GEOLOGICA BALCANICA, 29. 3-4, Sofia, Decemb. 1999, p. 71-79

Convergence of minerals with -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 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 -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 . 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 , 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 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 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, , 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. 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. Florencite, an occurrence in 61o.nr. reon . .n-ao, 2; 231-239. the Zairian copperbelt. - Can ad. Mineralog., 18; 301-311. KawKaii, M. A. 1969. rpynna anyHHTa H ero CTpYJCTYPHbiX 78 8Ha.noroa.- 3an. BMO; 98, 2; 150-165. KyHoB, A., P. Haxoa, K. lienHBaHOB. 1996. BTopH'fHKTe KBap­ K8wKaii, M. A . 1970. AlryHHTlol. KX reBe3KC K Kcnonb3oaaHKe. UKTK npK )lK>HK (113TO'fHO Cpe.nHoropKe). - Cn. Ji'bnr. - M .• He.npa. T. I - 400 pp. .• T. n - 320 pp. reon . .n-ao, 57, 1; 1-8. Kawxaii, q , M . 1977. rpynna a.nyHtml K ero CTPYJCl)'pHblll KyHoB, A .• C. UoHeB, K. PeKa.noa, E. MaH.noaa, H. CTecj)aHoB. aHa.noroa. ~ liak)', 3JJM, 158 pp. 1993. BTopK'fHK cyncj)aTK, cj)occj)aTK H cyncj)aTo-cj)occj)aTK KonbkOBCkK, E .• Jl. MaHeB. 1988. Ma.naacJto py.nHo none. - B: OT 3naTHO·Cpe6'bpHOTO py.nonpOIIBneHKe 06K'fHHK (I13T. OnoaHO·UHHkOBHTe Haxo.nKIUa a JiloJIJ"llpKJI, 10.11. TexHHKa, Pc.nonK).-B: PaJBHTHe H8 6'bJir.MKHepan., C.; 34-35. C<$Kll; 37-64. Ha$TanK, JI., 0 . ManKHOB. 1988. )laBK.IlKOBCKO py.nHo none.­ KocTOB, 11. 1960. ncea.noMa.naxHT H ruryMOOryMBT . HOBB B: OnoBHO-UKHKOBKTe Haxo.nKma B Ji'bnrapHll, TexHHKa, MHHepa.nB 3a 6'b.11rapKll. - Cn. Ji'bJIT. reon . .n-ao, I; 75-77. Cocj)Hll; 64-72. KocTOB, 11. 1993. MHHepa.norHJI. - lli.n. TellHKKa, C<$Bll; naHaiiOTOB, B. 1964. Pa3npe.neneHHe Ha onOBOTO 8 KpeMH­ 734 pp. KOBCKOTO JKene30py.llHO HaxO,IlHlUe B'bB 8p'b3Ka C HJIKOH K3· KoCTOB, 11 .• B. 6peCKOBCKa, H. MHR'Ie&a~HOBa, r. H. MeHeHKll Ha na.neoreorpacj)cKKTe ycnoBKJI B paiioHa. - Cn. KHpoa. 1964. MKHepa.nHTe a Ji'b.11rapu. - C .• lli.n. liAH; Ji'bJir. reon . .n-ao, 1; 65-73. 540 pp. neTPOB, n. 1993. MKHepa.noo6p83yBaHe OT C'bBpeMeHHKTe KyHOB, A. 1986. MHHepa.norHJI H 30Ha.JTHOCT Ha BTOpH'fHHTe K>lKHo6'bJirapcKK XK.IlPOTepMH. - B: PaJBHTKe Ha 6'bnrapc­ KB8pUHTH OT ceaepo3ana.nH8Ta 'faCT Ha nepHcpepHliTa Ha KaTa MKHepanorKJI. C.; 46-47. 6opoBHWKaT8 aynxaHo-Tenoncn .nenpecu.- ABTopecpe­ llocnenOB, r. 1963. 0 npo6neMe KOHBepreHUHK B neTPOrpa­ paT H8 KaH,Il . .llHC.; 30 C. cj}KK K reonorKK. - B: C6. .. npo6neMbr MarMbr H reHe3Kca KyHoB, A. 1991. BTopK'IHH napUHTM oT ceaepOH3TO'fHaTa K3BeplKeHHblll nopo.n", MocKaa,I13Jl. AH CCCP, 260-271. nepHcj)epHll Ha 6opoaHWnUiaynnHcJtH paiioH. I. reonoro­ Pa.noHoaa, T. 1960.113cne.naaHKJI B'bpxy MHHep8nOlKKKJI c'bc­ nCTPorpa4K:K8 X8p8KTepRCTHJta H8 XK.IlpOTepMa.JJHO H3Me­ Taa H OKOnopy.llHHTe H3MeHeHHll Ha M8.1llKapOBCKOTO no· HeHH 30HH. • reoXHM., MHHepa.n. H nCTPQn., 28; 46-72. nHMeTanHo Haxo.nHme B I13TO'fHHTe Po.nonH. - Tp. reon. KyHoB, A. 1993. KoHaepreHUHJI Ha MHHepa.nHTe OT rpynan li'bJirapHll, cep. reoxHM. H non. H3K., I; 115-197. Ha a.nyHHTa H HeroBHTe CTP)'IC'T)'PHH aHa.JJ03H. - B: Pa3BH· Pa.noHoaa, T. 1966. 3oHanHOCT Ha xH.npoTepManHHTe MeT8· THe Ha 6'bJir.MKHepa.n .• C.; 33-34. MOpcj}KTH H MliCTOTO Ha a.nyHHTOBHTe KB8pUHTH B TIIX npH KYHOB, A. 1994. BTopH'fHH xaapURTH OT ceaepoH3TO'fHaTa C. llonKHUH, llaHarK>pCKO. JiJB. reon. H-T, 15; 129-143. nepHcj)epHll Ha 6opoBHWKHJI aynnRCKH paiioH. II. MHHe­ Pa.noHoBa, T. 1969. 3oHanbHOCTb nponKnHTOB H BTOPK'fHbJX pa.norHll H 30Ha.JJHOCT. • reoXKM., MHHepan. H neTPOn., 29; KBapUKTOB KpaceH·lleTenoBCKOii 30Hbl ll8HarK>pCKoro 17-36. paiioHa. - reon. PYJlH. MeCTOp .• 2; 53-63. KyHOB, A. 1994. BTopH'fHH xaapuHTH oT ceaepoH3TO'IHaTa Pa.nOHOBa, T. 1970. nponHJlHTH H BTOPK'fHH KBapUKTH OT nepHcj}epHll Ha JiopOBHWJtKJI aynnHCJtK paiiOH. lll. reHe· UeHTPa.JJHOTO Cpe.nHoropHe H TeXHHTe C'bOTHoweHHll c 3HC H npaKTH\feCKO 3H8'feHHe. • reoXHM., MHHepan. H neT· Me.nHo-nKpKTHKTe opy.niiBaHKll. - l13a. reon. K·T, cep. reo­ pon .• 29; 37-44. XKM., MHHepan. K nCTPOrp., 19; 179-187. KyRoB, A. 1996. K8KOKCeHHT, xopxHT, XHHc.na.nHT H nnYJ1.16o­ P8.noHoaa, T. 1972. AnyHHT OT BTOPH'fHKTe KapuKTH Ha Cna­ ryMHT OT HaxO.IlHlUC qan8, linO'fHH Po.nonH. - reoxHM., xKeBcKoTo py.nHo none. - I13B. reon. H-T, cep. reoxHM., MHHepa.n. H OCTPOn., 31; 61·64. MKHepan. H OCTPOrp, 21; 85-96. KyHOB, A. 1999. H8X0.11H1Ue "qan8"- npRMep 38 Jn8THo-no­ Pa.noHoaa, T. 1973. MeTacoMaTK'fHH K3MeHeHHll Ha cKanHTe nHMeTa.JJH8 enHTepMa.JJH8 Opoll&a OT HHCKocyncj}H,IleH (8Jly· a 3ae3.nencKHJI py.neH paiioH. - I13B. reon. H·T, cep. reo­ n8p·cepHUHTOB) THO. • MHHHO .neno H reon., J-2; 50-54. XKM., MHHepan. H neTPOrp., 22; 123-140. KyHoB, A., K. 6enHB8HOB. 1992. HoaH .llaHHH 38 noKanHH Me· Pa.noHoaa, T ., Jl. CTecj)aHOB. 1974. llHpocj)HnHT OT MC.IlHOTO T8COM8THTK B PoceHCKKll naneoayJIKaH. - B: lloCTKlKeHKII HaxO.IlHlUC Acapen, naHarK>pCKO. B: MHHeporeHe3HC, c .. H 38.118\fH Ha 6'bJir.MHHepan. K nCTPQn., C.; 49-50. TexHHKa; 219-227. KyHoB, A., K. 6enHB8HOB. 1996. BTopH'IRH napUKTH a ueHT· PawKoa, P. 1962. )lHacnopoaH BTOPK'fHH KBapUHTH a 3eMnH­ pa.nHaTa 'faCT Ha liaxa.nlKHWJtOTO py.nHo none. - Cn. Ji·bnr. meTo Hac. CnaxHeao, XacxoacKo. - Cn. Ji'bnr. reon . .n-ao, reon . .n-ao, 57, 2; 75-78. 3; 263-274. KyHoa, A ., M. BenHHOBa, JI. llYHeB. 1981. HoBble cae.neHHll o CMKpHOB, B.l1. 1960. KoHaepreHTHOCTb KOn'fe.naHHbLX Mec­ BTOPK'fHbtx xaapuHTaX B BoCTO'IHbiX Po.nonax. - )loKn. TOpolK,IleHKii. - BecTHKK MrY, cep.IV, reonorHll, 2, liAH, 34, II; 1533-1536. 19-26. KyHoa, A., M. BenHHoaa, JI. llYHeB. 1986. CZ>occj)aTHble H YcTKeB, E. 1961. CZ>. 10. JleBHHCOH -JieccHHr H HeKOTOpbre cynbcj}aTHble MKHepanbl CnaxHeBCJtoro py.nHoro non11. - npo6neMbl coapeMeHHoii neTPorpacj)HH. - I13B. AH B: JlocTHlKeHHll 6onr.reon. C., Tex.HHita, 144-1.49. CCCP, cep. reon., 3; 3-35. KyHOB, A., B. 11BaHOBa-naHaiiOTOBa. 1976. HOBH .118HHH 3a re­ UaeTaHoB, P. 1979. 3oHanHoCT Ha nponHnKTHTe H BTOpH'fHH ­ onOlKKHll CTPOelK K npOliBHTe Ha XH.IlPOTepManHa .neiiHOCT Te KBapUHTH a 3H.napoacKoTo py.nHo none. - ro.n. CY, 8 H3TO'IHHJI KOHTaKT Ha rpaMaTHJtOBK.Kll HHTPYJHB. • reo· reon.·reorp. cj}aK., KH. 1-reon., 73; 136-146. XKM., MHHepan. K OCTPOn., 5; 168-175. UaeTaHOB, P. 1979a. XH.npoTepMa.nHH MencoMaTHTH OT KyHoB, A, JI. Kaueaa. H. PaiiHOB. 1997. EnKTepManHH aprH­ B'bpnH6pelKKOTO py.nHo none. - ro.n. CY. reon.-reorp. nH3HTK H C'bn'bTCTBalUK rH OKOnopy.llHH H3MeHCHKll 8 RO· cj)ax., KH. 1-reon., 73; 146-158. nHMeTa.JJHOTO HaxO.IlHlUe 6pllcToao, lliTO'fHH Po.nonK. - UaeTaHoB, P. 1982. AprKnH3HTbl H BTOpH'fHbre KBapuHTbl a reoXHM., MHHepa.n. H OCTPOn., 32; 67-84. no3.nHenaneo3oiicKKX aynxaHH'feCKHX nopo.nax 3ana.nHbiX KYHOB, A., E. MaH.noaa. 1997. CynepreHHK MHHepanH OT Au­ 6anxaH (6onrapH11). - )loKn. liAH, 35, 10, 1411 - 1413. Ag HaXO.IlHlUe 06H'IHHK (I13TO'fHK Po.nonK). - Cn. Ji'bnr. UaeTaHOB, P.,l1. CnaBKnOB. 1980. rH.npoTepManbHble MeTa· reon . .n-ao, 58, I; 19-24. coMaTK'IecxHe cj)opMaUHH K K>ry OT r. COJononll, IOro­ KyHoa, A., P. Haxoa. 1996. KKceno-cyncj)aTeH H a.nynap-cepH· BocTO'IHall 6onrapHll. - JloKn. liAH, 33, 3; 371 - 374. UHTOB THO H3MeHeHHJI 8 paiioHa H3TO'fHO OT C. ropHOCen­ qHn'faxoaa, C. 1993. TexHoreHeH a.nyHHT OT Me.llHO-nHpHTHO­ UH, 11aaiinoarpa.ncKo. - B: HoaoCTH a reonorKJITa Ha 6'bJI· TO H8X0.11H1Ue EnlUKUa - naHarK>pCKH py.neH paiioH. - B: rapHll, C6. pe3K>MeTa, Hay'f. ceCHll, VI KOHrpec firJl; 31-32. Pa3BHTKe Ha 6'b.11rapcxan MHHepanorHll. C .• 59p. KyHoB, A., P. HaKoB. 1997. PeueHTHa MHHepanK3aUHJI a p8iio­ qyxpOB, ez>. 1980. 0 KOHBepreHUKH HCKOTOpbtx fHnepreHHblX Ha Ha c.c. KaMHnCKK .non K JlaM6yx, fuaiinoarpa.ncKo. - B: H rHnoreHHbLX npoueccoa MHHepa.noo6pa3oaaHHll. - B: 50 ro.nHHK cneuKanHocT reonorKll, 106KneeH c6opHKK, llpo6neMbl TeOpHH o6pa30BaHKJI KOpbl BbiBCTpHBaHHll H YHHB. 113.11. "Ca. Kn. OxpH.IlCKK"; 66-69. 3K3oreHHble MeCTopolK.neKHll. MocKaa, HayKa, 101 - 115. 79