Water Soluble Salts in Degradation Processes of Stony Architectural Monuments in the Upper Silesia

Geological Quarterly, 1998,42 (2): 209-220

Water soluble salts in degradation processes of stony architectural monuments in the Upper Silesia

Malgorzata LABUS

Labus M. (1998) - Woter soluble sails in dcgrndation processes of stony nrchiteehuui monuments in the Upper Silcsia. Geol. Quill1., 42 (2): 209-220. WnrsUlwa.

The study goals were aimed 111 obtaining infonnation on corrosion products of rocks used in architectural monuments in the Upper Silesia. Samples from four monume ntal buildings located 01 margins of the Upper Silesia were IlSCd in the study. Three of them nrc located in the western pill1 of the region: a castle at Tasuk, a grain elcvatorat Stare Gliwice and castle ruins III Chud6w, and one is located in the eastern part (a cn.~ tle 01 6(;dzill). Samples of rocks from area significantl y lcss affected by atmospheric COlltnmillDtion (castle ruins at MimII' in the 1um Kmkowsko..czC5tochowska region) were analp.ed for comparison. Samples of sandstone, limestone and granitoids were analY1.ed with X-ray dirfraCLornetry and microstructurnlll1lalyscs. Cnemical analyses were conducted for aqucOllS solutioos of powdered rock samples. The following compounds wert detected in the sltJdicd snmples: sulphates, chlorides, nitrntes and carbonates. Total snUnilY in the samples of sandstone lind limcslone Wll.~ calculated, based on the resulls ofche mical analyses and X-my difCractolTlCtry . The highest salinity was detected in the samples from lhe castle ruins al Chud6w.

Mu/gunil/U LahU.f, Irmifu/e ofAppli ed Geology, Silesilln Tu/micul University, Akodemicko 2, 44- /00Gliwice. Poland (reuived: 3.02./998; ocupltd; 22.02.1998).

Key words: Upper Silesia, architectural monuments, air pollution, building stone detcriOl1ltion, wfttersoluble salts.

INTRODUCTION fonn various types of incrustations: hard and dense (i.e. calcium carbonate), fluffy (sodium sulphate) or glassy (potas sium sulphate). Aqueous solutions of salts migrating in the stony elements Rock corrosion causes increased crystallization salt press of buildings significantly affect weathering processes of these ure. Degradation results from crystal formation and growth, structures. Corrosion mechanisms are based on physical and and from hydration and hydration pressure. Intensity of these chemical processes, with water being their important compo processes, as degrading forces, is associated with salt solution nent, dissolving and Iransporling salts, and occasionally their concentrations, crystallographic form, salt aqueous solubility hydrolysis (S. Skibinski, 1989). Salts soluble in water are coefficient, temperature and frequency of rock wetting and natural components of many rocks, they also fonn in the drying (P. A. Baedecker etal., 1992; B. O. Fobe et al., 1995 ; hazardous amounts in reactions between gaseous atmospheric R. U)fvendahl el ai., 1992; H. Sweewers, R. van Gricken, pollutants and primary components of rocks. Separations 1992). within the rock structure are the most hazardous symptoms of degradation caused by dissolving salts. Presence of dissolvi ng salts reduce rock cohesiveness and compactness, and cause loss of mechanical strength of rocks resulti ng from chemical STUDY SCOPE AND METHODS decomposition of mineral components. The most noticeable symptoms of salt activity are their crystalline efflorescence on rock surfaces, which depending on salt type and quantity, The study was conducted using samples of four monumental objects located at margins of GOP (the Upper Table 1 Samples of construction rucks were collected, so that they possibly represent all lithologic types used in the studied List of samples anatpad uslngspecific methods objects. Additionally, samples of exposed and of protected, for example by vegetation (assuming that affecting processes depend on degree of wetness and rate of rock drying), wall fragments were collected. Outer layers of weathered surfaces, which sover some rocks, and grout were also sampled. Sarnp- Iing of all objects was accompanied by lithological inventory of construction materials. Samples in all objects were collected at elevation oC0.5-2.0 rn above the land surface. Some samples collected at Chud6w were collected at elevation of 0.3 m (lw, 15p, I lg and 18g). Symbols which include sample number and lithological type were used for sample designation. Sandstone samples were designated with letters "p", limestones as letter "w", and eratic blocks as letter "g" (granitoids). Samples of grout were designated with letter "2". List of analyzed samples is presented in Table 1. Because of the specificity of construction materials, in many cases, the amount of colIected samples was insufficient for all planned analyses. This fact complicated interpretation of the msuIts and caused necessity of application of analogies observed macroscopically. Detailed identification of phase composition of rocks and coatings at external surfaces was conducted, based on the results of X-ray diffractometry. X-ray diffractometry was conducted on powdered samples. Analyses were conducted using TUR-61/HZG-4 diffractometer, with monochmmatic, Fe-filtered CoKa radiation in the range of 5-35 0.X-ray diffraction was also used to identify the precipitates formed on glass slides by drying the extracts of soluble components of the rock samples. The XRD patterns were obtained with GEIGERFLEX diffractometer (Rigaku-DenkG using Fe-fil- trated CoKa radiation, Phases were identified based on the reference data in Mineral Powder Diffraction File (1986) and V. I. Mikheev (1957). Precipitates on glass slides were also examined in polarized light using Reichert MF2 optical microscope. Scan- ning electron microscopy (SEW with chemical analyzer was used for seIected samples to characterize composition of subsurface layers. Samples were prepared as cuts both perpendicular and parallel to the external, weathered part of rock sampIes. SarnpIes were carbon-coated. Samples 1w, 1Zp and 3g were analyzed with ISM-5300 SEM equipped with WNK- ISISdetector which allowed to identify light elements (atomic number 24). Other samples were examined with JEOL Super- probe 733 electron microscope equipped with JC XA 733 microprobe. Elements heavier than Z = 8 were identified using w -limestones, p -srmdsmnes, g- eratic bIocks (granitoids), z -gm~ ts energy-dispersive spectrometer. Carbon and nitmgen were analyzed with wavelengthdispersive spectrometer. Quantita- tive analysis of carbon was of limited precision due to carbon-coating on sample surfaces. Silesian Industrial Region), three of them located in western Qualitative chemical analyses included some of the ions part: a castle at Toszek, a grain elevator at Stare Gliwice and @, K', ca2', lMg2', NO?,SO$-, Cl3 in aqueous solutions castle ruins atChud6w and ane located in eastern part (acastIe at Bedzin). For comparison, rock samples from an object of powderd samples. These analyses were aimed at determi- located in a region of significantly less atmospheric pollution nation of soIuble substances, especially salts which are pro- were analyzed. Castle ruins at Mirdw (JucaKrakowsko-Czp- ducts of rock weathering. tochowska) is the object. Water soluble salts in degmdation of stony monuments 211

Fig. 1. XRD pattern: A - sample from a dark incrustation on dolomitic limestone (53~.Bqdzin castle), B - grout sample (62, Chud6w castle ruins), C - sandstone sample (I 4p, Toszek castle) C -calcile, D -dolomite. G -gypsum, Q -quarts Sn -syngenite, Br - brushite, F -frondelite, A - bloditc. Ki -kiiscritc, N - nitmnatrite, R - rulile Dyfdtogmm rentgenowski:A - pr6bki cicmnego nashpienia na wapieniu dolomitycznym (53w, zarnek w Bqdzinie), B - pr6bki zapwy (bz, ruiny zamku w Clrudowie). C - pr6bki piaskowca (14p, 7ame.k w Toszku) C - Ucyt, D -dolornit, G - gips, Q -kwarc, Sn -syngenit, Br- brushyt, F-frondelit, A-astrachanit, Ki-kizwyS Irl -nitron~tryt, R -mtyl

X-RAY DETRACI'OMETRY of thick black incrustation on the rock surface (sample 53w) was analyzed. FoIlowing minerds were identified: dolomite, caIcite, gypsum, quartz and syngenite (&SO4 .CaS04. HzO) various lithological types (Fig. 1A). In &per parts ofa sample 56~only dolomite and differentmonumental objmtsg weeanalyzed with calcite, and ina sample 5Zw - dolomite and small diffractometry. Samples of dolomitic limestones were coI- ofgypsum were identified, respectively. Iecttd in the Bedzin castle. Mineral composition of a sample Fig. 2. Total elemcnt composition: A -dark incrustation on nn external dolomitic limestone surface (54w,Bedzin castle), B -external zone in a dolomitic limestone sample (54w) in a distance oF250 pm rmm the surface (B~dzincastlc), C - polyhalile crystal MgK2Cm(S@)4 4 2H70,with admixturn of iron and mangancsc oxides in a sandstone mple(2p, Chud6w ca~tlcruins), D -incrustations on sandstone (6p. Chud6w castle ruins). 1E - incrustations in a limcstane sample (9w, Chuddw castle ruins), F- external surface oClimestone (I I w, Taszek castle), 6: -surface in sandsione (45~.Mjr6w castle ruins) Zbimy sklad pienvimtkowy: A - ciemnego naskorupienia na zewwtrznej powierzchni wapienia dolomitycznego (54w, zamek w Bedzinie). B - zewnetnnejstrery pr6bki wapieniadolomityuncgo(S4w)w odteg4o$ci25(3podpowienchni (mrnckw Bedzinie),C-krysaalu polihlihalitu MgK2&2(S04)4 2H20 wnz z dornieszkumi 1lenk6w Fe i Mn w prdbae piaskowca (2p, miny mmku w Chudowie), D - naskompiefi na piasknwcu (6p, ruiny zamku w Chudowie), E - naskompieit w pr6bce wapienia (9w. miny zamku w Chudowie), F - zewn~umejpowienchni wapienia (I lw, zamek w Toszku), C - puwierzchni piaskowctl(45p, ruiny zamku w Mirowie)

X-ray diffractometry was used to anaIyze sampIes of brushite (CaHPQ4 . 2Hz0), dicalcium phosphate dihydrate sandstone. limestone, granitoids and construction grout, col- (DCPD), is associated with alteration of bones (A. Bolewski, lected in the Chud6w castle ruins. In sample lp quartz, feld- 19821, which in this particular case may be related toold grout spars (mostiy albite), and also illite, chlorite, gypsum and technology, where often not entirely burnt animal bones were kieserire were identified. Analysis of the external strongly added to grout. Though frondelite, an anhydrous phosphate weathered portion of this sample indicated presence of quartz, MnFe3[P04]3[0H]5, typically occurs with goethite in oxidn- calcite, gypsum, rnirabilite (NazSOd - 10HzO) and sylvine. In tion zones. Potassium in the grout sample 72 may be related sample 6p only quark, feldspars, clay minerals (kaolinite and to appIications of charcoal in old methods of lime calcination. illite) and gypsum were identified. In samples of limestone, The sample 23p, colIected in the Stare Gliwice grain in addition to their predominant cornpanent calcite, small elevator, is composed entirely of quartzite and no other, than quantities of quartz and also hanksite (9Na2S04 . 2Na2C03- quartz, minerals were detected. X-ray diffractometry of lime- KCI) in samples Iw and 4w, or hexahydrite in samples 5w, stone (24w) also did not indicate any contaminants or pro- were identified. Composition of two granitoid samples was ducts of rock weathering (exclusiveIy pure calcium analyzed in samples 2g and 3g. In addition to minerals typical carbonate). In a sample 2 1g on1 y typical natumlly occurring for these rocks (i.e. quam and feldspars) small quantities of components of granitoids were detected. gypsum were detected. Calcium carbonate and quartz are In samples collected in the Toszek castle, in addition to major minerals of the grout used in the Chud6w castle. X-ray naturally occurring sandstone components like quartz, feld- diffractometry also indicated presence of potassium nitrate spars, muscovite, biotite, occasionally chlorite, the following (KNO3) in the sample 72, and of gypsum, brushite and fron- salts were identified: delite in the sample 62 respectively (Fig. 1B). Presence of Water soluble salts in degndation of stony monuments 21 3

- gypsum CaS04 - 2H20(incrustation in a sample I lp Table 2 and in samples 12p and 14p), Mineral compdtion obtained from XRD diflractometry - thenardite Na2S04 (1 2p), of precipitates formed on glass slides by drying the extract of soluble - szomolnoki te (FeS04 . H20(1 2p3, cornponenis (w ncertain components given in paranthesis) -themonatrite NazC0y HzO (incrustation in 12p), - hexahydrite MgS04 - 6Hz0 (12p), - syIvine KC1 (1 2p), Sample -kieserite MgS04 - H20 (14~1, symbol Mineral composition - nitronatrite NaPQ (14p), -blodite Na2Mg[S04]2 -4H2O(I4p). lp gypsum, halite, northupik -MgC03 . Na2CCh. NaCl 14p in 12p kaolinite, illite (chlorite, rnetnaluminite - A14[SO4(O~lo] Diffractogrnm of a sandstone sample is presented 5Hz0, fairchiidite - K2Ca[C03]~) Figure IC. 14p illite, Mg-chamosite, muscovite Two samples of the same Iimestone (1lw) from the To- 2 1p gypsum. kaolinite. illite (fairchildite - &Ca[C@]a) szek castle were analyzed. In addition to calcite and gypsum, 1 lww gypsum (mxes ofsulphates) 1 lwz gypsum (traces of other su1phak.s). kaolinite. illite. smectik small quantities of silica were detected in one of the samples, 432 gypsum, calcite and blod ite (Na2Mg[S0412- 4H20)was detected in the other sample. ww - intenId pmt of limeston& wz -external part of limestone; other Sandstone samples collected in the Mirbw castle ruins explanations as in Table 1 (41p and 42p) are composed mostly of quartz and small quantities of gypsum. Only one sample of limestone 34w was X-RAY MICRODIFFRACTOMllTRY analyzed, which indicated only presence of natural component calcite. Additionally, two macroscopically different grout samples were analyzed. In sample 422 a greater amounts of quartz, calcite and gypsum were detected. Within a scope of X-ray-structural analyses, composition A dolomitic limestone sample 51w indicates pIates of of precipitates formed on glass slides by drying the extracts gypsum and dust grains composed of clay and silica. A cut of soluble components of some rock and grout samples was perpendicular to an external surface was analyzed in a do- determined. Results of these analyses are presented in Table lomitic limestone sample 54w aIIowed for detailed. It analysis 2. Precipitates, from powdered rock samples (sandstone, of a dark incrustation on the sample surface which thickness limestone, granite) as well as grout and brick samples on glass approached 3-4 mm. Industrial dust, gypsum, sylvine (KCl) slides were analyzed in polarized light with Reichen MF2 and grains of clay minerals were identified in the sample. optical microscope. These samples indicate crystals of gyp Gypsum becomes a dominant component of the incrustation sum,halite, and secondarily crystallized carbonates (PI. I and from a depth of 250 Krn to an interface with limestone (inter- 11). crystallized crystaIs of gypsum and limestone). Gypsum and

Table 3

Results of chemical analyses d aqueous solutiom ofs&tonc samples collected from objerts at Chudbw, Stare Gliwice, Twxk and Mirdw

Cations Anions Sample [miliequivalcntdgsample] [miliquivdentdg sample] Deficiency symbol anions [A)/ cations (K) ------NXI+ K* ca2' M~~ cations tad so? CI- anions total IPW 44.38 17.39 11 1.81 20.31 198.89 31 '74 31.74 52.Q7 115.55 A IPZ 21.44 19.76 349.49 - 3W.69 3.6 1 147.04 53.17 203.82 A 12pw 7.50 9.67 9.29 - 26.46 2.25 11.93 5.59 19.77 A 12pz 3.66 25.23 8.17 3.29 40.35 8.56 17.45 7.36 33.37 A 15pw 0.19 1.92 6.90 1-72 l0.n 4.72 13.42 - 18-14 K 15pz 9.62 21 -25 1831-61 107.28 1969.76 2.40 1288.08 + 1290.48 A 2lpw 0.17 122 6.55 6.55 14.69 - 14.29 - 14.29 A zip 0.62 223 16.87 4.60 24.32 + 14.76 - 14.76 A 41 pw - 0.08 6.10 - 6.18 - 1958 - 19.58 K 41pz 0.38 0.42 35.38 - 36.18 - 20.09 - 20.09 A 41pk - 0.50 40.16 - 40.66 - 31.60 - 31.60 A 42pw - 0.70 11.86 - 12.56 - 15.90 - 15-90 K 42pz 0.35 0.97 18.25 - 19.57 - 13.06 - 13.06 A pw - intcrnal part of sandstone. pz -external pan of sandstone, pk -contad betyeen sandstone and Limy grout 214 Malgorzata Labus

Table 4

Radts ofchcrnical analyses OF aqueous solutions of llrnestmesampIes collected from objects at Chud*,Stare Gliwiw, Toszck and Mildw

Cations [miliequivalentslgsample] Anions [milicquivalentslg sample] Deficiency Samplc nnions(A)/ symbol cat.'ionsIK) ------sd- C,- anions total Iww 7.42 257 16.75 - 26.74 11.27 6.23 6.78 24.28 A lwz 26.14 8.3 1 279.60 27.87 34 1.62 50.70 282.45 20.89 354.M K 4ww 0.33 0.41 5.45 - 6.21 - 1.69 0.67 2.36 A 4wz 0.46 0.70 8.45 - 9.61 2.38 0.70 - 3.08 A 22ww 3.71 7.58 11.36 6.24 28.89 17.52 5.03 3.78 36.33 K 22wz 6.56 9.76 5.078 20.98 88.08 61.50 43.63 5.69 112.82 K 24ww 13.00 8.W 68.82 5.28 96.09 65.34 46.01 1123 122.58 K 24wz 20.78 17.46 323.73 20.16 382.13 138.61 451.13 17,68 607.42 K 43ww 0.82 0.35 10.29 3.36 14.85 7.20 926 - 16.46 K 43wz 3.09 2.13 168.15 - 173.37 5.05 195.29 - 200.34 K S4ww 29.82 9.23 133.1 1 3728 219.44 69-18 164.47 27.32 260.97 K 54wz 40.95 15.40 178.95 60.38 295.68 101.34 214.22 33.83 249.39 K 56ww 17.63 8.03 68.36 49.81 143.83 1 19.12 26.10 58.1 6 203.38 K S6wz 18.76 8.49 1 10.21 40.32 177.78 125.1 1 71.47 53.99 254.57 K

Explanations as in Tnble 2

chlorides KC1 and NaCl are also present in the limestone MgS04. 7-0, since typical for these minerals microstalac- (Figs. 2A and B). tites were detected in the microscopic analysis. In a granite sample 3g, gypsum efflorescence was detected in fractures between crystals of quartz and feldspars. These localities enhance accumulations of dust pollutants. Similarly te other rocks X-ray pattern impulses caused by chlorine ions Accumulations of clay minerals, products of feldspar are present and their amp1 itude is related to potassium content, weathering, were often observed in sandstone intergranular which might reflect the presence of sylvine. pores. Sandstone cement often contains significant amounts ofiron oxides, thoughx-ray diffractometry indicates that they are accompanied by sulphur. In near-surface zones of the STARE GLlWICE analyzed samples elevated concentrations of sulphur, chIorine, potassium and calcite were observed. In sample 2p Quartzitic sandstone (23p) is relative]y less weathered. local accumulations of manganese were detected. Remaining SEM pictures display a smooth external surface without mat- X-ray diffractometry background impulses are prcdud by ings and efflorescence typical for secondaty minerals. Some aluminosilicates v~g.ZC). other quartz grains are slightly fractured. In deeper zones, at Incrustations characterized by elevated concentrations of a distance of tens of micrometres from the surface, small iron and sulphur were found in sandstone 6p, which may quantities of clay minerals accumulate, where also elevated. indicate presence of iron sulphate (FeS04 . HzO)- szomol- in comparison to background, concentrations of iron ions nokite or more often occurring FeS04. 7Hz0- melanterite were observed. In limestone (24w),similaily to sample 9w at fig. 2D). Small crystds of KC1 occur in the incrustations. Chuddw, recrystallized calcite crystals are present in addition Additionally, smaIl gypsum crystals are present as well. In to small quantities of gypsum. sample T3p, except for platy accumulations of clay minerals. no other weathering products were determined. SmalI amount of zinc brings attention in sandstone sample 15p, which is TOSZEK probably related to dust contaminants. Secondarily crystallized crystals, mostly CaC03 and gyp Elevated amounts of sulphur, calcium, iron, sodium and sum CaS04. 2H20, are present at external surfaces of lime potassium, as we11 as presence of anthropogenic dust were stone samples. Results of analysis of sample 9w indicate observed in sandstone samples from the Toszek castle walls, significant amounts of suIphur and calcium (present as gyp- Surfaces of these rocks ate cavered with spotty, rubbing off, sum) and very small quantities of magnesium, potassium, and dusty coating. In sandstone (14p) gypsum (in significant iron (Fig. 2E). Diffraction lines of the latter ones may be quantities), calcium nitrate -nitrocalcite Ca(NQ3)a,as well caused by cIay rnineraIs which cement caIcite grains, or may as sylvine KC1 and halite NaCl were identified. be caused by small quantities of arcanite KzS04 and epsomite Large quantities of gypsum, iron oxides and hydroxides, and admixtures of KC1 occur in sandstone (12p). In sample Table 5

Content of soluble in water salts in samples of sandstones and limestones, based on the results of chemical analyses of aqueous solutions and results of X-ray-structural analyses

Carbo- Complex Sulphates Chlorides Azotanes Sample nates salts symbol szomol- hexa- nitro- nitro- nitram- thermo- mirabilite arcanite kieserite sylvine halite nitrokalite hanksite gypsum thenardite nokite hydrite epsomite natrite calcite Mg(N03)2 mite natrite

IPW 963 1420 1485 1726 1700 963 lpz 12655 - 1686 1254 - 296 12pw 986 134 - - 365 227 270 12pz 704 260 175 377 482 865 - 15pw 593 28 195 60 121 - 15pz 98384 1547 2161 - 7440 197 21pw 525 26 105 484 21pz 629 44 192 573 41pw 526 - 7 41pz 1668 27 36 4lpk 2977 - 43 42pw 1021 - 61 283 42pz 1011 33 85 - lww 250 - - 180 244 338 288 Iwz 19719 924 1695 567 733 4158 1135 4ww 137 32 13 - - - 9 4wz 61 - - 72 40 99 - 22ww 7 4 9 5 - 7 14 22wz 86 10 12 13 13 36 43 24ww 39 12 - 6 or 9 or 10 10 2 48 32 24wz 110 6 26 6 or 9 or 10 5 - - 44 43ww 3 - - 1.4 or 2.4 or2.7 0.2 0.4 2 0.5 43wz 146 0.7 16 - - 3 2 - - 54ww 164 12 19 or32 or35 10 15 20 54wz 255 32 9 or15 or17 21 13 65 24 16 or 35 7 11 38 15 50 56ww chloromagnezite 56wz 159 38 bishofite 81 16 28 82 19 175

Explanations as in Tables 2 and 3 216 Malgon

Table 6 nate were observed. A dark coating is present on a surface of the limestone sample 43w.X-my diffractometry mostly indi- Total salinity in sandstonrs and limpstones- based on the Table 5 cated presence of gypsum, as well as iron compounds and silica grains.

RESUL,TS OF CHEMICAL ANALYSES

Samples of analyzed sandstones and limestones were prepared from two zones: external @z and wz designation~)and internal (pw and ww designations). Chemical composition of a contact between a sandstone and a limy grout (pk designation) was analyzed in the sample 41p. Concentrations of soluble in water substances were measured in aqueous extracts from powdered rock samples. Results of chemical analyses of aqueous extracts from the samples described above are presented in Tables 3 and 4. Sulphates, nitrates and chlorides are present in aqueous solutions obtained from rock samples, which indicates presence of soluble in water salts. Deficiency of anions, caused by the absence of analysis of a carbonate ion c*, typically occur in sandstone samples. Predominant cation deficiency in limestones was supplemented by ammonium NH$ and iron ~e~'ions.

RECAPITULATION

Based on comparison between obtained results with results of X-ray diffractometry, a list of soluble in water salts which may occur in analyzed rock samples was prepared Explanations in Tables 2 and 3 (Table 5). Qualitative composition of saluble in water salts in analyzed samples was estimated, based on chemical analyses and comparison with results of X-ray structural analysis and 32p significant nccurnulations of gypsum plates and sporadic microstructural analysis, in cases where they were available. occurrence of barium were observed. It should be noticed that many of the substances listed in the Composition of a limestone (I lw) external surface (Fig. table may be subjected to hydration or dehydration, depend- 2F) indicates occurrence of silicon and aluminum ions, which ing on external conditions. Particularly szomoInokite (FeS04 results from the presence of cIay minerals on the sample RzO),as a mineral typically occurring in dry conditions may surface; phosphorus is probably associated with naturally be easily hydrated, which produces tetrahydrate plagionite or occurring apatite in carbonate rocks. In this sample smaller, heptahydrate rnelanterite. Degree of saIt hydration depends than in other carbonate rocks analyzed, amounts of CaS04. not only on a season but also on short-term weather fluctua- 2H20 accompanied by relatively large amounts of sylvine tions. Sample preparation procedures also affect degree of were indicated by SBM microscopy. hydration. Total salinities (expressed as weight %) of analy zed sandstanes and Iimestones are presented in Table 6, and were calculated as sum of soluble in water salts, presented in Table 5. In external, near-surfam zones of the analyzed samples, In sandstoncsample42p,in addition tonaturalIy occurring total salinity is significantly higher (Table 6). Only in a rock components (quartz and iron oxides and hydroxides), sandstone sample 42p from Mirbw, the opposite tendency was only very small quantities of gypsum were identified. Larger observed but relative differences between salinities are small. concentrations of sulphur ions, not associated with ,the In sampie4Ip, a grout contact zone is characterized by higher presence of calcium, occur in sample 45p (Fig. 2G).Potas- salinity than that of the external zone in the same sample. It sium and magnesium sulphates may occur in sample as well. indicates intensive chemical reactions in this zone. Products some Potassium may partly react with a chlorine ion. In of these reactions remain in rocks; they are not easily leach- places, stalactite-typedripforms composed of calcium carbo- Water soluble salts in degradation of stony monuments 217 able as they are in the external part. Based on the study results, external zones of samples 15p (10.97%),lp (1 -59%)and 1w clastic rocks (sandstones) are presumably characterized by (2.89%). higher salinity than in carbonate rocks. Only an external zone Based on the study results it appears that magnitude of limestone at Chudbw I w indicates very high salinity and atmospheric, industrial and bransport related pollution does particularly high gypsum content. The highest total salinity not affect directly degree of salinity of stony materiaIs. Sarn- was measured in rocks from the Chud6w castle ruins, particu- ples of rocks collected in the Mir6w castle ruins, despite its lady the external zone of sandstone sample 15p. Significantly location in relatively less industrialized region, do not reflect higher than in asample E p, salinity in this case may result from lower values of salinity than these measured in samples from a fact that sample 15p was collected at lower elevation above the B~dzincastle walls. It partly results from the fact that the ground surface (ca. 30 cm); sample I p was collected at few-rnillimetre thick, gypsum-salt coatings form on dolomitic elevation ca. 80 cm. Similar tendency occurs between lime 1irnestone surfaces in Eedzin, where soluble substances pre- stone samples lw and 4w, although difference in salinity is cipitate from migrating in fractures solutions. Thus in rock here significantly smaller. Observation presented above jndi- itself, amounts of soluble in water salts is relatively small. cates that some salts might originate from soils. Based on the comparison of total salinity in analyzed Considering an assumption used in stony materials pres- samples, it may be concluded that amount of soluble in water ervation that 1% by weight content of all salts in a material is salts is mostly dependent on lithological: type, and in a much the maximum altowable salinity (P. StepieA et al., 19931, it lesser degree on magnitude of atmospheric pollution. should be concluded that rock samples from the Chudbw castle ruins are characterized by excessive salinity. It refers to

BAEDECKER P. A., REDDY M. M., REIMANN K. J., SCIAMARELLA MIKHEeV V. I. (1957) - Rentgenometrichesky opdelitel minadov. C. A. (I 992) -Effccts of acidic deposition on the erosion of cahonate Moskva stone-experimental results from the U.S. Mntional Acid Precipitation MINERAL POWDER DIPFRACTION FlLE (1986) - InL Centre for Assessment Program (NAPAP). Atmosph. Envimn., 26E, p. 147-158, Diffraction Data. no, 2. SKIBI~~SKIS. (1989) - Odsalanie kamiennych obiektbw zabytkowych BOLEWSKI A. (1 982)- Minedogia szneg6haWyd. Ckol. Warszawa. (Metoda elekldializy membmnowej). Biblioteka Muzealnictwa i Och- FOBE B. O., VLEUGELS G. J., ROEKENS & J., VAN GRIEKEN R. E., rony Zabytkdw. B, 84. Wmzawa. HERMOSIM B., ORTEGA-CALVO J. J., DEL lWC0 A, S., SAIZ STE;PIE~~P., KOZtOWSKL R., MAGIERA J. (1993) - Problemy konser- JIMENEZ C. (1995)-Organic and inorganic oornpounds in limestone wacji obiekt6w architektonicznych z dolornitu na przyktadzie baro- wcnthcring crusts from cathednls in Soulhem and Western Europe. kowych bram w ogrodzeniu Katodry Wawelskiej. Ochr. Zabytkbw,4, p. hvimn. Sc.Tcchnol., 29, p. 1691-1701, no. 6, 338-346. L~FVENDAHLR., BYLUND CH.,GUSTAFFSON-BELZACO M., SWEEWERS H.,VAN GRICKEN R. (1992) - Analytical study of the NORD A. G. (1992)- Building stom nnd sculptural de&riomtians. In: dcteriontion ofsandstone, marble md granite. Atmosph. Envimn..26B, Air pollution and the Swedish Herit;ge. Rapporl RIK 6. The Ccntd p. 159-1 63, no. 2. Broad of National Antiquites and rbe National Historid Muscums, p. 51-99.

SOLE ROZPUSZCZALW W WODm W PROCJBACH MSZCZEW KAMIENNYCH ZABYTKQW BUDOWLANYCHNA G~IWYMSLASHEU

Streszczenie

Jednym z najistotniejszych czynnikdw wplywajacych na pmbieg i wymienionych obiekt6w pobrana pr6bki piaskowc6w, wapieni i granitoi- intcnsywnoSrS wietrzenin kamiennego bodulca jest sila krystdimcji soli roz- d6w, a w niekt6rychprzypadknchr6wniekprdbki zapnwy rnumkiej i cegiet puszcznlnych w wodzie. Sole tnkie, migrujqce w skale za poGdnictwem (tab. I). wody porowej, powsrajq w wyniku naturalnego rozkhdu mineraI6w skdo- Badmia rentgenowskie wykady, opr6cz typowych skhdnikh mine- twhczych, a hkie w wyniku korozji kamienin spotqgowanej oddzidym- mlnych, abecnoSE siarcmbw. azotandw. chlork6w i soli zloionych (fig. 1. nicm zanicczyszczeri atmosferycznych. tab. 2). Mikroanalizy rentgenowskie wykazuj~w pnypowierzchniowych Przeanalizowano sklad chemiczny saefpnypowierzchniowych sknl dla partiach badanych prdbek podwyiszone zawm-toki siarki, chloru i klaw. W uzyskania in~omcjio produktach ich komzji. Eadaninprzeprowdznno na ciemnych naskorupieniach, wystepujwych gl6wnie na powierzchniach wa- prdbkach skat wpcych budulcemczterech obiekt6w zabylkewych znajdu- picni doIomitycmych pocbodz~~cychz zamku w Btdzinie, wysepujq pyly jqcych sic na obrzelmiach GdrnoSlqskiego Okregu Przemyslowego: trzech przemysIowe, gips, chlorki i minenfy ihqk (fig. 2, tabl. I i n). w czGci zachodniej [zamck w Toszku, spichlerz w StiuychGliwicachi miny Analizy chemiczne abj~lyoznaczenia ilokiowe niektdrychjon6w (Nat, zamku w Chudowie) oraz jednego w cqSci wschodnicj (zamck w Eqdzinie). K*, ca2', h4PZ+.NO;, SO&, CI-) w roztwonch wodnych uzyskmych ze Por6wnawczo pmbdano ponadto pfibki pochdwce z ruin mkuw Mi- sproszkowmych pr6bck skd (tab. 3 i 4). mwie (Jura Krakowsko-Cqstmhowska) zlokalizowanego w regionie o znn- Por6wnujqc uzyskane wyniki z rezultatami analiz rentgenewskich, ze- cznie mniejssym stopniu zaniecgyszczenia atmosferycznego. Z stawiono wykaz soli rozpuszczalnych w wodzie, jakie mogwysRpoW w badnnych pr6bhch skat (tab. 5). W suefach przypowierzchniowy~hbada- wystepujacych w badanych sknhch, znajdujasie chlorki, siarczmy, mtmy nych skat zasolenie sumaycznejest wyhz(tab. 6). Stopieii zasolenia sM i soIe zlokone. Notowme one nie tylbw wykwitach i naskorupieniach, zalety gWwnic od Ich typu Iitologicmego. Najsilniejszemu wictrzeniu ule- ale rakie w przypewienchniowych partiach blokdw skalnych. Elementy gaja sknly ooktuchnwe, w mniejszym stopniu skaty v&glmowe; skilly mag- kamiennc w doInych partiech rnurbw wykazuja wyism molenie sumqz- mowe sq najbardziej odpomc. WbrM soli mxpuszczalnych w wodzie, nc nii pozoatale, co wskazuje na cdciowe pmhodzenie soli z gruntu.

EXPLANATIONS OF PLATES

PLATE I PLATE I1

Fig. 3. Crystals of gypsum and halite crystallized from incrnstations in silty Fig. 5. Crystals of gypsum crystalliaed from grout sample 432 in Mi& sandstone in the ToszekcastIe (pallel nicols) (pdlcl nicols) ~~ gipsu i halitu wylqstalizowane z naskanrpieri z piaskruw- KryszMy gipu wylaystdizowane z pr66ki zaprawy 432 2 Mirowa c6w mubwcowych z zarnku w Toszku (nikofe skdnc) (nikole skdne) Fig. 4. Gypsum frum incrustations on dolomitic limtstones in the B~dzin Pig. 6.Seoondmy crystallid carbonates and gypsum from sediment depo- cnstle (cmssed nicoIs) sited on a brick at Toszek (parallel nicols) Gips z nnskonrpie6 na wapieniach dolomitymych z zamku w Bqdzi- Wttjrnie wykrystalizowane~glanyi gips zosndupowstalegonacegle nie (nikole sknyzownne) -Toszek (nikole skobne) Fig 3

fig. 4

MdgorzahLABUS -Water soluble salts in degradation processes of stony architectural monuments in the Upper Silesin PLATS II Geol. Quart., 1998.42 (2)

Fig. 5

Fig. 6

Matgorzata LABUS -Water solublc salts in degradation procmses of stony architectural monuments in the Upper Silesia