

010

01

01

01

01 0

01

00

1

016

100

01

001

750

0533

mai

n lo

de14

5II

cpa

le v

iole

t

012

01

011

01

01 0

01

00

1

028

120

01

001

520

0434

mai

n lo

de14

5II

cpa

le v

iole

t

01

01

01

01

01 0

01

00

1

007

10

01

001

750

3035

mai

n lo

de14

5II

cvi

olet

0

16

065

0

59

017

0

32 1

28

01

6

333

01

250

250

581

0640

lode

fi lli

ng21

5II

cpa

le v

iole

t

080

0

01

029

0

01

022

05

5 0

01

1

89 1

45

040

006

000

541

Mik

hale

tz33

5II

cpa

le v

iole

t

036

ndash

016

ndash

020

03

0 0

17

1

19 1

20

067

ndashndash

44Vo

dena

skal

am

ain

lode

370

IIc

pale

vio

let

0

36

01

017

01

01 0

86

01

0

152

04

20

011

120

015

45m

ain

lode

370

IIc

pale

vio

let

5

67

001

0

14

001

0

01 0

41

00

1

626

138

30

020

280

001

46m

ain

lode

370

IIc

pale

vio

let

0

46

078

0

57

020

0

01 0

96

01

8

316

04

80

012

640

5452

mai

n lo

de38

5II

cpa

le v

iole

t ndash

ndash

019

ndash

012

05

5 0

15

1

04 0

02

022

ndashndash

236 B Zidarova








x SxG V x




















238 B Zidarova














(540) Dy3+-O2

(674754) Er3+-O2 ndash(553) Sm3+-Fi

ndash(578))






240 B Zidarova


(480)Sm3+(567)









cub(572)IFndash

















skalaI 515 043 194 053 088I 418 037 202 042 086I 673 051 200 059 090I 778 033 213 046 087


skala IIa 4345 022 3061 000 092 IIa 1533 033 1495 100 087


skala IIb 378 035 826 100 082



40 Vodenaskala

IIc 010 100 286 033 400 IIc 024 080 247 033 071


110 IIc 023 212 248 025 090 IIc 041 045 527 150 040

145 IIc 107 048 587 080 075 IIc 013 333 302 000 075

370 IIc 035 046 1370 000 085

242 B Zidarova



ndash(578) (REE)
















180 degC(YO2)o

220 degCREE2+

280 degCY2+

320 degC(REEO2)o

380 degCSm2+-Ce4+


244 B Zidarova




ndash and

















Absorption bands

I CeSmYb





SmYb






ndashndash 580 nm

246 B Zidarova













Levelm


ZoneNо



400 nm 600 nm 80 I smoky 1 400 323 857 500 748








Fig

12

OTS

of fl

uor

ites

from

diff

eren

t lev

els

and

min

eral

ogic

al v

arie

ties

from

the

Slav

yank

a de

posi

t Le

gend

key

1 ndash

em

bedd

ing

rock

s 2

ndash v

arie

ty I

3 ndash

var

iety

IIa

4 ndash

varie

ty II

b 5

ndash va

riety

IIc

6 ndash

suga

r-gra

ined

qua

rtz

248 B Zidarova






















(306) Sm2+(425) Fi

ndash(400) 2Fi

ndash(580)


(306) Sm2+(340) 2Fi

ndash(580)


ndash(580)


ndash(400) 2Fi

ndash(580)



(420) MO2 ndash(565) Sm2+

(620)


(480) MO2 ndash(560) Sm2+

(620)


(440) (YO2)o(520)


(440) MO2 ndash(560)


(440) (YO2)o(520) Sm2+

(660)


(560) Sm2+(620)


(440) MO2 ndash(560)

250 B Zidarova
















7500 nm 9300 nm 7500 nm 9300 nmVodena

skala












ble

14 I

nfl u

ence

of t

he R

EE o

n th

e co

lour

and

lum

ines

cenc

e of

fl uo

rite

varie

ties f

rom

the

Slav

yank

a de

posi

t

Varie

tyI

IIa

IIb

IIc

T h degC

153 ndash 20

2(f

requ

ently

155 ndash1

97)

140 ndash

178

(fre

quen

tly 1

45 ndash1

72)

120 ndash

157

(fre

quen

tly 1

26 ndash1

53)

103 ndash

119

(fre

quen

tly 1

10 ndash1

15)

REE

ppm

165

1ndash14

312

333 ndash

687

33

30 ndash

461

80

07ndash 3

479

colo

urgr

een

dark

-vio

let

viol

et p

ale

viol

etvi

olet

pal

e vi

olet

PLS

gree

nda

rk-v

iole

tvi

olet

pale

vio

let

XR

LSD

y-Sm

type

spec

traD

y ty

pe sp

ectra

Dy

type

spec

traU

nallo

yed

type

spec

traTL

S18

0 degС

ndash (Y

O2)deg

def

ectiv

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

130-

150

degС ndash

REE

O2+

- Ondash d

ipol

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

180

degС ndash

(YO

2)deg d

efec

tive

cent

er22

0 degC

ndash R

EE2+

cubi

c ce

nter

28

0 degС

ndash Y

2+ cu

bic

cent

er

320

degС ndash

(REE

O2)deg

def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

OA

SY

b2+(2

653

65)

Ce3+

(306

) Sm

2+(4

25)

F indash (4

00)

2Findash (5

80)

Yb2+

(265

365

) C

e3+(3

06)

Sm2+

(340

) 2F

indash (580

)Y

b2+(2

473

10)

2Findash (5

80)

Yb2+

(310

) F i

ndash (400

) 2F

indash (580

)

252 B Zidarova

Fig

14

Spe

ctro

scop

ic c

hara

cter

istic

s (X

RLS

TLS

OTS

IR

S) o

n ra

w (

__)

and

synt

hetic

(---

) fl u

orite

s fro

m th

e Sla

vyan

ka d

epos

it an

d ar

ea o

f the

thei

r app

licat

ion

(UV

ndash u

ltrav

iole

t V

ndash v

isib

le I

R ndash

infr

ared

)









480 Sm3+







I(V IR)

002 0001 001 0003 ndash 00006 001 1868 3982 638 285 304 401 127

IIa

(IR)003 006 001 0003 0006 002 003 820 1735 1042 365 1036 1741 134

IIb

(V IR)0001 0003 001 002 0006 0003 0003 013 ndash 010 ndash 008 010 004

IIb


IIb


IIb

(IR)0006 010 003 0005 00001 0003 ndash 398 716 266 170 181 400 133

IIb


IIc


IIc

(UVV IR)001 001 0008 0005 0006 0006 0003 018 ndash 035 010 045 081 011

IIc


254 B Zidarova





ndash(400) and 2Fi



5 Discussion

















2+ 2

2CaFCa F

[(a ) (a ) Ksp 1]









256 B Zidarova






(572) ndash Sm3+(567)
















ndash(400) and 2Fi
















6 Conclusions


258 B Zidarova







Acknowledgements



References






































260 B Zidarova












































































262 B Zidarova























dena

skal

am

ain

lode

40

IIc

viol

et

003

ndash

012

ndash

015

03

2 0

07

0

70 0

09

047

ndashndash

2m

ain

lode

40

IIc

viol

et ndash

ndash

001

ndash ndash

ndash ndash

0

01 ndash

ndashndash

ndash4

mai

n lo

de 8

0II

cvi

olet

ndash ndash

0

10 ndash

ndash 0

10

00

4

024

01

25ndash

ndashndash

5m

ain

lode

80

IIc

viol

et

015

ndash

013

ndash

012

06

4 0

26

1

30 0

23

019

ndashndash

7m

ain

lode

80

IIc

viol

et ndash

ndash

011

0

04

007

01

4 ndash

0

36 ndash

050

071

ndash10

apop

hysi

s 8

0II

cvi

olet

1

00 ndash

1

55

068

1

60 3

42

110

1 1

926

02

80

470

72ndash

14m

ain

lode

80

IIc

viol

et

014

ndash

013

ndash

010

02

5 0

04

0

66 0

56

040

ndashndash

15m

ain

lode

80

IIc

pale

vio

let

0

20 ndash

0

35

010

0

45 0

81

01

1

202

02

20

560

44ndash

17m

ain

lode

80

IIc

pale

vio

let

0

30

001

0

24

012

0

01 0

49

00

1

118

06

10

022

230

0118

mai

n lo

de 8

0II

cpa

le v

iole

t

192

2

30

030

0

01

020

06

2 0

01

5

36 3

10

032

006

058

19m

ain

lode

80

IIc

pale

vio

let

ndash ndash

0

10 ndash

ndash 0

15

ndash

025

ndashndash

ndashndash

21na

rrow

80

IIc

pale

vio

let

0

35 ndash

0

47

011

0

41 1

25

41

4

673

02

80

330

41ndash

23ex

tract

ion

110

IIc

viol

et

021

ndash

020

ndash

018

03

9 0

10

1

08 0

54

046

ndashndash

24ch

ute

110

IIc

viol

et ndash

ndash

001

ndash ndash

ndash ndash

0

01 ndash

ndashndash

ndash26

mai

n lo

de11

0II

cpa

le v

iole

t

022

ndash

013

ndash

011

02

3 0

02

0

71 0

96

048

ndashndash

27m

ain

lode

110

IIc

pale

vio

let

ndash ndash

0

06 ndash

ndash 0

15

ndash

021

10

0ndash

ndashndash

31m

ain

lode

110

IIc

pale

vio

let

0

43

086

0

40

001

0

01 0

79

02

4

274

05

40

010

140

6732

mai

n lo

de14

5II

cpa

le v

iole

t

010

01

01

01

01 0

01

00

1

016

100

01

001

750

0533

mai

n lo

de14

5II

cpa

le v

iole

t

012

01

011

01

01 0

01

00

1

028

120

01

001

520

0434

mai

n lo

de14

5II

cpa

le v

iole

t

01

01

01

01

01 0

01

00

1

007

10

01

001

750

3035

mai

n lo

de14

5II

cvi

olet

0

16

065

0

59

017

0

32 1

28

01

6

333

01

250

250

581

0640

lode

fi lli

ng21

5II

cpa

le v

iole

t

080

0

01

029

0

01

022

05

5 0

01

1

89 1

45

040

006

000

541

Mik

hale

tz33

5II

cpa

le v

iole

t

036

ndash

016

ndash

020

03

0 0

17

1

19 1

20

067

ndashndash

44Vo

dena

skal

am

ain

lode

370

IIc

pale

vio

let

0

36

01

017

01

01 0

86

01

0

152

04

20

011

120

015

45m

ain

lode

370

IIc

pale

vio

let

5

67

001

0

14

001

0

01 0

41

00

1

626

138

30

020

280

001

46m

ain

lode

370

IIc

pale

vio

let

0

46

078

0

57

020

0

01 0

96

01

8

316

04

80

012

640

5452

mai

n lo

de38

5II

cpa

le v

iole

t ndash

ndash

019

ndash

012

05

5 0

15

1

04 0

02

022

ndashndash

236 B Zidarova








x SxG V x




















238 B Zidarova














(540) Dy3+-O2

(674754) Er3+-O2 ndash(553) Sm3+-Fi

ndash(578))






240 B Zidarova


(480)Sm3+(567)









cub(572)IFndash

















skalaI 515 043 194 053 088I 418 037 202 042 086I 673 051 200 059 090I 778 033 213 046 087


skala IIa 4345 022 3061 000 092 IIa 1533 033 1495 100 087


skala IIb 378 035 826 100 082



40 Vodenaskala

IIc 010 100 286 033 400 IIc 024 080 247 033 071


110 IIc 023 212 248 025 090 IIc 041 045 527 150 040

145 IIc 107 048 587 080 075 IIc 013 333 302 000 075

370 IIc 035 046 1370 000 085

242 B Zidarova



ndash(578) (REE)
















180 degC(YO2)o

220 degCREE2+

280 degCY2+

320 degC(REEO2)o

380 degCSm2+-Ce4+


244 B Zidarova




ndash and

















Absorption bands

I CeSmYb





SmYb






ndashndash 580 nm

246 B Zidarova













Levelm


ZoneNо



400 nm 600 nm 80 I smoky 1 400 323 857 500 748








Fig

12

OTS

of fl

uor

ites

from

diff

eren

t lev

els

and

min

eral

ogic

al v

arie

ties

from

the

Slav

yank

a de

posi

t Le

gend

key

1 ndash

em

bedd

ing

rock

s 2

ndash v

arie

ty I

3 ndash

var

iety

IIa

4 ndash

varie

ty II

b 5

ndash va

riety

IIc

6 ndash

suga

r-gra

ined

qua

rtz

248 B Zidarova






















(306) Sm2+(425) Fi

ndash(400) 2Fi

ndash(580)


(306) Sm2+(340) 2Fi

ndash(580)


ndash(580)


ndash(400) 2Fi

ndash(580)



(420) MO2 ndash(565) Sm2+

(620)


(480) MO2 ndash(560) Sm2+

(620)


(440) (YO2)o(520)


(440) MO2 ndash(560)


(440) (YO2)o(520) Sm2+

(660)


(560) Sm2+(620)


(440) MO2 ndash(560)

250 B Zidarova
















7500 nm 9300 nm 7500 nm 9300 nmVodena

skala












ble

14 I

nfl u

ence

of t

he R

EE o

n th

e co

lour

and

lum

ines

cenc

e of

fl uo

rite

varie

ties f

rom

the

Slav

yank

a de

posi

t

Varie

tyI

IIa

IIb

IIc

T h degC

153 ndash 20

2(f

requ

ently

155 ndash1

97)

140 ndash

178

(fre

quen

tly 1

45 ndash1

72)

120 ndash

157

(fre

quen

tly 1

26 ndash1

53)

103 ndash

119

(fre

quen

tly 1

10 ndash1

15)

REE

ppm

165

1ndash14

312

333 ndash

687

33

30 ndash

461

80

07ndash 3

479

colo

urgr

een

dark

-vio

let

viol

et p

ale

viol

etvi

olet

pal

e vi

olet

PLS

gree

nda

rk-v

iole

tvi

olet

pale

vio

let

XR

LSD

y-Sm

type

spec

traD

y ty

pe sp

ectra

Dy

type

spec

traU

nallo

yed

type

spec

traTL

S18

0 degС

ndash (Y

O2)deg

def

ectiv

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

130-

150

degС ndash

REE

O2+

- Ondash d

ipol

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

180

degС ndash

(YO

2)deg d

efec

tive

cent

er22

0 degC

ndash R

EE2+

cubi

c ce

nter

28

0 degС

ndash Y

2+ cu

bic

cent

er

320

degС ndash

(REE

O2)deg

def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

OA

SY

b2+(2

653

65)

Ce3+

(306

) Sm

2+(4

25)

F indash (4

00)

2Findash (5

80)

Yb2+

(265

365

) C

e3+(3

06)

Sm2+

(340

) 2F

indash (580

)Y

b2+(2

473

10)

2Findash (5

80)

Yb2+

(310

) F i

ndash (400

) 2F

indash (580

)

252 B Zidarova

Fig

14

Spe

ctro

scop

ic c

hara

cter

istic

s (X

RLS

TLS

OTS

IR

S) o

n ra

w (

__)

and

synt

hetic

(---

) fl u

orite

s fro

m th

e Sla

vyan

ka d

epos

it an

d ar

ea o

f the

thei

r app

licat

ion

(UV

ndash u

ltrav

iole

t V

ndash v

isib

le I

R ndash

infr

ared

)









480 Sm3+







I(V IR)

002 0001 001 0003 ndash 00006 001 1868 3982 638 285 304 401 127

IIa

(IR)003 006 001 0003 0006 002 003 820 1735 1042 365 1036 1741 134

IIb

(V IR)0001 0003 001 002 0006 0003 0003 013 ndash 010 ndash 008 010 004

IIb


IIb


IIb

(IR)0006 010 003 0005 00001 0003 ndash 398 716 266 170 181 400 133

IIb


IIc


IIc

(UVV IR)001 001 0008 0005 0006 0006 0003 018 ndash 035 010 045 081 011

IIc


254 B Zidarova





ndash(400) and 2Fi



5 Discussion

















2+ 2

2CaFCa F

[(a ) (a ) Ksp 1]









256 B Zidarova






(572) ndash Sm3+(567)
















ndash(400) and 2Fi
















6 Conclusions


258 B Zidarova







Acknowledgements



References






































260 B Zidarova












































































262 B Zidarova
















236 B Zidarova








x SxG V x




















238 B Zidarova














(540) Dy3+-O2

(674754) Er3+-O2 ndash(553) Sm3+-Fi

ndash(578))






240 B Zidarova


(480)Sm3+(567)









cub(572)IFndash

















skalaI 515 043 194 053 088I 418 037 202 042 086I 673 051 200 059 090I 778 033 213 046 087


skala IIa 4345 022 3061 000 092 IIa 1533 033 1495 100 087


skala IIb 378 035 826 100 082



40 Vodenaskala

IIc 010 100 286 033 400 IIc 024 080 247 033 071


110 IIc 023 212 248 025 090 IIc 041 045 527 150 040

145 IIc 107 048 587 080 075 IIc 013 333 302 000 075

370 IIc 035 046 1370 000 085

242 B Zidarova



ndash(578) (REE)
















180 degC(YO2)o

220 degCREE2+

280 degCY2+

320 degC(REEO2)o

380 degCSm2+-Ce4+


244 B Zidarova




ndash and

















Absorption bands

I CeSmYb





SmYb






ndashndash 580 nm

246 B Zidarova













Levelm


ZoneNо



400 nm 600 nm 80 I smoky 1 400 323 857 500 748








Fig

12

OTS

of fl

uor

ites

from

diff

eren

t lev

els

and

min

eral

ogic

al v

arie

ties

from

the

Slav

yank

a de

posi

t Le

gend

key

1 ndash

em

bedd

ing

rock

s 2

ndash v

arie

ty I

3 ndash

var

iety

IIa

4 ndash

varie

ty II

b 5

ndash va

riety

IIc

6 ndash

suga

r-gra

ined

qua

rtz

248 B Zidarova






















(306) Sm2+(425) Fi

ndash(400) 2Fi

ndash(580)


(306) Sm2+(340) 2Fi

ndash(580)


ndash(580)


ndash(400) 2Fi

ndash(580)



(420) MO2 ndash(565) Sm2+

(620)


(480) MO2 ndash(560) Sm2+

(620)


(440) (YO2)o(520)


(440) MO2 ndash(560)


(440) (YO2)o(520) Sm2+

(660)


(560) Sm2+(620)


(440) MO2 ndash(560)

250 B Zidarova
















7500 nm 9300 nm 7500 nm 9300 nmVodena

skala












ble

14 I

nfl u

ence

of t

he R

EE o

n th

e co

lour

and

lum

ines

cenc

e of

fl uo

rite

varie

ties f

rom

the

Slav

yank

a de

posi

t

Varie

tyI

IIa

IIb

IIc

T h degC

153 ndash 20

2(f

requ

ently

155 ndash1

97)

140 ndash

178

(fre

quen

tly 1

45 ndash1

72)

120 ndash

157

(fre

quen

tly 1

26 ndash1

53)

103 ndash

119

(fre

quen

tly 1

10 ndash1

15)

REE

ppm

165

1ndash14

312

333 ndash

687

33

30 ndash

461

80

07ndash 3

479

colo

urgr

een

dark

-vio

let

viol

et p

ale

viol

etvi

olet

pal

e vi

olet

PLS

gree

nda

rk-v

iole

tvi

olet

pale

vio

let

XR

LSD

y-Sm

type

spec

traD

y ty

pe sp

ectra

Dy

type

spec

traU

nallo

yed

type

spec

traTL

S18

0 degС

ndash (Y

O2)deg

def

ectiv

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

130-

150

degС ndash

REE

O2+

- Ondash d

ipol

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

180

degС ndash

(YO

2)deg d

efec

tive

cent

er22

0 degC

ndash R

EE2+

cubi

c ce

nter

28

0 degС

ndash Y

2+ cu

bic

cent

er

320

degС ndash

(REE

O2)deg

def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

OA

SY

b2+(2

653

65)

Ce3+

(306

) Sm

2+(4

25)

F indash (4

00)

2Findash (5

80)

Yb2+

(265

365

) C

e3+(3

06)

Sm2+

(340

) 2F

indash (580

)Y

b2+(2

473

10)

2Findash (5

80)

Yb2+

(310

) F i

ndash (400

) 2F

indash (580

)

252 B Zidarova

Fig

14

Spe

ctro

scop

ic c

hara

cter

istic

s (X

RLS

TLS

OTS

IR

S) o

n ra

w (

__)

and

synt

hetic

(---

) fl u

orite

s fro

m th

e Sla

vyan

ka d

epos

it an

d ar

ea o

f the

thei

r app

licat

ion

(UV

ndash u

ltrav

iole

t V

ndash v

isib

le I

R ndash

infr

ared

)









480 Sm3+







I(V IR)

002 0001 001 0003 ndash 00006 001 1868 3982 638 285 304 401 127

IIa

(IR)003 006 001 0003 0006 002 003 820 1735 1042 365 1036 1741 134

IIb

(V IR)0001 0003 001 002 0006 0003 0003 013 ndash 010 ndash 008 010 004

IIb


IIb


IIb

(IR)0006 010 003 0005 00001 0003 ndash 398 716 266 170 181 400 133

IIb


IIc


IIc

(UVV IR)001 001 0008 0005 0006 0006 0003 018 ndash 035 010 045 081 011

IIc


254 B Zidarova





ndash(400) and 2Fi



5 Discussion

















2+ 2

2CaFCa F

[(a ) (a ) Ksp 1]









256 B Zidarova






(572) ndash Sm3+(567)
















ndash(400) and 2Fi
















6 Conclusions


258 B Zidarova







Acknowledgements



References






































260 B Zidarova












































































262 B Zidarova

























238 B Zidarova














(540) Dy3+-O2

(674754) Er3+-O2 ndash(553) Sm3+-Fi

ndash(578))






240 B Zidarova


(480)Sm3+(567)









cub(572)IFndash

















skalaI 515 043 194 053 088I 418 037 202 042 086I 673 051 200 059 090I 778 033 213 046 087


skala IIa 4345 022 3061 000 092 IIa 1533 033 1495 100 087


skala IIb 378 035 826 100 082



40 Vodenaskala

IIc 010 100 286 033 400 IIc 024 080 247 033 071


110 IIc 023 212 248 025 090 IIc 041 045 527 150 040

145 IIc 107 048 587 080 075 IIc 013 333 302 000 075

370 IIc 035 046 1370 000 085

242 B Zidarova



ndash(578) (REE)
















180 degC(YO2)o

220 degCREE2+

280 degCY2+

320 degC(REEO2)o

380 degCSm2+-Ce4+


244 B Zidarova




ndash and

















Absorption bands

I CeSmYb





SmYb






ndashndash 580 nm

246 B Zidarova













Levelm


ZoneNо



400 nm 600 nm 80 I smoky 1 400 323 857 500 748








Fig

12

OTS

of fl

uor

ites

from

diff

eren

t lev

els

and

min

eral

ogic

al v

arie

ties

from

the

Slav

yank

a de

posi

t Le

gend

key

1 ndash

em

bedd

ing

rock

s 2

ndash v

arie

ty I

3 ndash

var

iety

IIa

4 ndash

varie

ty II

b 5

ndash va

riety

IIc

6 ndash

suga

r-gra

ined

qua

rtz

248 B Zidarova






















(306) Sm2+(425) Fi

ndash(400) 2Fi

ndash(580)


(306) Sm2+(340) 2Fi

ndash(580)


ndash(580)


ndash(400) 2Fi

ndash(580)



(420) MO2 ndash(565) Sm2+

(620)


(480) MO2 ndash(560) Sm2+

(620)


(440) (YO2)o(520)


(440) MO2 ndash(560)


(440) (YO2)o(520) Sm2+

(660)


(560) Sm2+(620)


(440) MO2 ndash(560)

250 B Zidarova
















7500 nm 9300 nm 7500 nm 9300 nmVodena

skala












ble

14 I

nfl u

ence

of t

he R

EE o

n th

e co

lour

and

lum

ines

cenc

e of

fl uo

rite

varie

ties f

rom

the

Slav

yank

a de

posi

t

Varie

tyI

IIa

IIb

IIc

T h degC

153 ndash 20

2(f

requ

ently

155 ndash1

97)

140 ndash

178

(fre

quen

tly 1

45 ndash1

72)

120 ndash

157

(fre

quen

tly 1

26 ndash1

53)

103 ndash

119

(fre

quen

tly 1

10 ndash1

15)

REE

ppm

165

1ndash14

312

333 ndash

687

33

30 ndash

461

80

07ndash 3

479

colo

urgr

een

dark

-vio

let

viol

et p

ale

viol

etvi

olet

pal

e vi

olet

PLS

gree

nda

rk-v

iole

tvi

olet

pale

vio

let

XR

LSD

y-Sm

type

spec

traD

y ty

pe sp

ectra

Dy

type

spec

traU

nallo

yed

type

spec

traTL

S18

0 degС

ndash (Y

O2)deg

def

ectiv

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

130-

150

degС ndash

REE

O2+

- Ondash d

ipol

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

180

degС ndash

(YO

2)deg d

efec

tive

cent

er22

0 degC

ndash R

EE2+

cubi

c ce

nter

28

0 degС

ndash Y

2+ cu

bic

cent

er

320

degС ndash

(REE

O2)deg

def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

OA

SY

b2+(2

653

65)

Ce3+

(306

) Sm

2+(4

25)

F indash (4

00)

2Findash (5

80)

Yb2+

(265

365

) C

e3+(3

06)

Sm2+

(340

) 2F

indash (580

)Y

b2+(2

473

10)

2Findash (5

80)

Yb2+

(310

) F i

ndash (400

) 2F

indash (580

)

252 B Zidarova

Fig

14

Spe

ctro

scop

ic c

hara

cter

istic

s (X

RLS

TLS

OTS

IR

S) o

n ra

w (

__)

and

synt

hetic

(---

) fl u

orite

s fro

m th

e Sla

vyan

ka d

epos

it an

d ar

ea o

f the

thei

r app

licat

ion

(UV

ndash u

ltrav

iole

t V

ndash v

isib

le I

R ndash

infr

ared

)









480 Sm3+







I(V IR)

002 0001 001 0003 ndash 00006 001 1868 3982 638 285 304 401 127

IIa

(IR)003 006 001 0003 0006 002 003 820 1735 1042 365 1036 1741 134

IIb

(V IR)0001 0003 001 002 0006 0003 0003 013 ndash 010 ndash 008 010 004

IIb


IIb


IIb

(IR)0006 010 003 0005 00001 0003 ndash 398 716 266 170 181 400 133

IIb


IIc


IIc

(UVV IR)001 001 0008 0005 0006 0006 0003 018 ndash 035 010 045 081 011

IIc


254 B Zidarova





ndash(400) and 2Fi



5 Discussion

















2+ 2

2CaFCa F

[(a ) (a ) Ksp 1]









256 B Zidarova






(572) ndash Sm3+(567)
















ndash(400) and 2Fi
















6 Conclusions


258 B Zidarova







Acknowledgements



References






































260 B Zidarova












































































262 B Zidarova




























(540) Dy3+-O2

(674754) Er3+-O2 ndash(553) Sm3+-Fi

ndash(578))






240 B Zidarova


(480)Sm3+(567)









cub(572)IFndash

















skalaI 515 043 194 053 088I 418 037 202 042 086I 673 051 200 059 090I 778 033 213 046 087


skala IIa 4345 022 3061 000 092 IIa 1533 033 1495 100 087


skala IIb 378 035 826 100 082



40 Vodenaskala

IIc 010 100 286 033 400 IIc 024 080 247 033 071


110 IIc 023 212 248 025 090 IIc 041 045 527 150 040

145 IIc 107 048 587 080 075 IIc 013 333 302 000 075

370 IIc 035 046 1370 000 085

242 B Zidarova



ndash(578) (REE)
















180 degC(YO2)o

220 degCREE2+

280 degCY2+

320 degC(REEO2)o

380 degCSm2+-Ce4+


244 B Zidarova




ndash and

















Absorption bands

I CeSmYb





SmYb






ndashndash 580 nm

246 B Zidarova













Levelm


ZoneNо



400 nm 600 nm 80 I smoky 1 400 323 857 500 748








Fig

12

OTS

of fl

uor

ites

from

diff

eren

t lev

els

and

min

eral

ogic

al v

arie

ties

from

the

Slav

yank

a de

posi

t Le

gend

key

1 ndash

em

bedd

ing

rock

s 2

ndash v

arie

ty I

3 ndash

var

iety

IIa

4 ndash

varie

ty II

b 5

ndash va

riety

IIc

6 ndash

suga

r-gra

ined

qua

rtz

248 B Zidarova






















(306) Sm2+(425) Fi

ndash(400) 2Fi

ndash(580)


(306) Sm2+(340) 2Fi

ndash(580)


ndash(580)


ndash(400) 2Fi

ndash(580)



(420) MO2 ndash(565) Sm2+

(620)


(480) MO2 ndash(560) Sm2+

(620)


(440) (YO2)o(520)


(440) MO2 ndash(560)


(440) (YO2)o(520) Sm2+

(660)


(560) Sm2+(620)


(440) MO2 ndash(560)

250 B Zidarova
















7500 nm 9300 nm 7500 nm 9300 nmVodena

skala












ble

14 I

nfl u

ence

of t

he R

EE o

n th

e co

lour

and

lum

ines

cenc

e of

fl uo

rite

varie

ties f

rom

the

Slav

yank

a de

posi

t

Varie

tyI

IIa

IIb

IIc

T h degC

153 ndash 20

2(f

requ

ently

155 ndash1

97)

140 ndash

178

(fre

quen

tly 1

45 ndash1

72)

120 ndash

157

(fre

quen

tly 1

26 ndash1

53)

103 ndash

119

(fre

quen

tly 1

10 ndash1

15)

REE

ppm

165

1ndash14

312

333 ndash

687

33

30 ndash

461

80

07ndash 3

479

colo

urgr

een

dark

-vio

let

viol

et p

ale

viol

etvi

olet

pal

e vi

olet

PLS

gree

nda

rk-v

iole

tvi

olet

pale

vio

let

XR

LSD

y-Sm

type

spec

traD

y ty

pe sp

ectra

Dy

type

spec

traU

nallo

yed

type

spec

traTL

S18

0 degС

ndash (Y

O2)deg

def

ectiv

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

130-

150

degС ndash

REE

O2+

- Ondash d

ipol

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

180

degС ndash

(YO

2)deg d

efec

tive

cent

er22

0 degC

ndash R

EE2+

cubi

c ce

nter

28

0 degС

ndash Y

2+ cu

bic

cent

er

320

degС ndash

(REE

O2)deg

def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

OA

SY

b2+(2

653

65)

Ce3+

(306

) Sm

2+(4

25)

F indash (4

00)

2Findash (5

80)

Yb2+

(265

365

) C

e3+(3

06)

Sm2+

(340

) 2F

indash (580

)Y

b2+(2

473

10)

2Findash (5

80)

Yb2+

(310

) F i

ndash (400

) 2F

indash (580

)

252 B Zidarova

Fig

14

Spe

ctro

scop

ic c

hara

cter

istic

s (X

RLS

TLS

OTS

IR

S) o

n ra

w (

__)

and

synt

hetic

(---

) fl u

orite

s fro

m th

e Sla

vyan

ka d

epos

it an

d ar

ea o

f the

thei

r app

licat

ion

(UV

ndash u

ltrav

iole

t V

ndash v

isib

le I

R ndash

infr

ared

)









480 Sm3+







I(V IR)

002 0001 001 0003 ndash 00006 001 1868 3982 638 285 304 401 127

IIa

(IR)003 006 001 0003 0006 002 003 820 1735 1042 365 1036 1741 134

IIb

(V IR)0001 0003 001 002 0006 0003 0003 013 ndash 010 ndash 008 010 004

IIb


IIb


IIb

(IR)0006 010 003 0005 00001 0003 ndash 398 716 266 170 181 400 133

IIb


IIc


IIc

(UVV IR)001 001 0008 0005 0006 0006 0003 018 ndash 035 010 045 081 011

IIc


254 B Zidarova





ndash(400) and 2Fi



5 Discussion

















2+ 2

2CaFCa F

[(a ) (a ) Ksp 1]









256 B Zidarova






(572) ndash Sm3+(567)
















ndash(400) and 2Fi
















6 Conclusions


258 B Zidarova







Acknowledgements



References






































260 B Zidarova












































































262 B Zidarova
















240 B Zidarova


(480)Sm3+(567)









cub(572)IFndash

















skalaI 515 043 194 053 088I 418 037 202 042 086I 673 051 200 059 090I 778 033 213 046 087


skala IIa 4345 022 3061 000 092 IIa 1533 033 1495 100 087


skala IIb 378 035 826 100 082



40 Vodenaskala

IIc 010 100 286 033 400 IIc 024 080 247 033 071


110 IIc 023 212 248 025 090 IIc 041 045 527 150 040

145 IIc 107 048 587 080 075 IIc 013 333 302 000 075

370 IIc 035 046 1370 000 085

242 B Zidarova



ndash(578) (REE)
















180 degC(YO2)o

220 degCREE2+

280 degCY2+

320 degC(REEO2)o

380 degCSm2+-Ce4+


244 B Zidarova




ndash and

















Absorption bands

I CeSmYb





SmYb






ndashndash 580 nm

246 B Zidarova













Levelm


ZoneNо



400 nm 600 nm 80 I smoky 1 400 323 857 500 748








Fig

12

OTS

of fl

uor

ites

from

diff

eren

t lev

els

and

min

eral

ogic

al v

arie

ties

from

the

Slav

yank

a de

posi

t Le

gend

key

1 ndash

em

bedd

ing

rock

s 2

ndash v

arie

ty I

3 ndash

var

iety

IIa

4 ndash

varie

ty II

b 5

ndash va

riety

IIc

6 ndash

suga

r-gra

ined

qua

rtz

248 B Zidarova






















(306) Sm2+(425) Fi

ndash(400) 2Fi

ndash(580)


(306) Sm2+(340) 2Fi

ndash(580)


ndash(580)


ndash(400) 2Fi

ndash(580)



(420) MO2 ndash(565) Sm2+

(620)


(480) MO2 ndash(560) Sm2+

(620)


(440) (YO2)o(520)


(440) MO2 ndash(560)


(440) (YO2)o(520) Sm2+

(660)


(560) Sm2+(620)


(440) MO2 ndash(560)

250 B Zidarova
















7500 nm 9300 nm 7500 nm 9300 nmVodena

skala












ble

14 I

nfl u

ence

of t

he R

EE o

n th

e co

lour

and

lum

ines

cenc

e of

fl uo

rite

varie

ties f

rom

the

Slav

yank

a de

posi

t

Varie

tyI

IIa

IIb

IIc

T h degC

153 ndash 20

2(f

requ

ently

155 ndash1

97)

140 ndash

178

(fre

quen

tly 1

45 ndash1

72)

120 ndash

157

(fre

quen

tly 1

26 ndash1

53)

103 ndash

119

(fre

quen

tly 1

10 ndash1

15)

REE

ppm

165

1ndash14

312

333 ndash

687

33

30 ndash

461

80

07ndash 3

479

colo

urgr

een

dark

-vio

let

viol

et p

ale

viol

etvi

olet

pal

e vi

olet

PLS

gree

nda

rk-v

iole

tvi

olet

pale

vio

let

XR

LSD

y-Sm

type

spec

traD

y ty

pe sp

ectra

Dy

type

spec

traU

nallo

yed

type

spec

traTL

S18

0 degС

ndash (Y

O2)deg

def

ectiv

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

130-

150

degС ndash

REE

O2+

- Ondash d

ipol

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

180

degС ndash

(YO

2)deg d

efec

tive

cent

er22

0 degC

ndash R

EE2+

cubi

c ce

nter

28

0 degС

ndash Y

2+ cu

bic

cent

er

320

degС ndash

(REE

O2)deg

def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

OA

SY

b2+(2

653

65)

Ce3+

(306

) Sm

2+(4

25)

F indash (4

00)

2Findash (5

80)

Yb2+

(265

365

) C

e3+(3

06)

Sm2+

(340

) 2F

indash (580

)Y

b2+(2

473

10)

2Findash (5

80)

Yb2+

(310

) F i

ndash (400

) 2F

indash (580

)

252 B Zidarova

Fig

14

Spe

ctro

scop

ic c

hara

cter

istic

s (X

RLS

TLS

OTS

IR

S) o

n ra

w (

__)

and

synt

hetic

(---

) fl u

orite

s fro

m th

e Sla

vyan

ka d

epos

it an

d ar

ea o

f the

thei

r app

licat

ion

(UV

ndash u

ltrav

iole

t V

ndash v

isib

le I

R ndash

infr

ared

)









480 Sm3+







I(V IR)

002 0001 001 0003 ndash 00006 001 1868 3982 638 285 304 401 127

IIa

(IR)003 006 001 0003 0006 002 003 820 1735 1042 365 1036 1741 134

IIb

(V IR)0001 0003 001 002 0006 0003 0003 013 ndash 010 ndash 008 010 004

IIb


IIb


IIb

(IR)0006 010 003 0005 00001 0003 ndash 398 716 266 170 181 400 133

IIb


IIc


IIc

(UVV IR)001 001 0008 0005 0006 0006 0003 018 ndash 035 010 045 081 011

IIc


254 B Zidarova





ndash(400) and 2Fi



5 Discussion

















2+ 2

2CaFCa F

[(a ) (a ) Ksp 1]









256 B Zidarova






(572) ndash Sm3+(567)
















ndash(400) and 2Fi
















6 Conclusions


258 B Zidarova







Acknowledgements



References






































260 B Zidarova












































































262 B Zidarova






















skalaI 515 043 194 053 088I 418 037 202 042 086I 673 051 200 059 090I 778 033 213 046 087


skala IIa 4345 022 3061 000 092 IIa 1533 033 1495 100 087


skala IIb 378 035 826 100 082



40 Vodenaskala

IIc 010 100 286 033 400 IIc 024 080 247 033 071


110 IIc 023 212 248 025 090 IIc 041 045 527 150 040

145 IIc 107 048 587 080 075 IIc 013 333 302 000 075

370 IIc 035 046 1370 000 085

242 B Zidarova



ndash(578) (REE)
















180 degC(YO2)o

220 degCREE2+

280 degCY2+

320 degC(REEO2)o

380 degCSm2+-Ce4+


244 B Zidarova




ndash and

















Absorption bands

I CeSmYb





SmYb






ndashndash 580 nm

246 B Zidarova













Levelm


ZoneNо



400 nm 600 nm 80 I smoky 1 400 323 857 500 748








Fig

12

OTS

of fl

uor

ites

from

diff

eren

t lev

els

and

min

eral

ogic

al v

arie

ties

from

the

Slav

yank

a de

posi

t Le

gend

key

1 ndash

em

bedd

ing

rock

s 2

ndash v

arie

ty I

3 ndash

var

iety

IIa

4 ndash

varie

ty II

b 5

ndash va

riety

IIc

6 ndash

suga

r-gra

ined

qua

rtz

248 B Zidarova






















(306) Sm2+(425) Fi

ndash(400) 2Fi

ndash(580)


(306) Sm2+(340) 2Fi

ndash(580)


ndash(580)


ndash(400) 2Fi

ndash(580)



(420) MO2 ndash(565) Sm2+

(620)


(480) MO2 ndash(560) Sm2+

(620)


(440) (YO2)o(520)


(440) MO2 ndash(560)


(440) (YO2)o(520) Sm2+

(660)


(560) Sm2+(620)


(440) MO2 ndash(560)

250 B Zidarova
















7500 nm 9300 nm 7500 nm 9300 nmVodena

skala












ble

14 I

nfl u

ence

of t

he R

EE o

n th

e co

lour

and

lum

ines

cenc

e of

fl uo

rite

varie

ties f

rom

the

Slav

yank

a de

posi

t

Varie

tyI

IIa

IIb

IIc

T h degC

153 ndash 20

2(f

requ

ently

155 ndash1

97)

140 ndash

178

(fre

quen

tly 1

45 ndash1

72)

120 ndash

157

(fre

quen

tly 1

26 ndash1

53)

103 ndash

119

(fre

quen

tly 1

10 ndash1

15)

REE

ppm

165

1ndash14

312

333 ndash

687

33

30 ndash

461

80

07ndash 3

479

colo

urgr

een

dark

-vio

let

viol

et p

ale

viol

etvi

olet

pal

e vi

olet

PLS

gree

nda

rk-v

iole

tvi

olet

pale

vio

let

XR

LSD

y-Sm

type

spec

traD

y ty

pe sp

ectra

Dy

type

spec

traU

nallo

yed

type

spec

traTL

S18

0 degС

ndash (Y

O2)deg

def

ectiv

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

130-

150

degС ndash

REE

O2+

- Ondash d

ipol

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

180

degС ndash

(YO

2)deg d

efec

tive

cent

er22

0 degC

ndash R

EE2+

cubi

c ce

nter

28

0 degС

ndash Y

2+ cu

bic

cent

er

320

degС ndash

(REE

O2)deg

def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

OA

SY

b2+(2

653

65)

Ce3+

(306

) Sm

2+(4

25)

F indash (4

00)

2Findash (5

80)

Yb2+

(265

365

) C

e3+(3

06)

Sm2+

(340

) 2F

indash (580

)Y

b2+(2

473

10)

2Findash (5

80)

Yb2+

(310

) F i

ndash (400

) 2F

indash (580

)

252 B Zidarova

Fig

14

Spe

ctro

scop

ic c

hara

cter

istic

s (X

RLS

TLS

OTS

IR

S) o

n ra

w (

__)

and

synt

hetic

(---

) fl u

orite

s fro

m th

e Sla

vyan

ka d

epos

it an

d ar

ea o

f the

thei

r app

licat

ion

(UV

ndash u

ltrav

iole

t V

ndash v

isib

le I

R ndash

infr

ared

)









480 Sm3+







I(V IR)

002 0001 001 0003 ndash 00006 001 1868 3982 638 285 304 401 127

IIa

(IR)003 006 001 0003 0006 002 003 820 1735 1042 365 1036 1741 134

IIb

(V IR)0001 0003 001 002 0006 0003 0003 013 ndash 010 ndash 008 010 004

IIb


IIb


IIb

(IR)0006 010 003 0005 00001 0003 ndash 398 716 266 170 181 400 133

IIb


IIc


IIc

(UVV IR)001 001 0008 0005 0006 0006 0003 018 ndash 035 010 045 081 011

IIc


254 B Zidarova





ndash(400) and 2Fi



5 Discussion

















2+ 2

2CaFCa F

[(a ) (a ) Ksp 1]









256 B Zidarova






(572) ndash Sm3+(567)
















ndash(400) and 2Fi
















6 Conclusions


258 B Zidarova







Acknowledgements



References






































260 B Zidarova












































































262 B Zidarova
















242 B Zidarova



ndash(578) (REE)
















180 degC(YO2)o

220 degCREE2+

280 degCY2+

320 degC(REEO2)o

380 degCSm2+-Ce4+


244 B Zidarova




ndash and

















Absorption bands

I CeSmYb





SmYb






ndashndash 580 nm

246 B Zidarova













Levelm


ZoneNо



400 nm 600 nm 80 I smoky 1 400 323 857 500 748








Fig

12

OTS

of fl

uor

ites

from

diff

eren

t lev

els

and

min

eral

ogic

al v

arie

ties

from

the

Slav

yank

a de

posi

t Le

gend

key

1 ndash

em

bedd

ing

rock

s 2

ndash v

arie

ty I

3 ndash

var

iety

IIa

4 ndash

varie

ty II

b 5

ndash va

riety

IIc

6 ndash

suga

r-gra

ined

qua

rtz

248 B Zidarova






















(306) Sm2+(425) Fi

ndash(400) 2Fi

ndash(580)


(306) Sm2+(340) 2Fi

ndash(580)


ndash(580)


ndash(400) 2Fi

ndash(580)



(420) MO2 ndash(565) Sm2+

(620)


(480) MO2 ndash(560) Sm2+

(620)


(440) (YO2)o(520)


(440) MO2 ndash(560)


(440) (YO2)o(520) Sm2+

(660)


(560) Sm2+(620)


(440) MO2 ndash(560)

250 B Zidarova
















7500 nm 9300 nm 7500 nm 9300 nmVodena

skala












ble

14 I

nfl u

ence

of t

he R

EE o

n th

e co

lour

and

lum

ines

cenc

e of

fl uo

rite

varie

ties f

rom

the

Slav

yank

a de

posi

t

Varie

tyI

IIa

IIb

IIc

T h degC

153 ndash 20

2(f

requ

ently

155 ndash1

97)

140 ndash

178

(fre

quen

tly 1

45 ndash1

72)

120 ndash

157

(fre

quen

tly 1

26 ndash1

53)

103 ndash

119

(fre

quen

tly 1

10 ndash1

15)

REE

ppm

165

1ndash14

312

333 ndash

687

33

30 ndash

461

80

07ndash 3

479

colo

urgr

een

dark

-vio

let

viol

et p

ale

viol

etvi

olet

pal

e vi

olet

PLS

gree

nda

rk-v

iole

tvi

olet

pale

vio

let

XR

LSD

y-Sm

type

spec

traD

y ty

pe sp

ectra

Dy

type

spec

traU

nallo

yed

type

spec

traTL

S18

0 degС

ndash (Y

O2)deg

def

ectiv

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

130-

150

degС ndash

REE

O2+

- Ondash d

ipol

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

180

degС ndash

(YO

2)deg d

efec

tive

cent

er22

0 degC

ndash R

EE2+

cubi

c ce

nter

28

0 degС

ndash Y

2+ cu

bic

cent

er

320

degС ndash

(REE

O2)deg

def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

OA

SY

b2+(2

653

65)

Ce3+

(306

) Sm

2+(4

25)

F indash (4

00)

2Findash (5

80)

Yb2+

(265

365

) C

e3+(3

06)

Sm2+

(340

) 2F

indash (580

)Y

b2+(2

473

10)

2Findash (5

80)

Yb2+

(310

) F i

ndash (400

) 2F

indash (580

)

252 B Zidarova

Fig

14

Spe

ctro

scop

ic c

hara

cter

istic

s (X

RLS

TLS

OTS

IR

S) o

n ra

w (

__)

and

synt

hetic

(---

) fl u

orite

s fro

m th

e Sla

vyan

ka d

epos

it an

d ar

ea o

f the

thei

r app

licat

ion

(UV

ndash u

ltrav

iole

t V

ndash v

isib

le I

R ndash

infr

ared

)









480 Sm3+







I(V IR)

002 0001 001 0003 ndash 00006 001 1868 3982 638 285 304 401 127

IIa

(IR)003 006 001 0003 0006 002 003 820 1735 1042 365 1036 1741 134

IIb

(V IR)0001 0003 001 002 0006 0003 0003 013 ndash 010 ndash 008 010 004

IIb


IIb


IIb

(IR)0006 010 003 0005 00001 0003 ndash 398 716 266 170 181 400 133

IIb


IIc


IIc

(UVV IR)001 001 0008 0005 0006 0006 0003 018 ndash 035 010 045 081 011

IIc


254 B Zidarova





ndash(400) and 2Fi



5 Discussion

















2+ 2

2CaFCa F

[(a ) (a ) Ksp 1]









256 B Zidarova






(572) ndash Sm3+(567)
















ndash(400) and 2Fi
















6 Conclusions


258 B Zidarova







Acknowledgements



References






































260 B Zidarova












































































262 B Zidarova






























180 degC(YO2)o

220 degCREE2+

280 degCY2+

320 degC(REEO2)o

380 degCSm2+-Ce4+


244 B Zidarova




ndash and

















Absorption bands

I CeSmYb





SmYb






ndashndash 580 nm

246 B Zidarova













Levelm


ZoneNо



400 nm 600 nm 80 I smoky 1 400 323 857 500 748








Fig

12

OTS

of fl

uor

ites

from

diff

eren

t lev

els

and

min

eral

ogic

al v

arie

ties

from

the

Slav

yank

a de

posi

t Le

gend

key

1 ndash

em

bedd

ing

rock

s 2

ndash v

arie

ty I

3 ndash

var

iety

IIa

4 ndash

varie

ty II

b 5

ndash va

riety

IIc

6 ndash

suga

r-gra

ined

qua

rtz

248 B Zidarova






















(306) Sm2+(425) Fi

ndash(400) 2Fi

ndash(580)


(306) Sm2+(340) 2Fi

ndash(580)


ndash(580)


ndash(400) 2Fi

ndash(580)



(420) MO2 ndash(565) Sm2+

(620)


(480) MO2 ndash(560) Sm2+

(620)


(440) (YO2)o(520)


(440) MO2 ndash(560)


(440) (YO2)o(520) Sm2+

(660)


(560) Sm2+(620)


(440) MO2 ndash(560)

250 B Zidarova
















7500 nm 9300 nm 7500 nm 9300 nmVodena

skala












ble

14 I

nfl u

ence

of t

he R

EE o

n th

e co

lour

and

lum

ines

cenc

e of

fl uo

rite

varie

ties f

rom

the

Slav

yank

a de

posi

t

Varie

tyI

IIa

IIb

IIc

T h degC

153 ndash 20

2(f

requ

ently

155 ndash1

97)

140 ndash

178

(fre

quen

tly 1

45 ndash1

72)

120 ndash

157

(fre

quen

tly 1

26 ndash1

53)

103 ndash

119

(fre

quen

tly 1

10 ndash1

15)

REE

ppm

165

1ndash14

312

333 ndash

687

33

30 ndash

461

80

07ndash 3

479

colo

urgr

een

dark

-vio

let

viol

et p

ale

viol

etvi

olet

pal

e vi

olet

PLS

gree

nda

rk-v

iole

tvi

olet

pale

vio

let

XR

LSD

y-Sm

type

spec

traD

y ty

pe sp

ectra

Dy

type

spec

traU

nallo

yed

type

spec

traTL

S18

0 degС

ndash (Y

O2)deg

def

ectiv

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

130-

150

degС ndash

REE

O2+

- Ondash d

ipol

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

180

degС ndash

(YO

2)deg d

efec

tive

cent

er22

0 degC

ndash R

EE2+

cubi

c ce

nter

28

0 degС

ndash Y

2+ cu

bic

cent

er

320

degС ndash

(REE

O2)deg

def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

OA

SY

b2+(2

653

65)

Ce3+

(306

) Sm

2+(4

25)

F indash (4

00)

2Findash (5

80)

Yb2+

(265

365

) C

e3+(3

06)

Sm2+

(340

) 2F

indash (580

)Y

b2+(2

473

10)

2Findash (5

80)

Yb2+

(310

) F i

ndash (400

) 2F

indash (580

)

252 B Zidarova

Fig

14

Spe

ctro

scop

ic c

hara

cter

istic

s (X

RLS

TLS

OTS

IR

S) o

n ra

w (

__)

and

synt

hetic

(---

) fl u

orite

s fro

m th

e Sla

vyan

ka d

epos

it an

d ar

ea o

f the

thei

r app

licat

ion

(UV

ndash u

ltrav

iole

t V

ndash v

isib

le I

R ndash

infr

ared

)









480 Sm3+







I(V IR)

002 0001 001 0003 ndash 00006 001 1868 3982 638 285 304 401 127

IIa

(IR)003 006 001 0003 0006 002 003 820 1735 1042 365 1036 1741 134

IIb

(V IR)0001 0003 001 002 0006 0003 0003 013 ndash 010 ndash 008 010 004

IIb


IIb


IIb

(IR)0006 010 003 0005 00001 0003 ndash 398 716 266 170 181 400 133

IIb


IIc


IIc

(UVV IR)001 001 0008 0005 0006 0006 0003 018 ndash 035 010 045 081 011

IIc


254 B Zidarova





ndash(400) and 2Fi



5 Discussion

















2+ 2

2CaFCa F

[(a ) (a ) Ksp 1]









256 B Zidarova






(572) ndash Sm3+(567)
















ndash(400) and 2Fi
















6 Conclusions


258 B Zidarova







Acknowledgements



References






































260 B Zidarova












































































262 B Zidarova
















244 B Zidarova




ndash and

















Absorption bands

I CeSmYb





SmYb






ndashndash 580 nm

246 B Zidarova













Levelm


ZoneNо



400 nm 600 nm 80 I smoky 1 400 323 857 500 748








Fig

12

OTS

of fl

uor

ites

from

diff

eren

t lev

els

and

min

eral

ogic

al v

arie

ties

from

the

Slav

yank

a de

posi

t Le

gend

key

1 ndash

em

bedd

ing

rock

s 2

ndash v

arie

ty I

3 ndash

var

iety

IIa

4 ndash

varie

ty II

b 5

ndash va

riety

IIc

6 ndash

suga

r-gra

ined

qua

rtz

248 B Zidarova






















(306) Sm2+(425) Fi

ndash(400) 2Fi

ndash(580)


(306) Sm2+(340) 2Fi

ndash(580)


ndash(580)


ndash(400) 2Fi

ndash(580)



(420) MO2 ndash(565) Sm2+

(620)


(480) MO2 ndash(560) Sm2+

(620)


(440) (YO2)o(520)


(440) MO2 ndash(560)


(440) (YO2)o(520) Sm2+

(660)


(560) Sm2+(620)


(440) MO2 ndash(560)

250 B Zidarova
















7500 nm 9300 nm 7500 nm 9300 nmVodena

skala












ble

14 I

nfl u

ence

of t

he R

EE o

n th

e co

lour

and

lum

ines

cenc

e of

fl uo

rite

varie

ties f

rom

the

Slav

yank

a de

posi

t

Varie

tyI

IIa

IIb

IIc

T h degC

153 ndash 20

2(f

requ

ently

155 ndash1

97)

140 ndash

178

(fre

quen

tly 1

45 ndash1

72)

120 ndash

157

(fre

quen

tly 1

26 ndash1

53)

103 ndash

119

(fre

quen

tly 1

10 ndash1

15)

REE

ppm

165

1ndash14

312

333 ndash

687

33

30 ndash

461

80

07ndash 3

479

colo

urgr

een

dark

-vio

let

viol

et p

ale

viol

etvi

olet

pal

e vi

olet

PLS

gree

nda

rk-v

iole

tvi

olet

pale

vio

let

XR

LSD

y-Sm

type

spec

traD

y ty

pe sp

ectra

Dy

type

spec

traU

nallo

yed

type

spec

traTL

S18

0 degС

ndash (Y

O2)deg

def

ectiv

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

130-

150

degС ndash

REE

O2+

- Ondash d

ipol

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

180

degС ndash

(YO

2)deg d

efec

tive

cent

er22

0 degC

ndash R

EE2+

cubi

c ce

nter

28

0 degС

ndash Y

2+ cu

bic

cent

er

320

degС ndash

(REE

O2)deg

def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

OA

SY

b2+(2

653

65)

Ce3+

(306

) Sm

2+(4

25)

F indash (4

00)

2Findash (5

80)

Yb2+

(265

365

) C

e3+(3

06)

Sm2+

(340

) 2F

indash (580

)Y

b2+(2

473

10)

2Findash (5

80)

Yb2+

(310

) F i

ndash (400

) 2F

indash (580

)

252 B Zidarova

Fig

14

Spe

ctro

scop

ic c

hara

cter

istic

s (X

RLS

TLS

OTS

IR

S) o

n ra

w (

__)

and

synt

hetic

(---

) fl u

orite

s fro

m th

e Sla

vyan

ka d

epos

it an

d ar

ea o

f the

thei

r app

licat

ion

(UV

ndash u

ltrav

iole

t V

ndash v

isib

le I

R ndash

infr

ared

)









480 Sm3+







I(V IR)

002 0001 001 0003 ndash 00006 001 1868 3982 638 285 304 401 127

IIa

(IR)003 006 001 0003 0006 002 003 820 1735 1042 365 1036 1741 134

IIb

(V IR)0001 0003 001 002 0006 0003 0003 013 ndash 010 ndash 008 010 004

IIb


IIb


IIb

(IR)0006 010 003 0005 00001 0003 ndash 398 716 266 170 181 400 133

IIb


IIc


IIc

(UVV IR)001 001 0008 0005 0006 0006 0003 018 ndash 035 010 045 081 011

IIc


254 B Zidarova





ndash(400) and 2Fi



5 Discussion

















2+ 2

2CaFCa F

[(a ) (a ) Ksp 1]









256 B Zidarova






(572) ndash Sm3+(567)
















ndash(400) and 2Fi
















6 Conclusions


258 B Zidarova







Acknowledgements



References






































260 B Zidarova












































































262 B Zidarova































Absorption bands

I CeSmYb





SmYb






ndashndash 580 nm

246 B Zidarova













Levelm


ZoneNо



400 nm 600 nm 80 I smoky 1 400 323 857 500 748








Fig

12

OTS

of fl

uor

ites

from

diff

eren

t lev

els

and

min

eral

ogic

al v

arie

ties

from

the

Slav

yank

a de

posi

t Le

gend

key

1 ndash

em

bedd

ing

rock

s 2

ndash v

arie

ty I

3 ndash

var

iety

IIa

4 ndash

varie

ty II

b 5

ndash va

riety

IIc

6 ndash

suga

r-gra

ined

qua

rtz

248 B Zidarova






















(306) Sm2+(425) Fi

ndash(400) 2Fi

ndash(580)


(306) Sm2+(340) 2Fi

ndash(580)


ndash(580)


ndash(400) 2Fi

ndash(580)



(420) MO2 ndash(565) Sm2+

(620)


(480) MO2 ndash(560) Sm2+

(620)


(440) (YO2)o(520)


(440) MO2 ndash(560)


(440) (YO2)o(520) Sm2+

(660)


(560) Sm2+(620)


(440) MO2 ndash(560)

250 B Zidarova
















7500 nm 9300 nm 7500 nm 9300 nmVodena

skala












ble

14 I

nfl u

ence

of t

he R

EE o

n th

e co

lour

and

lum

ines

cenc

e of

fl uo

rite

varie

ties f

rom

the

Slav

yank

a de

posi

t

Varie

tyI

IIa

IIb

IIc

T h degC

153 ndash 20

2(f

requ

ently

155 ndash1

97)

140 ndash

178

(fre

quen

tly 1

45 ndash1

72)

120 ndash

157

(fre

quen

tly 1

26 ndash1

53)

103 ndash

119

(fre

quen

tly 1

10 ndash1

15)

REE

ppm

165

1ndash14

312

333 ndash

687

33

30 ndash

461

80

07ndash 3

479

colo

urgr

een

dark

-vio

let

viol

et p

ale

viol

etvi

olet

pal

e vi

olet

PLS

gree

nda

rk-v

iole

tvi

olet

pale

vio

let

XR

LSD

y-Sm

type

spec

traD

y ty

pe sp

ectra

Dy

type

spec

traU

nallo

yed

type

spec

traTL

S18

0 degС

ndash (Y

O2)deg

def

ectiv

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

130-

150

degС ndash

REE

O2+

- Ondash d

ipol

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

180

degС ndash

(YO

2)deg d

efec

tive

cent

er22

0 degC

ndash R

EE2+

cubi

c ce

nter

28

0 degС

ndash Y

2+ cu

bic

cent

er

320

degС ndash

(REE

O2)deg

def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

OA

SY

b2+(2

653

65)

Ce3+

(306

) Sm

2+(4

25)

F indash (4

00)

2Findash (5

80)

Yb2+

(265

365

) C

e3+(3

06)

Sm2+

(340

) 2F

indash (580

)Y

b2+(2

473

10)

2Findash (5

80)

Yb2+

(310

) F i

ndash (400

) 2F

indash (580

)

252 B Zidarova

Fig

14

Spe

ctro

scop

ic c

hara

cter

istic

s (X

RLS

TLS

OTS

IR

S) o

n ra

w (

__)

and

synt

hetic

(---

) fl u

orite

s fro

m th

e Sla

vyan

ka d

epos

it an

d ar

ea o

f the

thei

r app

licat

ion

(UV

ndash u

ltrav

iole

t V

ndash v

isib

le I

R ndash

infr

ared

)









480 Sm3+







I(V IR)

002 0001 001 0003 ndash 00006 001 1868 3982 638 285 304 401 127

IIa

(IR)003 006 001 0003 0006 002 003 820 1735 1042 365 1036 1741 134

IIb

(V IR)0001 0003 001 002 0006 0003 0003 013 ndash 010 ndash 008 010 004

IIb


IIb


IIb

(IR)0006 010 003 0005 00001 0003 ndash 398 716 266 170 181 400 133

IIb


IIc


IIc

(UVV IR)001 001 0008 0005 0006 0006 0003 018 ndash 035 010 045 081 011

IIc


254 B Zidarova





ndash(400) and 2Fi



5 Discussion

















2+ 2

2CaFCa F

[(a ) (a ) Ksp 1]









256 B Zidarova






(572) ndash Sm3+(567)
















ndash(400) and 2Fi
















6 Conclusions


258 B Zidarova







Acknowledgements



References






































260 B Zidarova












































































262 B Zidarova
















246 B Zidarova













Levelm


ZoneNо



400 nm 600 nm 80 I smoky 1 400 323 857 500 748








Fig

12

OTS

of fl

uor

ites

from

diff

eren

t lev

els

and

min

eral

ogic

al v

arie

ties

from

the

Slav

yank

a de

posi

t Le

gend

key

1 ndash

em

bedd

ing

rock

s 2

ndash v

arie

ty I

3 ndash

var

iety

IIa

4 ndash

varie

ty II

b 5

ndash va

riety

IIc

6 ndash

suga

r-gra

ined

qua

rtz

248 B Zidarova






















(306) Sm2+(425) Fi

ndash(400) 2Fi

ndash(580)


(306) Sm2+(340) 2Fi

ndash(580)


ndash(580)


ndash(400) 2Fi

ndash(580)



(420) MO2 ndash(565) Sm2+

(620)


(480) MO2 ndash(560) Sm2+

(620)


(440) (YO2)o(520)


(440) MO2 ndash(560)


(440) (YO2)o(520) Sm2+

(660)


(560) Sm2+(620)


(440) MO2 ndash(560)

250 B Zidarova
















7500 nm 9300 nm 7500 nm 9300 nmVodena

skala












ble

14 I

nfl u

ence

of t

he R

EE o

n th

e co

lour

and

lum

ines

cenc

e of

fl uo

rite

varie

ties f

rom

the

Slav

yank

a de

posi

t

Varie

tyI

IIa

IIb

IIc

T h degC

153 ndash 20

2(f

requ

ently

155 ndash1

97)

140 ndash

178

(fre

quen

tly 1

45 ndash1

72)

120 ndash

157

(fre

quen

tly 1

26 ndash1

53)

103 ndash

119

(fre

quen

tly 1

10 ndash1

15)

REE

ppm

165

1ndash14

312

333 ndash

687

33

30 ndash

461

80

07ndash 3

479

colo

urgr

een

dark

-vio

let

viol

et p

ale

viol

etvi

olet

pal

e vi

olet

PLS

gree

nda

rk-v

iole

tvi

olet

pale

vio

let

XR

LSD

y-Sm

type

spec

traD

y ty

pe sp

ectra

Dy

type

spec

traU

nallo

yed

type

spec

traTL

S18

0 degС

ndash (Y

O2)deg

def

ectiv

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

130-

150

degС ndash

REE

O2+

- Ondash d

ipol

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

180

degС ndash

(YO

2)deg d

efec

tive

cent

er22

0 degC

ndash R

EE2+

cubi

c ce

nter

28

0 degС

ndash Y

2+ cu

bic

cent

er

320

degС ndash

(REE

O2)deg

def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

OA

SY

b2+(2

653

65)

Ce3+

(306

) Sm

2+(4

25)

F indash (4

00)

2Findash (5

80)

Yb2+

(265

365

) C

e3+(3

06)

Sm2+

(340

) 2F

indash (580

)Y

b2+(2

473

10)

2Findash (5

80)

Yb2+

(310

) F i

ndash (400

) 2F

indash (580

)

252 B Zidarova

Fig

14

Spe

ctro

scop

ic c

hara

cter

istic

s (X

RLS

TLS

OTS

IR

S) o

n ra

w (

__)

and

synt

hetic

(---

) fl u

orite

s fro

m th

e Sla

vyan

ka d

epos

it an

d ar

ea o

f the

thei

r app

licat

ion

(UV

ndash u

ltrav

iole

t V

ndash v

isib

le I

R ndash

infr

ared

)









480 Sm3+







I(V IR)

002 0001 001 0003 ndash 00006 001 1868 3982 638 285 304 401 127

IIa

(IR)003 006 001 0003 0006 002 003 820 1735 1042 365 1036 1741 134

IIb

(V IR)0001 0003 001 002 0006 0003 0003 013 ndash 010 ndash 008 010 004

IIb


IIb


IIb

(IR)0006 010 003 0005 00001 0003 ndash 398 716 266 170 181 400 133

IIb


IIc


IIc

(UVV IR)001 001 0008 0005 0006 0006 0003 018 ndash 035 010 045 081 011

IIc


254 B Zidarova





ndash(400) and 2Fi



5 Discussion

















2+ 2

2CaFCa F

[(a ) (a ) Ksp 1]









256 B Zidarova






(572) ndash Sm3+(567)
















ndash(400) and 2Fi
















6 Conclusions


258 B Zidarova







Acknowledgements



References






































260 B Zidarova












































































262 B Zidarova

















Fig

12

OTS

of fl

uor

ites

from

diff

eren

t lev

els

and

min

eral

ogic

al v

arie

ties

from

the

Slav

yank

a de

posi

t Le

gend

key

1 ndash

em

bedd

ing

rock

s 2

ndash v

arie

ty I

3 ndash

var

iety

IIa

4 ndash

varie

ty II

b 5

ndash va

riety

IIc

6 ndash

suga

r-gra

ined

qua

rtz

248 B Zidarova






















(306) Sm2+(425) Fi

ndash(400) 2Fi

ndash(580)


(306) Sm2+(340) 2Fi

ndash(580)


ndash(580)


ndash(400) 2Fi

ndash(580)



(420) MO2 ndash(565) Sm2+

(620)


(480) MO2 ndash(560) Sm2+

(620)


(440) (YO2)o(520)


(440) MO2 ndash(560)


(440) (YO2)o(520) Sm2+

(660)


(560) Sm2+(620)


(440) MO2 ndash(560)

250 B Zidarova
















7500 nm 9300 nm 7500 nm 9300 nmVodena

skala












ble

14 I

nfl u

ence

of t

he R

EE o

n th

e co

lour

and

lum

ines

cenc

e of

fl uo

rite

varie

ties f

rom

the

Slav

yank

a de

posi

t

Varie

tyI

IIa

IIb

IIc

T h degC

153 ndash 20

2(f

requ

ently

155 ndash1

97)

140 ndash

178

(fre

quen

tly 1

45 ndash1

72)

120 ndash

157

(fre

quen

tly 1

26 ndash1

53)

103 ndash

119

(fre

quen

tly 1

10 ndash1

15)

REE

ppm

165

1ndash14

312

333 ndash

687

33

30 ndash

461

80

07ndash 3

479

colo

urgr

een

dark

-vio

let

viol

et p

ale

viol

etvi

olet

pal

e vi

olet

PLS

gree

nda

rk-v

iole

tvi

olet

pale

vio

let

XR

LSD

y-Sm

type

spec

traD

y ty

pe sp

ectra

Dy

type

spec

traU

nallo

yed

type

spec

traTL

S18

0 degС

ndash (Y

O2)deg

def

ectiv

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

130-

150

degС ndash

REE

O2+

- Ondash d

ipol

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

180

degС ndash

(YO

2)deg d

efec

tive

cent

er22

0 degC

ndash R

EE2+

cubi

c ce

nter

28

0 degС

ndash Y

2+ cu

bic

cent

er

320

degС ndash

(REE

O2)deg

def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

OA

SY

b2+(2

653

65)

Ce3+

(306

) Sm

2+(4

25)

F indash (4

00)

2Findash (5

80)

Yb2+

(265

365

) C

e3+(3

06)

Sm2+

(340

) 2F

indash (580

)Y

b2+(2

473

10)

2Findash (5

80)

Yb2+

(310

) F i

ndash (400

) 2F

indash (580

)

252 B Zidarova

Fig

14

Spe

ctro

scop

ic c

hara

cter

istic

s (X

RLS

TLS

OTS

IR

S) o

n ra

w (

__)

and

synt

hetic

(---

) fl u

orite

s fro

m th

e Sla

vyan

ka d

epos

it an

d ar

ea o

f the

thei

r app

licat

ion

(UV

ndash u

ltrav

iole

t V

ndash v

isib

le I

R ndash

infr

ared

)









480 Sm3+







I(V IR)

002 0001 001 0003 ndash 00006 001 1868 3982 638 285 304 401 127

IIa

(IR)003 006 001 0003 0006 002 003 820 1735 1042 365 1036 1741 134

IIb

(V IR)0001 0003 001 002 0006 0003 0003 013 ndash 010 ndash 008 010 004

IIb


IIb


IIb

(IR)0006 010 003 0005 00001 0003 ndash 398 716 266 170 181 400 133

IIb


IIc


IIc

(UVV IR)001 001 0008 0005 0006 0006 0003 018 ndash 035 010 045 081 011

IIc


254 B Zidarova





ndash(400) and 2Fi



5 Discussion

















2+ 2

2CaFCa F

[(a ) (a ) Ksp 1]









256 B Zidarova






(572) ndash Sm3+(567)
















ndash(400) and 2Fi
















6 Conclusions


258 B Zidarova







Acknowledgements



References






































260 B Zidarova












































































262 B Zidarova
















248 B Zidarova






















(306) Sm2+(425) Fi

ndash(400) 2Fi

ndash(580)


(306) Sm2+(340) 2Fi

ndash(580)


ndash(580)


ndash(400) 2Fi

ndash(580)



(420) MO2 ndash(565) Sm2+

(620)


(480) MO2 ndash(560) Sm2+

(620)


(440) (YO2)o(520)


(440) MO2 ndash(560)


(440) (YO2)o(520) Sm2+

(660)


(560) Sm2+(620)


(440) MO2 ndash(560)

250 B Zidarova
















7500 nm 9300 nm 7500 nm 9300 nmVodena

skala












ble

14 I

nfl u

ence

of t

he R

EE o

n th

e co

lour

and

lum

ines

cenc

e of

fl uo

rite

varie

ties f

rom

the

Slav

yank

a de

posi

t

Varie

tyI

IIa

IIb

IIc

T h degC

153 ndash 20

2(f

requ

ently

155 ndash1

97)

140 ndash

178

(fre

quen

tly 1

45 ndash1

72)

120 ndash

157

(fre

quen

tly 1

26 ndash1

53)

103 ndash

119

(fre

quen

tly 1

10 ndash1

15)

REE

ppm

165

1ndash14

312

333 ndash

687

33

30 ndash

461

80

07ndash 3

479

colo

urgr

een

dark

-vio

let

viol

et p

ale

viol

etvi

olet

pal

e vi

olet

PLS

gree

nda

rk-v

iole

tvi

olet

pale

vio

let

XR

LSD

y-Sm

type

spec

traD

y ty

pe sp

ectra

Dy

type

spec

traU

nallo

yed

type

spec

traTL

S18

0 degС

ndash (Y

O2)deg

def

ectiv

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

130-

150

degС ndash

REE

O2+

- Ondash d

ipol

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

180

degС ndash

(YO

2)deg d

efec

tive

cent

er22

0 degC

ndash R

EE2+

cubi

c ce

nter

28

0 degС

ndash Y

2+ cu

bic

cent

er

320

degС ndash

(REE

O2)deg

def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

OA

SY

b2+(2

653

65)

Ce3+

(306

) Sm

2+(4

25)

F indash (4

00)

2Findash (5

80)

Yb2+

(265

365

) C

e3+(3

06)

Sm2+

(340

) 2F

indash (580

)Y

b2+(2

473

10)

2Findash (5

80)

Yb2+

(310

) F i

ndash (400

) 2F

indash (580

)

252 B Zidarova

Fig

14

Spe

ctro

scop

ic c

hara

cter

istic

s (X

RLS

TLS

OTS

IR

S) o

n ra

w (

__)

and

synt

hetic

(---

) fl u

orite

s fro

m th

e Sla

vyan

ka d

epos

it an

d ar

ea o

f the

thei

r app

licat

ion

(UV

ndash u

ltrav

iole

t V

ndash v

isib

le I

R ndash

infr

ared

)









480 Sm3+







I(V IR)

002 0001 001 0003 ndash 00006 001 1868 3982 638 285 304 401 127

IIa

(IR)003 006 001 0003 0006 002 003 820 1735 1042 365 1036 1741 134

IIb

(V IR)0001 0003 001 002 0006 0003 0003 013 ndash 010 ndash 008 010 004

IIb


IIb


IIb

(IR)0006 010 003 0005 00001 0003 ndash 398 716 266 170 181 400 133

IIb


IIc


IIc

(UVV IR)001 001 0008 0005 0006 0006 0003 018 ndash 035 010 045 081 011

IIc


254 B Zidarova





ndash(400) and 2Fi



5 Discussion

















2+ 2

2CaFCa F

[(a ) (a ) Ksp 1]









256 B Zidarova






(572) ndash Sm3+(567)
















ndash(400) and 2Fi
















6 Conclusions


258 B Zidarova







Acknowledgements



References






































260 B Zidarova












































































262 B Zidarova
























(306) Sm2+(425) Fi

ndash(400) 2Fi

ndash(580)


(306) Sm2+(340) 2Fi

ndash(580)


ndash(580)


ndash(400) 2Fi

ndash(580)



(420) MO2 ndash(565) Sm2+

(620)


(480) MO2 ndash(560) Sm2+

(620)


(440) (YO2)o(520)


(440) MO2 ndash(560)


(440) (YO2)o(520) Sm2+

(660)


(560) Sm2+(620)


(440) MO2 ndash(560)

250 B Zidarova
















7500 nm 9300 nm 7500 nm 9300 nmVodena

skala












ble

14 I

nfl u

ence

of t

he R

EE o

n th

e co

lour

and

lum

ines

cenc

e of

fl uo

rite

varie

ties f

rom

the

Slav

yank

a de

posi

t

Varie

tyI

IIa

IIb

IIc

T h degC

153 ndash 20

2(f

requ

ently

155 ndash1

97)

140 ndash

178

(fre

quen

tly 1

45 ndash1

72)

120 ndash

157

(fre

quen

tly 1

26 ndash1

53)

103 ndash

119

(fre

quen

tly 1

10 ndash1

15)

REE

ppm

165

1ndash14

312

333 ndash

687

33

30 ndash

461

80

07ndash 3

479

colo

urgr

een

dark

-vio

let

viol

et p

ale

viol

etvi

olet

pal

e vi

olet

PLS

gree

nda

rk-v

iole

tvi

olet

pale

vio

let

XR

LSD

y-Sm

type

spec

traD

y ty

pe sp

ectra

Dy

type

spec

traU

nallo

yed

type

spec

traTL

S18

0 degС

ndash (Y

O2)deg

def

ectiv

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

130-

150

degС ndash

REE

O2+

- Ondash d

ipol

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

180

degС ndash

(YO

2)deg d

efec

tive

cent

er22

0 degC

ndash R

EE2+

cubi

c ce

nter

28

0 degС

ndash Y

2+ cu

bic

cent

er

320

degС ndash

(REE

O2)deg

def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

OA

SY

b2+(2

653

65)

Ce3+

(306

) Sm

2+(4

25)

F indash (4

00)

2Findash (5

80)

Yb2+

(265

365

) C

e3+(3

06)

Sm2+

(340

) 2F

indash (580

)Y

b2+(2

473

10)

2Findash (5

80)

Yb2+

(310

) F i

ndash (400

) 2F

indash (580

)

252 B Zidarova

Fig

14

Spe

ctro

scop

ic c

hara

cter

istic

s (X

RLS

TLS

OTS

IR

S) o

n ra

w (

__)

and

synt

hetic

(---

) fl u

orite

s fro

m th

e Sla

vyan

ka d

epos

it an

d ar

ea o

f the

thei

r app

licat

ion

(UV

ndash u

ltrav

iole

t V

ndash v

isib

le I

R ndash

infr

ared

)









480 Sm3+







I(V IR)

002 0001 001 0003 ndash 00006 001 1868 3982 638 285 304 401 127

IIa

(IR)003 006 001 0003 0006 002 003 820 1735 1042 365 1036 1741 134

IIb

(V IR)0001 0003 001 002 0006 0003 0003 013 ndash 010 ndash 008 010 004

IIb


IIb


IIb

(IR)0006 010 003 0005 00001 0003 ndash 398 716 266 170 181 400 133

IIb


IIc


IIc

(UVV IR)001 001 0008 0005 0006 0006 0003 018 ndash 035 010 045 081 011

IIc


254 B Zidarova





ndash(400) and 2Fi



5 Discussion

















2+ 2

2CaFCa F

[(a ) (a ) Ksp 1]









256 B Zidarova






(572) ndash Sm3+(567)
















ndash(400) and 2Fi
















6 Conclusions


258 B Zidarova







Acknowledgements



References






































260 B Zidarova












































































262 B Zidarova
















250 B Zidarova
















7500 nm 9300 nm 7500 nm 9300 nmVodena

skala












ble

14 I

nfl u

ence

of t

he R

EE o

n th

e co

lour

and

lum

ines

cenc

e of

fl uo

rite

varie

ties f

rom

the

Slav

yank

a de

posi

t

Varie

tyI

IIa

IIb

IIc

T h degC

153 ndash 20

2(f

requ

ently

155 ndash1

97)

140 ndash

178

(fre

quen

tly 1

45 ndash1

72)

120 ndash

157

(fre

quen

tly 1

26 ndash1

53)

103 ndash

119

(fre

quen

tly 1

10 ndash1

15)

REE

ppm

165

1ndash14

312

333 ndash

687

33

30 ndash

461

80

07ndash 3

479

colo

urgr

een

dark

-vio

let

viol

et p

ale

viol

etvi

olet

pal

e vi

olet

PLS

gree

nda

rk-v

iole

tvi

olet

pale

vio

let

XR

LSD

y-Sm

type

spec

traD

y ty

pe sp

ectra

Dy

type

spec

traU

nallo

yed

type

spec

traTL

S18

0 degС

ndash (Y

O2)deg

def

ectiv

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

130-

150

degС ndash

REE

O2+

- Ondash d

ipol

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

180

degС ndash

(YO

2)deg d

efec

tive

cent

er22

0 degC

ndash R

EE2+

cubi

c ce

nter

28

0 degС

ndash Y

2+ cu

bic

cent

er

320

degС ndash

(REE

O2)deg

def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

OA

SY

b2+(2

653

65)

Ce3+

(306

) Sm

2+(4

25)

F indash (4

00)

2Findash (5

80)

Yb2+

(265

365

) C

e3+(3

06)

Sm2+

(340

) 2F

indash (580

)Y

b2+(2

473

10)

2Findash (5

80)

Yb2+

(310

) F i

ndash (400

) 2F

indash (580

)

252 B Zidarova

Fig

14

Spe

ctro

scop

ic c

hara

cter

istic

s (X

RLS

TLS

OTS

IR

S) o

n ra

w (

__)

and

synt

hetic

(---

) fl u

orite

s fro

m th

e Sla

vyan

ka d

epos

it an

d ar

ea o

f the

thei

r app

licat

ion

(UV

ndash u

ltrav

iole

t V

ndash v

isib

le I

R ndash

infr

ared

)









480 Sm3+







I(V IR)

002 0001 001 0003 ndash 00006 001 1868 3982 638 285 304 401 127

IIa

(IR)003 006 001 0003 0006 002 003 820 1735 1042 365 1036 1741 134

IIb

(V IR)0001 0003 001 002 0006 0003 0003 013 ndash 010 ndash 008 010 004

IIb


IIb


IIb

(IR)0006 010 003 0005 00001 0003 ndash 398 716 266 170 181 400 133

IIb


IIc


IIc

(UVV IR)001 001 0008 0005 0006 0006 0003 018 ndash 035 010 045 081 011

IIc


254 B Zidarova





ndash(400) and 2Fi



5 Discussion

















2+ 2

2CaFCa F

[(a ) (a ) Ksp 1]









256 B Zidarova






(572) ndash Sm3+(567)
















ndash(400) and 2Fi
















6 Conclusions


258 B Zidarova







Acknowledgements



References






































260 B Zidarova












































































262 B Zidarova























ble

14 I

nfl u

ence

of t

he R

EE o

n th

e co

lour

and

lum

ines

cenc

e of

fl uo

rite

varie

ties f

rom

the

Slav

yank

a de

posi

t

Varie

tyI

IIa

IIb

IIc

T h degC

153 ndash 20

2(f

requ

ently

155 ndash1

97)

140 ndash

178

(fre

quen

tly 1

45 ndash1

72)

120 ndash

157

(fre

quen

tly 1

26 ndash1

53)

103 ndash

119

(fre

quen

tly 1

10 ndash1

15)

REE

ppm

165

1ndash14

312

333 ndash

687

33

30 ndash

461

80

07ndash 3

479

colo

urgr

een

dark

-vio

let

viol

et p

ale

viol

etvi

olet

pal

e vi

olet

PLS

gree

nda

rk-v

iole

tvi

olet

pale

vio

let

XR

LSD

y-Sm

type

spec

traD

y ty

pe sp

ectra

Dy

type

spec

traU

nallo

yed

type

spec

traTL

S18

0 degС

ndash (Y

O2)deg

def

ectiv

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

130-

150

degС ndash

REE

O2+

- Ondash d

ipol

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

180

degС ndash

(YO

2)deg d

efec

tive

cent

er22

0 degC

ndash R

EE2+

cubi

c ce

nter

28

0 degС

ndash Y

2+ cu

bic

cent

er

320

degС ndash

(REE

O2)deg

def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

280

degС ndash

Y2+

cubi

c ce

nter

32

0 degС

ndash (R

EEO

2)o def

ectiv

e ce

nter

380

degС ndash

Sm

2+-C

e4+ d

ipol

e ce

nter

OA

SY

b2+(2

653

65)

Ce3+

(306

) Sm

2+(4

25)

F indash (4

00)

2Findash (5

80)

Yb2+

(265

365

) C

e3+(3

06)

Sm2+

(340

) 2F

indash (580

)Y

b2+(2

473

10)

2Findash (5

80)

Yb2+

(310

) F i

ndash (400

) 2F

indash (580

)

252 B Zidarova

Fig

14

Spe

ctro

scop

ic c

hara

cter

istic

s (X

RLS

TLS

OTS

IR

S) o

n ra

w (

__)

and

synt

hetic

(---

) fl u

orite

s fro

m th

e Sla

vyan

ka d

epos

it an

d ar

ea o

f the

thei

r app

licat

ion

(UV

ndash u

ltrav

iole

t V

ndash v

isib

le I

R ndash

infr

ared

)









480 Sm3+







I(V IR)

002 0001 001 0003 ndash 00006 001 1868 3982 638 285 304 401 127

IIa

(IR)003 006 001 0003 0006 002 003 820 1735 1042 365 1036 1741 134

IIb

(V IR)0001 0003 001 002 0006 0003 0003 013 ndash 010 ndash 008 010 004

IIb


IIb


IIb

(IR)0006 010 003 0005 00001 0003 ndash 398 716 266 170 181 400 133

IIb


IIc


IIc

(UVV IR)001 001 0008 0005 0006 0006 0003 018 ndash 035 010 045 081 011

IIc


254 B Zidarova





ndash(400) and 2Fi



5 Discussion

















2+ 2

2CaFCa F

[(a ) (a ) Ksp 1]









256 B Zidarova






(572) ndash Sm3+(567)
















ndash(400) and 2Fi
















6 Conclusions


258 B Zidarova







Acknowledgements



References






































260 B Zidarova












































































262 B Zidarova
















252 B Zidarova

Fig

14

Spe

ctro

scop

ic c

hara

cter

istic

s (X

RLS

TLS

OTS

IR

S) o

n ra

w (

__)

and

synt

hetic

(---

) fl u

orite

s fro

m th

e Sla

vyan

ka d

epos

it an

d ar

ea o

f the

thei

r app

licat

ion

(UV

ndash u

ltrav

iole

t V

ndash v

isib

le I

R ndash

infr

ared

)









480 Sm3+







I(V IR)

002 0001 001 0003 ndash 00006 001 1868 3982 638 285 304 401 127

IIa

(IR)003 006 001 0003 0006 002 003 820 1735 1042 365 1036 1741 134

IIb

(V IR)0001 0003 001 002 0006 0003 0003 013 ndash 010 ndash 008 010 004

IIb


IIb


IIb

(IR)0006 010 003 0005 00001 0003 ndash 398 716 266 170 181 400 133

IIb


IIc


IIc

(UVV IR)001 001 0008 0005 0006 0006 0003 018 ndash 035 010 045 081 011

IIc


254 B Zidarova





ndash(400) and 2Fi



5 Discussion

















2+ 2

2CaFCa F

[(a ) (a ) Ksp 1]









256 B Zidarova






(572) ndash Sm3+(567)
















ndash(400) and 2Fi
















6 Conclusions


258 B Zidarova







Acknowledgements



References






































260 B Zidarova












































































262 B Zidarova
























480 Sm3+







I(V IR)

002 0001 001 0003 ndash 00006 001 1868 3982 638 285 304 401 127

IIa

(IR)003 006 001 0003 0006 002 003 820 1735 1042 365 1036 1741 134

IIb

(V IR)0001 0003 001 002 0006 0003 0003 013 ndash 010 ndash 008 010 004

IIb


IIb


IIb

(IR)0006 010 003 0005 00001 0003 ndash 398 716 266 170 181 400 133

IIb


IIc


IIc

(UVV IR)001 001 0008 0005 0006 0006 0003 018 ndash 035 010 045 081 011

IIc


254 B Zidarova





ndash(400) and 2Fi



5 Discussion

















2+ 2

2CaFCa F

[(a ) (a ) Ksp 1]









256 B Zidarova






(572) ndash Sm3+(567)
















ndash(400) and 2Fi
















6 Conclusions


258 B Zidarova







Acknowledgements



References






































260 B Zidarova












































































262 B Zidarova
















254 B Zidarova





ndash(400) and 2Fi



5 Discussion

















2+ 2

2CaFCa F

[(a ) (a ) Ksp 1]









256 B Zidarova






(572) ndash Sm3+(567)
















ndash(400) and 2Fi
















6 Conclusions


258 B Zidarova







Acknowledgements



References






































260 B Zidarova












































































262 B Zidarova






















2+ 2

2CaFCa F

[(a ) (a ) Ksp 1]









256 B Zidarova






(572) ndash Sm3+(567)
















ndash(400) and 2Fi
















6 Conclusions


258 B Zidarova







Acknowledgements



References






































260 B Zidarova












































































262 B Zidarova
















256 B Zidarova






(572) ndash Sm3+(567)
















ndash(400) and 2Fi
















6 Conclusions


258 B Zidarova







Acknowledgements



References






































260 B Zidarova












































































262 B Zidarova



















ndash(400) and 2Fi
















6 Conclusions


258 B Zidarova







Acknowledgements



References






































260 B Zidarova












































































262 B Zidarova
















258 B Zidarova







Acknowledgements



References






































260 B Zidarova












































































262 B Zidarova

















References






































260 B Zidarova












































































262 B Zidarova
















260 B Zidarova












































































262 B Zidarova






















































262 B Zidarova
















Investigation of fluorite from the Slavyanka deposit, Bulgaria as a material for application in the...

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Transcript of Investigation of fluorite from the Slavyanka deposit, Bulgaria as a material for application in the...