GEOLOGICA BALCANICA, 29. 3-4, Sofia, Decemb. 1999, p. 71-79
Convergence of minerals with alunite-type structure (phosphates, phosphates-sulfates and sulfates), some cases from Bulgaria
Angel Kunov
Geological Institute, Bulgarian Academy of Sciences, 1113 Sofia, Bulgaria (e-mail: [email protected]) (Received: January 05, 1996) (Revised version received: February 12. 1998) (Accepted for publication: July 2, 1998)
A. KyHOB - KoHeepzeHquR MUHepa11oe co cmpyKmypou aAy Abstract. In the geology some cases of convergence are often HumOBozo muna (¢oc¢ambl, ¢oc¢amo-cy11b{/jambl u cyllb established. The forming of same minerals under different ¢ambl) Ha npuMepax U3 5o11Zapuu. B reonorHH 'faCTo yCTa conditions makes difficult the determination of their genesis as Ha&nH&aiOTCll npOliBJieHHJI KOHBepreHUHH. 06pa30BaHHe o.n well as the processes responsible for their origin. In the nature HHX H TeX liCe MHHepanOB B pa3JJH'fHbiX ycnOBHJIX JaTpy.nH.AeT many typomorphic minerals are known. noJHaHHe CYll.lHOCTH MHHepanoo6pa3YJOll.lHX npoueccoa Hre The minerals with alunite-type structure (phosphate, phos
HeJHca MHHepanoa. phates with additional S04 groups, sulfates and arsenates) of B npHpo.ne H3BeCTHbl MHOrHe MHHepanbl, KOTOpble JIBJIJIIOTCJI fer broad opportunities for studies on the convergence. In Bul THnoMopQ>HbiMH .nn.A paJnH'fHbiX npoueccoa. MHHepanbl co garia occur and are proved phosphates (plumbogummite, flo
cTpyKTypoii anyHHToaoro THna (Q>ocQ>aTbl, Q>ocQ>aTo-cynb rencite), phosphates with additional S04 groups ( corkite, hins Q>aThl, cynbQlaTbl H apceHaTbl) npe.nnaraiOT wHpOKHe BOJ dalite, svanbergite, woodhauseite) and sulfates (alunite, MOJKHOCTH ,nJlll H3y'feHHJI KOHBepreHTHOCTH. jarosite, plumbojarosite, osarizawaite, beavearite). Most of EionbWHHCTBO H3 onHcaHHbiX B EionrapHH Q>ocQ>aTOB (nJJIOM- them have been found related to ores and wall-rock alterations 6oryMMHT, QlJJOpeHCHT), QlOCQlaTO-CYJlbQlaTOB (KOpKHT, rHHC in localities with hroad occurrence of hydrothermal-metaso .nanHT, CBaH6eprHT, ay.nxaYJeHT) H CYJibQlaTOB (anYHHT, llp0- matic and supergene processes . 3HT, nJIIOM60llp03HT, OCapH3a&aHT, 6HBepHT) yCTaHOBJieHO Based on main charactetistic features endogene and exogene npH HCCJie,no&aHHH opy.neHeHHH H OKOnopy.nHbiX H3MeHeHHH alunites and jarosites are established. The so far found hins B paiioHax C HHTeHCHBHbiM pa3BHTHeM rH,npoTepManbHO-Me dalite, plumbogummite, osari.zawaite and beaverite are of su TaCOMaTH'feCKHX H cynepreHHbiX npoueccoa . pergene origin. The svanbergite and woodhauseite are found .l{oKaJaHbl KaK :m.noreHHble, TaK H cynepreHHble anyHHTbl H being of hydrothermal-metasomatic or undetermined origin. llp03HTbl. 06 yCTaHOBJieHHbiX .no CHX nop rHHC.nanHTax, The correct genetic interpretations have an important practi nniOM6oryMMHTaX. ocapH3a&aHTax H 6HaepHTax npe.nnonara cal and theoretical value. Therefore all data on the geological eTCll cynepreHHbiH reHe3HC, a 0 CBaH6eprHTax H ay.nxaYJeHTax environment in which alunite and its structural analogues oc - rH.npoTepManbHO-MeTaCOMaTH'feCKHH reHC3HC. cur, the results of their experimental and theoretical model BblliCHeHHe reHeJHCa MHHepanOB HMeeT npaKTH'feCKOe HTeO ling, and established relations between conditions of forming peTH'feCKoe JHa'feHHe. B 3TOM CMblcne HHTepec npe.ncrnan.A and minerals composition are valuable. IOT .naHHble 0 reonorH'feCKHX yCJIOBHJIX o6pa30BaHHJI anyHH Ta H ero CTpyKTypHbiX aHanOrOB, pe3yJibTaTbl 3KCnepHMeH TanbHOrO H TeOpeTH'feCKOrO MO.nenHpOBaHHJI, BbiJIBJieHHe cxo.ncT&a H OTJIH'IHJI, ycrnHo&neHHble Ja&HCHMOCTH MeJK.ny yCJIOBHJIMH QlOpMHpOBaHHll, COCTaBOM H CTpYJCTYPOH 3THX MHHepanoa.
Kunov, A. 1999. Convergence of minerals with alunite-type structure (phosphates, phosphates-sulfates and sulfates), some cases from Bulgaria. - Geologica Bale., 29. 3-4; 71 -79. Key words: convergence, alunite, alunite-type structure, alunite group and structural analogues, phos phates, phosphates-sulfates and sulfates.
71 Introduction duces the motion of "petrographic convergence". Some cases of convergence are frequently The term "convergence" originates from the Latin found in geology. The origination of identical "convergentio" meaning similitude, likeness, and minerals in different conditions creates some dif "converger", be similar, bring near. First it has been ficulties for the recognition of the processes and broadly used in the biology and later on introduced their genesis. In nature are well known many min into geology. In geology it has been applied to end erals that are typomorphic for different processes. products with obvious {apparent) similarities, but For example, chlorites are characteristic for the having originated from different processes. As are regional metamorphism, diaphthoresis and hydro sult, they may possess similar individual features or thermal alterations. The convergence is also relations, but are not of a single origin (fiocnenoo, strongly expressed among the clay minerals, being 1963). Loewinsson-Lessing (JieoHHCOH-JleccHHr, of sedimentary, hydrothermal or supergene origin. 1949) introduced the idea about the heterogeneity The minerals of alunite type structure, phos
into the rock-forming process. Raguin (1957) ex phates, phosphates with additional SO4 groups, amined the convergence in metallogeny. Smirnov sulfates and arsenates (Pabst, 1947; Kato, 1971, (CMHpHoB, 1960) comments the convergence prop 1977, Ka111Kaii, 1969, 1970) offer broad opportuni erties of the so called "kolchedan" deposits (mas ties for studying the processes of convergence. sive sulfide deposits). Ustiev (YcTHeo, 1961) intro- Kashkai (Ka111Kaii, 1969) following their crystallo-
R A 0 J: N
:n
II .u uz
a IC B y u '1
E E R G c B
Fig. I. Deposits and occurrences of alunite and minerals of alunite-type texture in Bulgaria. (morpho-structural zones after 6oH'IeB, 1971) I -Stara Planina Zone: I - Granichak, Toumbarite; 2 - Sredogriv; 3 - Pesochnitsa; 4 - Pic Haydoushki Vruh; 5 - lgnatitsa; 6 - Osenovlak; 7- Kremikovtsi; II- Sredna Gora Zone: 8- Krousha; 9- Pishtene; 10- Gourgoulyat; II - Breznik; 12- Zlatousha; 13- Klisoura; 14- Ourvich; 15- Zheleznitsa; 16-Choupetlovo; 17- Goma Dikanya, Lisets; 18- Yarlovo; 19- Stoudenets; 20- Yamkite; 21 - Verinsko; 22 - Golyama Rakovitsa; 23 - Chelopech; 24 - Asarel; 25 - Krasen; 26 - Petelovo, Borova Mogila; 27 - Pesovets; 28 - Radka; 29 - Tsar Asen; 30 - Elshitsa; 31 -Prohorovo; 32 - Bakadzhik; 33 - Zidarovo; 34 - Vurli Bryag; 35 - Alefo Toumba; 36 - Kavatsite; 37 - Duni; 38- Sveta Agalina; 39- Ropotamo; 40- Gramatikovo; III- Kraishte Zone: 41 - Kroushev Dol; 42- Zhabliano; 43 - Kozhouh; IV - Rhodopian Zone: 44 - Sapareva Banya; 45 - Petrovo; 46 - Stomanovo; 47 - Govedamik; 48 - Shtipcheniovo; 49 - Vurba; 50 - Ribnitsa; 51 - Borieva; 52 - Murzyan; 53 - Eniovche; 54 - Gabrovo; 55 - Sumitsa; 56 - Boukovo; 57 - Bryastovo; 58- Svetlina; 59- Sousam; 60- Spahievo (Chala); 61 - Obichnik; 62- Pcheloyad; 63- Zvezdel; 64- Sumak; 65 - Madzharovo, Brousevtsi; 66 - Popsko; 67 - Kamilski Dol; 68 - Gomoseltsi
72 structural peculiarities united them into a "Group Established mineral species of the alunite and its structural analogues". So far and their occurrence about 35-40 minerals have been established and described from this group, which represent only Phosphate minerals the half of all possible end members of the isomor phic rows. For all these minerals Kashkai (Kam Plumbogummite- Alfb(POJ£0H)~Hp KaH, 1977) determines the chemical formula It has been described in the zones of oxidation of ] ) , M[R(OH)2 3(A04 2 where: some lead-zinc and gold-silver deposits from the M - mono-valent cations : K+, Na+, Rb+, Ag+, Rhodopes (KocTos, 1960; KocToB et al., 1964; NH/. ~0; two-valent: Ca2+, Sr2+, Ba+, p})l+; three QseTauosa, 1993; Kyuos et al., 1993; Kyuos, valent: BP+ and some lantanoids (Ce, Y, Yb, etc.); 1996). It forms small spheroidal aggregates or R- AI, FeH, Ga, In, CrH; globular crusts with radial to concentric and fine A - S6+, pS+, AsS+. fibrous texture. Occasionally are observed unclear rhombohedral forms (Tabl. I). The colour varies Kostov (KocTos, 1993) accepts for the sulfates from white to light bluish and yellow-brownish. thHe for(AmuladABmlS
10 Geologica Balcanica, 29.3-4 73 Table 1 Occurrence and genesis of minerals with alunite-type structure in Bulgaria
Minerals Genetic Type Occurrence, region Main references 1 2 3 4 Phosphates plumbogummite supergene Shtipcheniovo (48) Kostov, 1960 ) AI3Pb(P04 2(0H),.H20 Vurba (49) KonbKOBCKH (KoCToa et al., 1964) Cha1a (60) KyHOB, 1996 Madzharovo (65) KonbKOBCKH (KoCToB et al., 1964) Brousevtsi (65) Tzvetanova, 1995 florensite hydrothermal AI Ce(P0 ) (0H) Duni (37), Sveta Agalina (38) Kunov et al., 1992; KyHoB et at., 1996 3 4 2 6 metasomatic Phosphates-Sulfates corkite supergene Chala (60) KyHOB, 1996
PbFe 3(PO4 )(SO4 )(0H)6 Obichnilc (61) KyHoB, MaH.noaa, 1996 Pcheloyad (62) Tsonev, unpublished data Madzharovo (65) KonbKOBCJCH (KoCToa et al., 1964) Brousevtsi (65) Tzvetanova, 1995 hinsdalite supergene Chala (60) KyHOB, 1996
PbAI3(PO 4)(SO 4)(0H), Obichnik (61) KyHoa et aL, 1993; KYHOB, MaH.Iloaa, 1997 Pcheloyad (62) Tsonev, unpublished data Madzharovo (65) KonbKOBCJCH (KoCToa et at., 1964) svanbergite not clear Asarel (24) Velinov et al., 1991 Spahievo Ore Field KyHoB et al., 1986; SrAl 3(PO 4)(SO 4)(0H), (Bryastovo - 57, Chala • 60) Kunov et at., 1986 hydrothermal· Chelopech (23) Chipchakova, unpublished data metasomatic Velinova, unpublished data Bakadzhik Ore Field Kunov, unpublished data Sveta Agalina (38), Duni (37) KyHoa,EenHaaHoB, 1992 woudhauseite not clear Asarel (24) Velinov et aL, 1991
CaAI3(Po.xso.)(OH), hydrothermal Duni (37) KyHOB, DenHBaHOB, 1992; metasomatic KyHoa et al., 1996 Sulfates alunite supergene Haydoushki Vruh (4), KapaHOB, 1971 ) KAI 3(S04 2 (OH), Zhablyano (42) Obichnik (61) KyHoa,MaH,IlOBa, 1997 technogenetic Elshitsa (30) 'IHn'laJCoaa, 1993 synthetic AcnaHliH H .llp., 1976 hydrothermal lgnatitsa (5) QBCTaHOB, 1982 metasomatic Sredna Gora Zone Radonova, Velinov, 1969 Krousha (8) BenHHOB, 1970, 1973 Pishtene (9) BenHHOB, 1971, 1973 Gourgoulyat (10) Stoynov et al., unpublished data Breznik (II) BenHHOB, 1967, 1973 Zlatousha (12) Kunov, Ferdov, unpublished data KJisoura (13) BenHHOB, 1971, 1973; EaTaH,Il)JCHeB et at., 1978 Chelopech (23) Radonova, Velinov, 1969 Asarel (24) Pa,lloHoaa, CTeciJalloB, 1974; lirHaTOBCkH,QBCTaHOB, 1981 Krasen-Petelovo (25, 26) Pa.l{OHOBB, 1969 Pesovets (27) Pa,noHoaa, 1969 Bakadzhik Ore Field (32) KyHoa,EenHBaHoa, 1996 Zidarovo (33) QBeTaHOB, 1981 southern of Sozopol, QBCTaHoa, CnaaHnoa, 1979; Kavatsite (36), Duni (37), KyHOB,DenHBaHOB, 1993; Ropotamo (39) Ky11oa et al., 1996 Stoma novo ( 46) Velinov et at., 1972 Spahievo Ore Field PatuKOB, 1962;Pa.noHoaa, 1972; (Gabrovo · 54, Sumitsa · 55, KYHOB et al., 1981; Boukovo • 56, Bryastovo • 51, Velinov et at., 1990; Svetlina - 58, Sousam - 59 KYHOB, 1991; Spahievo - 60) KyHOB, 1993 Madzharovo (65) Velinov, Aslanian, 1981; Velinov, Nokov, 1991
74 2 3 4 Gomoseltsi (67) KyHoa, Huoa, 1996 toewigite synthetic AcnaHliH, lleTpOaa, 1975; AcnaHliH et al., 1976 Jarosite• supergene Granichak, Toumbarite• (1 ), Kunov et al., unpublished data ) KFe3(S04 2(0H)6 Sredogriv• (2), Pesochnitsa • (3) Plumbojarosite• • Haydoushki Vruh• (4) KapaHoB, 1971
PbFe6(SO4 ).{0H)12 lgnatitsa•, •• (5) fbeTaHOB, 1979 Osenovlak• (6) KyHoa, Ha11:oa, 1998 Kremikovtsi•• (7) llaHaiiOTOB, 1964 Krousha• (8), Pishtene• (9), BenKHOB, 1973; Gourgoulyat• (10), Breznik• (11), Zlatousha• (12), KJisoura• (13), Choupetlovo• (16) Ourvich• (14), Zheteznitsa• Kunov, unpublished data (15), G. Dikanya•, Lisets• (17), Yarlovo• (18) Stoudenets• (19) Jior,llaHOB, 1987 Yamkite• (20) Velinov, Nokov, 1991 Verinsko• (21) Zhelyazkova et al., unpublished data Golyama Rakovitsa • (22) Velinov, Kunc.>v, unpublished data Chelopech• (23) Pa.llOHoaa, 1969 Asaret• (24) Jior.llaHOB, 1980 Krasen (25), Petelovo (26), Pa.llOHoaa, 1963; Pesovets (27), Radka (28), Jior,llaHOB (1980) Tsar Asen (29), Elshitsa (30)•••• Prohorovo• (31) Kunov, Nakov, unpublished data Bakadzhitc• (32) KyHoa,EenKBaHoB, 1996 Zidarovo• (33), Vurli Bryag• QaeTaHOB, 1979; 1979a; (34), A1efo Toumba• (35) QaeTaHOB, CnaaKnoa, 1980 Kavatsite• (36), Duni• (37), KyHoa et al., 1996; Ropotamo• (39) Kunov et at., unpublished data Gramatikovo• (40) KyHoa, HaaHoaa-llaHaiioToaa (1976) Kroushev dot• (41) Kunov et at., unpublished data Kozhuh• (43) Bon'laHoaa et at., 1974 Davidkovo Ore Field •, •• Ha¢nanK,~anKHOB, 1988 Govedamik ( 47), Shtipcheniovo (48) ~dan Ore Field: Vurba • • after Kol'kovski, Zidarov (Kocroa et at., (49), Ribnitsa .. (50), 1964); Kona.~:oacJtK, MaHea, 1988 Borieva• (51), ~urzian• (52), Enuvche.. (53) Spahievo Ore Fietd•, •• PaUIKoa, 1962;P8,1loHoaa, 1972; (54-60) KyHoa et at., 1981; KYHOB, 1991; KyHoa et at., 1997 Obichnik•(61) KyHoa.~aK,IlOBa, 1997 Zvezdet•(63) P8.1lOHOB8, 1973 Sumak•(64) Kunov et at., unpublished data ~dzharovo•(65) PUOHOB8, 1960 Popsko•(66) Kunov, unpublished data Gomoseltsi• (68) Kunov, Nakov, unpublished data Kamilski Dot• (67) KyHoa, Huoa, 1997 hydrothermal Kozhouh• (43), llerpoa, 1993 Sapareva Banya• {44) osarizawaite ) PbCuAI2(SO4 2(0H), supergene Chala(60) Kunov, 1995 beaverite
Pb(Cu,Fe.AIMSO) 2(0H), supergene Chala (60) Kunov, Petrov unpublished data The numbers in parentheses are the same as on Fig. 1
75 PLATE I SEM JEOL JSM-T300 (analyzed by E. Mandova). 1 - Plumbogummite - unclear rhomboedric forms. 2 - Hinsdalite - psedocubic and tabular crystals. 3 - Alunite - flake-like (pinacoidal) habit.
PLATE II
SEM JEOL JSM-T300 (analyzed by E. Mandova). 1 - Alunite - pseudocubic habit. 2 - Jarosite - pseudocubic habit. 3 - Osarizawaite - tabular habit.
lopech, and in the localities: Duni, Cap Sveta lated grains and aggregates among the ground Agalina and Kokurzhenski Bair (KyHoB et al., mass, often intragrowing with quartz. In some cas 1986; Kunov et al., 1986; KyuoB, EenHBaHOB, 1992; es the alunite replaces the kaolinite, develops at KyHoB et al., 1996). Some data on the occurrence the expenses of pyrophyllite or is being corroded of svanbergite as well as the first data for wood by diaspore. Two types of habits occur: pinacoidal hauseite in Bulgaria have been published in rela (Tables 1, 3) and rhombohedric (Tables 2, 1). Both tion to the ·secondary quartzite (alunite, pyrophyl forms are found together and/or separately. The lite-containing diaspore, diaspore-alunite, alunite potassium alunites are dominating. A tendency to containing, zunyite- and alunite-containing pyro transition from Na-containing to K-containing phyllite types) of the mineral deposit Asarel (Veli alunites from the Srednogorie to the Rhodopes is nov et al., 1992). Here some mutual transitions established. into the row of both minerals are described. In the The supergene alunite of Zhabliano and Haid locality ofDuni alunite, svanbergite and woodhau oushki Vruh (KapaHoB, 1971) has been formed "in seite are well distinguished, and a second phase, situ" at a conventional temperature, during a con but of the row svanbergite-woodhauseite-florencite tinuous effect of the sulphur acid formed by the is also found (KynoB et al., 1996). The svanbergite oxidation of pyrite, contained into the clays and and the woodhauseite are lightly yellow to yellow, concretions. The high content of potassium into pseudocubic with close optic characteristics. the rocks suggests a possible potassium type of the Kostov, Breskovska (1989) refer the hinsdalite, alunite. The microprobe pictures exhibit some svanbergite and corkite to the phosphates with shapes characteristics for the rhombohedric habit. mixed anions (with a SO 4 group, of planar (layer The alunite from the Obichnik occurrence (KyHoB, like) type). MaH.uosa, 1997) forms a compact, white coloured mass into veinlets, together with limonite, hema Sulfates tite, jarosite, kaolinite and hinsdalite. It has a po tassium composition, forming crystals with rhom Alunite- KAllSO~jOH)6 bohedric (pseudocubic) habit. The mineral com position suggests a supergene origin, resulting After overview data ofVelinov and Kunov (BenHHOB, from the effect of the sulphur acid, obtained from KyHoB, 1989, 1996), the alunite is a mineral ofbroad the pyrite oxidation. occurrence in Bulgaria. As this overview is giving a The technogenetic alunite from the Elshitsa quite detail characteristics of all so far known alunite mineral deposit forms a vein-like shaped body up occurrences in Bulgaria, only the principle and com to 2m long. It has a white or light grey colour or is mon features will be given hereafter. slightly pigmented by iron hydroxides. Its is pos The overview and Table 1 clearly show, that the sessing a pinacoidal habit, being formed at a depth hydrothermal-metasomatic type is the best ex of 25-30m, as result of a fire, occurred into the pressed. These are mainly occurrences and mani mine, in a presumably high pressure and probable festations of alunite secondary quartzites and argi temperature of 350°-500° (tlnntfaKOBa, 1993). llisites, developed at the expense of intermediate, Synthetic alunite has been produced at a tem less often basic, and only in one case, of acid in perature of more than 2000 and increased pressure composition volcanic rocks. The alunite associates (36-150atm) (AcnauHH et al., 1976). These authors with quartz, kaolinite, dickite, sericite, hydromicas, prove, that the increasing of the temperature leads diaspore, pyrophyllite, apatite, hematite, rutile and to the increasing of the quantity of crystals with in single cases with barite, zunyite and topaz. It is pinacoidal habit, compare to these of rhombohe also replacing pseudomorphically feldspars and dric one. mafites, infills necks and veinlets, forms single iso- So far loewigite (alunite with increased water
76 PLATE I
Kunov, Geologica Bale., 29.3-4 PLATE II
Kunov, Geologica Bale., 29.3-4 content) has not been established in any natural cal and theoretical significance. They are based on deposit, but has been artificially acquired (Acna all data treating the geological environment in """· llerposa, 1975; AcnaHBH et al., 1976}. Its which they occur, theoretical and experimental presence among alunite quartzites from the Sur modelling, determined similarities and differences nitsa deposit is admissible, due to a suggested en as well the as established relationship between the dothermic effect at 290° (BenHHOB et al., unpub conditions of forming and their composition and lished data). Its presence needs to be confirmed by texture. additional infra-red and differential-thermal anal Numerous data treating different aspects of the yses, because of its similarity when forming alunite have been published, e.g., the monograph pseudocubic crystals, similar to the alunite. by Kashkai (KalllKaif, 1970). The alunite has also been the main subject of interest for Bulgarian Jarosite- KFelSO~jOH)6 mineralogists. The jarosite is also relatively well and Plumbojarosite- PbFe,jSO~JOH) 12 studied. Existing data for the remaining minerals from the considered group, and in particular for Both minerals are well known from many occur Bulgaria, are significantly less numerous. rences in Bulgaria, but no precise studies on them Hall (1978) determines three main varieties of are available. They are characteristic for the zones alunite: vein-type, replacement-type, and sedimen of oxidation of the ore manifestations from the tary one. Kashkai (KalllKaif, 1970) defines: volcan West Srednogorie (BeJIHHOB, 1973), the Cu-pyrite ogenetic, contact (intrusion-related), alunitization and Cu-porphyry deposits of the Panagyurishte from ascending hydrothermal and descending sul region (Pa.nouoBa, 1963; :Oor.nauos, 1987}, the phate solutions, supergenic, artificial, synthetic, lead-zinc, base-metals and Au-Ag deposits from formed after fires in coal beds. So far in Bulgaria the Rhodopes (KocTOB et al. 1964; Kyuos, 1991; have been established: hydrothermal-metasomatic, KyuoB, Mau.nosa, 1997; etc.). Usually they form sedimentary, vein, technogenetic, supergene and earthy masses, veinlets, necks, and other forms, synthetic types. consisting of cryptocrystalline aggregates. Some Most of the classifications are based on a genet SEM photographs of jarosite confirm its rhombo ic principle, but not always the used terminology. hedric forms (Tables 2, 3). For example, the mentioning of vein-type is ex In the locality of Ignatitsa has been established pressing more the morphology (of the crystals or a jarosite, containing anomalous amount of Ag the occurrence), but the origin could be quite dif and Pb. This led Tsvetanov (li.BeTaHOB, 1982) to ferent. Therefore, the described vein-type alunite the admission, that it may be conferred to the lead from the Madzharovo deposit (Velinov, Aslanian, or silver varieties or to the plumboargentojarosite. 1981) may be conferred to the hydrothermal-meta Jarosite formed by recent hot hydrotherms has somatic type, formed by ascending sulphate hydro been established in the vicinities of Kozhouh thermal solutions or mixed ones with descending (76°C) and Sapareva Bania (98°C) (TierpoB, 1993). sulphate solutions. For the alunites in Bulgaria the following fea Osarizawaite- PbCuAijSO~jOH) 6 tures have been established: and Beaverite - Pb(Cu,Fe.AIJlSO~/OH} 6 - the potassium chemistry is dominating (BenH So far they have been established only in the min HOB, KyuoB, 1989), no matter of the genetic type; eral deposit of Chala, together with hinsdalite, the habits are not depending on the K:Na ratio; plumbogumite and anglesite, malachite, brochan - into superficial conditions only the rhombohe tite and other minerals in quartz veins cutting dric type is formed, deeper occur both rhombohe quartz-sericite metasomatites and into veins con dric and pinacoidal types, further at depth, only taining galena and sphalerite. Both minerals occur the pinacoidal one is found. The experimental in cryptocrystalline masses in which they are studies of Aslanian et al. (1976) show a space dis mixed and are difficult to be determined micro tribution of the rhombohedric and pinacoidal hab scopically. The SEM pictures of osarizawaite show its, related to precise physical-chemical condi its planar and rhombohedric habit (Tables 2, 3). tions. The established supergene alunites are The osarizawaite is green, blue, blue-greenish and rhombohedric in difference to the technogenetic yellow-greenish coloured, the beaverite being dom one from the Elshitsa Deposit (t.IHn'laKoBa, 1993) inantly yellow-greenish to yellow-brown coloured and the hydrothermal ones found at depth, both (Kunov, 1995; KyuoB, llerpos, unpublished data). being pinacoidal. This confirms the forming of pseudocubic alunite into superficial conditions and the dependence of the pinacoidal habit on Discussion depth, pressure and temperature. This leads to the suggestion, that the pinacoidal habit is an impor The correct genetic conclusions on the alunite and tant component for the limitation of the conver its structural analogues have an important practi- gence uncertainity, concerning the genesis of the 77 alunite.· This gives better opportunities for faster Ossaka, J., J. Hirabayashi, K. Okada, R. Kobayashi and T. genetic interpretations. Hayashi. Crystal structure of minamiite, a new mineral of It is well known, that the jarosite is a typical the alunite group. - Amer. Mineral., 67; 114-119. Pabst, A. 1947. Computations on svanbergite, woodhouseite product resulting from the decomposition of iron and alunite.- Amer. Mineral., 32; 16-30. sulfides (mainly pyrite) under the effect of solu Radon ova, T., I. Velinov. 1969. The alunite facies of the sec tions with a pH less than 3 (lJyxpoo, 1980). The ondary quartzites in the Srednogorian zone. - Compt. experimental studies on the synthetic jarosite give Rend. Acad. Bulg. Sci., 22, 3; 321-324. evidences to Kashkai (KawKaH, 1977) to consider Raguin, E. 1957. Les conwergences dans Ia classification met allogenique. - Neues Jahrb. ineral., Geol. und Palaontol., the jarosite, after its temperature range of forming Abhandl., Bd 91; 271-277. as a characteristic secondary supergene mineral. Tzvetanova, Y. 1995. Corkite from Brussevtsi, East Rhodope At the same time he is mentioning some cases of Massif, Bulgaria.- C. R. Acad. bulg. Sci., 48, 5; 47-50. hypogene jarosite. The Bulgarian data (KocTOB et Velinov, 1., S. Aslanian. 1981. Vein-type alunite from Bulgar al., 1964) show its place mainly into the zones of ia. - Compt. Rend. Acad. Bulg. Sci., 34, 10; 1417-1419. Velinov, 1., M. Gorova, H. Neykov. 1991. Svanbergite and oxidation. Petrov (lleTpoB, 1993) is describing woodhouseite from the Asarel porohyry-copper deposit jarosite deposed of recent mineralised hydro (Bulgaria). - Compt. Rend. Acad bulg. Sci., 44, 2; 45-48. therms with temperatures of 76° and 98°C. Out of Velinov, 1., M. Kanazirski, A. Kunov. 1990. Formational na doubt it is an indubitable contribution to the con ture and phisicochemical conditions of formation of the vergence of the alunite. The jarosite may also be metasomatic rocks in the Spahievo ore field (Eastern Rhodope Mts., Bulgaria). - Geologica Bale., 20. 4; 49-63. found, formed at the expenses of the pyrite oxida Velinov,l., N. Katzkov, A. Soukov. 1972. First information on tion, which is a feature increasing its convergence secondary quartzites on paleogenic rhyolites in the Middle uncertainty. Rhodope Massif. - Compt. Rend. Acad. Bulg. Sci., 25, 9; The hinsdalite and plumbgummite are found 1249-1252. Velinov,l., S. Nokov. 1991. Main types and metallogenic signif into the zones of oxidation of some lead-zinc de icance of the Madzharovo hydrothermally altered oligocene posits, which makes probable their supergene ori volcanics. - Com pt. Rend. Acad. bulg Sci., 44 9; 65-68. gin. The found of florencite and woodhauseite in AcnaHliH, c .. H. BenHHOB, M. BenHHOBa. 1976. reHeTH'IeCKKe Bulgaria are still insufficient for a prompt opinion THnbl anYHKTa K 3KCnepKMeHTanbHble ycnOBHll HX CHHTe- about their origin. Some published data suggest 3KpOBaHKll.- reoXHM., MHHepan. K neTpOn., 5; 144-155. their possible convergence properties. A supergene 6aTaH.IlliCHeB, H., H. BenHHOB, A. KyHOB, n. qonaKOB. 1978. ~aUHanHH K CTpYKTypHH OC06eHOCTK Ha npeXO,IleH THn origin for the osarizawaite and beaverite from Cha cepHK H nHpHTHH py.nonpoliBneHHll npH c. KnMcypa, Co la may be admitted. lj)Miicxo. - reoXKM., MHHepan. H ne-rpon., 9; 63-79. EenHBaHoa, K., P. Haxoa, T. KepeCTe.llliCHliH, A. KyHoa. 1992. Acknowledgements and comments. This study has been carried C-rpoeliC Ha CMnHCTapckHll aynxaHo-nnYTOHK'IeH ueHn.p. out through the financial support of the National Fund "Sci B: lloCTHliCeHMll K38.1l8'1K Ha 61.nr.MKHepan. H ne-rpon., C.; entific investigations", Project NZ-433. The author is deeply 49-50. grateful to Research professor J. Minceva-Stefanova for the Eor.naHOB, 6. 1987. Me.nHKTe HaxO.IlKll.la Ha 6D.nrapHll.- C., critical and useful review of the manuscript. TeXKHJCa, 388 pp. Some data into the text and tables for synthesised minerals 6pecxoacxa, B., 6. Maapy.n'IHea, 3. HnHeB, H. Banuapoa, H. with an alunite texture have been included aiming to provide BenKHOB, n. HoliCapoa. 1976. Ma.nliCapoacxoe py.nHoe more information. none. - reoxHM., MKHepan. H ne-rpon., 5; 23-57. BenKHOB, H. 1967. nponHnHTH H BTOpH'IHH JCBapUHTH 8 paiio Ha Ha 6pC3HHJC. H3B. reon. K-T, cep. reOXHM., MHHepan. H References ne-rporp., 16; 205-220. BenHHOB, H. 1970. 3oHanHoCT H reHC3HC Ha nponHnHTHTe K BTOpH'IHKTe ~~:aapUKTH B paiioHa Ha cenaTa KnKcypa H Hall, R. 1978. World nonbauxite aluminium resources - llKweHe. - lba. reon. K-T, cep. reoxHM., MHHepan. H neT alunite.- Geol. Surv. Prof. Paper, 1076- A; 35 pp. porp., 20; 151-166. Kato, T. 1971. The crystal structures of goyazite and wood BenHHOB, H. 1973. MHHepanoro-ne-rponoliCKH aHanK3 Ha xH.n houseite.- Neues Jahrb. Mineral. Monatsh.; 241-247. poTepManHo H3MeHCHHTC ropHOKpe,llHK aynKaHKTH OT 3a Kato, T. 1977. Further refinement of the woodhouseite struc R8,1lHOTO Cpe.nHoropHe. - AaTopelj)epaT 3a npH.no6HaaHe tures. - Neues Jahrb. Mineral. Monatsh. ; 54-58. Ha CTeneHTa .nonop Ha reonoro-MHHepanorH'IeCKHTe Hay Kostov, 1., V. Breskovska. 1989. Phosphate, arsenate and van KK, C., reon. H-T; 26 C. adate minerals. Crystal, Chemistry and Classification. - K.l. BenHHOB, H., A. KYHOB. 1989. AnyHKTH.- B: HeMeTanHK no Ohridski Univeriry Press, Sofia; 212 pp. ne3HH H3KonaeMH B 6D.nrapKll, T. 2. EH.noreHHH npOMKW Kunov, A., K. Belivanov, Ts. Iliev. 1992. First florencite-(Ce) neHH MHHepanH H cxanH. C.; TexHHKa, 160-178. find in Bulgaria. - Compt.rendAcad.bulg.Sci.; 45, 7, 53-55. BenMHOB, H., A. KyHoa.· 1996. Oll.le Be.llHDlK 3a anyHHTOBHTe Kunov, A., I. Velinov, Y. Yanev, R. Nakov, N. Stephanov. 1994. KBBPUHTH, TliXHaTa pOnll H3Ha'leHHe. - MKHHO ,llenO K reo Adularia-sericite type of wall-rock alteration of the epither norHll, 2-3; 23-28. mal Au-Ag mineral occurrence of Obichnik (Eastern Bon'laHoaa, E., A Kan'leaa, B. W}'MJiliHCJCHii. 1974. 0 MHHepa Rhodopes, Bulgaria)- Compt. Rend. Acad. bulg. Sci., 47, 8; nax 30Hax OKHcnCHHll rH,IlpOTepManbHOH MHHepanH3aUHH B 61-64. paiioHe ropbl KoJKYX. - Cn. 61o.nr. reon . .n-ao; 3, 334-338. Kunov, A., M. Velinova, L. Punev. 1986. Phosphate Minerali HrHaTOBCJCH, n., P. UaeTaHOB. 1981. AnyHHT OT HaxO.IlHll.le sation in the Spahievo ore field.- Crystal Chemistry of Min Acapen. Py.no.no6HB, 6; 3-6. erals. Procc.of the 13-th Gen.Meet.the IMA,Varna, 1982; KapaHOB, Xp. 1971. AnyHHT H xanoH3HT a KOHTHHeHTanHHTe 877-889. ce.llHMeHTK Ha xeTaHliCa OT KpaHuteTo H la61.p.neTo. - Cn. Lefebvre, J., C. Gasparini. 1980. 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