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Biodeterioration and conservation status of marble monuments on Crimea W. Krumbein*, E. Bogomolova^, A. Gorbushina',L. Parana', O. Rybalchenko', S. Ryshov\ E. Sagulenko', D. Vlasov' "Car/ von Ossietzky University of Oldenburg,P.O. Box 2503 D- 26111, Oldenburg, Germany ^Chersonesus Musuem-preserve, Sevastopol 335045, Crimea ^St. Petersburg State University, Universitetskaya emb. 7/9, St Petersburg 199034, Russia Introduction The investigations of biodeterioration and conservation of stone monuments in the Mediterranean basin are concentrated mainly in the last decades in the countries and sites on the Mediterranean itself /Anagnostidis et al. 1992 ; Diakumaku et al. 1994; Krumbein , Urzi,1992,1993;Urzi et al.1992,1993,1994/. Crimean ancient Greek colonies - a periphery of antique world are, nevertheless, the integral part of the culture of that period /Minns,1913; Reinach,lS97; Sokolov,1973/. The first Hellenic colonies on the Northern coast of the Black sea were founded in YII- YI B.C. In the words of the famous orator Cicero,they were like a border sewn on the vast expanse of barbarian lands. Stretching along the coast, they never penetrated far inland. The territory of Western and Southern Crimea, adjacent to the sea, belonged to the Chersonesus State. The town Chersonesus of the Tauride (422-421 B.C.),(Greek for peninsula) that was the last Hellenic colony in Crimea, and also earlier settlments : Kalos Limen (IY B.C.) and Kerkinitida (YI B.C.) were the centres of Chersonesus country. The Eastern coast of Crimea was the part of Bosporian Kingdom, which united ancient cities on both sides of contemporary Kerch strait. These settlements appeared in YI B.C. as independent and then, in 480 B.C. they united. Pantykapea was the centre of antique Bosporian Kingdom and situated on low-lying terraces, on slopes and the top of mountain Mythridad, (now Kerch). Fig. 1. Archeological excavations on Crimea have been carrying out since last century. Investigations and creation of detailed appearance of most of the antique towns are impeded by contemporary buildings. Transactions on the Built Environment vol 15, © 1995 WIT Press, www.witpress.com, ISSN 1743-3509

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Biodeterioration and conservation status of

marble monuments on Crimea

W. Krumbein*, E. Bogomolova^, A. Gorbushina', L. Parana', O.

Rybalchenko', S. Ryshov\ E. Sagulenko', D. Vlasov'

"Car/ von Ossietzky University of Oldenburg, P.O. Box 2503 D-

26111, Oldenburg, Germany

Chersonesus Musuem-preserve, Sevastopol 335045, Crimea

St. Petersburg State University, Universitetskaya emb. 7/9, St

Petersburg 199034, Russia

Introduction

The investigations of biodeterioration andconservation of stone monuments in the Mediterraneanbasin are concentrated mainly in the last decades inthe countries and sites on the Mediterranean itself/Anagnostidis et al. 1992 ; Diakumaku et al. 1994;Krumbein , Urzi,1992,1993;Urzi et al.1992,1993,1994/.

Crimean ancient Greek colonies - a periphery ofantique world are, nevertheless, the integral part ofthe culture of that period /Minns,1913; Reinach,lS97;Sokolov,1973/. The first Hellenic colonies on theNorthern coast of the Black sea were founded in YII-YI B.C. In the words of the famous orator Cicero,theywere like a border sewn on the vast expanse ofbarbarian lands. Stretching along the coast, theynever penetrated far inland. The territory of Westernand Southern Crimea, adjacent to the sea, belongedto the Chersonesus State. The town Chersonesus of theTauride (422-421 B.C.),(Greek for peninsula) that wasthe last Hellenic colony in Crimea, and also earliersettlments : Kalos Limen (IY B.C.) and Kerkinitida(YI B.C.) were the centres of Chersonesus country. TheEastern coast of Crimea was the part of BosporianKingdom, which united ancient cities on both sides ofcontemporary Kerch strait. These settlements appearedin YI B.C. as independent and then, in 480 B.C. theyunited. Pantykapea was the centre of antique BosporianKingdom and situated on low-lying terraces, on slopesand the top of mountain Mythridad, (now Kerch). Fig. 1.

Archeological excavations on Crimea have beencarrying out since last century. Investigations andcreation of detailed appearance of most of theantique towns are impeded by contemporary buildings.

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196 Architectural Studies, Materials & Analysis

Chersonesus of the Tauride , which outlivedHellenistic, Roman and Bysantine epoches and wasruined in 1287 by tartars , is the exception . Nowthere is a large archeological museum-preservationon it's territory,where even today anyone can strollalong the ancient streets, visit the antique theatre,admire the polychrome mosaics floors in templesdecorated with marble relief compositions,colomns. Figs. 2,3.

The most valuable exhibits, which were discoveredin the antique settlements and in necropolises onCrimea, are kept now in museum' collections of Russiaand Ukraine. Other monuments are awaiting for theirdiscovery. The aim of our work was to investigateconservation status with special respect tobiodeterioration , of marble and limestone monumentsbeing exposed outdoors in archeological sites inCrimea in comparison with monuments of Mediterraneancountries. The two directions of scientificinvestigations were followed:

(1) Field experiments:- macroscopic observations in situ of signs of

deterioration, classified as biological attack ;sampling; estimation of effectivity of protectivetreatments,that have been already used to the moment;

(2) Lab experiments:- recognition and identification of marble infected

by black fungi; isolation and identification of blackfungi destroyed marble ; studying of somephysiological characteristics of isolated strainsin pure cultures; modelling experiments on marbleslabs.

Materials and methodsSamplingField investigations and collecting of samples

were carried out during the period of autumn-spring-summer seasons of 1993 - 1994. Altogether threeexpeditions took place, one of which consisted ofscientists from Russia, Germany, Ukraine.

We carried out macroscopic visual observationsand documented photographically signs ofbiodeterioration and alteration of stone monumentsduring the field investigations.

The remains of buildings in settlement,the ruinsof marble basilics of Y, YI, YII centuries, medievalpolychrome mosaics, marble columns and sculptures inthe museum garden were investigated in Chersonesus.Some of marble sarcophagus and stelaes, exhibiting

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Architectural Studies, Materials & Analysis 197

outdoors and under the roof were the objects of ourstudies in Kerch and Feodosia. Also the ruins offormer settlements around Pantykapea, such asMyrmeky, Tiritaki, Nymphea were investigated.

Marble and limestoneAccording to historico - archeological data ,

Crimean limestone and marble imported from islandProoonnessus were used for creating monuments andbuildings in antique Crimea.

As the result of microbiological analysis, somebacteria, algae, lichens and also fungi, especiallyblack fungi that are considered to be the main agentsof marble destruction, were discovered on CrimeanMonuments made of marble and limestone.

For isolation of fungi some replies on stickTESA films and agar- print technique were used fromthe surface of stone monuments as nondestructivemethods. In lab the isolation of fun^i from pieces ofdamaged marble was conducted with the help ofsterilized injeotional needle and binocularmicroscope. The identification of black fungi wascarried out by reference books of Ellis, 1993.Different physiological tests of fungi were conductedsuch as acid production ( Krumbein, 1992; Krumbein etal. 1993) , ESR - speotroscopy studies of melaninssynthesis ( Gorbushina et al. 1993, Soukharjevsky etal.1994), resistance to heavy and transition metals( Mamonova et al. 1992 ) and utilization of differentcarbon and nitrogen sources .

The methods of batch cultures , includingcultivating on marble slabs, on Petry dishes and inflat- bottom microtiter plates were used.

Experimental methodsThe fluorescence and optic microscopy, SEM/ TEM

analys i s, transmi tt i ng and reflect i on photometryTv- image analysis, ESR spectroscopy were used.

Results and discussionMacroscopic observation of principal destruction

patterns showed agress i ve i nfl uence of bothenvironmental and microbiological factors that istypical for Mediterranean countries (Krumbein et al"1992, 1993; Urzi et al. 1992, 1994; Zezza ,1994). Themain decay factors of environment are : marine spray,atmosphere sulphatic agress ion and other technogenicpollution in industrial cities (Sevastopol, Kerch) ,seasonal cycles of freezing - melting, alternating

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198 Architectural Studies, Materials & Analysis

repeatedly during the day; strong autumn winds andflooding of some remains owing to rising of sea levelover 5 meters since antique tine.

As for biodeterioration patterns, on thesurface of marble, that has been exposed outdoors fora long time, the associations of fungi, lichens andalgae are forming. The depth of fungal penetrationinto marble depends much on structure and compositionof substratum, and also on it's age and time ofexposition outdoors. On many samples it reached5-8 mm. At the same time cracks that are parallel thesurface, are often filled with green-blue algae, thatcan find there necessary moisture and protection fromsurplus sun light. It should be noted that thechemical treatments such as fungicides, consolidants(KO-9, KO-15 ), hydrophobic films ( Wacker H, 290A)used for protection of marble monuments duringpast decades in Chersonesus were effective only inthe time period 0.5- 1 year. As the typical signs ofdeterioration of marble by fungi the presence on it'ssurface of hyphal structures and microcolonies(Staley et al. 1982) , sometimes stretching intosubstratum, can be mentioned. Fig. 4. The crust,consisting of different structures of fungi andothers microorganisms and also of deposits ofminerals having biological origin was discoveredon many samples of antique marble. We observedlimestone ruins in Pantykapea, covered with 5-10 mmlayer of deposits on which the boundaries of thailornof endolythic lichens could be clearly seen. On thefragments of monuments that were excavated atdifferent years, the obvious boundaries of sectionscan be seen. They evidence about more favourableconditions for exhibits conservation, especiallymosaics, under the ground as was early pointed bySaiz-Himenez et al. 1991.

Marble samples is characterized by structuralheterogeneity, the maximums in distribution of poresthat were determined by the method of mercuryintrusive porometry are at 0.3-lmkm and 5-7mkm ,Kumzerov et al. 1994.

We managed to isolate more than 60 strains ofhyphomycetes from the surface of damaged Proconessusmarble. They belong to different taxonomic groups.Among them there are widespread soil fungi fromgenera Alternaria, Botrytis, Hyphoderma,Cladosporium,Penicilium, Aspergillus, Phoma, Pestalotia, Fusarium.

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Architectural Studies, Materials & Analysis 199

Nearly half of all the isolated strains had nospeculation or formed only chlamidospores in theconditions of pure cultures. All investigatedmicromycetes had pigmentation, and nearly 90% ofstrains were dark colored and contained"melaninsin the cell walls concern TEM and ESR analysisme most interesting are the fungi that r.an beclassified as black yeasts *De Hoog et al. 1977)causing intensive colour changing and slowly "hutpersistently like stealth viruses destroying ofmaterials .Fig.5. Yeast - like melanin containingfungi can be probably considered as the constantinhabitants of stone surface. Thev are well adaptedLO the existence on such mineral substratum asmarble and have approximately 100 times highestthe minimal inhibiting concentrations to metal ions<,han museum cultures.

t he fung i i nhab i t i ng mar bl e andoiodeteri oration status of Crimean monuments weinvestigated were compared to those previouslystudied in the western Mediterranean Basin . As asummary a general line of biological attack <eems tobe existing for all monuments in the Mediterraneanclimatic range.

The present status of this work is in beginningso we are intend to focus our future reseach on themechanisms involved in black fungi and mineralsinteraction in order to develop and apply effectivetechnologies for the conservation and restoration nfmar b 1 e monume nts.

^ Tt,T support by VW-Stiftung, grant 1/68 491 andof INTAS , grant INTAS - 93 - 1059, is gratefullyacknowledged.

REFERENCES

Anagnostidis K. , Germann O.K. , Gross M(\rumbein W. E. , Zisi 3. , Pantazidou A., Urzi C , and&,agari ML 1992. Biodeterioration of marbles, of therarthenon and Propyleae, Acropolis, Athens -associated organisms, decay, structures andtreatment suggest i ons. I n the conser vat i on ofmonuments in the Mediterranean Basin, Proc 2nd IntSymp. , Geneva, pp. 305-325.

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Diakumaku E. , Gorbushina A. A. , Krumbein W. E. ,Panina L. K. , Soukharjevski S. 1994. Black fungi inmarble and limestones - an esthetical, chemical andphysical problem for the conservation of monuments.Proc. 2nd Int. Syrnp. b i ode teri oration & bi ode gradation•-SEM. Sevilia,Spain.

Ellis M. B. Dematiaceoue Hyphomycetes. 1993.Commonwealth Mycological Inst. Kew,Surray. England.

Ellis M. B. More Dematiaceoue Hyphomycetes. 1993.Commonwealth Mycological Inst, Kew ,Surray. England.

De Hoog,G. S. , and Hermanides-Nijhof, E. J. ,1977.The black yeast and allied Hyphomycetes. Stud. Mycol.15,1-221.

Gorbushina, A. A. , Krumbein, W. E. , Hamrnan, C. H. ,Panina, L. K. , Soukharjevski, 3. , and Wollenzien, U. ,1993. Role of Black Fungi in Color Change andBiodeterioration of Antique Marbles. GeomicrobiologyJournal, 11:205-221.

Krumbein, W. E. , 1992. Color changes of buildingstones and their direct and indirect biologicalcauses. Proc. 7th Int. Cong. Deterioration andConservation of stone, ZNEC, Lissabon, pp. 443-452.

Krumbein, W. E. , and Urzi,C. 1992. Biologicallyinduced decay phenomena of antique marbles - Somegeneral considerations. In:Conservation of monumentsin the Mediterranean Basin, Proc. 2nd Int. Symp. ,Geneva, pp. 219-235.

Krumbein, W. E. , and Urzi,C. 1993. Bi ode teri orationprocesses of monuments as a part of global climatechange. In: Conservation of stone and other materials,London, pp. 558-564.

Krumbein, W. E. , Diakumaku, E. , Petersen, K. ,Warscheid, T. , and Urzi, C. 1993. Interactions ofmicrobes with consolidants and biocides used in theconservation of rocks and mural paintings. Proc.:Conservation of stone and other materials. Paris,France.

Kumzerov Yu . , Krumbein W. E. , Kurochkin V. E. ,Panina L.K. , Soucharjevsky 3. 1994. Monument stoneidentification: spectroscopy, heat capacity,porosity.Proc. 23 Intern. Oonferens. "Archaeometry"., METU,Ankara,Turkey.

Mamonova I. V. , Kurochk in V. E. , Paramonov G. A. ,Petrjakov A. 0. , Panina L. K. 1992. The determination ofthreshold concentrations of biocides for museumexhibits by a photometric method. Intern.Bi ode teri oration & Biodegradation. 30:303-312.

Minns E.H. 1913.Scythians and Greeks. Cambridge.Reinach S. 1892. Antiquites du Bospore

Cimmerien. Paris.

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Saiz - Jimenez C. , Garcia - Rowe J. , Rodriguez-Hidalgo J.M. 1991. Biodeterioration of polychromeRoman mosaics. Intern. Biodeterioration., v. 2R,pp. 65-79.

Sokolov G. 1973. Antiquites on Black Sea. Avrora.Leningrad.

Soukharjevsky S. ,Gorbushina A. A. , Krumbein W. E.Panina L. K. 1994. Recognition and identification ofmarbles and marble infecting black fungi using E3Rtechniques. Proc. 3nd Intern. Symp. Conservation ofmonuments in the Mediterranean Basin, eds. V. Fassina,H.Ott, , F. Zezza. pp. 335-341.

Staley, J.T. , Palmer,F., and Adams, J.B. 1982.Microcolonial fungi: common inhabitants on desertrocks ? Science, 215:1093-1095.

Urzi, C. , Krumbein, W. E. , and Warsheid,T. 1992.On the question of biogenic color changes ofMediterranean monuments ( coating- crust -microstromatolite - patina - scalbatura - skin - rock- varnish). In:The conservation of Monuments in theMediterranean Basin, Proc. ;?nd Int. Svrno. ,Geneva,pp. 397-420. " ^

Urzi,0. , Krumbein, W. E. , Criseo, G. ,Gorbuchina,A. A., Wollenzien U. 1993. Are color changes ofrocks caused by climate, pollution, biological growthor by interaction of the bhree? Conservation of^^toneand other materials., London, pp.279- 286.

Urzi C. , Krumbein W. E. , Lyalikova N. ,Petushkova Ju. , Wollenzien U. , Zagari M. 1994.Microbiological investigation of marbles exposed tonatural and antropogenic influences in nothern andsouthern climates. Proc. 3nd Intern. Symp.Conservation of monuments in the Medit-.errenean Basin.eds, V. Fassina ,H. Ott. , F. Zezza. pp. 297-304.

Zezza F. 1994. Marine spray and pollutedatmosphere as factors of damage to monuments in theMediterranian coastal environment. Proc. 3nd Int. SympConservation of monuments in the Mediterranean Basin.pp. 269-273.

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Fig. 1 The position of the former Hellenic colonieson Crimea:1 - Chersonesus of the Tauride,2 - Pantykapea

Fig.2 Chersonesus of the Tauride.View on the temples"Basilica in basilica"

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Fig. 3 Medieval polychrome mosaic from Crimea.

Fig.4 Fragment of the surface of ancient marblemonument damaged by yeast-like black fungi.

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Fig.5 Black fungi strain Ch56 isolated from marblecolumn.

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